text:
Patent US8183310 - Fluorescent brighteners, methods of preparation thereof, fluorescent ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign in<nobr>Advanced Patent Search</nobr>PatentsA compound of Formula (I) wherein R1, R2, and R3 are independently at each occurrence hydrogen, a halogen, a cyano functionality, a C1-C20 aliphatic functionality, a C3-C10 cycloaliphatic functionality or a C3-C20 aromatic functionality, with the proviso that R2 and R3 are not hydrogen when R1 is a methyl...http://www.google.com/patents/US8183310?utm_source=gb-gplus-sharePatent US8183310 - Fluorescent brighteners, methods of preparation thereof, fluorescent brightener compositions, and methods of preparation and uses thereofAdvanced Patent SearchPublication numberUS8183310 B2Publication typeGrantApplication numberUS 12/561,764Publication dateMay 22, 2012Filing dateSep 17, 2009Priority dateNov 21, 2005Also published asCN101379038A, CN101379038B, EP1966145A2, US7608715, US8507590, US20070117887, US20110065843, US20120203001, WO2007062002A2, WO2007062002A3Publication number12561764, 561764, US 8183310 B2, US 8183310B2, US-B2-8183310, US8183310 B2, US8183310B2InventorsShantaram Narayan Naik, Adil Minoo Dhalla, Yogendrasinh Bharatsinh ChauhanOriginal AssigneeSabic Innovative Plastics Ip B.V.Export CitationBiBTeX, EndNote, RefManPatent Citations (14), Non-Patent Citations (12), Referenced by (2), Classifications (11), Legal Events (1) External Links: USPTO, USPTO Assignment, EspacenetFluorescent brighteners, methods of preparation thereof, fluorescent brightener compositions, and methods of preparation and uses thereofUS 8183310 B2Abstract A compound of Formula (I)
wherein R1, R2, and R3 are independently at each occurrence hydrogen, a halogen, a cyano functionality, a C1-C20 aliphatic functionality, a C3-C10 cycloaliphatic functionality or a C3-C20 aromatic functionality, with the proviso that R2 and R3 are not hydrogen when R1 is a methyl or hydrogen; R4 and R5 are independently at each occurrence hydrogen, a halogen, a cyano functionality, a C1-C20 aliphatic functionality, a C3-C10 cycloaliphatic functionality or a C3-C10 aromatic functionality; R7 and R8 are independently at each occurrence, a halogen, a cyano functionality, a C1-C20 aliphatic functionality, a C3-C10 cycloaliphatic functionality or a C3-C10 aromatic functionality; R6 is a C2-C20 aliphatic functionality, a C3-C10 cycloaliphatic functionality or a C3-C20 aromatic functionality; and �n� and �m� are each independently integers having a value of 0 to 3.
wherein �p� is an integer having a value of 2 to 4.
2. The composition of claim 1, wherein �p� is an integer having a value of 2.
3. The composition of claim 1, wherein �p� is an integer having a value of 3.
4. The composition of claim 1, wherein �p� is an integer having a value of 4.
5. The composition of claim 1, wherein the compound of Formula (II) is present in an amount of about 0.05 weight percent to about 20 weight percent, based on the total weight of the composition.
6. The composition of claim 1, wherein the polymer component comprises a polycarbonate.
a compound having Formula (III)
9. The composition of claim 8, wherein the compound of Formula (II) is present in an amount of about 0.05 weight percent to about 20 weight percent, based on the total weight of the composition.
10. The composition of claim 8, wherein the polymer component comprises a polycarbonate.
11. An article comprising the composition of claim 8. Description
CROSS-REFERENCE TO RELATED APPLICATIONS This application is a division of U.S. patent application Ser. No. 11/285,336, filed Nov. 21, 2005, now U.S. Pat. No. 7,608,715.
BACKGROUND OF THE INVENTION This disclosure relates to fluorescent brighteners. More particularly the disclosure relates to fluorescent brighteners, methods of preparing the fluorescent brighteners, compositions comprising the fluorescent brighteners, in particular polymer compositions comprising the fluorescent brighteners, and uses thereof.
Fluorescent brighteners, also known as fluorescent whitening agents, fluorescent whiteners, optical brighteners, and optical whiteners, are additives that alter the visual properties of polymers. Fluorescent brighteners are colorless to weakly colored organic compounds. When in solution, applied to a substrate, or combined with a polymer, they absorb primarily ultraviolet light in the 300 to 400 nanometer (nm) range. Most of the absorbed energy is then re-emitted as visible violet-to-blue fluorescent light in the 400 to 500 nm range. Fluorescent brighteners thus help to mask inherent yellowness in discolored polymers and impart unique, robust color to specialty plastic products.
There are very few fluorescent brighteners exhibiting high Tg values. In addition, many fluorescent brighteners decompose at temperatures commonly used to process polymers. One high Tg fluorescent brightener is 2,2′-(2,5-thiophenediyl) bis[5-(1,1-dimethylethyl)]-benzoxazole, (CAS No. [7128-64-5]) available from Ciba under the trade name UVITEX�-OB. Nonetheless, there remains a need in the art for fluorescent brighteners that have a high Tg to enable their use in a wide variety of polymers, especially thermoplastic polymers.
SUMMARY OF THE INVENTION Disclosed herein is a compound of Formula (I)
wherein R1, R2, and R3 are independently at each occurrence hydrogen, a halogen, a cyano functionality, a C1-C20 aliphatic functionality, a C3-C10 cycloaliphatic functionality, or a C3-C20 aromatic functionality, with the proviso that R2 and R3 are not hydrogen when R1 is a methyl or hydrogen; R4 and R5 are independently at each occurrence hydrogen, a halogen, a cyano functionality, a C1-C20 aliphatic functionality, a C3-C10 cycloaliphatic functionality, or a C3-C10 aromatic functionality;
R7 and R8 are independently at each occurrence, a halogen, a cyano functionality, a C1-C20 aliphatic functionality, a C3-C10 cycloaliphatic functionality, or a C3-C10 aromatic functionality; R6 is a C2-C20 aliphatic functionality, a C3-C10 cycloaliphatic functionality, or a C3-C20 aromatic functionality; and �n� and �m� are each independently integers having a value of 0 to 3.
In one embodiment a process for preparing a compound of Formula (I) comprises reacting an anhydride compound of Formula (IV) with an aniline compound of Formula (V)
in the presence of a first solvent to provide a compound of Formula (VI)
reacting the compound of Formula (VI) with a hydroxy compound of Formula (VII)
R6�OH (VII)
in the presence of a base and a second solvent to provide a compound of Formula (I)
wherein R1, R2, and R3 are independently at each occurrence hydrogen, a halogen, a cyano functionality, a C1-C20 aliphatic functionality, a C3-C10 cycloaliphatic functionality, or a C3-C20 aromatic functionality, with the proviso that R2 and R3 are not hydrogen when R1 is a methyl or hydrogen;
R4 and R5 are independently at each occurrence hydrogen, a halogen, a C1-C20 aliphatic functionality, a C3-C10 cycloaliphatic functionality, or a C3-C10 aromatic functionality;
R7 and R8 are independently at each occurrence a halogen, a C1-C20 aliphatic functionality, a C3-C10 cycloaliphatic functionality, or a C3-C10 aromatic functionality;
R6 is a C2-C20 aliphatic functionality, a C3-C10 cycloaliphatic functionality, or a C3-C20 aromatic functionality;
X is a halogen selected from chlorine, bromine or iodine; and
�n� and �m� are each independently integers having a value of 0 to 3.
Also disclosed herein are compositions comprising the compound of Formula (I), methods of making the compositions, and articles comprising the composition comprising the compound of Formula (I).
DETAILED DESCRIPTION OF THE INVENTION Disclosed herein are compounds having high Tg and that in some embodiments may be used as fluorescent brighteners.
The singular forms �a�, �an� and �the� include plural referents unless the context clearly dictates otherwise. All ranges disclosed herein are inclusive of the endpoint and independently combinable (for example ranges of �up to 25 weight (wt.) percent, with 5 wt. percent to 20 wt. percent desired,� is inclusive of the endpoints and all intermediate values of the ranges of �5 wt. percent to 25 wt. percent�).
�BPA� is herein defined as bisphenol A, and is also known as 2,2-bis(4-hydroxyphenyl)propane, 4,4′-isopropylidenediphenol, and p,p-BPA.
Unless otherwise specified, the term �cycloaliphatic functionality� designates cyclic aliphatic functionalities having a valence of at least one, and comprising an array of atoms which is cyclic but which is not aromatic. The cycloaliphatic functionality may include heteroatoms such as nitrogen, sulfur, selenium, silicon, and oxygen, or may be composed exclusively of carbon and hydrogen. A �cycloaliphatic functionality� may be linked via the cyclic group or via another group on the cyclic group. For example, a cyclohexylmethyl group (C6H11CH2�) is a cycloaliphatic functionality that comprises a cyclohexyl ring (the array of atoms which is cyclic but which is not aromatic) and a methylene group (the noncyclic component). A �cycloaliphatic moiety� may further be unsubstituted or substituted, i.e., comprising one or more noncyclic components, including functional groups such as alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, halogen(s), conjugated dienyl groups, alcohol groups, ether groups, carboxylic acid groups, acyl groups (for example carboxylic acid derivatives such as esters and amides), amine groups and nitro groups, provided that the functional group(s) do not substantially adversely impact the intended function of the compound. For example, the 4-methylcyclopent-1-yl group is a C6 cycloaliphatic functionality comprising a methyl group, wherein the methyl group is an alkyl functional group. Similarly, the 2-nitrocyclobut-1-yl group is a C4 cycloaliphatic functionality comprising a nitro group, wherein the nitro group is a functional group. Exemplary cycloaliphatic functionalities include cyclopropyl, cyclobutyl, 1,1,4,4-tetramethylcyclobutyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, cyclohexyl, and cyclopentyl.
As used herein, the term �aromatic functionality� refers to an array of atoms having a valence of at least one, and comprising at least one aromatic group. The array of atoms comprising the at least one aromatic group may include heteroatoms such as nitrogen, sulfur, selenium, silicon, and oxygen, or may be composed exclusively of carbon and hydrogen. As used herein, the term �aromatic functionality� includes but is not limited to phenyl, pyridyl, furanyl, thienyl, naphthyl, phenylene, and biphenyl functionalities. The aromatic functionality may also include nonaromatic components. For example, a benzyl group is an aromatic functionality that comprises a phenyl ring (the aromatic group) and a methylene group (the nonaromatic component). Similarly a tetrahydronaphthyl functionality is an aromatic functionality comprising an aromatic group (C6H3) fused to a nonaromatic component �(CH2)4�. An �aromatic functionality� may further be unsubstituted or substituted with a wide range of functional groups such as alkyl groups, haloalkyl groups, haloaromatic groups, halogens, alcohol groups, ether groups, carboxylic acid groups, acyl groups (for example carboxylic acid derivatives such as esters and amides), amine groups and nitro groups, provided that the functional group(s) do not substantially adversely impact the intended function of the compound. For example, the 4-methylphenyl functionality is a C7 aromatic functionality comprising a methyl group, wherein the methyl group is an alkyl functional group. Similarly, the 2-nitrophenyl group is a C6 aromatic functionality comprising a nitro group, wherein the nitro group is a functional group. Exemplary aromatic functionalities include, but are not limited to phenyl, 4-trifluoromethylphenyl, 4-chloromethylphen-1-yl, 3-trichloromethylphen-1-yl (3-CCl3Ph-), 4-(3-bromoprop-1-yl)phen-1-yl (4-BrCH2CH2CH2Ph-), 4-aminophen-1-yl (4-H2NPh-), 4-hydroxymethylphen-1-yl (4-HOCH2Ph-), 4-methylthiophen-1-yl (4-CH3SPh-), 3-methoxyphen-1-yl, 2-nitromethylphen-1-yl (2-NO2CH2Ph-), and naphthyl.
As used herein the term �aliphatic functionality� refers to an organic functionality having at least one carbon, a valence of at least one, and consisting of a linear or branched array of atoms that is not cyclic. The array of atoms comprising the aliphatic functionality may include heteroatoms such as nitrogen, sulfur, silicon, selenium, and oxygen or may be composed exclusively of carbon and hydrogen. An �aliphatic functionality� may be unsubstituted or substituted with a wide range of functional groups such as alkyl groups, haloalkyl groups, halogens, alcohol groups, ether groups, carboxylic acid groups, acyl groups (for example carboxylic acid derivatives such as esters and amides), amine groups, and nitro groups, provided that the functional group(s) do not substantially adversely impact the intended function of the compound. For example, the 4-methylpent-1-yl is a C6 aliphatic functionality comprising a methyl group, wherein the methyl group is a functional group which is an alkyl group. Similarly, the 4-nitrobut-1-yl group is a C4 aliphatic functionality comprising a nitro group, wherein the nitro group is a functional group. Exemplary aliphatic functionalities include, but are not limited to methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, trifluoromethyl, bromodifluoromethyl, chlorodifluoromethyl, chloromethyl, trichloromethyl, bromoethyl, 2-hexyl, hexamethylene, hydroxymethyl (�CH2OH), mercaptomethyl (�CH2SH), methylthio (�SCH3), methylthiomethyl (�CH2SCH3), methoxy, methoxycarbonyl (CH3OCO�), nitromethyl (�CH2NO2) and thiocarbonyl.
In one embodiment compounds of Formula (I) are disclosed,
wherein R1, R2, and R3 are independently at each occurrence hydrogen, a halogen, a cyano functionality, a C1-C20 aliphatic functionality, a C3-C10 cycloaliphatic functionality, or a C3-C20 aromatic functionality, with the proviso that R2 and R3 are not hydrogen when R1 is a methyl or hydrogen; R4 and R5 are independently at each occurrence hydrogen, a halogen, a cyano functionality, a C1-C20 aliphatic functionality, a C3-C10 cycloaliphatic functionality, or a C3-C10 aromatic functionality; R7 and R8 are independently at each occurrence a halogen, a cyano functionality, a C1-C20 aliphatic functionality, a C3-C10 cycloaliphatic functionality, or a C3-C10 aromatic functionality; R6 is a C2-C20 aliphatic functionality, a C3-C10 cycloaliphatic functionality, or a C3-C20 aromatic functionality; and �n� and �m� are each independently integers having a value of 0 to 3.
In one embodiment, R1, R4, and R5 are each hydrogen, R2 and R3 are each a C2-C6 aliphatic functionality that can be the same or different, R7 and R8 are independently at each occurrence a halogen, a cyano functionality, or a C1-C6 aliphatic functionality, and n and m are each 0 to 3.
In a specific embodiment R1, R4, and R5 are hydrogen, R2 and R3 are both a C3 aliphatic functionality, R6 is a C2-C4 aliphatic functionality or a C6-18 aromatic functionality and n and m are each 0.
In one embodiment the compound is of Formula (II) or Formula (III)
wherein in Formula (II) �p� has a value of 2 to 4. The compound of Formula (II) when �p� is 2 to 4 may be referred to as 2-(2,6-diisopropylphenyl)-6-(2-hydroxyethoxy)-benzo[de]isoquinoline-1,3-dione; 2-(2,6-diisopropylphenyl)-6-(3-hydroxypropoxy)-benzo[de]isoquinoline-1,3-dione and 2-(2,6-diisopropyl-phenyl)-6-(4-hydroxy-butoxy)-benzo[de]isoquinoline-1,3-dione, respectively, and the compound of Formula (III) may be referred to as 2-(2,6-diisopropylphenyl)-6-[4-(1-methyl-1-phenylethyl)-phenoxy]-benzo[de]isoquinoline-1,3-dione.
In one embodiment a process for making the fluorescent brightener compound of Formula (I) is as follows. An anhydride compound of Formula (IV), wherein X is a halogen, is reacted with an aniline compound of Formula (V)
in the presence of a first solvent to provide a compound of Formula (VI) wherein R1, R2, R3, R4, R5, R7, R8, �n,� and �m� have the same meaning as defined above.
Suitable anhydride compounds of Formula (IV) include 4-bromo-1,8-naphthalic anhydride, 4,5-dibromo-1,8-naphthalic anhydride, 2-benzoyl-4-bromo-1,8-naphthalic anhydride, 2-acetyl-4-bromo-1,8-naphthalic anhydride, 2-ethyl-4-bromo-1,8-naphthalic anhydride, 4,6-dibromo-1,8-naphthalic anhydride, and combinations comprising at least one of the foregoing anhydrides.
Suitable aniline compounds of Formula (V) include 2,6-diisopropylaniline, 4-propylaniline, 4-iodo-2-methylaniline, 4-bromo-3-methylaniline, 3-bromo-2,4,6-trimethylaniline, 2-bromo-4-chloro aniline, 4-(1H-imidazol-1-yl)-aniline, and combinations comprising at least one of the foregoing aniline compounds.
The amount of the aniline compound of Formula (V) employed in the reaction can be about 1.0 mole to about 3.0 moles per mole of anhydride compound of Formula (IV) employed. Within this range the amount may be greater than or equal to 1.2 moles, or, more specifically, greater than or equal to about 1.5 moles. Also within this range the amount may be less than or equal to about 2.5 moles, or, more specifically less than or equal to about 2.0 moles.
Specific examples of suitable first solvents that can be employed in the reaction of the anhydride compound of Formula (IV) with the aniline compound of Formula (V) to produce the compound of Formula (VI) include, but are not limited to acetic acid, propionic acid, butanoic acid, ethanol, methanol, propanol, iso-propanol, butanol, iso-butanol, toluene, xylene, dichloromethane, dichloroethane, chloroform, chlorobenzene, ortho-dichlorobenzene, trichlorobenzene, dimethylformamide, diethylacetamide, tetrahydrofuran, dimethylsulfoxide, or combinations of one or more of the foregoing solvents. In one embodiment the solvent employed comprises acetic acid. In certain embodiments the amount of solvent employed in the reaction of the anhydride compound of Formula (IV) with the aniline compound of Formula (V) can be about 10 moles to about 50 moles liters per mole of anhydride compound of Formula (IV). Within this range the amount may be greater than or equal to about 15 moles, or, more specifically, greater than or equal to about 20 moles. Also within this range the amount may be less than or equal to about 40 moles, or, more specifically less than or equal to about 30 moles.
The temperature at which the reaction of the anhydride compound of Formula (IV) with the aniline compound of Formula (V) takes place may be about 80� C. to about 180� C. Within this range the temperature may be greater than or equal to about 90� C., or, more specifically, greater than or equal to about 100� C. Also within this range the temperature may be less than or equal to about 160� C., or, more specifically, less than or equal to about 150� C. The time taken for the reaction of the anhydride compound of Formula (IV) with the aniline compound of Formula (V) can be about 3 hours to about 20 hours. Within this range the time may be greater than or equal to about 5 hours, or, more specifically, greater than or equal to about 10 hours. Also within this range the time may be less than or equal to about 18 hours, or, more specifically, less than or equal to about 15 hours.
The compound of Formula (VI) is reacted with a hydroxy compound of Formula (VII)
wherein R6 is as described above, in the presence of a base and a second solvent to provide a compound of Formula (I) as described above.
Suitable hydroxy compounds of Formula (VII) include, but are not limited to, 1,2-ethylene diol, 1,3-propylene diol, 1,4-butane diol, 4-cumyl phenol, 1,6-hexane diol, 1,7-heptanediol, 1,8-octane diol, 1,4-cyclohexane diol, 1,2-cyclohexane diol, and combinations comprising at least one of the foregoing hydroxy compounds.
The amount of hydroxy compound of Formula (VII) employed in the reaction can be 1 mole to 5 moles per mole of compound of Formula (VI). Within this range the amount may be greater than or equal to about 2 moles, or, more specifically, greater than or equal to about 2.5 moles. Also within this range the amount may be less than or equal to about 4.5 moles, or, more specifically, less than or equal to about 4 moles.
Suitable bases include but are not limited to alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, or alkaline earth metal carbonates. Specific alkali metal hydroxides or alkaline earth metal hydroxides include but are not limited to sodium hydroxide, lithium hydroxide, potassium hydroxide, rubidium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, and magnesium hydroxide.
In one embodiment a catalyst may be employed in reaction of the compound of Formula (VI) with the hydroxide of Formula (VII). Without being bound to theory it is believed that use of the catalyst will help to increase the speed of the reaction, thereby decreasing reaction time. Suitable catalysts include, but are not limited, to phase transfer catalysts such as tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium fluoride trihydrate, tetrabutylammonium hydrogen sulfate, tetrabutylammonium iodide, tetrabutylammonium thiocyanate, tetrabutylammonium tetrafluoroborate, benzyltributylammonium chloride, benzyltriethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium hydrogen sulfate, methyltrioctadecylammonium bromide, methyltrioctylammonium bromide, methyltrioctylammonium chloride, tetraethylammonium bromide, tetraethylammonium chloride, tetraethylammonium fluoride dihydrate, tetraethylammonium hexafluorophosphate, tetraethylammonium tetrafluoroborate, tetrahexylammonium hydrogen sulfate, tetramethylammonium bromide, tetramethylammonium chloride, tetraoctylammonium bromide, tetraoctylammonium chloride, polyethylene glycol, hexamethylphosphoramide, tributylmethylphosphonium chloride, tributylmethylphosphonium chloride, hexyltributylphosphonium bromide, tributylmethylammonium chloride, tris[2-(2-methoxyethoxy)ethyl]amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane, dicyclohexano-24-crown-8, dicyclohexano-18-crown-6,18-Crown-6, dibenzo-24-crown-8, dibenzo-18-crown-6,15-crown-5,1-aza-15-crown-5,12-crown-4, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride and tributylhexadecylphosphonium bromide. Combinations comprising at least one of the foregoing catalysts can be used.
Specific examples of suitable second solvents include but are not limited to toluene, xylene, dichloromethane, dichloroethane, chloroform, chlorobenzene, ortho dichlorobenzene, trichlorobenzene, dimethylformamide, diethylacetamide, tetrahydrofuran, dimethylsulfoxide, or combinations comprising at least one of the foregoing solvents. The amount of second solvent employed in the reaction of compound of Formula (VI) with the hydroxy compound of Formula (VII) can be about 5 moles to about 100 moles per mole of the compound of Formula (VI). Within this range the amount may be greater than or equal to about 10 moles, or, more specifically, greater than or equal to about 20 moles. Also within this range the amount may be less than or equal to about 90 moles, or, more specifically, less than or equal to about 80 moles. In certain embodiments the hydroxy compound of Formula (VII) may be used in addition to or instead of the second solvent. In this embodiment the amount of the hydroxy compound present in the reaction can be 5 moles to 105 moles per mole of the compound of Formula (VI).
The temperature of the reaction of the compound of Formula (VI) with the hydroxy compound of Formula (VII) can be about 80� C. to about 180� C. Within this range the temperature may be greater than or equal to about 90� C., or, more specifically, greater than or equal to about 100� C. Also within this range the temperature may be less than or equal to about 160� C., or, more specifically, less than or equal to about 150� C. The time for the reaction of compound of Formula (VI) with the hydroxy compound of Formula (VII) can be about 4 hours to about 15 hours. Within this range the time may be greater than or equal to about 6 or, more specifically, greater than or equal to about 8 hours. Also within this range the time may be less than or equal to about 14 hours, or, more specifically, less than or equal to about 12 hours.
A polymer composition is also disclosed herein, said composition comprising a polymer and a compound of Formula (I) as described above and or a compound of Formula (VIII)
wherein R9, R19, and R11 are independently at each occurrence hydrogen, a halogen, a cyano functionality, a C1-C20 aliphatic functionality, a C3-C10 cycloaliphatic functionality or a C3-C20 aromatic functionality; R4 and R5 are independently at each occurrence hydrogen, a halogen, a cyano functionality, a C1-C20 aliphatic functionality, a C3-C10 cycloaliphatic functionality or a C3-C10 aromatic functionality; R7 and R8 are independently at each occurrence, a halogen, a cyano functionality, a C1-C20 aliphatic functionality, a C3-C10 cycloaliphatic functionality or a C3-C10 aromatic functionality; R6 is a C2-C20 aliphatic functionality, a C3-C10 cycloaliphatic functionality or a C3-C20 aromatic functionality, �n� and �m� are each independently integers having a value of 1 to 3 and a polymer.
In one embodiment, R1, R2, R3, R4, and R5 are independently at each occurrence hydrogen or a C2-C6 aliphatic functionality, R7 and R8 are independently at each occurrence a halogen, a cyano functionality, or a C1-C6 aliphatic functionality, and n and m are each 0 to 3.
The compounds may be prepared in a similar manner as described for the preparation of the compound of Formula (I).
The compounds of Formulas (I) and (VIII) can have utility as fluorescent brighteners. In one embodiment, a compound that can be used as a fluorescent brightener has an absorption maximum in the 300 to 400 nm range, and an emission maximum in the 400 to 500 nm range, measured in an appropriate solvent, such as dichloromethane. Fluorescent brighteners find utility as an additive to a wide range of materials, including textiles, paper, detergents, and polymers. For example fluorescent brighteners can be used to impart a �whiter-than-white� appearance to polymers pigmented with titanium dioxide; to produce a bluish tinge in clear polymers, masking yellowness; to make lightly colored polymers appear more brilliant; and/or to aid in restoring whiteness to recycled polymers.
One or more of the foregoing effects can be observed with the naked eye, or measured using a tristimulus reflection colorimeter, using the CIELAB color scale, L*, a*, and b*, where L* defines lightness, the a* axis denotes green/red (+/−) and the b* axis defines blue/yellow (+/−). Higher L* values indicate that more light is reflected. Addition of fluorescent brighteners can result in lower b* values. The blue color range occupies the negative (−) side of the b* axis, while the yellow color range occupies the positive side. The lower the b* value, the less yellow color is perceived by the naked eye, and likewise, lower b* values indicate greater perception of whiteness and blue color. Accordingly, when used as fluorescent brighteners, the compounds of Formula (I) decrease the b* value of the composition containing a compound of Formulas (I) relative to the same composition without the compound of Formula (I). In one embodiment the b* value of the composition containing the compound of Formula (I) is decreased by at least 5% of the b* value of the same composition without the compound of Formula (I). Similarly, when used as fluorescent brighteners, the compounds of Formula (VIII) decrease the b* value of the composition containing a compound of Formulas (VIII) relative to the same composition without the compound of Formula (VIII). In one embodiment the b* value of the composition containing the compound of Formula (VIII) is decreased by at least 5% of the b* value of the same composition without the compound of Formula (VIII).
Both of the compounds of Formula (I) and (VIII) (singly or in combination) can be used in the brightening of polymers, especially thermoplastic polymers, for example, polycarbonates, polyesters, polyimides, polyamides, polyetherimides, thermoplastic polyurethanes, epoxide containing polymers, polyvinylchlorides, and others. It is also possible to use combinations comprising one or more of foregoing polymers, for example combinations of polycarbonates and/or polycarbonate copolymers with polyamides, polyesters, other polycarbonates; copolyester-polycarbonates, olefin polymers such as acrylonitrile-butadiene-styrene (ABS), polystyrene, polyethylene; polysiloxanes, polysilanes and/or polysulfones. As used herein, a �combination� is inclusive of all mixtures, blends, and alloys. When the combination is with a non-thermoplastic polymer, in certain embodiments the non-thermoplastic polymer(s) may be present in an amount of less than or equal to 40 weight percent, more specifically less than or equal to 35 weight percent and most specifically less than or equal to about 30 weight percent, based on the total weight of the polymer composition.
When used as an fluorescent brightener in a polymer composition, the compounds of Formula (I) and/or (VIII) can be present in an amount of about 0.05 weight percent to about 20 weight percent, based on the total weight of the composition.
In addition to the polymer, the polymer composition may include various additives ordinarily incorporated in resin compositions of this type, with the proviso that the additives are preferably selected so as to not significantly adversely affect the desired properties of the thermoplastic composition. Mixtures of additives may be used. The amounts of such additives will depend on the desired properties of the composition, and are readily determinable by one of ordinary skill in the art without undue experimentation.
Exemplary additives include such materials as fillers or reinforcing agents, thermal stabilizers, radiation stabilizers, antioxidants, light stabilizers, ultraviolet (UV) light stabilizers, plasticizers, visual effect enhancers, extenders, antistatic agents, catalyst quenchers, mold release agents, flame retardants, infrared shielding agents, whitening agents, blowing agents, anti-drip agents, impact modifiers and processing aids. The different additives that can be incorporated in the polymer compositions of the present invention are typically commonly used and known to those skilled in the art.
Suitable fillers or reinforcing agents include, for example, silicates and silica powders such as aluminum silicate (mullite), synthetic calcium silicate, zirconium silicate, fused silica, crystalline silica graphite, natural silica sand, or the like; boron powders such as boron-nitride powder, boron-silicate powders, or the like; oxides such as TiO2, aluminum oxide, magnesium oxide, or the like; calcium sulfate (as its anhydride, dihydrate or trihydrate); calcium carbonates such as chalk, limestone, marble, synthetic precipitated calcium carbonates, or the like; talc, including fibrous, modular, needle shaped, lamellar talc, or the like; wollastonite; surface-treated wollastonite; glass spheres such as hollow and solid glass spheres, silicate spheres, cenospheres, aluminosilicate (armospheres), or the like; kaolin, including hard kaolin, soft kaolin, calcined kaolin, kaolin comprising various coatings known in the art to facilitate compatibility with the polymeric matrix resin, or the like; single crystal fibers or �whiskers� such as silicon carbide, alumina, boron carbide, iron, nickel, copper, or the like; fibers (including continuous and chopped fibers) such as asbestos, carbon fibers, glass fibers, such as E, A, C, ECR, R, S, D, or NE glasses, or the like; sulfides such as molybdenum sulfide, zinc sulfide or the like; barium compounds such as barium titanate, barium ferrite, barium sulfate, heavy spar, or the like; metals and metal oxides such as particulate or fibrous aluminum, bronze, zinc, copper and nickel or the like; flaked fillers such as glass flakes, flaked silicon carbide, aluminum diboride, aluminum flakes, steel flakes or the like; fibrous fillers, for example short inorganic fibers such as those derived from blends comprising at least one of aluminum silicates, aluminum oxides, magnesium oxides, and calcium sulfate hemihydrate or the like; natural fillers and reinforcements, such as wood flour obtained by pulverizing wood, fibrous products such as cellulose, cotton, sisal, jute, starch, cork flour, lignin, ground nut shells, corn, rice grain husks or the like; organic fillers such as polytetrafluoroethylene; reinforcing organic fibrous fillers formed from organic polymers capable of forming fibers such as poly(ether ketone), polyimide, polybenzoxazole, poly(phenylene sulfide), polyesters, polyethylene, aromatic polyamides, aromatic polyimides, polyetherimides, polytetrafluoroethylene, acrylic resins, poly(vinyl alcohol) or the like; as well as additional fillers and reinforcing agents such as mica, clay, feldspar, flue dust, fillite, quartz, quartzite, perlite, tripoli, diatomaceous earth, carbon black, or the like, or combinations comprising at least one of the foregoing fillers or reinforcing agents.
The fillers and reinforcing agents may be coated with a layer of metallic material to facilitate conductivity, or surface treated with silanes to improve adhesion and dispersion with the polymeric matrix resin. In addition, the reinforcing fillers may be provided in the form of monofilament or multifilament fibers and may be used either alone or in combination with other types of fiber, through, for example, co-weaving or core/sheath, side-by-side, orange-type or matrix and fibril constructions, or by other methods known to one skilled in the art of fiber manufacture. Suitable cowoven structures include, for example, glass fiber-carbon fiber, carbon fiber-aromatic polyimide (aramid) fiber, and aromatic polyimide fiberglass fiber or the like. Fibrous fillers may be supplied in the form of, for example, rovings, woven fibrous reinforcements, such as 0-90 degree fabrics or the like; non-woven fibrous reinforcements such as continuous strand mat, chopped strand mat, tissues, papers and felts or the like; or three-dimensional reinforcements such as braids.
Suitable thermal stabilizer additives include, for example, organophosphites such as triphenyl phosphite, tris-(2,6-dimethylphenyl)phosphite, tris-(mixed mono- and di-nonylphenyl)phosphite; phosphonates such as dimethylbenzene phosphonate, phosphates such as trimethyl phosphate, and combinations comprising at least one of the foregoing heat stabilizers.
Non-limiting examples of antioxidants that can be used in the polymer compositions include tris(2,4-di-tert-butylphenyl)phosphite; 3,9-di(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane; 3,9-di(2,4-dicumylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane; tris(p-nonylphenyl)phosphite; 2,2′,2″-nitrilo[triethyl-tris[3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2′-diyl]phosphite]; 3,9-distearyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane; dilauryl phosphite; 3,9-di[2,6-di-tert-butyl-4-methylphenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane; tetrakis(2,4-di-tert-butylphenyl)-4,4′-bis(diphenylene)phosphonite; distearyl pentaerythritol diphosphite; diisodecyl pentaerythritol diphosphite; 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite; tristearyl sorbitol triphosphite; tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene diphosphonite; (2,4,6-tri-tert-butylphenyl)-2-butyl-2-ethyl-1,3-propanediolphosphite; triisodecylphosphite; and combinations comprising at least one of the foregoing antioxidants.
Non-limiting examples of UV stabilizers that can be used include 2-(2′-hydroxyphenyl)-benzotriazoles, for example, the 5′-methyl-; 3′,5′-di-tert.-butyl-; 5′-tert-butyl-; 5′-(1,1,3,3-tetramethylbutyl)-; 5-chloro-3′,5′-di-tert-butyl-; 5-chloro-3′-tert.-butyl-5′-methyl-; 3′-sec.-butyl-5′-tert.-butyl-; 3′-alpha-methylbenzyl-5′-methyl; 3′-alpha-methylbenzyl-5′-methyl-5-chloro-; 4′-hydroxy-; 4′-methoxy-; 4′-octoxy-; 3′,5′-di-tert.-amyl-; 3′-methyl-5′-carbomethoxyethyl-; and 5-chloro-3′,5′-di-tert-amyl-derivatives; and Tinuvin� 234 (available from Ciba Specialty Chemicals). Also suitable are the 2,4-bis-(2′-hydroxyphenyl)-6-alkyl-s-triazines, for example, the 6-ethyl-; 6-heptadecyl-; and 6-undecyl-derivatives. 2-Hydroxybenzophenones can also be used, for example, the 4-hydroxy-; 4-methoxy-; 4-octoxy-; 4-decyloxy-; 4-dodecyloxy-; 4-benzyloxy-; 4,2′,4′-trihydroxy-; 2,2′,4,4′-tetrahydroxy- and 2′-hydroxy-4,4′-dimethoxy-derivatives. 1,3-bis-(2′-Hydroxybenzoyl)-benzenes, for example, 1,3-bis-(2′-hydroxy-4′-hexyloxy-benzoyl)-benzene; 1,3-bis-(2′-hydroxy-4′-octyloxy-benzoyl)-benzene; and 1,3-bis-(2′-hydroxy-4′-dodecyloxybenzoyl)-benzene may also be employed. Esters of optionally substituted benzoic acids, for example, phenylsalicylate; octylphenylsalicylate; dibenzoylresorcin; bis-(4-tert-butylbenzoyl)-resorcin; benzoylresorcin; 3,5-di-tert-butyl-4-hydroxybenzoic acid-2,4-di-tert-butylphenyl ester or -octadecyl ester or -2-methyl-4,6-di-tert-butyl ester may likewise be employed. Acrylates, for example, alpha-cyano-beta, beta-diphenylacrylic acid-ethyl ester or isooctyl ester, alpha-carbomethoxy-cinnamic acid methyl ester, alpha-cyano-beta-methyl-p-methoxy-cinnamic acid methyl ester or -butyl ester or N-(beta-carbomethoxyvinyl)-2-methyl-indoline may likewise be employed. Oxalic acid diamides, for example, 4,4′-di-octyloxy-oxanilide; 2,2′-di-octyloxy-5,5′-di-tert-butyl-oxanilide; 2,2′-di-dodecyloxy-5,5-di-tert-butyl-oxanilide; 2-ethoxy-2′-ethyl-oxanilide; N,N′-bis-(3-dimethyl-aminopropyl)-oxalamide; 2-ethoxy-5-tert-butyl-2′-ethyloxanilide and the mixture thereof with 2-ethoxy-2′-ethyl-5,4′-di-tert-butyl-oxanilide; or mixtures of ortho- and para-methoxy- as well as of n- and p-ethoxy-disubstituted oxanilides are also suitable as UV stabilizers. Preferably the ultraviolet light stabilizer is 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole; 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole; 2-[2-hydroxy-3,5-di-(alpha, alpha-dimethylbenzyl)phenyl]-2H-benzotriazole; 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole; 2-hydroxy-4-octyloxybenzophenone; nickel bis(O-ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate); 2,4-dihydroxybenzophenone; 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole; nickel butylamine complex with 2,2′-thiobis(4-tert-butylphenol); 2-ethoxy-2′-ethyloxanilide; and 2-ethoxy-2′-ethyl-5,5′-ditert-butyloxanilide. Combinations comprising at least one of the foregoing UV stabilizers can be used.
Plasticizers, lubricants, and/or mold release agents additives may also be used. There is considerable overlap among these types of materials, which include, for example, phthalic acid esters such as dioctyl-4,5-epoxy-hexahydrophthalate; tris-(octoxycarbonylethyl)isocyanurate; tristearin; di- or polyfunctional aromatic phosphates such as resorcinol tetraphenyl diphosphate (RDP), the bis(diphenyl) phosphate of hydroquinone and the bis(diphenyl) phosphate of bisphenol-A; poly-alpha-olefins; epoxidized soybean oil; silicones, including silicone oils; esters, for example, fatty acid esters such as alkyl stearyl esters, for example, methyl stearate; stearyl stearate and pentaerythritol tetrastearate, mixtures of methyl stearate and hydrophilic and hydrophobic nonionic surfactants comprising polyethylene glycol polymers, polypropylene glycol polymers, and copolymers thereof, for example, methyl stearate and polyethylene-polypropylene glycol copolymers in a suitable solvent; and waxes such as beeswax, montan wax, paraffin wax. Combinations comprising at least one of the foregoing materials can be used.
Visual effect enhancers, sometimes known as visual effects additives or pigments or colorants may be present in an encapsulated form, a non-encapsulated form, or laminated to a particle comprising polymeric resin. Some non-limiting examples of visual effects additives are aluminum, gold, silver, copper, nickel, titanium, stainless steel, nickel sulfide, cobalt sulfide, manganese sulfide, metal oxides, white mica, black mica, pearl mica, synthetic mica, mica coated with titanium dioxide, metal-coated glass flakes, and colorants, including but not limited, to Perylene Red. The visual effect additive may have a high or low aspect ratio and may comprise greater than 1 facet. Dyes may be employed such as Solvent Blue 35, Solvent Blue 36, Disperse Violet 26, Solvent Green 3, Anaplast Orange LFP, Perylene Red, and Morplas Red 36. Fluorescent dyes may also be employed including, but not limited to, Permanent Pink R (Color Index Pigment Red 181, from Clariant Corporation), Hostasol Red 5B (Color Index #73300, CAS #522-75-8, from Clariant Corporation) and Macrolex Fluorescent Yellow 10GN (Color Index Solvent Yellow 160:1, from Bayer Corporation). Pigments such as titanium dioxide, zinc sulfide, carbon black, cobalt chromate, cobalt titanate, cadmium sulfides, iron oxide, sodium aluminum sulfosilicate, sodium sulfosilicate, chrome antimony titanium rutile, nickel antimony titanium rutile, and zinc oxide may be employed. Combinations comprising at least one of the foregoing visual effects additives can be used. Visual effect additives in encapsulated form usually comprise a visual effect material such as a high aspect ratio material like aluminum flakes encapsulated by a polymer. The encapsulated visual effect additive can have the shape of a bead.
The term �antistatic agent� refers to monomeric, oligomeric, or polymeric materials that can be processed into polymer resins and/or sprayed onto materials or articles to improve conductive properties and overall physical performance. Examples of monomeric antistatic agents include glycerol monostearate, glycerol distearate, glycerol tristearate, ethoxylated amines, primary, secondary and tertiary amines, ethoxylated alcohols, alkyl sulfates, alkylarylsulfates, alkylphosphates, alkylaminesulfates, alkyl sulfonate salts such as sodium stearyl sulfonate, sodium dodecylbenzenesulfonate, quaternary ammonium salts, quaternary ammonium resins, imidazoline derivatives, sorbitan esters, ethanolamides, betaines, and combinations comprising at least one of the foregoing monomeric antistatic agents.
Exemplary polymeric antistatic agents include certain polyesteramides, polyether-polyamide (polyetheramide) block copolymers, polyetheresteramide block copolymers, polyetheresters, or polyurethanes, each containing polyalkylene oxide units that may be polyalkylene glycol moieties, for example, polyethylene glycol, polypropylene glycol and polytetramethylene glycol. Such polymeric antistatic agents are commercially available, such as, for example, Pelestat� 6321 (Sanyo), Pebax� H1657 (Atofina), and Irgastat� P18 and P22 (Ciba-Geigy). Other polymeric materials that may be used as antistatic agents are inherently conducting polymers such as polyaniline (commercially available as PANIPOL�EB from Panipol), polypyrrole and polythiophene (commercially available from Bayer), which retain some of their intrinsic conductivity after melt processing at elevated temperatures. Combinations comprising at least one of the foregoing polymeric antistatic agents can be used. In one embodiment, carbon fibers, carbon nanofibers, carbon nanotubes, carbon black, or any combination of the foregoing may be used in a polymeric resin containing chemical antistatic agents to render the composition electrostatically dissipative.
Non-limiting examples of mold release compositions, combinations of which can be used, include esters of long-chain aliphatic acids and alcohols such as pentaerythritol, guerbet alcohols, long-chain ketones, siloxanes, alpha.-olefin polymers, long-chain alkanes and hydrocarbons having 15 to 600 carbon atoms.
Non-limiting examples of flame retardants that can be used include potassium diphenylsulfone sulfonate, perfluoroalkane sulfonates, the phosphite esters of polyhydric phenols such as resorcinol and bisphenol A, and combinations comprising at least one of the foregoing flame retardants.
The thermoplastic composition may optionally comprise an impact modifier. The impact modifier may be added to the thermoplastic composition in an amount of about 1 percent to about 30 percent by weight, based on the total weight of the composition. Suitable impact modifiers include those comprising one of several different rubbery modifiers such as graft or core shell rubbers or combinations comprising at least one of these modifiers. Impact modifiers are illustrated by acrylic rubber, ASA rubber, diene rubber, organosiloxane rubber, ethylene propylene diene monomer (EPDM) rubber, styrene-butadiene-styrene (SBS) rubber, styrene-ethylene-butadiene-styrene (SEBS) rubber, acrylonitrile-butadiene-styrene (ABS) rubber, methacrylate-butadiene-styrene (MBS) rubber, styrene acrylonitrile copolymer and glycidyl ester impact modifier.
Non-limiting examples of processing aids that can be used include Doverlube� FL-599 (available from Dover Chemical Corporation), Polyoxyter� (available from Polychem Alloy Inc.), Glycolube� P (available from Lonza Chemical Company), pentaerythritol tetrastearate, Metablen� A-3000 (available from Mitsubishi Rayon) and neopentyl glycol dibenzoate.
Radiation stabilizers may also be present in the thermoplastic composition, specifically gamma-radiation stabilizers. Suitable gamma-radiation stabilizers include diols, such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, meso-2,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 1,4-pentanediol and 1,4-hexandiol; alicyclic alcohols such as 1,2-cyclopentanediol and 1,2-cyclohexanediol; branched acyclic diols such as 2,3-dimethyl-2,3-butanediol (pinacol), and polyols, as well as alkoxy-substituted cyclic or acyclic alkanes. Alkenols with sites of unsaturation are also a useful class of alcohols, examples of which include 4-methyl-4-penten-2-ol, 3-methyl-pentene-3-ol, 2-methyl-4-penten-2-ol, 2,4-dimethyl-4-penten-2-ol, and 9-decen-1-ol. Another class of suitable alcohols is the tertiary alcohols, which have at least one hydroxy substituted tertiary carbon. Examples of these include 2-methyl-2,4-pentanediol (hexylene glycol), 2-phenyl-2-butanol, 3-hydroxy-3-methyl-2-butanone and cycloaliphatic tertiary carbons such as 1-hydroxy-1-methyl-cyclohexane. Another class of suitable alcohols is hydroxymethyl aromatics, which have hydroxy substitution on a saturated carbon attached to an unsaturated carbon in an aromatic ring. The hydroxy substituted saturated carbon may be a methylol group (�CH2OH) or it may be a member of a more complex hydrocarbon group such as would be the case with (�CR7HOH) or (�CR2 7OH) wherein R7 is a complex or a simply hydrocarbon. Specific hydroxy methyl aromatics may be benzhydrol, 1,3-benzenedimethanol, benzyl alcohol, 4-benzyloxy benzyl alcohol and benzyl alcohol. Specific alcohols are 2-methyl-2,4-pentanediol (also known as hexylene glycol), polyethylene glycol, polypropylene glycol.
Where a foam is desired, a blowing agent may be added to the composition. Suitable blowing agents include for example, low boiling halohydrocarbons; those that generate carbon dioxide; blowing agents that are solid at room temperature and that when heated to temperatures higher than their decomposition temperature, generate gases such as nitrogen, carbon dioxide, ammonia gas or the like, such as azodicarbonamide, metal salts of azodicarbonamide, 4,4′ oxybis(benzenesulfonylhydrazide), sodium bicarbonate, ammonium carbonate, or the like, or combinations comprising at least one of the foregoing blowing agents.
Anti-drip agents may also be used, for example a fibril forming or non-fibril forming fluoropolymer such as polytetrafluoroethylene (PTFE). The anti-drip agent may be encapsulated by a rigid copolymer as described above, for example styrene-acrylonitrile copolymer (SAN). PTFE encapsulated in SAN is known as TSAN. Encapsulated fluoropolymers may be made by polymerizing the encapsulating polymer in the presence of the fluoropolymer, for example an aqueous dispersion. TSAN may provide significant advantages over PTFE, in that TSAN may be more readily dispersed in the composition. A suitable TSAN may comprise, for example, about 50 wt. percent PTFE and about 50 wt. percent SAN, based on the total weight of the encapsulated fluoropolymer. The SAN may comprise, for example, about 75 wt. percent styrene and about 25 wt. percent acrylonitrile based on the total weight of the copolymer. Alternatively, the fluoropolymer may be pre-blended in some manner with a second polymer, such as for, example, an aromatic polycarbonate resin or SAN to form an agglomerated material for use as an anti-drip agent. Either method may be used to produce an encapsulated fluoropolymer.
The thermoplastic polymer compositions may be manufactured by methods generally available in the art, for example, in one embodiment, powdered polymer resin and/or other optional components are first blended, for example in a Henschel� high speed mixer. Other low shear processes including but not limited to hand mixing may also accomplish this blending. The blend is then fed into the throat of a twin-screw extruder via a hopper. Alternatively, one or more of the components may be incorporated into the composition by feeding directly into the extruder at the throat and/or downstream through a sidestuffer. Such additives may also be compounded into a masterbatch with a desired polymeric resin and fed into the extruder. The extruder is generally operated at a temperature higher than that necessary to cause the composition to flow. The extrudate is immediately quenched in a water batch and pelletized. The pellets may be one-fourth inch long (6.35 millimeter) or less as desired. Such pellets may be used for subsequent molding, shaping, or forming.
Shaped, formed, or molded articles comprising the polymer compositions are also provided. The polymer compositions may be molded into useful shaped articles by a variety of means such as injection molding, extrusion, rotational molding, blow molding and thermoforming to form articles such as, for example, computer and business machine housings such as housings for monitors, handheld electronic device housings such as housings for cell phones, electrical connectors, and components of lighting fixtures, ornaments, home appliances, roofs, greenhouses, sun rooms, swimming pool enclosures and automotive applications, for example forward lighting enclosures for car headlamps).
The reagents used for the present study are laboratory reagent grades and were used without further purifications. Sources for the reagents were as follows: 4-Bromonaphthalic anhydride (Anshan Huifeng Chemical Co. Ltd. China), Acetic acid (S.D. Fine. Chem., Min. assay 99%), Aniline (S.D. Fine. Chem., Min. assay 98%), Diethyl aniline (Aldrich Chemicals, purity 98.00%), Ethylene glycol (S.D. Fine. Chem., Min. assay 98.0%), Propylene glycol, (S.D. Fine chem., India, min. assay 99%), Butane diol (Aldrich Chemicals, purity 99.00), Sodium Hydroxide (S.D. Fine. Chem., Min. assay 99%), UVITEX� OB (Ciba Specialty Chemicals).
TLC using the eluent system ethyl acetate:n-Hexane (10:90) was used to monitor progress of reactions.
Structure was determined using 1H-NMR on a Bruker 300 MHz spectrophotometer.
HPLC data were obtained using Shimadzu HPLC Class-VP instrument and RP Xterra column-C18 (a HPLC column manufactured by Waters, USA), 4.6�50 millimeters (mm), 5 micrometers (μm).
TGA analyses were carried out using a TGA 2950 instrument equipped with an auto sampler, and available from TA Instruments.
The UV-VIS spectral characteristics of the fluorescent whiteners (lambda maximum (λmax) absorption) were measured in dichloromethane in the wavelength region of 300 nm to 800 nm using a double beam UV/VIS Perkin-Elmer Lambda 900 UV/VIS/NIR spectrophotometer.
Fluorescence properties of fluorescent whiteners (lambda maximum (λmax) emission, were evaluated using Hitachi-F-4500 spectrophotometer. Molded chips of 1 mm thickness containing 0.005% of compound of Formulas (I) or (VIII) along with polycarbonate were used to determine fluorescence properties.
Example 1 This example describes the preparation of 2-(2,6-diisopropyl-phenyl)-6-(2-hydroxyethoxy)-benzo[de]isoquinoline-1,3-dione in two steps.
Step A: Preparation of N-(2,6-diisopropyl phenyl)-4-bromo naphthalimide A mixture of 4-bromo-1,8-naphthalic anhydride (10 g (grams)), 2,6-diisopropylaniline (6.74 g) and acetic acid (75 milliliters (ml)) was heated under reflux with stirring for 10 (hrs (hours)). The reaction mixture was cooled to room temperature and filtered. The solids obtained were washed first with acetic acid and then with water, and dried at 120� C. for 8 hrs to obtain 13.1 g of the product.
Step B: Preparation of 2-(2,6-diisopropyl-phenyl)-6-(2-hydroxy-ethoxy)-benzo[de]isoquinoline-1,3-dione A mixture of N-(2,6-diisopropyl phenyl)-4-bromo naphthalimide (4.0 grams (g)), sodium hydroxide (0.54 g), and 1,2-ethylene glycol (50 milliliters (ml)) was stirred at 120� C. for 10 hrs. The reaction mixture was cooled to room temperature, 100 ml water was added to the mixture, and the separated solid was filtered, washed with water, and dried at 100� C. for 8 hrs to obtain the crude product in a yield of 2.25 g. The crude product was further purified using column chromatography in an eluent system consisting of ethyl acetate and n-hexane mixture (20:80). 1H-NMR: 1.06 δ (d, 12 protons); 2.63 δ (m, 2 proton); 3.92 δ (m, 2 protons); 4.38 δ (triplet, 2 protons); 5.14 δ (Triplet, 1 proton); 7.36 δ (m, 4 protons); 7.88 δ (m, 1 protons); 8.54 δ (Triplet, 2 protons); 8.76 δ (d, 1 protons); Mass (M+): 418.
Example 2 This example describes the preparation of 2-(2,6-diisopropyl-phenyl)-6-(3-hydroxypropoxy)-benzo[de]isoquinoline-1,3-dione.
A mixture of N-(2,6-diisopropylphenyl)-4-bromo naphthalimide (4.0 g, as prepared in Step A of example 1), sodium hydroxide (0.54 g) and 1,3-propane diol (50 ml) was stirred at 120� C. for 10 hrs. The reaction mixture was cooled to room temperature, 100 ml water was added to the mixture, and the separated solid was filtered, washed with water, and dried at 100� C. for 8 hrs to obtain the crude product in a yield of 3.1 g. The crude product was further purified using column chromatography in an eluent system consisting of ethyl acetate and n-hexane mixture (20:80). 1H-NMR: 1.18 δ (d, 12 protons); 2.01 δ (s, 1 proton); 2.25 δ (m, 2 protons); 3.96 δ (m, 2 protons); 4.47 δ (m, 2 proton); 7.13 δ (m, 1 protons); 7.34 δ (m, 2 protons); 7.48 δ (m, 1 protons); 7.76 δ (m, 1 protons); 8.65 δ (m, 3 protons).
Example 3 This example describes the preparation of 2-(2,6-diisopropyl-phenyl)-6-(4-hydroxy-butoxy)-benzo[de]isoquinoline-1,3-dione.
A mixture of N-(2,6-diisopropyl phenyl)-4-bromo naphthalimide (4.0 g as prepared in Step A of example 1), sodium hydroxide (0.54 g) and 1,3-butane diol (50 ml) was stirred at 120� C. for 10 hrs. The reaction mixture was cooled to room temperature, 100 ml water was added to the mixture, and the separated solid was filtered, washed with water, and dried at 100� C. for 8 hrs to obtain the crude product in a yield of 3.1 g. The crude product was further purified using column chromatography in an eluent system consisting of ethyl acetate and n-hexane mixture (20:80). 1H-NMR: 1.17 δ (m, 12 protons); 1.68 δ (s, 1 proton); 1.90 δ (m, 2 protons); 2.12 δ (m, 2 protons); 2.76 δ (m, 2 proton); 3.82 δ (m, 2 protons); 4.38 δ (m, 2 protons); 7.343 δ (m, 4 protons); 7.77 δ (m, 1 protons); 8.69 δ (m, 3 protons).
Example 4 This example describes the preparation 2-(2,6-diisopropyl-phenyl)-6-[4-(1-methyl-1-phenyl-ethyl)-phenoxy]-benzo[de]isoquinoline-1,3-dione.
A mixture of N-(2,6-diisopropyl phenyl)-4-bromonaphthalimide (4.0 g), potassium hydroxide (0.77 g) and dimethylformamide (30 ml), 18-crown-6 (0.02 g), and p-cumylphenol (3.89 g) was stirred at 50� C. for 6 hours. The reaction mixture was cooled to room temperature, 100 ml water was added to the mixture, and the separated solid was filtered, washed with water and dried at 60� C. for 8 hrs to obtain the crude product in a yield of (5.0 g). The crude product was further purified by carrying out column chromatography (silica gel 60-120 mesh) using ethyl acetate and n-hexane mixture (20:80). H-NMR: 1.18 δ (m, 12 protons); 1.79 δ (s, 6 proton); 2.79 δ (m, 2 protons); 7.34 δ (m, 14 protons); 7.83 δ (m, 1 protons); 8.56 δ (m, 1 protons); 8.79 δ (m, 2 proton).
Example 5 This example describes the preparation of 6-(2-hydroxy-ethoxy)-2-p-tolyl-benzo[de]isoquinoline-1,3-dione.
Step A: Preparation of 6-bromo-2-p-tolyl-benzo[de]isoquinoline-1,3-dione A mixture of 4-Bromo 1,8 naphthalic anhydride (10 g), p-toluidine (4.08 g) and acetic acid (75 ml) was refluxed with stirring for 10 hours. Water (200 ml) was added at room temperature, the separated solid was filtered, washed with acetic acid followed by water and dried at 100� C. for 8 hours to yield 11.5 g of the product.
Step B: 6-(2-hydroxy-ethoxy)-2-p-tolyl-benzo[de]isoquinoline-1,3-dione A mixture of 6-bromo-2-p-tolyl-benzo[de]isoquinoline-1,3-dione (4.0 g), sodium hydroxide (0.65 g), and 1,2-ethylene glycol (50 ml) was maintained under reflux with stirring at 120� C. for 10 hrs. The reaction mixture was then cooled to room temperature and water (100 ml) was added to the mixture. The solid that separated out was filtered, washed with water, and dried at 100� C. for 8 hours (Yield=2.71 g). The crude product was purified using 120 ml monochlorobenzene and 0.25 g activated charcoal to obtain pure product weighing 1.32 g. H1-NMR: 2.39 δ (s, 3 protons); 3.92 δ (m, 2 proton); 4.35 δ (t, 2 protons); 5.13 δ (t, 1 proton); 7.22 δ (m, 2 protons); 7.31 δ (m, 3 protons); 7.83 δ (t, 1 proton); 8.44 δ (m, 2 protons); 8.68 δ (d, 1 proton).
Example 6 This example describes the preparation of 6-(3-hydroxy-propoxy)-2-phenyl-benzo[de]isoquinoline-1,3-dione.
Step A: Preparation of 6-bromo-2-phenyl-benzo[de]isoquinoline-1,3-dione A mixture of 4-bromo-1,8-naphthalic anhydride (10 g), aniline (3.54 g) and acetic acid (75 ml) was refluxed with stirring for 10 hrs. The reaction mixture was then cooled to room temperature, whereupon solid separated out. The solid was filtered, washed with water (50 ml) followed by acetic acid (50 ml) and dried at 100� C. for 8 hours (Yield=10.8 gm).
Step B: Preparation of 6-(3-Hydroxy-propoxy)-2-phenyl-benzo[de]isoquinoline-1,3-dione A mixture of 6-bromo-2-phenyl-benzo[de]isoquinoline-1,3-dione (4.0 g), sodium hydroxide (0.67 g) and 1,3-propane diol (50 ml) was maintained with stirring at 120� C. for 10 hrs. The reaction mixture was cooled to room temperature. Water (100 ml) was added to the mixture and solid separated out. The solid was filtered, washed with water, and dried at 100� C. for 8 hours to provide a crude product in a yield of 1.90 g. The crude product was purified using mono chloro benzene (60 ml) and activated charcoal (0.20 g). The weight of the of the purified product obtained was 1.15 g. 1H-NMR: 3.93 δ (m, 2 protons); 4.35 δ (m, 1 proton); 2.25 δ (m, 2 protons); 3.96 δ (m, 2 protons); 4.47 δ (m, 2 proton); 7.13 δ (m, 2 protons); 5.14 δ (m, 1 proton); 7.36 δ (m, 3 protons); 7.51 δ (m, 3 protons); 7.84 δ (m, 1 proton); 8.46 δ (m, 2 protons); 8.69 δ (m, 1 proton).
Example 7 This example describes the preparation of 6-(2-hydroxy-ethoxy)-2-phenyl-benzo[de]isoquinoline-1,3-dione.
A mixture of 6-bromo-2-phenyl-benzo[de]isoquinoline-1,3-dione (2.0 g; prepared in step A of Example 5), sodium hydroxide (0.34 g) and 1,2-ethylene glycol (25 ml) was maintained with stirring at 120� C. for 10 hrs. The reaction mixture was cooled to room temperature, water (100 ml) was added to the mixture and solid separated out. The solid was filtered, washed with water, and dried at 100� C. for 8 hours to provide a crude product in a yield of 1.80 g. 1H-NMR: 2.07 δ (m, 2 protons); 3.70 δ (m, 2 proton); 4.42 δ (t, 2 protons); 4.68 δ (t, 1 proton); 7.35 δ (m, 3 protons); 7.50 δ (m, 3 protons); 7.83 δ (t, 1 proton); 8.46 δ (m, 2 protons); 8.58 δ (d, 1 proton).
A summary of the above results for Examples 1-7 is shown in Table 1 below.
derivative (g)
0.77a g
5.00b NA
bCrude yield
Characterization of Examples 1-7 and Comparative Example 1 (CE-1) This example is a comparative study of the properties of a commercially available fluorescence brightener, UVITEX�-OB (Comparative Example 1) and Examples 1-7 above.
The samples were tested for Tg, lambda max absorption, and emission values. Results are shown in Table 2.
λ max Absorption
λ max Emission
Tg at % weight
The results provided in Table 2 indicate that the compounds of Formula (I) and Formula (VIII) absorb and emit at relatively lower wavelengths than the commercially available fluorescent brightener UVITEX� OB. Tg at 10 percent weight loss is a measure that indicates the temperature at which the compounds begin to decompose, and refers to the temperature at which the sample has a 10 percent loss in weight compared to the initial amount of sample used for measuring the glass transition temperature (Tg).
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS3310564Jan 18, 1962Mar 21, 1967Kasai ToshiyasuNovel 4-alkoxy naphthalimidesUS4814453May 29, 1987Mar 21, 1989Hoechst AktiengesellschaftNaphthalimides containing sulfuric acid ester groups, a process for their preparation and their useUS5310940Jan 19, 1993May 10, 1994Sumitomo Seika Chemicals Co., Ltd.Production of thiophene-2,5-dicarboxylic acid diesters, tetrahydrothiophene-2,5-dicarboxylic acid diesters and dibenzoxazolylthiophenesUS5817448Jan 24, 1997Oct 6, 1998Fuji Photo Film Co., Ltd.Silver halide photographic material and method for processing the sameUS6492032Oct 12, 2000Dec 10, 2002Eastman Chemical CompanyMixture of benzoxazolyl stilbenes with a bis(benzoxazolyl)-naphthalene, bis(benzoxazolyl)thiophene, a pyrazoline and/or a courmarin; photographic filmsUS7608715 *Nov 21, 2005Oct 27, 2009Sabic Innovative Plastics Ip B.V.Such as 2-(2,6-diisopropyl-phenyl)-6-(2-hydroxyethoxy)-benzo[de]isoquinoline-1,3-dione; whitening agentsUS20070117887 *Nov 21, 2005May 24, 2007Naik Shantaram NSuch as 2-(2,6-diisopropyl-phenyl)-6-(2-hydroxyethoxy)-benzo[de]isoquinoline-1,3-dione; whitening agentsGB2183667A Title not availableJPH03232858A Title not availableJPS56167383A Title not availableJPS59114546A Title not availableWO2005047265A1Nov 12, 2004May 26, 2005Basf AgUse of 4-cyano-naphthalene-1, 8-dicarboximide derivatives and related compounds to protect organic material from the damaging effects of lightWO2005102250A1Feb 28, 2005Nov 3, 2005Timo LuukasComposition comprising a monomer compound exhibiting an optical property, method making use of said composition, a monomer compound and a polymer containing said monomer compound and the use thereofWO2007014902A2Jul 27, 2006Feb 8, 2007Basf AgMultiple chromophores based on rylene* Cited by examinerNon-Patent CitationsReference1Application No. WO2007014902; Publication Date: Feb. 8, 2007; Abstract Only; 1 page.2Bojinov V et al.; "A New Method for Synthesis of 4-allyloxy-1,8-naphthalimide Derivatives for Use as Fluorescent Brighteners": Dyes and Pigments, Elsevier Applied Science Publishers, Barking, GB; vol. 51, No. 1; Oct. 1, 2001; pp. 57-61.3Cao Haishi et al.; "Matrix Screening of Substituted N-aryl-1,8-naphthalimides Reveals New Dual Fluorescent Dyes and Unusually Bright Pyridine Derivatives"; J. Org. Chem.; Journal of Organic Chemistry; vol. 70, No. 13; Jun. 24, 2005; pp. 4929-4934.4Database Registry (Online); Chemical Abstracts Service, Colombus, Ohio, US; Oct. 17, 2001; XP002481508.5Grabchev I et al.; "Copoylyermization and Photostabilization of Methylmethacrylate wtih 1,8-Naphthalimide Fluorescent Brighteners"; Journal of Photochemistry and Photobiology, A: Chemistry, Elsevier Sequoia, Lausanne, CH; vol. 142, No. 1; Jan. 1, 2001; pp. 73-78.6International Search Report; International Application No. PCT/US2006/044998; International Filing Date: Nov. 20, 2006; Date of Mailing: Jun. 9, 2008; 9 pages.7Japanese Patent No. 03232858; Publication Date: Oct. 16, 1991; Abstract Only; 1 page.8Japanese Patent No. 56167383; Publication Date: Dec. 23, 1981; Abstract Only; 1 page.9Japanese Patent No. 59114546; Publication Date: Jul. 2, 1984; Abstract Only; 1 page.10Li et al.; "A New Class of High Tg and Organosoluble Polynaphthalimides"; Polymer, Elsevier Science Publishers B.V., GB; vol. 48, No. 11; May 11, 2007; pp. 3082-3089.11Piroux F et al.; "On the Polynaphthalimide Synthesis-Infulence of Reaction Conditions"; Polymer, Elsevier Science Publishers B.V., GB; vol. 45, No. 19; Sep. 3, 2004; pp. 6445-6452.12Written Opinion of the International Searching Authority; International Application No. PCT/US2006/044998; International Filing Date: Nov. 20, 2006; Date of Mailing: Jun. 9, 2008; 15 pages.Referenced byCiting PatentFiling datePublication dateApplicantTitleUS8617356 *Apr 30, 2012Dec 31, 2013Nalco CompanyCompositions and processes for paperUS20120211185 *Apr 30, 2012Aug 23, 2012Prasad DuggiralaCompositions and processes for paper* Cited by examinerClassifications U.S. Classification524/89International ClassificationC08K5/3437Cooperative ClassificationC08K5/0041, C08L21/00, C07D221/14, C08K5/3437, C07D221/06European ClassificationC07D221/06, C08K5/3437, C07D221/14, C08K5/00P4Legal EventsDateCodeEventDescriptionMar 17, 2014ASAssignmentOwner name: SABIC INNOVATIVE PLASTICS IP B.V., NETHERLANDSEffective date: 20140312Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:032459/0798RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google

value: This website is a search engine provided by Google. Handling over 3.5 billion searches per day, it has a 92% share of the global search engine market.


text:
P. 1Gregory Schopen - On the Buddha and His Bones: The Conception of a Relic in the Inscriptions of NagarjunikondaGregory Schopen - On the Buddha and His Bones: The Conception of a Relic in the Inscriptions of NagarjunikondaRatings: (0)|Views: 139
|Likes: 7Published by Ɓuddhisterie2Journal of the American Oriental Society, 108 (1988): 527-537Journal of the American Oriental Society, 108 (1988): 527-537More info:Categories:Types, School WorkPublished by: Ɓuddhisterie2 on Sep 03, 2012Copyright:Attribution Non-commercialAvailability:Read on Scribd mobile: iPhone, iPad and Android.download as PDF, TXT or read online from ScribdFlag for inappropriate content|Add to collectionSee moreSee lesshttp://www.scribd.com/doc/104811400/Gregory-Schopen-On-the-Buddha-and-His-Bones-The-Conception-of-a-Relic-in-the-Inscriptions-of-Nagarjunikonda06/15/2013pdftextoriginal ON THE BUDDHA AND HIS BONES: THE CONCEPTION OF A RELIC IN THE INSCRIPTIONS OF NAGARJUNIKONDA
An attempt to show that when a doctrinally important passage in the Mahacetiya inscriptionsof Nagarjunikonda is punctuated properly, and its vocabulary placed in its proper context, itturns out to be yet another piece of evidence for a pervasive-though little noticed-early IndianBuddhist conception of a "relic."
NAGARJUNIKONDA,
the bottomof a man-made lake, was a rich source not only ofBuddhist and Hindu archaeological and art historicalremains, but also of inscriptions. It has proved to be,as a consequence, an equally rich source of conun-drums and a well-watered ground for speculation.There has been a persistent series of attempts, forexample, to see elements of the Mahayana in the earlyphases of Nggarjunikonda in spite of the fact thatthere is no actual epigraphical or art historical evi-dence for this movement anywhere in the Andhra areaprior to the 5th16th century
and in spite of thefact that what epigraphical and art historical evidencewe actually have richly documents the presence thereof non-Mahgygna groups.'
N. Dutt, "Discovery of a Bone Relic at an Ancient Centreof MahByHna,"
5 (1929): 794-96;Dutt, "Notes on the Nagarjunikonda Inscriptions,"
IndianHistorical Quarterly
7 (1931): 633-53;
Studies inEarly Buddhist Architecture of India
(Delhi, 1966), 74-96;E. S. Rosen, "Buddhist Architecture and Lay Patronageat Nagarjunakonda," in A. L. Dallapiccola and S.
Lalle-mant (eds.),
The StCpa, Its Religious, Historical and Archi-tectural Significance
(Wiesbaden, 1980), 112-26; A. and
The Lion's Roar of Queen ~rimdla
New York,1974), 1-4; A. Wayman, "The MahHsamghika and theTathagatagarbha,"
The Journal of the International Associa-tion of Buddhist Studies
1 (1978): 42-43; etc.-On theMahayana in Andhra art see D. Barrett, "The Later Schoolof Amaravati and Its Influence,"
28.2 (1954):41-53; D. Barrett,
Sculptures from Amaravati in the BritishMuseum
(London, 1954), 59; ~t.amotte, "MafijuSri,"
68 (1960): 4; on the Mahayana in epigraphicalsources see
Schopen, "Mahayana in Indian Inscriptions,"
The inscriptions from NZggrjunikonda are difficult.They are difficult because of "the want of precision ofwhich they show ample evidence." Vogel has notedthat "considering that these inscriptions were meantto be perpetual records of pious donations made byladies of royal blood, the careless manner in whichthey have been recorded isastonishing."' They arealso difficult because they are in many ways atypical.They contain a number of phrases and formulae notfound elsewhere in Indian Buddhist inscriptions sothat we do not have, in many cases, parallels to assist
This difficulty is offset, and then only in part, bythe fact that these inscriptions tend to be highlyrepetitive; there are frequently numerous "copies" ofthe same basic inscription.I would like here to look atone of these atypical phrases that has importantimplications for Buddhist doctrinal history, and to
21 (1979):1-19; Schopen, "The In-scription on the Kusan Image of Amitabha and the Char-acter of the Early Mahayana in India,"
The Journal of theInternational Association of Buddhist Studies
10.2 (1987):99-137. Since writing the first of these I have come across asingle instance of the Mahayana formula in an inscriptionfrom the Andhra area; it dates to the 5th century; see T. N.Ramachandran,
Ndgdrjunikonda
(Memoirs of the Ar-chaeological Survey of India, No. 71) (Calcutta, 1953), 29(111).
Ph. Vogel, "Prakrit Inscriptions from a Buddhist Siteat Nagarjunikonda,"
20 (1929):11-12.Cf.
Schopen, "Filial Piety and the Monk in thePractice of Indian Buddhism: A Question of 'Sinicization'Viewed from the Other Side,"
70 (1984): 121-22.
.lournu1 of the American Oriental Society
exploit the advantage that the existence of multiplecopies presents us with.Most of the pillar inscriptions connected with the
~ahdceti~a~
re structured in exactly the same way.They begin with
sidham,
"success!"; thisis followed usually by (2) an invocation to the Buddhawhich consists of the word
"adoration to,"followed by a string of epithets of the Buddha in thegenitive. Then comes
the name of the place atwhich the gift recorded was made, put in the locative;
the name of the donor, her 'pedigrees'and relation-ships:
the purpose or intent behind her gift:
thenature of the gift. etc. We will be concerned here onlywith the second and third elements: the invocationconsisting of the
plus the string of epithets inthe genitive, and the name of the place at which thegift was made in the locative.The first thing to notice is that the number ofepithets in the string of genitives following
varies. The fullest form of the formula containing theinvocation and the name of the location at which thegift was made is, in the Prakrit original:
namo bhagavato deva-raja-sakatasa supabudha-bo-dhino savamfiuno sava-sat-anukampakasa jita-raga-dosa-moha-vipamutasa
mahagani-vasabha-gapdha-
hathisa samma-sambudhasa dhatuvara-parigahitasamahacetiye
namah bhagavate devar%jasatkrt?tya suprabuddhabo-dhaye sarvajfiaya sarvasattvanukampak%ya-jitara-gadosamoha-
asaktighrn2jfiPna-)-vipramuktiiyamahsgani-vrsabhagandhahastine
bahusankhyaka-Sisya-mahacaryesu pradhanah) samyaksambuddhayadhatuvara-parigrhitaya
nirvSnaprZptSya)
[asmin]mahacaitye
Adoration to the Lord, the Supreme Buddha, hon-oured by the Lord of the gods, omniscient, compas-sionate towards all sentient beings. freed from lust,hatred and delusion which have been conquered byhim, the bull and musk-elephant among great spiri-Vogel, EI20 (1929), A2-A4; BlLB5; ClLC5; D2-D4; and
Citations in the text are made according to Vogel'sletter1 number system.
D. C. Sircar,
Select Inscriptions Bearing on Indian His-tor?: and Civilization,
2nd ed. (Ca!cutta, 1965). 230 (1 have
corrected two misprints in the passage cited).tual leaders, the perfectly Enlightened One, who isabsorbed by the best of the elements (i.e., by Nir-vana). At the Mahachetiya.
At least four "copies" of this same inscription omiteverything after
deva-riiju-sakatasa
samrna-sam-budhasa.
reading as a consequence:
namo bhagavato deva-raja-sakatasa samma-sambu-dhasa dhatuvara-parigahitasa mahacetiye
Vogel's interpretation of what he takes to be thelast of the string of
epithets-dhdtuvara-parigahitu,
"absorbed by the best of the elements (i.e.. by Nir-vana)"-was suggested to him by de la Vallee Poussinwho added: "If the inscriptions belonged to the Ma-hasanghikas, a conjectural explanation of
dhdtuvara
Dharrnadhdtu
would not be excluded. The
Dhar-rnadhdtu
was sometimes a kind of Buddhist Brahmanfor the followers of the ~ah2yIna."~ircar also hastaken the term in much the same way, glossing it with
nirvanaprdpta,
and Dutt, who translates the com-pound by "possessed of the excellent dhatu," wants tosee in it evidence that raises "the presumption that theAndhaka conception of Nirvana was different fromthat of the Theravadins or their sub-sect the MahiSB-sakas,"' which de la Vallee Poussin at least does notquery."'
Shastri, finally, sees in the expressionevidence indicating that "the Andhakas
upheld thedocetic theory and believed that the Buddha wassupra-mundane." and. following de la Vallke Poussin,that it "most probably alludes to the Kaya doctrine ofthe Mahayanists for whom the Buddha was not ahistorical personality.""This line of interpretation, which connects the ex-pression with the development of MahayIna scho-
20 (1929): 17.
(1929): 16 n. 2; B3, CI, D2 and D4.Vogel,
(1929): 29 n. 1.
Dutt, "Notes on the Nagarjunikonda Inscriptions," 649-50, and N. Dutt,
(Calcutta 1970),124-25.
L. de la Vallte Poussln, "Notes et
boud-dhiques,"
Mdlanges chinois et bouddhiques
1 (1931-32): 383.
An Outline of Early Buddhism (A His-torical Survey of Buddhology, Buddhist Schools and San-ghas Mainly Based on the Studj, of Pre-Gupta Inscriptions)
(Varanasi, 1965), 29-30; cf.
Shastri, "The LegendaryPersonality of the Buddha as Depicted in Pre-Gupta IndianInscriptions."
8(1960): 172-73.
529CHOPEN:
On the Buddha and his Bones
lastic definitions and conceptions of the Buddha, didnot go unquestioned. In editorial notes added toVogel's initial publication of the inscriptions in
Epi-graphia Indica,
H. Sastri said "to me it does notappear to be impossible that the Mahachetiya hasbeen specified in these inscriptions as 'protected by thecorporeal remains of the Buddha' and that the geni-tive case is used here to discriminate this
stiipa
fromothers not similarly c~nsecrated."'~Longhurst toowas inclined toward this interpretation.I3 Even Dutt,three years before his "notes" on Vogel's treatment ofthe inscriptions, seems to have gone in this direction:he refers to one of the inscriptions and says it records"the gift of a pillar..
to the caitya, enshrining a
dhdtu
of Sammiisamb~ddha."'~There are basically two problems here. The inter-pretation of Vogel et al. takes
dhatuvara-parigahita
asone of the series of epithets governed by the initial
H. Sastri et al. want it rather to be a kind of"partitive" genitive constructed with the following
rnahdcetiye.
This is the first problem. The second,quite simply, is the meaning of
dhdtuvaraparigahita,
the discussion so far having turned almost entirely onthe significance of the final member of the compound.The first problem arises in large part from the factthat the inscriptions are not punctuated. To quoteagain only the short form we find:
namo bhagavato deva-raja-sakatasa samma-sambu-dhasa dhatuvara-parigahitasa mahiicetiye
Vogel et al. understand a
or full stop after
dhdtuvaraparigahitasa.
Sastri's interpretation, how-ever, implies a full stop after
summa-sambudhasa.
Butat least two other inscriptions from Nagarjunikondaindicate that neither of these constructions of the textis correct. "Ayaka-pillar inscription B2" opens notwith the invocation to the Buddha, but with severallines praising the donor's father. The reference to thesite at which the gift was made does not occur untilalmost the very end of the inscription and reads:
bhagavato samma-sa[m]budhasa dhatuvaraparigahi-tasa mahscetiye imam khambham patidhapamta [rd.patithspitam] ti
20 (1929): 29 n. 1.
A. H. Longhurst,
The Buddhist Antiquities of Ndgar-junikonda, Madras Presidency
(Memoirs of the Archaeo-logical Survey of India, no. 54) (Delhi, 1938), 18.
Dutt, "Discovery of a Bone-Relic at an Ancient Centreof Mahayana," 794.
construction does not interfereit is clear that the genitives are constructed with
mahacetije.
dh~tuvaraparigahita
is an ad-jective modifying
This is fullyconfirmed by the "First Apsidal Temple inscriptionE.
This inscription also opens, like "Ayaka-pillarinscriotion B2," with the praise of a relative of thedoncr. Here the gift recorded is said to have beenmade at:
samma-sambudhasa
dhatu-[vara]li-parigahitasa
ma-hacetiya-padamiile
Once again, without the
genitive construction,there is no doubt as to how the text is to be constructed.In light of these two unambiguous cases it seems fairlysure that
dhatuvaraparigahitasa
everywhere must bean adjective modifying
summa-sambudhasa,
summa-sambudhasa dhdtuvaraparigahitasa
everywheremust be taken not as a part of the string of epithets inthe genitive governed by
but as a separateadjectival phrase modifying
mahdcetiye.
This is onlymore fully confirmed if we notice that although almostall our Niigarjunikonda inscriptions open with or con-tain a
invocation consisting of strings of
epithets of the Buddha. the collocation
samma-sam-budhasa dhdtuvara-parigahitasa
in inscrip-tions which make reference to the
mahacetiya
immediately precedes the noun
mahdcetiya
inthe locative. Just this much allows some improvementin our understanding of the text which, in the shortform of the formula, might now be read:
namo bhagavato deva-rsjasakatasa
samma-sambu-dhasa dhatuvaraparigahitasa mahacetiye
"Homage to the Blessed One, he who is honored by theKing of the Gods! At the Great Shrine of the PerfectlyEnlightened One who is
dhdtuvaraparigahita
While this is an improvement it still leaves us, ob-viously, with the problem of the meaning of
dhdtuva-raparigahita.
Although most previous discussions haveconcerned the meaning of the final member of thecompound and, only correlatively, the first, the mean-ing of the middle term
also be of significance.
dhatu-
in our inscriptions has been taken by most in-terpreters-as we have seen-in the sense of "sphere,""state," "condition," and assimilated to
nirvaa-dhdtu,
The "scribe" has omitted
here, but this is almostcertainly only another instance of the "carelessness" in theserecords noted by Vogel; cf. also
20 (1929): 21, nt. 2.
Activity (7)FiltersAdd to collectionReview Add NoteLikeShowingAllMost RecentReviewsAll NotesLikesYou've already reviewed this. Edit your review.Rating 0/5Post notePost reviewPost replyPost note and like1 hundred readsAmogavajra liked thisPrasad Praturi liked thisGabriele Burrini liked thisyphapan liked thisDeshpandem liked thisƁuddhisterie liked thisLoad more

type: global

value: This website is an American e-book and audiobook subscription service that includes one million titles.


text:
Let. It. Go.: How to Stop Running the Show and Start Walking in Faith - Kindle edition by Karen Ehman, New York Times Bestselling Author Candace Cameron Bure. Religion & Spirituality Kindle eBooks @ Amazon.com.
Let. It. Go.: How to Stop Running the Show and Start Walking in Faith Kindle Edition
$8.95 $1.46
$13.42 135 Used from $1.46 64 New from $8.95 1 Collectible from $7.25
Zip It: The Keep It Shut 40-Day Challenge Kindle Edition
Pressing Pause: 100 Quiet Moments for Moms to Meet with Jesus Kindle Edition
Keep It Shut: What to Say, How to Say It, and When to Say Nothing at All Kindle Edition
Amazon Best Sellers Rank: #147,148 Paid in Kindle Store (See Top 100 Paid in Kindle Store)
#140 in Kindle Store > Kindle eBooks > Religion & Spirituality > Christian Books & Bibles > Christian Living > Dating & Relationships
#282 in Kindle Store > Kindle eBooks > Religion & Spirituality > Christian Books & Bibles > Christian Living > Women's Christian Living
#524 in Books > Christian Books & Bibles > Christian Living > Dating & Relationships
5.0 out of 5 starsDefinitely a Book for Me!
With a dash of wit and a sprinkle of personal experience, Karen Ehman tells it like it is in Let. It. Go.: How to Stop Running the Show and Start Walking in Faith. She confesses to being a card-carrying member of Control Freaks Anonymous (an organization I know all too well) and explains how the Lord has taught her to let go and let God. I could relate to many of the situations Ehman referred to and learned some valuable lessons on how to release my white-knuckled grip on life and its many circumstances. Several things truly hit home with me, so much so that I jotted them down in my devotional journal so that I could remember and meditate on them. But I think the thing that hit me the most was this paragraph: "When we women try to be so on top of things--around the house, at work, in our marriages, in our parenting, and in community ventures--we think we're only taking our jobs seriously, performing our tasks with care, and carrying out the duties of our roles in a way that is excellent and thorough. So give us a break. We really are just trying to please God, right? I thought so. Sometimes I still think so. However, I happened upon a thought just a year or two ago that makes me wonder this: In attempting to be in command and control, are we trying to be godly or are we trying to be God?"
We studied Let It Go in our last small home group women's study. It was wonderful, so thought provoking. The study was a little hard to put together. You need both the book and study guide. The DVD was a review of the book and I'm not sure you need it. Just toward the end of the study I finally was able to create some sort of flow for the group. That's the only reason I gave it 4 stars. The women felt that it was one of the best studies they've done.
I just purchased Keep It Shut by Karen Ehman for the next study.
2.0 out of 5 starsThis author rarely uses scripture. I am currently in ...
This author rarely uses scripture.
I am currently in a Bible study using this book and I find it we don't have much depth to pull from.
Well I certainly agree with the concept that we should let things go and let God run the show of life, this author is average at her approach.
She even used a previous authors quote and didn't cite her🤔
5.0 out of 5 starsFor the Control Freak
My small group Bible study bought this book to read, as well the video and study book.
Karen Ehman does a good job of making you ask yourself, "Does this REALLY matter? Will this affect eternity?" The best chapter in the book to me was the one about how we talk to our children and to others; when we're trying to control a situation and how our words can affect others.
Her conversational style of writing makes this book an easy read and very relatable.
I do not, however, recommend the video sessions or the study book that go with this text - they're kind of redundant. The book alone is great by itself.
3.0 out of 5 starsGreat For Busy Christian Moms, Not So Much For Single Working Professionals
Great book, but if you're a working professional woman with no children, it may be hard to connect with the whole thing. I stopped about half way through because I just couldn't connected with the writer.
5.0 out of 5 starsLife group
My wife really liked this book. She has always had this type of problem and never knew how to change it. She now does understand it and has made many positive changes already that will last the rest of her life. She also loves the Christian perspective.
Karen does a wonderful job intertwining scripture and God's desires with the fight of letting him be in charge. I am so thankful for books like this! Through them I have hope and courage to try and try again to become the woman God wants me to be and that woman is a little more out of control.
A great book for young married women.
Great sequel to Keep it shut.
5.0 out of 5 starsGreat Book for Christian Women
Really helpful. I have been more focused on the needs and wants of my husband. I have been less interested in comparing myself to women who look better than me at the gym.Read more
Loved the book and its message. Great for men & women anyone struggling to stay in control instead of letting go and letting God be in control
Linda Ann Dennis
Excellent book. Would recommend everyone read this. Don't let the title fool you.
Our Ladies Bible Study has enjoyed this very much. A different perspective on familiar Scriptures. Great presentation.
love for a life rime
Love the book. We are reading this book as a Women's Church Group discussion and it has proven to be awesome.
Great bible study...buy the paper copy, not the Kindle...so much more practical for the quizzes.
This item: Let. It. Go.: How to Stop Running the Show and Start Walking in Faith

value: This website is an American multinational technology company which focuses on e-commerce, cloud computing, digital streaming, and artificial intelligence.


text:
particular system port avliable checking by using java [duplicate]
Sockets: Discover port availability using Java hi,
how can i check the particular system port is avliable or not by using java.
java asked Nov 4 '10 at 11:39
java networking asked Aug 22 '11 at 7:38
3,594184269
I understand that the following code can (perhaps not very efficiently) find out a free TCP port in Java:
ServerSocket socket= new ...
java sockets tcp asked Jul 16 '10 at 14:22
I'm trying to simulate tests of various run-throughs of my program, setting up a Jetty server in a @Before method and closing it down in an @After. My first test will run successfully, but upon ...
java testing junit jersey jetty asked Aug 3 '12 at 10:59
Edit: My prof asks "Every time the program discovers a running service it has to print the ...
java port asked Feb 10 '11 at 1:07
i have the need to discover open ports on a remote server. i wondering if this is possible. i was thinking i'd open a socket, and if this succeeds, it means that it's used ... otherwise, if i get an ...
java sockets asked Mar 8 '11 at 0:13
i am developing a torrent with Java and there is a small question i have. How can i get an open socket for my process in java? i need about 100 free sockets in a sequence, just like 10000-10100. All i ...
java sockets networking tcp port asked Jan 31 '11 at 14:30
I try to check if port 80 is available using the following method :
I have a Java application that checks if port 80 is available, if so, it runs a ...
java networking webserver port asked Mar 30 '13 at 13:03
I am developing eclipse plugin for our organization . We are opening multiple servers[minimum 10 servers] on a user machine using this plugin via eclipse . For starting servers we want port numbers ...
java java-ee port asked Jul 5 '12 at 9:45
1,66631948
java scala port asked Jul 28 '14 at 17:34
Singleton pattern - Server Socket
Im using this code: final int LOCK_PORT= 54321;
ServerSocket ss = new ServerSocket(LOCK_PORT);
The thing is that in the same port you cannot listen to 2 different applications (teachers ...
java asked May 6 '14 at 7:42
I'm currently working with sockets in Java.
I have created a listener which will connect to a ServerSocket. This works perfectly fine. However, if my application may encounter unexpected closure, the ...
java sockets asked Jan 4 '13 at 14:57
4,23671957
java linux sockets tcp zookeeper asked Jul 1 at 13:59
4,63122466
questions linked to/from Sockets: Discover port availability using Java

value: This website is a question and answer website for professional and enthusiast programmers. It is the flagship site of the Stack Exchange Network, created in 2008 by Jeff Atwood and Joel Spolsky.


text:
Patent US7034626 - Oscillator with closed series of four inductors and four capacitors with ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsAn object of the present invention is to provide an oscillator contributing to a reduction of power dissipation. An oscillator 10 comprises four inductors 11 — 1, 11 — 3, 11 — 2, and 11 — 4 connected in series to constitute a closed circuit, and four capacitors 12 — 1, 12 — 3, 12 — 2, and...http://www.google.com/patents/US7034626?utm_source=gb-gplus-sharePatent US7034626 - Oscillator with closed series of four inductors and four capacitors with connecting nodesAdvanced Patent SearchTry the new Google Patents, with machine-classified Google Scholar results, and Japanese and South Korean patents.Publication numberUS7034626 B2Publication typeGrantApplication numberUS 10/250,426PCT numberPCT/JP2002/000015Publication dateApr 25, 2006Filing dateJan 8, 2002Priority dateJan 10, 2001Fee statusPaidAlso published asEP1363390A1, EP1363390A4, US20040061563, WO2002056456A1Publication number10250426, 250426, PCT/2002/15, PCT/JP/2/000015, PCT/JP/2/00015, PCT/JP/2002/000015, PCT/JP/2002/00015, PCT/JP2/000015, PCT/JP2/00015, PCT/JP2000015, PCT/JP200015, PCT/JP2002/000015, PCT/JP2002/00015, PCT/JP2002000015, PCT/JP200200015, US 7034626 B2, US 7034626B2, US-B2-7034626, US7034626 B2, US7034626B2InventorsKoichi Akeyama, Peter VancorenlandOriginal AssigneeKawasaki Microelectronics, Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (9), Non-Patent Citations (3), Referenced by (7), Classifications (12), Legal Events (3) External Links: USPTO, USPTO Assignment, EspacenetOscillator with closed series of four inductors and four capacitors with connecting nodes
US 7034626 B2Abstract
Part (a) of FIG. 3 shows a top view of the spiral inductor 11. Part (b) of FIG. 3 shows a sectional view of the spiral inductor 11. The spiral inductor 11 is formed, as shown in the part (b) of FIG. 3, in an insulating layer 22 provided on a silicon substrate 21 with two layers of conductor pattern 11 a. An area below at least the inductor 11 of the silicon substrate 21 is set up to be higher in a substrate resistance as compared with areas other than the area. Specifically, a shallow-trench isolation is embedded in the area below at least the inductor 11 of the silicon substrate 21. In this manner, embedding the shallow-trench isolation in the area below at least the inductor 11 makes it possible to keep the parasitic capacitance between the inductor 11 and the silicon substrate 21 to be small. The shallow-trench isolation is shaped as a lattice. In this manner, shaping the shallow-trench isolation as a lattice may block a current on a surface of the silicon substrate 11, and thereby enhancing a resistance of the silicon substrate 21. Further, this feature makes it possible to expect an effect that winding of the silicon substrate 21 is reduced.
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS2556296Apr 26, 1949Jun 12, 1951Bell Telephone Labor IncHigh-frequency transistor oscillatorUS5629652May 9, 1996May 13, 1997Analog DevicesBand-switchable, low-noise voltage controlled oscillator (VCO) for use with low-q resonator elementsUS6417737 *Oct 18, 2000Jul 9, 2002Broadcom CorporationAdaptive radio transceiver with low noise amplificationUS6803829 *Jun 17, 2002Oct 12, 2004Broadcom CorporationIntegrated VCO having an improved tuning range over process and temperature variationsJP2000077610A Title not availableJP2000138530A Title not availableJPH118357A Title not availableJPH10126120A Title not availableJPH11126873A Title not available* Cited by examinerNon-Patent CitationsReference1Chi-Wa Lo et al., "2-V 900-MHz quadrature coupled LC oscillators with improved amplitude and phase matchings." Circuits and Systems 1999. ISCAS '99 Proceedings to the 1999 IEEE International Symposium on vol. 2, pp. 585-588, Fig 1.2Setou et al., "Control of Phase States in Ring Oscillators Sharing Inductors," pp. 813-816, 1997 IEEE International Symposium on Circuits and Systems, Jun. 9-12, 1997, Hong Kong.3Shojiro Nakahara et al., "Shuchu Teisuka 4GHz Branch Line Coupler", The Institute of Electronics, Infromation and Communication Engineers Zenkoku Takai Koen Ronbun Shu 3, Mar. 6, 1972, p. 721, lines 10-12, Figure 3.Referenced byCiting PatentFiling datePublication dateApplicantTitleUS7199675 *Aug 11, 2004Apr 3, 2007Information And Communication University Research And Industrial Cooperation GroupSource-injection parallel coupled LC-quadrature voltage controlled oscillatorUS7304548 *Jun 1, 2005Dec 4, 2007Information And Communications University Research And Industrial Cooperation GroupDifferential voltage controlled oscillator using complementary transistors cross-coupled in series, and transceiver using the sameUS7414484 *Sep 29, 2005Aug 19, 2008Altera CorporationVoltage controlled oscillator circuitry and methodsUS20050035823 *Aug 11, 2004Feb 17, 2005Information And Communication University Research And Industrial Cooperation GroupSource-injection parallel coupled LC-quadrature voltage controlled oscillatorUS20050264371 *Jun 1, 2005Dec 1, 2005Information And Communications University Research And Industrial Cooperation GroupDifferential voltage controlled oscillator using complementary transistors cross-coupled in series, and transceiver using the sameUS20070069831 *Sep 29, 2005Mar 29, 2007Altera CorporationVoltage controlled oscillator circuitry and methodsUS20090058541 *Feb 28, 2008Mar 5, 2009Zuo-Min TsaiHigh-frequency ring coupled Quad* Cited by examinerClassifications U.S. Classification331/117.0FE, 331/117.00R, 331/167, 331/57International ClassificationH03B1/00, H03B5/12, H03B27/00Cooperative ClassificationH03B5/1228, H03B5/1253, H03B5/1215, H03B27/00European ClassificationH03B27/00Legal EventsDateCodeEventDescriptionOct 31, 2003ASAssignmentOwner name: KAWASAKI MICROELECTRONICS, INC., JAPANFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:AKEYAMA, KOICHI;VANCORENLAND, PETER;REEL/FRAME:014098/0829;SIGNING DATES FROM 20031021 TO 20031029Sep 23, 2009FPAYFee paymentYear of fee payment: 4Sep 25, 2013FPAYFee paymentYear of fee payment: 8RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services


text:
P. 1IonIonRatings: (0)|Views: 202|Likes: 1Published by The'used Supper CuuexMore info:Published by: The'used Supper Cuuex on Nov 07, 2010Copyright:Attribution Non-commercialAvailability:Read on Scribd mobile: iPhone, iPad and Android.download as DOC, PDF, TXT or read online from ScribdFlag for inappropriate content|Add to collectionSee moreSee lesshttps://www.scribd.com/doc/41377150/Ion12/02/2013pdftextoriginal You're Reading a Free Preview
Activity (3)FiltersAdd to collectionReview Add NoteLikeShowingAllMost RecentReviewsAll NotesLikesYou've already reviewed this. Edit your review.Rating 0/5Post notePost reviewPost replyPost note and like1 thousand reads1 hundred readsDhyandra Nugrahandita liked thisLoad more
More From This UserUSULAN BAHANThe'used Supper CuuexTopic Proposal MhjThe'used Supper CuuexSTIKER.docxThe'used Supper Cuuexan Hut Ri Ke 63 (2008)The'used Supper CuuexKESALAMATAN DI LABARARORIUMThe'used Supper CuuexFungsi Bimbingan Dan Konseling AdalahThe'used Supper CuuexAnalisis Kebijakan Masalah BanjirThe'used Supper Cuuexalay gilakkkkkkkkThe'used Supper CuuexLa Rut AnThe'used Supper CuuexIonThe'used Supper CuuexRPP ipa kls 9 smt 1The'used Supper Cuuex


text:
The Opinion Pages|The Budget Fight Continues
| Editorial The Budget Fight Continues
In defense of their bill to slash federal spending by $61 billion over the next seven months, House Republicans claim they are trying to make the economy grow and create jobs. In truth, such deep and sudden cuts could derail the recovery, without ever addressing the real sources of budget deficits — mainly explosive health care costs and incessant high-end tax cuts.The question is whether the Obama administration and the Senate can prevail against the false rhetoric. Facts, analysis and the moral high ground all favor opponents of the measure. The aim is not to avoid difficult budget decisions, but to block the Republicans’ heedless effort while starting a reasoned budget debate.In a recent report, economists at Goldman Sachs estimated that the House cuts would reduce economic growth by 1.5 percentage points to 2 percentage points in the second and third quarters of 2011. That would devastate employment. As a rule of thumb, each percentage point drop in growth means a loss of 1.2 million jobs.The cuts also would be off point. All of them come from discretionary spending, a sliver of the budget that excludes the government’s biggest and fastest-growing outlays, chiefly Medicare and Medicaid. Over the past decade, Pentagon spending has accounted for almost all of the increase in discretionary outlays, with much of the rest going to homeland security, veterans benefits and the No Child Left Behind education initiative. Aside from defense, there is not a lot to cut prudently. Continue reading the main story
The list goes on. Small businesses would be hit by a 9 percent cut, or $84 million, to the Small Business Administration. Homeowners facing foreclosure and other Americans with legal problems would be hurt by a $70 million cut to legal aid. Financial regulators would endure deep cuts that would cripple their ability to carry out the Dodd-Frank financial reform law. That’s asking for another financial crisis.Given the need to placate House Republicans, some cuts are inevitable. Senators can turn to President Obama’s budget for 2012 as a template for cutting while preserving priorities. It’s time for leadership.In coming days, at the bottom of this page, we will further explore individual penny-and-pound-foolish cuts the House Republicans want to impose, their lack of impact on the deficit and their real-world impact, often on the most vulnerable Americans.

value: This website is an American daily newspaper based in New York City with a worldwide readership. Founded in 1851, the Times has since won 132 Pulitzer Prizes, the most of any newspaper, and has long been regarded within the industry as a national "newspaper of record".