text:
This invention provides a novel catalyst composed of a complex of an organic acid or its ester and a Lewis acid, preferably boron trichloride that can add olefin monomers to increase the molecular weight of the complex from as low as 200 to in excess of a million, with the complex being active viz., living, until the complex dies, viz., is decomposed or destroyed so that polymers in the liquid or easily liquefiable range of 300 to about 10,000 can be made of those more difficult to be liquefied or unliquefiable, viz., those of over 10,000 up to 100,000 or in some cases 500,000 and then those in the range of the elastomers, or moldable or extrudable plastics range having very high molecular weights, generally in excess of 100,000 up to in excess of 500,000 and having useful end groups such as the halogens and specifically chloride, allyl, acryl or methacryl, acetate or formate to name some of the more useful ones.
1. New compositions of matter having a molecular weight greater than 1000 and the structure selected from the class having the formula of: ##STR25## where R1, R2 and R3 may be hydrogen, halogen, or an organic moiety selected from the class of alkyl, aryl, cycloalkyl and alkoxy radicals;
R4 is methylene, polymethylene, ethylenic, acetylinic,
R8 is a trivalent organic moiety selected from the class of alkyl, aryl, cycloalkyl and alkoxy radicals; and
Y is hydrogen or alkyl;
wherein the polyolefin moiety is composed of a polymer of a monoolefin or a copolymer of a monoolefin and a diolefin, provided that when said diolefin is conjugated, the diolefin adds by 1,4- addition.
2. The new composition of claim 1 wherein the polyolefin segment of the composition of the formula is formed from an olefin having from 2 to about 20 carbon atoms.
3. The new composition of claim 1 wherein at least one part of the polyolefin segment of the formula is formed from a diolefin.
4. The new composition of claim 3 wherein the diolefin is a conjugated one.
5. The new composition of claim 1 wherein at least part of the polyolefin segment of the formula is derived from isobutylene.
6. The new composition of claim 1 wherein at least part of the polyolefin segment of the formula is derived from isoprene.
7. The new composition of claim 3 wherein said polyolefin segment is isobutylene with a minor portion of said segment being essentially isoprene.
This application is a division of application Ser. No. 07/156,538 which is a continuation-in-part of application Ser. No. 746,835 filed Jun. 20, 1985.
This invention relates to a novel class of complexes, useful as living polymerization catalysts to produce novel polymers having specific end groups and especially new type polymers such as butyl rubber and related polymers. More particularly, this invention relates to novel complex compounds containing or incorporating at least one or a number of olefinic monomers but sufficient to give a range of molecular weights from the very low range of about 200, 500 or 10,000 to the extremely high range of 500,000 or a million and higher. Specifically, this invention provides a so-called living polymer preparation method that allows polymers to be made as homopolymers, random copolymers, to highly specialized block copolymers, or terpolymers, and the like.
Truly living polymerization, i.e., truly terminationless and chain transferless polymerizations, are a most desirable objective of the synthetic polymer chemist. If the rates of both termination and chain transfer are zero, Rt =Rtr =0, and the rate of initiation is larger than that of propagation Ri >Rp, polymer molecule weights are determined by the ratio [M]/[I] (i.e., monomer over initiator concentrations) and Mw /Mn will be reasonably small. If Ri is instantaneous and/or Ri >>Rp, then Mw /Mn ˜1.0. Living polymerizations are not only of scientific interest, but also of great commercial consequence, and several industrial processes are based on living systems, e.g., cis-1,4-polybutadiene, triblock copolymers of styrene/butadiene/styrene, polytetrahydrofuran, but these are not carbocationic polymerization processes.
Although great efforts have been made to develop living carbocationic polymerizations, success remains rather limited. The only truly living carbocationic systems described to date are those achieved by Higashimura, Sawamoto, et al. involving the HI/I2 initiator system and the highly cationically reactive monomers such as vinyl ethers, p-methoxy styrene and N-vinyl carbazole. Under certain well-defined experimental conditions, quasiliving carbocationic polymerizations approach those of truly living polymerizations but only under quite restrictive conditions, i.e., very low temperatures, continuous slow monomer addition (when the rate of monomer addition and that of monomers consumption are equal), and even then the rate of chain transfer is not exactly zero, but only approaches zero. Also, in quasiliving polymerizations, Rt is not zero, but termination is reversible so that over a reasonably long time period termination appears to be absent, hence the term "quasiliving.
FIG. 1: Mn versus amount of polymer for living polymerization of isobutylene using TMPO.BCl3 complex. FIG. 1 is a graph of the data in Table XIII(a) and (b).
FIG. 2: Mn versus amount of polymer for living polymerization of isobutylene using cumyl acetate.BCl3 complex in CH2 Cl2 solvent. FIG. 2 is a graph of the data in Table XIII(c).
FIG. 3: Mn versus amount of polymer for living polymerization of isobutylene using cumyl acetate.BCl3 complex in CHCl3 solvent. FIG. 3 is a graph of the data in Table XIII(d).
FIG. 4: Mn versus amount of polymer for living polymerization of isobutylene using dicumyl acetate.BCl3 complex. FIG. 4 is a graph of the data in Table XIII(h).
FIG. 5: Mn versus % conversion of monomer for living copolymerization of isobutylene/isoprene charge using cumyl acetate.BCl3 complex. FIG. 5 is a graph of the data in Table XV(a) and (b).
These graphs show the relationship between the Mn and the yield of polymer and that the graph passes through the intercept.
Recently, we have developed a series of new initiator systems that lead us to truly living polymerization systems for olefins such as isobutylene, copolymerization systems of an olefin such as isobutylene with a diolefin such as isoprene, and to new telechelic end reactive polymers of isobutylene or related olefins.
This invention concerns a new family of initiating systems, a new process for making polymers and a series of new products having specific end groups thereon.
The family of initiating systems is based on organic acids or esters in conjunction with a Lewis acid, preferably BCl3, as illustrated by the following formulae: ##STR1## where R1 in the above formula may be H, halogen, an organic moiety such as methyl and related alkyl, or aryl groups, preferably up to about 14 to 20 carbon atoms, alkylene groups such as --CH═CH2 and related lower alkylene groups, preferably 2 to about 8 carbon atoms, and groups containing hetero atoms and related groups such as alkylene chloride, methylene to butylene alkoxy, preferably up to about 14 to 20 carbon atoms;
R2 may be H, methyl and related alkyl groups containing preferably from 1 to about 14 to 20 carbon atoms, in general R2 can be the same as R2 ;
R3 may be methyl, or related alkyls of preferably 2 to about 20 carbon atoms or aryls such as phenyl, cycloalkyls, or vinyl or allyl groups or a CH2 ═group, in general R3 can be the same as R2 ;
R4 may be (CH2)x, or other moiety such as --CH2 --CH2 --, acetylenic such as --CC--, or arylene such as ##STR2## or ethylenic such as --CH═CH-- and related homologous groups; where x is 1 to about 20 and preferably 1 to 10 in value;
R5 may be alkylenes such as --CH2 --, and substituted alkylenes such as ##STR3## or other well known groups where II and methyl have been replaced to produce the related homologous series that yield many lactones having alkyl, aryl, alkaryl, arylalkyl and cycloalkyl groups substituted on the carbon in the lactone ring;
R6 may be the same as R1 but preferably limited to H or alkyls such as methyl or ethyl or aryl; and
R7 is an alkylene group containing carbon atoms to complete the lactone ring over the range of 3 to about 20 carbon atoms or more or an alkylene group having the hydrogen atoms on at least one of the carbon atoms substituted with other carbon atoms or customary carbon atom substituents;
R8 may be a three valent organic moiety ##STR4##
It should be appreciated that R2 in the above formulae can be the same or different.
The polymerization can be carried out at an appropriate temperature by contacting preferably in a liquid diluent the olefinic monomer or monomers, the organic acid or ester and BCl3 or related Lewis acid. The diluents preferably are hydrocarbons such as n-butane, n-pentane, n-hexane, isopentane, neopentane, benzene, toluene, methylcyclohexane or chlorinated hydrocarbons such as CH2 Cl2, CH3 Cl, C2 H5 Cl, chlorobenzene, ethylidene, dichloride, propyl chloride, to name a few of the representative ones well known to the art. Mixed solvents can also be used.
As to the mixing sequence of the ingredients, they may be done without regard to sequence. For example, one can premix the organic ester and BCl3 in a solvent and then add the monomer in a solvent, or premix the ester and the monomer in a solvent and then add the BCl3 in a solvent. Generally, the polymerization starts upon the introduction of the last needed ingredient when the temperature is maintained below the decomposition temperature of the complex which generally is below minus 10� C. but in some cases may be above 40� C. Bulk polymerization, i.e., in the absence of a solvent, can also be carried out.
The polymerization, generally, can be carried out continuously by mixing two streams of chemicals, ester and BCl3 preferably mixed with monomer in appropriate solvents, or ester and monomer mixed with BCl3 or related Lewis acid at a temperature below the decomposition temperature of the complex formed.
In a special embodiment, we also have discovered that the polymerization can be carried out above the decomposition temperature of the complex provided certain precautions are taken, to give savings in refrigeration costs and thus achieve economy in production. These precautions in one embodiment call for the complex of an organic acid or ester with a Lewis acid to be formed below the decomposition temperature of the complex and be maintained below such temperature until their use to initiate the polymerization.
Since the formation of the initiating organic acid or ester--Lewis acid complex is instantaneous, in another embodiment, the reaction can also be carried out by mixing the monomer and initiator, and then introducing the Lewis acid, at a temperature that is higher than the decomposition temperature of the initiating complex. These complexes may have its molecular weight increased by addition of the olefin monomers thereto, either alone, in combination, or in series, at a temperature below or above the complexes decomposition temperature provided the temperature at which the addition or polymerization of the olefin occurs is such that the rate of decomposition of the complex is low so that the decomposition of the complex does not prevent or occur before the polymerization of the olefin.
In this special embodiment, the premade or in situ made complex of an organic acid or ester and a Lewis acid at a temperature where the half life of the complex is about 5 minutes to an hour or more is mixed with the olefin monomer or monomers with or without suitable solvents at a temperature where the polymerization rate preferably is sufficient to substantially complete the polymerization prior to decomposition of a sufficient amount of the complex to stop or prevent the polymerization going to the desired degree of completion. For instance, the premix of the ester and monomer is made and then mixed with the Lewis acid or, in some cases, mixture of Lewis acid can form the complex essentially instantaneously and thus initiate monomer polymerization and complete said polymerization prior to decomposition of the complex to prevent formation of polymer of the desired molecular weight.
To specifically illustrate this special embodiment, any of the complexes set forth herein or made according to the teachings hereof, could be made at a temperature below its decomposition temperature, for instance about minus 10� C. to minus 40� C., preferably in a hydrocarbon or chlorohydrocarbon solvent at a very high concentration, viz., a catalyst concentrate. Then, this premade complex is added with mixing to a suitable reactor that contains the olefin monomer at a temperature of about 10� to 50� C., where the complex effects polymerization of the olefin in the mixture at a temperature preferably of about 10� to 50� prior to decomposition of sufficient complex to stop the polymerization prior to obtaining a polymer of the desired molecular weight.
In another embodiment, the premade complex made below its decomposition temperature simultaneously is charged and mixed with the monomer to give a mixture above the decomposition temperature of the complex, and the mixing is controlled to give a temperature where the rate of decomposition of the complex is sufficiently so low that the undecomposed complex effects sufficient polymerization of the monomer to give the desired polymer of the desired molecular weight. It being undestood that when sufficient of the complex has decomposed, the reaction stops. Thus, we have discovered that polymerization under these special embodiment conditions can be practiced because the rates of polymerizations are relatively fast, usually being complete in a manner of one to three minutes and in nearly all cases, in a matter of 30 minutes while the rate of decomposition is such to give a half life of about 5 minutes to an hour at temperatures of about 20� C. to 30� C. Therefore, not only homopolymers but copolymers and block polymers can be made above the decomposition temperature of the complex when these precautions are taken.
The polymerization most likely occurs by the opening of the ester bond and monomer insertion, as illustrated by the following schematic and illustrative equation: ##STR5## Using the last formula in the above equation, we will exemplify the monomer insertion in the following schematic equation: ##STR6## The complex counter anion is supernonnucleophilic, i.e., it does not assist or cause proton elimination from the carbocation. This is a very important characteristic that distinguishes our counter anions from other known nonnucleophilic counter anions, e.g., BCl4.sup.⊖, BF4.sup.⊖, and AlCl4.sup.⊖. In conventional polymerizations taking place in the presence of simple nonnucleophilic counter anions, the latter assists or causes proton elimination from the growing carbocationic center and thus a species arises that proceeds to protonate monomer. For example, with BF4.sup.⊖ counter anion: ##STR7## the latter protonates incoming monomer as follows: ##STR8## This sequence of events constitutes chain transfer to monomer and it is a most undesirable process for polymer chemists. First of all, this process reduces the molecular weight of the polymer that is formed, and secondly it yields polymers carrying an undesirable unreactive head-group ##STR9## Molecular weight control in systems that involve chain transfer to monomer is more difficult to achieve than in systems devoid of this process. Thus, an advantage of our invention is it avoids the above two shortcomings.
The complex anion of our invention is supernonnucleophilic and as such does not assist or cause deprotonation of the growing carbocationic center. Thus, chain transfer to monomer will not occur in our systems, and consequently molecular weight control can be accomplished by adjusting the relative concentrations of monomer and initiating system, i.e., molecular weight is a function of [M]0 /[I]0, where the subscripts include initial concentrations. The polymer will grow as long as monomer is available and the monomer is not prevented from reacting with the growing center, for example, by the growing center being coagulated from the system or decomposition of sufficient [I]0 to stop the polymerization.
Also on account of the supernonnucleophilic nature of our counter anions, the polymerization is devoid of termination, i.e., the polymerization is relatively terminationless until the temperature exceeds the decomposition temperature of the complex for sufficient time to reduce the [I]0 to zero. The growing center is kept "alive" for extended periods of time without losing its propogating ability. In contrast, in conventional polymerizations termination occurs most likely by a reaction between the growing cation and associated counter anion, for example as set forth hereinafter: ##STR10##
While uninterrupted growth can be maintained for extended periods of time with systems containing supernonnucleophilic counter anions, if termination is desired, say for the preparation of low molecular weight end-functionalyzed polymer, such a premature termination reaction can be brought about by either increasing the temperature of the polymerization system and thus decomposing the active growing complex, or by adding a strong nucleophilic terminating agent, such as methanol or ethanol, pyridine, ammonia, an alkyl amine, or water. Thus, our invention provides a mechanism of varying the molecular weight from several hundreds to the millions. These reactions may result in a Cl-terminated polymer (or a halogen-terminated polymer) most likely because of the following termination reaction: ##STR11## The concurrently formed BCl2 ester is unstable and is converted to other products. The tert.-chloride end group is a valuable end function and can be used in a variety of well known applications.
The BF3 complex yields acetate end groups under the same conditions by decomposition of the catalyst complex. The acetate end group is a valuable function, and its production yields a new composition of matter having valuable properties. For instance, it can be hydrolyzed to the alcohol end group to produce another new composition as illustrated by the following equation: ##STR12## Any of the well known olefin-based monomers may be used in this invention to produce polymers. The alpha-olefins having usually from 2 to about 20 and preferably 4 to 8 carbon atoms may be used alone or in conjunction with themselves with a diolefin, either conjugated or nonconjugated, to produce polymers or copolymers of varying molecular weight even as low as 300 to in excess of a million. These polymers can be low molecular weight liquid or viscous polymers of about 200 or 500 to 10,000 molecular weight units or the solid waxy to plastic or elastomeric materials of greater than 100,000 to 500,000 to a million or more molecular weight units. Examples of these olefins are those having 2 to 20 or more carbon atoms and are readily available as specific species such as ethylene, propylene, butylene, amylenes, hexylenes, heptylenes, octylenes, the styrenes, alpha-methyl styrenes, or the dienes either nonconjugated or conjugated such as butadiene, isoprene, piperylene, hexadienes and the octadienes, and the cyclic analogues of these such as 1,3-cyclohexadiene, to name a few of the well known and representative members.
Examples of the Lewis acids useful in this invention are BCl3, BF3, AlCl3, SnCl4, TiCl4, SbF5, FeCl3 and ZnCl2. Although BCl3 and BF3 are the preferred species, the other halogens and the Lewis acids also can be used by replacing one member for another one. Any of the organic acids and esters may be used provided they form a stable complex with the Lewis acids at a suitable polymerization temperature usually about minus 40� C. up to about 10� to 20� C., or if the rate of decomposition of the complex at higher temperatures is lower than the rate of polymerization. Also, the organic acids can be monocarboxylic acids, such as formic, acetic, and their homologues, say from 1 to 20 carbon atoms, with those less than 6 carbon atoms being preferred. The di- and tricarboxylic acids and higher can also be used. The mono-, di- and trifunctional acids offer a means of making polymers having certain specific mono-, di- or tri- end group functions such as chloride, formate, allylic, acrylic or methacrylic.
The nature of this invention and its many aspects and advantages may be more readily understood and appreciated by reference to the following representative and illustrative examples.
The general polymerization process used in Examples 1 to 11 was as follows:
A series of test tube runs were made by charging each test tube with solvent, monomer, viz., isobutylene, sometimes abbreviated as IB herein, and an initiator. The polymerization was started by the addition of BCl3 with or without solvent being present with the temperature being as given. The concentrations and results of these runs are given in Tables I through XII, according to the experimental run listed. The polymerization was, in most cases, very rapid, i.e., the conversions reached their final values within a few minutes. Nevertheless, to be sure that the reactions did proceed to completion, the polymerization time was extended to 30 minutes. After this time, the reactions were quenched by the addition of 3.0 ml of prechilled methanol. The polymer was recovered by a conventional workup, i.e., evaporation of volatiles, dissolution in n-hexane, decantation or filtration of inorganic residues such as boron compounds or the other Lewis acid residues, removal of hexane by evaporation at room temperature, etc. The fact that the products were not washed insured complete product recovery; i.e., no loss of low molecular weight components. The polymer products were characterized by a variety of techniques including IR, 1 H and 13 C NMR spectroscopy, osmometry and GPC with dual detection with infrared and ultraviolet.
A series of experiments were made using tert.-butyl acetate as the initiator. The results of the individual experiments, a total of 23 runs, are shown in Table I, together with the conditions (concentration of chemicals, temperatures, etc.) used.
According to the data, tert.-butyl acetate is an efficient initiator, molecular weight control can be readily achieved by controlling the [M]0 and [I]0, and chain transfer to monomer is absent even at 0� C. Since chain transfer to monomer did not occur at the relatively high temperature of 0� C., this reaction is also absent in runs carried out at lower temperatures, as indicated by 1 H NMR spectroscopy. Further, based on a variety of analytical techniques (IR, 1 H NMR, GPC), the polymers contain a tert.-butyl head group and a tert.-chlorine tail group, as shown by the following formula: ##STR13## using isobutylene as the monomer.
TABLE I__________________________________________________________________________ Monomer: isobutylene [M] = 1 mol/l Initiator: tert.-butylacetate [I] = as stated, mol/l Coinitiator: BCl3 [BCl3 ] = 2.6 � 10-1 mol/l Solvent: as stated Polymeriza- 30 minutes, unless stated otherwise tion Time:Run ConversionNumberTemp. �C. Solvent [I] Percent -- Mn -- Mw -- Mw /-- Mn__________________________________________________________________________1a 2.8 � 10-2 74.5* 6000 9400 1.61b -50� C. CH3 Cl 2.8 � 10-2 100* 7370 15000 2.01c 5.6 � 10-2 100 4240 7210 1.71d 5.6 � 10-2 100 4340 7420 1.71e 5.6 � 10-3 9.4 27400 48800 1.81f 5.6 � 10-3 13.5 31000 48200 1.51g 5.6 � 10-3 55.0** 22000 39000 1.81h 2.8 � 10-2 43.5 5480 10200 1.81i -30� C. CH3 Cl 2.8 � 10-2 87.5 4130 8400 2.01j 2.8 � 10-2 100 4650 8930 1.91k 5.6 � 10-2 100 2950*** 5590 1.91l 5.6 � 10-2 100 3360*** 6290 1.91m 5.6 � 10-2 100 3200*** 6200 1.91n 5.6 � 10-2 100 2750*** 5600 2.01o 5.6 � 10-3 100 27500 66800 2.41p -30� C. CH2 Cl2 2.8 � 10-2 100 4230 10420 2.41q 5.6 � 10-2 100 2470*** 5950 2.41r -20� C. CH2 Cl2 2.8 � 10-2 100 5940 10700 1.81s 5.6 � 10-2 100 2260*** 6900 3.01t -10� C. CH2 Cl2 2.8 � 10-2 100 4370 9200 2.11u 5.6 � 10-2 100 2040*** 5090 2.51v 0� C. CH2 Cl2 2.8 � 10-2 100 4000 8100 2.01w 5.6 � 10-2 100 2100*** 4560 2.2__________________________________________________________________________ *In these experimental runs, the polymerization time was 1 hour **In these experimental runs, the polymerization time was 100 minutes ***Examination of the polymer showed the absence of terminal unsaturation in the product indicating the absence of chain transfer to the monomer.
TABLE II__________________________________________________________________________Monomer: isobutylene, [ M] = 1 mol/lInitiator: 2,4,4-trimethylpentyl-2-acetate [I] = as statedCoinitiator: BCl3 = 2.6 10-2 mol/lSolvent: as statedTemperature: as statedPolymeriza- 30 minutestion Time:RunNumberTemp. �C. Solvent [I] Conversion % -- Mn -- Mw -- Mw /-- Mn__________________________________________________________________________2a 5.6 � 10-3 100 10500 21500 2.02b -50� C. CH3 Cl 2.8 � 10-2 100 1800 6300 3.62c 5.6 � 10-2 100 1400 3400 2.42d 5.6 � 10-3 100 10770 15750 1.462e -30� C. CH3 Cl 2.8 � 10-2 100 2090 5320 2.52f 2.8 � 10-2 100 2200 5650 2.52g 5.6 � 10-2 100 1290 2800 2.22h -30� C. CH3 Cl/n- 2.8 � 10-2 100 2260 3150 1.39 hexane (60:40)__________________________________________________________________________
Another series of experiments were made using 2,4,4-trimethylpentyl-2-acetate as the initiator instead of the tertiary butyl acetate of Example 1. The solvent was mixed with the initiator and monomer at the temperature indicated for the various runs in Table II and then were added to the reactor, and last the BCl3 was added. The runs from 2a through 2h show the molecular weight varied from about 1,300 to in excess of 10,000.
The experimental conditions of Examples 1 and 2 were used in this example except the initiator was benzyl acetate and the temperature varied from minus 30� to minus 50� C. and showed that polymer was produced over the range of molecular weights from about 30,000 to 125,000 and higher. The data for these experiments 3a through 3d is shown in Table III.
Ultraviolet spectrographic analysis of the polymers of Table III indicated the phenyl ring was in the polymer. Benzyl acetate is an initiator in conjunction with BCl3 for the polymerization of an olefin such as IB, and molecular weight control is possible. These polymers are new and have the following generic structure. ##STR14##
Thus, this method provides a method to produce polymers where the polyolefin segment can be any olefin segment such as polyisobutylene or PIB, polypentene, polyhexene, polyheptene, polyoctene, polystyrene, poly-alpha-methylstyrene, to name a few of the more common olefin monomer segments, or mixtures of these alpha-olefins or other alpha-olefins.
TABLE III__________________________________________________________________________ Monomer: isobutylene, [M] = 1 mol/l Initiator: benzyl acetate, [I] = as stated, mol/l Coinitiator: BCl3 [BCl3 ] = 2.6 � 10-1, mol/l Solvent: CH3 Cl Polymeriza- 30 minutes tion Time:Run TemperatureNumber�C. [I] Conversion % -- Mn -- Mw -- Mw /-- Mn__________________________________________________________________________3a 5.6 � 10-3 8.4 126300 228700 1.83b -50� C. 2.8 � 10-2 9.4 80200 139100 1.73c 5.6 � 10-2 12.5 66700 115800 1.73d -30� C. 5.6 � 10-2 5.6 36100 6100 1.7__________________________________________________________________________
A series of experiments were made according to the procedure of Example 1 using cumyl acetate as the initiator and the results of these experiments are reported in Table IVa, IVb and IVc.
NMR and ultraviolet analysis of the polymer of Table IVa indicated the structure shown: ##STR15## This structure is the same structure obtained by the polymerization of IB with the known cumyl chloride inifer system.
TABLE IV______________________________________Monomer: isobutylene, [M] = mol/lInitiator: cumyl acetate, [I] = as stated, mol/lCoinitiator: BCl3 expressed as [BCl3 ] = 2.6 � 10-1 mol/lSolvent: CH3 ClPolymeriza- 30 minutestion Time:Temperature: -30� C.Run ConversionNumber [I] % -- Mn -- Mw -- Mw /-- Mn______________________________________4a 5.80 � 10-4 16.2 19300 32700 1.74b 5.84 � 10-3 100* 8510 13600 1.64c 2.92 � 10-2 100 2000 3400 1.74d 5.84 � 10-2 100 1160 2820 2.4______________________________________ *Conversion was 100% after 1 minute of polymerization time.
Monomer: isobutylene, [ M] = 1 mol/lInitiator: cumyl acetate, [I] = as stated, mol/lCoinitiator: BCl3 expressed as [BCl3 ] = 2.8 � 10-1 mol/lSolvent: C2 H5 ClPolymeriza- 30 minutestion Time:Temperature: -30� C.RunNumber [I] Conversion % -- Mn -- Mw -- Mw /-- Mn______________________________________4b/a 5.6 � 10-3 100* 9500 14100 1.484b/b 2.8 � 10-2 100 2390 3980 1.664b/c 5.6 � 10-2 100 1260 2050 1.6______________________________________ *conversion was 100% after 1 minute of polymerization time.
Monomer: isobutylene, [ M] = as stated, mol/lInitiator: cumyl acetate, [I] = 5.6 � 10-3 mol/lCoinitiator: BCl3 [BCl3 ] = 2.8 � 10-1 mol/lSolvent: CH2 Cl2Polymeriza- 30 minutestion Time:Temperature: -10� C.Number [M] Conversion % -- Mn -- Mw -- Mw /-- Mn______________________________________4c/a 0.225 100 2640 5000 1.894c/b 0.45 100 5800 9900 1.74c/c 0.676 100 8200 13900 1.694c/d 0.9 100 10400 16300 1.57______________________________________
In these experimental runs, a difunctional initiator, 2,5-dimethyl-2,5-hexane diol diacetate was used in place of the initiator of Example 4 and the polymerization temperature was lower, namely minus 50� C.
2,5-Dimethyl-2,5-hexane diol diacetate is an initiator in conjunction with BCl3 for the polymerization of IB, and molecular weight control is possible. The polymer produced has the following structure: ##STR16## This composition has fully aliphatic telechelic end groups whereas the prior art telechelic polymers contained partial aromatic end groups. Again, this method provides a method to produce the above polymers where the PIB segment can be a polyolefin segment. Thus, in the generic formula for the above fully aliphatic telechelic end groups, composition of the PIB segment would be replaced with polyolefin segments, such as blocks of aliphatic olefins of about 2 to 20 carbon atoms and conjugated diolefin segments of 4 to 12 carbon atoms.
TABLE V______________________________________Monomer: isobutylene, [M] = 1 mol/lInitiator: 2,5-dimethyl-2,5-hexane diol diacetate, [I] = as stated, mol/lCoinitiator: BCl3 [BCl3 ] = 2.6 � 10-1 mol/lSolvent: CH3 ClPol. Time: 30 minutesTemperature: -50� C.RunNumber [I] Conversion % -- Mn -- Mw -- Mw /-- Mn______________________________________5a 5.6 � 10-3 5.2 35100 60600 1.75b 2.8 � 10-2 8.5 11100 20000 1.85c 5.6 � 10-2 9.0 6150 12500 2.0______________________________________
Another difunctional initiator as shown in Table VI was used in this run instead of the one used in Example 4.
Ultraviolet absorption of the polymers of Table VI indicated the presence of initiator segments, viz., triple bonds. The structure of this new polymer is as follows: ##STR17## Again, we have a fully aliphatic telechelic polymer which contains an acetylenic bond therein and the PIB segment can be any polyolefin segment such as polystyrene, polyoctene, and polypropylene by changing the monomer to the desired one; say, styrene for example or octadecene. Hence, the polyolefin segment can be homopolymeric, copolymers of different olefins of either aliphatic, cycloaliphatic or aryl in nature.
TABLE VI______________________________________Monomer: isobutylene, [M] = 1 mol/lInitiator: 2,5-dimethyl-2,5-hexyne diol diacetate, [I] = as stated, mol/lCoinitiator: BCl3 [BCl3 ] = 2.6 � 10-2 mol/lSolvent: CH2 Cl2Polymeriza- 30 minutestion Time:Temperature: -30� C.RunNumber [I] Conversion % -- Mn -- Mw -- Mw /-- Mn______________________________________6a 2.8 � 10-2 62.2 4000 5570 1.386b 5.6 � 10-2 66.7 3000 4140 1.38______________________________________
A series of runs were made at minus 30� C. with acetic acid as the initiator. The results of these runs are given in Table VII.
A series of runs were made at various temperatures with tert.-butyl formate as the initiator. The results are given in Table VIII.
Molecular weight control is possible by controlling [M]/[complex] ratio. Ultraviolet spectroscopy analysis indicates the presence of formate end groups in the products of Table VIII. Thus, according to this finding, we have a new composition of matter having the following structure: ##STR18## which is characterized by the presence of a formate end group.
Thus, by this method, polymers having the following structure can be made which have a formate end group: ##STR19## Where the initiator is a di- or trifunctional formate ester, di- and triformate terminated polyolefins are produced. Thus, homo- and copolymers having formate terminal groups are produced where R1 and R2 have values given hereinbefore.
TABLE VII______________________________________Monomer: isobutylene, [M] = 1 mol/lInitiator: acetic acid, [I] = as stated, mol/lCoinitiator: BCl3 [BCl3 ] = 2.6 � 10-2 mol/lSolvent: CH3 ClPolymeriza- 30 minutestion Time:Temperature: -30� C.RunNumber [I] Conversion % -- Mn -- Mw -- Mw /-- Mn______________________________________7a 5.6 � 10-3 100 11600 14800 1.257b 2.8 � 10-2 100 6700 9700 1.47c 5.6 � 10-2 100 4700 6900 1.5______________________________________
TABLE VIII__________________________________________________________________________Monomer: isobutylene [ M] = 1 mol/lInitiator: tert.-butyl formate [I] = as stated, mol/lCoinitiator: BCl3 [BCl3 ] = 1.1 � 10-1 mol/lSolvent: CH3 ClPolymeriza- 30 minutestion Time:Temperature: as statedRun ConversionNumberTemp. �C. [I] Percent -- Mn -- Mw -- Mw -- Mn__________________________________________________________________________8a 5.6 � 10-3 100 9200 79000 8.68b -30� C. 2.8 � 10-2 100 1700 10000 6.08c 5.6 � 10-2 100 900 5100 5.98d 2.8 � 10-4 63.0 109700 211000 1.98e 5.6 � 10-4 78.1 66400 157000 2.48f -40� C. 1.4 � 10-3 100 40500 10500 2.68g 2.8 � 10-3 100 22500 71600 3.18h 2.8 � 10-4 40.0 252800 421000 1.678i -50� C. 5.6 � 10-4 58.9 136000 334000 2.458j 1.4 � 10-3 100 38000 169000 4.58k 2.8 � 10-3 100 22900 69400 3.08l 5.6 � 10-3 100 12000 35000 2.88m 2.8 � 10-2 100 1700 13000 8.08n 2.8 � 10-4 32.0 197000 340000 1.78o -60� C. 5.6 � 10-4 17.2 241000 383000 1.68p 1.4 � 10-3 100 35000 172900 5.08q 2.8 � 10-3 100 28000 118000 4.15__________________________________________________________________________
In these runs, the initiator was an unsaturated formate, specifically allyl formate. The polymerization conditions and results of the runs are listed in Table IX.
Thus, in the experimental runs shown in Table IX, the compound of the formula was produced. ##STR20## This new composition of matter has an allyl head group. Molecular weight control was achieved from relatively low molecular weights of less than 8,000 to 10,000 to 13,000 up to very high molecular weights of 40,000 to 50,000 to an excess of 100,000. By use of di-, tri- and higher functional acids or esters, it is possible to produce di-, tri- and higher allyl terminated polyolefins where the polymer may be homo, block or copolymers of the olefins of 2 to about 20 carbon atoms, for example.
TABLE IX______________________________________Monomer: isobutylene [M] = 1 mol/lInitiator: allyformate [I] = as stated, mol/lCoinitiator: BCl3 [BCl3 ] = 2.6 � 10-1 mol/lSolvent: CH3 ClPolymeriza- 30 minutestion Time:Temperature: -30� C.Run ConversionNumber [I] Percent -- Mn -- Mw -- Mw -- Mn______________________________________9a 5.6 � 10-4 43.4 87000 155000 1.8 44.8 105000 172100 1.69b 1.12 � 10-3 77.0 46000 112000 2.4 74.2 58000 111000 1.99c 5.6 � 10-3 100 34000 56000 1.6 100 26000 47000 1.99d 2.8 � 10-2 100 15600 27100 1.7 100 13800 23600 1.79e 5.6 � 10-2 100 10200 19500 1.9 100 8200 16900 2.19f 1.12 � 10-1 100 6500 15300 2.3______________________________________
Another series of runs were made using tert.-butyl acrylate as the initiator, the solvents are listed in Table X. The results of these runs are shown in that table. It should be appreciated that other well known acrylate or methacrylate esters, such as methyl, ethyl or alkyls of 20 or more carbon atoms with the Lewis acids may be used as initiators to produce polymers having ethylenic unsaturation as the end group. Also, the acrylic and methacrylic esters of the diols, triols, tetraols and related polyols of the monomeric to polymeric polyols can be used. Thus, with the polymeric polyols, polymers can be produced having heterogeneous oxygen therein of one or two, up to those of a few hundred to over 5,000 to 10,000.
The following new composition of matter having the important acrylic tail group has been produced: ##STR21## This can be used to crosslink and modify other acrylic or methacrylic polymers. Thus, these reactions with acrylic and methacrylic initiators produce a new generic class of compositions of the following formula: ##STR22## where R is H or CH3. Thus, it is possible by changing the functionality of the acid or ester to produce polymers having one, two, three or more acrylic groups.
TABLE X__________________________________________________________________________Monomer: Isobutylene [M] = 1 mol/lInitiator: tert.-butyl acrylate [I] = as stated, mol/lCoinitiator: BCl3 [BCl3 ] = 2.6 � 10-1 mol/lSolvent: As statedTemperature: -30� C.Polymeriza- 30 minutestion Time:RunNumberSolvent [I] Conversion % -- Mn -- Mw -- Mw /-- Mn__________________________________________________________________________10a 5.6 � 10-3 16.2 -- -- --10b CH3 Cl.sub. 2.8 � 10-2 68.5 3800 7200 1.910c 5.6 � 10-2 100 2400 4200 1.810d 5.6 � 10-3 76.8 11000 42150 3.810e CH2 Cl2 2.8 � 10-2 100 4900 10700 2.2 -10f 5.6 � 10-2 100 3200 6900 2.1__________________________________________________________________________
To show that lactones, a special class of esters, could act as initiators with the various Lewis acids, a series of runs were made with γ phenyl-γ-butyrolactone as the initiator under conditions shown in Table XI, with the results shown. It should be noted it was possible to make polymers of very low molecular weight, less than about 4,000 to 8,000 and higher molecular weights of greater than 50,000, and the polymer at lower range was liquid to rubbery in the higher range.
TABLE XI__________________________________________________________________________Monomer: isobutylene [M] = 1 mol/lbutyrolactone [I] = as stated, mol/lCoinitiator: BCl3 [BCl3 ] = 2.6 � 10-1 mol/lSolvent: CH3 ClPolymeriza- 60 minutes unless stated otherwisetion Time:Temperature: -30� C.Run Conversion Nature ofNumber[I] Percent -- Mn -- Mw -- Mw /-- Mn Product__________________________________________________________________________11a 5.6 � 10-4 42.6 70300 121700 1.8 rubbery11b 55.7* 51000 91000 1.811c 1.12 � 10-3 22.1 62000 108000 1.7 --11d 53.7* 27000 74000 2.711e 5.6 � 10-3 28.1 17870 33600 1.911f 5.1* 14500 24400 1.711g 2.8 � 10-2 16.0 6380 33600 1.911h 54.1* 8500 14300 1.711i 5.6 � 10-2 25.9 4870 8100 1.7 liquid11j 69.8* 6680 10500 1.511k 1.12 � 10-1 100* 4800 7300 1.5__________________________________________________________________________ *indicates the polymerization time was extended to 2.5 hours.
In this series of runs at conditions of Table XII, tertiary butyl formate was used to produce polymers of propylene having an oily fluid to a viscous balsam nature. Thus, polypropylene polymers can be produced forming one or more formate terminal groups.
TABLE XII______________________________________Monomer: Propylene [M] = 1 mol/lInitiator: Tert-butyl formate [I] = as stated, mol/lCoinitiator: BCl3 [BCl3 ] = 2.6 � 10-1 mol/lSolvent: CH3 ClTemperature: -40� C.Polymeriza- 2.5 hourstion Time:RunNumber [I] Conversion % Nature of Product______________________________________12a 5.6 � 10-4 2.2 viscous balsam12b 1.11 � 10-3 6.6 viscous balsam12c 5.6 � 10-3 47.5 viscous fluid12d 5.6 � 10-2 91.9 viscous fluid12e 5.6 � 10-2 97.3 oily fluid______________________________________
To prove the living nature of IB or related olefins initated by the supernonnucleophilic counter anion complex, a number of experiments were run and then linear plots of Mn versus grams of polymer formed in the reactor (the figures shown herein) were constructed to see if the plots are linear and whether they cross the origin on extrapolation.
These series of experiments were run in a series of test tubes which were charged with 24 ml CH2 Cl2 2,4,4-trimethylpentyl-2-acetate hereinafter called TMPOAc (5.6�10-3 mol/l) and 0.5 ml IB, in that order, and thermoequilibrated at minus 30� C. Then the polymerization was started by introducing 0.5 ml BCl3 (liquefied) into the test tubes. The BCl3 concentration was 2.8�10-1 mol/l in the reactor. After 30 minutes of reaction time, the reaction in the first of the test tubes was killed by the addition of methanol, whereas an additional 0.5 ml IB was added to the rest of the tubes. After 30 minutes, the reaction in the second tube was killed whereas an additional 0.5 ml IB was added to the remaining tubes. This procedure was repeated until all the charges in the series of test tubes had been quenched. After conventional workup, the amount of polymer and its molecular weight and molecular weight distribution were determined. These data are given in Table XIIIa, and the corresponding plot is given in FIG. 1.
A similar series of experiments have been carried out with a different order of reagent addition. In this experiment, the TMPOAc and BCl3 were premixed in 12 ml CH2 Cl2 and into this system was added 0.5 ml IB dissolved in 12 ml CH2 Cl2 at minus 30� C. Thus, the initial concentrations of the ingredients, i.e., TMPOAc, BCl3 and IB were the same in both series. Except for this premixing of the TMPOAc and BCl3, the further course of the experiment was identical to that described above. FIG. 1 shows the plot of the results.
The fact that the Mn versus grams of PIB formed plot is linear and crosses the origin indicates the living nature of the polymerization system, i.e., each additional monomer increment contributes proportionally to the molecular weight.
The premixing of TMPOAc and BCl3 technique is advantageous as it produces narrower molecular weight distribution polymer than the TMPOAc and monomer and BCl3 addition sequence. This effect can be seen by inspecting the Mw /Mn columns. The Mw /Mn values are lower in the experiment with TMPOAc and BCl3 premixing.
An identical series of experiments have been carried out using CH3 Cl as the diluent. The data is shown in Table XIIIb and these data also yielded a plot similar to that of FIG. 1.
An identical series of experiments have been carried out with the cumyl acetate BCl3 complex initiator in CH2 Cl2 as the solvent. The data are shown in Table XIIIc and are plotted in FIG. 2. Note that one experiment was carried out at a temperature of minus 10� C.
An identical experiment has been carried out with cumyl acetate and BCl3 using CH3 Cl as the diluent. The data are shown in Table XIIId and are plotted in FIG. 3.
Similarly, three identical series of experiments have been carried out with cumyl acetate and BCl3 in various solvent systems. A mixture on a volume basis of 80/20 CH2 Cl2 /n-hexane [Table XIIIe], a mixture of 60/40 CH2 Cl2 [Table XIIIf], and C2 H5 Cl [Table XIIIg]. Corresponding plots of the data from these three experiments, indicated these were living polymerizations.
Finally, a series of experiments have been carried out by the dicumyl acetate BCl3 complex initiator. In this system, polymer growth is expected to occur at both acetate linkages. Table XIIIh and FIG. 4 show the data for these experiments.
TABLE XIII__________________________________________________________________________Monomer: isobutyleneInitiator: TMPOAc [I] = 5.6 � 10-3 mol/lCoinitiator: BCl3 [BCl3 ] = 2.8 � 10-1 mol/lSolvent: CH2 Cl2 (initial charge: 24 ml)Polymeriza- 30 minutes between each additiontion Time:Temperature: -30� C.Killing With: MeOH, (˜3 ml, precooled)RunNumberIsobutylene added, ml -- Mn -- Mw -- Mw /-- Mn Polymer Formed, g__________________________________________________________________________13(a)0.5 2300 12400 5.5 0.3013(b)0.5 + 0.5 3900 15700 4.1 0.6313(c)0.5 + 0.5 + 0.5 + 0.5 + 11600 20050 1.7 1.800.5 + 0.513(d)0.5 2900 11350 3.9 0.3113(e)0.5 + 0.5 4250 15100 3.6 0.5913(f)0.5 + 0.5 + 0.5 + 0.5 8500 187 2.2 1.2013(g)0.5 + 0.5 + 0.5 + 0.5 + 11500 18600 1.6 1.800.5 + 0.513a/h0.5 3000* 9050 3.0 0.3313a/i0.5 + 0.5 + 0.5 7800 19600 2.5 0.9613a/j0.5 + 0.5 + 0.5 + 0.5 + 0.5 10500 22580 2.1 1.4913a/k0.5 + 0.5 + 0.5 + 0.5 + 13000 22500 1.7 1.760.5 + 0.5__________________________________________________________________________ *premixed initiator/coinitiator helped to narrow MWD.Monomer: isobutyleneInitiator: TMPOAc [I] = 5.6 � 10-3 mol/lCoinitiator: BCl3 [BCl3 ] = 2.8 � 10-1 mol/lSolvent: CH3 Cl (initial charge: 24 ml)Polymeriza- 30 minutes between each additiontion Time:Temperature: -30� C.RunNumberIsobutylene added, ml -- Mn -- Mw -- Mw /-- Mn Polymer Formed, g__________________________________________________________________________13b/a0.5 2700 9950 3.7 0.2913b/b0.5 + 0.5 + 0.5 4420 13800 3.1 0.6413b/c0.5 + 0.5 + 0.5 + 0.5 + 8000 19200 2.4 0.940.5 + 0.513b/d0.5 2800 10900 3.9 0.3113b/e0.5 + 0.5 + 0.5 + 0.5 + 10900 21560 2.0 1.340.5 + 0.513b/f0.5 3000* 7000 2.3 0.3313b/g0.5 + 0.5 5300 9600 1.8 0.5513b/h0.5 + 0.5 + 0.5 7200 13000 1.8 0.8013b/i0.5 + 0.5 + 0.5 + 0.5 8800 15500 1.76 1.0413b/j0.5 + 0.5 + 0.5 + 0.5 + 0.5 10800 18360 1.7 1.2513b/k0.5 + 0.5 + 0.5 + 0.5 + 12850 20560 1.6 1.510.5 + 0.5__________________________________________________________________________ *with premixed initiator/coinitiator (30'); MWD narrowed.Monomer: isobutyleneInitiator: cumyl acetate [I] = 5.6 � 10-3 mol/lCoinitiator: BCl3 0.5 m BCl3 added in initial charge final [BCl3 ] = 2.8 � 10-1 mol/lSolvent: CH2 Cl2 (initial charge: 24 ml)Polymeriza- 30 minutes between each additiontion Time:Temperature: -30� C.RunNumberIsobutylene added, ml -- Mn -- Mw -- Mw /-- Mn Polymer Formed, g__________________________________________________________________________13c/a0.5 3100 6200 2.0 0.3113c/b0.5 + 0.5 5500 7650 1.4 0.6413c/d0.5 + 0.5 + 0.5 6800 9500 1.4 0.8713c/e0.5 + 0.5 + 0.5 + 0.5 8800 13100 1.48 1.1513c/f0.5 + 0.5 + 0.5 + 0.5 + 0.5 11000 15800 1.4 1.45__________________________________________________________________________ /initial solvent charge: 24 ml
13c/g2 2570 8400 3.2 1.2213c/h2 + 2 5600 10700 1.9 1.5013c/i2 + 2 + 2 6900 12400 1.8 3.5313c/j2 + 2 + 2 + 2 8900 15800 1.79 4.6213c/k2 + 2 + 2 + 2 + 2 10000 16000 1.6 5.76__________________________________________________________________________ /initial solvent charge: 96 ml, 2 ml BCl3 added, final [BCl3 ] concentration = 2.8 � 10-1 mol/l
Monomer: isobutyleneInitiator: cumyl acetate [I] = 5.6 � 10-3 mol/lCoinitiator: BCl3 0.5 m BCl3 added in initial charge final [BCl3 ] = 2.8 � 10-1 mol/lSolvent: CH3 Cl (initial charge: 24 ml)Polymeriza- 30 minutes between each additiontion Time:Temperature: -30� C.Killing With: MeOH, ˜3 ml, precooledRunNumberIsobutylene added, ml -- Mn -- Mw -- Mw /-- Mn Polymer Formed, g__________________________________________________________________________13d/a0.5 2730 5500 2.0 0.3113d/b0.5 + 0.5 3640 7080 1.94 0.4313d/c0.5 + 0.5 + 0.5 5040 8430 1.67 0.5913d/d0.5 + 0.5 + 0.5 + 0.5 6560 10360 1.58 0.7513d/e0.5 + 0.5 + 0.5 + 0.5 + 0.5 7160 11620 1.6 0.9013d/f0.5 + 0.5 + 0.5 + 0.5 + 8440 12850 1.5 1.120.5 + 0.513d/g0.25 1500 3040 2.0 0.1413d/h0.25 + 0.25 1860 3200 1.7 0.2013d/i0.25 + 0.25 + 0.5 2530 4850 1.9 0.3213d/j0.25 + 0.25 + 0.5 + 0.5 3800 7830 2.0 0.5013d/k0.25 + 0.25 + 0.5 + 0.5 + 4900 9500 1.9 0.600.5 + 0.513d/l0.25 + 0.25 + 0.5 + 0.5 + 6600 12000 1.7 0.760.5 + 0.5__________________________________________________________________________ The plot of this data is shown in FIG. 4.Monomer: isobutyleneInitiator: cumyl acetate [I] = 5.6 � 10-3 mol/lCoinitiator: BCl3 [BCl3 ] 2.8 � 10-1 mol/lSolvent: CH2 Cl2 /n-hexane, 80 v/20 v (initial charge 24 ml)Polymeriza- 30 minutes between each additiontion Time:Temperature: -30� C.RunNumberIsobutylene added, ml -- Mn -- Mw -- Mw /-- Mn Polymer Formed, g__________________________________________________________________________13e/a0.5 3500 5560 1.59 0.3613e/b0.5 + 0.5 + 0.5 4880 12950 2.66 0.5513e/c0.5 + 0.5 + 0.5 + 0.5 5400 16100 3.0 0.66__________________________________________________________________________Monomer: isobutyleneInitiator: cumyl acetate [I] = 5.6 � 10-3 mol/lCoinitiator: BCl3 [BCl3 ] 2.8 � 10-1 mol/lSolvent: CH2 Cl2 /n-hexane, 60 v/40 v (initial charge: 24 ml)Polymeriza- 30 minutes between each additiontion Time:Temperature: -30� C.RunNumberIsobutylene added, ml -- Mn -- Mw -- Mw /-- Mn Polymer Formed, g__________________________________________________________________________13f/a0.5 3450 6500 1.88 0.3513f/b0.5 + 0.5 + 0.5 + 0.5 + 0.5 4580 11390 2.48 0.4313f/c0.5 + 0.5 + 0.5 + 0.5 + 4750 12000 2.5 0.470.5 + 0.5__________________________________________________________________________Monomer: isobutyleneInitiator: cumyl acetate [I] = 5.6 � 10-3 mol/lCoinitiator: BCl3 [BCl3 ] 2.8 � 10-1 mol/lSolvent: C2 H5 Cl (initial charge: 24 ml)Polymeriza- 30 minutes between each additiontion Time:Temperature: -30� C.RunNumberIsobutylene added, ml -- Mn -- Mw -- Mw /-- Mn Polymer Formed, g__________________________________________________________________________13g/a0.5 3150 4830 1.5 0.3313g/b0.5 + 0.5 3400 6400 1.9 0.4013g/c0.5 + 0.5 + 0.5 3900 9720 2.49 0.4713g/d0.5 + 0.5 + 0.5 + 0.5 4100 11520 2.8 0.5413g/e0.5 + 0.5 + 0.5 + 0.5 + 0.5 5100 11350 2.8 0.6112g/f0.5 + 0.5 + 0.5 + 0.5 + 5200 16370 3.1 0.660.5 + 0.5__________________________________________________________________________Monomer: isobutyleneInitiator: dicumyl acetate [I] = 5.6 � 10-3 mol/lCoinitiator: BCl3 [BCl3 ] 2.8 � 10-1 mol/lSolvent: CH3 Cl (initial charge: 24 ml)Polymeriza- 30 minutes between each additiontion Time:Temperature: -30� C.RunNumberIsobutylene added, ml -- Mn -- Mw -- Mw /-- Mn Polymer Formed, g__________________________________________________________________________13h/a0.5 1730 3090 1.78 0.3213h/b0.5 + 0.5 2790 4750 1.7 0.5413h/c0.5 + 0.5 + 0.5 4260 6560 1.54 0.8513h/d0.5 + 0.5 + 0.5 + 0.5 5300 7610 1.44 1.0913h/e0.5 + 0.5 + 0.5 + 0.5 + 0.5 6500 9430 1.45 1.2813h/f0.5 + 0.5 + 0.5 + 0.5 + 7000 9760 1.39 1.470.5 + 0.5__________________________________________________________________________
A special embodiment of this invention relates to the random copolymerization of an alphaolefin such as those exemplified by isobutylene, propylene, pentene or hexene, with a diolefin, preferably a conjugated one such as those exemplified by isoprene, butadiene and piperylene. Thus, copolymers containing either a major or minor amount of diolefin can be produced. Isobutylene plus an isoprene copolymer containing up to 5 percent isoprene in the chain are articles of commerce. The random polymers produced by this invention have commercial utility as butyl rubbers and especially those having a molecular weight of a hundred thousand and 1 to 4 percent unsaturation. These rubbers are sulfur-vulcanizable, heat stable, chemically resistant general purpose rubbers which may be used in inner tubes and inner liners of tires, tubes, curing bladders, mountings, vibration dampers, etc., and are convertible to the halogenated form of butyl rubber for other usages. Heretofore, butyl rubber was made commercially by a heterogeneous low temperature (minus 100� C.) cationic suspension polymerization by the use of AlCl3 catalyst in methyl chloride diluent. In order to obtain commercially useful molecular weights, the polymerization has to be carried out at cryogenic temperatures, viz. below minus 100� C. Therefore, a lot of work has been directed towards the raising of this very low temperature requirement. Also, controlling molecular weight with the AlCl3 system is difficult, it requires changes in reactor temperature. Another problem with conventional polymerizations is reactor fouling. Fouling is the process during which polymer particles crosslink and agglomerate during the run and precipitate on the inner surfaces of the reactor. This adhering layer of crosslinked or gelled polymer decreases cooling efficiency so that molecular weight control becomes impossible. Thus, the reactor has to be shut off and the fouled polymer layer removed by a separate cumbersome and costly process. Great efforts have been extended to overcome fouling.
In Example 14, copolymerization of isobutylene with isoprene was demonstrated to occur readily with our complex catalyst, and that the copolymerization yields random copolymers whose overall composition can be controlled by the isobutylene/isoprene ratio in that charge, and that the molecular weight of the butyl rubber formed can be controlled by the ratio of [monomers]/[initiating complex], and that the copolymerization is living in nature. Also, the percent unsaturation can be controlled over a wide molecular weight range to yield new copolymers of alpha-olefins and dienes which may have higher molecular weights, i.e., in excess of a hundred thousand molecular weight and having unsaturation values of 1, 2, 3 to 5 mole percent and higher. Thus, copolymers having 1 to 90 and preferably 2 to 10 percent of diolefin are readily made.
A series of copolymerization experiments have been carried out under the following conditions: A series of three test tubes have been charged at minus 30� C. with 22.5 ml CH3 Cl, 2.0 ml isobutylene (0.94 mole/l) and 0.1 ml cumyl acetate (0.56�10-3 mole/l) in that order. Then in a series of three test tubes, isoprene was introduced, i.e., 0.05 ml (or 2.13 mole percent on isobutylene); 0.1 ml (or 4.26 mole percent on isobutylene); and 0.2 ml (or 8.52 mole percent on isobutylene) isoprene. Finally, the copolymerization were initiated by the introduction of 0.5 ml BCl3 (2.8 10-1 mole/l). The polymerization proceeded with occasional mixings at minus 30� C. for 30 minutes. Then the reactions were killed by adding 3 ml of prechilled methanol. After workup, the conversions, molecular weights, and overall compositions were determined. The latter was obtained by 1 H NMR spectroscopy which also indicated that the product contained the isoprene units in the chain in a 1,4-enchainment. Table XIV shows this data.
TABLE XIV__________________________________________________________________________ Monomer: isobutylene [M1 ] = 0.94 mol/l isoprene [M2 ] = as stated, mol/l Initiator: cumyl acetate [I] = 5.6 � 10-3 mol/l Coinitiator: BCl3 [BCl3 ] = 2.8 � 10-1 mol/l Solvent: CH3 Cl (initial charge 22.5 ml) Polymeriza- 30 minutes tion Time: Temperature: -30� C. Isoprene inRun the polymer,Number[M2 ] Conversion % -- Mn -- Mw -- Mn /-- Mw mole %__________________________________________________________________________14a 0.02 (2.13 m %) 85.0 9100 13100 1.48 --14b 0.04 (4.26 m %) 74.3 7150 11400 1.6 2.9114c 0.08 (8.52 m %) 51.8 5300 9300 1.75 4.3__________________________________________________________________________
Two additional series were carried out to demonstrate the living nature of the copolymerization. The charging of the series of tubes and the polymerization conditions have been described above in Example 14. In the first series of copolymerizations, three tubes were charged to give 4.26 mole percent isoprene in the isoprene solution (relative to isobutylene). After BCl3 addition, the reactions in the first, second and third tubes were killed at 25, 30 and 45 minutes. After workup, the conversions and molecular weights were determined. The data is shown in Table XVa and FIG. 5.
The second series of copolymerizations have been carried out with 2.13 mole percent isoprene (on isobutylene) in the charge. Copolymerizations were terminated after 5 and 10 minutes after BCl3 addition. In the third tube at 20 minutes, we added a fresh charge of 2.05 ml monomer mixture consisting of 2.0 ml isobutylene and 0.05 ml isoprene, i.e., a charge of 2.13 mole percent isoprene (on isobutylene), and allowed the reaction to proceed for an additional 30 minutes. After killing and workup, the conversion and the molecular weight of the polymers were determined. Table XVb and FIG. 5 show the results.
According to these data, the copolymerizations proceeded in a living manner as indicated by the linear Mn versus conversion plots crossing the origin.
The polymerizations described in this invention can be carried out as long as the initiating complex maintains its integrity to give a wide range of molecular weights. Tests determined that the tert.-butyl acetate BCl3 complex is stable up until at least minus 10� C. Therefore, living and other polymerization can be carried out up to at least minus 10� C. and even to the decomposition temperature of the complex which in most cases is near ambient or 10�-30� C. below it, but some initiator complexes allows operating temperatures above 0� C. Thus, butyl rubber can be made at much higher temperatures than heretofore.
TABLE XV______________________________________Monomer: isobutylene [-- M1 ] = 0.94 mol/l isoprene [-- M2 ] = 0.04 mol/l (4.26 mol %)Initiator: cumyl acetate [I] = 5.6 � 10-3 mol/lCoinitiator: BCl3 [BCl3 ] 2.8 � 10-1 mol/lSolvent: CH3 Cl (initial charge 22.5 ml)Polymeriza- as statedtion Time:Temperature: -30� C.Run Polymerization ConversionNumber Time % -- Mn -- Mw -- Mw /-- Mn______________________________________15a/a 15 minutes 58.0 5800 10480 1.815a/b 30 minutes 74.9 6900 11700 1.6915a/c 45 minutes 79.3 7500 11600 1.55______________________________________Monomer: isobutylene [-- M1 ] = 0.94 mol/l isoprene [-- M2 ] = 0.02 mol/l (2.13 mol %)Initiator: cumyl acetate [I] = 5.6 � 10-3 mol/lCoinitiator: BCl3 [BCl3 ] 2.8 � 10-1 mol/lSolvent: CH3 Cl (initial charge 22.5 ml)Polymeriza- as statedtion Time:Temperature: -30� C.Run Polymerization ConversionNumber Time % -- Mn -- Mw -- Mw /-- Mn______________________________________15b/a 5 minutes 77.1 7120 11400 1.615b/b 10 minutes 84.7 8450 13400 1.5515b/c 25 minutes -- -- -- --15b/d 30 minutes* 100 + 18.5 11200 16050 1.44______________________________________ *After 20 minutes polymerization time, 2.05 ml new isobutylene (2 ml) isoprene (0.05 ml = 2.13 m %) mixture was added and was allowed to polymerize for 30 minutes.
In this example, 0.06 ml tert.-butyl acetate (t-BuAC) and 0.2 ml BCl3 were mixed in 20 ml CH2 Cl2 at minus 10� C. After 1 hour at this temperature, the IR spectrum of the system (taken against the CH2 Cl2 solvent by the use of the matched cells) indicated the presence of the t-BuAC.BCl3 complex; i.e., presence of an absorption at 1570 cm-1 associated with the stretching vibration of the >C═O→BCl3 group (the uncomplexed >C═O showsν CO═1720 cm-1 in t-BuOAC).
Upon heating the t-BuAC.BCl3 complex to room temperature, the complex slowly decomposes to t-BuCl and CH3 COCl (ν CO═1800 cm-1 in CH3 COCl). After one hour at room temperature, 50 percent of the complex has decomposed.
Similar to these experiments, the TMPOAc.BCl3 complex is stable up until minus 10� C. but it decomposes quantitatively at room temperature to TMP-Cl and CH3 COCl, upon standing at this temperature for sufficient time.
The above two experiments can be regarded as model experiments for these polymer systems. Thus when a polymer prepared by the t-BuAC.BCl3 system in which CH3 Cl diluent at minus 30� C. after 30 minutes polymerization was examined, it showed the characteristic CO═1570 cm-1 vibration, indicating the presence of >CO BCl3 complex bond. After letting the system warm to room temperature overnight without killing the reaction, both 1 H NMR and IR spectroscopy showed the formation of an allyl chloride and CH3 COCl.
The fact that the polymer readily decomposes to the tert.-chloride ended structure has important preparative/synthetic implications as it provides a new avenue to valuable tert-chlorine terminated polymers. It is immediately apparent that by the use of difunctional acetate BCl3 complex initiators, i.e., dicumyl acetate BCl3 or other diacetates BCl3 complexes, valuable telechelic polyisobutylenes and related alpha-olefins or diolefin polymers can be prepared.
We have also discovered that the tert.-chloride groups can be quantitatively obtained not only by treating the polymerizing system to bring it to room temperature, but also by adding various nucleophilic killing or quenching agents, i.e., CH3 OH, (C2 H5)3 N, pyridine, ammonia, methanol, and sodium methoxide. These experiments were carried out by model and subsequent polymerization studies to show that any of the olefins can be polymerized by the Lewis acid organic acid or ester complex to give a novel polymerization process to produce new polymers.
New compositions of matter having the structure set forth in the formulae below can be made by this invention. ##STR23## wherein R1 is hydrogen, halogen or an organic moiety of an organic acid;
R2 is the same as R1 ;
R3 is the same as R2 ;
R4 is methylene or polymethylene, ethylenic, acetylenic, ##STR24## related homologous groups; R8 is a trivalent organic moiety; and
Y is a hydrogen or alkyl.
While in accordance with the patent statutes only the best mode and preferred embodiment of the invention has been illustrated and described in detail, it is to be understood that the invention is not limited thereto or thereby, but that the scope of the invention is defined by the appended claims.
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What are credit loans?
In the consumer lending arena, a credit loan describes a type of financing that is based primarily on the borrower's credit and does not require the borrower to pledge any valuable asset as collateral. It is not uncommon for credit loans to be called signature or personal loans.
Unlike obtaining a loan through more traditional means, such as a commercial bank or credit union, credit loan lenders will often make loans to those who have less-than-perfect credit. This can open up an avenue to funds for those who may have no other options available.
Credit loans are often structured as installment loans, with regularly scheduled "installment" payments that are amortized to pay off the credit loan's principal balance and all interest charges that may been incurred, by the end of the loan.
Can I Get a Credit Loan with Bad Credit Scores?
Although a credit loan is based primarily on the applicant's credit history, many credit loans do not require perfect credit records or high credit scores. In fact, some credit loan providers consider alternative credit reports or look beyond the person's credit score. This means that consumers with damaged or less-than-perfect credit, or no credit at all, may still qualify for a credit loan.
The specific credit requirements and restrictions for credit loans will vary depending on the lender. For example, some lenders rely on FICO credit scores, while other credit loan companies do not use this popular credit scoring system. And among those credit loan providers who do use credit scores, the minimum credit score requirements may also vary.
What do I Need to Qualify for a Credit Loan?
Although credit loan providers do have varying requirements, based on their underwriting guidelines, many credit lenders have the following qualification requirements:
- Income verification. Credit loan providers will require income documentation to confirm that the borrower has sufficient income to afford and repay the loan. Typical income verification requirements include recent paycheck stubs or bank statements. They may also contact the applicant's employer to confirm current employment.
- Identification. Credit loan companies take several steps to confirm the identity of all prospective borrowers. This may include copies of driver's licenses, social security cards or state IDs, as well as verification questionnaires.
- Checking accounts. Many credit loan lenders require that the borrower have an active checking account. In addition to directly depositing loan funds into the borrower's accounts, an active checking account may also be necessary to schedule timely installment loan payments.
- Credit history. Credit loans usually rely on the applicant's credit record to determine eligibility for the loan. But as noted earlier, many lenders do not require perfect credit records or very high credit scores in order to qualify for a loan.
Applying for a Credit Loan
Potential borrowers can often apply for a credit loan through the internet. In fact, many lenders today increasingly rely on online applications to speed up their originations. Direct lenders with fully functioning websites are often able to provide eligible credit loan applicants with a decision and loan offer in a matter of minutes – while allowing consumers to apply for a loan from the comfort and privacy of their own homes.
Combined with ACH direct deposits, online loan application and underwriting allow many consumers today to obtain their credit loan funds within one business day of approval.
Disclaimer: NetCredit does not provide financial advice, nor does it vouch for any vendor or service mentioned on our NetCredit consumer lending blog or internet loan dictionary. Always research and perform due diligence on any service provider or vendor before deciding to use them, and we recommend that you speak with a financial advisor regarding all decisions that will affect your finances.

subset: commoncrawl


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Elementary Education
Sample Schedules
- Catalog 2015-2016
- Catalog 2014-2015
- Catalog 2013-2014
- Catalog 2012-2013
- Catalog 2011-2012
- Catalog 2010-2011
- Catalog 2009-2010
- Catalog 2008-2009
- Catalog 2007-2008
Planning List
EPLs will only be available after all sections of a course are closed.
If a new section opens:
- The EPL for that course will be removed. Students will no longer be able to add their name to the list.
- The SEHS Advising Office will contact students via their Oakland University e-mail or phone number. Students will have 72 hours to add themselves to the new section.
- After the 72-hour time frame, the course will appear on SAIL. If additional seats remain open, students may continue to add themselves to the section through the SAIL system.
- If there is not a sufficient need for a class, no additional classes will be added to the schedule.


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Home Letters to the Editor Good greening sense
Good greening sense
To the Editor:
Marc Rosenbaum has it so right in his case for efficient construction in Greening Martha (on the back page of the September 9 issue). Pretty eloquent for an engineer too.
Paul Pimentel
Editor's Note: Paul Pimentel is chairman of the Vineyard Power cooperative.


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There Auto Be A LawThere Auto Be A Law (1963) - Krazy Kat Cartoon Episode Guide
This page has been viewed 12 times this month, and 462 times total.
- Krazy Kat Cartoon Episode GuideEpisode GuideTelevisionSeriesCartoon
- Traditional Animation
- Paramount Cartoon Studios
- Animation Studio: Bratri v Triku, Rembrandt Films
- Distributed by: Paramount Studios
- Cartoon Characters: Krazy Kat, Ignatz Mouse, Officer Pupp.
- Voice Actors: Penny Philips, Paul Frees.
- Directed By Al Kouzel, Gene Deitch.
- Produced By William L. Snyder, Al Brodax.
- Written By George Herriman.
- Music: Stepan Konicek, Jay Livingston, Ray Evans.
- First Aired on November 17, 1963.
- Originally Released in Syndication.
- Running Time: 6 minutes.
- Color
- Czechoslovakia / U.S.A.
Cartoon Summary:
Kokonino Kounty police gives Officer Pupp a motorcycle to capture Ignatz Mouse. However, Ignatz tricks Officer Pupp into driving off a cliff, among other pranks.
Additional Cartoon Pictures:
Cartoon Video:
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Cartoon Comments:
Do you love There Auto Be A Law, or do you think it is the worst cartoon ever? Let us know what you think! Surely you have an opinion... so share what you think. Take a minute and post your own comments about this cartoon here.


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Chicken Divan Jelly
|Unflavored gelatin
|1⁄2 Ounce (2 Envelopes)
|Cold water
|4 Cup (64 tbs)
|Chicken bouillon cubes
|Dried onion flakes
|2 Tablespoon
|Poultry seasoning
|1⁄2 Teaspoon
|Garlic salt
|1⁄4 Teaspoon
|Lemon juice
|1 Tablespoon
|Frozen broccoli flowerets
|10 Pound, cooked and chilled (1 Package)
|Diced cooked chicken
|12 Ounce
|Diced pimiento
|2 Tablespoon
1) In a saucepan, soak the gelatine in 1 cup of cold water.
2) Stir in bouillon and onion flakes.
3) Simmer, stirring constantly until gelatine dissolves.
4) Add the remaining water, poultry, seasoning, garlic salt and lemon juice.
5) Remove from heat, allow to cool.
6) Cover and place it in refrigerator until chill, stirring occasionally until thickened to the consistency of unbeaten egg white.
7) Dice the broccoli, reserving few pieces for garnish.
8) Lightly fold the chicken, pimiento and diced broccoli into gelatine mixture.
9) Arrange the florets in the bottom of 6 cup moulds.
10) Spoon the gelatine mixture equally in the cup moulds.
11) Place the moulds in the refrigerator until chilled.
12) Serve a small mixed salad on a serving plate and unmould the gelatine mixture on the salad, if desired.


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Golf Capsules
PARKER, Colo. The Europeans wanted to make history by winning the Solheim Cup on American soil for the first time.
They did even better than that Sunday.
Caroline Hedwall became the first player in Solheim Cup history to win all five of her matches, the last one with a splendid shot to 4 feet for birdie on the 18th for a 1-up win over Michelle Wie that assured Europe of keeping the cup.
More than an hour later, Cristie Kerr and Karine Icher played all the way to the 18th green until conceding each other birdies. That half-point made it 18-10 in favor of Europe, the biggest blowout since the Solheim Cup began in 1990.
And the Europeans did it with six rookies on their team, who combined to go 12-5-2.
Catriona Matthew, at 43 the oldest player on the team, rallied to halve her match against Gerina Piller that gave Europe 14 1/2 points and an outright win in America.
Charley Hull, the youngest player in Solheim Cup history at 17, capped off her amazing week by demolishing Paula Creamer 5 and 4 in a match that set the tone for Europe. Carlota Ciganda handed Morgan Pressel her first lost in singles in four appearances to go 3-0 for the week.
Europe still trails 8-5 in the competition, but this was the first time it has won back-to-back.
Matthew holed the winning the putt, but the Europeans really won Saturday afternoon when they swept the fourballs matches to build a 10 1/2-5 1/2 lead, matching the largest margin going into Sunday.
Patrick Reed won the Wyndham Championshipfor his first PGA Tour title, beating Jordan Spieth with a birdie on the second hole of a playoff.
Reed recovered from a drive on the par-4 10th that nearly went out of bounds and placed his second shot 7 feet from the pin. Spieth reached the green in two strokes but his 10-foot birdie putt trickled less than an inch wide of the cup. Reed then sank his birdie putt to end it.
Reed earned $954,000 money and 500 FedEx Cup points for winning the final tournament before the playoffs.
Reed and Spieth finished regulation at 14-under 266. Reed closed with a 4-under 66, and Spieth had a 65.
The 20-year-old Spieth, the John Deere winner in a playoff last month, was denied in his bid to become youngest two-time champion in the modern era of the PGA Tour.
John Huh and Brian Harman were two strokes behind. Harman had a 66, and Huh shot 68.
ENDICOTT, N.Y. (AP) - Bart Bryant won the Dick's Sporting Goods Open to becoming the Champions Tour's 1,000th tournament winner.
Bryant shot a tournament record-tying 10-under 62 in the second round and completed his first victory on the 50-and-over tour with 72. He finished at 16-under 200 to beat Russ Cochran and Corey Pavin by one shot.
For, the 50-year-old Bryant, who won in only his 14th start on the circuit, it was his first victory since winning the 2005 Tour Championship, ending a drought of 7 years, 9 months, 11 days. He also won the 2005 Memorial and the 2004 Valero Texas Open on the PGA Tour.


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Last summer a galaxy of fine-wine producers were invited to the Rheingau to celebrate the smart new winery extension to Robert Weil (see Rheingau 2011s revisited and A yen for quality). They were each asked to supply a magnum of one of their best wines to…
Written by 12 Nov 2013
Round the world in 21 great magnums
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Milan Music: Tradition & Innovation
Milan Music: Tradition & Innovation website (map)
Sponsor: IES Abroad
Location: Milan, Italy
This program welcomes music students of all Italian language levels and offers a full range of opportunities for instrumentalists, vocalists, composers, and music performance majors through Music courses at the IES Abroad Center. The Center Director, who is an active composer and music scholar, tailors a program that meets your particular musical needs and interests. Music students typically take one to three Music courses each term, combining private lessons with Scuola Civica instructors with music composition, history and theory courses at the IES Abroad Center. Students also have access to non-Music courses in Communications, Film Studies, History, Literature, Political Science as well as a credit-bearing internship option.
Program Type: Affiliated
- Full Year
- Fall
- Winter/Spring
- Affiliated for Music majors only
- Read Internships and Service Learning for specific information about earning credit for internships.
Admission Info:
To apply, Northwestern students must:
- Complete an NU Study Abroad Application by the appropriate deadline
- Complete an IES Abroad application by the program's deadline
Languages: Italian, English
Language Requirements:None; however, students are required to take one Italian-language course or one course taught in Italian on the program.
Students choose from the following housing options:
- Student apartments with 3-6 other IES students
- Collegio di Milano, a residence hall for Italian and international honors students (additional cost)
- Limited number of homestays in Milanese homes throughout the city
Program Costs:
Fall 2014: $30,315
Billed by Northwestern: $18,665
- Tuition: $16,165
Estimated additional costs: $11,650
- Housing: $4,235
- Meals: $3,120
- Airfare: $1,200
- Local transportation: $140
- Books & supplies: $300
- Personal expenses: $2,100
- Residence permit: $210
- IES insurance: $200


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They are the 200,000-person problem in China's backyard.
For the past 50 years, China has been the uncertain gateway for North Korean refugees seeking passage to South Korea. The most recent strategy has the North Koreans trying to seek asylum in the foreign embassies of Beijing, an effort that echoes the East German refugees who flooded the West German embassy in Prague in the former Czechoslovakia just months before the fall of the Berlin Wall.
Since March, residents say the once-sleepy row of embassies has been under siege. Dozens of refugees have scaled walls or found clever ways to sneak past Chinese police. One group of 25 even posed as tourists to gain admission to the Spanish embassy. Five have made their way into U.S. missions in the country.
China has been grating its teeth over the infractions. A week ago China released 26 refugees to South Korea — raising this year's total to more than 60 — but the country has showed signs that its patience is wearing thin.
No country has better relations with North Korea than China, but the nations have done little more to resolve their mutual problem than put up more barbed wire.
International Incidents
Enforcing its policy has been a political mess for the Chinese. Police caused an international flap in May when they chased a man into a Japanese mission, violating international law. Embassies are considered the sovereign territory of the flagged nation.
In another incident, television crews filmed Chinese police bloodying several diplomats as they dragged a man from a South Korean visa office. The episode prompted a response from the United States.
"We were appalled to find that the Chinese have apparently violated the diplomatic security of your embassy in Beijing, which seems to contravene all diplomatic etiquette," Deputy Secretary of State Richard Armitage said on South Korean television.
China called the incident "a pity" but defended its police.
Both the U.S. Senate and House have passed resolutions demanding that the Chinese government not return refugees to North Korea, where punishment means certain imprisonment, and possible execution. Last week lawmakers heard the testimony of a former refugee who said Chinese police trampled her while in their custody.
"Their stories won't let you sleep at night," said Sen. Sam Brownback, R.-Kan, who held the hearings. "If you're in a position to help some of these people get out, and we are, and you are, I would think we really need to move with some speed and urgency."
Risks and Rewards
Storming embassies has proven to be a gamble with hefty consequences. Chinese officials last month issued a notice to diplomats saying that all embassy intruders should be turned over to police. The crackdown has also been reported in North Korea, leading some officials to conclude that the refugees' new strategy is backfiring.
"There's been an increase in political, and personal insecurity for those North Koreans that are living in China," said Hazel Smith of the U.S. Institute of Peace. "[Refugees] are now terribly worried that they're going to be not left alone in the way that they have been left alone in past, and sent back to North Korea to face the food shortage and, of course, all the political problems that they face when they go back."
Despite the concerns, Norbert Vollersten, a German doctor who helped organize the successful rush on the Spanish embassy, said he would continue to battle for the refugees.


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Chevron Infinity Scarf: Free Pattern and Tutorial
10 Easy Garden Hacks for Under $20
Give Your Relationship and Love Life a Spring Cleaning
Brad Pitt & Angelina Jolie: When is it Time to Seek Help?
Money-Saving Life Hacks That Will Change Your Life
Watch Ellen Shut Down Bethenny Frankel's Ignorant Comments
Real Dating Advice: You Love It, He Loves It Not
5 Signs You're in a Lukewarm Relationship
'Naked Dresses' in Red Carpet History
14 Proven Ways to Cut Food Costs While Traveling
'Player Gets Played' Stars Discuss Moving On After Infidelity
6 Unusual Ways to Make Money From Home
9 Strategies to Lose Weight and Stop Dieting...Once and For All
50 Ways to Make a Fast $50
Real Advice: The Psychology of Online Dating
5 Ways to Save Money at Theme Parks This Summer
10 Strange and Sneaky Supermarket Savings Strategies
6 Edgy Pieces to Instantly Update Your Style
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Never Buy These Used Items
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Why We Want The Lesbian Taylor Swift Rumors To Be True
10 Celebs Who Made It Through Tough Times
9 Signs You're in the Right Relationship
Did Kristen Stewart's Mom Just Out Her?
Love Advice: How To Tell If a Guy Likes You
10 Ways to Become More Likeable in Business
Use This Clever Mental Trick to Lose Weight


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1. Soak the cashews in 2 cups of water.
2. In a blender, add the soaked cashew nuts along with the soaking liquid, 1/3 cup of agave syrup, 1/3 cup of maple syrup, 1/2 cup raw cacao chocolate and vanilla. Blend until smooth and creamy.
3. Pour into a freezer friendly container and place in the chiller and let it cool.
4. Pour the mix into an ice cream maker.
5. Put in 1 cup of vegan chocolate chips and mix well.
6. Place in the freezer for 2 hours.
7. Scoop into ice-cream bowls or cups and serve with vegan chocolate syrup or any other fruit topping if you like.


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Modular Kitchen Wall Storage Short Bar 1 1
cool and useful i got the short bar, the knife rack and the wide wire basket. these two items JUST fit the short bar, but i needed that length for the space i was using. mounted easily in minutes (thanks husband) and included all necessary hardware. it looks really cool--that rustic industrial feel that i believe can work in many style kitchens--and it also utilizes the wasted space between cabinet and counter. so yeah, useful and adds a cool funky element. for reference-i can fit about 5 large knives in the upper row and 7 steak knives in the lower. the basket now houses a two serving tea diffuser glass pot with a selection of packages of tea and room for much more. very satisfied. March 4, 2015
1-1 of 1
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DAVIE, Fla. (AP) Miami Dolphins receiver Davone Bess and linebacker Koa Misi have been ruled out of Sunday's game against Jacksonville.
JACKSONVILLE, Fla. (AP) The Jacksonville Jaguars have waived rookie receiver Kevin Elliott and activated rookie offensive lineman Austin Pasztor from the practice squad.
GREEN BAY (9-4) At CHICAGO (8-5)
Sunday, 1 p.m., FOX
OPENING LINE - Packers by 3
RECORD VS. SPREAD - Green Bay 7-6; Chicago 6-7
SERIES RECORD - Bears lead 92-87-6
JACKSONVILLE (2-11) At MIAMI (5-8)
Sunday, 1 p.m., CBS
OPENING LINE - Dolphins by 7
RECORD VS. SPREAD - Jacksonville 6-7; Miami 6-7
SERIES RECORD - Jaguars lead 3-2
IRVING, Texas (AP) NFL Commissioner Roger Goodell met with the director of Mothers Against Drunk Drivers the night before Wednesday's owners meetings in the Dallas area, where a Cowboys player wa


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Back on Sept 21, BD Gallof wrote an opinion piece about the Islanders Three headed Goalie Monster on LI, it can be found: here.
Over a month later and the Monster on LI has kept the Isles largely in games and posted a 2.22 GAA and .925 SV% so far as a unit. BD's still not wrong in his assessment of the situation (it's bad) and, more often than not, the Isles should roll with Montoya/Nabokov(My opinion), but DiPietro's good play on Saturday was helpful.
LI isn't so much the issue as what's gone on in Bridgeport. Through the first 9 games Anders Nilsson has looked like a goalie, Mikko Koskinen's been the forgotten man and Kevin Poulin....well, he hasn't been good, by any stretch of the imagination.
When you look at the numbers:
Nilsson: 3-1-0; 2.98 GAA; .902 SV% and 12 GA on 123 Shots
Poulin: 1-3-0; 4.71 GAA; .853 SV% and 17 GA on 116 Shots
Koskinen: 0-0-1; 1.99 GAA; .940 SV% and 3 GA on 50 Shots (Koskinen has had one start and 1 relief appearance)
you clearly see that the samples are pretty small for goalies overall workloads. However, giving these guys 25 starts each isn't going to help anything. There's no way to gauge any of these players (and each has been heralded as a top goalie prospect at one point or another and if groomed properly been said to be a starter in the NHL). Poulin has maybe had bad luck, or bad defenses or been rusty from last year's knee operation, but his numbers through only 4 games are a huge cause for concern, a Jonathan quick like tear of shutouts only brings his numbers from god awful to not bad.
Unfortunately, there isn't much the Isles can do at this point, they aren't in any condition to move a goalie (and if they are, it'd come from the NHL side with Nabokov you're likely choice), and there isn't much of a way to loan one to another organization at the AHL. The Isles could loan one out (Koskinen to get the minutes or Poulin to shake off the rust) to an ECHL franchise, but that's a tough call this early to ask an ECHL team, especially one playing well (like say the Utah Grizzlies) to bump their goalie tandems in favor of an NHL prospect and give them "favored goalie Status" for the season. To clear up things right now the Sound Tigers could take Poulin out and make sure he's 100% mentally and physically, but that's a bandage to the situation. But if any of these three are going to make the jump to the bigs and usurp the reins in LI and lead the team through Rick's umteenth injury, something needs to be done. They can give the hot hand starts, but they need to settle on two.
The Three-headed monster's been an institution since Koskinen came over from Finland (and probably before in the Yann Danis-JoeyMacz age) when he was teamed up with Scott Munroe and the fantastic Nate Lawson; last year he teamed up with: Lawson, Poulin, Joel Martin and Riley Gill; Koskinen actually played the most notching 36 games, Martin was next with 18. Koskinen's lost essentially two years of developments with the three headed monster and injuries. The Sound Tigers need to select two of the three and roll with them until one gets cold. They also need to find a place to loan the odd man out to to stay sharp, at this point the numbers say go with Nilsson and Koskinen; but Poulin is a huge talent, but he's a mess.
The Isles have a ton of talent in goal at both the NHL and AHL, but they have to pick two goalies at each level. there's nothing wrong with depth, but when it becomes a detriment to development, something needs to be done.
Again, there's no quick fix, and the Isles need to do something and break with the nonsensical idea that Bridgeport needs 3 Goalies.
Flame away folks.


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- Home
- About WIP
- Participating Entities
- Animas-La Plata Water Conservancy District
- City of Durango Utility Commission
- Colorado Water Resources and Power Development Authority
- Dolores Conservation District
- Dolores Water Conservancy District
- Empire Electric Association
- Florida Water Conservancy District
- La Plata Archuleta Water District
- La Plata Electric Association
- La Plata Water Conservancy District
- Mancos Conservation District
- Mancos Water Conservancy District
- Pagosa Area Water and Sanitation District (PAWSD)
- Pine River Irrigation District
- San Juan Water Conservancy District
- Southwestern Water Conservation District
- Town of Silverton
- Town of Telluride
- Regional Water Projects
- Animas-La Plata Project (Lake Nighthorse)
- Animas River Stakeholders
- Cloud Seeding Program
- Dolores Project (McPhee Reservoir)
- Dry Gulch Reservoir (Pending)
- Florida Project (Lemon Reservoir)
- Mancos Project (Jackson Gulch Reservoir)
- Long Hollow Reservoir
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- Water Information
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- Contact WIP
Clean Water Act
June 11, 2015--Senators vote to repeal Clean Water Rule that protects millions of miles of streams (Climate Progress)
Congressional Republicans are one step closer to blocking the Obama administration's attempt to clarify the EPA's regulatory powers under the Clean Water Act. On Wednesday, the Senate Environment and Public Works committee voted 11-9 to pass a bill that would effectively repeal the administration's recently announced regulations for water pollution.
October 20, 2014--Article discusses nation's connection to water, pricing schemes, steps toward sustainable future (Water World)
In Los Angeles and Toledo and across the U.S., historic drought, water-quality threats heightened by warming waters and poorly maintained infrastructure are converging to draw public attention to the value of fresh, clean water to a degree not seen since Congress passed the Clean Water Act in 1972.
In Los Angeles and Toledo and across the U.S., historic drought, water-quality threats heightened by warming waters and poorly maintained infrastructure are converging to draw public attention to the value of fresh, clean water to a degree not seen since Congress passed the Clean Water Act in 1972.
September 4, 2014--State Water Plan draws crowd (Pine River Times)
A group of legislators from around the state were in Durango on Aug.
September 1, 2014--Water: Battleground of the West (Durango Herald)
West of the invisible 100th meridian line separating the East from the West, Harold Baxstrom irrigates 180 acres of hay or pasture with water directly from Lemon Reservoir.
July 31, 2014--Tipton, EPA fight over water rule (Durango Herald)
It appears Mark Twain was right when he wrote, "Whiskey is for drinking; water is for fighting over." U.S. Rep.
July 28, 2014--Clean water is good for business (US News)
In 1969, the Cuyahoga River in Ohio caught fire for the 13th time in its sad 100 year history as an industrial dump and sewer. The fire, commemorated in song, spurred the creation of the Environmental Protection Agency in 1970 and the passage of the Clean Water Act soon after. The EPA has since cleaned up many of America's rivers, lakes and bays.
July 26, 2014--How frustration and inaction color EPA's efforts to enforce the Clean Water Act (Huffington Post)
For years, the U.S. Environmental Protection Agency has been frustrated in its efforts to pursue hundreds of cases of water pollution — repeatedly tied up in legal fights about exactly what bodies of water it has the authority to monitor and protect. Efforts in Congress to clarify the EPA's powers have been defeated.
July 20, 2014--U.S. water quality: No day at the beach (Denver Post)
What do you pack for a day at the shore? How about a hepatitis shot, antibiotic ointment, and a vomit bucket? A study conducted by the environmental organization NRDS found that as many as 10 percent of U.S.
July 16, 2014--One farmers group actually likes proposed EPA water rules (Fence Post)
The Rocky Mountain Farmers Union has broken ranks with many other water users in Colorado to support proposed rules meant to clear up discrepancies in U.S. Supreme Court rulings on the Clean Water Act. The group claims false claims are being made about the rules. The rules are proposed by the Environmental Protection Agency and the Army Corps of Engineers.
July 14, 2014--EPA's efforts to clarify the Clean Water Act upsets Colorado farmers (Colorado Public Radio)
The Environmental Protection Agency and the U.S. Army Corps of Engineers released a proposed rule in March that is intended to clarify which waterways are protected under the Clean Water Act.


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Web Content Display
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Charting the Course for Blended Learning
Blended learning presents unique challenges. However, equipped with the right support and resources, implementation and adoption can be manageable—and successful. This webinar provides educators valuable insight into successfully incorporating blended learning into their schools.
Online Language Learning—Recipe for Success
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ELL Common Core Challenges & Recommendations—On the Road to Academic Success
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text: Pasen REI-16 UI Determined to Become Center of Apple Lawsuit Jack LoftusProfileFollowUnfollow Jack LoftusFiled to: crapmodo PMP pasen Pasen REI-16 Media Players Ripoff Apple worstmodo 12/21/08 11:30amEditDelete Invite manuallyPromoteXDismissXUndismissBlock for gizmodoHideShare to KinjaGo to permalink The UI in this video of the Pasen REI-16 is pretty slick, if not vaguely familiar. Oh that's right. Just like their other player, the "iTouch," this one is also a blatant ripoff of Apple.Get them while they last when they arrive in January for about $130. [B4Tech] 37Reply 37Discuss


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The National ME/FM Action Network in Canada is competing for $100,000 for biomedical research of ME and FM in the Aviva Community Fund contest. With thanks to all who helped, they made it through the first round of voting into the Semi-Finals.
Discuss the article on the Forums.
When do you know you are ready to go back to work (full-time)?
Discussion in 'General ME/CFS News' started by Jeffy14, Dec 26, 2010.
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Pronunciation: Burghead
Added on: 2009-08-04 Listened: 174 timesin: place names, Scotland
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Tue Jan. 20, 2015
Early Super Bowl 49 Twitter Mailbag
How will the Seahawks defend Gronkowski? Will Richard Sherman's injury be a major factor? And how much trouble are the Jets in for owner Woody Johnson "tampering" with Darrelle Revis? That and more as Peter King answers your Twitter questions


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nanook (nanook)'s status on Tuesday, 24-Jun-14 15:32:43 PDT
'eskimo.com' web address outage - http://www.eskimo.com/news/eskimo-com-web-address-outage/about a year ago from WP-status-net at 47°45'20"N 122°20'29"W
'eskimo.com' web address outage - http://www.eskimo.com/news/eskimo-com-web-address-outage/
Eskimo North StatusNet is a microblogging service brought to you by Eskimo North. It runs the StatusNet microblogging software, version 1.1.1-release, available under the GNU Affero General Public License.
All Eskimo North StatusNet content and data are available under the Creative Commons Attribution 3.0 license.


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Comment: Re:Phase out fossil-fueled power plants by midcent (Score 5, Insightful) 308 308
Followed the link, searched for nuclear, didn't find it in the story. Closed the page.
If you are espousing 0 emission energy in the next 35 years, and you don't mention nuclear as a necessary component, then you are lying.


text: WASHINGTON (AP) — The managing director of the International Monetary Fund says the fund is "ready to assist Greece if requested to do so." The statement from Christine Lagarde is the first reaction from the IMF to yesterday's vote in Greece that decisively rejected further austerity measures in return for bailout loans. Greece has already failed to repay $1.7 billion that was due to the IMF last Tuesday.


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The study doesn't speculate about whether the teens who stopped smoking pot turned to other drugs. It also doesn't examine the gender differences in how teens reacted to drug-use trends.
Steven Shoptaw, a licensed psychologist and professor at the University of California, Los Angeles, said the study relies on some of the best available statistics, but one weakness is that it looks at averages across the country. "Think of averaging wind speeds across the country to develop an average wind speed for the U.S." said Shoptaw, who studies drug use. "While the U.S. average wind speed tells you something, you don't really know what it tells you, and you certainly can't rely on the measure to understand what is happening in specific areas of the country."
As for the differences between boys and girls in terms of intractable pot use in the face of societal trends, he said they have little meaning, because boys are more likely to engage in socially deviant behaviors like pot smoking.
More information
There's more for teens about pot use from the National Institutes of Health.
SOURCES: Michelle Little, Ph.D., postdoctoral fellow, Arizona State University, Tempe; Steven Shoptaw, Ph.D., psychologist and professor, University of California, Los Angeles; March 2008, Prevention Science
|Copyright©2008 ScoutNews,LLC.
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