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US 20060293487 A1 Abstract The present invention is to a chain of polyurethane, polyurethaneurea and/or polyurea segmented copolymer wherein the polyurethane, polyurethaneurea and/or polyurea segments contain a chain extender having an amide segment, an ester segment, or a combination of amide and ester segments.
Claims(40) 1. A chain extended polyurethane, polyurethaneurea and/or polyurea segmented copolymer comprising a polyol soft segment linked via a urethane or urea linkage to a hard segment having an amide segment, an ester segment or a combination of amide and ester segments as represented by Formula I
�R�B�(R′�B)n�R� (I) wherein each B represents an �N(H)C(O)�, �C(O)N(H)�, �C(O)�O� or �O�C(O)-moiety; each R and R′ is a member selected from the group consisting of alkylene moieties, alicyclic moieties, arylene moieties, alkaryl moieties, arylalkyl moieties and heterocyclic moieties, and n has a value of 0 to 6. 2. The copolymer of
3. The copolymer of
�R�C(O)N(H)�R′�N(H)C(O)�R� �R�N(H)C(O)�R′�C(O)N(H)�R� �R�N(H)C(O)�R′�N(H)C(O)�R� wherein each R and R′ is a member selected from the group consisting of alkylene moieties, alicyclic moieties, arylene moieties and heterocyclic moieties. 4. The copolymer of
�R�C(O)O�R′�OC(O)�R� �R�OC(O)�R′�C(O)O�R� �R�OC(O)�R′�OC(O)�R� wherein each R and R′ is a member selected from the group consisting of alkylene moieties, alicyclic moieties, arylene moieties and heterocyclic moeities. 5. The copolymer of
6. The copolymer according to
7. The copolymer of
8. The copolymer of
9. The copolymer of
10. The polyol of
11. The polyol of
12. The copolymer of
13. The copolymer according to
14. The copolymer of
15. The copolymer of
16. The copolymer of
17. The copolymer of
18. The copolymer of
19. An elastomer, fiber or extruded foam made from a copolymer of
20. A method for producing a chain extended polyurethane, polyurethaneurea and/or polyurea segmented copolymer comprising reacting in a one-shot process a polyol, a polyisocyanate, and a chain-extender of the formula
X�R�B�(R′�B)n�R�X (II) wherein each B represents an �N(H)C(O)�, �C(O)N(H)�, �C(O)�O� or �O�C(O)-moiety; each R and R′ is a member selected from the group consisting of alkylene moieties, alicyclic moieties, arylene moieties, alkaryl moieties, arylalkyl moieties or heterocyclic moieties; n has a value of 0 to 6; X is an isocyanate reactive group; and the equivalent ratio of NCO groups on the isocyanate to active hydrogen groups on the polyol plus the chain extender is between 1:0.7 and 1:1:3, and the molar ratio of the chain extender to polyol is between 0.15:1 and 75:1. 21. A method for producing a chain extended polyurethane, polyuethaneurea and/or polyurea segmented copolymer comprising reacting an isocyanate-terminated prepolymer with a chain extender of the formula
X�R�B�(R′�B)n�R�X (II) wherein each B represents an �N(H)C(O)�, �C(O)N(H)�, �C(O)�O� or �O�C(O)-moiety; each R and R′ is independently chosen from the group consisting of alkylene moieties, alicyclic moieties, arylene moieties, alkaryl or arylalkyl moieties or heterocyclic 20 moieties; n has a value of 0 to 6; X is an isocyanate reactive group; and the isocyanate terminated prepolymer is the reaction product of a polyisocyanate and a polyol, where the equivalent ratio of NCO groups on the isocyanate to active hydrogen groups on the polyol plus the chain extender is between 1:0.7 and 1:1:3, and the molar ratio of the chain extender to polyol is between 0.15:1 and 75:1. 22. The method of
23. The method of
24. The method of
25. The method of
26. The method of
27. The method of
28. The chain extended polyurethane, polyurethaneurea and/or polyurea segmented copolymer according to
29. The copolymer of
30. The copolymer of
31. The copolymer of
32. The copolymer of
33. The copolymer of
34. The method according to
35. The method according to
36. The method according to
37. The method according to
38. The method according to
39. The method according to
40. The method according to
Description The invention relates to isocyanate based copolymers and in particular to chain extenders for producing such materials. Polyurethanes, polyurethaneureas and polyureas (PUU) are elastomeric materials consisting of segment block copolymers composed of hard and soft segments. PUU can generally be formed by the reaction of a polyol, an isocyanate and a chain extender. The hard segment generally consists of the isocyanate and the chain extender and the soft segment is the polyol. In PUU generally, 1,4-butanediol is used as the chain extender. Other diol chain extenders include ethanediol, diethylene glycol, dipropylene glycol ethylene glycol, and 1,6-hexanediol. In addition diamines like ethylene diamine, propylene diamine, tetramethylene diamine and hexamethylene diamine and amino-alcohols like ethanolamine and hexanolamine can also be used in producing PUU. It is an object of the present invention to incorporate suitable amide, ester or amide-ester chain extenders in the PUU copolymers. The chain extenders of the present invention produce elastomers which have enhanced melt stability and enhanced hardness and improved elastic behavior. Also the low temperature flexibility is improved and the crystallization is fast which are advantages for processes using these materials as it allows for shortened process time. The present invention is to a chain extended polyurethane, polyurethaneurea and/or polyurea segmented copolymer wherein the polyurethane, polyurethaneurea or polyurea segment is attached via a urethane or urea linkage to a chain extender having an amide segment, an ester segment or a combination of amide and ester segments as represented by Formula I
The PUU copolymers of the present invention are preferably made from polyol soft segments, isocyanate (NCO) and a chain extender containing amide, ester or a combination of amide and ester linkages. The polyol soft segment and the isocyanete may be prereacted to form an isocyanate terminated prepolymer, which is then reacted with the extender. As compared to copolymers prepared from commonly used chain extenders, such as aliphatic diols and diamines, the copolymers of the present invention are found to be semi-crystalline materials that crystallize fast and have a high modulus. In addition the materials have a low Tg, a low-temperature flexibility (low Tflex), sharp Tflow (melting temperature, Tm), a virtually temperature independent modulus in the rubbery plateau regions in combination with excellent elastic properties (low compression set) and a good thermal stability. If the copolymer is a linear or a nearly linear polymer it is most often homogeneous in the molten state and upon cooling, crystallization is rapid. The copolymers of the present invention are further characterized by a well defined uniform soft segment and well defined uniform hard segment. These linear uniform copolymers are therefore homogeneous in a molten state and show clear phase separation upon cooling. These �linear� and uniform PUU are easily melt-processable and reprocessable by extrusion, injection molding, compression molding and fiber spinning. In a preferred synthesis route, the PUU copolymer is prepared by the reaction between a chain extender containing an NCO-reactive group and an NCO terminated prepolymer. Chain extenders containing such reactive groups can be represented by the formula
Generally at least 50 percent, and preferably at least 70 percent of the �R�B�(R′�B)n�R� segments are uniform in length as measured by 1H-NMR. In a preferred embodiment the segments are symmetrical, meaning that for n−1, each R is the same and for n=3, each R is the same and each R′ is the same. Preferred amide extender segments �R�B�(R′�B)n�R� are chosen from the group consisting of
Preferred ester extender segments �R�B�(R′�B)n-R� are chosen from the group consisting of
Amide extenders useful in the present invention are amide containing compounds which contain two isocyanate reactive groups, generally active-hydrogen groups, such as �OH, primary or secondary amines , �SH and �COOH. The chain extenders for use in the present invention can be prepared during the copolymerization process or prepared first before adding to the polymerization medium. For example, chain extenders containing a diamide can be formed by the reaction of a diacid with an amine, preferably a diamine. Dicarboxylic acids used are available commercially or can be prepared using known processes in the art. For example, to produce a dicarboxylic acid containing an aromatic ring, the ring can be alkylated via a Friedel-Crafts alkylation followed by oxidation of the alkyl side chains. Examples of commonly commercially available aromatic dicarboxylic acids include dicarboxylic acid isomers of benzene and napthalene. Examples of dicarboxylic acids based on alkyl groups include maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebatic acid and dodecandioc acid. In a preferred embodiment of the present invention, the chain extenders are formed by the reaction of one or more aromatic dicarboxylic acids with one or more alkyl diamines. By way of further example, a diamide chain extender (n=1) formed by the reaction of an aryl dicarboxylic acid (dimethyl terephthalate) with a diamine (1,6-diaminohexane) can be represented by the following as described in the literature (J. Krijgsman, D. Husken, R. J. Gaymans, Polymer, 44 (2003), 7043-7053) and WO Publications 91/13930 and 2003/070807:
This reaction can be carried out in the bulk or in solution at 50�-150� C. As the resulting diamine product (designated 6T6) crystallizes easily, it is preferably isolated by crystallization, which takes place in the reaction medium as soon as it is formed. On filtration the excess 1,6-diaminohexane is washed out. This diamine extender reacts during the polymerization with an isocyanate group to form a urea group. A tetra-amide extender (n=3) formed by reaction on an aryl dicarboxylic acid (dimethyl terephthalate) (T) with a diamine (1,6-diaminohexane) (6) can be represented by the following: 2 T-dimethyl+6−>T6T-dimethyl
The synthesis of compounds like T6T-dimethyl is described in GB Pat. 1,365,952, 1971 and P. J. M. Serrano, A. C. M. van Bennekom, R. J. Gaymans, Polymer, 39 (1998), 5773-5780). The synthesis of 6T6T6-diamine from T6T-dimethyl can best be carried out in solution. As the 6T6T6-diamine crystallizes easily it is preferably isolated by crystallization, which takes place in the reaction medium as soon as it is formed. On filtration the excess diamine is washed out. Ester extenders useful in the present invention are ester containing compounds which contain two isocyanate reactive groups, generally active-hydrogen groups, such as �OH, primary or secondary amines, �SH and �COOH. The chain extenders for use in the present invention can be prepared during the copolymerization process or prepared first before adding to the polymerization medium. For example, chain extenders containing a diester are formed by the reaction of a diacid with an alcohol, preferably a diol, via standard procedures in the art. Generally the starting materials are diacids like terephthalic acid or diacid ester like dimethyl terephthalate. The ester compounds can also be obtained by alcoholysis of polyesters. Examples of commercially available diols based on alkyl groups include ethylene glycol, propylene glycol, butane diol, pentane diol, hexanediol, heptane diol, octane diol, decane diol ans dodecane diol. Cornmercially available aromatic diols include hydroquinone and other benzene and naphthalene diols. Soft segments useful in the present invention are built from compounds which contain two or more isocyanate reactive groups, generally active-hydrogen groups, such as �OH, primary or secondary amines, �SH and �COOH. Representative of suitable segments are generally known and are described in such publications as High Polymers, Vol. XVI; �Polyurethanes, Chemistry and Technology�, by Saunders and Frisch, Interscience Publishers, New York, Vol. I, pp. 32-42, 44-54 (1962) and Vol II. Pp. 5-6, 198-199 (1964); Organic Polymer Chemistry by K. J. Saunders, Chapman and Hall, London, pp. 323-325 (1973); and Developments in Polyurethanes, Vol. I, J. M. Burst, ed., Applied Science Publishers, pp. 1-76 (1978). Representative of suitable segments include polyester, polylactone, polyether, polyolefin, polycarbonate polyols, and various other segments. Illustrative of the polyester polyols are the poly(alkylene alkanedioate) glycols that are prepared via a conventional esterification process using a molar excess of an aliphatic glycol with relation to an alkanedioic acid. Illustrative of the glycols that can be employed to prepare the polyesters are ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol and other butanediols, 1,5-pentanediol and other pentane diols, hexanediols, decanediols, and dodecanediols. Preferably the aliphatic glycol contains from 2 to 8 carbon atoms. Illustrative of the dioic acids that may be used to prepare the polyesters are maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, 2-methyl-1,6-hexanoic acid, pimelic acid, suberic acid, and dodecanedioic acids. Preferably the alkanedioic acids contain from 4 to 12 carbon atoms. Illustrative of the polyester polyols are poly(hexanediol adipate), poly(butylene glycol adipate), poly(ethylene glycol adipate), poly(diethylene glycol adipate), poly(hexanediol oxalate), and poly(ethylene glycol sebecate). Polylactone polyols useful in the practice of this invention are the di-or tri- or tetra-hydroxyl in nature. Such polyol are prepared by the reaction of a lactone monomer; illustrative of which is δ-valerolactone, ε-caprolactone, ε-methyl-ε-caprolactone, and ξ-enantholactone, is reacted with an initiator that has active hydrogen-containing groups; illustrative of which is ethylene glycol, diethylene glycol, propanediols, 1,4-butanediol, 1,6-hexanediol, and trimethylolpropane. The production of such polyols is known in the art; see, for example, U.S. Pat. Nos. 3,169,945, 3,248,417, 3,021,309 to 3,021,317. The preferred lactone polyols are the di-, tri-, and tetra-hydroxyl functional ε-caprolactone polyols known as polycaprolactone polyols. The polyether polyols include those obtained by the alkoxylation of suitable starting molecules with an alkylene oxide, such as ethylene, propylene, butylene oxide, or a mixture thereof. Examples of initiator molecules include water, ammonia, aniline or polyhydric alcohols such as dihyric alcohols having a molecular weight of 62-399, especially the alkane polyols such as ethylene glycol, propylene glycol, hexamethylene diol, glycerol, trimethylol propane or trimethylol ethane, or the low molecular weight alcohols containing ether groups such as diethylene glycol, triethylene glycol, dipropylene glyol or tripropylene glycol. Other commonly used initiators include pentaerythritol, xylitol, arabitol, sorbitol and mannitol. Preferably a poly(propylene oxide) polyols include poly(oxypropylene-oxyethylene) polyols is used. Preferably the oxyethylene content should comprise less than about 40 weight percent of the total and preferably less than about 25 weight percent of the total weight of the polyol. The ethylene oxide can be incorporated in any manner along the polymer chain, which stated another way means that the ethylene oxide can be incorporated either in internal blocks, as terminal blocks, may be randomly distributed along the polymer chain, or may be randomly distributed in a terminal oxyethylene-oxypropylene block. These polyols are conventional materials prepared by conventional methods. Other polyether polyols include the poly(tetramethylene oxide) polyols, also known as poly(oxytetramethylene) glycol, that are commercially available as diols. These polyols are prepared from the cationic ring-opening of tetrahydrofuran and termination with water as described in Dreyfuss, P. and M. P. Dreyfuss, Adv. Chem. Series, 91, 335 (1969). Polycarbonate containing hydroxy groups include those kown per se such as the products obtained from the reaction of diols such as propanediol-(1,3), butanediols-(1,4) and/or hexanediol-(1,6), diethylene glycol, triethylene glycol or tetraethylene glycol with diarylcarbonates, for example diphenylcarbonate or phosgene. Illustrative of the various other polyols suitable for use in this invention are the styrene/allyl alcohol copolymers; alkoxylated adducts of dimethylol dicyclopentadiene; vinyl chloride/vinyl acetate/vinyl alcohol copolymers; vinyl chloride/vinyl acetate/hydroxypropyl acrylate copolymers, copolymers of 2-hydroxyethylacrylate, ethyl acrylate, and/or butyl acrylate or 2-ethylhexyl acrylate; copolymers of hydroxypropyl acrylate, ethyl acrylate, and/or butyl acrylate or 2-ethylhexylacrylate. Generally for use in the present invention, the hydroxyl terminated polyol has a number average molecular weight of 200 to 10,000. Preferably the polyol has a molecular weight of from 300 to 7,500. More preferably the polyol has a number average molecular weight of from 400 to 5,000. Based on the initiator for producing the polyol, the polyol will have a functionality of from 1.5 to 8. Preferably the polyol has a functionality of 2 to 3 and more preferably a measured functionality of 1.9 to 2.5. Most preferred are polyols having a theoretical functionality of 2. Having a functionality of near 2 is important for obtaining high molecular weight and the linear character of the resulting PUU copolymer. Although not preferred, blends of polyols may be used especially for those polyols which have individually a theoretical functionality of 2. Preferably the polyol used with the chain extenders of the present invention have a polydispersity of less than 1.2, and more preferable 1.10 or less. The polydispersity of the polymer or polymer blend is defined as the ratio of Mw/Mn where Mw is the weight average molecular weight and Mn is the number average molecular weight. Preferably the unsaturation level of the polyol is below 0.020, more preferably below 0.015 and even more preferably below 0.010 meq unsaturation/gram of polyol. Also suitable as soft segments are flexible chain segments as mentioned above that are amine terminated and or acid terminated, like the Jeffamine� polyoxyalkyleneamines (Jeffamine is a trademark of Huntsman Chemicals). The isocyanates which can be used are polyfunctional isocyanates well known to those skilled in the art. Suitable polyisocyanates include aliphatic, cycloaliphatic and aromatic polyfunctional, particularly bifunctional, isocyanates. Examples of suitable aromatic isocyanates include the 4,4′-, 2,4′ and 2,2′-isomers of diphenylmethane diisocyante (MDI), blends thereof and polymeric and monomeric MDI blends toluene-2,4- and 2,6-diisocyanates (TDI), m- and p-phenylenediisocyanate, chlorophenylene-2,4-diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanate-3,3′-dimehtyldiphenyl, 3-methyldiphenyl-methane-4,4′-diisocyanate and diphenyletherdiisocyanate and 2,4,6-triisocyanatotoluene, 1,5-napthalene diisocyanate and 2,4,4′-triisocyanatodiphenylether. Aliphatic or cycloaliphatic polyisocyanates having between 2 and 18 carbon atoms, preferably between 4 and 12 carbon atoms can be used. Examples include ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, isophorone diisocyanate, cyclohexane 1,4-diisocyanate, cyclohexane 1,3-diisocyanate, 4,4′-dicyclohexyhmethane diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane; 2,4- and 2,6-hexahydrotoluene diisocyanate, 4,4′- and 2,4′-diisocyanatodicyclohexylmethane, saturated analogues of the above mentioned aromatic isocyanates. Mixtures of isocyanates may be used, such as the conm mercially available mixtures of 2,4- and 2,6-isomers of toluene diisocyanates. A crude polyisocyanate may also be used in the practice of this invention, such as crude toluene diisocyanate obtained by the phosgenation of a mixture of toluene diamine or the crude diphenylmethane diisocyanate obtained by the phosgenation of crude methylene diphenylamine. TDI/MDI blends may also be used. Mixtures of the various aliphatic, cycloaliphatic and/or aromatic isocyanates may also be used. In a preferred embodiment, the isocyanate is one or more isomers of TDI. The isocyanate-terminated prepolymer is generally prepared by the reaction of an excess of polyisocyanate with the polyol under standard conditions known in the art. The polyisocyanate is present at an excess to provide an NCO:OH ratio of greater than 2:1 to 20:1. Preferably the NCO:OH ratio is 2.5:1 to 10:1. Most preferably ratio is 3.2:1 to 8:1 The unreacted isocyanate monomer is removed from the prepolymer by distillation or other treatment to a concentration of less than 3 percent, preferably less than 1 percent, more preferably less than 0.5 percent, and yet more preferably less than 0.1 percent by weight of unreacted polyisocyanate in the prepolymer. The temperatures for affecting reaction between the polyisocyanate and polyol are generally up to 120� C. To facilitate the formation of the urethane bond between the isocyanate and polyol, a catalyst may be used. Such catalysts are known in the art and include tertiary amine compounds, amines with isocyanate reactive groups and organmetallic compounds. Alternatively the polyol can be added to the polyisocyanate at a controlled rate, as known in art, such as disclosed in WO 96/34904, to produce prepolymers having a low residual free isocyanate monomer. The prepolymer compositions generally contain from 0.1 to 20, more preferably 0.2 to 15 and more preferably from 0.3 to 10 and most preferably from 0.4 to 8 weight percent unreacted NCO. In some applications, it may be applicable to have from 1 up to 2 percent unreacted NCO, The amount of hard segment in the polymer can be varied in the range 3 to 60 wt percent, preferably 5 to 50 wt percent according the performance criteria required by the specific polymer application. The copolymers obtained differ in their properties according to the chemical composition selected and the content of the hard segment. Thus, it is possible to obtain soft, tacky compositions, thermoplastic and elastomeric products varying in hardness up to glasshard duroplasts. The hydrophilicity of the products may also vary within certain limits. The elastic products may be thermoplastically processed at elevated temperatures, for example at 100 to 280� C., providing they are not chemically crosslinked. The use of the chain extenders according to the invention results in products having an increased hard segment length and an increase in the hard segment density and as a result both the modulus and the elasticity increases. Also the modulus higher is less temperature dependant and low temperature flexibility improved. With the use of amide, esteramide or ester extenders the hard segment concentration and the segment length can be increased without having processing problems like too high melting temperatures. The PUU copolymers can be made by reacting in a �one-shot� process a polyol, an polyisocyanate, preferably a diisocyanate, and the chain-extender of Formula 1 where the equivalent ratio of NCO groups on the isocyanate to active hydrogen groups on the polyol plus the chain extender is between 1:0.7 and 1:1:3, preferably between 1:0.9 and 0.9:1 and the molar ratio of the chain extender to polyol is between 0.15:1 and 75:1. In another embodiment, the PUU copolymer is made by reaction an isocyanate-terminated prepolymer with a chain extender of Formula II, the isocyanate terminated prepolymer being the reaction product of a polyisocyanate and a polyol, where the equivalent ratio of NCO groups on the isocyanate to active hydrogen groups on the polyol plus the chain extender is between 1:0.7 and 1:1:3, preferably between 1:0.9 and 0.9:1 and the molar ratio of the chain extender to polyol is between 0.15:1 and 75:1. The PUU copolymers may be prepared in the bulk or in solution. A process that starts with a solvent, which solvent is stripped as the reaction progresses is a very controlled way to obtain high molecular weight polymers. A bulk process can be in the melt at elevated temperatures and as the reaction rates are high a reactive extrusion process seems very suitable for these materials. The mixing of the reactants can be carried out at ambient temperature and the resulting mixture is then heated to a temperature of the order 40� C. to 130� C., preferably to a temperature of 90� C. to 120� C. Alternatively, one or more of the reactants is preheated to a temperature within the above ranges before the admixing is carried out. For producing elastomers, the isocyanate index, defined as the number of equivalents of NCO groups in the prepolymer divided by the total number of isocyanate reactive hydrogen atom equivalents in the extender multiplied by 100, ranges from 75 to 140, and preferably from 85 to 120. The PUU copolymers may optionally contain UV stabilizers, auxiliary substances and additives. Examples include lubricants, such as fatty acid esters and the metal soaps thereof, fatty acid amides and silicone compounds, antiblocking agents, inhibitors, stabilizers to protect against heat and discoloration, flame retardant, dyes, pigments, inorganic and organic filers and reinforcing agents or plasticizers and foaming agents. Plasticizers include esters of polybasic carboxylic acids with monohydric alcohols. Polymeric plasticizers, such as polyesters of adipic acid, sebacid acid or phthalic acid can also be used. Petroleum-based hydrocarbon distillates, phenol alkylsufonates and phenyl paraffin sulfonates are other examples of plasticizers. The copolymers of the present invention may be used to produce fibers, adhesives, moldings, in particular to produce extrudates, for example films, and injection molded articles. Moreover, the copolymers may be used as sinterable powder for producing moldings in the form of sheets and hollow articles. Futhermore, elastomers are used in a variety of applications including formation of shaped articles subjected to severe mechanical stresses, such as tires, rollers and cone belts, wheels for industrial or for recreational goods, elastomers for footwear applications and tooling compounds. The copolymers are also suitable for closed cell and open cell foamed products like mattresses, cushions, car seats. These cellular products might be obtained by during polymerization or after polymerization by extrusion foaming. The following examples are provided to illustrate the present invention. The examples are not intended to limit the scope of the present invention and should not be so interpreted. All percentages are by weight unless otherwise noted. Prepolymers PP1 is a TDI terminated prepolymer based on a diol having a molecular weight of approximately 1010, obtained from The Dow Chemical Company as VORASTAR� B1505. The TDI used is a mixture of 2,4- and 2,6-TDI. PP2 is a TDI terminated prepolymer based on a diol having a molecular weight of 2000, obtained from Aldrich and the TDI is 2,4-TDI PP3 is a TDI terminated prepolymer based on the diol ACCLAIM� 4220N polyol obtained from Bayer AG. ACCLAIM is a trademark of Bayer. The prepolymer is prepared by adding 5.26 g (0.030 moles) of 2,4-TDI to a 250 ml stainless steel reactor and the reactor temperature is brought 40� C. The polyol, (57.97 g, 0.015 moles) is added dropwise while stirring to ensure an excess of TDI at all times. After addition, the reaction is continued for four hours. PP4 is a TDI terminated prepolymer based on a poly(tetramethylene oxide) with diol-endgroups having a molecular weight of approximately 1500, obtained from Crompton Corp., LF-900A. PP5 is a MDI terminated prepolymer based on a poly(tetramethylene oxide) with diol-endgroups having a molecular weight of approximately 2000, obtained from Crompton Corp., LFM300. PP6 is a (hexamethylenediisocyanate) HDI terminated prepolymer based on a poly(tetramethylene oxide) with diol-endgroups having a molecular weight of approximately 1500-2000, obtained from Crompton Corp., LFH520/580. PP7 is a (hexamethylenediisocyanate) HDI terminated prepolymer based on a poly(tetramethylene oxide) with diol end groups having a molecular weight of approximately 1000-1500, obtained from Crompton Corp. For the nomenclature of the hard segment in the Examples, R′ of Formulas I and II is designated A for an adipatic group and T for a terephthalic group. The number is the number of carbon atoms in the R group in Formulas I and II. Synthesis of 6T6-Diamine Chain Extender A chain extender designated 6T6-diamine is prepared by the reaction of 1,6-diaminohexane and dimethyl terephthalate. In a 1-liter round bottom flask, fitted with a reflux condenser, nitrogen inlet and thermocouple, is added 278.1 g (2.39 moles) of 1,6-diaminohexane and 46.5 g (0.24 moles) of dimethyl terephthalate. The reaction is allowed to proceed for 8 hours at 80� C. The formed white solid is washed in 2 liters of hot toluene (80� C.) and filtered (glass filter, pore size 3). The wash procedure is repeated two times. Recrystallization of the product, designated 6T6-diamine was recrystallized in butyl acetate (20 g/1.5 liters) and found to have a molecular weight of 362.52 gmol−1. The final product is dried in vacuo before use. The product yield is 15.04 g, the melting is temperature 178� C. and the heat of fusion 130 J/g. The NMR spectrum of this compound is given in The uniformity of the 6T6 product is determined by 1H-NMR from the methylene protons at the amide side at 3.69 ppm and methylene protons at amine side at 3.31 ppm. The ratio (R) [methylene amide side at 3.69 /methylene amine side at 3.31] (R3.69/3.3 1) is 1.0 for 6T6 and 2.0 for 6T6T6. The uniformity is approximated by [2-(R3.69/3.31)�100 percent]. Synthesis of 6T6T6-Diamine Chain Extender A chain extender designated 6T6T6-diamine is prepared from diphenyl terephthalate (DPT) and 1,6-diaminohexane. The DPT is prepared by adding 180 g terephthaloyl dichloride (0.9 moles) to 171.51 g (1.82 moles) of molten phenol (65� C.) The mixture is then heated to 95� C. and the reaction is allowed to proceed for one hour. The mixture forms a white solid. Subsequently the mixture is washed with deionized water and then with hot ethanol (70� C.). The product is dried and is found to have a molecular weight of 193.2 and calculated to be 95 percent pure based on 1H-NMR analysis. The product is dried in vacuo prior to use. The DPT (96.25 g, 0.30 moles) is dissolved in 250 ml of m-xylene and 25 ml of dimethyl formamide at 120� C. over a period of 30 minutes. Subsequently, 1,6-diaminohexane (6.0 g, 0.05 moles) dissolved in 50 ml of m-xylene is added to the DPT-solution. The components are allowed to react overnight at 120� C. The formed solid white precipitated, is designated T6T-diphenyl (MW 564.64 gmol-1) and is washed in m-xylene at 120� C. The second step of synthesis consisted of a reaction between T6T-diphenyl and 1,6-diaminohexante. T6T-diphenyl (22.57 g, 0.04 moles) and 1,6-diaminohexane (93.0 g, 0.80 moles) are weighed in a reactor as described in Example 1. To this mixtures is added 350 ml of N-methyl-2-pyrrolidinone (NMP). The temperature of the reaction is increased to 140� C. to dissolve the T6T-diphenyl, after which the reaction was carried out at 120� C. overnight. A white product designated 6T6T6-diamine is formed, having a M.W. of 608.83 gmol−1. The material is washed in chloroform at 50� C. . The NMR spectrum of this compound is given in Synthesis of Diamine-diamides: 3A3, 4A4, 6A6, 12A12 Chain Extenders A chain extender designated 3A3-diamine-diamide, 4A4-diamine-diamide, 6A6-diamine-diamide and 12A12-diamine-diamide are prepared by the reaction of 1,3-propandiamine, 1,4-butanediamine, 1,6-hexanediamine or 1,12-dodecanediamine respectively with dimethyl adipate. The synthesis of the 6A6-diamine segment is carried out as follows. To a round bottom flask with flat flange, a reflux condenser with a calcium chloride tube, magnetic stirrer, nitrogen inlet and thermocouple is added 500 gram 1,6-diaminohexane (4,30 mol) and 54 gram dimethyl adipate (0,3 mol). As catalyst 3 ml 0,5 M Natrium methanolate oxide is added (0,5 mol percent). The reaction is carried out at 75� C. for 6 hours. The extender was washed with diethylether to remove the excess of diamine. Recrystallisation is necessary in order to purify the extenders and this is done according to;
The other extenders were synthesized as per the procedure for the 6A6 prepolymer. All the products are dried in vacuo before use. The yield, melting temperature and heat fusion for the 4A4 dinaine diaminde and 6A6 diamine-diamide are given in the following table.
A chain extender designated 3T3-diol-diamine is prepared by reaction of 3-aminopropanol with dimethyl terephthalate. In a 500 ml round bottom flask with flat flange, a reflux condenser with a calcium chloride tube, magnetic stirrer, nitrogen inlet and thermocouple, is added 100 g (1,3 mol) 3-aminopropanol and 22 g dimethyl terephthalate (0,11 mol). The reaction is allowed to proceed for 16 hours at 120� C. After cooling the reaction product is precipitated in chloroform and filtered. The product was washed several times with diethylether. 3A3-diol-diamide was made in a similar way. Synthesis of Diol-diester 3T3, 4T4, 6T6 Chain Extenders Chain extenders designated 3T3-diol-diester, 4T4-diol-diester or 6T6-diol-diester are prepared by the reaction of a 1,3-propandiol, 1,4-butanediol or 1,6 hexanediol respectively with dimethyl terephthalate. For the synthesis of the 6T6-diol-diester hard, to a 1-liter round bottom flask with flat flange, a reflux condenser with a calcium chloride tube, magnetic stirrer, nitrogen inlet and thermocouple, is added 236 g (2,0 mol) 1,6-hexanediol and 39 g dimethyl terephthalate (0,2 mol). As catalyst titanium tetrabutoxide (0,08 g) is added. The reaction is allowed to proceed for 5 hours at 175� C. The 4T4- and 6T6 diol-diesters were prepared in a similar manner. The diol diesester extenders are recrystallized in water. Chain Extension of Prepnolymers Reaction with 6T6-diamine: To a 250 ml stainless steel reactor, which is constantly flushed with nitrogen, is added 23.23 grams of 2,4-TDI terminated PP2, after which is added 3.66 g of 6T6-diamine. This is followed by the addition of Irganox 1330 (antioxidant obtained from Ciba Specialty Chemicals) at a level of 1 percent wt of the prepolymer and 80 ml of anhydrous N,N-dimethylacetamide. The reaction is carried out at 120� C. for 5 hours with mixing. Upon completion, the solvent is stripped in vacuo (pressure <0.4 mbar) at 120� C. After cooling the tough transparent polymer is granulated. The above procedure is used for chain extension with other chain extenders, with adjustment of the amount of chain extender and/or prepolymer to added to maintain approximately a 1:1 molar ratio of NCO groups of the prepolymer to NCO reactive groups on the chain extender. Sample Preparation Injection Moulding Polymers with flow temperatures in the appropriate range (up to 190� C.) are injection moulded using a small-scale (10-30 g.) manually operated injection moulding machine (Arburg H). The obtained samples (70�9�2 mm) are used for Dynamical Mechanical Analysis (DMA) and compression set experiments. Compression Moulding Segmented polyurethanes that did not flow below 200� C. are processed through compression moulding. Approximately 2.5 g. of polymer is cut into small pieces and dried overnight. The material is spread uniformly into a bar-shaped mould (8�1.8�0.2 cm), which is placed between two preheated metal press plates. Prior to pressing, air is removed from the polymer in the mould by dumping (that is quickly pressurising the sample, followed by depressurising). This procedure is repeated four times. A Lauffer 40 press is used to press the samples at 10 Mp (�8.5 MPa) at 20� C. This temperature is maintained for 3 minutes, after which time the sample is left to cool under pressure. The resulting test bars are cut from the mould and used for characterization purposes. Property Measurements Viscometry Viscosity determinations are carried out with a capillary Ubbelohde (type 0C) at 25� C., using a polymer solution with a concentration of 0.1 g/dl in dimethyl acetamide (DMAc). Compression Set Samples for the compression determinations are cut from injection moulded bars and. dried before use. A compression of 25 percent is applied for 24 hours by placing the samples between two metal plates at room temperature (ASTM 395 B standard). Half an hour after the load is released, sample thickness is determined. The compression set is determined as:
Torsion behavior of polymer samples, prepared by means of injection moulding and dried before use, are studied at a frequency of 1 Hz. A Myrenne ATM3 torsion pendulum is used, at 0,1 percent strain and a heating rate of 1� C. / min. Storage modulus G′ and loss modulus G″ are measured as a function of temperature, starting at −100� C. The glass transition temperature (Tg) are determined as the maximum of the loss modulus curve. The flow temperature (Tfl) of the sample are defined as the temperature at which the storage modulus reached a value of 1 MPa (or 0.5 MPa for soft materials). The shear modulus of a polymer sample was determined as the value for the storage modulus at 25� C. In addition, this measurement provides information concerning the temperature range within which the polymer is applicable. The rubber plateau should be temperature independent (that is horizontal), which means that the modulus of the elastomer remains constant. The temperature at which the rubber plateau begins is referred to as the flex temperature Tflex. Melt Viscosity The melt viscosity of polymer samples is determined in time at constant melt temperature and piston speed, using a capillary flow rheometer. The rheometer determines the force necessary to push the polymer melt through a capillary. From this force, the melt viscosity can be calculated using the following equation.
Examples 1-3 are PUU copolymers based on 2,4-TDI-propolymers containing a 2000 MW diol (PP2). The properties of the elastomers are given in Table 1.
Table 1 shows that with increasing extender length, the Tg and Tflex temperatures decrease, meaning a better low temperature flexibility for the amide extended polymers. Also with increasing extender length the modulus (G′) increases to values much higher than those obtainable with hard segments known in the art, such as hexane diamine (ex. 1 C) and surprisingly at the same time the compression set values decreased. The flow temperature (Tflow) increased strongly too. DMA experiments are carried out on polymers derived from PP1. The results also show that by extending the hard segment length, the rubbery plateau becomes much more temperature independent and Tfl (w increases with 60-70� C. The results given in Table 1 and The melt stability of Polymer 2 (Example 2) was studied by measuring the melt viscosity as function of time at 200� C. and a shear rate of 57.5s−1 ( The effect of hard segment concentration at increasing soft segment length is displayed by the results given in Table 2.
Table 2 shows the influence of extender segment length at different soft segment length. Increasing the extender segment length increases the modulus strongly with a decreases of the Tg and a decreasing compression set. At the same time the flow temperatures increase. Example 7-9 are PUU copolymers based on the prepolymers PP4, PP5 and PP6 ended with the 6A6-diamine-diamide. The properties of the resulting products are given able 3.
Table 3. shows the influence of diisocyanate on the mechanical and thermal prperties. The polymers based on HDI-diisocyanate were found to have a higher G′ moldulus. Examples 10-18 are PUU copolymers based on the prepolymers PP7 and different nders. Examplel 9C is a control based on 1,3-propanediol. The properties of the resulting polyurethaneureas are given in Table 4.
Table 4 shows the influence of the type of extender on mechanical and thermal properties. For the diamine-diamide extender the highest moduli could be obtained with even number of methylene units. For the diol-diamide and diol-diester the odd number of methylene units in the amino alcohol and diol give the highest moduli. These moduli are also higher than the comparative sample 19 with 1,3-propanediol. Another observed effect is the extenders with a terephthalic group (T) have higher moduli and Tflows compared to an adipic acid group (A). Other embodiments of the invention will be apparent to those skilled in the art from a consideration of this specification or practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with the true scope and spirit of the invention being indicated by the following claims. Classifications
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Results for "back to the future"
This is a fake video from HUVrTech featuring Christopher Lloyd (Doc Brown), Tony Hawk and a handful of other celebrities (including Terrell Owens and Moby) lying about riding a real hoverboard. The CG is decent, but the whole thing is impossible to believe. Plus they made the... / Continue →
According to a Nike designer, back to the future style powerlaces are coming out next year, THE SAME YEAR MARTY HAS THEM IN THE MOVIE. Just don't get your hopes up for a hoverboard because that shit ain't happening. ...as Sole Collector tells it, designer Tinker Hatfield show... / Continue →
This is a t-shirt printed with Marty McFly's iconic look from Back to the Future (available on Amazon for ~$30). Which, for the record, is a maroon t-shirt, blue plaid button-up, bi-color jean jacket, and red vest. Marty was into LAYERING. Me? I'm into wearing as little as ... / Continue →
A live action musical of Back to the Future is coming to London's West End next year, with a possible Broadway run if it proves successful enough. AND HOW COULD IT NOT? You think there's going to have a real DeLorean on stage or just a cardboard cutout? The film's original... / Continue →
After receiving the requisite number of votes on the CUUSO website, being green-lit by the company, and acquiring the licensing rights, LEGO has unveiled their official Back to the Future time traveling DeLorean playset. And this is it. The limited edition drops August 1st fo... / Continue →
This is a $30 iPad case available at Firebox that looks like the Grays Sports Almanac from Back To The Future II. It also looks like a great way to get your iPad stolen for the case alone. I don't even own an iPad and I want that case. I'm not sure what I'd put in it though ... / Continue →
This is the old west time-traveling train from Back to the Future III recreated in LEGO by Back to the Future and LEGO fan Masashi. It's an electric set and works on LEGO train tracks, but is currently only a LEGO Cuuso project and will undoubtedly be denied manufacture by LEG... / Continue →
Stop everything and empty your bank account, because Griff's 'Pit Bull' hoverboard used in Back to the Future II is for sale on eBay. And it's only $13,000 -- for a fully functioning hoverboard! "GW? I don't think it actually hovers." WHAT? For $13,000 it damn well better h... / Continue →
A Back to the Future DeLorean LEGO set that started on the LEGO Cuusoo website is becoming a reality after reaching the mandatory 10,000 votes and getting the green light from LEGO (after securing the licensing rights). The set will be available mid 2013 and come with enough b... / Continue →
This is a conceptual time traveling DeLorean taxi. It's not real though (context clue: conceptual), it's just a marketing piece made by Mike Lubrano for Nooka, a "New York based fashion brand with a futuristic philosophy." What exactly IS their futuristic philosophy? Sadly, ... / Continue →


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David Blaine's got nothing on Tim Connolly.
Like a street magician, Connolly knifed his way through the heart of the Philadelphia defense in the opening period of Sunday's fifth game of the Eastern Conference Quarterfinal.
The Sabres center zigged, and Flyers forward Sami Kapanen zagged.
Then, after pulling the puck around like he was teasing a cat, Connolly smoothly deposited it in the top right corner, just over the glove of Philly goalie Robert Esche.
It was all the scoring the Sabres would need in a 3-0 victory that put Buffalo back ahead in the series.
As if the dramatic goal wasn't enough, Connolly started a play at the end of the second period, earning the second assist on J.P. Dumont's power-play tally.
It's almost enough to make you say things you never thought you'd say — like could he some day be captain Tim Connolly? Sure Chris Drury wears the C, but Connolly has made a compelling case as the heart and soul of the Sabres, a guy who seems to score big goals and even scares the opposition with his uncanny playmaking abilities.
Connolly knew why the Flyers laid off of him, but he made the right adjustments.
"I was looking to pass it to one side or the other and I think they knew that," he said. "I think a lot of teams know that when I get over the blue line I'm looking to pass the puck. And I am."
The Flyers have a superstar in Peter Forsberg, someone who breaks open tight games and scores even though teams are plotting to stop him.
Connolly, who's only trailing Forsberg in playoff scoring by a single point, is doing the same.
Not bad for a guy many assumed wouldn't make it back onto the Sabres roster with a salary that eclipses $1million.
"He was off the radar," Lindy Ruff said. "I didn't even expect it coming through training camp. But what I saw in training camp was passion and desperation. It had nothing to do with his offensive skills. It was a determination to put his body on the line."
While Connolly isn't the only guy putting his neck on the line at crunch time, he's becoming the face of the team's offense. And even though that face was slammed by an errant puck off the stick of Paul Gaustad in the team's warmup on Sunday, it wasn't enough to keep him from the lineup.
Again, odd — nobody who follows the Sabres figured the phrase "tough as nails" and Tim Connolly would ever be written together.
"I was hard on him at times," Ruff said. "But he made an exhibition to block shots, to finish, to become a decent defensive player. We figured he'd made a commitment in the off-season to get stronger and quicker. He matured. I don't think I can take any credit.
"He decided to become the player everyone thought he'd be."
Contact group sports editor Tim Schmitt at (716) 282-2311, Ext. 2266.
May 1, 2006
SABRES: Tim Connolly is giving captain-like performance
Sabres head back to Philly with 3-2 series edge.
- Sports
- Bisons win on late rally in Florida
- Bills re-sign starting TE Chandler
- NU hockey readies for Air Force series
- Niagara's Mason named to NABC All-Stars
- N-W's Klettke honored with Elia Scholarship
- Blue Jays option Storey, LaRoche to Buffalo
- UB's McCrea named MAC Player of the Year University at Buffalo senior Javon McCrea was named the 2013-14 Mid-American Conference men's basketball Player of the Year on Wednesday, earning 20 of the 25 first-place votes.
- Buono, Kwiatkowski take first in Niagara Cup events
- Junior Sabres release 2nd round schedule
- Starpoint sends nearly a dozen to swimming sectionals
- More Sports Headlines


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If you're on my LJ, that probably means you've read my novel The Other Guy or at least have heard of it, and I hope you a) have thoroughly enjoyed it, or b) are about to thoroughly enjoy it. (There is no alternative to thorough enjoyment; I'm sorry.)
( About the novelCollapse )
( Where to buyCollapse )
I'm not really sure what I'm going to be doing with this journal yet, but it's here, and you're here, and that makes me happy. :) Feel free to hang around, say hi, ask questions, etc., and I'll do my best to be outrageously interesting.
There's a passage in Notes about W.J.C. Scott-Bentinck, an eccentric recluse who has since become my role model. He communicated with his servants entirely by written notes, had food delivered to his room using a miniature railway system, and, if a servant saw him by accident, froze like a statue until they passed. After his death, his heirs found a room stuffed to the gills with "hundreds of green boxes, each of which contained a single dark brown wig." He sounds amazing, and I want to be him when I grow up. Failing that, the Simpsons version of Thomas Pynchon.
In other news, I hope you're all having a brilliant holiday season! If that is not your thing, I hope you are enjoying a regular week of the month! Whatever you're celebrating or not, I wish you all light and love and no end of good books to keep you company. ♥
Some of you have added me on Google+ or LinkedIn or other things. I appreciate it so much when you guys take the time to reach out to me, and if I haven't responded to these adds, it's not because I'm snubbing you or anything; it's simply because I don't use those tools. I'm only currently active on Livejournal, Goodreads and Twitter. Of course, with my spotty updating record, you are well within your rights to laugh at my use of the word 'active'. (I'm also namesquatting on Tumblr, with ambiguous plans to do something with it if I ever get this next book off the ground.)
In other news, if you were one of the poor, unfortunate souls, as I was, who missed the Neverwhere radio play during its original airing on BBC Radio 4, YouTube has come to the rescue: Episode 1. Take an already brilliant story and add James McAvoy, Natalie Dormer and Benedict Cumberbatch? YES PLEASE.
Today was Seattle's Pride Parade. It was a hot, hot day and I managed to get a nice farmer's tan standing out there for about twenty minutes. Unfortunately, twenty minutes was about all I got to see of the parade, as I had other places to be (I think next year I should make it a point to actually attend rather than seeing a fraction of it by happenstance). Even so, being a part of it for that tiny portion was a pleasure; such a lovely, celebratory mood permeating the whole of downtown. Just beautiful.
- Eisenberg's McSweeney's column Bream Gives Me Hiccups: Restaurant Reviews From a Privileged Nine-Year-Old is pretty much exactly what it says on the tin, and yet so much more. Simultaneously amusing, honest and heartbreaking. Seriously, I teared up reading the most recent one. (Caveat: I also tear up sometimes at Hallmark card commercials, so use that as your gauge for how emotionally unstable I am.)
- You've probably seen Ryan Gosling Won't Eat His Cereal, but just in case this managed to give your attention the slip, here is, um, Ryan Gosling refusing to eat his cereal. I can't explain why it's so funny. It just is, okay?
- I tweeted about this some time back, but it's still pretty much my favorite thing ever: Epic 23-Year Game of Tag. Totally insane and so inspired.
- As mentioned in a previous post, Good Omens by Neil Gaiman and Terry Pratchett is only the best book ever on the face of the earth. (You think I suffer from hyperbole, but I do love that book something fierce.) Here, a comprehensive reference guide to Good Omens. Most excellent.
- Joss Whedon was the commencement speaker at his alma mater Wesleyan this year. His speech is, quite simply, beautiful. Let's all aspire to be like him when we grow up, yes?
- And we finish off with more Eisenberg. He's also a regular contributer to The New Yorker; recently he did a short script entitled Marv Albert is My Therapist. And then they got him and Marv Albert to perform it, to a nation's delight.
TIME), education and prevention is key. It's never too early to start, as with this video-book aimed at the littluns:
And the next time you see a loved one making their inner hair cells sad, perhaps some gentle accosting wouldn't go amiss. They'll thank you for it later. (Probably. I mean, I totally would.)
If I had a quarter for every time I could quite clearly hear someone's music even though their earbuds were jammed into their earholes, I'd never have to scrounge for laundry money ever again. Ever! And while having unlimited laundry funds would be awesome for me, irreversible hearing loss is awesome for nobody. With the risk of hearing loss increasing in recent years, especially in younger populations (And the next time you see a loved one making their inner hair cells sad, perhaps some gentle accosting wouldn't go amiss. They'll thank you for it later. (Probably. I mean, I totally would.)
A conversation between Julie Bozza, author of The Apothecary's Garden, and Cary Attwell, author of The Other Guy. We hope you enjoy reading it as much as we enjoyed conversing!
Having zero brain power at the end of the day means most of my bedtime reading is limited to large-print, children's books. Not that I say this in a particularly plaintive way, because children's books are awesome. I've been dipping into my well-loved, aged collection of Enid Blytons recently, which are not only greatly imaginative but also come with the delightful memory of my older sister reading from The Banana Robber to me.
There's just something so comforting about going back to books from childhood, for the same reasons so many of us have a favorite fuzzy old sweater or a tatty stuffed animal that Goodwill probably won't even accept. (Not that I would ever give my Cheer Bear away.) It's a reminder that there's a place where life can be simple for a little while, where fairies exist, happy endings are guaranteed, tears always dry up, and everyone gets what they deserve.
What are some of your favorite things to fall back on when you need time away from the nonsense life throws at you?
1. Where the popcorn comes into play is that the properties of its questionable flavoring in some of the microwaveable varieties may actually have a hand in causing dementia. -- Chapter One
Afraid some enthusiastic microwaveable popcorn lobbyist might read my book and accuse me of besmirching popcorn's good name, I did consider taking this part out -- or at least sprinkling the word allegedly throughout the sentence with a liberal hand, but I really like little bits of throwaway trivia. And at the time of writing, I had just learned about it so I was itching to share (and ruin everyone's quintessential film-watching experiences, naturally. You're welcome.)
To be fair, eating butter-flavored popcorn probably isn't going to give you dementia. The study referenced regards food industry workers' chronic exposure to the flavoring ingredient, diacetyl, during the manufacturing process. Researchers found that the ingredient increased the risk of toxic damage to brain cells similar to the way proteins clump together in Alzheimer's disease. Which is still not to say that diacetyl definitely does link to dementia, but that it's a possibility.
Source: Science Daily
2. "Maybe," I said smoothly. "But Aristotle once said that people with curly hair can't be trusted, so..." -- Chapter Two
I first heard about this on QI, a wonderfully funny and informative British comedy panel quiz show, on their Fingers and Fumbs episode (S6E7). Apparently Aristotle was super into physiognomy, which reads a person's character or personality from facial features. He wrote a whole book on it, The Secrets of Nature Relating to Physiognomy, in which pretty much every facial feature signifies something horrible. Of the curly-haired: "He is by nature proud and bold, dull of apprehension, soon angry, and a lover of venery, and given to lying, malicious and ready to do any mischief."
So my characterization of Emory? Nailed it.
Source: Project Gutenberg
3. "Hi, Mithter J," said Abby, smiling the untroubled smile of five-year-olds everywhere. -- Chapter Five
This one isn't really a wild claim by either Emory or Nate; I just wanted to talk about it. Abby has a frontal lisp here, doing a 'th' for an 's'. Though this has no relevant impact on the storyline at all, in my mind she actually has a lateral lisp. However, dialogue with a lateral lisp is very difficult to spell. I'll let this lovely little girl from Horrible Histories demonstrate what that sounds like*:
Incidentally, Horrible Histories is a brilliant, award-winning historical sketch show for children, and everyone should watch it.
The difference between frontal and lateral lisps, other than, obviously, tongue placement, is that the former is a typical developmental error that could potentially resolve on its own with maturity, while the latter is not a typical developmental error and almost always requires speech therapy, regardless of age.
Source: My school learnin's. (If you really want, I'm sure I can scare up some actual references for you.)
*=Not a diagnosis; that's just what it sounds like to me.
4. "No one can resist the face of a Lhasa Apso; it's been scientifically proven." -- Nate, Chapter Seven
Okay, this one Nate pulled right out of his shapely bum. But I mean, come on. Have you seen a Lhasa Apso? They're adorable.
Porn and kissing scenes. They fill me with dread. Don't get me wrong -- porn is great; who doesn't like a nice little rough-and-tumble scene every now and then? I'm perpetually in awe of writers who can do it easily and do it well because I am very, very much not in those ranks. As it is, I'm already an excruciatingly slow writer; I agonize over every sentence and reread and edit as I go (I hear this is one of the mortal sins in novel writing; oops) and when it gets to body parts touching other body parts, it's about ten times worse. I find it one of the most difficult things to write, in the history of ever.
What if it comes out like an instruction manual for a shelf? Insert screw A into slot B. Gross.
But Cary, you say, you didn't even write porn in The Other Guy. What the crap are you whining about? Yes, true, I weaseled out of that one; I didn't think the story absolutely needed it. (Also, does it weird anyone else out to read sexytimes in the first person?)
I'm writing porn now, though, in my next story. After all the above whinging, I'm writing it, and the reason for that is simple: because my characters want to do it. When they come knocking on my brain and tell me stuff like that, I have to give in. Not without some kicking and screaming on my end, but when it comes right down to it, the characters always win. And they should; it's their story, after all.
A couple years ago, my BFF M and I co-wrote a story. It was to be a real epic. You know: Romance! Betrayal! Swordfights! Sex! (I made her write all the sex scenes.) We planned it meticulously over hours of phone calls and capslock emails, chapter to chapter, scene by scene, outlines bleeding from our eyes. As we got going, though, one of the peripheral characters started poking his head in and messing things up a bit. He was barely even a peripheral character to begin with; we knew he existed as part of the landscape and we weren't going to give him any lines.
"Go away," we said. "Go and guard that door or something. We have important things to do."
So he went and stood guard. Then he started talking to the girl on the other side of the door. And worse, she started talking back.
"Stop it, this isn't part of the plan," we said, though we eyed them with great curiosity. How interesting.
By the end of the story, he was the second lead in a romance never intended to happen. It didn't capsize our original plot, the bones of it were still very much there. Would it still have been a decent story if we didn't let him elbow his way in? Sure. M is a fab storyteller and the process of writing with her was in itself a joy. Would we still be as proud of it if we'd stuck, point by point, to our outline? Doubt it.
Characters fight back. Try to shove them in a direction they don't want to go, and it ruins everyone's day. I learned it writing that story with my BFF, and I'm learning it still. Sometimes I try to push through with my authorial power. "La la la not listening," I say, and then I end up having to axe entire scenes because I didn't listen. The other day, one of them yelled at me, "But it doesn't make any fiscal sense!" Yes, thank you, nerd. Scene scrapped.
Speaking of wielding authorial power, I'm currently wading around in that wasteland known as Writer's Block (0 out of 5 stars; not recommended) because I had an idea to make my characters go and have a nice hometown visit with their family. It would be all kinds of sweet and homey. Turns out, they don't want to. Why, I don't know; I still think it's a fantastic idea, so we're stalemating. I'm willing to wait this one out. Sometimes you just have to put your foot down.
I think we all know who's going to win in the end. (Hint: it's not me. Ugh.)


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Awards Ceremonies
An interesting article, but a couple of important bones to pick.
First, to associate money and corruption itself smacks of colonialism. Traditions must generate and distribute financial resources to move through time. The Buddhist tradition in India, for example, only appears in the archaeological record when it begins to amass significant resources. Second, I think the size of the *yoga market* means that there is something much more going on than recurrent faddism. The people who move and shake the yoga movement are serious, committed, and hardly exotic in the way the elite yoga from the last century may have seemed to some.
And one more question, perhaps the key one – what would yoga look like if it had NOT *sold out*? The counterculture? The New Age? or were these sell-outs as well?
Did you "sell out" when you wrote a book about yoga? At the core of sincere yoga styles is the ability to keep your heart open in an often intellectually driven society. Sure, it has it's human qualities and many interpretations but consider focusing on the good as well and offering a more balanced perspective. Paramahansa's influence has uplifted and brought much comfort as well as connected practitioners to their own spirit and vitality. The bottom line- that is not selling out.
It seems that yoga has gotten so big that it is hard to tell whether someone is selling out or not. I think you need to realize that even charging for classes is a form of selling out. It is an ancient tradition that should be shared with everyone not just the small few that can afford it. That said, maybe it is necessary for people to make some money for them to continue to do what they are doing. In other words it is better that they charge for yoga if the other option is for them not to spread the yoga goodness at all.
The question that needs to be asked is if the person "selling-out" is really doing it for money that is necessary, or if they are doing it for other reasons. But who are we to say? It feels good to assume that they are being unethical because it "seems" wrong. 7-up surely seems to be deserving of a "sell-out" classification. And it feels good to take up arms to preserve the purity of something we hold so strongly in our hearts. But there are surely people who are pure of heart and a book is another venue to share ideas…
and surely there are people who are turning yoga into a commodity on a small and grand scale and this I do not support. But in order to be shared with more people there are going to be sacrifices along the way. Should we take up arms about this? or reserve the judgment for the people we really know? I think if we hold yoga in our hearts we shouldn't judge the things we do not know so quickly. Is there a danger in letting people "sell out"?
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A number of black students at Harvard University have taken part in a project called "I, Too, Am Harvard" seeking to share experiences in academia and in life that have left them feeling misunderstood, ignored and often insulted. At the center of the campaign is a series of photographs of students, many displaying written messages ranging from quotes of civil rights leaders to personal thoughts. Most eye-catching and perhaps cringe-worthy among the messages are those recalling comments students say were directed at them, including "I don't even think of you as black," and "Can you read?"View Slideshow


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What's Next For SEO?
I spent a good chunk of this past weekend thinking about SEO, and specifically the data that SEOs rely on to quantify success and identify next steps in the optimization continuum. Fueling my curiosity (this time) was an article by Vanessa Fox that appeared in Search Engine Land on Friday, "Will [Not Provided] Ever Reach 100% In Web Analytics?"
Fox's piece noted the recent decision by Google to make secure search the default on its Chrome browser, thereby preventing the flow of organic keyword data through to analytics tools as part of the referral information. Add Chrome to the growing number of avenues that have become shut off to SEOs looking to optimize site experiences based on the keywords used by inbound visitors (Chrome now joins Firefox and authenticated Google users).
It was even discovered recently that Google is looking to hire marketing managers who would be tasked with encouraging users to "search on Google, search more often, and search while signed-in."
This trend is especially worrisome when considering other recent news. This past November, Google began to crack down on SEO analytics tools that provided scraped data to users (in this case, SEO "rank" data), by revoking API access to some of its products. Essentially, Google sent a very clear message to software companies that if they scrape search rank data from its results pages, they would lose access to other crucial data channels.
Bottom line is that keyword [not provided] will continue to account for a greater share of inbound organic keyword referrals from Google, and Google doesn't want you tracking rank data of any kind if it involves scraping its results set. As a result, there should be an increasing reliance on Webmaster Tools and the search query details it provides -- and those details are limited relative to what we're used to.
We're slowing approaching an operating environment where keyword rank and visit data, once the embodiment of SEO performance, are no more. Thinking ahead to that day has me wrestling with the question, "So where does SEO go from there?"
The honest answer I can share today is: I have no idea. But I do have a few beliefs.
Let me begin with an acknowledgement that there have already been a plethora of articles written that provide practical, "replace this report with that one" perspectives. Frankly, I'm more interested intellectually in the aggregate evolutionary arc we're observing.
SEO is not dead
As Raven CEO Patrick Keeble noted in his company's announcement that it was eliminating rank data (generated by scraping search results pages), "Abandoning your comfort zone for the sake of growth and stability" can be a positive in the long-term, even if painful in the near-term. I like that line of thinking.
Though rank data has been lauded for years as being a misguided key performance indicator of SEO success, most of us still provided that data in summary reports. It was the tangible among a set of largely intangible services. The SEO world's equivalent to the print ad, rank data was understood by both clients and bosses.
Keyword queries. on the other hand, seem more difficult to let go of. Ever since John Battelle embedded this notion of "database of intentions" into our brains, we've built entire businesses and even industries by optimizing against those set of self-reported intentions. Now we have to do without.
Remaining positive though, and embracing Keeble's spirit of evolution in the pursuit of "growth and stability," I believe this signals an end to SEO functioning as a silo'd activity. SEO itself is not dead. Rather, the days of search "optimizing" a website may be numbered. Content marketing, and brand storytelling through digital communications channels, appear to be the heir to legacy SEO. The confluence of previously disparate tactics (for some) will support content distribution across search, social, and even more explicit advertising channels (display, broadcast media).
And we're not wanting for supporting performance metrics. Social in particular has produced a tremendous number of additional data points to investigate and optimize for, all criticisms of social channel performance aside.
That's where I believe SEO is headed: a place where everyone acknowledges it as a best-practice content marketing tactic supporting broader digital communications. We'll judge individual Web pages, PDFs and other pieces of digital content relative to their contribution to the goals established by the organization. Keyword-specific performance seems destined to become secondary to content-specific performance.
That's what I believe is next for SEO.
2 comments on "What's Next For SEO?".
- If all true, the democratization of the internet is over. How can a local bakery compete with major brands? At least with SEO, there was a chance at under $1000 a month to be seen. Hopefully localization continues to play a part, but already we see that Goog rarely give both the website and the Places/+ listing visibility under the same search term.
- Hi Ryan - the future of SEO is WPO - web presence optimization. And for exactly the reasons you mention: with Google data getting more difficult to come by, marketers need to produce content that's worth reading and sharing, optimize it and distribute it beyond the corporate website. But they also need to optimize (where possible) and amplify earned and paid content elsewhere in addition to their own site content.
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Coney Island Inspired Carnival Birthday Party
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As a huge fan of carnival/circus themes, I'm feeling pretty giddy over this fabulously creative Vintage 1940's Carnival Birthday Party by January from Cupc
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Kapaa, Hawaii 2BR Condo Rental (#30997)
2 Bedrooms / Sleeps 6
3 Bath
Hot Tub, Cable, Internet
BBQ, Beach Front, Ocean View, Laundry
$ 300 Estimated Per Night |
Click for exact pricing and availability.
This amazing Five-Star Resort has breathtaking views. There are two-bedrooms, and three baths. There is also a state of the art kitchen with brand new appliances and very open breakfast bar with hardwood flooring and granite counters. The location is perfect a few steps from the ocean and right outside is a lazy river-style, saline pool with two water slides and travertine deck, three sandy bottom jacuzzi spas, children's sandy beach pool, a large beachfront bar and in-house health spa.
The Master suite has a King size bed. There is a queen in the second room and the living room has a queen sleeper sofa. This condo can sleep 6. There is a state of the art kitchen that is the envy to even those who are not the best of cooks. It is a great space fo entertaining and for family and friends. There is also a great lanai area to look out at the ocean views or of the beautiful resort.
There is a lazy river-style, saline pool with two water slides and travertine deck, three sandy bottom jacuzzi spas, children's sandy beach pool, a large beachfront bar and in-house health spa. If that is not enough just a short walk from your room and you are on the beautiful waters of the Pacific Ocean. If you are here on your honeymoon or here with friends and family this condo can be enjoyed by all.
In the Air you can enjoy Helicopter and airlplane tours of this beautiful island. On land you can enjoy biking, hiking, horseback riding, camping, golf/tennis, hunting, motorcycling/ATV's, Luau's, musuems, and guided tours. On water you can enjoy boating, kayaking, fishing, whale/dolphin watching, sailing and all types of water boat tours. In the water you can enjoy water skiing, snorkeling/deep sea diving, windsurfing and surfing. For the whole family there is also a great boat tour where you can go snorkeling with the family and all other great water activities.
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Libec RHP75 New Tripod Head with PH-8B Pan Handle, Supports 37.5 lbs
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Professional Fluid Head with extendable pan handles. Supports 17kg / 37.5lb. Fully adjustable Continuous Counterbalance technology. Offers Perfect Counterbalance. Unique Balance Stabilizer Mechanism to prevent the slightest wobble on image. Accurately stop camera precisely at any tilt angle. Smooth balancing system. Impeccable drag and torque system. Seven-step pan and tilt torque switch. One-touch attachment and release. Operate At As Low As -40 Degrees F. Extendable Pan Handle With A Rubber Grip. 75mm Ball Head. Great for ENG and fast moving objects
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Plate attachment | 3.8" / 9.65cm screw x 2 |
Spare screw | 3.8" / 9.65cm |
Payload | 17kg / 37.5lbs |
Weight | 3.8kg / 8.37lbs |


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NewsWorks reports that the union which represents PGW's employees will oppose selling the gas utility to a private owner.
Mom, Who Accused Police of Assault, Arrested for Shoplifting
The Daily News reports: "In November, Marissa Sargeant publicly accused Tullytown Borough police of "brutally" assaulting her son, Joey Williams, 14, after he was arrested on shoplifting charges at the Walmart on Route 13. She posted photos of his swollen face on Facebook. They went viral, with supporters comparing it to the Rodney King beating. Now, three months after the Bucks County District Attorney's Office cleared the officers of wrongdoing, Sargeant is in prison on felony charges that she shoplifted from the same Walmart, police said." Sergeant has been unable to post bail.
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The union — which may be striking soon — has a few things going against it. SEPTA workers aren't (ahem) always highly thought of in Philly anyway. They're fighting for benefits, paid by us, that few of us would get in our own private sector lives. And when push comes to shove, the union's trump card is to make you and me — the commuting and driving public — feel as much pain as possible. That's what the strike is designed to do, after all.
We're the hostage in these negotiations. It's bound to produce some antagonism.
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CBSSports.com reports: "Penn State University Board of Trustees member Alvin Clemens announced his resignation Friday, the Associated Press reported, saying that the Board's 2011 decision to fire Joe Paterno represented a 'rush to injustice.'"
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CBSPhilly reports that Mayor Nutter is trying, again, to get approval for a cigarette tax to fund Philly schools:
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The Star-Ledger reports that Chris Christie gathered just 8 percent of the vote—good for fourth place—in a presidential straw poll over the weekend at CPAC, the largest annual gathering of conservative activists. Rand Paul, Ted Cruz, and Ben Carson each placed ahead of Christie. (Though it may say something about the peculiar makeup of CPAC activists that Carson—whom you've probably never heard of) beat Christie. Rick Santorum was right behind with 7 percent of the vote.
It may not make much difference: While Mitt Romney has won the CPAC poll a number of times before his 2012 nomination, the only other candidate to win in recent years has been Ron Paul. CPAC's activists are influential, but they don't determine everything.
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The Delco Times reports on three new routes operating out of the Philadelphia International Airport this weekend:
"Swinger Guru" Spoke at School Assembly
Philly.com reports that a "swinger guru" spoke at a Thursday school assembly in the Upper Dublin school district north of Philadelphia, and that school officials are now apologizing.
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The Patriot-News reports: "One of the biggest talking points in the debate over the future of Pennsylvania's state store system is "border bleed" — the number of Pennsylvanians who drive across state lines to buy booze. But it seems neighboring states are also losing customers to Pennsylvania."


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China's First Apple Launch Underwhelms
With no new announcements and the iPhone 5C's surprisingly hefty price tag, Beijing's first Apple launch event failed to bring the house down. Jane Lee gets a blogger's eye view of the festivities.
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Ashlyn Treadway (23) died when she lost control of her vehicle
Filed Under:
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Published: Nov 23, 2012 @ 12:05 AM
Ashlyn Treadway (23)
Aug 25, 2012
Cause of Death:
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Beaumont, TX
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Ashlyn was born in Beaumont, TX, January 21, 1989 the daughter of Leslie Charles Treadway and Rilea Wallace.
Ashlyn was beautiful inside and out with a loving heart. She enjoyed singing, shopping, and riding four wheelers. She loved animals of all types and always ended her conversations with, "I love you." She will be sadly missed by all who knew and loved her. Ashlyn attended Beaumont schools the majority of her life and was home schooled in her final year.
She leaves behind to cherish her memory her mother Rilea Wallace, father Leslie Treadway, sister Brea Treadway, brother Lathan Treadway and wife Kristin, maternal grandparents Rev. Jerrol and Glenda Wallace, maternal aunts and uncles Rev. Michael and Tamara Mahaney, and Derrick and Jessica Wallace. In addition she leaves her four cousins, Hunter, Kyler, and Mykal Mahaney, and Madison Wallace.
Visitation for Ashlyn will be held Thursday August 30, 2012 at Moss Hill Pentecostal Church from 5-8PM. Funeral services will be held 2PM Friday, August 31, 2012 at the Apostolic Church of Beaumont 3333 Eastex Freeway Beaumont, Texas 77706.
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Madonna's 'W.E.' Pushed to Feb. 3 Release After Awards-Qualifying Run
The switch in release plans is designed to avoid a crowded Christmas calendar and to take advantage of Madonna's widely rumored Super Bowl performance.
Madonna's W.E. has joined a bevy of upcoming films that are opting for a one-week awards qualifying run before Dec. 31 but delaying their official release in theaters until after the new year in order to avoid the crowded year-end corridor.
W.E. launches its qualifying run Dec. 9, when the film was previously scheduled to debut in theaters. But the fim's release date has been moved to Feb. 3, the Weinstein Co. confirmed Wednesday.
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The switch in plans also is designed to take advantage of Madonna's widely rumored performance at the Super Bowl on Feb. 5.
W.E., charting the love affair between Wallis Simpson and Britain's Prince Edward, who abdicated the throne in order to marry Simpson, is hardly alone in opting for an awards-qualifying run versus a full-blown release. Other titles doing the same include Albert Knobbs, Rampart, We Need to Talk About Kevin and Coriolanus, also from the Weinstein Co.
Once a film plays in its qualifying run, usually in one or two theaters in Los Angeles, distributors can send out screeners to awards groups.
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The practice is more popular than ever this year, largely thanks to the success of last year's Biutiful, which Roadside Attractions didn't officially open in theaters until Jan. 28 following a qualifying run in December. The film, which earned Javier Bardem an Oscar nomination for best actor, was able to benefit from awards attention as it rolled out in theaters, grossing $5.1 million in the U.S., a strong showing for a dark, foreign-language film.
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Sep 20, 2011 | Posted by: roboblogger | Full story: CBS Atlanta
When it comes to health care savings, President Barack Obama's deficit plan borrows a familiar strategy from corporate America's playbook: cut costs or shift them to others.
"Proud To Be An American" Since: Apr 07 12,938 Location hidden |
Judged: 4 2 1 |
Judged: 4 2 2 It will do no good to wait for the politicians to suddenly atone for their sins. They are too busy trying to keep their jobs, to do their jobs. It will do no good to wait for the media to suddenly remember its origins as the 'free press,' the watchdog of democracy envisioned by Jefferson. They are too busy trying to get exclusive details about exactly how the bank robbers emptied the public's pockets, to give a damn about telling anybody what they looked like, or which way they went. There is a tide pushing back the rights of each of us, and it has been artificially induced by union-bashing and the sowing of hatreds and fears, and now this ever-more-institutionalized economic battering of the average American. It will continue, and it will crush us, because those who created it are organized and unified and hell-bent. And the only response for us is to be organized and unified and hell-bent in return. We must find again the energy and the purpose of the 1960's and early 1970's and we must protest this in the streets. We must arise, non-violently but insistently. The world may be watching - but Americans arent seeing it except here- spread this! http://www.youtube.com/watch... |
"Obama tells the right to..." Since: Jun 07 10,847 shhhh... STFU, you lost... |
Judged: 7 6 6 |
"Obama tells the right to..." Since: Jun 07 10,847 shhhh... STFU, you lost... |
Judged: 7 6 5 Wow, so profound and so mature you must feel so proud that you have given up on such juvenile slogans as you emasculated yourself into adulthood; Congratulations. |
"your life is great" Since: Aug 09 7,846 you poop in clean water |
Judged: 1 1 1 |
United States |
Judged: 3 2 2 Something tells me that you are listening to non-existant voices The Repub plan is to phase out welfare Obama's plan is a truckload of high explosives BTW, Obama has NOT won, he blew up all chance of that |
"If it ain't broke don't fix it" Since: Jul 09 17,081 www.blanketsandstuff.com |
Judged: 4 3 3 LOL. Speaking of destroying Medicare, Oblunder is still doing his best to take it out by trying to take away another $200B. |
"Proud To Be An American" Since: Apr 07 12,938 Location hidden |
Judged: 3 2 2 Attention Moron Cow Patty!!! You sound angry probably because you were not first to post. I believe you will be the last fool standing for an obamanation. Fall on those swords, you deserve 'em and we need to be entertained. |
Since: Dec 07 22,500 |
Judged: 4 3 2 Profound and mature, yet you still claim to be a Marine, you accused Bush of spraying Chemtrails on everyone and you're still clicking your own agree buttons under false topix names. You are one pathetic loser. |
Judged: 1 1 |
Judged: 3 2 2 Obama's plan, as bad as it sounds, is a thousand times preferable to the utter bankruptcy the Republicans have in mind for Medicare and Social Security. However, paying the doctors less may just cause a lot more of them to stop accepting Medicare patients. It's happening right now and could get worse. |
Since: Nov 08 105,011 Location hidden |
Judged: 1 1 1 REPORT: SOLYNDRA execs to plead the Fifth... HOUSE TO PROBE OBAMA ACTIONS ON GOV'T LOAN... Billionaire Disputes Company Sought White House Help... Second witness says White House tried to steer testimony... |
1 post removed
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Since: Nov 08 105,011 Location hidden |
Judged: 2 1 1 First you loons establish death panels, then you call them review boards, and now you want to cut Medicare........you're going to kill granny and grandpa if it kills you........pardon the pun. |
"If it ain't broke don't fix it" Since: Jul 09 17,081 www.blanketsandstuff.com |
Judged: 3 1 1 I don't know whether to despise or feel sorry for libtards; If Oblunder gets his way, he will have drained almost $1 trillion out of medicare, yet libtards applaud it. How pathetic. |
"Obama tells the right to..." Since: Jun 07 10,847 shhhh... STFU, you lost... |
Judged: 5 3 3 I forgot that most of you right-wingers arent intelligent and have a limited vocabulary what I should have said was Grow up. |
United States |
Judged: 2 1 1 It would require seniors to pay MORE for their Medicare benefits while cutting payments to doctors. It would shift Medicaid costs to the states. Even AARP blasted sections of the plan that would require seniors to pay more for certain Medicare benefits. The proposals would RAISE deductibles and require CO-PAYS for some services. TIME TO VOTE OUT THE LIAR OF CHIEF IN 2012. VOTE OUT DEMOCRAT SENATORS IN 2012. THEN RECLAIM AMERICA. LET'S BE PROUD AGAIN! |
United States |
Judged: 2 1 Despise them. If you feel sorry for them, it might give credence to the fact that they are brainless But they are clueless and destructive, not brainless |
"Obama tells the right to..." Since: Jun 07 10,847 shhhh... STFU, you lost... |
Judged: 5 4 4 You know it would go a long way in helping you keep up if you would just read the article before you post your ignorance the voices that you claim that I hear is me quoting the article, you idiot. |
United States |
Judged: 1 What you SHOULD have said is "15 levels beyond 'cupcake's comprehension'" Not to worry, cupcake. Somneday you'll understand (maybe) |
"If it ain't broke don't fix it" Since: Jul 09 17,081 www.blanketsandstuff.com |
MCP must be the exception then, because his posts indicate that he is TOTALLY brainless. |
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