KOSOKU AKIHIRO (US)
CLAIMS Claim 1. A hydrophobic polymer composition, comprising: a homopolymer of a hydrophobic monomer, a copolymer containing at least 30 wt % of the hydrophobic monomer or a mixture of the homopolymer and the copolymer; wherein the hydrophobic monomer is selected from the group consisting of vinyl neo-pentanoate, vinyl 2-ethylhexanoate, vinyl neo-nonanoate, vinyl neo-decanoate, vinyl neo-undecanoate, vinyl neo-dodecanoate and highly branched vinyl esters of formula (I): H2C=C(R)-O-C(O)-C(R1)(R2)(R3) (I) wherein R is –H or –CH3, and R1, R2 and R3 are each independently C1 to C10 alkyl groups; and wherein the hydrophobic polymer composition is in the form of free-flowing beads containing the homopolymer and/or copolymer in a content of at least 95 wt %. Claim 2. The hydrophobic polymer composition of claim 1, wherein a molecular weight of the homopolymer and/or the copolymer is from 50,000 to 300,000 g/mole and a ratio Mw/Mn is from 2.0 to 5.0. Claim 3. The hydrophobic polymer composition of claim 1 or 2, wherein an optical clarity as measured by transmission of light of wavelength of 580 nm of a cast sheet of the resin having a thickness of 1.0 mm is 80% or higher according to ASTM D1003. Claim 4. The hydrophobic polymer composition of any one of claims 1 to 3, wherein a glass transition temperature (Tg) of the homopolymer and/or copolymer is from 0 to 100ºC. Claim 5. The hydrophobic polymer composition of any one of claims 1 to 4, wherein a water solubility of the hydrophobic monomer is from completely insoluble to less than 0.01 g/100g H2O. Claim 6. The hydrophobic polymer composition of any one of claims 1 to 5, which comprises the copolymer containing at least 30 wt % of the hydrophobic monomer, wherein the copolymer further comprises at least one comonomer selected from the group consisting of styrene, a derivative of styrene, ethylene, propylene, 1,3-butadiene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, (meth)acrylamide, an optionally substituted C1-C30 alkyl ester of acrylic acid, and an optionally substituted C1-C30 alkyl ester of methacrylic acid. Claim 7. The hydrophobic polymer composition of any one of claims 1 to 6, wherein a particle diameter of the free-flowing beads is from 50 to 500 microns. Claim 8. The hydrophobic polymer composition of any one of claims 1 to 7, which comprises the homopolymer of a hydrophobic monomer. Claim 9. The hydrophobic polymer composition of any one of claims 1 to 8, which comprises the copolymer, wherein the copolymer contains a mixture of the hydrophobic monomers. Claim 10. A method to prepare the hydrophobic polymer composition of any one of claims 1 to 9, comprising: charging to a pressurizable reactor equipped with a dispersing agitation system an aqueous solution of an inorganic salt and a polymeric water-soluble material; adding an organic peroxide and/or azo initiator to the aqueous solution; adding a charge of the hydrophobic monomer or a charge of a mixture of monomers including at least 30 wt % of the hydrophobic monomer to the aqueous solution to obtain a two phase monomer oil/aqueous mixture; agitating the two phase mixture at a speed to disperse the monomer and organic peroxide phase in the form of oil droplets having a size from 50 to 1000 microns in the aqueous phase to form a reaction mixture; pressurizing the reactor with a gas chemically inert to the reaction mixture; heating the reaction mixture at a polymerization temperature while maintaining the agitation at a dispersion speed to retain the monomer oil phase in the form of the droplets until polymerization completion and formation of solid beads; heat treating the polymerization complete bead mixture at a temperature from 5 to 25ºC above the polymerization temperature for 1 to 10 hours; cooling the heat-treated polymerization complete bead mixture to 50 ºC or less to obtain a slurry of homopolymer or copolymer beads and aqueous mother liquor; removing the homopolymer or copolymer beads from the mother liquor; and drying the homopolymer or copolymer beads to obtain free flowing beads having a particle diameter from 50 to 500 microns; wherein a water solubility of the hydrophobic monomer ranges from completely insoluble to less than 0.01g/100 g water. Claim 11. The method of claim 10, further comprising adding at least one sulfur- containing compound selected from the group consisting of alkyl and substituted alkyl thioglycolates, alkyl and substituted alkyl mercaptans and alkyl and substituted alkyl mercaptopropionates to the charge of the hydrophobic monomer or mixture of monomers including the hydrophobic monomer. Claim 12. The method of claim 11, wherein the at least one sulfur-containing compound is selected from the group consisting of methyl thioglycolate, ethyl thioglycolate, butyl thioglycolate, octyl thioglycolate, 2-ethylhexyl thioglycolate, isooctyl thioglycolate, 3- methoxybutyl thioglycolate, ethylene bis (thioglycolate), polyethylene bis (thioglycolate), 1,4- butanediol bis (thioglycolate), 1,6-hexanediol bis (thioglycolate), pentaerythritol tetrakis (thioglycolate), stearyl thioglycolate, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, butyl 3-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, isooctyl 3-mercaptopropionate, 3-methoxybutyl 3-mercaptopropionate, tridecyl 3- mercaptopropionate, ethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3- mercaptopropionate), 1,4-butanediol bis (3-mercaptopropionate), 1,6-hexanediol bis (3- mercaptopropionate), trimethylol propane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), stearyl 3-mercaptopropionate. Claim 13. The method of any one of claims 10 to 12, wherein a monomer conversion rate to polymer or copolymer is at least 99%. Claim 14. The method of any one of claims 10 to 13, further comprising washing and centrifuging the copolymer beads removed from the mother liquor before drying the copolymer beads. Claim 15. The method of any one of claims 10 to 14, wherein the polymeric water- soluble material is at least one selected from the group consisting of hydroxyethyl cellulose, alkali metal salts of poly(meth)acrylic acid, an ammonium salt of poly(meth)acrylic acid, polyvinyl alcohol and polyvinylpyrrolidone . Claim 16. The method of any one of claims 10 to 15, wherein a content of the polymeric water soluble material in the aqueous solution is from 0.01 to 0.1 parts per 100 parts of water. Claim 17. The method of any one of claims 10 to 16, wherein the inorganic salt of the aqueous solution is an inorganic salt of an alkali metal, an alkaline earth metal or a transition metal. Claim 18. The method of any one of claims 10 to 17, wherein the inorganic salt of the aqueous solution is an alkali metal sulfate, an alkali metal nitrate, an alkali metal phosphate, an alkali metal carbonate, an alkali metal bicarbonate or an alkali metal halide. Claim 19. The method of any one of claims 10 to 18 wherein a content of the inorganic salt in the aqueous solution is from 0.1 to 0.5 parts per 100 parts of water. Claim 20. The method of any one of claims 10 to 19, wherein the organic peroxide is employed and is selected from the group consisting of dibenzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, t-hexyl peroxypivalate, t-butyl peroxypivalate, di(3,5,5- trimethylhexanoyl) peroxide, di(4-methylbenzoyl) peroxide, di(3-methylbenzoyl) peroxide, benzoyl(3-methylbenzoyl) peroxide, t-hexyl peroxy-2-ethylhexanoate, 1,1,3,3- tetramethylbutyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5- di(2-ethyhexanoylperoxy)hexane, tert-amyl peroxypivalate, tert-amyl peroxyisobutylate, tert- amyl peroxy-2-ethylhexanoate and t-butyl peroxybenzoate. Claim 21. The method of any one of claims 10 to 20, wherein a content of the organic peroxide is from 0.1 to 2.0 parts relative to 100 parts of total monomer. Claim 22. The method of any one of claims 10 to 13, wherein the azo initiator is employed and is selected from the group consisting of 2,2'-azobis-isobutyronitrile, 2,2'-azobis-2- methylbutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis(1-acetoxy-1-phenylethane) and dimethyl 2,2'-azobisisobutyrate. Claim 23. The method of any one of claims 10 to 22, wherein a content of the charge of the hydrophobic monomer or the charge of the mixture of monomers including the hydrophobic monomer is from 25 to 100 parts per 100 parts of the water. Claim 24. The method of any one of claims 10 to 23, wherein the mixture of monomers including a hydrophobic monomer is charged and the mixture further comprises at least one monomer selected from the group consisting of a vinyl C9-C30 alkyl ether, styrene, a derivative of styrene, ethylene, propylene, 1,3-butadiene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, (meth)acrylamide, an optionally substituted C1-C30 alkyl ester of acrylic acid, and an optionally substituted C1-C30 alkyl ester of methacrylic acid. Claim 25. The method of any one of claims 10 to 24, wherein the reaction mixture does not comprise a surfactant or micelle forming agent. Claim 26. The method of any one of claims 10 to 25, wherein the mixture of monomers including a hydrophobic monomer is charged and the mixture does not comprise a cross-linking monomer. Claim 27. The method of any one of claims 10 to 26, wherein the polymerization temperature is from 50 ºC to 95ºC. Claim 28. A method to prepare a hydrophobic polymer composition, comprising: charging to a pressurizable reactor equipped with a dispersing agitation system an aqueous solution of an inorganic salt and a polymeric water-soluble material; adding an organic peroxide and/or azo initiator to the aqueous solution; adding a charge of a hydrophobic monomer or a charge of a mixture of monomers including at least 30 wt % of a hydrophobic monomer to the aqueous solution to obtain a two phase monomer oil/aqueous mixture; agitating the two-phase mixture at a speed to disperse the monomer, organic peroxide and/or azo initiator phase in the form of oil droplets having a size from 50 to 1000 microns in the aqueous phase to form a reaction mixture; pressurizing the reactor with a gas chemically inert to the reaction mixture; heating the reaction mixture at a polymerization temperature while maintaining the agitation at a dispersion speed to retain the monomer oil phase in the form of the droplets until polymerization completion and formation of solid beads; heat treating the polymerization complete bead mixture at a temperature from 5 to 25ºC above the polymerization temperature for 1 to 10 hours; cooling the heat-treated polymerization complete bead mixture to 50 ºC or less to obtain a slurry of homopolymer or copolymer beads and aqueous mother liquor; removing the homopolymer or copolymer beads from the mother liquor; and drying the homopolymer or copolymer beads to obtain free flowing beads having a particle diameter from 50 to 500 microns; wherein a water solubility of the hydrophobic monomer ranges from completely insoluble to less than 0.01g/100 g water, the hydrophobic monomer is selected from the group consisting of vinyl neo-pentanoate, vinyl 2-ethylhexanoate, vinyl neo-nonanoate, vinyl neo-decanoate, vinyl neo-undecanoate, vinyl neo-dodecanoate and highly branched vinyl esters of formula (I): H2C=C(R)-O-C(O)-C(R1)(R2)(R3) (I) wherein R is –H or –CH3, and R1, R2 and R3 are each independently C1 to C10 alkyl groups, and the hydrophobic polymer composition is obtained in the form of free-flowing beads containing the homopolymer and/or copolymer in at least 95% by weight. Claim 29. The method of claim 28, further comprising adding at least one sulfur- containing compound selected from the group consisting of methyl thioglycolate, ethyl thioglycolate, butyl thioglycolate, octyl thioglycolate, 2-ethylhexyl thioglycolate, isooctyl thioglycolate, 3-methoxybutyl thioglycolate, ethylene bis (thioglycolate), polyethylene bis (thioglycolate), 1,4-butanediol bis (thioglycolate), 1,6-hexanediol bis (thioglycolate), pentaerythritol tetrakis (thioglycolate), stearyl thioglycolate, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, butyl 3-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl 3- mercaptopropionate, isooctyl 3-mercaptopropionate, 3-methoxybutyl 3-mercaptopropionate, tridecyl 3-mercaptopropionate, ethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate), 1,4-butanediol bis (3-mercaptopropionate), 1,6-hexanediol bis (3- mercaptopropionate), trimethylol propane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), stearyl 3-mercaptopropionate. Claim 30. The method of claim 28 or 29, wherein a monomer conversion rate to polymer or copolymer is at least 99%. Claim 31. The method of any one of claims 28 to 30, wherein the hydrophobic monomer is at least one selected from the group consisting of vinyl neo-pentanoate, vinyl 2- ethylhexanoate, vinyl neo-nonanoate, vinyl neo-decanoate, vinyl neo-undecanoate, and vinyl neo-dodecanoate. Claim 32. The method of any one of claims 28 to 31, further comprising washing and centrifuging the polymer or copolymer beads removed from the mother liquor before drying the polymer or copolymer beads. Claim 33. The method of any one of claims 28 to 32, wherein the polymeric water- soluble material is selected from the group consisting of hydroxyethyl cellulose, alkali metal salts of poly(meth)acrylic acid, an ammonium salt of poly(meth)acrylic acid, polyvinyl alcohol and polyvinylpyrrolidone. Claim 34. The method of any one of claims 28 to 33, wherein a content of the polymeric water-soluble material in the aqueous solution is from 0.01 to 0.1 parts per 100 parts of water. Claim 35. The method of any one of claims 28 to 34, wherein the inorganic salt of the aqueous solution is an inorganic salt of an alkali metal, an alkaline earth metal or a transition metal. Claim 36. The method of any one of claims 28 to 35, wherein the inorganic salt of the aqueous solution is an alkali metal sulfate, an alkali metal nitrate, an alkali metal phosphate, an alkali metal carbonate, an alkali metal bicarbonate or an alkali metal halide. Claim 37. The method of any one of claims 28 to 36, wherein a content of the inorganic salt in the aqueous solution is from 0.1 to 0.5 parts per 100 parts of water. Claim 38. The method of any one of claims 28 to 37, wherein the organic peroxide is employed and is selected from the group consisting of dibenzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, t-Hexyl peroxypivalate, t-Butyl peroxypivalate, di(3,5,5- trimethylhexanoyl) peroxide, di(4-methylbenzoyl) peroxide, di(3-methylbenzoyl) peroxide, benzoyl(3-methylbenzoyl) peroxide, t-hexyl peroxy-2-ethylhexanoate, 1,1,3,3- tetramethylbutyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, 2,5-Dimethyl-2,5- di(2-ethyhexanoylperoxy)hexane, tert-amyl peroxypivalate, tert-amyl peroxyisobutylate, tert- amyl peroxy-2-ethylhexanoate and t-butyl peroxybenzoate. Claim 39. The method of any one of claims 28 to 38, wherein a content of the organic peroxide is from 0.1 to 2.0 parts relative to 100 parts of total monomer. Claim 40. The method of any one of claims 28 to 39, wherein the azo initiator is employed and is selected from the group consisting of 2,2'-azobis-isobutyronitrile, 2,2'-azobis-2- methylbutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis(1-acetoxy-1-phenylethane) and dimethyl 2,2'-azobisisobutyrate. Claim 41. The method of any one of claims 28 to 40, wherein a content of the charge of the hydrophobic monomer or the charge of the mixture of monomers including the hydrophobic monomer is from 25 to 100 parts per 100 parts of the water. Claim 42. The method of any one of claims 28 to 41, wherein the mixture of monomers including a hydrophobic monomer is charged and the mixture further comprises at least one monomer selected from the group consisting of a vinyl C9-C30 alkyl ether, styrene, a derivative of styrene, ethylene, propylene, 1,3-butadiene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, (meth)acrylamide, an optionally substituted C1-C30 alkyl ester of acrylic acid, and an optionally substituted C1-C30 alkyl ester of methacrylic acid. Claim 43. The method of any one of claims 28 to 42, wherein the reaction mixture does not comprise a surfactant or micelle forming agent. Claim 44. The method of any one of claims 28 to 43, wherein the mixture of monomers including a hydrophobic monomer is charged and the mixture does not comprise a cross-linking monomer. Claim 45. The method of any one of claims 28 to 44, wherein the polymerization temperature is from 50 ºC to 95ºC. |
In the same manner as described above the hydrophobic polymers described in the following Table 2 were prepared and analyzed. The light transmission data was obtained by dissolving the hydrophobic resin composition in toluene at 40 to 50% solids content. A film of the solution was prepared using a drawdown bar appropriately sized to provide a 1 mm dry film upon evaporation of the toluene. The dry film was cut to appropriate size and light transmission to light of 580 nm according to ASTM D1003 was measured. The samples were also evaluated for adhesiveness to polypropylene according to ASTM D3359 as indicated in Fig.2. The samples were prepared as 40% resin in toluene solutions with or without plasticizer. A drawdown of the solution on a polypropylene substrate was prepared and dried. The tape test according to ASTM D3359 was then performed to obtain the results shown in Table 2. Monomer conversion rate is defined as a percentage conversion of monomer to polymer. % = weight of polymer / (weight of monomer + weight of polymer). Monomer conversion rate is determined by gas chromatography. Polymer dispersity is defined as the ratio Mw / Mn and is determined by GPC analysis. The plasticizer employed was Hexamoll® DINCH, which is 1,2-cyclohexane dicarboxylic acid diisononyl ester. As this was tested to reflect possible actual utility any general plasticizer, known to one of skill in the art of adhesives may be employed.
The abbreviations of the Tables are defined as follows: VV-9: vinyl neononanoate VV-10: vinyl neodecanoate IBOMA: isobornyl methacrylate LMA: lauryl methacrylate 2-EHA: 2-ethylhexylacrylate MMA: methyl methacrylate BA: butyl acrylate t-BMA: tert-butyl methacrylate 2-EHTG: ethylhexyl thioglycolate NOM: n-octyl mercaptan AIBN: azobisisobutyronitrile LPO: lauryl peroxide BPO: benzoyl peroxide As indicated in Table 2 all homopolymers and copolymers according to the present disclosure exhibit a % light transmission of greater than 80% according to ASTM D1003 at 580nm and a polymer wt% of 99.0% or greater. It is noted that Examples 20 to 23 are not hydrophobic copolymers according to the present disclosure due to low light transmission and/or low monomer conversion rate. Adhesion performance according to ASTM D3359 is a function of hydrophobic monomer content, the comonomer used and comonomer content as well as the molecular weight of the polymer. When high content of hydrophobic monomer is present such as shown in Examples 1 and 11, adhesion to polypropylene is at the highest rating regardless of the molecular weight of the polymer. When less hydrophobic comonomers are included, adhesion performance to polypropylene is improved with the addition of a plasticizer.
Next Patent: INSERTER NEEDLE HUB COMPRISING A ROTATABLE NEEDLE SHIELD