Reactive block copolymers for the preparation of inorganic tubule-polymer composites
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08J-003/18
C08K-003/34
C08L-083/02
출원번호
US-0072173
(2008-02-25)
등록번호
US-8557907
(2013-10-15)
발명자
/ 주소
Santos, Leticia Flores
Montiel, Alfonso González
Alvarado, María Dolores Baeza
Rodríguez, Edgar Espinoza
출원인 / 주소
Macro-M S.A. de C.V.
대리인 / 주소
Hodgson, Stephen S.
인용정보
피인용 횟수 :
0인용 특허 :
26
초록▼
A method for modifying an inorganic tubule, such as halloysite, cylindrite, boulangerite, or imogolite, with a functionalized block copolymer for improving compatibility with a thermoplastic or thermoset polymer matrix and a composition for the modified inorganic tubule and for the modified inorgani
A method for modifying an inorganic tubule, such as halloysite, cylindrite, boulangerite, or imogolite, with a functionalized block copolymer for improving compatibility with a thermoplastic or thermoset polymer matrix and a composition for the modified inorganic tubule and for the modified inorganic tubule-polymer matrix are provided. In one embodiment, the block copolymer can be added to a slurry of the inorganic tubules. The pH of the slurry can be manipulated to promote ionic bonding between the inorganic tubules and one block of the block copolymer. The other block of the block copolymer is selected for compatibility with the polymer matrix for a particular application.
대표청구항▼
1. A modified inorganic tubule composition, comprising: a) inorganic tubules; andb) a block copolymer added to the inorganic tubules for compatibilizing the inorganic tubules with a polymeric material, thereby making the modified inorganic tubule composition, the block copolymer having a composition
1. A modified inorganic tubule composition, comprising: a) inorganic tubules; andb) a block copolymer added to the inorganic tubules for compatibilizing the inorganic tubules with a polymeric material, thereby making the modified inorganic tubule composition, the block copolymer having a composition comprising:a first block comprising charged monomers or monomers that upon pH changes can become charged andmonomeric units of a vinyl monomer; anda second block comprising monomeric units of one or more vinyl monomers andmonomeric units of the charged monomers or monomers that upon pH change can become charged from the first block,wherein the amount of the block copolymer in the modified inorganic tubule composition is between about 0.001% and about 50% by weight,wherein the amount of inorganic tubules in the modified inorganic tubule composition is at least about 50% by weight, andwherein at least one block in the block copolymer tends to attach to and/or interact with the inorganic tubules and at least one other block in the block copolymer tends to attach to and/or interact with the polymeric material. 2. The modified inorganic tubule of claim 1, wherein the charged monomers or monomers that upon pH change can become charged monomers in the first block have a functional group selected from the group consisting of: ammonium; alkyl ammonium; aryl ammonium (—N+R(3-n-m)ArmHn where (n+m)≦3); aryl and alkyl phosphonium (—P+R(3-n-m)ArmHn where (n+m)≦3); aryl and alkyl sulfonium (—S+R(2-n-m)ArmHn where (n+m)≦2); substituted ammonium (—N+X1X2X3); phosphonium (—P+X1X2X3); and sulfonium (—S+X1X2), wherein R is an alkyl group, wherein Ar is an aryl group, wherein X1, X2 and X3 are each individually H or a C1-C20 group, wherein said C1-C20 group is selected from the group consisting of alkyl, aryl, perfluoroalkyl, arylalkyl, and alkylaryl, and wherein one or more of the members of said group consisting of alkyl, aryl, perfluoroalkyl, arylalkyl or alkylaryl may be substituted with one or more substituents selected from the group consisting of oxygen, nitrogen, chlorine, fluorine, bromine, iodine, sulfur and phosphorous. 3. The modified inorganic tubule of claim 1, wherein the second block of the block copolymer comprises vinyl monomers with a functional group selected from the group consisting of acid, hydroxyl, epoxy and amino. 4. The modified inorganic tubule of claim 1, wherein the second block of the block copolymer is hydrophobic. 5. The modified inorganic tubule of claim 1, wherein the inorganic tubules are selected from the group consisting of: synthetic inorganic tubules, modified inorganic tubules and natural tubules selected from the group consisting of halloysite, cylindrite, boulangerite, imogolite, and mixtures thereof. 6. The inorganic tubule of claim 1, wherein the inorganic tubule has two or more overlapping layers with an interlayer space between the layers and a lumen, the lumen having an inner surface, and wherein the inorganic tubule contains one or more metals, inorganic, organic, organometallic or coordination compounds introduced either in the interlayer space or into the inner surface of the lumen. 7. The composition of claim 1, further comprising additional inorganic or organic cations or anions. 8. A modified inorganic tubule composition, comprising: a) 50-99.999% wt of inorganic tubules; andb) 0.001-50% wt of a block copolymer comprising: a first block comprising charged monomers or monomers that upon pH change can become charged and monomeric units of one or more vinyl monomers; anda second block comprising monomeric units of one or more vinyl monomers,wherein the block copolymer modifies the inorganic tubules thereby making the modified inorganic tubule composition, andwherein at least one block in the block copolymer tends to be compatible with the inorganic tubules and at least one other block in the block copolymer tends to be compatible with a polymeric material. 9. The modified inorganic tubule of claim 8, wherein the negatively charged monomers or monomers that upon pH change can become negatively charged monomers in the first block have functional groups selected from Lewis acids, Brönsted acids, sulphate, sulphonate, sulfonic acid, carboxylic acids, hydroxyl, anhydride, mercapto, thio, and acid hydrogens including, but not limited to, alfa carboxyl hydrogens and substituted derivatives thereof. 10. The modified inorganic tubule of claim 8, wherein the second block of the block copolymer comprises vinyl monomers with a functional group selected from the group consisting of acid, hydroxyl, epoxy and amino. 11. The modified inorganic tubule of claim 8, wherein the second block of the block copolymer is hydrophobic. 12. The modified inorganic tubule of claim 8, wherein the inorganic tubule is a synthetic inorganic tubule, a modified inorganic tubule and/or a natural tubule selected from the group consisting of halloysite, cylindrite, boulangerite, and imogolite. 13. The inorganic tubule of claim 8, wherein the inorganic tubule has two or more overlapping layers with an interlayer space between the layers and a lumen, the lumen having an inner surface, and wherein the inorganic tubule contains one or more metals, inorganic, organic, organometallic or coordination compounds introduced either in the interlayer space or into the inner surface of the lumen. 14. A process for producing the modified inorganic tubule composition of claim 1, comprising the steps of: a) dispersing the inorganic tubules in a dispersion medium; andb) adding the block copolymer. 15. The process of claim 14, wherein the block copolymer is dispersed in the same or a different dispersion medium. 16. The process of claim 14, further comprising adjusting the pH of the inorganic tubule-block copolymer mixture. 17. The process of claim 14, further comprising isolating the modified inorganic tubules. 18. The process of claim 14, wherein the dispersion medium is selected from the group consisting of water, methanol, ethanol, propanol, isopropanol, ethyleneglycol, 1,4-butanediol, glycerin, dimethyl sulfoxide, N,N-dimethylformamide, acetic acid, formic acid, pyridine, aniline, phenol, nitrobenzene, acetonitrile, acetone, methyl ethyl ketone, chloroform, carbon disulfide, propylene carbonate, 2-methoxyethanol, ether, carbon tetrachloride, n-hexane, and combinations thereof. 19. A process for producing the modified inorganic tubule composition of claim 8, comprising the steps of: a) dispersing the inorganic tubules in a dispersion medium; andb) adding the block copolymer. 20. The process of claim 19, wherein the block copolymer is dispersed in the same or a different dispersion medium. 21. The process of claim 19, further comprising adjusting the pH of the inorganic tubule-block copolymer mixture. 22. The process of claim 19, further comprising isolating the modified inorganic tubules. 23. The process of claim 19, wherein the dispersion medium is selected from the group consisting of water, methanol, ethanol, propanol, isopropanol, ethyleneglycol, 1,4-butanediol, glycerin, dimethyl sulfoxide, N,N-dimethylformamide, acetic acid, formic acid, pyridine, aniline, phenol, nitrobenzene, acetonitrile, acetone, methyl ethyl ketone, chloroform, carbon disulfide, propylene caronate, 2-methoxyethanol, ether, carbon tetrachloride, n-hexane, and combinations thereof. 24. A composition for an inorganic tubule-polymer composite material, comprising: a) the modified inorganic tubules of claim 1; andb) a polymer matrix. 25. The composition of claim 24, wherein the polymer matrix comprises a thermoplastic polymer. 26. The composition of claim 24, wherein the polymer matrix comprises a thermoset polymer. 27. The composition of claim 24, further comprising fillers, additives and/or compatibilizers. 28. The composition of claim 27, wherein fiber glass is added as a filler at between about 5% wt to about 80% wt. 29. A composition for an inorganic tubule-polymer composite material, comprising: a) the modified inorganic tubules of claim 8; andb) a polymer matrix. 30. The composition of claim 29, wherein the polymer matrix comprises a thermoplastic polymer. 31. The composition of claim 29, wherein the polymer matrix comprises a thermoset polymer. 32. The composition of claim 29, further comprising fillers, additives and/or compatibilizers. 33. The composition of claim 32, wherein fiber glass is added as a filler at between about 5% wt to about 80% wt. 34. The composition of claim 1, wherein the modified inorganic tubule composition contains less than about 10% wt of the block copolymer, and wherein the inorganic tubules are halloysite. 35. The composition of claim 1, wherein the charged monomers or monomers that upon pH change can become charged are selected from the group consisting of N,N′-dialkylaminoalkyl methacrylate, N,N′-diarylaminoalkyl methacrylate, N,N′-dialkylaminoalkyl acrylate, and N,N′-diarylaminoalkyl acrylate. 36. The composition of claim 8, wherein the charged monomers or monomers that upon pH change can become charged are selected from the group consisting of N,N′-dialkylaminoalkyl methacrylate, N,N′-diarylaminoalkyl methacrylate, N,N′-dialkylaminoalkyl acrylate, and N,N′-diarylaminoalkyl acrylate. 37. The composition of claim 1, wherein the charged monomers or monomers that upon pH change can become charged comprise 2-dimethylaminoethyl methacrylate, and wherein the inorganic tubules are halloysite. 38. A process for producing the modified inorganic tubule composition of claim 6, comprising the steps of: a) dispersing inorganic tubules in a dispersion medium;b) adding a block copolymer, wherein the block copolymer comprises a first block comprising charged monomers or monomers that upon pH changes can become charged and monomeric units of a vinyl monomer; and a second block comprising monomeric units of one or more vinyl monomers and monomeric units of the charged monomers or monomers that upon pH change can become charged from the first block; andc) recovering the modified inorganic tubule composition of claim 6. 39. A process for producing the modified inorganic tubule composition of claim 13, comprising the steps of: a) dispersing inorganic tubules in a dispersion medium;b) adding a block copolymer, wherein the block copolymer comprises a first block comprising charged monomers or monomers that upon pH changes can become charged and monomeric units of a vinyl monomer; and a second block comprising monomeric units of one or more vinyl monomers and monomeric units of the charged monomers or monomers that upon pH change can become charged from the first block; andc) recovering the modified inorganic tubule composition of claim 13. 40. A composition for an inorganic tubule-polymer composite material, comprising: a) the modified inorganic tubules of claim 6; andb) a polymer matrix. 41. A composition for an inorganic tubule-polymer composite material, comprising: a) the modified inorganic tubules of claim 13; andb) a polymer matrix. 42. The modified inorganic tubule composition of claim 1, wherein the amount of the block copolymer in the modified inorganic tubule composition is at least about 0.04% and less than about 10% by weight. 43. The modified inorganic tubule composition of claim 1, wherein the amount of the block copolymer in the modified inorganic tubule composition is at least about 0.1% and less than about 10% by weight. 44. The modified inorganic tubule composition of claim 8, wherein the amount of the block copolymer in the modified inorganic tubule composition is at least about 0.04% and less than about 10% by weight. 45. The modified inorganic tubule composition of claim 8, wherein the amount of the block copolymer in the modified inorganic tubule composition is at least about 0.1% and less than about 10% by weight. 46. The modified inorganic tubule composition of claim 1, further comprising an agent in and/or on the inorganic tubules, wherein the agent is selected from the group consisting of an ammonium salt, a potassium salt, a cesium salt, a rubidium salt, an iron salt, a silver salt, a copper salt, a transition metal salt, an organometallic compound, a coordination compound, an inorganic compound, an organic compound, a conductive material, a flame-retardant material, an agent for elution of a mineral, a light emitting substance, a colorant, an antioxidant, an emulsifier, an antifungal agent, a pesticide, a fragrance, a dye, an optical brightener, a self-healing polymer, a plasticizer, an antibiotic, an antihelmetic, an antifouling compound, an enzyme, a peptide, bacterial spores, fungi, a hormone, an herbicide and combinations thereof. 47. The modified inorganic tubule composition of claim 8, further comprising an agent in and/or on the inorganic tubules, wherein the agent is selected from the group consisting of an ammonium salt, a potassium salt, a cesium salt, a rubidium salt, an iron salt, a silver salt, a copper salt, a transition metal salt, an organometallic compound, a coordination compound, an inorganic compound, an organic compound, a conductive material, a flame-retardant material, an agent for elution of a mineral, a light emitting substance, a colorant, an antioxidant, an emulsifier, an antifungal agent, a pesticide, a fragrance, a dye, an optical brightener, a self-healing polymer, a plasticizer, an antibiotic, an antihelmetic, an antifouling compound, an enzyme, a peptide, bacterial spores, fungi, a hormone, an herbicide and combinations thereof. 48. A composition for an inorganic tubule-polymer composite material, comprising: a) the modified inorganic tubule composition of claim 46; andb) a polymer matrix. 49. A composition for an inorganic tubule-polymer composite material, comprising: a) the modified inorganic tubule composition of claim 47; andb) a polymer matrix. 50. The composition of claim 8, wherein the second block of the functionalized block copolymer includes monomers from the first block that are charged or that can become charged upon a change in pH. 51. The composition of claim 8, wherein the charged monomers or monomers that upon pH change can become charged comprise 2-dimethylaminoethyl methacrylate. 52. The composition of claim 8, wherein each of the first and second blocks comprise a copolymer of styrene and 2-dimethylaminoethyl methacrylate. 53. The composition of claim 8, wherein at least one of the first and second blocks of the block copolymer comprises a copolymer of 4-tert-butylstyrene and 2-dimethylaminoethyl methacrylate.
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