CN1717449A - Come the thermoplastic elastomer of the polyvinyl butyral acetal of self-crosslinking - Google Patents
Come the thermoplastic elastomer of the polyvinyl butyral acetal of self-crosslinking Download PDFInfo
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- CN1717449A CN1717449A CN 200380104176 CN200380104176A CN1717449A CN 1717449 A CN1717449 A CN 1717449A CN 200380104176 CN200380104176 CN 200380104176 CN 200380104176 A CN200380104176 A CN 200380104176A CN 1717449 A CN1717449 A CN 1717449A
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 27
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 title claims description 76
- 238000004132 cross linking Methods 0.000 title claims description 12
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 title claims description 10
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 title claims description 10
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- 238000012986 modification Methods 0.000 claims description 18
- 230000004048 modification Effects 0.000 claims description 17
- -1 polypropylene Polymers 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 239000004800 polyvinyl chloride Substances 0.000 claims description 6
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229920001971 elastomer Polymers 0.000 claims description 5
- 239000000806 elastomer Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920001634 Copolyester Polymers 0.000 claims description 2
- 229930182556 Polyacetal Natural products 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920006324 polyoxymethylene Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 229920003317 Fusabond® Polymers 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 102100035474 DNA polymerase kappa Human genes 0.000 description 4
- 101710108091 DNA polymerase kappa Proteins 0.000 description 4
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000012815 thermoplastic material Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical class C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 2
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- MCPSMQGVSYDFLC-UHFFFAOYSA-N formaldehyde;2-octylphenol Chemical compound O=C.CCCCCCCCC1=CC=CC=C1O MCPSMQGVSYDFLC-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000012858 resilient material Substances 0.000 description 2
- 229920003987 resole Polymers 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- UXMYUFHUUYBDLL-UHFFFAOYSA-N 2,2-dimethyl-3-(oxiran-2-ylmethoxy)propan-1-ol Chemical compound OCC(C)(C)COCC1CO1 UXMYUFHUUYBDLL-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229920003054 adipate polyester Polymers 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- ZDWGXBPVPXVXMQ-UHFFFAOYSA-N bis(2-ethylhexyl) nonanedioate Chemical compound CCCCC(CC)COC(=O)CCCCCCCC(=O)OCC(CC)CCCC ZDWGXBPVPXVXMQ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- RIZMRRKBZQXFOY-UHFFFAOYSA-N ethion Chemical compound CCOP(=S)(OCC)SCSP(=S)(OCC)OCC RIZMRRKBZQXFOY-UHFFFAOYSA-N 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 229920003031 santoprene Polymers 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention is a kind of thermoplastic elastomer (TPE) composition that contains crosslinked elastomeric PVB and thermoplastic polymer, and prepares described TPE method for compositions.
Description
Background of the present invention
Invention field
The present invention relates to contain the thermoplastic elastomer of polyvinyl butyral acetal.
Description of Related Art
Polyvinyl butyral acetal (PVB) is a kind of thermoplastic material that can be used for giving the anti-crushing performance of glass, for example can be applied to the window glass of windshield and dwelling house and buildings.The preparation of polyvinyl butyral acetal is known and in industrial enforcement.For example Butacite is a kind of polyvinyl butyral products of being produced by E.I.DuPont de Nemours and Company.Also production polyvinyl butyral products of Solutia.
Known that PVB and other polymer materials blend have practicality.For example, United States Patent (USP) 5 514 752 has been put down in writing the PVB/ polypropylene blend, and United States Patent (USP) 5 770 654 has been put down in writing the PVB/ polyamide blend.United States Patent (USP) 6 506 835 has been put down in writing the PVB/PVC blend.PVB can improve flexibility, polarity and the toughness of polyolefine, polymeric amide and polyvinyl chloride.But it is not no problem that PVB is used for blend polymer.
Because the adhesion trend certainly of PVB, PVB is a kind of material that is difficult to handle.The PVB sheet can stick together or combination, reaches to be very difficult to intensity that these layers are separated, even reaches the degree that can not separate these layers.This irreversible of PVB is called " adhesion " from sticking to PVB manufacturing field.In case PVB " adhesion " is even then processing may also can be exceedingly difficult.The common refrigerated storage of PVB is to reduce the trend of adhesion.Use the refrigeration launch vehicle to transport PVB by the same token.The trend of adhesion can make the manufacturing processed of blending PVB very complicated and difficult.It can be very expensive process that the successive processes of processing PVB is moved, so be not practical industrial operation.Adhesion with PVB composition one sample loading mode of homogeneous can take place in the blend of PVB and other material.So, be difficult to obtain the blend of PVB and other polymkeric substance with a kind of cost effective manner.
Thermoplastic elastomer (TPEs) be by a kind of resilient material and a kind of thermoplastic material in conjunction with and the matrix material that obtains.TPEs disperses and crosslinked resilient material in the external phase of thermoplastic material.The example of conventional TPEs comprises Advanced Elastomers Systems, the Santoprene of Inc. and DSM Elastomers, the Sarlink of Inc..
TPEs has obtained application aspect a lot, for example comprise flexible pipe, pipe, liner, sealing, sheet material band, electric wire and cable shell, wheel and handle.Up to the present the TPEs that does not comprise PVB.
Summary of the invention
The present invention is a kind of thermoplastic elastomer (TPE) composition, and it contains crosslinked polyvinyl butyral acetal (PVBX) and thermoplastic polymer, and wherein thermoplastic polymer is the external phase of TPE, and elastomeric PVB X is dispersed in the external phase.
On the other hand, the present invention is the method that a kind of preparation contains the PVBX elastomer compositions that is scattered in the thermoplastic polymer external phase, this method may further comprise the steps: in the presence of thermoplastic polymer, use the cross-linking modified nonadherent PVB composition of linking agent to form PVBX, formed PVBX as the dispersive elastomerics be present in thermoplastic polymer mutually in.
The TPE blend of blending PVB is can be desirable, because compare with conventional TPEs, PVB can increase adhesive power, the minimizing color of TPEs of the present invention and increase polarity, thereby improves oil-proofness.
Detailed Description Of The Invention
In one embodiment, the present invention is a kind of TPE, and it comprises crosslinked polyvinyl butyral acetal (PVBX) elastomerics, and this PVBX is that nonadherent polyvinyl butyral acetal (PVB) composition by modification obtains.Unmodified PVB is the glue that a kind of energy flows and is brought together, and its meeting adhesion is usually when temperature is higher than about 4 ℃ (about 40 °F).For this reason, be difficult to PVB is transformed into intermingling material, especially by the successive method.The modification PVB that is applied in the present invention's practice is free-pouring, does not have adhesion (non-adhesion) when temperature is higher than about 4 ℃.The modification PVB composition that is fit to is on the books in U.S. Provisional Patent Application sequence number 60/224126, is incorporated herein its whole disclosures as a reference.
Be applicable to that the modification PVB that the present invention puts into practice can be purchased.For example, can buy trade name from E.I.DuPontde Nemours and Company (DuPont) is ECOCITE
TMModification PVB.The properties-correcting agent that is suitable for the object of the invention comprises for example Fusabond P MD-353D, Fusabond A MG-423D and Fusabond E MB-496D, the DuPont supply.
The PVB of modification can use and anyly can carry out crosslinked with the linking agent of the hydroxyl reaction of PVB.The linking agent of Shi Yonging is the molecule of any polyfunctionality herein, thereby wherein the functional group of this linking agent is the type that can form the cross-linked network of PVB polymer molecule with the hydroxyl reaction of PVB.The linking agent that is fit to comprises for example polycarboxylic acid and/or its functional equivalents of binary, ternary and quaternary carboxylic acid.For the functional equivalents of the carboxylic acid of the object of the invention comprises for example carboxylicesters, carboxylic acid anhydride and mixed acid anhydride, carboxylic acid halides, alkyl sulfonic ester and lactone.Linking agent with mixed functionality may be adapted at using here.Those skilled in the art will know that other useful linking agent that is fit to here, and do not repel and use these linking agents in the present invention because list these linking agents herein.The linking agent that is fit to for example comprises: hexanodioic acid, Succinic Acid, toxilic acid, citric acid, ethylenediamine tetraacetic acid (EDTA) (EDTA), Succinic anhydried, maleic anhydride, Tetra hydro Phthalic anhydride, 1,2, the 4-benzenetricarboxylic anhydride, pyromellitic dianhydride (PMDA), benzophenone tetracarboxylic dianhydride (BTDA), methyl vinyl ether-maleic acid copolymer, styrene-maleic anhydride copolymer, the isomer of terephthalic acid, Succinic Acid half methyl esters, 4,4 '-methylenediphenyl diisocyanates (MDI), 2,4-tolylene diisocyanate (TDI), the vulcabond oligopolymer, the end capped polypropylene glycol of TDI for example, the end capped polyethylene glycol adipate of TDI, TDI is end capped to gather 1, the end capped polyoxyethylene glycol of 4-butyleneglycol and/or TDI, naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), PPDI (PPDI).The linking agent that is fit to for example can also comprise: diepoxides, as glycerin diglycidyl ether, neopentyl glycol glycidyl ether, bisphenol A diglycidyl ether, polypropylene glycol diglycidyl ether, diglycidyl ether of ethylene glycol, 1,4-butanediol diglycidyl ether and polyethyleneglycol diglycidylether.The linking agent that is fit to for example can also comprise: silane, and as 3-aminopropyl triethoxysilane, vinyltriethoxysilane, vinyltrimethoxy silane.The linking agent that is fit to for example can also comprise: resol, and as octyl phenol-formaldehyde resin, dihydroxymethyl resol.The linking agent that is fit to for example can also comprise: melamine resin.
PVBX is a kind of elastomerics, and it can be in PVB or modification PVB and linking agent reaction back formation.The conventional use of PVB in blend polymer is difficult, so preferably use the PVB of modification in practice of the present invention.
The PVBX quantity that is contained among the TPE can account for about 1wt% of TPE gross weight to about 99wt%.The quantity of preferred PVBX is that about 25wt% arrives about 95wt%, and preferred quantity is that about 50wt% arrives about 90wt%, and most preferred quantity is that about 75wt% is to about 90%.
Thermoplastic polymer can be any formation discrete mutually but demonstrate polymkeric substance with PVB or modification PVBK functional compatibility.For example, thermoplastic polymer can be a polyolefine, as polypropylene or polyethylene, comprises high density polyethylene(HDPE) (HDPE); Polyvinyl chloride; Polymeric amide; Polycarbonate; Polyacrylic acid; Polyacrylic ester; Polymethylmethacrylate; Polystyrene; Styrol copolymer; Polyvinylidene dichloride; Polyester; Polyacetal; Copolyesters; And polysulfones.The content of thermoplastic polymer can be that about 99wt% arrives about 1wt%, and preferred quantity is that about 75wt% arrives about 5wt%, and more preferably approximately 50wt% is to about 10wt%, and most preferably about 25wt% is to about 10wt%.
In another embodiment, the present invention is the method that preparation contains the TPE of PVBX and thermoplastic polymer.In the present invention, modification PVB is crosslinked to form the PVBX elastomerics among the present invention.The PVB of modification can obtain from PVB and properties-correcting agent reaction, and perhaps the PVB of modification can be purchased.The preparation of modification PVB is described in U.S. Provisional Patent Application sequence number 60/224126 in detail.For example, in order to prepare modification PVB, can heat PVB in the presence of properties-correcting agent, properties-correcting agent has the anhydride functional group of hydroxyl activity group such as Fusabond P, and Fusabond P can buy from E.I.DuPont de Nemours and Company.
According to the character of linking agent, the catalyzer that is used for crosslinking reaction can be inessential.The preferred catalyzer that uses is to promote crosslinking reaction.According to the characteristic and the functionality of linking agent, those skilled in the art will know that what catalyzer is fit to.For example, if linking agent be polycarboxylic acid then can use conventional esterifying catalyst, if linking agent is ester then can uses conventional transesterification catalyst.For example, divalent tin catalysts is suitable for here using.For example stannous octoate, stannous acetate and tin protochloride are the useful catalyzer of purpose described herein.On the contrary, peroxide catalyst not effect in practice of the present invention.The quantity of the catalyzer that adds also depends on the character of reactant.The amount of catalyzer that one skilled in the art will appreciate that general adding is many more, and reaction will take place soon more.Determine the appropriate level of the needed catalyzer of concrete crosslinking reaction to belong to those of ordinary skills' technology category.
Can add other optional component, as antioxidant, pigment, dyestuff, filler, softening agent etc.For example, filler such as carbon black, talcum powder, lime carbonate and clay are suitable for here using.Softening agent such as dimixo-octyl phthalate (DINP), di(2-ethylhexyl)azelate, adipate polyester, nonane diacid polyester, tri trimellitate-2-ethylhexyl also are adapted at using here.The antioxidant that is suitable for using herein comprises Ciba Specialty Chemicals, the Ethanox 702 of the Irganox 1010 of Inc. supply and Albemarle Corp. supply.
Preferably, TPEs of the present invention have greater than 800psi tensile strength (maximum) and greater than 200% elongation.
Embodiment
Propose just illustrative purposes for example of embodiment and Comparative Examples, do not intend limiting the scope of the invention by any way.
In an embodiment, for each mixture, except linking agent, each component all 200 ℃ with 100-150rpm in the Haake/Brabender mixing roll according to the ratio blend shown in the table 1, become even up to mixture.Be warmed up to 230 ℃ and in blend, add linking agent then, continue to mix 2 minutes in the stable back of moment of torsion.Every kind of mixture shifts out the back from mixing roll and flattens rapidly, quenching in dry ice, then in vacuum drying oven in drying at room temperature.Comparative Examples does not contain hexanodioic acid.
Table 1
| Component | Embodiment 1 a Wt.％ | Embodiment 2 Wt.% | Embodiment 3 Wt.% | Embodiment 4 Wt.% |
| Polypropylene 1 | 13.9 | 13.7 | 13.6 | 13.4 |
| PVB | 83.2 | 82.1 | 81.5 | 80.4 |
| Fusabond P 2 | 2.8 | 2.7 | 2.7 | 2.7 |
| Stannous acetate | 0 | 0.7 | 0.7 | 0.7 |
| Hexanodioic acid | 0 | 0.7 | 1.4 | 2.7 |
| Irganox1010 | 0.1 | 0.1 | 0.1 | 0.1 |
1Profax 6323
2MD-353D
aComparative Examples is not the embodiment of the invention.
Blend is tested, and the result provides in table 2.
Table 2
| Performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| MI 1190℃，2160g | 4.8 | 0.6 | 0.2 | 0.0 |
| MI 1190℃，21.6kg | - | - | 67 | 14 |
| Ultimate tensile strength (PSI) | 3817 | 3106 | 3315 | 869 |
| Maximum elongation rate (%) | 285 | 243 | 243 | 89 |
| Shore hardness A (0/15 second) | 77/68 | 81/72 | 85/74 | 82/68 |
| Shore hardness D (0/15 second) | 54/23 | 53/22 | 54/25 | 53/22 |
| Compression set 2(％) | 48/113 | 46/113 | 42/106 | 32/75 |
1The MI=melt index
2At 23 ℃ and 100 ℃
As the blend of describing in the preparation table 3 as described in the embodiment in the his-and-hers watches 1, but all the components except that DINP be 180 ℃ of blend up to uniformly, add DINP and blend 1 minute then.Sample shifts out, flatten, quenching in dry ice, then in vacuum drying oven in drying at room temperature.
The peroxide cross-linking agent of table 3 is invalid when crosslinked PVB, and this can obtain proof by melt index and not remarkable minimizing of compression set.
Table 3
| Component | Embodiment 5 a Wt.％ | Embodiment 6 a Wt.％ | Embodiment 7 a Wt.％ | Embodiment 8 a Wt.％ |
| Polyvinyl chloride | 16.1 | 16.1 | 16.0 | 15.9 |
| PVB | 64.5 | 64.3 | 64.1 | 63.7 |
| Fusabond MG 423D | 3.2 | 3.2 | 3.2 | 3.2 |
| DINP | 16.1 | 16.1 | 16.0 | 15.9 |
| Luperco 231 XL | 0 | 0.32 | 0.64 | 1.27 |
1E80428-68
aComparative Examples is not the embodiment of the invention.
Blend is tested, and the result provides in table 4.
Table 4
| Performance | Embodiment 5 a | Embodiment 6 a | Embodiment 7 a | Embodiment 8 a |
| MI 1190℃，2160g | 0.7 | 1.3 | 1.4 | 3.5 |
| MI 1190℃，21.6kg | 192 | 207 | 192 | 295 |
| Ultimate tensile strength (PSI) | 2584 | 2405 | 2534 | 2323 |
| Maximum elongation rate (%) | 342 | 339 | 346 | 346 |
| Shore hardness A (0/15 second) | 82/68 | 80/64 | 78/63 | 76/60 |
| Shore hardness D (0/15 second) | 51/20 | 45/17 | 50/18 | 45/16 |
| Compression set 2(％) | 49/96 | 49/101 | 44/111 | 47/106 |
1The MI=melt index
2At 23 ℃ and 100 ℃
aComparative Examples is not the embodiment of the invention.
The linking agent of table 5 is effective linking agents, compares with the Comparative Examples 8 in the table 6, and the minimizing of melt index and compression set has proved this point.
Table 5
| The embodiment numbering | PP 1 | Mod G 2 | MDI 3 | TDI 4 | PEA(TDI) 5 | BTDA 6 | EGDE 7 | A-1100 silane 8 | R-7500 9 |
| 8 | 50 | 50 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| 9 | 49.5 | 49.5 | 1.0 | 0 | 0 | 0 | 0 | 0 | 0 |
| 10 | 46.5 | 46.5 | 0 | 7.0 | 0 | 0 | 0 | 0 | 0 |
| 11 | 41.7 | 41.7 | 0 | 0 | 16.7 | 0 | 0 | 0 | 0 |
| 12 | 49.5 | 49.5 | 0 | 0 | 0 | 1 | 0 | 0 | 0 |
| 12A | 47.6 | 47.6 | 0 | 0 | 0 | 4.8 | 0 | 0 | 0 |
| 13 | 43.5 | 43.5 | 0 | 0 | 0 | 0 | 13.0 | 0 | 0 |
| 14 | 45.5 | 45.5 | 0 | 0 | 0 | 0 | 0 | 9.0 | 0 |
| 15 | 41.7 | 41.7 | 0 | 0 | 0 | 0 | 0 | 0 | 16.6 |
1Profax 6323;
2See Table 6;
34,4 '-methylenediphenyl diisocyanates;
42,4 toluene diisocyanate;
5The end capped poly-hexanodioic acid second diester of TDI;
6Benzophenone tetracarboxylic dianhydride;
7Ethylene glycol diglycidylether;
8The 3-aminopropyl triethoxysilane;
9Octyl phenol-formaldehyde resin
Table 6
| The embodiment numbering | Melt index 1 | Melt index 2 | Shore hardness D | 70 ℃ of compression sets |
| 8 | 6 | 124 | 58 | 93 |
| 9 | 0 | 10 | 62 | 82 |
| 10 | 0 | 16 | 67 | 81 |
| 11 | 0 | 18 | 50 | 81 |
| 12 | 0 | 19 | 63 | 80 |
| 12A | 0 | 11 | 65 | 83 |
| 13 | 0 | 30 | 49 | 93 |
| 14 | 0 | 22 | 64 | 90 |
| 15 | 0 | 48 | 63 | 90 |
1190℃，2160g
2190℃，10kg
Claims (18)
1. a thermoplastic elastomer (TPE) composition, it contains crosslinked polyvinyl butyral acetal (PVBX) and thermoplastic polymer, and wherein thermoplastic polymer is the external phase of TPE, and elastic PVBX is scattered in the external phase.
2. the composition of claim 1, wherein the quantity that exists of PVBX is that about 25wt% is to about 95wt%.
3. the composition of claim 2, wherein the quantity that exists of PVBX is that about 50wt% is to about 90wt%.
4. the composition of claim 3, wherein the quantity that exists of PVBX is that about 75wt% is to about 90wt%.
5. the composition of claim 1, wherein PVBX is the product that modification PVB and linking agent carry out crosslinking reaction, described linking agent is selected from: polycarboxylic acid or its functional equivalents; Vulcabond; With the vulcabond oligopolymer.
6. the composition of claim 1, wherein external phase is at least a thermoplastic polymer that is selected from following polymers: polypropylene; Polyethylene; Polyvinyl chloride; Polystyrene; Polymeric amide; Polycarbonate; Polyacrylic acid; Polyacrylic ester; Polymethylmethacrylate; Styrol copolymer; Polyvinylidene dichloride; Polyester; Polyacetal; Copolyesters; And polysulfones.
7. the composition of claim 6, wherein external phase is polypropylene or polyvinyl chloride.
8. the composition of claim 7, wherein external phase is polypropylene.
9. the composition of claim 1, wherein the quantity that exists of thermoplastic polymer is that about 75wt% is to about 5wt%.
10. the composition of claim 9, wherein the quantity that exists of thermoplastic polymer is that about 50wt% is to about 10wt%.
11. the composition of claim 10, wherein the quantity of thermoplastic polymer existence is that about 25wt% is to about 10wt%.
12. one kind prepares the method that contains the PVBX elastomer compositions that is scattered in the thermoplastic polymer external phase, this method may further comprise the steps: when thermoplastic polymer exists, in crosslinking reaction, use the cross-linking modified nonadherent PVB composition of a kind of linking agent to form PVBX, formed PVBX as the dispersive elastomerics be present in thermoplastic polymer mutually in.
13. the method for claim 12, wherein linking agent is a kind of following reagent that is selected from: polycarboxylic acid or its functional equivalents; Vulcabond; With the vulcabond oligopolymer.
14. the method for claim 13 wherein uses catalyzer to react with catalytic crosslinking.
15. one kind prepares the method that contains the PVBX elastomer compositions that is scattered in the thermoplastic polymer external phase, this method comprises following step: (1) mixes PVB, thermoplastic polymer and PVB properties-correcting agent; (2) in the presence of thermoplastic polymer modification PVB to form the nonadherent PVB/ thermoplastic polymer mixtures of modification; (3) thus form PVBX with the cross-linking modified nonadherent PVB/ thermoplastic polymer composition of linking agent, this PVBX as the dispersive elastomerics be present in thermoplastic polymer mutually in.
16. a resilient, crosslinked polyvinyl butyral acetal composition (PVBX), it is to obtain by the method that comprises the steps: (1) heats PVB to obtain nonadherent PVB composition in the presence of properties-correcting agent; (2) the PVB composition of heat modification is to obtain elastic PVBX in the presence of PVB linking agent and catalyzer, and wherein condition is enough to make between PVB and the linking agent crosslinking reaction takes place.
17. goods by the TPE preparation of compositions of claim 1.
18. the goods of claim 17, wherein these goods are flexible pipe, pipe, liner, sealing, sheet material, band, electric wire and cable shell, wheel, sole, film or handle.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US42945602P | 2002-11-27 | 2002-11-27 | |
| US60/429,456 | 2002-11-27 | ||
| US10/721,531 | 2003-11-25 |
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| CN1717449A true CN1717449A (en) | 2006-01-04 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967249A (en) * | 2010-09-29 | 2011-02-09 | 广州市奥吉斯新材料有限公司 | Toughening polystyrene, preparation method thereof and use thereof |
| CN102174238A (en) * | 2011-03-04 | 2011-09-07 | 浙江德斯泰塑胶有限公司 | Formula for preparing high-strength PVB (Polyvinyl Butyral) sheet |
| CN107163508A (en) * | 2017-06-02 | 2017-09-15 | 叶剑明 | A kind of copolymerization polycarbonate composition of stress crack resistant and preparation method thereof |
-
2003
- 2003-11-26 CN CN 200380104176 patent/CN1717449A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967249A (en) * | 2010-09-29 | 2011-02-09 | 广州市奥吉斯新材料有限公司 | Toughening polystyrene, preparation method thereof and use thereof |
| CN102174238A (en) * | 2011-03-04 | 2011-09-07 | 浙江德斯泰塑胶有限公司 | Formula for preparing high-strength PVB (Polyvinyl Butyral) sheet |
| CN107163508A (en) * | 2017-06-02 | 2017-09-15 | 叶剑明 | A kind of copolymerization polycarbonate composition of stress crack resistant and preparation method thereof |
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