CN1315982A - Foams prepared from blends of syndiotactic polypropylenes and thermoplastic polymers - Google Patents
Foams prepared from blends of syndiotactic polypropylenes and thermoplastic polymers Download PDFInfo
- Publication number
- CN1315982A CN1315982A CN99810453A CN99810453A CN1315982A CN 1315982 A CN1315982 A CN 1315982A CN 99810453 A CN99810453 A CN 99810453A CN 99810453 A CN99810453 A CN 99810453A CN 1315982 A CN1315982 A CN 1315982A
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- Prior art keywords
- porous plastics
- resin
- polymer blend
- weight
- spp
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000000203 mixture Substances 0.000 title claims abstract description 150
- 239000006260 foam Substances 0.000 title claims abstract description 92
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 67
- -1 polypropylenes Polymers 0.000 title abstract description 24
- 239000004743 Polypropylene Substances 0.000 title abstract description 15
- 229920001155 polypropylene Polymers 0.000 title abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 266
- 239000011347 resin Substances 0.000 claims abstract description 266
- 239000002952 polymeric resin Substances 0.000 claims abstract description 41
- 229920003023 plastic Polymers 0.000 claims description 306
- 239000004033 plastic Substances 0.000 claims description 306
- 239000003795 chemical substances by application Substances 0.000 claims description 64
- 229920002959 polymer blend Polymers 0.000 claims description 49
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 36
- 206010000269 abscess Diseases 0.000 claims description 32
- 238000001125 extrusion Methods 0.000 claims description 32
- 229920002313 fluoropolymer Polymers 0.000 claims description 28
- 239000004811 fluoropolymer Substances 0.000 claims description 28
- 239000011324 bead Substances 0.000 claims description 27
- 239000004416 thermosoftening plastic Substances 0.000 claims description 22
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 17
- 229920001519 homopolymer Polymers 0.000 claims description 17
- 239000000155 melt Substances 0.000 claims description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 15
- 239000004793 Polystyrene Substances 0.000 claims description 13
- 239000005977 Ethylene Substances 0.000 claims description 12
- 229920005672 polyolefin resin Polymers 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 210000000689 upper leg Anatomy 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- 235000011089 carbon dioxide Nutrition 0.000 claims description 4
- 229920001684 low density polyethylene Polymers 0.000 claims description 3
- 239000004702 low-density polyethylene Substances 0.000 claims description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 238000009413 insulation Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 56
- 238000002360 preparation method Methods 0.000 description 40
- 238000000034 method Methods 0.000 description 36
- 238000005187 foaming Methods 0.000 description 28
- 238000001816 cooling Methods 0.000 description 27
- 238000002156 mixing Methods 0.000 description 22
- 239000002861 polymer material Substances 0.000 description 22
- 239000000126 substance Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 20
- 230000032683 aging Effects 0.000 description 19
- 210000004027 cell Anatomy 0.000 description 13
- 239000002984 plastic foam Substances 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- 238000013016 damping Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000004088 foaming agent Substances 0.000 description 10
- 229920002223 polystyrene Polymers 0.000 description 10
- 238000012856 packing Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 229920000098 polyolefin Polymers 0.000 description 8
- 239000002937 thermal insulation foam Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 230000005855 radiation Effects 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 230000035939 shock Effects 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 238000007664 blowing Methods 0.000 description 5
- 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 5
- 230000004927 fusion Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000001757 thermogravimetry curve Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000009102 absorption Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 238000010923 batch production Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920005990 polystyrene resin Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000003856 thermoforming Methods 0.000 description 4
- 239000004604 Blowing Agent Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000002253 acid Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- WXGNWUVNYMJENI-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)F WXGNWUVNYMJENI-UHFFFAOYSA-N 0.000 description 2
- BOUGCJDAQLKBQH-UHFFFAOYSA-N 1-chloro-1,2,2,2-tetrafluoroethane Chemical compound FC(Cl)C(F)(F)F BOUGCJDAQLKBQH-UHFFFAOYSA-N 0.000 description 2
- 241001253206 Andrias Species 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 229920003345 Elvax® Polymers 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
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- 238000005469 granulation Methods 0.000 description 2
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- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000004620 low density foam Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- KDWQLICBSFIDRM-UHFFFAOYSA-N 1,1,1-trifluoropropane Chemical compound CCC(F)(F)F KDWQLICBSFIDRM-UHFFFAOYSA-N 0.000 description 1
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- BHNZEZWIUMJCGF-UHFFFAOYSA-N 1-chloro-1,1-difluoroethane Chemical compound CC(F)(F)Cl BHNZEZWIUMJCGF-UHFFFAOYSA-N 0.000 description 1
- YACLCMMBHTUQON-UHFFFAOYSA-N 1-chloro-1-fluoroethane Chemical class CC(F)Cl YACLCMMBHTUQON-UHFFFAOYSA-N 0.000 description 1
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 1
- BRIQSYPMWHUJGW-UHFFFAOYSA-N 2,2-difluoropropane Chemical compound [CH2]C(C)(F)F BRIQSYPMWHUJGW-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- KLZDCUBZWUSEGO-UHFFFAOYSA-N CC.F.F.F.F.F Chemical compound CC.F.F.F.F.F KLZDCUBZWUSEGO-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 101100168796 Mus musculus Cspp1 gene Proteins 0.000 description 1
- TXAMMAGYRNMFNW-UHFFFAOYSA-N NN.C1=CC=CC=C1.[S] Chemical compound NN.C1=CC=CC=C1.[S] TXAMMAGYRNMFNW-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
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- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
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- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
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Abstract
Foams prepared from a blend of a syndiotactic polypropylene (sPP) resin and a foamable thermoplastic polymer resin are provided which exhibit a combination of desirable properties which have heretofore been difficult, if not impossible, to achieve. The foams of the present invention are useful in applications such as thermal insulation, packaging, and the formation of molded articles such as cups, and trays.
Description
The present invention relates generally to porous plastics, relate more specifically to porous plastics by syndiotactic polypropylene and foamable thermoplastic polymer resin's blend preparation.
Porous plastics is used for various uses, comprises that thermal isolation, packing reach the formation such as moulded partss such as cup and plates.According to the end-use of porous plastics, the expectation porous plastics represents the combination of specific character or character.For example, when as insulating material or amortizing packaging material, it is quite expectation that porous plastics expand into low density.
In addition, the porous plastics with high texturing temperature is desired for several applications, comprises the insulation in the hot environment.Wait the special use of insulation foam according to this and decide, it also expects these porous plastics except that having high texturing temperature also is flexible.Degree of flexibility and thermal distortion demand are decided according to the end-use of insulation foam.For example, in the use of some automobile or when being used for the insulation of hot-water line, need have and be higher than 90 ℃ or in the flexible foam of some situation greater than 110 ℃-120 ℃ heat-drawn wire.In addition, for meeting underwriter laboratory test UL1191 appendix A, as the porous plastics of filler in the individual floatation device except that needs very soft and tool flexible, also need to resist for a long time 60 ℃ temperature.
But it is difficult to reach flexible (that is low elastic modulus) and the character of high heat-drawn wire in the same foam plastics.Typically, the heat-drawn wire of flexible (that is the Young's modulus) of given resin and resin is all directly related with the fusing point of resin.In other words, (that is, high flexible) resin needs resin to have lower fusing point usually, and the resin with high texturing temperature needs resin to have high melt point usually to have low elastic modulus.In addition, even find the character of flexible and high heat-drawn wire in identical resin or resin blend, resin or resin blend also may not foam, and maybe can not foam by the method that makes things convenient for such as extrusion method.Branched polyolefin resin by the preparation of high-pressure free radical method can become flexible foam by extrusion foaming, but porous plastics is used the shortage temperature tolerance for some.The example of branched polyolefin resin comprises that having density range is 0.915g/cm
3To 0.932g/cm
3The low density polyethylene homopolymer resin, and the multipolymer of ethene and vinyl ester (such as vinyl-acetic ester and methyl acrylate).By catalysis process (for example, use Ziegler-Natta type or metallocene catalyst) the line type polyolefin homopolymer resin of preparation (such as, high density polyethylene(HDPE) and isotatic polypropylene (iPP) resin) has higher heat-drawn wire, but be difficult to foam by extrusion method.In addition, the porous plastics that waits the toughness homopolymer resin to make thus lacks flexible.The less linear copolymers resin of toughness can make by catalysis process, but this resin experience same shortage as homopolymer is expandable.The use temperature of polyolefin resin foam plastics can be by crosslinked increase.For example, can under the temperature that is higher than uncrosslinked porous plastics, use, but use temperature (it is lower than 100 ℃) is not high enough for some application from the crosslinked plastic foam that ldpe resin makes.In addition, the high and recovery that can not circulate of the preparation cost of crosslinked plastic foam.
From the high melting-point polyolefins resin (for example, high density polyethylene(HDPE) and iPP) porous plastics that makes with the blend of new LDPE (film grade) (LDPE) is difficult to expand into low-density foam by extrusion method, the freezing transfer of the resin with high melting point that depends on the foaminess difference because porous plastics expands.When being applied to cross-linking method, this blend causes another kind of difficulty.In the method, foamable composition is extruded into sheet material in low temperature, and wherein whipping agent and linking agent keep not being activated basically.Usually, the required processing temperature of dystectic line type polyolefin surpasses the ultimate temperature of whipping agent and linking agent, and may make its activation prematurely.
But, decide according to specific end-use, be not to expect that all insulation foam is a flexible.Rigid foamed plastics with high texturing temperature is also for desired.The rigid insulation porous plastics is generally made by alkyl aromatic polymkeric substance (such as, polystyrene), and it is because the consideration of environment, increases with carbonic acid gas and expands.But, represent little abscess-size with carbon dioxide expanded low-density foam (such as, polystyrene).
But, can be easy to be shaped and be easy to preparation by extrusion method easily for making rigid foamed plastics, need make porous plastics have the abscess-size of expansion.Porous plastics with small cells size not only is difficult to be extruded into the large section, and also is difficult to processing (for example, sheet or be cut into final shape).For making it be easy to preparation, expectation makes porous plastics have abscess-size greater than 0.4mm.
Existing many effort are in order to prepare the alkyl aromatic porous plastics (referring to for example United States Patent (USP) 4,229,396 and 5,489,407) of the abscess-size with expansion by adding the various additives that are used to enlarge abscess-size.But typical abscess enlarges the heat-drawn wire that additive is difficult to add in the forcing machine and is easy to influence foam article.
Except that insulation foam with high texturing temperature (it is 1) flexible or 2) rigidity and have the abscess-size of expansion), being higher than the flexible foam that 0 ℃ thermoplastic polymer makes by Tg is to need noise and shock damping and desired in order to the end-use of damping packing.When being used for damping packing or shock damping, flexible foam is protected goods by the impact and the vibration energy that absorb in its foam structure.This energy is absorbed in gas phase and the polymer phase.Porous plastics with cell wall of the heat of irreversibly mechanical energy being dispersed into is desired.Fluoropolymer resin the second-order transition temperature (Tg) of resin can disperse most effectively down mechanical energy (referring to for example polymer property, the third edition, the 14th chapter, " acoustic properties ", D.w.VanKrevelen, Elsevier, Amserdam-London, New York-Tokyo, 1990).Most of conventional polyolefins resin (such as, polyethylene and polypropylene) be flexible, but have lower Tg, that is, be lower than 0 ℃, thereby, can not be used for the end-use of damping packing or shock damping.
Therefore, still there is following demand in this area: the flexible foam that 1) has high texturing temperature; 2) have the high rigidity alkyl aromatic porous plastics that is out of shape the abscess-size of heat and expansion, it is easy to preparation, and distortion heat is stable therebetween; And 3) be higher than the flexible thermoplastic porous plastics that 0 ℃ thermoplastic polymer makes from Tg.
Can satisfy these needs by the present invention.Therefore, the invention provides the prepared polymer foam of blend by syndiotactic polypropylene (sPP) resin and foamable thermoplastic polymer resin.
Therefore, in first embodiment of the present invention, provide the polymer foam from the blend preparation of sPP resin and flexible thermoplastic fluoropolymer resin, it is a flexible, and has high texturing temperature.Can be used as insulation foam in the hot environment that needs flexible foam according to the polymer foam of first embodiment of the invention, use and the insulation of hot-water line such as, some automobile.In addition, because the sPP resin has 4 ℃ Tg, so also be applicable to as damping packing or noise or shock damping product according to the polymer foam of first embodiment of the invention.
Typical polymer blend porous plastics according to first embodiment is as follows:
The polymer blend porous plastics comprises: a) the sPP resin of 0.1 weight % to 60 weight %; And b) the flexible thermoplastic fluoropolymer resin of 40 weight % to 99.9 weight %;
The polymer blend porous plastics comprises: a) the sPP resin of 10 weight % to 50 weight %; And b) the flexible thermoplastic fluoropolymer resin of 50 weight % to 90 weight %; And
The polymer blend porous plastics comprises: a) the sPP resin of 30 weight % to 50 weight %; And b) the flexible thermoplastic fluoropolymer resin of 50 weight % to 70 weight %.
In second embodiment of the present invention, the polymer foam by the blend preparation of sPP resin and rigid thermoplastic polymer resin is provided, it is an inflexible, has high texturing temperature, and has the abscess-size of expansion.SPP resin additive in order to the abscess-size that enlarges the rigid thermoplastic polymer porous plastics is easy to add in the forcing machine, and can not influence the heat-drawn wire of porous plastics.
Typical polymer blend porous plastics according to second embodiment of the invention is as described below:
The polymer blend porous plastics comprises: a) the sPP resin of 0.1 weight % to 60 weight %; And b) the rigid thermoplastic polymer resin of 40 weight % to 99.9 weight %; And
The polymer blend porous plastics comprises: a) the sPP resin of 0.2 weight % to 5 weight %; And b) the rigid thermoplastic polymer resin of 95 weight % to 99.8 weight %.
Fig. 1 describes the differential scanning calorimetric thermogram after foundation porous plastics of the present invention is extruded.
Fig. 2 is the differential scanning calorimetric thermogram that is described in 120 ℃ of aging foundation porous plastics of the present invention after 5 days.
The invention provides porous plastics by sPP resin and thermoplastic polymer resin's blend preparation.Polymer blend porous plastics of the present invention represents the combination of required character, and it was reached in being difficult to (if not can not time) in the past.
For example, first embodiment of the present invention provides the polymer foam by the blend preparation of sPP resin and flexible thermoplastic fluoropolymer resin, and it is a flexible, and has high texturing temperature., use and the insulation of hot-water line as the insulation foam in the hot environment that needs flexible foam according to the polymer blend porous plastics of first embodiment of the invention such as some automobile.The dimensional stability of the flexible insulation foam of first embodiment of the invention only is better than from the porous plastics of flexible thermoplastic fluoropolymer resin preparation.As previously mentioned, the flexible foam with high heat distortion temperature prepares as the expandable thermoplastic polymer resin in the blend by using the flexible thermoplastic fluoropolymer resin.Though do not desire to be subject to any particular theory, believe that the interpolation of sPP resin makes the blend foam plastics have high heat-drawn wire, and cause the porous plastics expansible that comes from the slow crystallization rate of resin seldom to disturb.The slow crystallization rate of sPP (represent injection molding long cycling time problem) is advantageously used in the preparation of porous plastics of the present invention.Because crystallization rate slowly, sPP resin can crystallizations under the blowing temperature of flexible thermoplastic fluoropolymer resin, but at ambient temperature or the porous plastics for preparing first embodiment of the invention by blend and stable after the heating period second time between crystallization.In case crystallization, sPP resin component provides the porous plastics of the blend with high deformation heat, and this is because crystalline high-melting-point (that is, 130 ℃).This phenomenon confirms by the dsc of Figure 1 and Figure 2.Fig. 1 describe according to of the present invention by 50/50 weight the LDPE resin and the differential scanning calorimetric thermogram of the porous plastics of the resin extruded preparation of sPP, it is shown in about 113 ℃ of heat absorptions, and does not have heat absorption when about 130 ℃ (sPP crystalline fusing point).The porous plastics that Fig. 2 describes Fig. 1 is in about 120 ℃ of differential scanning calorimetric thermograms after aging 5 days, and it is shown in about 113 ℃ of heat absorptions, and heat absorption when about 130 ℃ (sPP crystalline fusing point).Differential scanning calorimetric thermogram confirmation LDPE resin and sPP resin illustrated in figures 1 and 2 are immiscible mixed, and the sPP resin in the blend carries out crystallization between about 120 ℃ heating period.
In addition, the sPP resin component of blend is not crystallization fully between the aging time of porous plastics at ambient temperature, but pines for observing further crystallization in adding subsequently.Secondary crystal can be advantageously used in the thermoforming of foam article, because amorphous sPP molecule meets the distortion of plastic foam sheet material and shape, but further crystallization during thermoforming, thereby helps the curing of articles thermoformed therefrom.Interpolation sPP resin also promotes the dimensional stability of flexible foam.For example, find by sPP resin and the blend preparation of LDPE resin and with Trimethylmethane expansible porous plastics of the present invention than having more dimensional stability with Trimethylmethane expansible LDPE resin foam plastics.The dimensional stability of this increase is beat all, at least reported a kind of sPP resin and had low-crystallinity (about 30%) [referring to Wheat, w.R. the rheology of the syndiotactic polypropylene character " explain " ANTEC 95 Preprint] and to the higher perviousness [referring to Schardl, " syndiotactic polypropylene Overview Clear Impact polymkeric substance " ANTEC 95 Preprint of people such as J.] of gas and steam.
In addition, the insulating polymer porous plastics according to first embodiment of the invention also is suitable as damping packing or noise and shock damping product.The sPP resin has 4-6 ℃ Tg, thereby makes mechanical energy be dispersed into heat effectively.But independent sPP resin is difficult for foaming by extrusion method.By contrast, not only can foam according to the sPP resin of first embodiment of the invention and the blend of flexible thermoplastic fluoropolymer resin, and formed porous plastics also has the character of indivedual components resin.Therefore, the porous plastics that expection is made by this immiscible blend polymer has different Tg, thereby, expect that this porous plastics helps the noise and the shock damping of the frequency and the temperature of wide region.
Second embodiment of the invention provides the polymer foam by the blend preparation of sPP resin and rigid thermoplastic polymer resin, and it is an inflexible, has high texturing temperature, and has the abscess-size of expansion.Therefore, the polymer blend porous plastics of second embodiment of the invention is suitable for as the insulation foam in the application that needs the processing porous plastics.The sPP resin additive that is used to enlarge the abscess-size of rigid thermoplastic polymer porous plastics is easy to add in the forcing machine, and can not influence the heat-drawn wire of porous plastics.Do not know acrylic resin and at least a rigid thermoplastic polymer resin (such as, polystyrene) compatible (referring to for example United States Patent (USP) 4,386,187, embodiment 18 and 22, and United States Patent (USP) 5,460,818, embodiment 3), and the foaming and intumescing of incompatible polymers blend generally is difficult (referring to for example United States Patent (USP) 4 when not having compatible additive, 020,025), adding the sPP resin in polystyrene resin can not disturb, but help the expansion of polystyrene resin, this fact is unexpected.
In arbitrary embodiment of the present invention, sPP resin and foamable thermoplastic polymer resin are usually with 0.1: 99.9 to 60: 40 part by weight blend.In the first embodiment, wherein foamable thermoplastic polymer resin is the flexible thermoplastic fluoropolymer resin, and the sPP resin is 10: 90 to 50: 50 to the preferred proportion of flexible thermoplastic fluoropolymer resin, preferred 30: 70 to 50: 50 especially ratio.In second embodiment, wherein foamable thermoplastic polymer resin is the rigid thermoplastic polymer resin, and the sPP resin is 0.1: 99.9 to 5: 95 to the preferred proportion of rigid thermoplastic polymer resin.
The suitable sPP resin that is used for arbitrary embodiment comprises the multipolymer of all syndyotactic in fact alfons and propylene and polymerisable monomer.Typical example comprises the multipolymer of polyacrylic homopolymer, propylene and ethene, and the multipolymer of propylene and 1-butylene, these homopolymer and multipolymer preferably have 0.05dg/ and divide the melt flow rate (MFR) of dividing to 50dg/, and these homopolymer and multipolymer especially preferably have 0.1dg/ and divide the melt flow rate (MFR) of dividing to 10dg/.Also preferably has sPP resin greater than 75% degree of syndiotacticity.The example of suitable sPP resin is that to have melting index be 2dg/ branch (with ASTM D-1238 in 230 ℃/2.16 kilograms measurements), and density is 0.88g/cm
3And fusing point is 130 ℃ a sPP resin.The example of these sPP resins is co-polymer polypropylene resins of the syndiotaxy form of EOD-96-28 and EOD-96-07 grade, can be available from Fina Oil and chemical company.
Being applicable to that thermoplastic resin of the present invention comprises can be by all types of thermoplastic polymer of extrusion method foaming.The example that is applicable to the flexible thermoplastic fluoropolymer resin of first embodiment of the invention comprises (but being not limited thereto) flexible polyolefin resin, such as the LDPE resin, the ethylene resin, and iPP, wherein preferably have melting index and be 0.1dg/ and divide the resin that divides to 20dg/, and especially preferably to have melting index be that 0.2dg/ divides the resin that divides to 10dg/.In addition, when the flexible thermoplastic fluoropolymer resin was ethylene, vinyl acetate content was that 5% to 30% resin is preferred, and preferred especially vinyl acetate content is 8% to 20% resin.Moreover, when the flexible thermoplastic fluoropolymer resin is iPP, when the resin that is applied to have when tg δ is less than 1.5 extrusion method high fondant-strength is preferred, and (tg δ is the ratio of out-of-phase modulus to storage modulus to preferred especially tg δ less than 1.2 resin, its sample that is to use the thick and 25mm diameter of 2.5mm is measured in the vibration rate of 190 ℃ and 1 radian per second, as United States Patent (USP) 5,527, shown in 573).The example of suitable ethylene resin is ELVAX 460 resins, can derive from Du-Pont-Dow Inc..The example of suitable iPP resin is the iPP resin of the high fondant-strength of PRO-FAX PF-814 grade, can derive from Montell polyolefine Co.NV..The example that is applicable to the rigid thermoplastic polymer resin of second embodiment of the invention is the alkyl aromatic resin, such as, polystyrene resin.The example that is applicable to the suitable polystyrene of second embodiment of the invention is that molecular-weight average is less than 240,000 polystyrene.
Randomly, nucleator can be added in the foamable blend.The amount that is used to prepare the nucleator of porous plastics of the present invention changes according to the composition of required abscess-size, blowing temperature and nucleator.Useful nucleator comprises the mixture of lime carbonate, barium stearate, calcium stearate, talcum, clay, titanium dioxide, silicon-dioxide, barium stearate, diatomite, citric acid, and acid and sodium bicarbonate.When using, the consumption of nucleator can be in the scope of the per 100 parts by weight polymer resin blends (pph) of 0.01 to 5 weight part.
The whipping agent that is used to prepare porous plastics of the present invention comprises all types of whipping agent known in the art; Physics and chemical foaming agent and composition thereof comprise inorganic foaming agent, organic blowing agent and chemical foaming agent.Suitable inorganic foaming agent comprises carbonic acid gas, nitrogen, argon gas, water, air and helium.Organic blowing agent comprises the aliphatic hydrocrbon that contains 1-6 carbon atom, the fatty alcohol that contains 1 to 3 carbon atom, and contains the halogenated wholly or in part aliphatic hydrocrbon of 1 to 4 carbon atom.Aliphatic hydrocrbon comprises methane, ethane, propane, normal butane, Trimethylmethane, Skellysolve A, reaches iso-pentane, neopentane.Fatty alcohol comprises methyl alcohol, ethanol, n-propyl alcohol and Virahol.Halogenated wholly or in part aliphatic hydrocrbon comprises chlorine carbide, fluorine carbide and chlorofluorocarbons.Be used for chlorine carbide of the present invention and comprise methyl chloride, methylene dichloride, monochloroethane and 1.Be used for fluorine carbide of the present invention and comprise fluoromethane, methylene fluoride, fluoroethane, 1,1-C2H4F2 C2H4F2 (HFC-152a), 1,1,1-Halothane (HGC-143a), 1,1,1,2-Tetrafluoroethane (HFC-134a), 1,1,2,2-Tetrafluoroethane (HFC-134), pentafluoride ethane, R 116,2,2-difluoropropane, 1,1,1-trifluoro propane and 1,1,1,3, the 3-pentafluoropropane.Be used for partially halogenated chlorofluorocarbons of the present invention and comprise chlorodifluoromethane (HCFC-22), 1,1-two chloro-1-fluoroethanes (HCFC-141b), 1-chloro-1,1-C2H4F2 C2H4F2 (HCFC-142b), 1,1-two chloro-2,2,2-Halothane (HCFC-123) and 1-chloro-1,2,2,2-Tetrafluoroethane (HCFC-124).Complete halogenated chlorofluorocarbons also can use, but because environmental factors and not preferred.Be used for chemical foaming agent of the present invention and comprise nitrine two carboxamides, nitrine bis-isobutyronitrile, benzene sulphur hydrazine, 4,4-oxygen benzene sulfo group-semicarbazides, right-toluene sulfo group semicarbazides, N, N '-dimethyl-N, the mixture of N '-dinitrobenzene isophthaloyl amine and three hydrazine triazines, sodium bicarbonate and sodium bicarbonate and citric acid.The mixture of all these whipping agents also can be considered in the scope of the invention.The type of optimal whipping agent is according to deciding in order to the method and the required porous plastics density that prepare porous plastics.Be used for extrusion method and be pneumatogen, wherein preferred volatility organic blowing agent in order to the preferred whipping agent of the batch process for preparing mouldable bead.The preferred whipping agent that is used for the crosslinked foaming method is decomposable whipping agent and nitrogen.
The adding polymer melt material is the every kg of polymer of 0.1 to 5 gram mole with the amount of the whipping agent of the gel of preparation formation porous plastics, preferably 0.4-4 gram mole every kg of polymer, the most preferably every kg of polymer of 0.9-3 gram mole.
Porous plastics of the present invention is optional further to comprise infrared absorbent (transmission hold back agent), such as carbon black, graphite and titanium dioxide, to promote insulating power.During use, the consumption of infrared absorbent can be to be 1.0 to 25 weight % of benchmark with porous plastics interpolymer blend weight, preferred 4.0 to 10.0 weight %.Carbon black can be an any kind known in the art, and, acetylene black black such as furnace black, heat and pipeline are black.Preferred carbon black is that heat is black.Preferred hot black have 150nm or bigger median size.
Preferred porous plastics of the present invention represents dimensional stability.Though sPP resin itself is as stability control agent in some cases, but still expectation comprises the dimensional stability of extra stability control agent with further promotion porous plastics of the present invention.For example, when the sPP resin with the blend of polyethylene or ethylene resin in consumption be less than 30% and blend when expanding with Trimethylmethane, the stability control agent except that the sPP resin is desired.In the unicellular structure basically that is prepared thick (that is, greater than 4mm) sheet material and plate-like product (thicker than 12mm) by aforementioned blend, stability control agent is special expectation.Relatively, when forming basically open-cell foamed plastics, extra stability control agent may be unnecessary or not be expected.
Dimensional stability is measured the percentage of the initial volume of porous plastics by porous plastics volume between aging time, measures in porous plastics expanded back 30 seconds.Use this definition, 80% or the more porous plastics of replying initial volume in one month are endurable, and reply 85% or more porous plastics be preferred, reply 90% or more porous plastics be particularly preferred.Volume is measured by the volume displaced proper method such as water.
Preferred stability control agent comprises C
10-24The acid amides of lipid acid and ester.This reagent is found in United States Patent (USP) 3,644, and 230 and 4,214,054.Most preferred reagent comprises stearyl stearylamide, Zerol, glycerine list benzoic ether and Sorbitol Powder monostearate.Typically, the consumption of this stability control agent is in the scope of 0.1 to 10 part of per 100 parts of polymkeric substance.
Various additives can be added in the porous plastics of the present invention, such as, mineral filler, pigment, antioxidant, acid scavenger, UV light absorber, fire retardant, processing aid and extrusion aid.
Polymer blend porous plastics of the present invention can comprise extrusion method and batch process by technology known to the those skilled in the art and program preparation, and it is to use decomposable whipping agent and linking agent, preferred extrusion method.
Polymer blend porous plastics of the present invention can be crosslinked or uncrosslinked.Excellence instruction in order to the method for preparing polymer foam structure and processing treatment thereof is found in C.P.Park, " foamed polyolefine plastic ", the 9th chapter, polymer foam and technical manual, D.Klempner and K.C.Frisch edit, Hanser Publishers, Munich, Vienna, New York Barcelona (1991).
Uncrosslinked porous plastics of the present invention can be by traditional extrusion foaming method preparation.Foam structure generally is prepared as follows: the blend that heats premixed sPP resin and thermoplastic polymer resin (promptly, polymer materials) to form plasticizing or melt polymer material, form foamable gel to wherein adding whipping agent, and extrude this gel to form the porous plastics product via mould.Before whipping agent mixed, polymer materials was heated to the temperature of its Tg or fusing point or is higher than these temperature.Whipping agent can mix or sneak into melt polymer material by any methods known in the art, such as using forcing machine, mixing tank or blender.Whipping agent and melt polymer material are mixed under the elevated pressures of homodisperse whipping agent therein in being enough to avoid melt polymer material to expand in a large number and being enough to.Randomly, in the plasticizing or fusion before, nucleator can by blend in polymer melt or with the blend of polymer materials dry type.Foamable gel is cooled to lesser temps usually, so that the physical properties of foam structure reaches best.Then, the decompression or the zone of lower pressure are extruded or be delivered to gel via the mould of desired shape, to form foam structure.But the zone of lower pressure is a pressure is lower than the pressure that foamable gel is kept before extruding via mould.Lower pressure can be superatmospheric pressure or subatmospheric power (vacuum), but the preferred atmosphere voltage levels.
Uncrosslinked porous plastics of the present invention can the form with coalescent strand form by the sPP resin extruded through the branch manifold mould and thermoplastic polymer resin's pre-compounded blends (that is polymer materials).The configuration of manifold contacts the adjacent fluid that melt extrudes thing during foaming process, and contact surface is bonded to each other to form the foam structure of homogeneous with enough bondings.Melt extrude the form that the logistics body is taked line thigh or section bar from die orifice is effusive, it foams on demand, coalescent and bonded to each other to form homogeneous structural.Expect that coalescent individual wire thigh or section bar need to keep adhesion in homogeneous structural, to avoid the line thigh in preparing, be shaped and using delamination under the stress that porous plastics was met with.The device and method for preparing the foam structure of coalescent line thigh form can be referring to United States Patent (USP) 3,573, and 152 and 4,324,720.
Foam structure of the present invention also is configured as uncrosslinked foaming plastic bead, and it is suitable for being molded as goods.Foaming plastic bead can be by extrusion method or batch process preparation.In extrusion method, be attached to the porous plastics line thigh granulation that the porous mold of conventional foam plastics extrusion device comes out certainly and form foaming plastic bead.Foaming plastic bead, if need, in the fusing point that is lower than sPP resin heating down, so the sPP molecule is crystallizable, thereby forms false network structure, it provides the bursting apart property of heat resistanceheat resistant of foaming plastic bead.In batch process, discrete resin particle (such as granular resin particle) is suspended in the liquid medium, and they are insoluble in fact in liquid medium, such as, water; In autoclave or other pressurizing vessel, under elevated pressure and temperature, by whipping agent being introduced liquid medium and flooding with whipping agent; Drain into barometric point or depressor area fast and form foaming plastic bead with expansion.This method is instructed in United States Patent (USP) 4,379, and 859 and 4,464,484.
Crosslinked plastic foam of the present invention can be by using the crosslinked plastic foam method that can decompose porous plastics or passing through traditional extrusion method preparation.
When the application use can be decomposed the crosslinked plastic foam method of porous plastics, crosslinked plastic foam of the present invention can be prepared as follows: by with decomposable chemical foaming agent blend and heating sPP resin and thermoplastic polymer resin's pre-mixing blend (promptly, polymer materials) to form foamable plasticizing or melt polymer material, extrude this foamable melt polymer material via mould, be included in the melt polymer material crosslinked, and this melt polymer material is under the comparatively high temps, to discharge whipping agent to form foam structure.Polymer materials and chemical foaming agent can pass through any device mixing well known in the art and molten mixing, such as using forcing machine, mixing tank or blender.Chemical foaming agent be preferable over heated polymerizable thing material to the fusion form with the blend of polymer materials dry type, add in fusion mutually the time but also can work as polymer materials.Can be by adding linking agent or coming induced cross-linking by radiation.Induced cross-linking also is exposed under the comparatively high temps, so that foaming or expansion can take place simultaneously or successively produce.If use linking agent, it is to be added in the polymer materials in the mode identical with chemical foaming agent.Moreover if use linking agent, foamable melt polymer material is heated or is exposed to and preferably is lower than 150 ℃ temperature, to avoid linking agent or whipping agent to decompose and to avoid crosslinked too early.If use radiation crosslinking, foamable melt polymer material is heated or is exposed to and preferably is lower than 160 ℃ temperature, decomposes to avoid whipping agent.Foamable molten polymer is extruded or is carried to form foamable structure via the mould of desired shape.Then, but foaming structure in raise higher temperature (normally 150 ℃ to 250 ℃) is crosslinked down or expand (such as, in baking oven) to form foam structure.When using radiation crosslinking, but foaming structure by radiation so that polymer materials is crosslinked, then, expand down in above-mentioned comparatively high temps.Can use linking agent or radiation that structure is advantageously made sheet or lamellar according to aforesaid method.
Can decompose in the crosslinked foaming method of the agent of giving out a contract for a project in use, except that using linking agent or radiation, crosslinked also can passing through as C.P.Park, Supra, the described crosslinked with silicane of the 9th chapter is finished.
Crosslinked plastic foam of the present invention also can pass through to use as GB2, and 145, the extrusion method of the described long-land mould of 961A is made the successive thick plate structure.In the method, polymkeric substance, decomposable whipping agent and linking agent mix in forcing machine, heat this mixture so that crosslinked polymer and whipping agent is decomposed in the long-land mould; And via mouth contour forming and carrying out, and lubricate the contact surface of mould by suitable lubricant away from foam structure with foam structure.
Crosslinked plastic foam of the present invention also can form the crosslinked plastic foam bead that is suitable for being molded as goods.Be the preparation foaming plastic bead, (such as granular resin particle) indivedual resin particles are suspended in insoluble in fact liquid medium, such as, water; In autoclave or other pressurizing vessel, under elevated pressure and temperature, flood with linking agent and whipping agent; And drain into barometric point fast or depressor area forms foaming plastic bead with expansion.A kind of particular form is that polymer beads floods with whipping agent, and cooling is discharged from container, then by heating or steam expanded.In the deriving of aforesaid method, styrene monomer can flood into suspended particle with linking agent, to form the graft copolymerization body with polymer materials.Whipping agent can be impregnated in the resin particle when suspension or anhydrous state.Expandable bead expands by steam-heated cal(l)andria then, and comes molding by the traditional molding methods that is used for inflatable polyethylene foams bead.
Foaming plastic bead comes molding by any method known in the art, such as, foaming plastic bead is injected in the mould, compression mould is so that the bead compression, and uses such as the steam-heated cal(l)andria bead, so that bead is coalescent and welding forms goods.Randomly, before injecting mould, bead available air or other whipping agent preheating.The excellence instruction of aforesaid method and molding methods is found in C.P.Park, Supra, 227-233 page or leaf, United States Patent (USP) 3,886,100; 3,959,189; 4,168,353 and 4,429,059.But foaming plastic bead also can be by preparing the mixture of polymkeric substance, linking agent and decomposition of the mixture in suitable mixing device or forcing machine, and make mixture forming particle and heated particle so that it is crosslinked and expand and prepare.
Other has other preparation to be suitable for being molded as the method for the crosslinked plastic foam bead of goods.With the polymer materials fusion and in conventional foam plastics extrusion device and physical foaming agent and mixing, form successive porous plastics line thigh basically.Porous plastics line thigh is formed foaming plastic bead by granulating or granulation.Then, foaming plastic bead can pass through radiation crosslinking.Crosslinked foaming plastic bead can come aggegation and be molded as various goods by the above-mentioned method that is used for other expanded bead.The other instruction of this method can be referring to United States Patent (USP) 3,616, and 365 and C.P.Park, Supra, 224-228 page or leaf.
In addition, the crosslinked with silicane technology can be used for extrusion method.The instruction of this method is found in C.P.Park, Supra, the 9th chapter and United States Patent (USP) 4,714,716.When silane crosslinking process uses with traditional extrusion method, polymkeric substance and vinyl functional base silane or nitrine functional group silane grafting and be extruded into porous plastics.Then, the porous plastics of extruding is exposed in the moist warm air crosslinked to carry out.
Crosslinked plastic foam of the present invention can pass through porous plastics method in blocks or foam materials method or any C.P.Park, Supra, and the 9th chapter, the described method of 229-235 page or leaf prepares.
Though, usually be closed pore basically in essence, porous plastics of the present invention can be perforate or closed pore.In addition, the abscess-size of porous plastics of the present invention (that is, cell diameter) is 0.01mm to 10mm, preferred 0.1mm to 5mm, preferred especially 0.4mm to 3mm.In addition, the density of porous plastics of the present invention is 9kg/m
3To 200kg/m
3, preferred density is 11kg/m
3To 100kg/m
3, most preferred density is 15kg/m
3To 50kg/m
3
Porous plastics of the present invention can be any physical structure known in the art, such as, the sheet material of extruding, shaft-like, slab, section bar, pearl and round.Foam structure also can be by making expandable bead be molded as any said structure or any other structure forms.
Therefore, according to aforementioned, following porous plastics is represented typical froth plastics of the present invention:
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %; And b) the foamable thermoplastic polymer resin of 40 weight % to 99.9 weight %;
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %; And b) the foamable thermoplastic polymer resin of 40 weight % to 99.9 weight %; The density of this porous plastics is 9kg/m
3To 300kg/m
3, preferred 11kg/m
3To 100kg/m
3, and more preferably 15kg/m
3To 50kg/m
3
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %; And b) the flexible thermoplastic fluoropolymer resin of 40 weight % to 99.9 weight %;
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %; And b) the flexible thermoplastic fluoropolymer resin of 40 weight % to 99.9 weight %; The density of this porous plastics is 9kg/m
3To 300kg/m
3, preferred 11kg/m
3To 100kg/m
3, and more preferably 15kg/m
3To 50kg/m
3
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %; And b) the rigid thermoplastic polymer resin of 40 weight % to 99.9 weight %;
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %; And b) the rigid thermoplastic polymer resin of 40 weight % to 99.9 weight %; The density of this porous plastics is 9kg/m
3To 300kg/m
3, preferred 11kg/m
3To 100kg/m
3, and more preferably 15kg/m
3To 50kg/m
3
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %; And b) the flexible polyolefin resin of 40 weight % to 99.9 weight %;
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %; And b) the flexible polyolefin resin of 40 weight % to 99.9 weight %; The density of this porous plastics is 9kg/m
3To 300kg/m
3, preferred 11kg/m
3To 100kg/m
3, and more preferably 15kg/m
3To 50kg/m
3
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %; And b) the LDPE resin of 40 weight % to 99.9 weight %;
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %; And b) LDPE of 40 weight % to 99.9 weight %; The density of this porous plastics is 9kg/m
3To 300kg/m
3, preferred 11kg/m
3To 100kg/m
3, and more preferably 15kg/m
3To 50kg/m
3
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %, and it is the homopolymer of propylene; And b) the foamable thermoplastic polymer resin of 40 weight % to 99.9 weight %;
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %, and it is the homopolymer of propylene; And b) the foamable thermoplastic polymer resin of 40 weight % to 99.9 weight %; The density of this porous plastics is 9kg/m
3To 300kg/m
3, preferred 11kg/m
3To 100kg/m
3, and more preferably 15kg/m
3To 50kg/m
3
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %, and it is the homopolymer of propylene; And b) the flexible thermoplastic fluoropolymer resin of 40 weight % to 99.9 weight %;
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %, and it is the homopolymer of propylene; And b) the flexible thermoplastic fluoropolymer resin of 40 weight % to 99.9 weight %; The density of this porous plastics is 9kg/m
3To 300kg/m
3, preferred 11kg/m
3To 100kg/m
3, and more preferably 15kg/m
3To 50kg/m
3
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %, and it is the homopolymer of propylene; And b) the rigid thermoplastic polymer resin of 40 weight % to 99.9 weight %;
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %; And b) the rigid thermoplastic polymer resin of 40 weight % to 99.9 weight %; The density of this porous plastics is 9kg/m
3To 300kg/m
3, preferred 11kg/m
3To 100kg/m
3, and more preferably 15kg/m
3To 50kg/m
3
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %, and it is the homopolymer of propylene; And b) the flexible polyolefin resin of 40 weight % to 99.9 weight %;
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %, and it is the homopolymer of propylene; And b) the flexible polyolefin resin of 40 weight % to 99.9 weight %; The density of this porous plastics is 9kg/m
3To 300kg/m
3, preferred 11kg/m
3To 100kg/m
3, and more preferably 15kg/m
3To 50kg/m
3
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %, and it is the homopolymer of propylene; And b) the LDPE resin of 40 weight % to 99.9 weight %;
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %, and it is the homopolymer of propylene; And b) the LDPE resin of 40 weight % to 99.9 weight %; The density of this porous plastics is 9kg/m
3To 300kg/m
3, preferred 11kg/m
3To 100kg/m
3, and more preferably 15kg/m
3To 50kg/m
3
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %, and it is the alfon that has greater than 75% degree of syndiotacticity; And b) the foamable thermoplastic polymer resin of 40 weight % to 99.9 weight %;
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %, and it is the alfon that has greater than 75% degree of syndiotacticity; And b) the foamable thermoplastic polymer resin of 40 weight % to 99.9 weight %; The density of this porous plastics is 9kg/m
3To 300kg/m
3, preferred 11kg/m
3To 100kg/m
3, and more preferably 15kg/m
3To 50kg/m
3
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %, and it is the alfon that has greater than 75% degree of syndiotacticity; And b) the flexible thermoplastic fluoropolymer resin of 40 weight % to 99.9 weight %;
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %, and it is the alfon that has greater than 75% degree of syndiotacticity; And b) the flexible thermoplastic fluoropolymer resin of 40 weight % to 99.9 weight %; The density of this porous plastics is 9kg/m
3To 300kg/m
3, preferred 11kg/m
3To 100kg/m
3, and more preferably 15kg/m
3To 50kg/m
3
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %, and it is the alfon that has greater than 75% degree of syndiotacticity; And b) the rigid thermoplastic polymer resin of 40 weight % to 99.9 weight %;
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %, and it has the degree of syndiotacticity greater than 75%; And b) the rigid thermoplastic polymer resin of 40 weight % to 99.9 weight %, it is an alfon; The density of this porous plastics is 9kg/m
3To 300kg/m
3, preferred 11kg/m
3To 100kg/m
3, and more preferably 15kg/m
3To 50kg/m
3
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %; And b) the ethylene resin of 40 weight % to 99.9 weight %;
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %; And b) the ethylene resin of 40 weight % to 99.9 weight %; The density of this porous plastics is 9kg/m
3To 300kg/m
3, preferred 11kg/m
3To 100kg/m
3, and more preferably 15kg/m
3To 50kg/m
3
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %; And b) the iPP resin of 40 weight % to 99.9 weight %;
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %; And b) the iPP resin of 40 weight % to 99.9 weight %; The density of this porous plastics is 9kg/m
3To 300kg/m
3, preferred 11kg/m
3To 100kg/m
3, and more preferably 15kg/m
3To 50kg/m
3
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %; And b) the alkyl aromatic fluoropolymer resin of 40 weight % to 99.9 weight %;
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %; And b) the alkyl aromatic fluoropolymer resin of 40 weight % to 99.9 weight %; The density of this porous plastics is 9kg/m
3To 300kg/m
3, preferred 11kg/m
3To 100kg/m
3, and more preferably 15kg/m
3To 50kg/m
3
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %; And b) the poly styrene polymer resin of 40 weight % to 99.9 weight %;
The polymer foam of blend comprises: a) the sPP resin of 0.1 weight % to 60 weight %; And b) the poly styrene polymer resin of 40 weight % to 99.9 weight %; The density of this porous plastics is 9kg/m
3To 300kg/m
3, preferred 11kg/m
3To 100kg/m
3, and more preferably 15kg/m
3To 50kg/m
3
Following is embodiments of the invention, and is not in order to limit the scope of the invention.Unless other indication is arranged, all percentage, umber or ratio are by weight.
Be to use the screwe-type xtruder preparation of 19mm diameter from the following example of the porous plastics of the blend of sPP resin and expandable thermoplastic polymer resin preparation, its have the feed, fusion and the metering zone end that are positioned at general sequence be used for mix and the refrigerative additional areas.On the forcing machine bucket between metering and mixing zone, be provided for the opening that whipping agent injects.In the cooling zone terminal, its attached mould manifold with rectangular aperture.The height of opening is adjustable, and width is set at 38mm.The preparation of embodiment 1 sPP resin and LDPE resin blend porous plastics
The preparation that embodiment 1 confirms according to porous plastics of the present invention, wherein by the blend preparation of 50/50 weight LDPE resin and sPP resin, it is to use Trimethylmethane to foam as whipping agent and by extrusion method.Test according to the porous plastics of this embodiment preparation is shown that blend polymer can be by extruding foaming, and porous plastics is dimensional stability, and the higher temperature of ability.
The LDPE resin that has prepared 50/50 weight (has the melting index (testing in 190 ℃/2.16kg with ASTM D-1238) that 0.7dg/ divides, 0.923g/cm
3Density, and 115 ℃ fusing point (sentencing dsc (DSC) decision in endotherm(ic)peak between 10 ℃ of/minute heating period)) the polypropylene copolymer resin with the syndiotaxy form of EOD 96-28 grade (can derive from Fina Oil and chemical company, has the melt flow rate (MFR) (testing in 230 ℃/2.16kg) that 2dg/ divides, 0.88g/cm with ASTM D-1238
3Density and 130 ℃ of fusing points) the particulate state blend.
Particulate resins (is by talcum powder (nucleator) with adding packing material, 0.2 part per 100 parts of resins (pph), and Irganox 1010 antioxidants (deriving from Ciba-Ceigy company), 0.1pph forms) blend add in the forcing machine with the homogeneous speed of 3.26kg/h.It is 160 ℃ that the temperature in forcing machine district remains in feed zone, is 190 ℃ in melting zone, is 200 ℃ in metering zone, and is 200 ℃ in the mixing zone.Trimethylmethane (whipping agent) injects in the mixing zone with the uniform rate of 414g/h (12.7pph).The temperature of cooling zone lowers gradually, and adjusts mould openings to make good porous plastics.For example, in 107 ℃ cooling zone temperature, 105 ℃ die temperature, and the mould openings of 1.0mm obtain the excellent porous plastics of unicellular structure (open cell content is measured as about 32% with the program A of ASTM D-2856) basically.Porous plastics has 24.8g/cm
3Density, the abscess-size of 1.2mm, the thickness of about 12mm and the width of about 19mm.Test the dimensional stability of the porous plastics of 1 embodiment 1
The porous plastics that embodiment 1 has just been made cuts the long porous plastics sample into about 15cm, in extruding the volume that the back was measured the porous plastics sample in about 2 minutes, then, periodically measures between aging time at ambient temperature.When being contracted to the about 97% time of initial volume, porous plastics represents excellent size stability, and surpasses 30 minutes and no longer shrink in extruding the back.Return back to 100% of its initial volume fully in 1 day inner foam plastics.Test the thermostability of the porous plastics of 2 embodiment 1
Extrude back 1 day, the porous plastics of embodiment 1 preparation is cut into the long sample of 8cm.Sample is placed in the heat transfer stove that keeps 121 ℃, and its volume of periodic monitor.Porous plastics volume (in the percentage of its initial volume) function as exposure duration in the stove as shown in table 1 is represented:
Table 1
| Digestion time | ????0 | 1.5 hour | 1 day | 2 days | 5 days |
| Porous plastics volume (%) | ????100 | ????78 | ????75 | ????70 | ????71 |
As seen, porous plastics be contracted to initial volume 70% and be exposed between the pliotherm period in prolongation and keep this volume, and the polyethylene foams that to observe the identical LDPE resin that is used for embodiment 1 be benchmark bursts apart fully in this temperature.The high thermal resistance of blend porous plastics is further with the previous DSC thermal map support of discussing of Fig. 1 and Fig. 2.In Fig. 1 and Fig. 2, the thermal map of the aging porous plastics (Fig. 2) of porous plastics of extruding (Fig. 1) and stove compares.Stove aged porous plastics is exposed to 121 ℃ of temperature 5 days.The aging porous plastics of stove locates to show sharp-pointed crest in about 130 ℃ and about 113 ℃.By contrast, the porous plastics of extruding is not shown in 130 ℃ of strong crests of locating, and this peak is a sPP crystalline melting peak.Thermal map shows that the LDPE resin and the sPP resin that are used for embodiment 1 are immiscible mixed, and the sPP resin in the blend carries out crystallization between 121 ℃ of heating period.Test the thermoforming character of the porous plastics of 3 embodiment 1
The porous plastics that embodiment 1 is made is cut into the long sample of two 5cm, and in 121 ℃ of stove internal heating 5 minutes.Then, from stove, take out the porous plastics of heating, and immediately by applying gentle pressure so that be stacked in another person's top.The porous plastics sample represents gratifying tackiness, and significant the contraction do not occur, and this represents that foamable pearl can make from the porous plastics of embodiment 1, and the porous plastics of embodiment 1 can carry out thermoforming.Comparative Example A An is from sPP resins porous plastics
The porous plastics of preparation Comparative Example A An is so that test is separately from the foaming and intumescing character of the porous plastics of sPP resins.
The co-polymer polypropylene resin of the syndiotaxy form of EOD 96-28 grade (derives from FinaOil and chemical company, has the melt flow rate (MFR) (testing in 230 ℃/2.16kg with ASTM D-1238) that 2dg/ divides, 0.88g/cm
3Density and 130 ℃ of fusing points) with the talcum (nucleator) of 0.4pph and Irganox 1010 (the deriving from Ciba-Geigy Corp.) blend of 0.1pph.Blend adds in the forcing machine with the homogeneous speed of 3.10kg/h.The temperature in forcing machine zone keeps 160 ℃ in feed zone, keeps 190 ℃ in melting zone, keeps 200 ℃ in metering zone, and keeps 200 ℃ in the mixing zone.Trimethylmethane (whipping agent) injects the mixing zone with the homogeneous speed of 414g/h (12.7pph).The temperature of cooling zone to be once reducing about 5 ℃ and reduce to 80 ℃ gradually from 160 ℃, and keeps 5 to 10 minutes in this temperature, whether makes good porous plastics so that watch.Die temperature keeps the temperature identical with the cooling zone.When the cooling zone temperature was reduced to 95 ℃, a mouthful mould opening remained in 0.8mm.When being lower than 95 ℃, mould is relaxed a little to be opened, to discharge the pressure that increases.Test sPP resin expandable of 4 Comparative Example A An
The melt that above-mentioned Comparative Example A An makes can not expand reducing under 95 ℃ the temperature at all.In being lower than under 95 ℃ the temperature, porous plastics expands a little, but bursts apart immediately.In 80 ℃, forcing machine pressure fast rise, the expression melt viscosity is too high and freezing in the cooling zone.Can not stand the reduction of further cooling temperature.Conclusion: independent sPP resin can not expand into stable porous plastics by extrusion method.
The preparation of the blend foam plastics of embodiment 2 and Comparative Examples B sPP resin and LDPE resin
The preparation that embodiment 2 confirms according to porous plastics of the present invention, its blend from LDPE resin and sPP resin makes, and wherein changes the percentage of sPP resin so that detect sPP resin content in the blend to the influence of the character such as expandable and dimensional stability of porous plastics.Comparative Examples B is only by the porous plastics of LDPE resins.
Make the LDPE resin by the predetermined proportion shown in the table II and (have the melting index (testing in 190 ℃/2.16kg) that 0.7dg/ divides, 0.923g/cm with ASTM D-1238
3Density, and 115 ℃ fusing point (sentencing dsc (DSC) in endotherm(ic)peak between 10 ℃ of/minute heating period measures)) the co-polymer polypropylene resin with the syndiotaxy form of EOD 96-07 grade (can derive from Fina Oil and chemical company, has the melt flow rate (MFR) (testing in 230 ℃/2.16kg) that 2dg/ divides, 0.88g/cm with ASTM D-1238
3Density and 130 ℃ of fusing points) the particulate state blend.
The blend of particulate resin and 0.2pph talcum powder (nucleator) adds (because the difference of the feed character in the blend in the forcing machine with the homogeneous speed of 3.1kg/h, actual rate of extrusion changes in about 3kg/h to 3.2kg/h scope slightly, makes speed keep identical even make great efforts by adjusting the screw rod speed of rotation).The temperature in forcing machine zone keeps 160 ℃ in feed zone, keeps 190 ℃ in melting zone, keeps 200 ℃ in metering zone, and keeps 220 ℃ in the mixing zone.The temperature that keeps the cooling zone is shown in the table II.Trimethylmethane (whipping agent) is injected in the mixing zone with the speed shown in the table II.The temperature of cooling zone lowers gradually and adjusts mould openings to prepare good porous plastics.Die temperature keeps 110 ℃ in Comparative Examples B, embodiment 2.1 to 2.3, keep 105 ℃ in embodiment 2.4 and 2.5.For table each prescription shown in the II, under the temperature of the cooling zone of the best and from the mould openings of 1.1mm to 1.2mm, obtain the porous plastics sample.
The dimensional data of porous plastics is shown in the table II, and it also comprises density, abscess-size and perforate data.
The table II
| Comparing embodiment or embodiment numbering | SPP measures (%) 1 | Trimethylmethane amount (ppg) 2 | Blowing temperature (℃) 3 | Porous plastics density (kg/m 3) 4 | Abscess-size (mm) 5 | Perforate (%) 6 | Dimensional stability | |||
| Divide (%) 7 | 1 day (%) | 1 week (%) 8 | 1 month (%) | |||||||
| ?????B | ?????0 | ????9.2 | ????108 | ????38.0 | ?0.43 | ?13 | ?64 | ?67 | ?92 | ????100 |
| ????2.1 | ????10 | ????9.1 | ????109 | ????41.8 | ?0.90 | ?18 | ?59 | ?59 | ?80 | ????94 |
| ????2.2 | ????20 | ????9.3 | ????113 | ????36.0 | ?0.81 | ?12 | ?73 | ?78 | ?92 | ????98 |
| ????2.3 | ????30 | ????9.4 | ????113 | ????36.2 | ?1.25 | ?16 | ?89 | ?89 | ?95 | ????98 |
| ????2.4 | ????40 | ????9.4 | ????109 | ????41.3 | ?1.16 | ?47 | ?98 | ?98 | ?98 | ???102 |
| ????2.5 | ????50 | ????9.8 | ????107 | ????56.1 | ?1.25 | ?67 | ?ND | ?ND | ?ND | ????ND |
Annotate:
1The percentage of sPP resin in the blend
2The umber of blended Trimethylmethane in 100 parts of fluoropolymer resins
3Make the solidification value of the cooling zone of porous plastics
4With the density of the porous plastics of water displacement after definite aging two months, kg/m
3
5With the abscess-size that ASTM D-3576 determines, mm
6With the open cell content that ASTM D-2856-A determines, %
7The minimum volume of the porous plastics between the envrionment temperature aging time is in the percentage of initial volume.For all porous plastics, minimum volume resulted from one day
8Specific aged porous plastics volume under the envrionment temperature is in the percentage of initial volume.
ND=does not determine
As show shown in the II, the prescription that contains the highest 40% sPP resin obtains the porous plastics of good quality.The 50/50 blend foam plastics of LDPE/sPP be it seems low-grade fever under selected 107 ℃ of cooling temperatures.The porous plastics thickness range is 6.1mm to 8.2mm, porous plastics width range 14.7mm to 18.4mm.Cut out the sample of the about 15cm of length from the porous plastics of new system, and the volume of porous plastics sample detected in extruding the back in about 2 minutes, and between the envrionment temperature aging time, regularly detect.Conclusion
Blend is easy to produce than the big abscess-size of pure LDPE resin.The blend that contains 40 and 50% sPP is easy to develop and more open abscess.The dimensional stability of porous plastics that the sPP resin improved has been added in demonstration.Contain 30% or the blend of more sPP content provide and have gratifying dimensional stability and between aging time, have greater than the long-pending porous plastics of 89% minimum foaming plastic body.
The preparation of the blend foam plastics of embodiment 3 and comparing embodiment CsPP resin and LDPE resin
The preparation that embodiment 3 confirms according to porous plastics of the present invention, whether it is the blend preparation from LDPE resin and sPP resin, wherein change the amount of whipping agent and can improve by high-load whipping agent so that determine to have the expandable of blend of high sPP resin content.Also reduce the temperature of cooling zone so that determine that it is to the effect of porous plastics expansible.
Make the LDPE resin by the predetermined proportion shown in the table III and (have the melting index (testing in 190 ℃/2.16kg) that 0.7dg/ divides, 0.923g/cm with ASTM D-1238
3Density, and 115 ℃ fusing point (sentencing dsc (DSC) in endotherm(ic)peak between 10 ℃ of/minute heating period determines)) the co-polymer polypropylene resin with the syndiotaxy form of EOD 96-07 grade (can derive from Fina Oil and chemical company, has the melt flow rate (MFR) (testing in 230 ℃/2.16kg) that 2dg/ divides, 0.88g/cm with ASTM D-1238
3Density and 130 ℃ of fusing points) the particulate state blend.
The blend of particulate resin and 0.2pph talcum powder (nucleator) adds (because the difference of the feed character in the blend in the forcing machine with the homogeneous speed of 3.1kg/h, actual rate of extrusion changes in about 3kg/h to 3.2kg/h scope a little, makes speed keep identical even make great efforts by adjusting the screw rod speed of rotation).The temperature in forcing machine zone keeps 160 ℃ in feed zone, keeps 190 ℃ in melting zone, keeps 200 ℃ in metering zone, and keeps 220 ℃ in the mixing zone.The temperature that keeps the cooling zone is shown in the table III.Trimethylmethane (whipping agent) is injected in the mixing zone with the speed shown in the table III.The temperature of cooling zone lowers gradually and adjusts mould openings to prepare good porous plastics.Die temperature keeps 110 ℃ in comparing embodiment C, embodiment 3.1 and 3.2, and keeps 100 ℃ in embodiment 3.3.For each prescription shown in the table III, the mould openings that reaches under the temperature of the cooling zone of the best from 1.1mm to 1.2mm obtains the porous plastics sample.
The dimensional data of porous plastics is shown in the table III, and it also comprises density, abscess-size and perforate data.
The table III
| Comparing embodiment or embodiment numbering | SPP measures (%) 1 | Trimethylmethane amount (PPg) 2 | Blowing temperature (℃) 3 | Porous plastics density (kg/m 3) 4 | Abscess-size (mm) 5 | Perforate (%) 6 | Dimensional stability | ||
| Divide (%) 7 | 1 day (%) 8 | 1 month (%) 8 | |||||||
| ????C | ????0 | ????12.0 | ????100 | ????29.3 | ?0.95 | ?41 | ?50 | ?50 | ?90 |
| ????3.1 | ????20 | ????12.0 | ????100 | ????29.7 | ?1.16 | ?36 | ?66 | ?66 | ?94 |
| ????3.2 | ????50 | ????11.4 | ????90 | ????29.1 | ?1.35 | ?36 | ?99 | ?102 | ?104 |
| ????3.3 | ????60 | ????14.0 | ????82 | ????33.3 | ?2.31 | ?81 | ?ND | ?ND | ?ND |
Annotate:
1The percentage of sPP resin in the blend
2The umber of blended Trimethylmethane in 100 parts of fluoropolymer resins
3Make the solidification value of the cooling zone of porous plastics
4With the density of the porous plastics of water displacement after definite aging two months, kg/m
3
5With the abscess-size that ASTM D-3576 determines, mm
6With the open cell content that ASTM D-2856-A determines, %
7The minimum volume of the porous plastics between the envrionment temperature aging time is in the percentage of initial volume.For all porous plastics, minimum volume resulted from one day
8Specific aged porous plastics volume under the envrionment temperature is in the percentage of initial volume.
ND=does not determine
As show shown in the III, the good foam plastics make from containing the blend that is up to 50% sPP resin.40/60 LDPE/sPP blend is the bottom line of the workability of porous plastics.For preparing porous plastics from blend, the temperature of cooling zone must be reduced to 82 ℃.Porous plastics produces MIN satisfactory degree with high-load perforate.The density of all porous plastics is lower, represents high-load whipping agent.The apparent open cell content of porous plastics is higher, greater than 36%.The boring method of ASTM D-2856-A is easy to excessively assess the open cell content of flexible foam.Density that the porous plastics tool that the porous plastics that makes in these embodiments makes than embodiment 2 is lower and lower modulus cause the open cell content measuring error bigger.For the explanation of excessive assessment perforate is to be found out by the data of the dimensional stability of LDPE porous plastics.Though, apparent open cell content higher (41%), porous plastics shrinks between aging time and reaches 50%, and replys slower.
Embodiment 4 and comparing embodiment D are by the porous plastics of the blend preparation of sPP resin and ethylene resin
The preparation that embodiment 4 confirms according to porous plastics of the present invention, it is the blend preparation from the sPP resin of ethylene (EVA) resin and different content, so that determine the effect of sPP resin content to the dimensional stability of the expandable and porous plastics of blend.Comparing embodiment D is only made by the EVA resin.
By the predetermined proportion of table shown in the IV make Elvax 460 resins (Du Pont-Dow] [nc. company provides, and has the melting index that 2.5dg/ divides (with ASTM D-1238 in 230 ℃/2.16kg test), 0.941g/cm
3Density, and 88 ℃ fusing point) (can derive from Fina Oil and chemical company, have the melt flow rate (MFR) that 2dg/ divides, 0.88g/cm with the co-polymer polypropylene resin of the syndiotaxy form of EOD 96-07 grade
3Density and 130 ℃ of fusing points) the particulate state blend.
The table IV
| Comparing embodiment or embodiment numbering | SPP measures (%) 1 | Trimethylmethane amount (PPg) 2 | Blowing temperature (℃) 3 | Porous plastics density (kg/m 3) 4 | Abscess-size (mm) 5 | Perforate (%) 6 | Dimensional stability | |||||
| Divide (%) 7 | 1 day (%) | 10 days (%) | 1 month (%) 8 | 2 months (%) | 3 months (%) | |||||||
| ????D | ????0 | ????12.7 | ????90 | ????30.4 | ????0.9 | ????83 | ????25 | ????32 | ????52 | ????72 | ????87 | ????90 |
| ????4.1 | ????10 | ????13.1 | ????85 | ????28.0 | ????1.0 | ????75 | ????32 | ????40 | ????68 | ????89 | ????97 | ????100 |
| ????4.2 | ????20 | ????13.6 | ????85 | ????27.2 | ????1.0 | ????67 | ????55 | ????80 | ????103 | ????103 | ????104 | ????105 |
| ????4.3 | ????30 | ????16.7 | ????76 | ????21.0 | ????0.9 | ????83 | ????92 | ????96 | ????98 | ????99 | ????98 | ????99 |
| ????4.4 | ????40 | ????17.3 | ????75 | ????22.8 | ????0.8 | ????90 | ????94 | ????98 | ????94 | ????95 | ????95 | ????95 |
Annotate:
1The percentage of sPP resin in the blend
2The umber of blended Trimethylmethane in 100 parts of fluoropolymer resins
3Make the solidification value of the cooling zone of porous plastics
4With the density of the porous plastics of water displacement after definite aging two months, kg/m
3
5With the abscess-size that ASTM D-3576 determines, mm
6With the open cell content that ASTM D-2856-A determines, %
7The minimum volume of the porous plastics between the envrionment temperature aging time is in the percentage of initial volume.For all porous plastics, minimum volume resulted from one day
8Specific aged porous plastics volume under the envrionment temperature is in the percentage of initial volume.
ND=does not determine
The blend of particulate resin and 0.4pph talcum powder (nucleator) adds (because the difference of the feed character in the blend in the forcing machine with the homogeneous speed of 3kg/h, as show shown in the IV, actual rate of extrusion is reduced to 2.6kg/h from 3kg/h when fixed extruder screw speed of rotation).The temperature in forcing machine zone keeps 120 ℃ in feed zone, keeps 150 ℃ in melting zone, keeps 180 ℃ in metering zone, and keeps 180 ℃ in the mixing zone.The temperature that keeps the cooling zone is shown in the table IV.Trimethylmethane (whipping agent) is injected in the mixing zone with the speed shown in the table IV: for comparing embodiment D and embodiment 4.1 and 4.2 are 380g/h, for embodiment 4.3 and 4.4 is that 450g/h is (because the feeding rate of polymkeric substance and whipping agent changes, the amount of whipping agent changes from 12.7pph to 17.3pph in the resin, referring to the table IV).The die clearance remains in 1.75mm in whole test, and die temperature remains in and is lower than 0 ℃ to 5 ℃ of cooling zone temperature.The dimensional stability data of porous plastics (referring to the method for embodiment 1) are shown in the table IV, and it also comprises density, abscess-size and perforate data.
As show shown in the IV, good porous plastics is to make from containing the blend that is up to 40% sPP resin.With respect to the perforate data, the porous plastics that comparing embodiment D and embodiment 4.1 and 4.2 make is when with when test finger extruding being closed pore basically.The porous plastics that embodiment 4.3 and 4.4 makes is perforate.Moreover the perforate data of flexible polyolefins porous plastics are insecure.The eva foam plastics that comparing embodiment D makes meet with over-drastic and shrink (minimum volume=25%), contain 83% perforate even ASTM D-2856-A represents porous plastics.Conclusion
Moreover, the blend of sPP resin and foamable Ethylene/vinyl acetate resin makes good porous plastics, and show sPP resin improved dimensional stability, and the sPP resin content is 30% or produces the porous plastics with gratifying dimensional stability when bigger.Test the thermostability of the porous plastics of 5 comparing embodiment D and embodiment 4
After aging 16 days, the porous plastics that comparing embodiment D and embodiment 4 make is tested 2 described heat and is exposed test.The porous plastics sample is placed in the stove, and it remains in 90 ℃.After 1 hour, and after 8 hours, remove the change of sample and measurement volumes, shown in the table V.
The table V
| The numbering of comparing embodiment or embodiment | SPP content (%) 1 | Volume keeps | |
| 1 hour (%) 2 | 8 hours (%) | ||
| ????D | ????0 | ????24 | ????16 |
| ????4.1 | ????10 | ????75 | ????57 |
| ????4.2 | ????20 | ????37 | ????31 |
| ????4.3 | ????30 | ????68 | ????69 |
| ????4.4 | ????40 | ????85 | ????83 |
1The percentage of the sPP resin in the blend
2The volume of the porous plastics between 90 ℃ of aging times keeps
As show shown in the V, all porous plastics all shrink, but the porous plastics that contains the sPP resin keeps porous plastics (comparing embodiment D) tool that its volume ratio do not contain the sPP resin largely.The porous plastics that makes from the blend that contains 40% sPP resin keeps 83% volume after 8 hours in stove.Embodiment 5 prepares porous plastics from the blend of sPP resin and iPP resin
In embodiment 5, the iPP resin of foamable high fondant-strength (HMS) and the blend of sPP resin are used for preparation according to porous plastics of the present invention.
The iPP resin of high fondant-strength that makes the Pro-fax PF-814 grade of 50/50 weight (derives from Montell polyolefine Co.N.V., has the melting index that 3dg/ divides (with ASTMD-1238 in 230 ℃/2.16kg test), 0.90g/cm
3Density, and 160 ℃ fusing point) (can derive from FinaOil and chemical company, have the melt flow rate (MFR) that 2dg/ divides, 0.88g/cm with the co-polymer polypropylene resin of the syndiotaxy form of EOD 96-28 grade
3Density and 130 ℃ of fusing points) the particulate state blend.
With the particulate resin blend and by 0.2pph talcum powder (
4Nucleator) and the additive packing thing premix formed of Irganox 1010 antioxidants (deriving from Ciba-Geigy Corp.) of 0.1pph and add in the forcing machine with the homogeneous speed of 4.2kg/h.Keep temperature in the cooling zone, feed zone keeps 160 ℃, keeps 190 ℃ in melting zone, keeps 200 ℃ in metering zone, and keeps 200 ℃ in the mixing zone.Trimethylmethane (whipping agent) is injected in the mixing zone with the uniform rate of 10.7pph.Mould openings remains in about 0.8mm.Adjust the temperature of cooling zone and adjust mould openings to prepare good porous plastics.Under the cooled region temperature in 170 ℃ to 160 ℃ scopes, obtain the good foam plastics of unicellular structure basically.For example, has 26.3kg/m in 160 ℃ of porous plastics that make
3Density, the abscess-size of 1.8mm, 17% open cell content, the thickness of about 1imm, and the width of about 20mm.Porous plastics is strong and tough.Comparing embodiment E prepares porous plastics from the blend of sPP resin and iPP resin
In comparing embodiment E, repeat the program of embodiment 5, but use 20/80 the identical iPP and the blend of sPP resin, but not 50/50 blend.Under cooling zone temperature, do not make porous plastics from 180 ℃ to 150 ℃ of scannings.Embodiment 6 and comparing embodiment F prepare porous plastics from the blend of sPP resin and polystyrene resin
In embodiment 6, the blend of polystyrene (PS) resin and sPP resin is with carbon dioxide expanded, uses and used same apparatus of embodiment 1 and substantially the same program.Comparing embodiment F is only from the PS resins.
(having molecular-weight average is 150,000, density 1.059/cm to make the PS resin
3, and 104 ℃ Tg) (can derive from Fina Oil and chemical company, have the melt flow rate (MFR) that 2dg/ divides (with ASTM D-1238 in 230 ℃/2.16kg test), 0.88g/cm with the sPP resin of EOD 96-07 grade
3Density and 130 ℃ of fusing points) with the particulate state blend of predetermined proportion shown in the table VI.
The blend of particulate resin and 0.1pph barium stearate merges with homogeneous speed premix and adds in the forcing machine.It is as follows that the temperature in forcing machine zone keeps: keep 130 ℃ in feed zone, keep 160 ℃ in melting zone, keep 200 ℃ in metering zone, and keep 200 ℃ in the mixing zone.Carbonic acid gas injects the mixing zone with the uniform rate of 4.6pph.The temperature of cooling zone is adjusted in 132 ℃ to 134 ℃ scope to prepare good porous plastics.Die temperature remains in uniform 145 ℃ in whole process.Mould openings remains in the permanent opening of 1.5mm.Thickness, porous plastics density, abscess-size and open cell content are shown in the table IV.
The table VI
| Comparing embodiment and embodiment numbering | SPP content (%) 1 | Rate of extrusion (kg/h) 2 | Thickness (mm) 3 | Width (mm) 4 | Porous plastics density (kg/m 3) 5 | Abscess-size (mm) 6 | Perforate (%) 7 |
| ????F | ????0 | ????4.8 | ????16 | ????19 | ????61.6 | ????0.33 | ????0 |
| ????6.1 | ????2 | ????4.1 | ????20 | ????23 | ????64.8 | ????0.70 | ????0 |
| ????6.2 | ????5 | ????3.9 | ????19 | ????22 | ????66.5 | ????0.69 | ????0 |
| ????6.3 | ????20 | ????3.7 | ????17 | ????22 | ????70.0 | ????1.44 | ????27 |
1SPP resin percentage in the blend
2The rate of extrusion of fluoropolymer resin, kg/h
3Porous plastics thickness, mm
4The porous plastics width, mm
5The density of the porous plastics in an aging week, kg/m
3, determine with the water displacement
6With the abscess-size that ASTM D-3576 determines, mm
7With the open cell content that ASTM D-2856-A determines, %
As show shown in the VI, the sPP resin makes cross-sectional sizes and abscess-size become big.The porous plastics that contains 2% and 5% sPP resin shows do not have perforate.80/20 PS/sPP resin blend provides the porous plastics with some perforates.
Claims (37)
1. polymer blend porous plastics comprises:
A) the sPP resin of 0.1 weight % to 60 weight %; And
B) the foamable thermoplastic polymer resin of 40 weight % to 99.9 weight %.
2. according to the polymer blend porous plastics of claim 1, wherein this porous plastics has 9kg/m
3To 300kg/m
3Density.
3. according to the polymer blend porous plastics of claim 2, wherein this porous plastics has 11kg/m
3To 100kg/m
3Density.
4. according to the polymer blend porous plastics of claim 3, wherein this porous plastics has 15kg/m
3To 50kg/m
3Density.
5. according to the polymer blend porous plastics of claim 1, wherein this foamable thermoplastic polymer resin is the flexible thermoplastic fluoropolymer resin.
6. according to the polymer blend porous plastics of claim 1, wherein this foamable thermoplastic polymer resin is the rigid thermoplastic polymer resin.
7. according to the polymer blend porous plastics of claim 5, wherein this foamable thermoplastic polymer resin is flexible polyolefin resin.
8. according to the polymer blend porous plastics of claim 7, wherein this flexible polyolefin resin is the LDPE resin.
9. polymer blend porous plastics according to Claim 8, wherein this LDPE resin has 0.1dg/ and divides the melting index of dividing to 20dg/.
10. according to the polymer blend porous plastics of claim 10, this sPP resin homopolymer that is propylene wherein.
11. according to the polymer blend porous plastics of claim 10, wherein this sPP resin has 0.05dg/ and divides the melt flow rate (MFR) of dividing to 50dg/.
12. according to the polymer blend porous plastics of claim 10, wherein this sPP resin has the degree of syndiotacticity greater than 75%.
13. according to the polymer blend porous plastics of claim 1, this sPP resin multipolymer that is propylene and ethene wherein.
14. according to the polymer blend porous plastics of claim 13, wherein this sPP resin has 0.05dg/ and divides the melt flow rate (MFR) of dividing to 50dg/.
15. according to the polymer blend porous plastics of claim 13, wherein this sPP resin has the degree of syndiotacticity greater than 75%.
16. according to the polymer blend porous plastics of claim 1, this sPP resin multipolymer that is propylene and 1-butylene wherein.
17. according to the polymer blend porous plastics of claim 16, wherein this sPP resin has 0.05dg/ and divides the melt flow rate (MFR) of dividing to 50dg/.
18. according to the polymer blend porous plastics of claim 16, wherein this sPP resin has the degree of syndiotacticity greater than 75%.
19. according to the polymer blend porous plastics of claim 5, wherein this flexible polyolefin resin is the ethylene resin.
20. according to the polymer blend porous plastics of claim 19, wherein this ethylene resin has 5% to 30% vinyl acetate content.
21. according to the polymer blend porous plastics of claim 19, wherein this ethylene resin has 0.1dg/ and divides the melting index of dividing to 20dg/.
22. according to the polymer blend porous plastics of claim 5, wherein this flexible polyolefin resin is foamable iPP resin.
23. according to the polymer blend porous plastics of claim 22, wherein this foamable iPP resin is the resin of high fondant-strength when being used for tg δ less than 1.5 extrusion method.
24. according to the polymer blend porous plastics of claim 6, wherein this rigid thermoplastic polymer resin is the PS resin.
25. according to the polymer blend porous plastics of claim 24, wherein this PS resin has and is less than 240,000 molecular-weight average.
26. according to the polymer blend porous plastics of claim 5, wherein the sPP resin in this blend porous plastics is in 10% to 50% scope.
27. according to the polymer blend porous plastics of claim 26, wherein the sPP resin in this blend porous plastics is in 30% to 50% scope.
28. according to the polymer blend porous plastics of claim 1, wherein this blend porous plastics prepares by extrusion method.
29. according to the polymer blend porous plastics of claim 28, wherein this extrusion method uses Trimethylmethane as whipping agent.
30. according to the polymer blend porous plastics of claim 29, wherein this extrusion method uses carbonic acid gas as whipping agent.
31. according to the polymer blend porous plastics of claim 1, wherein this blend porous plastics has the abscess-size of 0.01mm to 10mm.
32. according to the polymer blend porous plastics of claim 1, wherein this blend porous plastics is not crosslinked.
33. according to the polymer blend porous plastics of claim 1, wherein this blend porous plastics is crosslinked.
34. according to the polymer blend porous plastics of claim 1, wherein this blend porous plastics is a sheet-form.
35. according to the polymer blend porous plastics of claim 1, wherein this blend porous plastics is the sheet material form.
36. according to the polymer blend porous plastics of claim 1, wherein this blend porous plastics is coalescent line thigh foam plastics slab form.
37. according to the polymer blend porous plastics of claim 1, wherein this blend porous plastics is a bead form.
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|---|---|---|---|
| US9835298P | 1998-08-28 | 1998-08-28 | |
| US60/098,352 | 1998-08-28 |
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|---|---|
| CN1315982A true CN1315982A (en) | 2001-10-03 |
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|---|---|---|---|
| CN99810453A Pending CN1315982A (en) | 1998-08-28 | 1999-08-26 | Foams prepared from blends of syndiotactic polypropylenes and thermoplastic polymers |
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|---|---|
| EP (1) | EP1115778A1 (en) |
| JP (1) | JP2002523587A (en) |
| KR (1) | KR20010074903A (en) |
| CN (1) | CN1315982A (en) |
| AU (1) | AU758494B2 (en) |
| BR (1) | BR9913436A (en) |
| CA (1) | CA2339107A1 (en) |
| CZ (1) | CZ2001480A3 (en) |
| HU (1) | HUP0103328A3 (en) |
| IL (1) | IL141266A0 (en) |
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| RU (1) | RU2232781C2 (en) |
| TR (1) | TR200100608T2 (en) |
| WO (1) | WO2000012594A1 (en) |
| ZA (1) | ZA200100802B (en) |
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| CN101845253A (en) * | 2009-03-25 | 2010-09-29 | 罗门哈斯公司 | Be used for preparing the composition of porous ethylene-vinyl-acetic ester coating |
| CN108473622A (en) * | 2016-01-13 | 2018-08-31 | 道达尔研究技术弗吕公司 | Pipeline including syndiotactic polypropylene |
| CN115386166A (en) * | 2022-09-19 | 2022-11-25 | 成都金发科技新材料有限公司 | Polypropylene composite material, preparation method and application |
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| KR100720084B1 (en) * | 1998-12-24 | 2007-12-07 | 삼성전자주식회사 | Thin film transistor substrate for liquid crystal display |
| KR20030028457A (en) * | 2000-03-17 | 2003-04-08 | 다우 글로벌 테크놀로지스 인크. | Polyolefin foam useful for sound and thermal insulation |
| ATE323125T1 (en) | 2000-03-17 | 2006-04-15 | Dow Global Technologies Inc | HIGH OPERATING TEMPERATURE POLYOLEFINE FOAM FOR ACOUSTIC USE |
| AU2001238200B2 (en) | 2000-03-17 | 2004-10-21 | Dow Global Technologies Inc. | Acoustic absorption polymer foam having improved thermal insulating performance |
| KR100508909B1 (en) * | 2001-05-23 | 2005-09-14 | 주식회사 아산케미칼 | Method for Preparing Pellet-Type Foams Of Non-crosslinked Polypropylene Resin Having Lower Melting Point |
| RU2467036C1 (en) * | 2011-04-05 | 2012-11-20 | Александр Сергеевич Баймурзаев | Method of producing biodegradable foam plastic |
| US8883280B2 (en) | 2011-08-31 | 2014-11-11 | Berry Plastics Corporation | Polymeric material for an insulated container |
| US9758292B2 (en) | 2011-06-17 | 2017-09-12 | Berry Plastics Corporation | Insulated container |
| US20140262916A1 (en) | 2013-03-14 | 2014-09-18 | Berry Plastics Corporation | Container |
| WO2015024018A1 (en) | 2013-08-16 | 2015-02-19 | Berry Plastics Corporation | Polymeric material for an insulated container |
| WO2016118838A1 (en) | 2015-01-23 | 2016-07-28 | Berry Plastics Corporation | Polymeric material for an insulated container |
| EP3181635A1 (en) * | 2015-12-18 | 2017-06-21 | Borealis AG | A compounded polyethylene composition, process for its manufacturing and articles comprising it |
| IT201600079947A1 (en) | 2016-07-29 | 2018-01-29 | Versalis Spa | Expandable polymeric composition containing ethylene-vinyl acetate copolymers |
| US11091311B2 (en) | 2017-08-08 | 2021-08-17 | Berry Global, Inc. | Insulated container and method of making the same |
| CN118202023A (en) | 2021-11-05 | 2024-06-14 | 埃克森美孚化学专利公司 | Polypropylene viscosity modifier and lubricating oil thereof |
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| JPS58122934A (en) * | 1982-01-18 | 1983-07-21 | Kanegafuchi Chem Ind Co Ltd | Preparation of thermoplastic resin prefoamed particle |
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| JP3204424B2 (en) * | 1993-02-18 | 2001-09-04 | 三菱化学フォームプラスティック株式会社 | Polypropylene resin foam particles |
| US5460818A (en) * | 1994-04-12 | 1995-10-24 | The Dow Chemical Company | Compatibilized blend of olefinic polymers and monovinylidene aromatic polymers |
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-
1999
- 1999-08-26 CA CA002339107A patent/CA2339107A1/en not_active Abandoned
- 1999-08-26 HU HU0103328A patent/HUP0103328A3/en unknown
- 1999-08-26 WO PCT/US1999/019410 patent/WO2000012594A1/en not_active Application Discontinuation
- 1999-08-26 EP EP99942480A patent/EP1115778A1/en not_active Withdrawn
- 1999-08-26 CZ CZ2001480A patent/CZ2001480A3/en unknown
- 1999-08-26 RU RU2001108364/04A patent/RU2232781C2/en not_active IP Right Cessation
- 1999-08-26 JP JP2000567602A patent/JP2002523587A/en active Pending
- 1999-08-26 TR TR2001/00608T patent/TR200100608T2/en unknown
- 1999-08-26 AU AU55847/99A patent/AU758494B2/en not_active Ceased
- 1999-08-26 IL IL14126699A patent/IL141266A0/en unknown
- 1999-08-26 BR BR9913436-5A patent/BR9913436A/en not_active Application Discontinuation
- 1999-08-26 KR KR1020017002696A patent/KR20010074903A/en not_active Application Discontinuation
- 1999-08-26 CN CN99810453A patent/CN1315982A/en active Pending
-
2001
- 2001-01-29 ZA ZA200100802A patent/ZA200100802B/en unknown
- 2001-02-27 NO NO20011001A patent/NO20011001L/en not_active Application Discontinuation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845253A (en) * | 2009-03-25 | 2010-09-29 | 罗门哈斯公司 | Be used for preparing the composition of porous ethylene-vinyl-acetic ester coating |
| CN108473622A (en) * | 2016-01-13 | 2018-08-31 | 道达尔研究技术弗吕公司 | Pipeline including syndiotactic polypropylene |
| CN115386166A (en) * | 2022-09-19 | 2022-11-25 | 成都金发科技新材料有限公司 | Polypropylene composite material, preparation method and application |
| CN115386166B (en) * | 2022-09-19 | 2023-08-29 | 成都金发科技新材料有限公司 | Polypropylene composite material, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000012594A1 (en) | 2000-03-09 |
| BR9913436A (en) | 2001-05-22 |
| HUP0103328A3 (en) | 2003-06-30 |
| EP1115778A1 (en) | 2001-07-18 |
| CA2339107A1 (en) | 2000-03-09 |
| JP2002523587A (en) | 2002-07-30 |
| AU5584799A (en) | 2000-03-21 |
| NO20011001D0 (en) | 2001-02-27 |
| NO20011001L (en) | 2001-02-27 |
| AU758494B2 (en) | 2003-03-20 |
| KR20010074903A (en) | 2001-08-09 |
| TR200100608T2 (en) | 2001-06-21 |
| ZA200100802B (en) | 2001-08-07 |
| RU2232781C2 (en) | 2004-07-20 |
| CZ2001480A3 (en) | 2001-10-17 |
| HUP0103328A2 (en) | 2001-12-28 |
| IL141266A0 (en) | 2002-03-10 |
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