CN114621572B - Carbon dioxide copolymer composition and preparation method thereof - Google Patents
Carbon dioxide copolymer composition and preparation method thereof Download PDFInfo
- Publication number
- CN114621572B CN114621572B CN202111118663.XA CN202111118663A CN114621572B CN 114621572 B CN114621572 B CN 114621572B CN 202111118663 A CN202111118663 A CN 202111118663A CN 114621572 B CN114621572 B CN 114621572B
- Authority
- CN
- China
- Prior art keywords
- epoxy compound
- carbon dioxide
- dioxide copolymer
- epoxy
- filler
- 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.)
- Active
Links
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Natural products O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 43
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 43
- 229920001577 copolymer Polymers 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000000945 filler Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000004593 Epoxy Substances 0.000 claims description 53
- 150000001875 compounds Chemical class 0.000 claims description 46
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 33
- -1 acid anhydride compounds Chemical class 0.000 claims description 29
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 25
- 239000004611 light stabiliser Substances 0.000 claims description 16
- 229920001610 polycaprolactone Polymers 0.000 claims description 14
- 239000004632 polycaprolactone Substances 0.000 claims description 14
- 235000011187 glycerol Nutrition 0.000 claims description 13
- 239000004014 plasticizer Substances 0.000 claims description 13
- 239000007822 coupling agent Substances 0.000 claims description 12
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 239000010452 phosphate Substances 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 239000000049 pigment Substances 0.000 claims description 9
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 8
- 230000003712 anti-aging effect Effects 0.000 claims description 7
- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- 125000002256 xylenyl group Chemical group C1(C(C=CC=C1)C)(C)* 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 9
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 239000002023 wood Substances 0.000 description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 5
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 229920000704 biodegradable plastic Polymers 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 5
- 239000008116 calcium stearate Substances 0.000 description 5
- 235000013539 calcium stearate Nutrition 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 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 4
- 230000000052 comparative effect Effects 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 4
- 229920000881 Modified starch Polymers 0.000 description 3
- 239000004368 Modified starch Substances 0.000 description 3
- 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 3
- 235000013312 flour Nutrition 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 235000019426 modified starch Nutrition 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UWDMKTDPDJCJOP-UHFFFAOYSA-N 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-ium-4-carboxylate Chemical compound CC1(C)CC(O)(C(O)=O)CC(C)(C)N1 UWDMKTDPDJCJOP-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000001384 succinic acid Substances 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
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000723347 Cinnamomum Species 0.000 description 1
- 229920002261 Corn starch Polymers 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
- 241000196324 Embryophyta Species 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000209 biodegradability test Toxicity 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000011499 joint compound Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- TUUQISRYLMFKOG-UHFFFAOYSA-N trihexyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCCCCCOC(=O)CC(C(=O)OCCCCCC)(OC(C)=O)CC(=O)OCCCCCC TUUQISRYLMFKOG-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- APVVRLGIFCYZHJ-UHFFFAOYSA-N trioctyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CCCCCCCCOC(=O)CC(O)(C(=O)OCCCCCCCC)CC(=O)OCCCCCCCC APVVRLGIFCYZHJ-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention relates to C08L 3/02, in particular to a carbon dioxide copolymer composition and a preparation method thereof. The preparation method comprises the following raw materials: PPCP, filler; the mass ratio of the PPCP to the filler is 100 (1-500). The carbon dioxide copolymer composition prepared by the carbon dioxide copolymer composition and the preparation method thereof provided by the invention not only has excellent mechanical properties and degradability, but also has good hydrophobicity.
Description
Technical Field
The invention relates to C08L 3/02, in particular to a carbon dioxide copolymer composition and a preparation method thereof.
Background
The carbon dioxide copolymer uses carbon dioxide as a raw material, and has excellent biodegradability, thus being an ideal full-degradable plastic variety. In recent years, with the development of science and technology, degradable materials related to carbon dioxide copolymers are rapidly developed, so that the problem of white pollution can be fundamentally solved, and the sustainable development of green is promoted. However, the popularization and application of the degradable material prepared by the carbon dioxide copolymer are limited by factors such as non-ideal thermal and mechanical properties.
The patent CN202011020665.0 provides a functional degradable material with controllable degradation period and a preparation method thereof, and the functional degradable material with different degradation periods is prepared by interaction among polybutylene terephthalate, carbon dioxide-based copolymer, polybutylene succinate, auxiliary agent and the like, and can be suitable for different degradation periods. But its application is limited due to poor light stabilizer properties.
The patent CN201811563967.5 provides a stretch-proof degradable barrier plastic packaging film and a preparation method thereof, wherein carbon dioxide copolymer and maleic anhydride are used as raw materials, and substances such as monodisperse silica microspheres and the like are added in an auxiliary manner, so that not only is the mechanical property improved, but also the thermal stability of an intermediate barrier layer is improved. However, the preparation is complex, the production cost is high, and the requirements of customers cannot be fully met.
Disclosure of Invention
In order to solve the above technical problem, a first aspect of the present invention provides a composition of carbon dioxide copolymer, comprising the following raw materials: PPCP, filler; the mass ratio of the PPCP to the filler is 100 (1-500).
Preferably, the raw materials further comprise at least one of epoxy compounds, phosphate compounds, plasticizers, acid anhydrides, coupling agents, lubricants, anti-aging systems, pigments, citric acid and benzoyl peroxide.
Preferably, the raw materials comprise, by weight, 100 parts of PPCP, 1-500 parts of filler, 2-5 parts of epoxy compounds, 0.5-1.5 parts of phosphate compounds, 3-5 parts of plasticizers, 1.5-2.5 parts of acid anhydride compounds, 1-2 parts of coupling agents, 0.2-0.5 part of lubricants, 0.3-0.7 part of anti-aging systems, 1-3 parts of pigments, 0.7-1.5 parts of citric acid and 0.1-0.2 part of benzoyl peroxide.
Packing material
Preferably, the filler comprises an inorganic filler and/or an organic filler.
Preferably, the inorganic filler comprises at least one of calcium carbonate, talcum powder, clay, white carbon black, barium sulfate, aluminum hydroxide, magnesium hydroxide, asbestos, glass beads, glass fiber, red mud, fly ash and carbon black.
Preferably, the organic filler comprises at least one of starch, wood flour and plant straw.
Further preferably, the mass ratio of the PPCP to the filler is 100 (50-300).
Still more preferably, the mass ratio of PPCP to filler is 100 (80-120).
Epoxy compound
Preferably, the epoxy compound includes a first epoxy compound and a second epoxy compound. The weight ratio of the first epoxy compound package to the second epoxy compound is (8-12): (1-3).
Preferably, the epoxy value of the first epoxy compound is 6.5-7.5.
Preferably, the average molecular weight of the first epoxy compound is 800-1200.
Preferably, the iodine value of the first epoxy compound is 0.67/100g, and the acid value is 0.7KOH/g.
Preferably, the second epoxy compound has an epoxy equivalent of 270 to 350.
Preferably, the average molecular weight of the second epoxy compound is 7000 to 7500.
The composition of the carbon dioxide copolymer prepared by taking PPCP as a matrix and various fillers as reinforcing filler substances has excellent biodegradability and mechanical properties. But is limited by the property of the material, so that the processing window is narrow, the defects of thermal degradation and the like are easy to occur, and the application range is severely limited. According to the invention, unexpected researches show that the processing performance and the mechanical property and the thermal stability of the epoxy compound can be obviously improved by adding the epoxy compounds with different epoxy values. It is presumed that the epoxy group contained in the epoxy compound can react with the active group contained in the substance such as PPCP, so that the disperse phase becomes blurred, the acting force between two phase interfaces is improved, and the melt viscosity of the composition of the carbon dioxide copolymer is improved, so that the composition of the carbon dioxide copolymer has better processability, and further the mechanical property and thermal degradability of the carbon dioxide copolymer are improved.
In a preferred embodiment, the weight ratio of the epoxy compound to the plasticizer is (3-4): (3-4).
Phosphate compound
Preferably, the phosphate compound comprises at least one of triphenyl phosphite, trialkyl phosphate, toluene xylene phosphate and diphenyl octyl phosphate.
Further preferably, the phosphate ester compound includes triphenyl phosphite and diphenyl monooctyl phosphate. The weight ratio of the triphenyl phosphite to the diphenyl monooctyl phosphate is (5-8): (1-3).
In a preferred embodiment, the weight ratio of the plasticizer to the phosphate compound is (3-4): (0.7-1.2).
Anhydride compound
Preferably, the acid anhydride compound comprises at least one of maleic anhydride, succinic anhydride, phthalic anhydride, and trimellitic anhydride.
Plasticizer(s)
Preferably, the plasticizer comprises at least one of glycerol, polyethylene glycol, polypropylene glycol, citrate, sorbitol ester, polycaprolactone.
Further preferably, the plasticizer comprises glycerol, citrate, polycaprolactone. The weight ratio of the glycerin, the citric acid ester and the polycaprolactone is (5-8): (1-2): (2-3).
The unexpected study of the present invention shows that the degradability and mechanical properties of the composition of carbon dioxide copolymer can be significantly improved by glycerol, citrate, and polycaprolactone, presumably due to the insertion of plasticizer between molecular chains of the composition of carbon dioxide copolymer, while glycerol, citrate, and polycaprolactone containing polar groups will interact with active groups contained in the composition of carbon dioxide copolymer, especially when the weight ratio of glycerol, citrate, and polycaprolactone is (5-8): (1-2): and (2-3), the interaction force among molecular chains and the arrangement density of the molecular chains among unit cells of the composition of the carbon dioxide copolymer can be effectively improved, and the plasticizing effect and the water resistance of the system are enhanced.
Preferably, the polycaprolactone has an average molecular weight of 45000-55000.
Preferably, the citrate comprises at least one of triethyl citrate, tributyl citrate, trioctyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, acetyl trioctyl citrate, and acetyl tri-n-hexyl citrate.
Coupling agent
Preferably, the coupling agent comprises at least one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent and a rare earth coupling agent.
Further preferably, the coupling agent is a silane coupling agent.
Preferably, the silane coupling agent comprises at least one of gamma-aminopropyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane, gamma-glycidoxypropyl trimethoxysilane, vinyltriethoxysilane, vinyltris (beta-methoxyethoxy) silane.
Further preferably, the silane coupling agent comprises gamma-aminopropyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane. The weight ratio of the gamma-aminopropyl triethoxysilane to the gamma-methacryloxypropyl trimethoxysilane is (1-3): (5-8).
Lubricant
Preferably, the lubricant includes stearic acid, calcium stearate and polyethylene wax. The weight ratio of the stearic acid to the calcium stearate to the polyethylene wax is 1: (1-2): (3-5).
Preferably, the polyethylene wax has an average molecular weight of 1600 to 2200.
Anti-aging system
Preferably, the antioxidant system comprises a light stabilizer and an antioxidant. The weight ratio of the light stabilizer to the antioxidant is (3-5): (1-3).
Preferably, the light stabilizer is a hindered amine light stabilizer.
Preferably, the average molecular weight of the light stabilizer is 3000 to 4000.
Preferably, the hindered amine light stabilizer is a polymer of succinic acid and 4-hydroxy-2, 6-tetramethyl-1-piperidinol.
Preferably, the antioxidants include antioxidant 1010, antioxidant 168, and thiosulfate DLTDP. The weight ratio of the antioxidant 1010 to the antioxidant 168 to the thiosulfate DLTDP is (8-12): (13-17): (5-10).
Pigment
Preferably, the pigment comprises at least one of channel black, titanium dioxide, cadmium yellow, phthalocyanine blue, ultramarine blue, iron oxide red, azo red and azo yellow.
Further preferably, the pigment is titanium dioxide.
Preferably, the rutile type content in the titanium dioxide is more than or equal to 98%.
In a preferred embodiment, the weight ratio of the anhydride-based compound to citric acid is (1.8-2.3): (0.8-1.2).
In a second aspect, the present invention provides a method for preparing a composition of carbon dioxide copolymer, comprising the steps of: 1) Pre-mixing PPCP and filler; 2) The mixture was fed into a melt kneading apparatus to prepare the mixture.
Preferably, the preparation method comprises the following steps: the PPCP and the filler are dried for 4 hours at 60 ℃ in advance, then mixed for 3 minutes in a mixer, then the rest raw materials are added for continuous mixing for 2 minutes, finally the premix is added into a double-screw extruder, and extrusion granulation is carried out at 100 ℃ to 180 ℃ to obtain the carbon dioxide copolymer composition.
The beneficial effects are that:
the existing biodegradable plastics on the market at present are to realize excellent degradability, and often adopt methods for sacrificing other performances, so that the prepared biodegradable plastics are poor in mechanical property, easy to thermally degrade, photodegradation and the like, the service cycle of the biodegradable plastics is seriously influenced, and the application range of the biodegradable plastics is limited.
According to the carbon dioxide copolymer composition prepared by taking PPCP as a matrix and taking various fillers as reinforcing filler materials, through the addition of epoxy compounds with different epoxy values and the adoption of a glycerol, citrate and polycaprolactone composite plasticizing system, the intermolecular interaction of the carbon dioxide copolymer composition is improved, so that the carbon dioxide copolymer composition has good mechanical properties and hydrophobicity, meanwhile, a specific anti-aging system is assisted to remove free radicals, the degradation and aging chain reaction of the carbon dioxide copolymer composition is inhibited, the light stability and the heat stability of the carbon dioxide copolymer composition are further improved, and the service cycle of biodegradable plastics is prolonged. Besides, the composition for preparing the carbon dioxide copolymer has wide universality and can be used for preparing sheets and pipes, film products, injection molding parts, foaming products, various cushioning packaging and heat insulation materials and the like.
Detailed Description
Examples
Example 1
A composition of carbon dioxide copolymer comprising the following raw materials: 100 parts of PPCP, 100 parts of filler, 3.2 parts of epoxy compound, 1.2 parts of phosphate compound, 2 parts of anhydride compound, 3.2 parts of plasticizer, 1.2 parts of coupling agent, 0.4 part of lubricant, 0.6 part of anti-aging system, 1.5 parts of pigment, 1 part of citric acid and 0.12 part of benzoyl peroxide.
The PPCP is purchased from Shandong Unixin environmental protection technology Co.
The filler is calcium carbonate, the calcium carbonate is heavy calcium carbonate, and the calcium carbonate is subjected to surface treatment by using 1% titanate coupling agent. The filler has an average particle size of 23um. The filler was purchased from Cinnamomum Lin Shisan Xin New Material Co.Ltd.
The epoxy compound comprises a first epoxy compound and a second epoxy compound. The weight ratio of the first epoxy compound package to the second epoxy compound is 10:2. the epoxy value of the first epoxy compound is 6.83. The average molecular weight of the first epoxy compound is 1000. The iodine value of the first epoxy compound is 0.67/100g, and the acid value is 0.7KOH/g. The first epoxy compound is epoxidized soybean oil, and is purchased from Termoplasticos Del Sur S.A, model: greenSoft D epoxidized soybean oil. The second epoxy compound has an epoxy equivalent of 310. The average molecular weight of the second epoxy compound is 7250. The second epoxy compound is purchased from Shanghai sea ice new material science and technology Co., ltd., model: ADR-4468.
The phosphate compound comprises triphenyl phosphite and diphenyl octyl phosphate. The weight ratio of the triphenyl phosphite to the diphenyl monooctyl phosphate is 7:2.
the anhydride compound is maleic anhydride.
The plasticizer comprises glycerin, citric acid ester and polycaprolactone. The weight ratio of the glycerin, the citric acid ester and the polycaprolactone is 7:2:3. the citrate is acetyl tributyl citrate, and the average molecular weight of the polycaprolactone is 50000. Purchased from Hunan Seiko Material technology Co., ltd., model: PCL-6500.
The coupling agent is a silane coupling agent. The silane coupling agent comprises gamma-aminopropyl triethoxysilane and gamma-methacryloxypropyl trimethoxysilane. The weight ratio of the gamma-aminopropyl triethoxysilane to the gamma-methacryloxypropyl trimethoxysilane is 2:6.
the lubricant includes stearic acid, calcium stearate and polyethylene wax. The weight ratio of the stearic acid to the calcium stearate to the polyethylene wax is 1:1.5:3.5. the average particle size of the calcium stearate is 75um. The polyethylene wax has an average molecular weight of 1900. The lubricants were all purchased from Shandong Baoliley plastics aids Co.
The antioxidant system comprises a light stabilizer and an antioxidant. The weight ratio of the light stabilizer to the antioxidant is 4:2. the light stabilizer is a hindered amine light stabilizer. The average molecular weight of the light stabilizer was 3550. The hindered amine light stabilizer is a polymer of succinic acid and 4-hydroxy-2, 6-tetramethyl-1-piperidinol (CAS number: 65447-77-0). The light stabilizers were purchased from Yixing city angel synthetic chemistry Co., ltd., model: hindered amine light stabilizer 622. The antioxidant comprises antioxidant 1010, antioxidant 168 and thiosulfate DLTDP. The weight ratio of the antioxidant 1010 to the antioxidant 168 to the thiosulfate DLTDP is 10:15:8.
the pigment is titanium dioxide. The rutile type content in the titanium dioxide is 99%. The pigment was purchased from the company Jishun Ind Co., dongguan.
A method of preparing a composition of carbon dioxide copolymer comprising the steps of: the PPCP and the filler are dried for 4 hours at 60 ℃ in advance, then mixed for 3 minutes in a mixer, then the rest raw materials are added for continuous mixing for 2 minutes, finally the premix is added into a double-screw extruder, and extrusion granulation is carried out at 150 ℃ to obtain the carbon dioxide copolymer composition.
Example 2
A carbon dioxide copolymer composition, the specific embodiment of which is the same as in example 1, is different in that 60 parts of the filler is talc. The talc powder was surface-treated with 1% silane coupling agent. The average particle size of the talcum powder is 23um. The filler was purchased from the florida Yongfengda superfine talc mill.
Example 3
A carbon dioxide copolymer composition, the specific embodiment of which is the same as in example 1, is different in that the filler is 50 parts and the filler is modified starch. The modified starch is prepared from corn starch: the glycerol is obtained by extrusion granulation according to the weight ratio of 10:3. The modified starch was purchased from texas starch limited.
Example 4
A carbon dioxide copolymer composition, the specific embodiment of which is the same as in example 1, is different in that the filler is 50 parts and the filler is wood flour. The wood powder is pine wood powder, and the average grain diameter of the wood powder is 180um. The wood flour is purchased from the Lingshu county health Dan Kuangwu powder factory.
Comparative example 1
A carbon dioxide copolymer composition, the specific embodiment of which is the same as in example 1, is characterized in that the weight ratio of the first epoxy compound package to the second epoxy compound package is 7:2.
comparative example 2
A composition of carbon dioxide copolymer, the specific embodiment is the same as in example 1, wherein the weight ratio of glycerin, citrate and polycaprolactone is 7:2:1.
performance testing
The resulting carbon dioxide copolymer composition was placed in a single screw extruder at a controlled temperature of 195℃and a rotational speed of 70r/min to prepare a sheet, and the following test was conducted:
1. tensile property test: the test is carried out according to national standard GB/T1040.
2. Biodegradability test: the test is carried out according to national standard GB/T19277, the temperature is 58+/-2 ℃ and the composting time is 3 months.
TABLE 1 Performance test results
| Tensile strength MPa | Degradation rate% | |
| Example 1 | 23 | 100 |
| Example 2 | 22 | 100 |
| Example 3 | 22 | 100 |
| Example 4 | 21 | 100 |
| Comparative example 1 | 18 | 97 |
| Comparative example 2 | 16 | 96 |
Claims (5)
1. A composition of carbon dioxide copolymer, characterized by comprising the following raw materials: PPCP, filler; the mass ratio of the PPCP to the filler is 100 (1-500);
the raw materials also comprise epoxy compounds, phosphate compounds, plasticizers, acid anhydride compounds, coupling agents, lubricants, anti-aging systems, pigments, citric acid and benzoyl peroxide;
the epoxy compounds comprise a first epoxy compound and a second epoxy compound, wherein the weight ratio of the first epoxy compound to the second epoxy compound is 10:2;
the first epoxy compound is epoxidized soybean oil;
the plasticizer comprises glycerin, citric acid ester and polycaprolactone; the weight ratio of the glycerin, the citric acid ester and the polycaprolactone is 7:2:3, a step of;
the weight ratio of the epoxy compound to the plasticizer is 1:1;
the second epoxy compound has an epoxy equivalent of 310; the average molecular weight of the second epoxy compound is 7250; the second epoxy compound is purchased from Shanghai sea ice new material science and technology Co., ltd., model: ADR-4468.
2. The carbon dioxide copolymer composition according to claim 1, wherein the first epoxy compound has an epoxy value of 6.5 to 7.5.
3. The composition of any one of claims 1-2, wherein the phosphate compound comprises at least one of triphenyl phosphite, trialkyl phosphate, toluene xylenyl phosphate, diphenyl monooctyl phosphate.
4. The carbon dioxide copolymer composition of claim 1, wherein the anti-aging system comprises a light stabilizer and an antioxidant.
5. A method for preparing a carbon dioxide copolymer composition according to any of claims 1-4, comprising the steps of: the PPCP and the filler are dried for 4 hours at 60 ℃ in advance, then mixed for 3 minutes in a mixer, then the rest raw materials are added for continuous mixing for 2 minutes, finally the premix is added into a double-screw extruder, and extrusion granulation is carried out at 100 ℃ to 180 ℃ to obtain the carbon dioxide copolymer composition.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111118663.XA CN114621572B (en) | 2021-09-24 | 2021-09-24 | Carbon dioxide copolymer composition and preparation method thereof |
| PCT/CN2022/119739 WO2023045888A1 (en) | 2021-09-24 | 2022-09-20 | Carbon dioxide copolymer composition and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111118663.XA CN114621572B (en) | 2021-09-24 | 2021-09-24 | Carbon dioxide copolymer composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114621572A CN114621572A (en) | 2022-06-14 |
| CN114621572B true CN114621572B (en) | 2024-04-02 |
Family
ID=81897061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111118663.XA Active CN114621572B (en) | 2021-09-24 | 2021-09-24 | Carbon dioxide copolymer composition and preparation method thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN114621572B (en) |
| WO (1) | WO2023045888A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114621572B (en) * | 2021-09-24 | 2024-04-02 | 山东联欣环保科技有限公司 | Carbon dioxide copolymer composition and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033329A (en) * | 2007-01-18 | 2007-09-12 | 武汉理工大学 | Preparation method of full-degradation polylactic acid nano composite material |
| CN111073235A (en) * | 2019-09-30 | 2020-04-28 | 浙江工业大学 | Fast-crystallization high-temperature-resistant polylactic acid composition and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100999602A (en) * | 2006-12-18 | 2007-07-18 | 中山大学 | Degradable carbon dioxide plastic base composite material and preparation process thereof |
| CN101293994B (en) * | 2007-04-25 | 2012-05-30 | 河南天冠企业集团有限公司 | Multi-component totally degradable polymer composite and its preparation method |
| CN101935445B (en) * | 2010-09-21 | 2012-05-23 | 中国科学院长春应用化学研究所 | Carbon dioxide-propylene oxide copolymer composition |
| CN104910603A (en) * | 2015-06-26 | 2015-09-16 | 青岛农业大学 | Carbon-dioxide-base polymer/modified starch degradable agricultural mulching film and preparation method thereof |
| CN111378101B (en) * | 2020-04-26 | 2022-02-01 | 中山大学 | Preparation method of biodegradable carbon dioxide-based polyester-polycarbonate terpolymer |
| CN114621572B (en) * | 2021-09-24 | 2024-04-02 | 山东联欣环保科技有限公司 | Carbon dioxide copolymer composition and preparation method thereof |
-
2021
- 2021-09-24 CN CN202111118663.XA patent/CN114621572B/en active Active
-
2022
- 2022-09-20 WO PCT/CN2022/119739 patent/WO2023045888A1/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033329A (en) * | 2007-01-18 | 2007-09-12 | 武汉理工大学 | Preparation method of full-degradation polylactic acid nano composite material |
| CN111073235A (en) * | 2019-09-30 | 2020-04-28 | 浙江工业大学 | Fast-crystallization high-temperature-resistant polylactic acid composition and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023045888A1 (en) | 2023-03-30 |
| CN114621572A (en) | 2022-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110591270B (en) | Self-cleaning polypropylene plastic barrel and preparation method thereof | |
| CN102858821B (en) | Chlorine-resistant crosslinkable polyolefin compositions and articles made therefrom | |
| CN107474369B (en) | Polyethylene functional master batch and preparation method thereof | |
| US4017452A (en) | Polymer modified hydrophilic inorganic fillers for thermoplastic polymeric materials | |
| ITMI932485A1 (en) | BIODEGRADABLE COMPOSITION OF POLYETHYLENE CHEMICALLY LINKED WITH STARCH AND PROCEDURE FOR ITS PREPARATION | |
| CN114621572B (en) | Carbon dioxide copolymer composition and preparation method thereof | |
| CN112048124B (en) | Glass fiber reinforced polypropylene material with low-floating-fiber surface and preparation method thereof | |
| CN111925598B (en) | Scratch-resistant polypropylene composite material and preparation method thereof | |
| CN112048167A (en) | Degradable thermoplastic elastomer and preparation method thereof | |
| AU2021221902A1 (en) | Colorant and additive concentrate carrier system with efficacy over a wide range of polymeric processing temperatures | |
| KR101776999B1 (en) | Pellet available to complex degrade and rapidly become low-molecular substance for containing double bond and its preparing method | |
| CN1298777C (en) | Thermal oxidative degradation-promoting mother particle used for plastics and its preparation method | |
| CN112745665B (en) | Polypropylene material injection molding flow pattern effect master batch and preparation method thereof | |
| CN102079850A (en) | Enhanced and toughened fully degradable polylactic acid packaging material and preparation method thereof | |
| CN112029205B (en) | Environment-friendly composite plastic with pearlescent effect and multicolor pattern effect and preparation method thereof | |
| US6054529A (en) | Blends of and methods of blending EVOH polymers and ethylene based polymers having improved environmental stress cracking or environmental fatigue resistance, and products therefrom | |
| CN110183787B (en) | Rubber V-belt vulcanized rubber sleeve and production method thereof | |
| CN113861568B (en) | Polypropylene composite material and preparation method thereof | |
| US5637629A (en) | Reinforced polyolefinic thermoplastic composition | |
| EP0708144B1 (en) | Melt-processed blends containing poly(vinyl alcohol) | |
| CN111286127A (en) | Polypropylene composite material without tiger stripes at high temperature and preparation method thereof | |
| WO2013003591A2 (en) | Moisture resistant polymeric composites | |
| CN116376142A (en) | Micro-foaming PE material, preparation method and packaging cover | |
| CN115449195B (en) | Super-hydrophobic high-barrier soil moisture preservation, humidification and aging resistance full-biodegradable mulch film material and preparation method thereof | |
| US5457145A (en) | Reinforced polyolefinic thermoplastic composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |