WO2014202603A1 - Nucleating composition and thermoplastic polymer composition comprising such nucleating composition - Google Patents
Nucleating composition and thermoplastic polymer composition comprising such nucleating composition Download PDFInfo
- Publication number
- WO2014202603A1 WO2014202603A1 PCT/EP2014/062714 EP2014062714W WO2014202603A1 WO 2014202603 A1 WO2014202603 A1 WO 2014202603A1 EP 2014062714 W EP2014062714 W EP 2014062714W WO 2014202603 A1 WO2014202603 A1 WO 2014202603A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- thermoplastic polymer
- polymer composition
- composition according
- mfi
- nucleating
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 139
- 229920001169 thermoplastic Polymers 0.000 title claims description 91
- 239000002667 nucleating agent Substances 0.000 claims abstract description 49
- 239000000454 talc Substances 0.000 claims abstract description 40
- 229910052623 talc Inorganic materials 0.000 claims abstract description 40
- -1 salt compound Chemical class 0.000 claims abstract description 38
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims description 58
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 54
- 239000011159 matrix material Substances 0.000 claims description 23
- 229920001971 elastomer Polymers 0.000 claims description 20
- 239000004711 α-olefin Substances 0.000 claims description 18
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 13
- 239000005977 Ethylene Substances 0.000 claims description 13
- 239000000806 elastomer Substances 0.000 claims description 12
- 150000001451 organic peroxides Chemical class 0.000 claims description 8
- 229920001384 propylene homopolymer Polymers 0.000 claims description 8
- 235000012222 talc Nutrition 0.000 description 38
- 239000000654 additive Substances 0.000 description 19
- 239000004416 thermosoftening plastic Substances 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 16
- 229920001155 polypropylene Polymers 0.000 description 16
- 239000004743 Polypropylene Substances 0.000 description 15
- 150000002978 peroxides Chemical class 0.000 description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 11
- 229910052791 calcium Inorganic materials 0.000 description 11
- 239000011575 calcium Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000005060 rubber Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 101100439208 Caenorhabditis elegans cex-1 gene Proteins 0.000 description 5
- 101000668432 Homo sapiens Protein RCC2 Proteins 0.000 description 5
- 102100039972 Protein RCC2 Human genes 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
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002516 radical scavenger Substances 0.000 description 5
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 4
- UPFSMSDGKQSRLD-UHFFFAOYSA-N 2-hexylpropanedioic acid Chemical class CCCCCCC(C(O)=O)C(O)=O UPFSMSDGKQSRLD-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 235000006708 antioxidants Nutrition 0.000 description 3
- 125000002619 bicyclic group Chemical group 0.000 description 3
- 159000000007 calcium salts Chemical class 0.000 description 3
- AIXMJTYHQHQJLU-UHFFFAOYSA-N chembl210858 Chemical compound O1C(CC(=O)OC)CC(C=2C=CC(O)=CC=2)=N1 AIXMJTYHQHQJLU-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 239000012963 UV stabilizer Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 235000013365 dairy product Nutrition 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 235000013310 margarine Nutrition 0.000 description 2
- 239000003264 margarine Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- BOOBDAVNHSOIDB-UHFFFAOYSA-N (2,3-dichlorobenzoyl) 2,3-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC(C(=O)OOC(=O)C=2C(=C(Cl)C=CC=2)Cl)=C1Cl BOOBDAVNHSOIDB-UHFFFAOYSA-N 0.000 description 1
- GWQOYRSARAWVTC-UHFFFAOYSA-N 1,4-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=C(C(C)(C)OOC(C)(C)C)C=C1 GWQOYRSARAWVTC-UHFFFAOYSA-N 0.000 description 1
- WVGXBYVKFQJQGN-UHFFFAOYSA-N 1-tert-butylperoxy-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1OOC(C)(C)C WVGXBYVKFQJQGN-UHFFFAOYSA-N 0.000 description 1
- VVFNNEKHSFZNKA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-ene Chemical compound CC(C)(C)OOC(C)(C)C=CC(C)(C)OOC(C)(C)C VVFNNEKHSFZNKA-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 101100439211 Caenorhabditis elegans cex-2 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004129 EU approved improving agent Substances 0.000 description 1
- 239000004608 Heat Stabiliser Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XXHCQZDUJDEPSX-KNCHESJLSA-L calcium;(1s,2r)-cyclohexane-1,2-dicarboxylate Chemical compound [Ca+2].[O-]C(=O)[C@H]1CCCC[C@H]1C([O-])=O XXHCQZDUJDEPSX-KNCHESJLSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- FXDGCBFGSXNGQD-FAESFXMKSA-L disodium;(1s,2s,3r,4r)-bicyclo[2.2.1]heptane-2,3-dicarboxylate Chemical compound [Na+].[Na+].C1C[C@H]2[C@@H](C([O-])=O)[C@@H](C(=O)[O-])[C@@H]1C2 FXDGCBFGSXNGQD-FAESFXMKSA-L 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 238000010103 injection stretch blow moulding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000004978 peroxycarbonates Chemical class 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
Classifications
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
-
- 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
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- 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
-
- 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
- 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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/02—Heterophasic composition
Definitions
- the invention relates to a nucleating composition comprising a salt of a metal or organic cation of a cyclic dicarboxylic acid as a first nucleating agent.
- the invention also relates to a thermoplastic polymer composition comprising said nucleating composition.
- the invention further relates to a shaped article comprising said thermoplastic polymer composition.
- Such a nucleating composition is known from document EP 1379368 B1.
- This document discloses at least one metal salt of hexahydrophthalic acid (HHPA), e.g. calcium, strontium, lithium and monobasic aluminium salt, to be used as nucleating agent to produce thermoplastic compositions showing improved crystallization behaviour.
- HHPA hexahydrophthalic acid
- thermoplastic composition comprising a polyolefin; a nucleating agent comprising a dicarboxylate salt compound, e.g.
- bicyclic [2.2.1] heptane dicarboxylate salt available from Milliken & Company under the trade name Hyperform ® HPN-68; a first fatty acid salt having a first cationic counter ion selected from the group consisting of calcium, sodium, lithium and barium, e.g. calcium stearate; and a second fatty acid salt having a second cationic counter ion selected from the group of magnesium, aluminium and zinc, e.g. zinc stearate.
- Nucleating agents are chemical compounds or compositions that enable faster nucleation or a higher crystallization temperature of thermoplastic polymers, resulting in productivity gains during their processing and in improved mechanical and physical properties of articles made from such thermoplastics. These compounds provide nucleation sites for crystal growth during cooling of a thermoplastic molten composition.
- a nucleating agent such as talc and carboxylate salts, e.g. sodium benzoate.
- nucleating agents are highly unpredictable technology area. Small changes in a molecular structure of the nucleator can drastically alter the ability of a nucleating agent to nucleate effectively a polymer composition. There are still many unknowns regarding the effect of a nucleating agent on polymer morphology during (re-)crystallization of thermoplastics.
- a nucleating composition is known from document EP 1379368 B1.
- This document discloses at least one metal salt of hexahydrophthalic acid (HHPA), e.g. calcium, strontium, lithium and monobasic aluminium salt, to be used as nucleating agent to produce thermoplastic compositions showing improved crystallization behavior.
- HHPA hexahydrophthalic acid
- thermoplastic composition comprising a polyolefin; a nucleating agent comprising a dicarboxylate salt compound, e.g.
- bicyclic [2.2.1] heptane dicarboxylate salt available from Milliken & Company under the trade name Hyperform ® HPN-68; a first fatty acid salt having a first cationic counter ion selected from the group consisting of calcium, sodium, lithium and barium, e.g. calcium stearate; and a second fatty acid salt having a second cationic counter ion selected from the group of magnesium, aluminium and zinc, e.g. zinc stearate.
- thermoplastic composition such as the flexural modulus and the impact strength.
- nucleating composition comprising:
- nucleating composition of present invention results in highly improved mechanical properties such as stiffness and impact.
- Additional advantages of the nucleating composition according to the present invention include decreased warpage of shaped articles made from a nucleated thermoplastic polymer composition; higher heat deflection temperature (HDT) and improved top load. Additional advantages of the nucleating composition according to the present invention include a lower shrinkage caused by temperature change of shaped articles made from a nucleated thermoplastic polymer composition, as determined by Coefficient of Linear Thermal Expansion (CLTE) measured according to ASTM D696.
- CLTE measures the change in length per unit length of a material per unit change in temperature. Expressed as in/in/°F or cm/cm/°C, the CLTE is used to calculate the dimensional change resulting from thermal expansion. CLTE is especially important when components of an assembly have widely varying thermal expansion coefficients.
- the first nucleating agent in the composition according to the present invention comprises a calcium cis-hexahydrophthalate compound of Formula (I).
- Hyperform ® HPN-20ETM nucleating agent commercialized by Milliken comprises such a calcium cis-hexahydrophthalate compound of Formula (I) and a stearate-containing compound as acid scavenger, e.g. zinc stearate.
- the nucleating composition according to the present invention comprises talc as second nucleating agent.
- Talc is a common additive in industry, mostly used as reinforcing agent or filler and also as nucleating agent for various polymer compositions.
- Talc typically is considered a filler when employed in relatively high amounts, for example of about from 10 to 50 wt%, based on the total polymer composition. When talc is used under 5 wt%, it is no longer considered a filler but acts as nucleating agent.
- Talc may be employed in present invention in powder form, preferably having a particle size distribution defined by a d 50 of from 0.1 to 20 ⁇ ; more preferably of from 0.5 to 15 ⁇ ; or from 0.7 to 8 ⁇ to improve its nucleating behaviour.
- the first nucleating agent and the second nucleating agent can be present in the nucleating composition according to the invention in widely varying amounts, for example in a weight ratio of from 1 : 1200 to 2:1 ; preferably in a ratio of from 1 :500 to 1 :1 ; more preferably in a ratio of from 1 :100 to 1 :2; even more preferably in a ratio of from 1 :50 to 1 :5.
- the advantage of adding these components within these ratio limits lies in the possibility to control dimensional stability at fast cycle times and mechanical properties.
- the nucleating composition may be employed as powder, dry mix or liquid blend. It may be also mixed with other additives to form an additive pre-blend or it may be blended with a binder material in low concentrations, such as a wax or thermoplastic polymer that is compatible with the polymer for which the composition is intended to serve as nucleating agent.
- the nucleating composition can also be combined with a thermoplastic polymer as a masterbatch or concentrate.
- These blends may be provided, optionally, with acid scavengers and other additives, such as stabilizers; primary and secondary antioxidants.
- Suitable acid scavengers can include zinc stearate, calcium stearate or other stearate-based compounds, and hydrotalcite.
- thermoplastic polymer composition comprising a thermoplastic polymer and the nucleating composition according to present invention.
- thermoplastic refers to a polymeric material that melts upon exposure to sufficiently high temperatures, but re-solidifies (crystallizes) upon cooling. "Thermoplastic” particularly defines polymers having (semi-)crystalline morphology upon cooling.
- thermoplastic polymers include polyamides, such as polyamide-6, polyamide-6,6 or polyamide-4,6; polyolefins like polypropylenes, polyethylenes, polybutylene; polyesters, such as polyethylene terephthalate, polybutylene terephthalate; polyphenylene sulphide; polyurethanes; as well as any type of polymer blends and compounds and any combinations thereof.
- the thermoplastic polymer is a crystallisable polypropylene, like a propylene homopolymer, a random copolymer, or a so-called heterophasic or impact copolymer of propylene and ethylene and/or another alpha-olefin.
- the thermoplastic polymer is a heterophasic polypropylene copolymer.
- Such copolymer basically has at least a two- phase structure, consisting of a propylene-based semi-crystalline matrix and a dispersed elastomer phase, typically an ethylene-propylene rubber (EPR).
- EPR ethylene-propylene rubber
- These polypropylenes are generally prepared in one or more reactors, by polymerization of propylene in the presence of a catalyst system, and subsequent polymerization of a propylene-ethylene mixture; but can also be made by blending different (co)polymers.
- the resulting polymeric materials are heterophasic; studies have demonstrated the presence of four phases in heterophasic propylene-based copolymers: crystalline polypropylene, amorphous polypropylene, crystalline ethylene-propylene rubber, and amorphous ethylene-propylene rubber.
- the advantage of such polymer is improved impact resistance, especially at lower temperatures.
- the thermoplastic polymer is a heterophasic propylene copolymer comprising a matrix phase comprising propylene and a dispersed phase comprising an ethylene-alpha-olefin elastomer.
- the heterophasic propylene copolymer comprises from 60 to 92 wt% of a matrix phase comprising a propylene homopolymer and/or a propylene copolymer comprising at least 90 wt% of propylene and up to 10 wt% of ethylene and/or at least one C 4 to Cio alpha-olefin, and from 8 to 40 wt% of dispersed phase comprising an ethylene-alpha-olefin elastomer comprising from 40 to 65 wt% of ethylene and from 35 to 60 wt% of at least one C 3 to C-
- the percentage of matrix and dispersed component is based on the total weight of the heterophasic propylene copolymer; comonomer contents are based on copolymer component.
- the matrix phase is a propylene homopolymer and the mass dispersed phase is an ethylene-alpha-olefin elastomer comprising from 40 to 65 wt% of ethylene and from 35 to 60 wt% of propylene.
- the thermoplastic polymer composition according to present invention preferably contains of from 0.0025 to 0.1 wt% of the first nucleating agent based on the total thermoplastic polymer composition.
- a certain minimum amount of the first nucleating agent is needed to effectively influence nucleating behaviour and properties the polymer composition further comprising talc as nucleating agent; preferably, the nucleating composition contains therefore at least 0.004, 0.005, 0.008, 0.01 wt% of the first nucleating agent. Further increasing the amount of the first nucleating agent in the composition to above 0.1 wt% would hardly contribute to improving the properties of final product.
- the nucleating composition thus contains at most 0.08, 0.06, 0.05, 0.03 wt% of the first nucleating agent. It is a special advantage of the present invention that a relatively low amount of the first nucleating agent can be applied, in combination with the talc-based second nucleating agent; giving not only improved performance but also reducing costs.
- the amount of talc used as second nucleating agent in the polymer composition is preferably of from 0.1 to 5 wt%, more preferably from 0.2 to 4 wt%; or from 0.3 to 3 wt%, based on the total thermoplastic polymer composition.
- a certain minimum amount of talc is necessary to provide nucleating effect and good mechanical characteristics, such as stiffness.
- the nucleation composition contains thus at least 0.2, 0.3 or even 0.5 wt% of talc. If the nucleating composition would contain more than 3 wt% of talc, the additional amount might only behave as filler agent.
- the nucleation composition contains therefore at most 4 or 3 wt% of talc.
- the heterophasic propylene copolymer of the thermoplastic polymer composition according to the invention preferably has a MFI of at least 1 as determined by ISO 1 133 at 230 °C; 2.16 kg.
- the thermoplastic polymer composition further comprises an organic peroxide.
- Organic peroxides are known to be used for viscosity reduction. There are different ways in which the organic peroxides behave in conventional degradation processes upon heating and melting conditions. On one hand, under certain process conditions, the peroxides initially decompose to produce free radicals, which then abstract hydrogen from a tertiary carbon of the polypropylene backbone to form free radicals on the polymer, and which further recombine. On the other hand, peroxides initiate a breakage of the longest chains of the polymer molecules and, subsequently, this results in a decrease in viscosity of the polymer, an increase in melt flow rate, and a narrower molecular weight distribution, characteristics which are directly responsible for improved flow properties of polypropylene in order to make the product more suitable for certain applications.
- Suitable for present invention are organic peroxides having a decomposition half-life of less than 1 minute at the average process temperature during formation of the modified polypropylene compositions.
- Suitable organic peroxides include dialkyl peroxides, e.g. dicumyl peroxides, peroxyketals, peroxycarbonates, diacyl peroxides, peroxyesters and peroxydicarbonates.
- a dialkyl peroxides is employed in the process according to the present invention. More preferably, the peroxide is a,a'-bis-(tert- butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)-hexane or 3,6,9- Triethyl-3,6,9-trimethyl-1 ,4,7-triperoxonane.
- the organic peroxide of present invention may be applied in amount of between 0.01 wt % and 0.3 wt%, preferably between 0.05 and 0.25 wt% and more preferably between 0.1 and 0.2 wt% based on the total composition.
- the heterophasic propylene copolymer of the thermoplastic polymer composition according to the invention may have a MFI of at least 1 and less than 10 dg/min.
- composition according to the invention comprising this type of propylene copolymer having a medium MFI combines very high impact resistance, also at low temperatures, with high stiffness and offers good flow properties. By its design it is offering potential of cycle time reduction (shorter holding pressure times, faster injection speed and shorter cooling time), of down gauging and easiness of processing and better esthetics of the parts, reflected in a better sink mark capability. Due to its narrow molecular weight distribution, the very low tendency to warp and the excellent surface quality, the compositions according to the invention are typically used in injection moulding of suitcase shells, crates & boxes, appliances, electronic equipment and automotive parts including children's car seats. Accordingly, the present invention relates to shells, crates, boxes, appliances, electronic equipment and automotive parts including children's car seats comprising the thermoplastic polymer composition according to the invention comprising this type of propylene copolymer.
- the propylene homopolymer of the matrix phase has a MFI of at least 1 and less than 50 dg/min, e.g. 1 to 10 dg/min.
- the ethylene-alpha-olefin elastomer of the dispersed phase has a MFI of 0.01 to 0.5 dg/min.
- the mass dispersed phase may be an ethylene-alpha-olefin elastomer comprising from 40 to 60 wt% of ethylene and from 40 to 60 wt% of propylene.
- the polypropylene composition comprising such a heterophasic propylene copolymer was found to show a very high impact strength as well as a high flexural modulus.
- the mass dispersed phase may be an ethylene-alpha-olefin elastomer comprising from 60 to 65 wt% of ethylene and from 35 to 40 wt% of propylene.
- the polypropylene composition comprising such a heterophaseic propylene copolymer was found to show an extremely high impact strength.
- the thermoplastic polymer composition according to the invention wherein the heterophasic propylene copolymer has a MFI of at least 1 and less than 10 dg/min preferably has a MFI of at least 5 and less than 30 dg/min.
- the thermoplastic polymer composition according to the invention has a high stiffness. For purpose of the present invention, stiffness is determined by measuring the flexural modulus according to ASTM D790-10. Flexural modulus was determined on 3.2mm thick specimens according to IS037/2, parallel (flexural modulus II) and perpendicular (flexural modulus L) orientation.
- thermoplastic polymer composition according to the invention wherein the heterophasic propylene copolymer has a MFI of at least 1 and less than 10 dg/min preferably has a flexural modulus L of at least 1000 MPa, preferably at least 1 100 MPa, more preferably at least 1200 MPa.
- thermoplastic polymer composition according to the invention wherein the heterophasic propylene copolymer has a MFI of at least 1 and less than 10 dg/min preferably has a flexural modulus II of at least 1000 MPa, preferably at least 1 100 MPa, more preferably at least 1200 MPa.
- thermoplastic polymer composition according to the invention has a high impact strength.
- impact strength is determined by measuring the Izod impact strength at 23°C according to ISO 180 4A, Test geometry: 65*12.7*3.2 mm, notch 45° according to ISO 37/2 parallel and perpendicular orientation.
- thermoplastic polymer composition according to the invention wherein the heterophasic propylene copolymer has a MFI of at least 1 and less than 10 dg/min preferably has an Izod impact strength L (23 °C, kJ/m2) of at least 55, preferably at least 60.
- thermoplastic polymer composition according to the invention wherein the heterophasic propylene copolymer has a MFI of at least 1 and less than 10 dg/min preferably has an Izod impact strength II (23 °C, kJ/m2) of at least 5, preferably at least 6, more preferably at least 7, more preferably at least 8.
- the heterophasic propylene copolymer may have a MFI of at least 10 dg/min, preferably at most 90 dg/min, e.g. 20 to 50 dg/min, as determined by ISO 1 133 at 230 °C; 2.16 kg.
- the thermoplastic polymer composition according to the invention comprising this type of propylene copolymer is typically used in thin wall packing applications both for food and non-food segments. This includes pails and containers and yellow fats/margarine tubs and dairy cups. Materials have a good heat deflection temperature making it particularly suitable for hot fill applications.
- the composition according to the invention combine a high crystallization temperature, good flow behaviour in combination with an improved stiffness and good impact performance, also at low temperatures.
- the present invention relates to thin wall packing applications comprising the thermoplastic polymer composition according to the invention comprising this type of propylene copolymer.
- the heterophasic propylene copolymer having a MFI of at least 10 d/gmin as determined by ISO 1 133 at 230 °C; 2.16 kg comprises from 60 to 80 wt%, more preferably 65 to 75 wt%, of a matrix phase comprising a propylene homopolymer and/or a propylene copolymer comprising at least 90 wt% of propylene and up to 10 wt% of ethylene and/or at least one C 4 to C-io alpha-olefin, and from 20 to 40 wt% of, more preferably 25 to 35 wt%, of dispersed phase comprising an ethylene-alpha-olefin elastomer comprising from 40 to 65 wt% of ethylene and from 35 to 60 wt% of at least one C 3 to C-io alpha-olefin, preferably propylene.
- the thermoplastic polymer composition according to the invention comprising this type of propylene copolymer
- the propylene homopolymer of the matrix phase has a MFI of at least 50 dg/min, preferably at least 75 dg/min and preferably at most 90 dg/min.
- the ethylene-alpha-olefin elastomer of the dispersed phase has a MFI of 0.1 to 10 dg/min, e.g. 0.3 to 5 dg/min.
- thermoplastic polymer composition according to the invention wherein the heterophasic propylene copolymer has a MFI of at least 10 dg/min preferably has a MFI of at least 30 dg/min, e.g. 40 to 60 dg/min.
- the thermoplastic polymer composition according to the invention wherein the heterophasic propylene copolymer has a MFI of at least 10 dg/min preferably has a flexural modulus L of at least 1400 MPa, more preferably at least 1500 MPa.
- thermoplastic polymer composition according to the invention wherein the heterophasic propylene copolymer has a MFI of at least 10 dg/min preferably has a flexural modulus II of 1400 MPa, more preferably at least 1500 MPa.
- thermoplastic polymer composition according to the invention wherein the heterophasic propylene copolymer has a MFI of at least 10 dg/min preferably has an Izod impact strength L (23 °C, kJ/m2) of at least 5, preferably at least 6.
- thermoplastic polymer composition according to the invention wherein the heterophasic propylene copolymer has a MFI of at least 10 dg/min preferably has an Izod impact strength II (-20 °C, kJ/m2) of at least 5, preferably at least 6
- the thermoplastic polymer according to the invention may contain other additives, of which suitable example include clarifiers, stabilizers, e.g. UV stabilizers, acid scavenger, release agents, plasticizers, anti-oxidants, lubricants, anti-statics, scratch resistance agents, recycling additives, coupling agents, anti-microbials, anti-fogging additives, slip additives, anti-blocking additives, polymer processing aids, organic peroxides to control melt rheology, and the like.
- suitable example include clarifiers, stabilizers, e.g. UV stabilizers, acid scavenger, release agents, plasticizers, anti-oxidants, lubricants, anti-statics, scratch resistance agents, recycling additives, coupling agents, anti-microbials, anti-fogging additives, slip additives, anti-blocking additives, polymer processing aids, organic peroxides to control melt rheology, and the like.
- Such additives are well known in the art. The
- thermoplastic polymer composition according to the invention may also contain one or more of usual additives, like those mentioned above, including stabilisers, e.g. heat stabilisers, anti-oxidants, UV stabilizers; colorants, like pigments and dyes; clarifiers; surface tension modifiers; lubricants; flame-retardants; mould-release agents; flow improving agents; plasticizers; anti-static agents; impact modifiers; blowing agents; fillers and reinforcing agents; and/or components that enhance interfacial bonding between polymer and filler, such as a maleated polypropylene, in case the thermoplastic polymer is a polypropylene composition.
- stabilisers e.g. heat stabilisers, anti-oxidants, UV stabilizers; colorants, like pigments and dyes; clarifiers; surface tension modifiers; lubricants; flame-retardants; mould-release agents; flow improving agents; plasticizers; anti-static agents; impact modifiers; blowing agents; fillers and reinforcing agents; and
- the amount of additives depends on their type and function; typically is of from 0 to about 30 wt% ; preferably of from 0 to about 20 wt%; more preferably of from 0 to about 10 wt% and most preferably of from 0 to about 5 wt% based on the total composition.
- thermoplastic polymer composition of the invention may be obtained by mixing the nucleating composition according to present invention with the thermoplastic polymer, and optionally other additives by using any suitable means.
- the thermoplastic polymer composition of the invention is made in a form that allows easy processing into a shaped article in a subsequent step, like in pellet or granular form.
- the composition can be a mixture of different particles or pellets; like a blend of a thermoplastic polymer and a masterbatch of nucleating agent composition, or a blend of pellets of a thermoplastic polymer comprising one of the two nucleating agents and a particulate comprising the other nucleating agent, possibly pellets of a thermoplastic polymer comprising said other nucleating agent.
- thermoplastic polymer composition of the invention is in pellet or granular form as obtained by mixing all components in an apparatus like an extruder; the advantage being a composition with homogeneous and well-defined concentrations of the nucleating agents (and other components).
- thermoplastic polymer composition may then be processed by any conventional technique known in the art into a shaped article. Suitable examples include injection moulding, injection blow moulding, injection stretch blow moulding, rotational moulding, compression moulding, extrusion and extrusion compression moulding, extrusion blow moulding, sheet extrusion, film extrusion, cast film extrusion, foam extrusion, and thermoforming.
- the invention therefore further relates to a shaped article comprising the thermoplastic polymer composition according to the invention.
- thermoplastic polymer of the thermoplastic composition according to the invention when the thermoplastic polymer of the thermoplastic composition according to the invention is a heterophasic propylene copolymer having a MFI of at least 1 and less than 10 dg/min, suitable articles include shells, crates, boxes, appliances automotive exterior parts like bumpers, automotive interior parts like instrument panels and automotive parts under the bonnet.
- suitable articles include thin wall packing applications both for food and non-food segments, including pails and containers and yellow fats/margarine tubs and dairy cups.
- This material is a propylene heterophasic copolymer having a propylene polymer matrix wherein the propylene-based matrix (in this case a propylene homopolymer) is present in an amount of 75.5 wt% based on the total heterophasic propylene copolymer and 24.5 wt% of an ethylene-propylene copolymer consisting of 56.5 wt% of ethylene.
- the heterophasic propylene copolymer (4.1 kg) was extruded in a twin screw ZE21 extruder with 2.5 wt% talcum (Imerys steamic OOSD/G fine talcum) and this material was shifted with 0.12 wt% (based on the total composition) Luperco 802PP40 (di(tert- butylperoxyisopropylbenzene) as the peroxide to the desired melt flow index for the finished material.
- the formulation of these materials contained in addition 500 ppm of the processing aid Calcium stearate, 2000 ppm of the stabilizer Irganox B225 and 500 ppm HPN20E.
- the talcum, peroxide, calcium stearate, Irganox B225 and nucleating agent were mixed with the heterophasic copolymer prior to dosing it to the hopper of the extruder.
- the temperature profile in the extruder was 20-20-40-100-170-230-240-240-240 oC, at a throughput of 2.5 kg/h at 300 rpm.
- stiffness is determined by measuring the flexural modulus according to ASTM D790-10. Flexural modulus was determined on 3.2mm thick specimens according to IS037/2, parallel and perpendicular orientation.
- impact strength is determined by measuring the Izod impact strength at 23°C according to ISO 180 4A, Test geometry: 65*12.7*3.2 mm, notch 45° according to ISO 37/2 parallel and perpendicular orientation.
- melt flow rate also called melt flow index or melt index according to IS01 133 (2.16 kg/230°C).
- CLTE is measured according to ASTM D696 in parallel and perpendicular direction. Two types of temperature changes are employed for the measurements: a temperature change from 20 °C to 80 °C and a temperature change from -30 °C to 30 °C.
- shrinkage 3-D is measured according to ISO 294- 4. .
- Two types of shrinkage are measured: shrinkage after 24 hours at 23 °C and shrinkage after 24 hours at 23 °C followed by 1 hour at 90 °C.
- RC is the rubber content (propylene-ethylene copolymer) in the heterophasic copolymer
- RCC2 is the C2 (ethylene) content in the rubber part of the polymer.
- RC and RCC2 were measured with IR spectroscopy, which was calibrated using NMR according to known procedures.
- MFI heterophasic copolymer is the MFI of the starting heterophasic copolymer consisting of the matrix and the rubber.
- MFI final is the MFI of the final extruded composition of the heterophasic copolymer and additives such as talc, nucleating composition and peroxide.
- Comparison of CEx 2, CEx 3 and Ex 1 shows that the combination of talc and HPN20 has a synergistic effect on the flexural modulus.
- Comparison of CEx 1 and CEx 4 shows that ADK NA27 also increases the flexural modulus, but the izod impact L is decreased.
- Comparison of CEx 1 , Ex 1 and CEx 5 also shows that the combination of talc and HPN20 results in increase of both flexural modulus and izod impact, whereas the combination of talc and ADK NA27 results only in increase of flexural modulus.
- the difference in flexural modulus L and flexural modulus II is small by the use of HPN20.
- the difference in flexural modulus L and flexural modulus II is larger when ADK NA27 is used.
- Table 2 Medium MFI composition
- heterophasic copolymer 24.5 24.5 24.5 24.5 24.5 24.5
- Comparison of CEx 1 and CEx 6, and CEx 7 and CEx 8 shows that the increase in the MFI of the matrix leads to an increase in the flexural modulus and a large decrease in the izod impact strength.
- thermoplastic composition having a good flexural modulus and a sufficient level of impact strength.
- RCC2 (wt%) 56.5 56.5 56.5 56.5 56.5 56.5 56.5
- Irganox B225 stabilizer 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 (wt% )
- Acid scavenger Calcium 0.05 0.05 0.05 0.05 0.05 0.05 stearate (wt%)
- Irganox B225 stabilizer 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 (wt% )
- Acid scavenger Calcium 0.05 0.05 0.05 0.05 0.05 0.05 stearate (wt%)
- Comparison of Ex7 and CEx18 shows that the combination of talc and HPN20 is superior than the combination of talc and HPN68 in terms of the flexural modulus, impact strength, CLTE and shrinkage. Comparison of CEx14, Ex7 and CEx18 also shows that the combination of talc and HPN20 results in large improvements on the flexural modulus as well as CLTE and shrinkage, whereas the combination of talc and HPN 68 does not result in a large improvement in CLTE and the shrinkage is worsened.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a nucleating composition comprising: (a) a first nucleating agent, which comprises a cyclic dicarboxylate salt compound; and (b) a second nucleating agent, which comprises talc, wherein the cyclic dicarboxylate salt compound has the formula (I):
Description
NUCLEATING COMPOSITION AND THERMOPLASTIC POLYMER COMPOSITION COMPRISING SUCH NUCLEATING COMPOSITION
The invention relates to a nucleating composition comprising a salt of a metal or organic cation of a cyclic dicarboxylic acid as a first nucleating agent. The invention also relates to a thermoplastic polymer composition comprising said nucleating composition. The invention further relates to a shaped article comprising said thermoplastic polymer composition.
Such a nucleating composition is known from document EP 1379368 B1. This document discloses at least one metal salt of hexahydrophthalic acid (HHPA), e.g. calcium, strontium, lithium and monobasic aluminium salt, to be used as nucleating agent to produce thermoplastic compositions showing improved crystallization behaviour.
Several other documents also disclose metal salts employed as nucleating additives for thermoplastics. For example, US 2004/022031 1 A1 discloses the use of a specific hexahydrophthalic acid metal salt, e.g. calcium, strontium, lithium, or monobasic aluminium, as nucleating agent in various thermoplastics, particularly in polypropylene compositions. WO 2006/071721 discloses a thermoplastic composition comprising a polyolefin; a nucleating agent comprising a dicarboxylate salt compound, e.g. bicyclic [2.2.1] heptane dicarboxylate salt, available from Milliken & Company under the trade name Hyperform® HPN-68; a first fatty acid salt having a first cationic counter ion selected from the group consisting of calcium, sodium, lithium and barium, e.g. calcium stearate; and a second fatty acid salt having a second cationic counter ion selected from the group of magnesium, aluminium and zinc, e.g. zinc stearate.
Nucleating agents are chemical compounds or compositions that enable faster nucleation or a higher crystallization temperature of thermoplastic polymers, resulting in productivity gains during their processing and in improved mechanical and physical properties of articles made from such thermoplastics. These compounds provide nucleation sites for crystal growth during cooling of a thermoplastic molten composition. In polypropylenes, for example, a higher degree of crystallinity and more uniform crystalline structure is obtained by adding a nucleating agent such as talc and carboxylate salts, e.g. sodium benzoate. An overview of nucleating agents used in polypropylene-based compositions is given for example in Polym. Adv. Technol. 2007,
18, 685-695. However, it is commonly recognized that the use of nucleating agents is a highly unpredictable technology area. Small changes in a molecular structure of the nucleator can drastically alter the ability of a nucleating agent to nucleate effectively a polymer composition. There are still many unknowns regarding the effect of a nucleating agent on polymer morphology during (re-)crystallization of thermoplastics.
A nucleating composition is known from document EP 1379368 B1. This document discloses at least one metal salt of hexahydrophthalic acid (HHPA), e.g. calcium, strontium, lithium and monobasic aluminium salt, to be used as nucleating agent to produce thermoplastic compositions showing improved crystallization behavior.
Several other documents also disclose metal salts employed as nucleating additives for thermoplastics. For example, US 2004/022031 1 A1 discloses the use of a specific hexahydrophthalic acid metal salt, e.g. calcium, strontium, lithium, or monobasic aluminium, as nucleating agent in various thermoplastics, particularly in polypropylene compositions. WO 2006/071721 discloses a thermoplastic composition comprising a polyolefin; a nucleating agent comprising a dicarboxylate salt compound, e.g. bicyclic [2.2.1] heptane dicarboxylate salt, available from Milliken & Company under the trade name Hyperform® HPN-68; a first fatty acid salt having a first cationic counter ion selected from the group consisting of calcium, sodium, lithium and barium, e.g. calcium stearate; and a second fatty acid salt having a second cationic counter ion selected from the group of magnesium, aluminium and zinc, e.g. zinc stearate.
There is a demand for improving the mechanical properties of a thermoplastic composition such as the flexural modulus and the impact strength.
It is an object of the invention to provide a nucleating agent composition which results in highly improved mechanical properties of a thermoplastic composition such as the flexural modulus and the impact strength.
The objective is achieved according to the invention with a nucleating composition comprising:
(a) a first nucleating agent which comprises a cyclic dicarboxylate salt compound; and
(b) a second nucleating agent which comprises talc,
wherein the cyclic dicarboxylate salt compound has the formula (I):
Surprisingly, the nucleating composition of present invention results in highly improved mechanical properties such as stiffness and impact.
Document US 2007/0213439 A1 also discloses a nucleating composition comprising a mixture of two nucleating agents, the first nucleating agent comprising a dicarboxylate calcium salt, known as Hyperform® HPN-20E, but in this document the second nucleating agent comprises a bicyclic [2.2.1] heptane dicarboxylate salt, particularly Hyperform® HPN-68L. Also US 2008/0171834 A1 discloses a dicarboxylate calcium salt as first nucleating agent, but uses a bis-phenol phosphate compound as second nucleating agent in the nucleating composition. Thus, these references do not disclose nor suggest applying talc as nucleating agent in combination with a dicarboxylate calcium salt.
Additional advantages of the nucleating composition according to the present invention include decreased warpage of shaped articles made from a nucleated thermoplastic polymer composition; higher heat deflection temperature (HDT) and improved top load. Additional advantages of the nucleating composition according to the present invention include a lower shrinkage caused by temperature change of shaped articles made from a nucleated thermoplastic polymer composition, as determined by Coefficient of Linear Thermal Expansion (CLTE) measured according to ASTM D696. The CLTE measures the change in length per unit length of a material per unit change in temperature. Expressed as in/in/°F or cm/cm/°C, the CLTE is used to calculate the dimensional change resulting from thermal expansion. CLTE is especially important when components of an assembly have widely varying thermal expansion coefficients. Thermal expansion of a material is another important design factor, particularly in applications where plastic parts composed of polymer components are mated with metal parts or parts having metal inserts. Shrinkage can also be determined according to ISO 294-4 (shrinkage 3-D).
The advantages of the nucleating composition according to the present invention include one or combinations of the following favorable properties: flexural modulus, impact strength, CLTE and shrinkage. The first nucleating agent in the composition according to the present invention comprises a calcium cis-hexahydrophthalate compound of Formula (I).
Hyperform® HPN-20E™ nucleating agent commercialized by Milliken comprises such a calcium cis-hexahydrophthalate compound of Formula (I) and a stearate-containing compound as acid scavenger, e.g. zinc stearate.
The nucleating composition according to the present invention comprises talc as second nucleating agent. Talc is a common additive in industry, mostly used as reinforcing agent or filler and also as nucleating agent for various polymer compositions. Talc typically is considered a filler when employed in relatively high amounts, for example of about from 10 to 50 wt%, based on the total polymer composition. When talc is used under 5 wt%, it is no longer considered a filler but acts as nucleating agent.
Talc may be employed in present invention in powder form, preferably having a particle size distribution defined by a d50 of from 0.1 to 20 μΐη; more preferably of from 0.5 to 15 μΐη; or from 0.7 to 8 μΐη to improve its nucleating behaviour. The first nucleating agent and the second nucleating agent can be present in the nucleating composition according to the invention in widely varying amounts, for example in a weight ratio of from 1 : 1200 to 2:1 ; preferably in a ratio of from 1 :500 to 1 :1 ; more preferably in a ratio of from 1 :100 to 1 :2; even more preferably in a ratio of from 1 :50 to 1 :5. The advantage of adding these components within these ratio limits lies in the possibility to control dimensional stability at fast cycle times and mechanical properties.
The nucleating composition may be employed as powder, dry mix or liquid blend. It may be also mixed with other additives to form an additive pre-blend or it may be blended with a binder material in low concentrations, such as a wax or thermoplastic polymer that is compatible with the polymer for which the composition is intended to serve as nucleating agent. The nucleating composition can also be combined with a
thermoplastic polymer as a masterbatch or concentrate. These blends may be provided, optionally, with acid scavengers and other additives, such as stabilizers; primary and secondary antioxidants. Suitable acid scavengers can include zinc stearate, calcium stearate or other stearate-based compounds, and hydrotalcite.
The invention also relates to a thermoplastic polymer composition comprising a thermoplastic polymer and the nucleating composition according to present invention. As used herein, the term "thermoplastic" refers to a polymeric material that melts upon exposure to sufficiently high temperatures, but re-solidifies (crystallizes) upon cooling. "Thermoplastic" particularly defines polymers having (semi-)crystalline morphology upon cooling. Suitable examples of thermoplastic polymers include polyamides, such as polyamide-6, polyamide-6,6 or polyamide-4,6; polyolefins like polypropylenes, polyethylenes, polybutylene; polyesters, such as polyethylene terephthalate, polybutylene terephthalate; polyphenylene sulphide; polyurethanes; as well as any type of polymer blends and compounds and any combinations thereof. Preferably, the thermoplastic polymer is a crystallisable polypropylene, like a propylene homopolymer, a random copolymer, or a so-called heterophasic or impact copolymer of propylene and ethylene and/or another alpha-olefin. In a preferred embodiment of the invention, the thermoplastic polymer is a heterophasic polypropylene copolymer. Such copolymer basically has at least a two- phase structure, consisting of a propylene-based semi-crystalline matrix and a dispersed elastomer phase, typically an ethylene-propylene rubber (EPR). These polypropylenes are generally prepared in one or more reactors, by polymerization of propylene in the presence of a catalyst system, and subsequent polymerization of a propylene-ethylene mixture; but can also be made by blending different (co)polymers. The resulting polymeric materials are heterophasic; studies have demonstrated the presence of four phases in heterophasic propylene-based copolymers: crystalline polypropylene, amorphous polypropylene, crystalline ethylene-propylene rubber, and amorphous ethylene-propylene rubber. The advantage of such polymer is improved impact resistance, especially at lower temperatures.
Preferably, the thermoplastic polymer is a heterophasic propylene copolymer comprising a matrix phase comprising propylene and a dispersed phase comprising an ethylene-alpha-olefin elastomer.
Preferably, the heterophasic propylene copolymer comprises from 60 to 92 wt% of a matrix phase comprising a propylene homopolymer and/or a propylene copolymer comprising at least 90 wt% of propylene and up to 10 wt% of ethylene and/or at least one C4 to Cio alpha-olefin, and from 8 to 40 wt% of dispersed phase comprising an ethylene-alpha-olefin elastomer comprising from 40 to 65 wt% of ethylene and from 35 to 60 wt% of at least one C3 to C-|0 alpha-olefin, preferably propylene. The percentage of matrix and dispersed component is based on the total weight of the heterophasic propylene copolymer; comonomer contents are based on copolymer component. Preferably, the matrix phase is a propylene homopolymer and the mass dispersed phase is an ethylene-alpha-olefin elastomer comprising from 40 to 65 wt% of ethylene and from 35 to 60 wt% of propylene.
The thermoplastic polymer composition according to present invention preferably contains of from 0.0025 to 0.1 wt% of the first nucleating agent based on the total thermoplastic polymer composition. A certain minimum amount of the first nucleating agent is needed to effectively influence nucleating behaviour and properties the polymer composition further comprising talc as nucleating agent; preferably, the nucleating composition contains therefore at least 0.004, 0.005, 0.008, 0.01 wt% of the first nucleating agent. Further increasing the amount of the first nucleating agent in the composition to above 0.1 wt% would hardly contribute to improving the properties of final product. Preferably, the nucleating composition thus contains at most 0.08, 0.06, 0.05, 0.03 wt% of the first nucleating agent. It is a special advantage of the present invention that a relatively low amount of the first nucleating agent can be applied, in combination with the talc-based second nucleating agent; giving not only improved performance but also reducing costs.
The amount of talc used as second nucleating agent in the polymer composition is preferably of from 0.1 to 5 wt%, more preferably from 0.2 to 4 wt%; or from 0.3 to 3 wt%, based on the total thermoplastic polymer composition. A certain minimum amount of talc is necessary to provide nucleating effect and good mechanical characteristics, such as stiffness. Preferably, the nucleation composition contains thus at least 0.2, 0.3 or even 0.5 wt% of talc. If the nucleating composition would contain more than 3 wt% of talc, the additional amount might only behave as filler agent. Preferably, the nucleation composition contains therefore at most 4 or 3 wt% of talc.
Medium to high MFI of heterophasic propylene copolymer
The heterophasic propylene copolymer of the thermoplastic polymer composition according to the invention preferably has a MFI of at least 1 as determined by ISO 1 133 at 230 °C; 2.16 kg. In this case, the thermoplastic polymer composition further comprises an organic peroxide.
Organic peroxides are known to be used for viscosity reduction. There are different ways in which the organic peroxides behave in conventional degradation processes upon heating and melting conditions. On one hand, under certain process conditions, the peroxides initially decompose to produce free radicals, which then abstract hydrogen from a tertiary carbon of the polypropylene backbone to form free radicals on the polymer, and which further recombine. On the other hand, peroxides initiate a breakage of the longest chains of the polymer molecules and, subsequently, this results in a decrease in viscosity of the polymer, an increase in melt flow rate, and a narrower molecular weight distribution, characteristics which are directly responsible for improved flow properties of polypropylene in order to make the product more suitable for certain applications. The extent of each type of behaviour is generally influenced by the nature and concentration of the peroxide. Suitable for present invention are organic peroxides having a decomposition half-life of less than 1 minute at the average process temperature during formation of the modified polypropylene compositions. Suitable organic peroxides include dialkyl peroxides, e.g. dicumyl peroxides, peroxyketals, peroxycarbonates, diacyl peroxides, peroxyesters and peroxydicarbonates. Specific examples of these include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5- di(peroxybenzoato)-3-hexene, 1 ,4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butyl peracetate, a,a'-bis(tert-butylperoxy)diisopropylbenzene (Luperco® 802), 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexene, 2,5-dimethyl-2,5-di(tert- butylperoxy)-hexane, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl per- sec-octoate, tert-butyl perpivalate, cumyl perpivalate, and any combination thereof. Preferably, a dialkyl peroxides is employed in the process according to the present invention. More preferably, the peroxide is a,a'-bis-(tert- butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)-hexane or 3,6,9- Triethyl-3,6,9-trimethyl-1 ,4,7-triperoxonane.
The organic peroxide of present invention may be applied in amount of between 0.01 wt % and 0.3 wt%, preferably between 0.05 and 0.25 wt% and more preferably
between 0.1 and 0.2 wt% based on the total composition.
Medium MFI
The heterophasic propylene copolymer of the thermoplastic polymer composition according to the invention may have a MFI of at least 1 and less than 10 dg/min.
The composition according to the invention comprising this type of propylene copolymer having a medium MFI combines very high impact resistance, also at low temperatures, with high stiffness and offers good flow properties. By its design it is offering potential of cycle time reduction (shorter holding pressure times, faster injection speed and shorter cooling time), of down gauging and easiness of processing and better esthetics of the parts, reflected in a better sink mark capability. Due to its narrow molecular weight distribution, the very low tendency to warp and the excellent surface quality, the compositions according to the invention are typically used in injection moulding of suitcase shells, crates & boxes, appliances, electronic equipment and automotive parts including children's car seats. Accordingly, the present invention relates to shells, crates, boxes, appliances, electronic equipment and automotive parts including children's car seats comprising the thermoplastic polymer composition according to the invention comprising this type of propylene copolymer.
Preferably, the propylene homopolymer of the matrix phase has a MFI of at least 1 and less than 50 dg/min, e.g. 1 to 10 dg/min. Preferably, the ethylene-alpha-olefin elastomer of the dispersed phase has a MFI of 0.01 to 0.5 dg/min.
The mass dispersed phase may be an ethylene-alpha-olefin elastomer comprising from 40 to 60 wt% of ethylene and from 40 to 60 wt% of propylene. The polypropylene composition comprising such a heterophasic propylene copolymer was found to show a very high impact strength as well as a high flexural modulus.
The mass dispersed phase may be an ethylene-alpha-olefin elastomer comprising from 60 to 65 wt% of ethylene and from 35 to 40 wt% of propylene. The polypropylene composition comprising such a heterophaseic propylene copolymer was found to show an extremely high impact strength.
The thermoplastic polymer composition according to the invention wherein the heterophasic propylene copolymer has a MFI of at least 1 and less than 10 dg/min preferably has a MFI of at least 5 and less than 30 dg/min. The thermoplastic polymer composition according to the invention has a high stiffness. For purpose of the present invention, stiffness is determined by measuring the flexural modulus according to ASTM D790-10. Flexural modulus was determined on 3.2mm thick specimens according to IS037/2, parallel (flexural modulus II) and perpendicular (flexural modulus L) orientation.
The thermoplastic polymer composition according to the invention wherein the heterophasic propylene copolymer has a MFI of at least 1 and less than 10 dg/min preferably has a flexural modulus L of at least 1000 MPa, preferably at least 1 100 MPa, more preferably at least 1200 MPa.
The thermoplastic polymer composition according to the invention wherein the heterophasic propylene copolymer has a MFI of at least 1 and less than 10 dg/min preferably has a flexural modulus II of at least 1000 MPa, preferably at least 1 100 MPa, more preferably at least 1200 MPa.
The thermoplastic polymer composition according to the invention has a high impact strength. For purpose of the present invention, impact strength is determined by measuring the Izod impact strength at 23°C according to ISO 180 4A, Test geometry: 65*12.7*3.2 mm, notch 45° according to ISO 37/2 parallel and perpendicular orientation.
The thermoplastic polymer composition according to the invention wherein the heterophasic propylene copolymer has a MFI of at least 1 and less than 10 dg/min preferably has an Izod impact strength L (23 °C, kJ/m2) of at least 55, preferably at least 60.
The thermoplastic polymer composition according to the invention wherein the heterophasic propylene copolymer has a MFI of at least 1 and less than 10 dg/min preferably has an Izod impact strength II (23 °C, kJ/m2) of at least 5, preferably at least 6, more preferably at least 7, more preferably at least 8.
High MFI
The heterophasic propylene copolymer may have a MFI of at least 10 dg/min, preferably at most 90 dg/min, e.g. 20 to 50 dg/min, as determined by ISO 1 133 at 230 °C; 2.16 kg. The thermoplastic polymer composition according to the invention comprising this type of propylene copolymer is typically used in thin wall packing applications both for food and non-food segments. This includes pails and containers and yellow fats/margarine tubs and dairy cups. Materials have a good heat deflection temperature making it particularly suitable for hot fill applications. The composition according to the invention combine a high crystallization temperature, good flow behaviour in combination with an improved stiffness and good impact performance, also at low temperatures.
Accordingly, the present invention relates to thin wall packing applications comprising the thermoplastic polymer composition according to the invention comprising this type of propylene copolymer.
Preferably, the heterophasic propylene copolymer having a MFI of at least 10 d/gmin as determined by ISO 1 133 at 230 °C; 2.16 kg comprises from 60 to 80 wt%, more preferably 65 to 75 wt%, of a matrix phase comprising a propylene homopolymer and/or a propylene copolymer comprising at least 90 wt% of propylene and up to 10 wt% of ethylene and/or at least one C4 to C-io alpha-olefin, and from 20 to 40 wt% of, more preferably 25 to 35 wt%, of dispersed phase comprising an ethylene-alpha-olefin elastomer comprising from 40 to 65 wt% of ethylene and from 35 to 60 wt% of at least one C3 to C-io alpha-olefin, preferably propylene. The thermoplastic polymer composition according to the invention comprising this type of propylene copolymer with a relatively large amount of rubber shows a particularly desirable shrinkage property. Such polymer composition is especially suitable for thin wall packaging.
Preferably, the propylene homopolymer of the matrix phase has a MFI of at least 50 dg/min, preferably at least 75 dg/min and preferably at most 90 dg/min.
Preferably, the ethylene-alpha-olefin elastomer of the dispersed phase has a MFI of 0.1 to 10 dg/min, e.g. 0.3 to 5 dg/min.
The thermoplastic polymer composition according to the invention wherein the heterophasic propylene copolymer has a MFI of at least 10 dg/min preferably has a MFI of at least 30 dg/min, e.g. 40 to 60 dg/min.
The thermoplastic polymer composition according to the invention wherein the heterophasic propylene copolymer has a MFI of at least 10 dg/min preferably has a flexural modulus L of at least 1400 MPa, more preferably at least 1500 MPa. The thermoplastic polymer composition according to the invention wherein the heterophasic propylene copolymer has a MFI of at least 10 dg/min preferably has a flexural modulus II of 1400 MPa, more preferably at least 1500 MPa.
The thermoplastic polymer composition according to the invention wherein the heterophasic propylene copolymer has a MFI of at least 10 dg/min preferably has an Izod impact strength L (23 °C, kJ/m2) of at least 5, preferably at least 6.
The thermoplastic polymer composition according to the invention wherein the heterophasic propylene copolymer has a MFI of at least 10 dg/min preferably has an Izod impact strength II (-20 °C, kJ/m2) of at least 5, preferably at least 6
The thermoplastic polymer according to the invention may contain other additives, of which suitable example include clarifiers, stabilizers, e.g. UV stabilizers, acid scavenger, release agents, plasticizers, anti-oxidants, lubricants, anti-statics, scratch resistance agents, recycling additives, coupling agents, anti-microbials, anti-fogging additives, slip additives, anti-blocking additives, polymer processing aids, organic peroxides to control melt rheology, and the like. Such additives are well known in the art. The skilled person will know how to employ these additives in conventional effective amounts.
The thermoplastic polymer composition according to the invention may also contain one or more of usual additives, like those mentioned above, including stabilisers, e.g. heat stabilisers, anti-oxidants, UV stabilizers; colorants, like pigments and dyes; clarifiers; surface tension modifiers; lubricants; flame-retardants; mould-release agents; flow improving agents; plasticizers; anti-static agents; impact modifiers; blowing agents; fillers and reinforcing agents; and/or components that enhance interfacial bonding between polymer and filler, such as a maleated polypropylene, in case the thermoplastic polymer is a polypropylene composition. The skilled person can readily select any suitable combination of additives and additive amounts without undue experimentation. The amount of additives depends on their type and function; typically is of from 0 to about 30 wt% ; preferably of from 0 to about 20 wt%; more preferably of from 0 to about 10 wt% and most preferably of from 0 to about 5 wt% based on the
total composition.
The thermoplastic polymer composition of the invention may be obtained by mixing the nucleating composition according to present invention with the thermoplastic polymer, and optionally other additives by using any suitable means. Preferably, the thermoplastic polymer composition of the invention is made in a form that allows easy processing into a shaped article in a subsequent step, like in pellet or granular form. The composition can be a mixture of different particles or pellets; like a blend of a thermoplastic polymer and a masterbatch of nucleating agent composition, or a blend of pellets of a thermoplastic polymer comprising one of the two nucleating agents and a particulate comprising the other nucleating agent, possibly pellets of a thermoplastic polymer comprising said other nucleating agent. Preferably, the thermoplastic polymer composition of the invention is in pellet or granular form as obtained by mixing all components in an apparatus like an extruder; the advantage being a composition with homogeneous and well-defined concentrations of the nucleating agents (and other components).
The thermoplastic polymer composition may then be processed by any conventional technique known in the art into a shaped article. Suitable examples include injection moulding, injection blow moulding, injection stretch blow moulding, rotational moulding, compression moulding, extrusion and extrusion compression moulding, extrusion blow moulding, sheet extrusion, film extrusion, cast film extrusion, foam extrusion, and thermoforming. The invention therefore further relates to a shaped article comprising the thermoplastic polymer composition according to the invention. In particular, when the thermoplastic polymer of the thermoplastic composition according to the invention is a heterophasic propylene copolymer having a MFI of at least 1 and less than 10 dg/min, suitable articles include shells, crates, boxes, appliances automotive exterior parts like bumpers, automotive interior parts like instrument panels and automotive parts under the bonnet. When the thermoplastic polymer of the thermoplastic composition according to the invention is a heterophasic propylene copolymer having a MFI of at least 10 dg/min, suitable articles include thin wall packing applications both for food and non-food segments, including pails and containers and yellow fats/margarine tubs and dairy cups.
Although the invention has been described in detail for purposes of illustration, it is
understood that such detail is solely for that purpose and variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the claims. It is further noted that the invention relates to all possible combinations of features described herein, preferred in particular are those combinations of features that are present in the claims.
It is further noted that the term 'comprising' does not exclude the presence of other elements. However, it is also to be understood that a description on a product comprising certain components also discloses a product consisting of these components. Similarly, it is also to be understood that a description on a process comprising certain steps also discloses a process consisting of these steps. The range of values "A to B" used herein is understood to mean "at least A and at most B".
The invention is now elucidated by way of the following examples, without however being limited thereto.
Examples
Example 1
Several samples were prepared using a starting material having a melt flow index (MFI) of 1.5 dg/min. This material is a propylene heterophasic copolymer having a propylene polymer matrix wherein the propylene-based matrix (in this case a propylene homopolymer) is present in an amount of 75.5 wt% based on the total heterophasic propylene copolymer and 24.5 wt% of an ethylene-propylene copolymer consisting of 56.5 wt% of ethylene. The heterophasic propylene copolymer (4.1 kg) was extruded in a twin screw ZE21 extruder with 2.5 wt% talcum (Imerys steamic OOSD/G fine talcum) and this material was shifted with 0.12 wt% (based on the total composition) Luperco 802PP40 (di(tert- butylperoxyisopropylbenzene) as the peroxide to the desired melt flow index for the finished material. The formulation of these materials contained in addition 500 ppm of the processing aid Calcium stearate, 2000 ppm of the stabilizer Irganox B225 and 500 ppm HPN20E. The talcum, peroxide, calcium stearate, Irganox B225 and nucleating agent were mixed with the heterophasic copolymer prior to dosing it to the hopper of
the extruder.
The temperature profile in the extruder was 20-20-40-100-170-230-240-240-240 oC, at a throughput of 2.5 kg/h at 300 rpm.
For purpose of the present invention, stiffness is determined by measuring the flexural modulus according to ASTM D790-10. Flexural modulus was determined on 3.2mm thick specimens according to IS037/2, parallel and perpendicular orientation. For purpose of the present invention, impact strength is determined by measuring the Izod impact strength at 23°C according to ISO 180 4A, Test geometry: 65*12.7*3.2 mm, notch 45° according to ISO 37/2 parallel and perpendicular orientation.
For purpose of the present invention, flow is determined by measuring the melt flow rate, also called melt flow index or melt index according to IS01 133 (2.16 kg/230°C).
For purpose of the present invention, CLTE is measured according to ASTM D696 in parallel and perpendicular direction. Two types of temperature changes are employed for the measurements: a temperature change from 20 °C to 80 °C and a temperature change from -30 °C to 30 °C.
For purpose of the present invention, shrinkage 3-D is measured according to ISO 294- 4. . Two types of shrinkage are measured: shrinkage after 24 hours at 23 °C and shrinkage after 24 hours at 23 °C followed by 1 hour at 90 °C.
The results are summarized in Table 1. In the Tables:
RC is the rubber content (propylene-ethylene copolymer) in the heterophasic copolymer; RCC2 is the C2 (ethylene) content in the rubber part of the polymer.
RC and RCC2 were measured with IR spectroscopy, which was calibrated using NMR according to known procedures.
MFI heterophasic copolymer is the MFI of the starting heterophasic copolymer consisting of the matrix and the rubber.
MFI final is the MFI of the final extruded composition of the heterophasic copolymer
and additives such as talc, nucleating composition and peroxide.
Properties in the parallel and perpendicular directions are indicated with "II" and "L", respectively.
Comparative experiments and further experiments were performed and properties were measured as summarized in Tables 1-6.
Table 1 Medium MFI composition
Comparison of CEx 2, CEx 3 and Ex 1 shows that the combination of talc and HPN20 has a synergistic effect on the flexural modulus.
Comparison of CEx 1 and CEx 4 shows that ADK NA27 also increases the flexural modulus, but the izod impact L is decreased. Comparison of CEx 1 , Ex 1 and CEx 5 also shows that the combination of talc and HPN20 results in increase of both flexural modulus and izod impact, whereas the combination of talc and ADK NA27 results only in increase of flexural modulus. Furthermore, the difference in flexural modulus L and flexural modulus II is small by the use of HPN20. The difference in flexural modulus L and flexural modulus II is larger when ADK NA27 is used. Table 2 Medium MFI composition
Ex 1 Ex 2 Ex 3 Ex 4 Ex 5
Matrix (wt% based on
the heterophasic copolymer) 75.5 75.5 75.5 75.5 75.5
RC (wt% based on
the heterophasic copolymer) 24.5 24.5 24.5 24.5 24.5
RCC2 (wt%) 56.5 56.5 62 56.5 62
MFI matrix (dg/min) 4.7 4.7 4.3 4.7 4.3
MFI rubber (dg/min) 0.044 0.044 0.04 0.044 0.04
MFI heterophasic
copolymer (dg/min) 1.5 1.5 1.4 1.5 1.4
MFI final (dg/min) 14 14 14 20 20
Talc (wt%) 2.5 0.5 0.5 0.5 0.5
HPN20 (wt%) 0.05 0.025 0.025 0.025 0.025
ADK NA27 0 0 0 0 0
Irganox B225 (stabilizer)
(wt% ) 0.2 0.2 0.2 0.2 0.2
Acid scavenger Calcium
stearate (wt%) 0.05 0.05 0.05 0.05 0.05
Peroxide (wt%) 0.12 0.12 0.12 0.18 0.18
Flexural Modulus L (MPa) 1202 1 128 1257 1 135 1264
Flexural Modulus II (MPa) 1 198 1 127 1242 1 108 1254
Izod Impact L (23 °C, kJ/m2) 66.76 62.78 1 1.23 59.69 10.47
Izod Impact II (-20 °C, kJ/m ) 8.1 1 7.62 5.9 7.3 5.8
Comparison of Ex 2 and Ex 3, and Ex 4 and Ex 5 shows that the ethylene content in the ethylene-propylene copolymer rubber has an extremely large impact on the izod impact strength.
Table 3 Medium MFI composition
Comparison of CEx 1 and CEx 6, and CEx 7 and CEx 8 shows that the increase in the MFI of the matrix leads to an increase in the flexural modulus and a large decrease in the izod impact strength.
Comparison of CEx 1 and Ex 2, and CEx 7 and Ex 4 shows that the addition of both talc and HPN20 increases flexural modulus while maintaining the izod impact strength.
Table 4 High MFI composition
A thermoplastic composition was obtained having a good flexural modulus and a sufficient level of impact strength.
Table 5 Medium MFI composition
CEx9 CEx10 CEx1 1 CEx12 Ex6 CEx13
Matrix (wt% based on 75.5 75.5 75.5 75.5 75.5 75.5 the heterophasic
copolymer)
RC (wt% based on 24.5 24.5 24.5 24.5 24.5 24.5 the heterophasic
copolymer)
RCC2 (wt%) 56.5 56.5 56.5 56.5 56.5 56.5
MFI matrix (dg/min) 4.7 4.7 4.7 4.7 4.7 4.7
MFI rubber (dg/min) 0.044 0.044 0.044 0.044 0.044 0.044
MFI heterophasic 1.5 1.5 1.5 1.5 1.5 1.5 copolymer (dg/min)
MFI final (dg/min) 15.5 13.3 14.3 13.6 12.5 14.7
Talc (wt%) 0 0.5 0 0 0.5 0.5
HPN20E (wt%) 0 0 0.025 0 0.025 0
HPN68L (wt%) 0 0 0 0.05 0 0.05
Irganox B225 (stabilizer) 0.2 0.2 0.2 0.2 0.2 0.2 (wt% )
Acid scavenger Calcium 0.05 0.05 0.05 0.05 0.05 0.05 stearate (wt%)
Peroxide (wt%) 0.12 0.12 0.12 0.12 0.12 0.12
Flexural Modulus L (23C, 1068 1 1 12 1 166 1 126 1 192 1173 MPa)
Flexural Modulus II (23C, 1066 1 100 1 182 1 133 1 187 1155 MPa)
Izod impact L (23 °C, 57.06 57.81 58.37 55.98 58.43 53.64 kJ/m2)
Izod impact L (-20 °C, 7.06 7.08 7.51 7.34 7.3 6.9 kJ/m2)
CLTE 20°C-80°C L 152.5 147.4 142.1 155.4 140.8 154.5 (μm/m.K)
CLTE -30°C-30°C L 110.9 108.4 104.6 1 13.6 101.3 113.6 (μιτι/m.K)
CLTE 20°C-80°C II 154.1 144.6 138.1 150.2 134.4 149.3 (μιτι/m.K)
CLTE -30°C-30°C II 107.7 103.6 98.3 106.6 94.8 105.1 (μm/m.K)
Shrinkage after 24 hrs at 1.5053 1.4588 1.4757 1.5731 1.4451 1.5935 23°C L (%)
Shrinkage after 24hrs at 1.7338 1.6550 1.6753 1.8436 1.6414 1.8254 23°C+1 hr at 90°C L (%)
Comparison of CEx 10, 1 1 and Ex6 shows that the combination of talc and HPN20 has
a synergistic effect on the flexural modulus, CLTE and shrinkage.
Comparison of Ex6 and CEx13 shows that the combination of talc and HPN20 is superior than the combination of talc and HPN68 in terms of the flexural modulus, impact strength, CLTE and shrinkage. Furthermore, the combination of talc and HPN20 results in similar flexural modulus L and II, in comparison with the combination of talc and HPN68 which results in a large difference between flexural modulus L and II. The large difference between flexural modulus L and II causes a large internal stress which is unfavorable.
Comparison of CEx9, Ex6 and CEx13 also shows that the combination of talc and HPN20 results in improvements on the flexural modulus as well as CLTE and shrinkage, whereas the combination of talc and HPN 68 results only in increase of the flexural modulus.
Table 6 High MFI composition
CEx14 CEx15 CEx16 CEx17 Ex7 CEx18
Matrix (wt% based on 81.5 81.5 81.5 81.5 81.5 81.5 the heterophasic copolymer)
RC (wt% based on 18.5 18.5 18.5 18.5 18.5 18.5 the heterophasic copolymer)
RCC2 (wt%) 53 53 53 53 53 53
MFI matrix (dg/min) 82 82 82 82 82 82
MFI rubber (dg/min) 0.6 0.6 0.6 0.6 0.6 0.6
MFI heterophasic 33 33 33 33 33 33 copolymer (dg/min)
MFI final (dg/min) 53.4 56.0 47.0 55.7 48.7 48.8
Talc (wt%) 0 0.5 0 0 0.5 0.5
HPN20E (wt%) 0 0 0.025 0 0.025 0
HPN68L (wt%) 0 0 0 0.05 0 0.05
Irganox B225 (stabilizer) 0.2 0.2 0.2 0.2 0.2 0.2 (wt% )
Acid scavenger Calcium 0.05 0.05 0.05 0.05 0.05 0.05 stearate (wt%)
Peroxide (wt%) 0.026 0.026 0.026 0.026 0.026 0.026
Flexural Modulus L (23°C, 1303 1424 1551 1515 1612 1566 MPa)
Flexural Modulus II (23°C, 1320 1426 1566 1501 1589 1544 MPa)
Izod impact L (23 °C, kJ/m2) 6.41 5.95 6.6 5.71 5.98 5.7
Izod impact L (-20 °C, kJ/m2) 3.41 3.56 4.08 3.55 3.59 3.7
CLTE 20°C-80°C L 148.6 135.6 130.1 143.3 122.3 143.3 (μm m.K)
CLTE -30°C-30°C L 108.3 96.2 89.4 105.1 89.5 104.8 (μm m.K)
CLTE 20°C-80°C II 146.2 136.8 125.0 139.6 120.4 137.7 (μm m.K)
CLTE -30°C-30°C II 103.8 94.3 83.5 98.0 84.9 95.9 (μιτι/m.K)
Average shrinkage after 24 1.4183 1.4071 1.4150 1.4917 1.3884 1.4915 hrs at 23°C (%)
Average shrinkage after 1.6150 1.5715 1.6333 1.8254 1.5426 1.8183 24hrs at 23°C+1 hr at 90°C
(%)
Comparison of CEx15, CEx16 and Ex7 shows that the combination of talc and HPN20 has a synergistic effect on the flexural modulus, CLTE and shrinkage.
Comparison of Ex7 and CEx18 shows that the combination of talc and HPN20 is superior than the combination of talc and HPN68 in terms of the flexural modulus, impact strength, CLTE and shrinkage. Comparison of CEx14, Ex7 and CEx18 also shows that the combination of talc and HPN20 results in large improvements on the flexural modulus as well as CLTE and shrinkage, whereas the combination of talc and HPN 68 does not result in a large improvement in CLTE and the shrinkage is worsened.
Claims
A nucleating composition comprising:
(a) a first nucleating agent, which comprises a cyclic dicarboxylate salt compound; and
(b) a second nucleating agent, which comprises talc,
wherein the cyclic dicarboxylate salt compound has the formula (I):
The thermoplastic polymer composition a thermoplastic polymer, an organic peroxide and the nucleating composition according to claim 1 , wherein said thermoplastic polymer is a heterophasic propylene copolymer comprising a matrix phase comprising propylene and a dispersed phase comprising an ethylene-alpha-olefin elastomer, wherein the heterophasic propylene copolymer has a MFI of at least 1.
The thermoplastic polymer composition according to claim 2, wherein the heterophasic propylene copolymer comprises from 60 to 92 wt% of the matrix phase and from 8 to 40 wt% of the dispersed phase,
wherein the matrix phase comprises a propylene homopolymer and/or a propylene copolymer comprising at least 90 wt% of propylene and up to 10 wt% ofethylene and/or at least one C4 to Ci0 alpha-olefin and
wherein the ethylene-alpha-olefin elastomer of the dispersed phase comprises from 40 to 65 wt% of ethylene and from 35 to 60 wt% of at least one C3 to Cio alpha-olefin, preferably propylene.
The thermoplastic polymer composition according to claim 2 or 3, wherein the heterophasic propylene copolymer has a MFI of less than 10 dg/min.
The thermoplastic polymer composition according to claim 4, wherein the matrix phase has a MFI of at least 1 dg/min and preferably less than 50 dg/min.
The thermoplastic polymer composition according to claim 4 or 5, wherein the ethylene-alpha-olefin elastomer comprises from 40 to 60 wt% of ethylene and from 40 to 60 wt% of propylene.
7. The thermoplastic polymer composition according to any one of claims 4-6, wherein the thermoplastic polymer composition has a MFI of at least 5 and less than 30 dg/min.
8. The thermoplastic polymer composition according to any one of claims 4-7, wherein the thermoplastic polymer composition has a flexural modulus L of at least 1000 MPa, preferably at least 1 100 MPa, more preferably at least 1200 MPa.
9. The thermoplastic polymer composition according to any one of claims 4-8, wherein the thermoplastic polymer composition has an Izod impact strength L (23 °C, kJ/m2) of at least 55, preferably at least 60.
10. The thermoplastic polymer composition according to claim 2 or 3, wherein the heterophasic propylene copolymer has a MFI of at least 10 dg/min.
1 1. The thermoplastic polymer composition according to claim 10, wherein the matrix phase has a MFI of at least 50 dg/min.
12. The thermoplastic polymer composition according to claim 1 1 , wherein the thermoplastic polymer composition has a MFI of at least 30 dg/min.
13. The thermoplastic polymer composition according to any one of claims 10-12, wherein the thermoplastic polymer composition has a flexural modulus L of at least 1400 MPa, preferably at least 1500 MPa.
14. The thermoplastic polymer composition according to any one of claims 10-13, wherein the thermoplastic polymer composition has an Izod impact strength L
(23 °C, kJ/m2) of at least 5, preferably at least 6.
15. A shaped article comprising the thermoplastic polymer composition according to any one of claims 2 to 14.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201480028825.2A CN105431481B (en) | 2013-06-20 | 2014-06-17 | Nucleating composition and the thermoplastic polymer composition comprising this nucleating composition |
| BR112015031831A BR112015031831A2 (en) | 2013-06-20 | 2014-06-17 | nucleation composition and thermoplastic polymeric composition comprising such nucleation composition |
| US14/895,240 US20160122505A1 (en) | 2013-06-20 | 2014-06-17 | Nucleating composition and thermoplastic polymer composition comprising such nucleating composition |
| KR1020157032225A KR20160021756A (en) | 2013-06-20 | 2014-06-17 | Nucleating composition and thermoplastic polymer composition comprising such nucleating composition |
| EP14730547.8A EP3010968B1 (en) | 2013-06-20 | 2014-06-17 | Nucleating composition and thermoplastic polymer composition comprising such nucleating composition |
| EA201690046A EA029500B1 (en) | 2013-06-20 | 2014-06-17 | Nucleating composition and thermoplastic polymer composition comprising such nucleating composition |
| US15/869,177 US10240024B2 (en) | 2013-06-20 | 2018-01-12 | Nucleating composition and thermoplastic polymer composition comprising such nucleating composition |
Applications Claiming Priority (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP13173015 | 2013-06-20 | ||
| EP13173016.0 | 2013-06-20 | ||
| EP13173015.2 | 2013-06-20 | ||
| EP13173016 | 2013-06-20 | ||
| EP13180921 | 2013-08-19 | ||
| EP13180921.2 | 2013-08-19 | ||
| EP13180920.4 | 2013-08-19 | ||
| EP13180920 | 2013-08-19 | ||
| EP13187541.1 | 2013-10-07 | ||
| EP13187542 | 2013-10-07 | ||
| EP13187542.9 | 2013-10-07 | ||
| EP13187541 | 2013-10-07 |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US14/895,240 A-371-Of-International US20160122505A1 (en) | 2013-06-20 | 2014-06-17 | Nucleating composition and thermoplastic polymer composition comprising such nucleating composition |
| US15/869,177 Division US10240024B2 (en) | 2013-06-20 | 2018-01-12 | Nucleating composition and thermoplastic polymer composition comprising such nucleating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2014202603A1 true WO2014202603A1 (en) | 2014-12-24 |
Family
ID=50943327
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2014/062715 WO2014202604A1 (en) | 2013-06-20 | 2014-06-17 | Nucleating composition and thermoplastic polymer composition comprising such nucleating composition |
| PCT/EP2014/062714 WO2014202603A1 (en) | 2013-06-20 | 2014-06-17 | Nucleating composition and thermoplastic polymer composition comprising such nucleating composition |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2014/062715 WO2014202604A1 (en) | 2013-06-20 | 2014-06-17 | Nucleating composition and thermoplastic polymer composition comprising such nucleating composition |
Country Status (7)
| Country | Link |
|---|---|
| US (3) | US20160122505A1 (en) |
| EP (2) | EP3010969B1 (en) |
| KR (2) | KR20160021757A (en) |
| CN (2) | CN105229068B (en) |
| BR (2) | BR112015029350A2 (en) |
| EA (2) | EA029500B1 (en) |
| WO (2) | WO2014202604A1 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017009193A1 (en) | 2015-07-13 | 2017-01-19 | Sabic Global Technologies B.V. | Composition comprising heterophasic propylene copolymer |
| EP3162844A1 (en) * | 2015-10-26 | 2017-05-03 | SABIC Global Technologies B.V. | Polypropylene composition comprising a nucleating composition comprising aluminosilicate and an organic nucleating agent |
| EP3168261A1 (en) * | 2015-11-10 | 2017-05-17 | Borealis AG | Heterophasic polypropylene composition |
| EP3181625A1 (en) | 2015-12-18 | 2017-06-21 | SABIC Global Technologies B.V. | Composition comprising heterophasic propylene copolymer |
| WO2017144468A1 (en) | 2016-02-22 | 2017-08-31 | Sabic Global Technologies B.V. | Composition comprising heterophasic propylene copolymer |
| WO2018108927A1 (en) * | 2016-12-12 | 2018-06-21 | Sabic Global Technologies B.V. | Heterophasic propylene copolymer |
| WO2020023384A1 (en) * | 2018-07-24 | 2020-01-30 | Milliken & Company | Additive composition and method for producing a polymer composition using the same |
| EP3636710A1 (en) * | 2018-10-08 | 2020-04-15 | Borealis AG | Foamable polypropylene composition |
| WO2020169402A1 (en) | 2019-02-18 | 2020-08-27 | Sabic Global Technologies B.V. | Composition comprising heterophasic propylene copolymer |
| RU2772275C1 (en) * | 2018-07-24 | 2022-05-18 | Милликен Энд Компани | Additive composition and method for producing a polymer composition using said composition |
| US11969946B2 (en) | 2018-02-12 | 2024-04-30 | Structo Pte. Ltd. | Automated additive manufacturing device and method |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160021757A (en) * | 2013-06-20 | 2016-02-26 | 사우디 베이식 인더스트리즈 코포레이션 | Nucleating composition and thermoplastic polymer composition comprising such nucleating composition |
| CN107108996B (en) | 2014-12-02 | 2020-08-11 | Sabic环球技术有限责任公司 | Composition comprising a heterophasic propylene copolymer |
| US10882968B2 (en) | 2016-08-30 | 2021-01-05 | Lcy Chemical Corporation | Polypropylene foams and processes of making |
| CN107163402B (en) * | 2017-07-14 | 2019-09-06 | 东莞磐汩新材料有限公司 | A kind of modified polypropylene plastic and preparation method thereof |
| JP6397153B1 (en) | 2018-05-18 | 2018-09-26 | 株式会社Adeka | Granular nucleating agent, resin composition, molded article and method for producing the same |
| CN112771106A (en) * | 2018-09-26 | 2021-05-07 | 美利肯公司 | Additive composition and method for producing polymer composition using the same |
| CN115785523B (en) * | 2021-09-13 | 2023-10-10 | 华东理工大学 | Composition and application of alpha/beta composite nucleating agent for regulating and controlling mechanical properties of polypropylene |
| WO2023227736A1 (en) | 2022-05-27 | 2023-11-30 | Sabic Global Technologies B.V. | Polybutylene terephthalate composition for use in high-frequency radio-wave applications |
| WO2023227738A1 (en) | 2022-05-27 | 2023-11-30 | Sabic Global Technologies B.V. | Polypropylene composition for use in high-frequency radio-wave applications |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050038155A1 (en) * | 2003-08-12 | 2005-02-17 | Stephane Berghmans | Thermoplastics exhibiting excellent long-term hydrostatic strength for high-pressure applications |
| US20050101713A1 (en) * | 2003-11-07 | 2005-05-12 | Lake Kemper D.Jr. | Concentrates of saturated bicyclic dicarboxylate salts to facilitate use thereof as polymer nucleation additives |
| US20070213439A1 (en) * | 2006-03-08 | 2007-09-13 | Weihua Sonya Wolters | Nucleating agent additive compositions and methods |
Family Cites Families (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0008690D0 (en) * | 2000-04-07 | 2000-05-31 | Borealis Polymers Oy | Process |
| US6599971B2 (en) | 2001-03-29 | 2003-07-29 | Milliken & Company | Metals salts of hexahydrophthalic acid as nucleating additives for crystalline thermoplastics |
| ATE341581T1 (en) * | 2002-12-18 | 2006-10-15 | Borealis Tech Oy | FLAT FILM FOR THERMOFORMING AND METHOD FOR PRODUCING SAME |
| DE602004030248D1 (en) | 2003-07-30 | 2011-01-05 | Polyone Corp | NUCLEARED THERMOPLASTIC ELASTOMER CONTAINING COMPOSITION AND RELATED METHODS |
| US7572860B2 (en) * | 2003-08-05 | 2009-08-11 | Basell Poliolefine Italia S.R.L. | Polyolefin articles |
| US6995202B2 (en) * | 2003-11-07 | 2006-02-07 | Milliken & Company | Methods of nucleating thermoplastics using concentrates of saturated bicyclic dicarboxylate salts |
| US20060142452A1 (en) | 2004-12-23 | 2006-06-29 | Sonya Wolters | Polyolfins, methods of making polyolefins and related plastic additive compositions |
| US7786203B2 (en) | 2005-09-16 | 2010-08-31 | Milliken & Company | Polymer compositions comprising nucleating or clarifying agents and articles made using such compositions |
| CN101268131A (en) * | 2005-09-16 | 2008-09-17 | 美利肯公司 | Polymer compositions comprising nucleating or clarifying agents |
| US20080171834A1 (en) | 2006-12-19 | 2008-07-17 | Kien-Mun Tang | Thermoplastic and nucleating agent compositions and methods |
| CN102089370A (en) * | 2008-07-14 | 2011-06-08 | 北欧化工公司 | Polyolefin composition with low CLTE |
| EP2305723A1 (en) * | 2009-10-01 | 2011-04-06 | Total Petrochemicals Research Feluy | Propylene polymer with improved processability in thermoforming. |
| EP2397517B1 (en) * | 2010-06-16 | 2012-12-26 | Borealis AG | Propylene polymer compositions having superior hexane extractables/impact balance |
| EP2585527B1 (en) * | 2010-06-23 | 2015-01-14 | Basell Poliolefine Italia S.r.l. | Polyolefin composition for pipe systems and sheets |
| CN102391584B (en) * | 2011-10-12 | 2013-11-06 | 中国石油化工股份有限公司 | High-fluidity high-toughness polypropylene resin and preparation method thereof |
| CN102558683B (en) * | 2011-12-31 | 2014-01-22 | 广州呈和科技有限公司 | Polypropylene beta crystal form nucleating agent composition and application thereof |
| ES2730944T3 (en) * | 2013-01-29 | 2019-11-13 | Ineos Europe Ag | Injection molded polypropylene items |
| US9815975B2 (en) | 2013-03-25 | 2017-11-14 | Dow Global Technologies Llc | Film having good barrier properties together with good physical characteristics |
| US8642683B1 (en) | 2013-04-23 | 2014-02-04 | Ford Flobal Technologies, LLC | Polypropylene with bio-based and synthetic fillers for light weight material applications |
| KR20160021757A (en) * | 2013-06-20 | 2016-02-26 | 사우디 베이식 인더스트리즈 코포레이션 | Nucleating composition and thermoplastic polymer composition comprising such nucleating composition |
-
2014
- 2014-06-17 KR KR1020157032228A patent/KR20160021757A/en not_active Application Discontinuation
- 2014-06-17 US US14/895,240 patent/US20160122505A1/en not_active Abandoned
- 2014-06-17 BR BR112015029350A patent/BR112015029350A2/en active Search and Examination
- 2014-06-17 CN CN201480028818.2A patent/CN105229068B/en active Active
- 2014-06-17 CN CN201480028825.2A patent/CN105431481B/en active Active
- 2014-06-17 EP EP14731942.0A patent/EP3010969B1/en active Active
- 2014-06-17 BR BR112015031831A patent/BR112015031831A2/en active Search and Examination
- 2014-06-17 KR KR1020157032225A patent/KR20160021756A/en not_active Application Discontinuation
- 2014-06-17 EA EA201690046A patent/EA029500B1/en not_active IP Right Cessation
- 2014-06-17 EA EA201690047A patent/EA029175B1/en not_active IP Right Cessation
- 2014-06-17 WO PCT/EP2014/062715 patent/WO2014202604A1/en active Application Filing
- 2014-06-17 US US14/896,683 patent/US11136446B2/en active Active
- 2014-06-17 WO PCT/EP2014/062714 patent/WO2014202603A1/en active Application Filing
- 2014-06-17 EP EP14730547.8A patent/EP3010968B1/en active Active
-
2018
- 2018-01-12 US US15/869,177 patent/US10240024B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050038155A1 (en) * | 2003-08-12 | 2005-02-17 | Stephane Berghmans | Thermoplastics exhibiting excellent long-term hydrostatic strength for high-pressure applications |
| US20050101713A1 (en) * | 2003-11-07 | 2005-05-12 | Lake Kemper D.Jr. | Concentrates of saturated bicyclic dicarboxylate salts to facilitate use thereof as polymer nucleation additives |
| US20070213439A1 (en) * | 2006-03-08 | 2007-09-13 | Weihua Sonya Wolters | Nucleating agent additive compositions and methods |
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017009193A1 (en) | 2015-07-13 | 2017-01-19 | Sabic Global Technologies B.V. | Composition comprising heterophasic propylene copolymer |
| EP3162844A1 (en) * | 2015-10-26 | 2017-05-03 | SABIC Global Technologies B.V. | Polypropylene composition comprising a nucleating composition comprising aluminosilicate and an organic nucleating agent |
| EP3168261A1 (en) * | 2015-11-10 | 2017-05-17 | Borealis AG | Heterophasic polypropylene composition |
| WO2017081018A1 (en) * | 2015-11-10 | 2017-05-18 | Borealis Ag | Heterophasic polypropylene composition |
| EP3181625A1 (en) | 2015-12-18 | 2017-06-21 | SABIC Global Technologies B.V. | Composition comprising heterophasic propylene copolymer |
| WO2017102935A1 (en) | 2015-12-18 | 2017-06-22 | Sabic Global Technologies B.V. | Composition comprising heterophasic propylene copolymer |
| US10711125B2 (en) | 2015-12-18 | 2020-07-14 | Sabic Global Technologies B.V. | Composition comprising heterophasic propylene copolymer |
| WO2017144475A1 (en) | 2016-02-22 | 2017-08-31 | Sabic Global Technologies B.V. | Composition comprising heterophasic propylene copolymer |
| US10703891B2 (en) | 2016-02-22 | 2020-07-07 | Sabic Global Technologies B.V. | Composition comprising heterophasic propylene copolymer |
| WO2017144468A1 (en) | 2016-02-22 | 2017-08-31 | Sabic Global Technologies B.V. | Composition comprising heterophasic propylene copolymer |
| WO2018108927A1 (en) * | 2016-12-12 | 2018-06-21 | Sabic Global Technologies B.V. | Heterophasic propylene copolymer |
| CN110062775A (en) * | 2016-12-12 | 2019-07-26 | Sabic环球技术有限责任公司 | Heterophasic propylene copolymers |
| US11292898B2 (en) | 2016-12-12 | 2022-04-05 | Sabic Global Technologies B.V. | Heterophasic propylene copolymer |
| CN110062775B (en) * | 2016-12-12 | 2021-12-07 | Sabic环球技术有限责任公司 | Heterophasic propylene copolymer |
| US11969946B2 (en) | 2018-02-12 | 2024-04-30 | Structo Pte. Ltd. | Automated additive manufacturing device and method |
| JP2021530607A (en) * | 2018-07-24 | 2021-11-11 | ミリケン・アンド・カンパニーMilliken & Company | Additive composition and methods for producing polymer compositions using it |
| US11746212B2 (en) | 2018-07-24 | 2023-09-05 | Milliken & Company | Additive composition and method for producing a polymer composition using the same |
| US11118027B2 (en) | 2018-07-24 | 2021-09-14 | Milliken & Company | Additive composition and method for producing a polymer composition using the same |
| WO2020023384A1 (en) * | 2018-07-24 | 2020-01-30 | Milliken & Company | Additive composition and method for producing a polymer composition using the same |
| CN115785524B (en) * | 2018-07-24 | 2024-04-02 | 美利肯公司 | Additive composition and method for preparing polymer composition using the same |
| JP7019862B2 (en) | 2018-07-24 | 2022-02-15 | ミリケン・アンド・カンパニー | Additive composition and method for producing a polymer composition using it |
| CN112513158A (en) * | 2018-07-24 | 2021-03-16 | 美利肯公司 | Additive composition and method of preparing polymer composition using the same |
| RU2772275C1 (en) * | 2018-07-24 | 2022-05-18 | Милликен Энд Компани | Additive composition and method for producing a polymer composition using said composition |
| CN112513158B (en) * | 2018-07-24 | 2022-12-06 | 美利肯公司 | Additive composition and method of preparing polymer composition using the same |
| CN115785524A (en) * | 2018-07-24 | 2023-03-14 | 美利肯公司 | Additive composition and method of preparing polymer composition using the same |
| EP3636710A1 (en) * | 2018-10-08 | 2020-04-15 | Borealis AG | Foamable polypropylene composition |
| WO2020074335A1 (en) * | 2018-10-08 | 2020-04-16 | Borealis Ag | Foamable polypropylene composition |
| US12084564B2 (en) | 2018-10-08 | 2024-09-10 | Borealis Ag | Foamable polypropylene composition |
| WO2020169402A1 (en) | 2019-02-18 | 2020-08-27 | Sabic Global Technologies B.V. | Composition comprising heterophasic propylene copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| EA029500B1 (en) | 2018-04-30 |
| EA201690046A1 (en) | 2016-05-31 |
| CN105229068A (en) | 2016-01-06 |
| EA029175B1 (en) | 2018-02-28 |
| KR20160021757A (en) | 2016-02-26 |
| US11136446B2 (en) | 2021-10-05 |
| US20160137810A1 (en) | 2016-05-19 |
| US20180134868A1 (en) | 2018-05-17 |
| EP3010969B1 (en) | 2017-11-01 |
| US20160122505A1 (en) | 2016-05-05 |
| BR112015029350A2 (en) | 2017-07-25 |
| US10240024B2 (en) | 2019-03-26 |
| BR112015031831A2 (en) | 2017-07-25 |
| KR20160021756A (en) | 2016-02-26 |
| CN105431481A (en) | 2016-03-23 |
| EP3010968B1 (en) | 2017-03-22 |
| WO2014202604A1 (en) | 2014-12-24 |
| CN105431481B (en) | 2017-07-07 |
| EP3010969A1 (en) | 2016-04-27 |
| EA201690047A1 (en) | 2016-05-31 |
| EP3010968A1 (en) | 2016-04-27 |
| CN105229068B (en) | 2017-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10240024B2 (en) | Nucleating composition and thermoplastic polymer composition comprising such nucleating composition | |
| US11008440B2 (en) | Flame retardant propylene composition | |
| ES2625403T3 (en) | Process for the preparation of a composition comprising a heterophasic propylene copolymer and talc | |
| CN107108996B (en) | Composition comprising a heterophasic propylene copolymer | |
| JP6430643B2 (en) | How to extrude polypropylene | |
| KR102545024B1 (en) | Additive composition, and method for producing a polymer composition using the same | |
| EP3665223B1 (en) | Composition comprising heterophasic propylene copolymer | |
| WO2017144468A1 (en) | Composition comprising heterophasic propylene copolymer | |
| JP2017537195A (en) | How to extrude polypropylene | |
| EP3162844B1 (en) | Polypropylene composition comprising a nucleating composition comprising aluminosilicate and an organic nucleating agent | |
| EP3665224B1 (en) | Composition comprising heterophasic propylene copolymer | |
| EP3227382B1 (en) | Polypropylene composition comprising nucleating agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WWE | Wipo information: entry into national phase |
Ref document number: 201480028825.2 Country of ref document: CN |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14730547 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 20157032225 Country of ref document: KR Kind code of ref document: A |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 14895240 Country of ref document: US |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112015031831 Country of ref document: BR |
|
| REEP | Request for entry into the european phase |
Ref document number: 2014730547 Country of ref document: EP |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2014730547 Country of ref document: EP |
|
| WWE | Wipo information: entry into national phase |
Ref document number: IDP00201600218 Country of ref document: ID |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 201690046 Country of ref document: EA |
|
| ENP | Entry into the national phase |
Ref document number: 112015031831 Country of ref document: BR Kind code of ref document: A2 Effective date: 20151218 |