WO2023142505A1 - Aging-resistant and low-noise tpee fiber material - Google Patents
Aging-resistant and low-noise tpee fiber material Download PDFInfo
- Publication number
- WO2023142505A1 WO2023142505A1 PCT/CN2022/122351 CN2022122351W WO2023142505A1 WO 2023142505 A1 WO2023142505 A1 WO 2023142505A1 CN 2022122351 W CN2022122351 W CN 2022122351W WO 2023142505 A1 WO2023142505 A1 WO 2023142505A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- thermoplastic polyester
- polyester elastomer
- elastomer composition
- acid amide
- composition according
- Prior art date
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- 239000002657 fibrous material Substances 0.000 title claims abstract description 18
- 230000032683 aging Effects 0.000 title description 13
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 claims abstract description 57
- 239000000203 mixture Substances 0.000 claims abstract description 38
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims abstract description 29
- -1 vinyl aromatic compound Chemical class 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 20
- 239000000314 lubricant Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 12
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 11
- 239000000194 fatty acid Substances 0.000 claims abstract description 11
- 229930195729 fatty acid Natural products 0.000 claims abstract description 11
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 229920001002 functional polymer Polymers 0.000 claims abstract description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 3
- 239000002530 phenolic antioxidant Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000004593 Epoxy Substances 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 description 17
- 229920000728 polyester Polymers 0.000 description 11
- 229920001400 block copolymer Polymers 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 150000002193 fatty amides Chemical class 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003878 thermal aging Methods 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- XHAFIUUYXQFJEW-UHFFFAOYSA-N 1-chloroethenylbenzene Chemical compound ClC(=C)C1=CC=CC=C1 XHAFIUUYXQFJEW-UHFFFAOYSA-N 0.000 description 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- UJAWGGOCYUPCPS-UHFFFAOYSA-N 4-(2-phenylpropan-2-yl)-n-[4-(2-phenylpropan-2-yl)phenyl]aniline Chemical compound C=1C=C(NC=2C=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C=CC=1C(C)(C)C1=CC=CC=C1 UJAWGGOCYUPCPS-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003230 hygroscopic agent Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
-
- 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
- C08L2207/04—Thermoplastic elastomer
Definitions
- the present application relates to a TPEE fiber material which in particular has improved aging resistance and low noise properties and also has improved resistance to degradation. Furthermore, the present application also relates to a method for the preparation of such fiber materials.
- Thermoplastic polyester elastomer is a block copolymer, its structure usually contains high melting point, high hardness crystalline polyester hard segment and amorphous polyether or polyester with lower glass transition temperature soft segment.
- the elastomer has a two-phase association structure, in which the hard segment can play a physical cross-linking role to endow the product with a certain shape stability, and the soft segment can endow the material with high resilience in an amorphous manner.
- TPEE has both the softness and elasticity of rubber, and the rigidity and ease of processing of thermoplastics. Therefore, this material is widely used as a cushioning material in furniture, home appliances, office supplies, automobiles, trains, ships, or aerospace fields, such as office chairs, sofas, mattresses, carpets, seating seats in vehicles, etc. cushioning material.
- thermoplastic polyester elastomer raw material is extruded into a continuous bending, random entanglement, and partially thermally bonded random fiber material in a molten state, and then a three-dimensional network structure is obtained by contacting each other with liquid cooling body.
- CN103998668B discloses a three-dimensional network structure made of thermoplastic polyester elastomer material.
- the thermoplastic polyester elastomer is a polyester block copolymer having a high melting point crystalline polymer segment (a) and a low melting point polymer segment (b).
- this three-dimensional network structure can be used for seats and mattresses.
- the three-dimensional network structure has flexibility in the extrusion direction by alternately appearing low-volume-density loose regions and high-volume-density compact regions in a certain extrusion direction during manufacture, thereby endowing the manufactured
- the mattress has reduced noise and resistance to aging at eg 80°C or higher.
- the current market has put forward higher requirements for the aging resistance and noise reduction performance of TPEE fiber materials.
- the aging resistance of the TPEE fiber material can be further improved, especially at a temperature of 140° C. or higher, the fiber can be used in a considerable It does not lose its elasticity over a long period of time and maintains its structure.
- the frictional noise generated between the filaments can be further reduced to improve the ride experience of passengers.
- TPEE fiber materials are prone to degradation during the extrusion process, so there is an urgent need to improve the degradation resistance of TPEE materials.
- the inventors of the present application found that by screening and optimizing the additives added to the TPEE matrix, the above technical problems can be effectively improved, that is, TPEE with comprehensive improvement in high temperature aging resistance, noise reduction and degradation resistance can be obtained. fiber material.
- thermoplastic polyester elastomer composition comprising, based on the total weight of the composition:
- thermoplastic polyester elastomer TPEE 80-98% thermoplastic polyester elastomer
- tackifiers which are epoxy-functional polymers based on vinylaromatics and (meth)acrylic compounds.
- a second aspect of the invention relates to a process for the preparation of thermoplastic polyester elastomers according to the invention.
- thermoplastic polyester elastomer TPEE suitable for use in the present invention is known per se and is not particularly limited, as long as its structure contains both a high-melting crystalline polyester hard segment and an amorphous polyester with a lower glass transition temperature. Polyether or polyester soft segments.
- suitable thermoplastic polyester elastomers TPEE may include polyester-ether block copolymers having thermoplastic polyester as hard segments and polyalkylene glycols as soft segments, or aliphatic polyesters as soft segments. Segmented polyester-ester block copolymers.
- thermoplastic polyester elastomer TPEE may comprise hard segments of polyesters based on, for example, aromatic dicarboxylic acids and aliphatic diols and soft segments of aliphatic polyesters and/or polyethers. Segmented polyester-ester or polyester-ether block copolymers.
- polyester-ether block copolymer for example, at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7- Aromatic dicarboxylic acids such as dicarboxylic acid and diphenyl-4,4'-dicarboxylic acid, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, such as succinic acid, adipic acid, decane Aliphatic dicarboxylic acids such as diacid dimer acids, or their ester-forming derivatives, etc.; and at least one diol component selected from the group consisting of such as 1,4-butanediol, ethylene glycol, triethylene glycol, etc.
- dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene-2,6-dicar
- Aliphatic diols such as methylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, such as 1,1-cyclohexanedimethanol, 1,4-cyclohexane Alicyclic diols such as dimethanol, or their ester-forming derivatives; and at least one polyalkylene glycol selected from the following: such as polyethylene glycol, poly A ternary block copolymer composed of propylene glycol, polytetramethylene glycol or ethylene oxide-propylene oxide copolymer.
- polyester-ester block copolymer for example, a triblock composed of at least one of the above-mentioned dicarboxylic acid, diol, and polyester diol such as polylactone having a number average molecular weight of about 300 to 5,000 copolymer.
- polyester diol such as polylactone having a number average molecular weight of about 300 to 5,000 copolymer.
- terephthalic acid and/or naphthalene 2,6-dicarboxylic acid as dicarboxylic acid
- diol component Triblock copolymers of 1,4-butanediol, polytetramethylene glycol as polyalkylene glycol, or triblocks with polylactone as polyester diol copolymer Triblock copolymers of 1,4-butanediol, polytetramethylene glycol as polyalkylene glycol, or triblocks with polylactone as polyester diol copolymer.
- those comprising a polysiloxane-based soft segment or a polyolefin-based soft segment may also be used.
- These soft segments can be incorporated into thermoplastic polyester elastomers by copolymerization or blending.
- the soft segment content of the thermoplastic polyester elastomer is preferably 15% by weight or more, more preferably 25% by weight or more, further preferably 30% by weight or more, particularly preferably 40% by weight or more, and preferably It is 80 weight% or less, More preferably, it is 70 weight% or less.
- thermoplastic polyester elastomers are commercially available, for example, as Anitel from DSM or from DuPont or the like.
- thermoplastic polyester elastomer composition according to the present invention should also contain 0.1-3.0%, preferably 0.5-2.6%, more preferably 0.9-2.0% of a diphenylamine antioxidant based on the total weight of the composition.
- diphenylamine antioxidants are specifically selected (compared to other conventional antioxidants such as hindered phenols or phosphites, etc.) and used in the required amount of 0.1-3.0% for thermoplastic polymer
- the ester elastomer composition When used in the ester elastomer composition, the aging resistance of the fiber material prepared from the composition can be significantly improved after 7 days at 140° C., and the pulverization phenomenon can be significantly improved.
- the compression set of the material after this heat aging can reach ⁇ 11%, even ⁇ 10% and the compressive strength
- the rate of change reaches ⁇ 11%, such as ⁇ 10%, or even ⁇ 8%.
- diphenylamine compounds suitable for this application are a class of antioxidants, which realize the antioxidant function by capturing free radicals in the chain reaction of polymer degradation, eliminating peroxide free radicals and terminating the oxidation reaction.
- diphenylamine antioxidants are based on derivatives of diphenylamine compounds, including two categories of ketoneamines and alkylated diphenylamines. For example, they can have the following structural formula (I):
- R1 and R2 represent one or more, preferably one, substituents optionally located on the respective benzene rings, which are selected from C1-C18, preferably C2-C12 or C3-C10 alkyl or aralkyl groups, provided that the structural formula There is at least one R1 or R2 substituent in (I); and both R1 and R2 can also form a linear or branched alkylene group with C1-C8 such as C3-C6 connecting two benzene rings.
- R1 and R2 in the structural formula (I), and R1 and R2 represent one of the substituents located on the respective benzene rings, or both R1 and R2 form the alkylene group connecting two benzene rings group.
- the alkyl group is preferably a linear, branched or cyclic alkyl group having 1-18, more preferably 2-12 and 3-10 C atoms, such as methyl, ethyl, propyl butyl, pentyl, hexyl, heptyl, octyl, nonyl and their isomeric forms.
- the alkylene group is a linear or branched alkylene group preferably having 1-8 or 3-6 C atoms, such as ethylene, propylene, isopropylene and the like.
- the aralkyl group is preferably a phenylalkyl group, such as benzyl, phenethyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, phenylisopropyl and the like.
- Diphenylamine antioxidants are commercially available, for example as Naugard 445, BLE or DDA.
- the diphenylamine antioxidant is selected from the following:
- the inventors of the present application have found that when the amount of diphenylamine antioxidants is less than 0.1%, the antioxidant efficiency of the fiber material is low, the aging resistance is poor, and powdering is more likely to occur under heat aging conditions; When the amount of oxidizing agent is higher than 3.0%, the aging performance cannot be further improved.
- the inventors of the present application have also found that if 0.1-2.8%, preferably 0.3-2.3%, more preferably 0.5-1.8% of fatty acid amide lubricants are added to the composition based on the total weight of the composition, the Noise-reducing properties of fiber materials made from thermoplastic polyester elastomers combined with resistance to degradation of the material. If the amount of fatty amide lubricant added is too low, the expected noise reduction cannot be achieved.
- the extruded fiber filaments will be too smooth and difficult to bond and entangle between filaments, unable to form a three-dimensional network structure, and cause the product to be sticky , the rebound is slow, and it will also affect the thermal aging and degradation resistance to a certain extent.
- lubricant may also be referred to as "slip agent”.
- Fatty acid amide lubricants suitable for adding to the thermoplastic polyester elastomer composition of the present application to reduce the noise of fiber materials are compounds that contain amide groups and saturated or unsaturated aliphatic groups in terms of molecular structure.
- the fatty acid amide lubricant may contain one or more, for example two, amide groups in its molecule.
- the aliphatic group is then preferably a linear, branched or cyclic saturated or unsaturated aliphatic group preferably having 6-40, more preferably 8-30, such as 10-25 carbon atoms, and optionally There may be one or more, such as two, carbon-carbon double bonds.
- the fatty acid amide lubricant is selected from erucamide, oleic acid amide, stearic acid amide such as vinyl bis stearic acid amide or amide wax.
- Such fatty acid amide lubricants are known in the art and are commercially available.
- thermoplastic polyester elastomer composition especially 0.1-2.5%, preferably 0.5-2.2% of epoxy resin based on the total weight of the composition
- Functional tackifiers based on polymers of vinyl aromatic compound monomers and (meth)acrylic compound monomers can further improve the degradation resistance of polyester elastomers, especially when TPEE fiber materials are extruded When being squeezed out of the machine.
- the epoxy-functional polymer based on vinyl aromatic monomers and (meth)acrylic monomers is a polymer consisting mainly of vinyl aromatic monomer units and (meth)acrylic compound monomer units. A main chain is formed, and a plurality of polymers having side chain groups containing epoxy groups are grafted on the main chain.
- the epoxy-functional polymer based on vinyl aromatic monomers and (meth)acrylic monomers is 90%, preferably 95%, more preferably 98% or 99%, or even completely composed of vinyl It consists of an aromatic compound monomer unit and a (meth)acrylic compound monomer unit.
- Epoxy groups can be attached to the polymer backbone, for example via C1-C12, preferably C2-C8 (oxy)alkylene groups.
- (meth)acrylic compound refers to a compound with methacryloyl or acryloyl, preferably a compound with methacryloxy or acryloyloxy, such as methacrylic acid, acrylic acid, acrylic acid C1 -C12 alkyl ester, C1-C12 alkyl methacrylate, glycidyl methacrylate, glycidyl acrylate, etc.
- the vinyl aromatic compounds include styrene monomers and derivatives thereof, especially alkyl (such as C1-C8 alkyl) or halogen-substituted styrene monomers, such as styrene, ⁇ -methylstyrene, ⁇ -chlorostyrene or p-methylstyrene, etc., preferably styrene.
- alkyl such as C1-C8 alkyl
- halogen-substituted styrene monomers such as styrene, ⁇ -methylstyrene, ⁇ -chlorostyrene or p-methylstyrene, etc., preferably styrene.
- the tackifier is an epoxy-functionalized copolymer of styrene and glycidyl (meth)acrylate.
- the epoxy-functionalization of the polymers can be carried out in a conventional manner. For example, it can be achieved by adding a copolymerizable monomer with an epoxy group in an amount corresponding to the required epoxy equivalent when preparing the copolymer.
- the copolymerizable monomer having an epoxy group is, for example, a vinyl monomer having an epoxy group, especially glycidyl (meth)acrylate.
- the epoxy-functional polymer based on vinyl aromatic monomers and (meth)acrylic monomers has a weight average molecular weight of 20,000 to 400,000, preferably 50,000 to 200,000 and its epoxy equivalent can be in the range of For example between 100-800 g/mol, preferably 150-650 g/mol.
- the epoxy equivalent represents the mass of the resin containing 1mol of epoxy groups, expressed in g/mol.
- the weight-average molecular weight is measured by GPC using polystyrene as a standard sample.
- the epoxy equivalent can be measured according to the ASTM D1652 standard.
- additives can also be added to the thermoplastic polyester elastomer composition of the present invention, as long as these additives do not affect its performance in use and its molding process.
- Said other additives include, for example, other antioxidants such as hindered phenols and phosphites, UV absorbers such as benzophenones and benzotriazoles, other lubricants such as calcium stearate or silicone-based lubricants, Deodorants, antibacterial agents, antifungal agents, colorants, fragrances, flame retardants and hygroscopic agents, etc.
- said other additives are preferably added in an amount in the range of 0.1%-8%, eg 0.5-5%, based on the total weight of the thermoplastic polyester elastomer composition.
- phosphite antioxidants hindered phenolic antioxidants and/or ultraviolet absorbers are further used in the range of 0.5-1.5% based on the total weight of the composition.
- a second aspect of the present application relates to a method for preparing a thermoplastic polyester elastomer according to the present invention, comprising: i) providing the individual components of the thermoplastic polyester elastomer as described above and mixing them, ii) combining the resulting combination melt-extruding the material into fibrous strands at a temperature 10-120° C. higher than its melting point, and iii) randomly entangle and bend the obtained strands to form a three-dimensional network structure.
- fiber and “wire” are sometimes used interchangeably, and they refer to a thread-like material whose length is much greater than the cross-sectional diameter (for example, 20 times or more than 50 times), which can usually be melt-extruded get.
- the cross-sectional shape of the wire or fiber is not particularly limited, for example, it can be a circular cross-section, an elliptical cross-section, a polygonal cross-section, a hollow cross-section or other special-shaped cross-sections, etc., which can impart compression resistance, bulkiness, etc.
- step i) can be carried out in any mixing equipment known in the prior art.
- the individual components of the thermoplastic polyester elastomer composition are thoroughly mixed under agitation.
- the order of addition of the components is not particularly limited.
- the resulting mixture can be fed immediately to subsequent processing steps.
- Steps ii) and iii) are usually carried out successively and continuously.
- a common melt extruder can be used to heat the mixed thermoplastic elastomer composition to a temperature 10 to 120° C. higher than the melting point to make it into a molten state.
- the temperature of the extruder can be set at a temperature of 180-300°C, preferably 200-280°C. It is then sprayed downwards using a nozzle with multiple orifices and falls naturally to form a ring.
- the diameter of the ring, the fineness of the wire, and the number of joints are determined according to the distance between the nozzle surface and the take-up conveyor installed on the cooling medium that solidifies the resin, the melt viscosity of the resin, the diameter of the orifice, and the discharge amount.
- a pair of take-up conveyor belts installed on the cooling medium with an adjustable interval sandwiches and stops the ejected wire in a molten state to produce a ring.
- the resulting rings are thus brought into contact with each other, by which the rings form a random three-dimensional shape and the contact portions are fused.
- the continuous wires formed in a random three-dimensional shape and welded at the contact portion are continuously introduced into a cooling medium (preferably water at room temperature) to solidify to form a network structure.
- pseudocrystallization treatment is performed after cooling once.
- the pseudocrystallization treatment temperature is at least 10°C lower than the melting point (Tm).
- Tm melting point
- the drying temperature can be set to the annealing temperature, so that the pseudo-crystallization treatment can be performed at the same time.
- pseudocrystallization treatment may be performed separately.
- the prepared mesh structure can be cut into desired length or shape for cushioning material.
- the network structure of the present invention as a cushioning material, it is necessary to select the used resin, fineness, ring diameter, and bulk density according to the purpose of use and the site of use.
- the material according to the present invention has a wide range of applications, for example, it can be used as a cushioning material in furniture, home appliances, office supplies, automobiles, trains, ships or aerospace fields, such as in office chairs, sofas, mattresses, carpets, vehicles, etc. Take the cushioning material in the seat.
- thermoplastic polyester elastomer composition Preparation of thermoplastic polyester elastomer composition
- the combined material obtained in each embodiment is placed in a melting extruder, the temperature of the extruder is set at 210-260°C, and the single-hole spinning rate is 10-60g/min.
- Spray to the bottom of the spinneret hole After passing through the heat preservation area directly below the spinneret hole, the molten linear body is bent to form a ring, so that the contact part is welded to form a three-dimensional network structure, and the three-dimensional network structure in the molten state is pulled by the traction conveying plate chain to make it solidify. Subsequent performance tests were performed on the solidified three-dimensional network structure.
- the size of the sample is 100mm ⁇ 100mm, and the sample is stored at 140°C for 168 hours, and then conditioned for 24 hours in a standard environment. After measuring the height of the above-mentioned aged sample, compress the sample to 50% of the thickness of the sample, keep it at 70°C for 22 hours, and store it in a standard environment for 30 minutes in a free state, then measure the height of the sample again , to get the compressive deformation value.
- the method of ISO 2440 take a sample size of 100mm ⁇ 100mm, measure the length and width dimensions, and measure the compressive strength value of the sample in the prepared state.
- the sample was stored at 140°C for 168 hours, then conditioned for 24 hours in a standard environment, and then the compressive strength value after heat aging was tested according to the same procedure as the compressive strength value in the prepared state to obtain the compressive strength change.
- the size of the sample is 100mm ⁇ 100mm. After measuring the length and width, the compressive strength value of the sample in the prepared state is determined.
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Abstract
The present application relates to a thermoplastic polyester elastomer composition, which comprises, on the basis of the total weight of the composition: A) 80-98% of a thermoplastic polyester elastomer (TPEE); B) 0.1-3% of a diphenylamine antioxidant; C) 0.1-2.8% of a fatty acid amide lubricant; and D) 0.1-2.5% of a tackifier, which is an epoxy functional polymer based on a vinyl aromatic compound and a (meth)acrylic compound. In addition, the present application further relates to a method for preparing such a thermoplastic polyester elastomer fiber material. The fiber material according to the present invention can be used as a cushioning material in an office chair, a sofa, a mattress, a carpet, and a riding seat in a vehicle.
Description
本申请涉及一种TPEE纤维材料,其特别具有改善的耐老化性和低噪音性以及还具有改善的抗降解性。此外,本申请还涉及这种纤维材料的制备方法。The present application relates to a TPEE fiber material which in particular has improved aging resistance and low noise properties and also has improved resistance to degradation. Furthermore, the present application also relates to a method for the preparation of such fiber materials.
发明背景Background of the invention
热塑性聚酯弹性体(TPEE)是一种嵌段共聚物,其结构中通常包含高熔点、高硬度的结晶型聚酯硬链段和玻璃化转变温度较低的非晶型聚醚或聚酯软链段。该弹性体呈两相缔合结构,其中的硬链段能够起到物理交联作用而赋予制品一定的形状稳定性,软链段则能够无定形地赋予材料以高回弹性。TPEE同时具有橡胶的柔软性、弹性,以及热塑性塑料的刚性、易加工性。因此,这种材料广泛地用于家具、家电、办公用品、汽车、火车、船舶或航空航天领域中作为缓冲材料,例如办公椅、沙发、床垫、地毯、交通工具中的乘坐座椅中的缓冲材料。Thermoplastic polyester elastomer (TPEE) is a block copolymer, its structure usually contains high melting point, high hardness crystalline polyester hard segment and amorphous polyether or polyester with lower glass transition temperature soft segment. The elastomer has a two-phase association structure, in which the hard segment can play a physical cross-linking role to endow the product with a certain shape stability, and the soft segment can endow the material with high resilience in an amorphous manner. TPEE has both the softness and elasticity of rubber, and the rigidity and ease of processing of thermoplastics. Therefore, this material is widely used as a cushioning material in furniture, home appliances, office supplies, automobiles, trains, ships, or aerospace fields, such as office chairs, sofas, mattresses, carpets, seating seats in vehicles, etc. cushioning material.
通常,将热塑性聚酯弹性体原料在熔融状态下挤出成型为连续弯曲、无规缠结、部分热粘合的无规纤维材料,随后通过彼此接触用液体冷却而得到三维立体的网状结构体。Usually, the thermoplastic polyester elastomer raw material is extruded into a continuous bending, random entanglement, and partially thermally bonded random fiber material in a molten state, and then a three-dimensional network structure is obtained by contacting each other with liquid cooling body.
CN103998668B公开了一种由热塑性聚酯弹性体材料构成的立体网状结构。该热塑性聚酯弹性体是具有高熔点结晶性聚合物链段(a)和低熔点聚合物链段(b)的聚酯嵌段共聚物。在该文献中,这种立体网状结构可用于座椅和床垫。根据该文献,通过在制造期间在某一挤压方向中交替地出现低体积密度的疏松区与高体积密度的密实区,使得立体网状结构在挤压方向具有挠性,从而赋予制成的床垫具有降低的噪音和在例如80℃或更高温度下的耐老化性。CN103998668B discloses a three-dimensional network structure made of thermoplastic polyester elastomer material. The thermoplastic polyester elastomer is a polyester block copolymer having a high melting point crystalline polymer segment (a) and a low melting point polymer segment (b). In this document, this three-dimensional network structure can be used for seats and mattresses. According to this document, the three-dimensional network structure has flexibility in the extrusion direction by alternately appearing low-volume-density loose regions and high-volume-density compact regions in a certain extrusion direction during manufacture, thereby endowing the manufactured The mattress has reduced noise and resistance to aging at eg 80°C or higher.
然而,目前市场上对于TPEE纤维材料的耐老化性和降低噪音的性能提出了更高的要求。尤其是,当需要将这种纤维材料用于交通工 具的座椅缓冲材料时,希望能够进一步提高TPEE纤维材料的耐老化性,特别是在140℃或更高的温度下还能使得纤维在相当长的时间下不丧失弹性,维持其结构。此外,也希望能够进一步降低纤维丝间产生的摩擦噪音,改善乘客的乘坐体验。However, the current market has put forward higher requirements for the aging resistance and noise reduction performance of TPEE fiber materials. Especially, when needing to use this fiber material for the seat buffer material of vehicles, it is hoped that the aging resistance of the TPEE fiber material can be further improved, especially at a temperature of 140° C. or higher, the fiber can be used in a considerable It does not lose its elasticity over a long period of time and maintains its structure. In addition, it is also hoped that the frictional noise generated between the filaments can be further reduced to improve the ride experience of passengers.
另外,还发现TPEE纤维材料在挤出过程中容易出现降解的情况,因此也亟需改善TPEE材料的抗降解性。In addition, it is also found that TPEE fiber materials are prone to degradation during the extrusion process, so there is an urgent need to improve the degradation resistance of TPEE materials.
发明内容Contents of the invention
鉴于以上这些技术问题,本申请的发明人发现通过筛选和优化加入TPEE基体中的添加剂,能够有效改善上述的技术问题,即能够获得耐高温老化性、降噪性和抗降解性全面改善的TPEE纤维材料。In view of the above technical problems, the inventors of the present application found that by screening and optimizing the additives added to the TPEE matrix, the above technical problems can be effectively improved, that is, TPEE with comprehensive improvement in high temperature aging resistance, noise reduction and degradation resistance can be obtained. fiber material.
因此,本发明的第一个方面涉及一种热塑性聚酯弹性体组合物,其包含基于组合物总重量计:Therefore, a first aspect of the present invention relates to a thermoplastic polyester elastomer composition comprising, based on the total weight of the composition:
A)80-98%的热塑性聚酯弹性体TPEE;A) 80-98% thermoplastic polyester elastomer TPEE;
B)0.1-3%的二苯胺类抗氧化剂;B) 0.1-3% diphenylamine antioxidant;
C)0.1-2.8%的脂肪酸酰胺类润滑剂;C) 0.1-2.8% fatty acid amide lubricant;
D)0.1-2.5%的增粘剂,其为环氧官能的基于乙烯基芳族化合物与(甲基)丙烯酸系化合物的聚合物。D) 0.1-2.5% of tackifiers which are epoxy-functional polymers based on vinylaromatics and (meth)acrylic compounds.
本发明的第二个方面涉及根据本发明的热塑性聚酯弹性体的制备方法。A second aspect of the invention relates to a process for the preparation of thermoplastic polyester elastomers according to the invention.
适合用于本发明的热塑性聚酯弹性体TPEE本身是已知的并且没有特别的限制,只要其结构中同时包含高熔点的结晶型聚酯硬链段和玻璃化转变温度较低的非晶型聚醚或聚酯软链段。The thermoplastic polyester elastomer TPEE suitable for use in the present invention is known per se and is not particularly limited, as long as its structure contains both a high-melting crystalline polyester hard segment and an amorphous polyester with a lower glass transition temperature. Polyether or polyester soft segments.
因此,合适的热塑性聚酯弹性体TPEE可以包括其中具有热塑性聚酯作为硬链段和聚亚烷基二醇作为软链段的聚酯-醚嵌段共聚物,或者具有脂肪族聚酯作为软链段的聚酯-酯嵌段共聚物。Accordingly, suitable thermoplastic polyester elastomers TPEE may include polyester-ether block copolymers having thermoplastic polyester as hard segments and polyalkylene glycols as soft segments, or aliphatic polyesters as soft segments. Segmented polyester-ester block copolymers.
在一种有利的实施方式中,所述热塑性聚酯弹性体TPEE可以包括基于例如芳族二羧酸与脂族二元醇的聚酯的硬链段和脂肪族聚酯和/或聚醚软链段的聚酯-酯或聚酯-醚嵌段共聚物。In an advantageous embodiment, the thermoplastic polyester elastomer TPEE may comprise hard segments of polyesters based on, for example, aromatic dicarboxylic acids and aliphatic diols and soft segments of aliphatic polyesters and/or polyethers. Segmented polyester-ester or polyester-ether block copolymers.
作为聚酯-醚嵌段共聚物,例如,由选自如下的至少一种二羧酸:诸如对苯二甲酸、间苯二甲酸、萘-2,6-二甲酸、萘-2,7-二甲酸、二苯基-4,4’-二甲酸等芳香族二羧酸,诸如1,4-环己烷二羧酸等的脂环族二羧酸,诸如琥珀酸、己二酸、癸二酸二聚酸等的脂肪族二羧酸,或它们的可成酯的衍生物等;和选自如下的至少一种二醇成分:诸如1,4-丁二醇、乙二醇、三亚甲基二醇、四亚甲基二醇、五亚甲基二醇、六亚甲基二醇等的脂肪族二醇,诸如1,1-环己烷二甲醇、1,4-环己烷二甲醇等的脂环族二醇,或它们的可成酯的衍生物;以及选自如下的至少一种聚亚烷基二醇:诸如数均分子量约300~5000的聚乙二醇、聚丙二醇、聚四亚甲基二醇或环氧乙烷-环氧丙烷共聚物而构成的三元嵌段共聚物。As the polyester-ether block copolymer, for example, at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7- Aromatic dicarboxylic acids such as dicarboxylic acid and diphenyl-4,4'-dicarboxylic acid, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, such as succinic acid, adipic acid, decane Aliphatic dicarboxylic acids such as diacid dimer acids, or their ester-forming derivatives, etc.; and at least one diol component selected from the group consisting of such as 1,4-butanediol, ethylene glycol, triethylene glycol, etc. Aliphatic diols such as methylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, such as 1,1-cyclohexanedimethanol, 1,4-cyclohexane Alicyclic diols such as dimethanol, or their ester-forming derivatives; and at least one polyalkylene glycol selected from the following: such as polyethylene glycol, poly A ternary block copolymer composed of propylene glycol, polytetramethylene glycol or ethylene oxide-propylene oxide copolymer.
作为聚酯-酯嵌段共聚物,例如,由上述二羧酸、二醇和诸如数均分子量约300~5000的聚内酯等的聚酯二醇中的至少各一种构成的三元嵌段共聚物。若考虑到热粘接性、耐水解性、伸缩性、耐热性等,特别优选的是由作为二羧酸的对苯二甲酸或/和萘2,6-二甲酸、作为二醇成分的1,4-丁二醇、作为聚亚烷基二醇的聚四亚甲基二醇所形成的三元嵌段共聚物,或者是具有作为聚酯二醇的聚内酯的三元嵌段共聚物。As the polyester-ester block copolymer, for example, a triblock composed of at least one of the above-mentioned dicarboxylic acid, diol, and polyester diol such as polylactone having a number average molecular weight of about 300 to 5,000 copolymer. In consideration of thermal adhesiveness, hydrolysis resistance, stretchability, heat resistance, etc., it is particularly preferable to use terephthalic acid and/or naphthalene 2,6-dicarboxylic acid as dicarboxylic acid, and diol component Triblock copolymers of 1,4-butanediol, polytetramethylene glycol as polyalkylene glycol, or triblocks with polylactone as polyester diol copolymer.
在某些特殊情况中,例如也可以使用包含聚硅氧烷系软链段或聚烯烃系软链段的那些。这些软链段可以通过共聚或共混而引入热塑性聚酯弹性体中。In some special cases, for example, those comprising a polysiloxane-based soft segment or a polyolefin-based soft segment may also be used. These soft segments can be incorporated into thermoplastic polyester elastomers by copolymerization or blending.
在有利的实施方式中,热塑性聚酯弹性体的软链段含量优选为15重量%以上、更优选为25重量%以上、进一步优选为30重量%以上、特别优选为40重量%以上,以及优选为80重量%以下、更优选为70重量%以下。In an advantageous embodiment, the soft segment content of the thermoplastic polyester elastomer is preferably 15% by weight or more, more preferably 25% by weight or more, further preferably 30% by weight or more, particularly preferably 40% by weight or more, and preferably It is 80 weight% or less, More preferably, it is 70 weight% or less.
这样的热塑性聚酯弹性体是可商购获得的,例如可以作为Anitel从帝斯曼获得或者从杜邦等获得。Such thermoplastic polyester elastomers are commercially available, for example, as Anitel from DSM or from DuPont or the like.
根据本发明的热塑性聚酯弹性体组合物还应当包含基于组合物总重量计0.1-3.0%、优选0.5-2.6%、更优选0.9-2.0%的二苯胺类抗氧化 剂。本申请的发明人已经发现,当特别选用二苯胺类抗氧化剂(相比于其他常规抗氧化剂如受阻酚类或亚磷酸酯类等)并且以所要求的0.1-3.0%的量用于热塑性聚酯弹性体组合物中时,能够使得该组合物制得的纤维材料在140℃下7天后的耐老化性得到显著改善,能够显著改善粉化现象。特别是发现,当二苯胺抗氧化剂与如上所特定要求的另外的组分C)和D)配合使用时,在该热老化之后的材料压缩形变可以达到<11%、甚至<10%且压缩强度变化率达到<11%、例如<10%、甚至<8%。The thermoplastic polyester elastomer composition according to the present invention should also contain 0.1-3.0%, preferably 0.5-2.6%, more preferably 0.9-2.0% of a diphenylamine antioxidant based on the total weight of the composition. The inventors of the present application have found that when diphenylamine antioxidants are specifically selected (compared to other conventional antioxidants such as hindered phenols or phosphites, etc.) and used in the required amount of 0.1-3.0% for thermoplastic polymer When used in the ester elastomer composition, the aging resistance of the fiber material prepared from the composition can be significantly improved after 7 days at 140° C., and the pulverization phenomenon can be significantly improved. In particular it was found that when diphenylamine antioxidants are used in conjunction with the additional components C) and D) as specified above, the compression set of the material after this heat aging can reach <11%, even <10% and the compressive strength The rate of change reaches <11%, such as <10%, or even <8%.
适用于本申请的二苯胺类化合物是一类抗氧化剂,其通过捕捉聚合物降解链反应中的自由基,消除过氧化自由基终止氧化反应而实现抗氧化功能。一般而言,二苯胺类抗氧化剂基于二苯胺化合物的衍生物,包括酮胺、烷基化二苯胺两个类别,例如它们可以具有如下的结构式(I):The diphenylamine compounds suitable for this application are a class of antioxidants, which realize the antioxidant function by capturing free radicals in the chain reaction of polymer degradation, eliminating peroxide free radicals and terminating the oxidation reaction. Generally speaking, diphenylamine antioxidants are based on derivatives of diphenylamine compounds, including two categories of ketoneamines and alkylated diphenylamines. For example, they can have the following structural formula (I):
其中R1和R2表示任选的位于各自苯环上的一个或多个、优选一个取代基,其选自C1-C18、优选C2-C12或C3-C10的烷基或芳烷基,前提是结构式(I)中至少存在一个R1或R2取代基;并且R1和R2二者也可以形成连接两个苯环的具有C1-C8如C3-C6的直链或支化的亚烷基基团。wherein R1 and R2 represent one or more, preferably one, substituents optionally located on the respective benzene rings, which are selected from C1-C18, preferably C2-C12 or C3-C10 alkyl or aralkyl groups, provided that the structural formula There is at least one R1 or R2 substituent in (I); and both R1 and R2 can also form a linear or branched alkylene group with C1-C8 such as C3-C6 connecting two benzene rings.
优选的,在结构式(I)中存在R1和R2,并且R1和R2表示位于各自苯环上的一个所述取代基,或者R1和R2二者形成连接两个苯环的所述亚烷基基团。Preferably, there are R1 and R2 in the structural formula (I), and R1 and R2 represent one of the substituents located on the respective benzene rings, or both R1 and R2 form the alkylene group connecting two benzene rings group.
这里以及上下文中,所述的烷基优选是具有1-18、更优选2-12以及3-10个C原子的直链、支化或环状的烷基,例如甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基以及它们的异构形式。所述亚烷基基团是优选具有1-8或3-6个C原子的直链或支化的亚烷基,例如亚乙基、亚丙基、异亚丙基等。所述的芳烷基优选是苯烷基,如苯 甲基、苯乙基、α-甲基苄基、α,α-二甲基苄基、苯基异丙基等。Here and in the context, the alkyl group is preferably a linear, branched or cyclic alkyl group having 1-18, more preferably 2-12 and 3-10 C atoms, such as methyl, ethyl, propyl butyl, pentyl, hexyl, heptyl, octyl, nonyl and their isomeric forms. The alkylene group is a linear or branched alkylene group preferably having 1-8 or 3-6 C atoms, such as ethylene, propylene, isopropylene and the like. The aralkyl group is preferably a phenylalkyl group, such as benzyl, phenethyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylisopropyl and the like.
二苯胺类抗氧化剂是可市购获得的,例如以Naugard 445,BLE或DDA购得。Diphenylamine antioxidants are commercially available, for example as Naugard 445, BLE or DDA.
特别优选的,所述二苯胺类抗氧化剂选自如下:Particularly preferably, the diphenylamine antioxidant is selected from the following:
本申请的发明人已经发现当二苯胺类抗氧化剂的用量低于0.1%时纤维材料的抗氧化效率低,耐老化性较差,热老化条件下较容易发生粉化;而当二苯胺类抗氧化剂的用量高于3.0%时则无法进一步提升老化性能。The inventors of the present application have found that when the amount of diphenylamine antioxidants is less than 0.1%, the antioxidant efficiency of the fiber material is low, the aging resistance is poor, and powdering is more likely to occur under heat aging conditions; When the amount of oxidizing agent is higher than 3.0%, the aging performance cannot be further improved.
此外,本申请的发明人还发现,如果在组合物中添加基于组合物总重量计0.1-2.8%、优选0.3-2.3%、更优选0.5-1.8%的脂肪酸酰胺类润滑剂,则可以进一步改善由热塑性聚酯弹性体制得的纤维材料的降噪性,同时还能兼顾材料的抗降解性。如果添加脂肪酰胺类润滑剂的量过低,则无法达到预期的降噪性。而如果添加脂肪酰胺类润滑剂的量高于2.8%时,则导致挤出的纤维丝太光滑而难以发生丝与丝之间的粘接缠绕,无法形成立体网状结构,同时导致制品发粘,回弹慢,此外还会一定程度上影响热老化性和抗降解性。In addition, the inventors of the present application have also found that if 0.1-2.8%, preferably 0.3-2.3%, more preferably 0.5-1.8% of fatty acid amide lubricants are added to the composition based on the total weight of the composition, the Noise-reducing properties of fiber materials made from thermoplastic polyester elastomers combined with resistance to degradation of the material. If the amount of fatty amide lubricant added is too low, the expected noise reduction cannot be achieved. However, if the amount of fatty amide lubricant added is higher than 2.8%, the extruded fiber filaments will be too smooth and difficult to bond and entangle between filaments, unable to form a three-dimensional network structure, and cause the product to be sticky , the rebound is slow, and it will also affect the thermal aging and degradation resistance to a certain extent.
在本申请中,所谓“润滑剂”有时也称为“滑爽剂”。适用于加入本申请的热塑性聚酯弹性体组合物以降低纤维材料噪音的脂肪酸酰胺类润滑剂是这样一类化合物,从分子结构上看它们包含酰胺基以及饱和或不饱和的脂肪族基团。脂肪酸酰胺类润滑剂分子中可以包含一个或多个,例如两个酰胺基。脂肪族基团则优选是直链、支链或环状 的饱和或不饱和的脂族基团,其优选具有6-40、更优选8-30如10-25个碳原子,以及任选地可以具有一个或多个如两个碳碳双键。In the present application, the so-called "lubricant" may also be referred to as "slip agent". Fatty acid amide lubricants suitable for adding to the thermoplastic polyester elastomer composition of the present application to reduce the noise of fiber materials are compounds that contain amide groups and saturated or unsaturated aliphatic groups in terms of molecular structure. The fatty acid amide lubricant may contain one or more, for example two, amide groups in its molecule. The aliphatic group is then preferably a linear, branched or cyclic saturated or unsaturated aliphatic group preferably having 6-40, more preferably 8-30, such as 10-25 carbon atoms, and optionally There may be one or more, such as two, carbon-carbon double bonds.
特别优选的,所述脂肪酸酰胺类润滑剂选自芥酸酰胺、油酸酰胺、硬脂酸酰胺如乙烯基双硬脂酸酰胺或酰胺蜡等。Particularly preferably, the fatty acid amide lubricant is selected from erucamide, oleic acid amide, stearic acid amide such as vinyl bis stearic acid amide or amide wax.
这样的脂肪酸酰胺类润滑剂是本领域已知的并且可以商购获得。Such fatty acid amide lubricants are known in the art and are commercially available.
此外,发明人还发现,如果进一步在所述的热塑性聚酯弹性体组合物中加入一定量的增粘剂,特别是基于组合物总重量计0.1-2.5%、优选0.5-2.2%的环氧官能的基于乙烯基芳族化合物单体与(甲基)丙烯酸系化合物单体的聚合物的增粘剂,则能够进一步改善聚酯弹性体的抗降解性,特别是当TPEE纤维材料在挤出机中被挤出时。In addition, the inventors have also found that if a certain amount of tackifier is further added to the thermoplastic polyester elastomer composition, especially 0.1-2.5%, preferably 0.5-2.2% of epoxy resin based on the total weight of the composition Functional tackifiers based on polymers of vinyl aromatic compound monomers and (meth)acrylic compound monomers can further improve the degradation resistance of polyester elastomers, especially when TPEE fiber materials are extruded When being squeezed out of the machine.
所述环氧官能的基于乙烯基芳族化合物单体与(甲基)丙烯酸系单体的聚合物是一种主要由乙烯基芳族化合物单体单元和(甲基)丙烯酸系化合物单体单元构成主链,而在该主链上接枝有多个具有含环氧基的侧链基团的聚合物。有利的,所述环氧官能的基于乙烯基芳族化合物单体与(甲基)丙烯酸系单体的聚合物有90%、优选95%、更优选98%或99%、甚至完全由乙烯基芳族化合物单体单元和(甲基)丙烯酸系化合物单体单元构成。环氧基团可以例如通过C1-C12、优选C2-C8的(氧)亚烷基连接到聚合物主链上。The epoxy-functional polymer based on vinyl aromatic monomers and (meth)acrylic monomers is a polymer consisting mainly of vinyl aromatic monomer units and (meth)acrylic compound monomer units. A main chain is formed, and a plurality of polymers having side chain groups containing epoxy groups are grafted on the main chain. Advantageously, the epoxy-functional polymer based on vinyl aromatic monomers and (meth)acrylic monomers is 90%, preferably 95%, more preferably 98% or 99%, or even completely composed of vinyl It consists of an aromatic compound monomer unit and a (meth)acrylic compound monomer unit. Epoxy groups can be attached to the polymer backbone, for example via C1-C12, preferably C2-C8 (oxy)alkylene groups.
所述“(甲基)丙烯酸系化合物”指的是具有甲基丙烯酰基或丙烯酰基的化合物,优选具有甲基丙烯酰基氧基或丙烯酰基氧基的化合物,如甲基丙烯酸、丙烯酸、丙烯酸C1-C12烷基酯、甲基丙烯酸C1-C12烷基酯、甲基丙烯酸缩水甘油酯、丙烯酸缩水甘油酯等。The "(meth)acrylic compound" refers to a compound with methacryloyl or acryloyl, preferably a compound with methacryloxy or acryloyloxy, such as methacrylic acid, acrylic acid, acrylic acid C1 -C12 alkyl ester, C1-C12 alkyl methacrylate, glycidyl methacrylate, glycidyl acrylate, etc.
所述乙烯基芳族化合物包括苯乙烯单体及其衍生物,特别是烷基(如C1-C8的烷基)或卤素取代的苯乙烯单体,如苯乙烯、α-甲基苯乙烯、α-氯代苯乙烯或p-甲基苯乙烯等,优选苯乙烯。The vinyl aromatic compounds include styrene monomers and derivatives thereof, especially alkyl (such as C1-C8 alkyl) or halogen-substituted styrene monomers, such as styrene, α-methylstyrene, α-chlorostyrene or p-methylstyrene, etc., preferably styrene.
在一个优选的实施方式中,所述增粘剂是环氧官能化的苯乙烯和(甲基)丙烯酸缩水甘油酯的共聚物。In a preferred embodiment, the tackifier is an epoxy-functionalized copolymer of styrene and glycidyl (meth)acrylate.
聚合物的环氧官能化可以通过常规的方式进行。例如,可以通过在制备共聚物时加入对应所要求环氧当量的量的具有环氧基的可共聚 单体而实现。所述具有环氧基的可共聚单体例如具有环氧基的乙烯基单体,特别是如(甲基)丙烯酸缩水甘油酯。The epoxy-functionalization of the polymers can be carried out in a conventional manner. For example, it can be achieved by adding a copolymerizable monomer with an epoxy group in an amount corresponding to the required epoxy equivalent when preparing the copolymer. The copolymerizable monomer having an epoxy group is, for example, a vinyl monomer having an epoxy group, especially glycidyl (meth)acrylate.
这样的增粘剂的制备本身是已知的并且该产品可市购获得。有利的,该环氧官能的基于乙烯基芳族化合物单体与(甲基)丙烯酸系单体的聚合物具有2-40万,优选5-20万的重均分子量并且其环氧当量可以在例如100-800g/mol、优选150-650g/mol之间。所述环氧当量表示含1mol环氧基团的树脂的质量,以g/mol表示。The preparation of such tackifiers is known per se and the products are commercially available. Advantageously, the epoxy-functional polymer based on vinyl aromatic monomers and (meth)acrylic monomers has a weight average molecular weight of 20,000 to 400,000, preferably 50,000 to 200,000 and its epoxy equivalent can be in the range of For example between 100-800 g/mol, preferably 150-650 g/mol. The epoxy equivalent represents the mass of the resin containing 1mol of epoxy groups, expressed in g/mol.
在此,所述重均分子量以聚苯乙烯为标样采用GPC方法测得。Here, the weight-average molecular weight is measured by GPC using polystyrene as a standard sample.
在此,所述环氧当量可以按照ASTM D1652标准测得。Here, the epoxy equivalent can be measured according to the ASTM D1652 standard.
除了以上所述的这些组分之外,在本发明的热塑性聚酯弹性体组合物中还可以添加其他添加剂,只要这些添加剂不影响其使用性能及其成型加工。所述的其他添加剂包括例如其他抗氧化剂如受阻酚类和亚磷酸酯类,紫外线吸收剂如二苯甲酮和苯并三唑,其他的润滑剂如硬脂酸钙或有机硅类润滑剂,除味剂,抗菌剂,防霉剂,着色剂,芳香剂,阻燃剂和吸湿剂等。In addition to the components mentioned above, other additives can also be added to the thermoplastic polyester elastomer composition of the present invention, as long as these additives do not affect its performance in use and its molding process. Said other additives include, for example, other antioxidants such as hindered phenols and phosphites, UV absorbers such as benzophenones and benzotriazoles, other lubricants such as calcium stearate or silicone-based lubricants, Deodorants, antibacterial agents, antifungal agents, colorants, fragrances, flame retardants and hygroscopic agents, etc.
如果使用的话,所述其他添加剂的添加量优选在基于热塑性聚酯弹性体组合物的总重量计0.1%-8%,例如0.5-5%的范围内。If used, said other additives are preferably added in an amount in the range of 0.1%-8%, eg 0.5-5%, based on the total weight of the thermoplastic polyester elastomer composition.
优选的,还进一步使用基于组合物总重量计各自在0.5-1.5%范围的亚磷酸酯类抗氧化剂、受阻酚类抗氧化剂和/或紫外线吸收剂。同样也优选使用基于组合物总重量计各自在0.1-5%的硬脂酸钙和/或有机硅类润滑剂。Preferably, phosphite antioxidants, hindered phenolic antioxidants and/or ultraviolet absorbers are further used in the range of 0.5-1.5% based on the total weight of the composition. Preference is also given to using calcium stearate and/or silicone-based lubricants in amounts of 0.1 to 5% each, based on the total weight of the composition.
本申请的第二方面涉及制备根据本发明的热塑性聚酯弹性体的方法,包括:i)提供如上所述的热塑性聚酯弹性体的各个组分并将其混合,ii)将混合得到的组合物在高于其熔点10-120℃的温度下熔融挤出成纤维状的线材,和iii)使所得到的线材无规缠结和弯曲形成三维网状结构体。A second aspect of the present application relates to a method for preparing a thermoplastic polyester elastomer according to the present invention, comprising: i) providing the individual components of the thermoplastic polyester elastomer as described above and mixing them, ii) combining the resulting combination melt-extruding the material into fibrous strands at a temperature 10-120° C. higher than its melting point, and iii) randomly entangle and bend the obtained strands to form a three-dimensional network structure.
在本申请的上下文中,“纤维”与“线材”有时可互换使用,它们指的是长度远大于截面直径(例如20倍或50倍以上)的线状的材料,通常可以通过熔融挤出得到。所述线材或纤维的截面形状没有特 别限定,例如可以是圆形截面、椭圆形截面、多边形截面、中空截面或其他异形截面等,它们能够赋予抗压缩性、蓬松性等。In the context of this application, "fiber" and "wire" are sometimes used interchangeably, and they refer to a thread-like material whose length is much greater than the cross-sectional diameter (for example, 20 times or more than 50 times), which can usually be melt-extruded get. The cross-sectional shape of the wire or fiber is not particularly limited, for example, it can be a circular cross-section, an elliptical cross-section, a polygonal cross-section, a hollow cross-section or other special-shaped cross-sections, etc., which can impart compression resistance, bulkiness, etc.
第i)步的混合过程可以在任何现有技术中已知的混合设备中进行。优选的,在搅拌的条件下充分混合热塑性聚酯弹性体组合物的各个组分。组分的添加次序没有特别的限制。形成的混合物可以被立即输送入后续的处理步骤。The mixing process of step i) can be carried out in any mixing equipment known in the prior art. Preferably, the individual components of the thermoplastic polyester elastomer composition are thoroughly mixed under agitation. The order of addition of the components is not particularly limited. The resulting mixture can be fed immediately to subsequent processing steps.
第ii)和iii)步通常相继而连续地进行。在一个示例性的实施方式中,具体地,可以使用通常的熔融挤出机,将混合得到的热塑性弹性体组合物加热至比熔点高10~120℃的温度,使其为熔融状态。例如,在本发明中可以将挤出机温度设置为180-300℃、优选200-280℃的温度。然后利用具有多个孔口的喷嘴向下喷出,自然下降,形成环。此时,根据喷嘴面与设置在使树脂固化的冷却介质上的收取输送带的距离、树脂的熔融粘度、孔口的孔径和喷出量等而确定环直径和线材的纤度以及接合点数。利用设置在冷却介质上的可调整间隔的一对收取输送带夹着熔融状态的喷出线材并使其停留,从而产生环,通过将孔口的孔间隔设为产生环能够接触的孔间隔,从而使产生的环互相接触,通过接触,从而环形成无规的三维形态并且接触部发生熔接。接着,将形成无规的三维形态并且接触部熔接了的连续线材连续地引入到冷却介质(优选室温下的水)中固化形成网状结构体。Steps ii) and iii) are usually carried out successively and continuously. In an exemplary embodiment, specifically, a common melt extruder can be used to heat the mixed thermoplastic elastomer composition to a temperature 10 to 120° C. higher than the melting point to make it into a molten state. For example, in the present invention the temperature of the extruder can be set at a temperature of 180-300°C, preferably 200-280°C. It is then sprayed downwards using a nozzle with multiple orifices and falls naturally to form a ring. At this time, the diameter of the ring, the fineness of the wire, and the number of joints are determined according to the distance between the nozzle surface and the take-up conveyor installed on the cooling medium that solidifies the resin, the melt viscosity of the resin, the diameter of the orifice, and the discharge amount. A pair of take-up conveyor belts installed on the cooling medium with an adjustable interval sandwiches and stops the ejected wire in a molten state to produce a ring. The resulting rings are thus brought into contact with each other, by which the rings form a random three-dimensional shape and the contact portions are fused. Next, the continuous wires formed in a random three-dimensional shape and welded at the contact portion are continuously introduced into a cooling medium (preferably water at room temperature) to solidify to form a network structure.
接着,可以视需要进行除水干燥。作为本发明的一个示例性的方法,暂时冷却后,进行假结晶化处理。假结晶化处理温度至少比熔点(Tm)低10℃以上。通过单纯的热处理进行假结晶化时,耐热耐流挂性提高。另外,暂时冷却后,经过干燥工序时,将干燥温度设为退火温度,从而能够同时进行假结晶化处理。另外,可以另行进行假结晶化处理。Next, dehydration drying may be performed as necessary. As an exemplary method of the present invention, pseudocrystallization treatment is performed after cooling once. The pseudocrystallization treatment temperature is at least 10°C lower than the melting point (Tm). When pseudocrystallization is performed by simple heat treatment, heat resistance and sag resistance are improved. In addition, when passing through the drying step after cooling once, the drying temperature can be set to the annealing temperature, so that the pseudo-crystallization treatment can be performed at the same time. In addition, pseudocrystallization treatment may be performed separately.
最后,可以将制得的网状结构体切割成期望的长度或形状,用于缓冲材料。将本发明的网状结构体用于缓冲材料时,需要根据其使用目的、使用部位来选择所使用的树脂、纤度、环直径、体积密度。Finally, the prepared mesh structure can be cut into desired length or shape for cushioning material. When using the network structure of the present invention as a cushioning material, it is necessary to select the used resin, fineness, ring diameter, and bulk density according to the purpose of use and the site of use.
根据本发明的材料有着广泛的应用,例如可以用于家具、家电、 办公用品、汽车、火车、船舶或航空航天领域中作为缓冲材料,例如办公椅、沙发、床垫、地毯、交通工具中的乘坐座椅中的缓冲材料。The material according to the present invention has a wide range of applications, for example, it can be used as a cushioning material in furniture, home appliances, office supplies, automobiles, trains, ships or aerospace fields, such as in office chairs, sofas, mattresses, carpets, vehicles, etc. Take the cushioning material in the seat.
以下通过实施例来进一步阐释本发明,但是本发明显然不应限制为这些具体的实施例。The present invention is further illustrated by the following examples, but the present invention obviously should not be limited to these specific examples.
原料列表Raw material list
在实施例中采用以下原料The following raw materials are used in the examples
表1Table 1
热塑性聚酯弹性体组合物的制备Preparation of thermoplastic polyester elastomer composition
在高混机中加入100kg的TPEE,在搅拌条件下加入按照下表2所示百分比例(表中“\”表示不添加)的二苯胺类抗氧剂,受阻酚类抗氧剂,芥酸酰胺,乙烯基双硬脂酸酰胺,有机硅润滑剂和增粘剂,分别得到若干热塑性聚酯弹性体的组合料。Add 100kg of TPEE into the high mixer, and add diphenylamine antioxidants, hindered phenolic antioxidants, erucic acid according to the percentages shown in the following table 2 ("\" in the table means not added) under stirring conditions Amide, vinyl bis stearic acid amide, silicone lubricant and tackifier, respectively, to obtain a combination of several thermoplastic polyester elastomers.
将每个实施例所得的组合料放置于熔融挤出机中,挤出机温度设置为210~260℃,以单孔喷丝量为10~60g/min的速度向喷丝孔下方喷出,经过喷丝孔正下方的保温区域,熔融线状体弯曲而形成环,使接 触部分熔接,形成三维网状结构,通过牵引输送板链牵引熔融状态的三维网状结构体使其固化。将该固化后的三维网状结构体进行后续的性能测试。The combined material obtained in each embodiment is placed in a melting extruder, the temperature of the extruder is set at 210-260°C, and the single-hole spinning rate is 10-60g/min. Spray to the bottom of the spinneret hole, After passing through the heat preservation area directly below the spinneret hole, the molten linear body is bent to form a ring, so that the contact part is welded to form a three-dimensional network structure, and the three-dimensional network structure in the molten state is pulled by the traction conveying plate chain to make it solidify. Subsequent performance tests were performed on the solidified three-dimensional network structure.
性能测试Performance Testing
热老化压缩变形heat aging compression set
根据ISO 2440的方法,取试样大小为100mm×100mm,将试样于140℃存放168小时,然后在标准环境下调理24小时。在测量上述老化后的试样的高度后,将试样压缩至试样厚度的50%,在70℃温度条件下保持22小时,自由状态下存放在标准环境30分钟后,再次测量试样高度,得到压缩变形值。According to the method of ISO 2440, the size of the sample is 100mm×100mm, and the sample is stored at 140°C for 168 hours, and then conditioned for 24 hours in a standard environment. After measuring the height of the above-mentioned aged sample, compress the sample to 50% of the thickness of the sample, keep it at 70°C for 22 hours, and store it in a standard environment for 30 minutes in a free state, then measure the height of the sample again , to get the compressive deformation value.
热老化压缩强度变化Thermal aging compressive strength change
根据ISO 2440的方法,取试样大小为100mm×100mm,测量长宽尺寸后,测定制得状态下试样的压缩强度值。将试样于140℃存放168小时,然后在标准环境下调理24小时,再按照制得状态下测试压缩强度值的相同步骤测试热老化后的压缩强度值,得到压缩强度变化。According to the method of ISO 2440, take a sample size of 100mm×100mm, measure the length and width dimensions, and measure the compressive strength value of the sample in the prepared state. The sample was stored at 140°C for 168 hours, then conditioned for 24 hours in a standard environment, and then the compressive strength value after heat aging was tested according to the same procedure as the compressive strength value in the prepared state to obtain the compressive strength change.
压缩强度compressive strength
根据ISO 3386-1的方法,取试样大小为100mm×100mm,测量长宽尺寸后,测定制备状态下试样的压缩强度值。According to the method of ISO 3386-1, the size of the sample is 100mm×100mm. After measuring the length and width, the compressive strength value of the sample in the prepared state is determined.
噪音值Noise value
在静音房中(分贝数小于35),将试样置于平台上,匀速放上70kg砝码,分别采用分贝仪和人耳进行评估,用分贝仪读取重物下压过程中最大值,从感官上定性评价试样产生的声音大小。In a quiet room (the number of decibels is less than 35), put the sample on the platform, put a 70kg weight on it at a constant speed, use the decibel meter and the human ear to evaluate respectively, and use the decibel meter to read the maximum value during the process of pressing down the weight. Qualitatively evaluate the volume of sound produced by the sample from the senses.
熔融指数Melt Index
将制得的材料样品放入一固定内直径的金属套筒中加热和施加负荷,测量材料熔体在10分钟内从规定直径的口模中流出的质量。Put the prepared material sample into a metal sleeve with a fixed inner diameter to heat and apply a load, and measure the mass of the material melt flowing out of a die with a specified diameter within 10 minutes.
表2.各个实施例的组成和性能测试结果Table 2. Composition and performance test results of various embodiments
(带有*的实施例为根据本发明的)(embodiments with * are according to the present invention)
Claims (10)
- 热塑性聚酯弹性体组合物,其包含基于组合物总重量计:A thermoplastic polyester elastomer composition comprising, based on the total weight of the composition:A)80-98%的热塑性聚酯弹性体TPEE;A) 80-98% thermoplastic polyester elastomer TPEE;B)0.1-3%的二苯胺类抗氧化剂;B) 0.1-3% diphenylamine antioxidant;C)0.1-2.8%的脂肪酸酰胺类润滑剂;和C) 0.1-2.8% fatty acid amide lubricant; andD)0.1-2.5%的增粘剂,其为环氧官能的基于乙烯基芳族化合物与(甲基)丙烯酸系化合物的聚合物。D) 0.1-2.5% of tackifiers which are epoxy-functional polymers based on vinylaromatics and (meth)acrylic compounds.
- 根据权利要求1的热塑性聚酯弹性体组合物,其特征在于,所述组合物包含基于组合物总重量计0.5-2.6%、优选0.9-2.0%的二苯胺类抗氧化剂,和/或0.3-2.3%、优选0.5-1.8%的脂肪酸酰胺类润滑剂。The thermoplastic polyester elastomer composition according to claim 1, characterized in that the composition comprises 0.5-2.6%, preferably 0.9-2.0%, of diphenylamine antioxidants based on the total weight of the composition, and/or 0.3- 2.3%, preferably 0.5-1.8%, fatty acid amide lubricant.
- 根据权利要求1或2的热塑性聚酯弹性体组合物,其特征在于,所述二苯胺类抗氧化剂具有如下的结构式(I):According to the thermoplastic polyester elastomer composition of claim 1 and 2, it is characterized in that, described diphenylamine antioxidant has following structural formula (I):其中R1和R2表示任选的位于各自苯环上的一个或多个、优选一个取代基,其选自C1-C18、优选C2-C12或C3-C10的烷基或芳烷基,前提是结构式(I)中至少存在一个R1或R2取代基;并且R1和R2二者也可以形成连接两个苯环的具有C1-C8如C3-C6的直链或支化的亚烷基基团。wherein R1 and R2 represent one or more, preferably one, substituents optionally located on the respective benzene rings, which are selected from C1-C18, preferably C2-C12 or C3-C10 alkyl or aralkyl groups, provided that the structural formula There is at least one R1 or R2 substituent in (I); and both R1 and R2 can also form a linear or branched alkylene group with C1-C8 such as C3-C6 connecting two benzene rings.
- 根据前述权利要求任一项所述的热塑性聚酯弹性体组合物,其特征在于,所述亚烷基基团是具有1-8或3-6个C原子的直链或支化的亚烷基,例如亚乙基、亚丙基、异亚丙基,和/或所述的芳烷基是苯烷基,如苯甲基、苯乙基、α-甲基苄基、苯基异丙基。Thermoplastic polyester elastomer composition according to any one of the preceding claims, characterized in that the alkylene group is a linear or branched alkylene group having 1-8 or 3-6 C atoms group, such as ethylene, propylene, isopropylidene, and/or the aralkyl group is phenylalkyl, such as benzyl, phenethyl, α-methylbenzyl, phenylisopropyl base.
- 根据前述权利要求任一项所述的热塑性聚酯弹性体组合物,其特征在于,所述脂肪酸酰胺类润滑剂包含一个或两个酰胺基以及脂肪族基团,所述脂肪族基团选自直链、支链或环状的饱和或不饱和的脂族基团,其优选具有6-40、更优选8-30如10-25个碳原子,以及任选地可以具有一个或多个如两个碳碳双键。The thermoplastic polyester elastomer composition according to any one of the preceding claims, wherein the fatty acid amide lubricant comprises one or two amide groups and an aliphatic group selected from A linear, branched or cyclic saturated or unsaturated aliphatic group preferably has 6-40, more preferably 8-30 such as 10-25 carbon atoms, and optionally may have one or more such as Two carbon-carbon double bonds.
- 根据前述权利要求任一项所述的热塑性聚酯弹性体组合物,其特征在于,所述脂肪酸酰胺类润滑剂选自芥酸酰胺、油酸酰胺、硬脂酸酰胺如乙烯基双硬脂酸酰胺或酰胺蜡等。The thermoplastic polyester elastomer composition according to any one of the preceding claims, wherein the fatty acid amide lubricant is selected from the group consisting of erucamide, oleic acid amide, stearic acid amide such as vinyl distearic acid Amide or amide wax, etc.
- 根据前述权利要求任一项所述的热塑性聚酯弹性体组合物,其特征在于,所述组合物进一步包含基于组合物总重量计各自在0.5-1.5%范围的亚磷酸酯类抗氧化剂、受阻酚类抗氧化剂和/或紫外线吸收剂,和/或进一步包含基于组合物总重量计各自在0.1-5%的硬脂酸钙和/或有机硅类润滑剂。The thermoplastic polyester elastomer composition according to any one of the preceding claims, characterized in that the composition further comprises phosphite antioxidants, hindered Phenolic antioxidants and/or UV absorbers, and/or further comprising calcium stearate and/or silicone-based lubricants at 0.1-5% based on the total weight of the composition.
- 根据前述权利要求任一项所述的热塑性聚酯弹性体组合物,其特征在于,所述增粘剂为环氧官能的苯乙烯和(甲基)丙烯酸缩水甘油酯的共聚物,优选其环氧当量可以在例如100-800g/mol、优选150-650g/mol之间。Thermoplastic polyester elastomer composition according to any one of the preceding claims, characterized in that the tackifier is an epoxy-functional copolymer of styrene and glycidyl (meth)acrylate, preferably its cyclic The oxygen equivalent weight can be, for example, between 100-800 g/mol, preferably 150-650 g/mol.
- 制备热塑性聚酯弹性体纤维材料的方法,包括:i)提供如权利要求1至8任一项所述的热塑性聚酯弹性体组合物的各个组分并将其混合,ii)将混合得到的混合物在高于其熔点10-120℃的温度下熔融挤出成纤维状的线材,和iii)使所得到的线材无规缠结和弯曲形成三维网状结构体。A method for preparing a thermoplastic polyester elastomer fiber material, comprising: i) providing and mixing the components of the thermoplastic polyester elastomer composition according to any one of claims 1 to 8, ii) mixing the obtained The mixture is melt-extruded into fibrous strands at a temperature of 10-120° C. above its melting point, and iii) the resulting strands are randomly entangled and bent to form a three-dimensional network structure.
- 包含根据权利要求1至8任一项所述的热塑性聚酯弹性体组合物或由根据权利要求9所述的方法制得的热塑性聚酯弹性体纤维材 料的制品,其优选为办公椅、沙发、床垫、地毯、交通工具中的乘坐座椅中的缓冲材料。Comprising the thermoplastic polyester elastomer composition according to any one of claims 1 to 8 or the article of thermoplastic polyester elastomer fiber material obtained by the method according to claim 9, it is preferably an office chair, a sofa , mattresses, carpets, and cushioning materials in seats in vehicles.
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