CN111511820B - 发泡组合物 - Google Patents
发泡组合物 Download PDFInfo
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- CN111511820B CN111511820B CN201780097793.5A CN201780097793A CN111511820B CN 111511820 B CN111511820 B CN 111511820B CN 201780097793 A CN201780097793 A CN 201780097793A CN 111511820 B CN111511820 B CN 111511820B
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- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 238000005187 foaming Methods 0.000 title claims abstract description 53
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 36
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 24
- -1 peroxide compound Chemical class 0.000 claims abstract description 23
- 238000004132 cross linking Methods 0.000 claims abstract description 22
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 18
- 238000003860 storage Methods 0.000 claims abstract description 16
- 229920000768 polyamine Polymers 0.000 claims abstract description 13
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 11
- 239000006260 foam Substances 0.000 claims description 17
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 9
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 claims description 8
- 239000008240 homogeneous mixture Substances 0.000 claims description 8
- 239000002530 phenolic antioxidant Substances 0.000 claims description 7
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical group CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002318 adhesion promoter Substances 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 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 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001746 injection moulding Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 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 claims description 3
- SAIXZIVDXDTYCH-UHFFFAOYSA-N 3-chlorobenzene-1,2-diamine Chemical compound NC1=CC=CC(Cl)=C1N SAIXZIVDXDTYCH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
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- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims description 2
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 claims description 2
- CCNDOQHYOIISTA-UHFFFAOYSA-N 1,2-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1C(C)(C)OOC(C)(C)C CCNDOQHYOIISTA-UHFFFAOYSA-N 0.000 claims description 2
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 claims description 2
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 2
- CPGFMWPQXUXQRX-UHFFFAOYSA-N 3-amino-3-(4-fluorophenyl)propanoic acid Chemical compound OC(=O)CC(N)C1=CC=C(F)C=C1 CPGFMWPQXUXQRX-UHFFFAOYSA-N 0.000 claims description 2
- HLBZWYXLQJQBKU-UHFFFAOYSA-N 4-(morpholin-4-yldisulfanyl)morpholine Chemical compound C1COCCN1SSN1CCOCC1 HLBZWYXLQJQBKU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004156 Azodicarbonamide Substances 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 2
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043276 diisopropanolamine Drugs 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 3
- 230000000996 additive effect Effects 0.000 claims 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 13
- 229920003345 Elvax® Polymers 0.000 description 6
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- 239000001993 wax Substances 0.000 description 6
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 241000721047 Danaus plexippus Species 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- SOIFHCQNONSZGY-UHFFFAOYSA-N 2-(3,5-ditert-butyl-4-hydroxyphenyl)-n-[6-(propanoylamino)hexyl]propanamide Chemical compound CCC(=O)NCCCCCCNC(=O)C(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SOIFHCQNONSZGY-UHFFFAOYSA-N 0.000 description 1
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- BXIQXYOPGBXIEM-UHFFFAOYSA-N butyl 4,4-bis(tert-butylperoxy)pentanoate Chemical compound CCCCOC(=O)CCC(C)(OOC(C)(C)C)OOC(C)(C)C BXIQXYOPGBXIEM-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
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- C08J9/0023—Use of organic additives containing oxygen
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- C08J9/0028—Use of organic additives containing nitrogen
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- C08J9/102—Azo-compounds
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Abstract
本发明涉及一种发泡组合物,其包含至少一种乙烯‑乙酸乙烯酯(EVA)共聚物;至少一种发泡剂;至少一种过氧化物化合物;至少一种多胺;至少一种交联促进剂;至少一种主抗氧化剂;和至少一种辅助抗氧化剂;所述交联促进剂的含量为基于该组合物总重量的0.1重量%至3重量%。根据本发明通过在80℃至120℃的温度范围内固化所述发泡组合物而制得的发泡制品在130℃至200℃的烘烤窗口显示出高的初始体积膨胀率,并且在储存后显示出优异的稳定性。
Description
技术领域
本发明涉及一种发泡组合物,其包含至少一种乙烯-乙酸乙烯酯(EVA)共聚物;至少一种发泡剂;至少一种过氧化物化合物;至少一种多胺;至少一种交联促进剂;至少一种主抗氧化剂;和至少一种辅助抗氧化剂;所述交联促进剂的含量为基于该组合物总重量的0.1重量%至3重量%。根据本发明通过在80℃至120℃的温度范围内固化该发泡组合物而制得的发泡制品在130℃至200℃的烘烤窗口显示出高的初始体积膨胀率,并在储存后显示出优异的稳定性。
发明背景
发泡材料已被广泛应用于汽车、飞机以及建筑声学的许多地方的噪声控制应用中。
应用于汽车中时,通常根据汽车的生产线,将由包含发泡材料(诸如乙烯-乙酸乙烯酯(EVA)共聚物)的发泡组合物制成的发泡制品在160℃至200℃的烘烤窗口加热。由现有的发泡组合物制成的发泡制品在当前的发泡工艺中表现出良好的体积膨胀。然而,当前的烘烤窗口需要高能量输入,不符合全球节能趋势。
因此,需要开发一种能够在130℃至150℃的低烘烤窗口温度下充分膨胀的发泡组合物和一种由该发泡组合物制成的发泡制品。期望的是该发泡制品也适用于烘烤窗口为160℃至200℃的现有汽车生产线。
发明内容
本发明涉及一种发泡组合物,其包含:
(a)至少一种EVA共聚物;
(b)至少一种发泡剂;
(c)至少一种过氧化物化合物;
(d)至少一种多胺;
(e)至少一种交联促进剂;
(f)至少一种主抗氧化剂;以及
(g)至少一种辅助抗氧化剂;
其中,所述交联促进剂的含量为基于该组合物总重量的0.1重量%至3重量%。
由该发泡组合物制成的发泡制品在130℃至200℃的烘烤窗口表现出高的初始体积膨胀率,并且在40℃和50%RH的条件下储存6个月后显示出优异的稳定性。
本发明还涉及一种通过在80℃至120℃的温度范围内,优选地在95℃至105℃的温度范围内固化该发泡组合物而制成的发泡制品。
本发明还涉及一种由该发泡组合物通过以下步骤制成的发泡制品:
a)在15℃至55℃的温度下混合该发泡组合物的组分以形成均匀混合物;
b)通过在90℃至100℃的温度下进行挤出使均匀混合物粒化而获得发泡颗粒;以及
c)在95℃至105℃的温度下通过注塑成型而由发泡颗粒形成发泡制品。
本发明还涉及一种由该发泡组合物制成的泡沫制品。
本发明还涉及一种由发泡制品制成的泡沫制品。
本发明还涉及一种包括填充有该泡沫制品的车辆部件的车辆,其中,该车辆部件可以是车柱、车门或车身。
具体实施方式
在以下段落中,将对本发明进行更详细的描述。所描述的每个方面可以与任何其他一个或多个方面组合,除非有相反的明确说明。特别地,指示为优选或有利的任何特征可以与指示为优选或有利的任何其他一个或多个特征组合。
在本发明的上下文中,除非上下文中另有指示,否则将根据以下定义来解释所使用的术语。
如本文所使用的,单数形式的“一个”、“一种”和“该”包括单数和复数指代物,除非上下文中另有明确指示。
本文所使用的术语“包含(comprising,comprises)”和“包括(composed of)”与“含有(including,includes)”或“含有(contains,containing)”同义,并且是包括性的或开放式的,并且不排除其他非记述的成员、元素或工艺步骤。
数值端点的叙述包括在各个范围内的所有数字和分数,以及所列举的端点。
本说明书中引用的所有参考文献均通过引用全文并入本文中。
除非另有定义,否则用于公开本发明的所有术语,包括技术术语和科学术语,均具有本发明所属领域的普通技术人员通常所理解的含义。通过进一步的指导,包括术语定义以更好地理解本发明的教导。
EVA共聚物
本发明的EVA共聚物是指任何常见的EVA共聚物,优选地乙酸乙烯酯(VA)含量为12重量%或更多,且熔体指数在190℃/2.16kg下为2-25g/10min,更优选地VA含量为18重量%至30重量%,且通过ASTM D1238测量在190℃/2.16kg下熔体指数为2.5-15g/10min。
可商购的EVA共聚物的示例是,例如,得自Dupont的Elvax 250;得自Dupont的Elvax 260;以及得自Dupont的Elvax 460。
在本发明的一些实施方式中,本发明的发泡组合物中EVA共聚物的量为基于该组合物总重量的45重量%至70重量%,优选地为50重量%至60重量%。
发泡剂
本发明的发泡剂是指任何常见发泡剂,并且可选自4,4′-氧代双(苯磺酰肼)(OBSH)、偶氮二甲酰胺、偶氮二甲酸二异丙酯及其任何组合。
在本发明的一些实施方式中,该发泡剂优选地为OBSH。
可商购发泡剂的示例是,例如,得自IMCD Australia Limited的OBSH;以及得自Western Reserve Chemical的OBSH。
在本发明的一些实施方式中,本发明的发泡剂的量为基于该组合物总重量的15重量%至30重量%,优选地为20重量%至25重量%。
过氧化物化合物
本发明的过氧化物化合物是指任何常见的过氧化物化合物,优选地为有机过氧化物。过氧化物化合物用作用于交联EVA共聚物的交联剂。
过氧化物化合物的示例包括但不限于2,5-二甲基-2,5-二(叔丁基过氧)己烷、过氧化苯甲酸叔丁酯、过氧化苯甲酰、二(叔丁基过氧化异丙基)苯、过氧化二异丙苯、1,1-二-(叔丁基过氧基)-3,3,5-三甲基环己烷、4,4-双(叔丁基过氧化)戊酸丁酯及其任何组合。
可商购的过氧化物化合物的示例为,例如,得自Arkema的DCP40;以及得自Vanderbilt Chemicals的Varox 231XL。
在本发明的一些实施方式中,过氧化物化合物的量为基于该组合物总重量的0.1重量%至10重量%,优选地为0.2重量%至6重量%,更优选地为1.5重量%至3重量%。
多胺
本发明的多胺是指任何常见的多胺,并且用作用于交联EVA共聚物的交联剂。
多胺的示例包括但不限于二乙基甲苯二胺、氯二氨基苯(chlorodiaminobenzene)、二乙醇胺、二异丙醇胺、三乙醇胺、三丙醇胺、1,6-己二胺及其任何组合。
可商购的多胺是例如得自T&K Toka的Fujicure-FXR-1090FA。
在本发明的一些实施方式中,多胺的量为基于该组合物总重量的0.001重量%至2重量%,优选地为0.005重量%至0.5重量%。
交联促进剂
本发明的交联促进剂是指能够在较低温度下引起发泡的任何常见交联促进剂。交联促进剂包括但不限于三羟甲基丙烷三甲基丙烯酸酯、二乙基二硫代氨基甲酸锌、二(吗啉-4-基)二硫化物(di(morpholin-4-yl)disulphide)、四硫化双五亚甲基秋兰姆及其任何组合。
可商购交联促进剂的示例是例如得自Sartomer的SR350;以及得自Evonik的VISIOMER TMPTMA。
在本发明的一些实施方式中,交联促进剂的量为基于该组合物总重量的0.1重量%至3重量%,优选地为1重量%至2重量%。
主抗氧化剂
本发明的主抗氧化剂在过氧自由基氧化中间体向非自由基氢过氧化物的转化中充当氢原子供体,并防止EVA共聚物发生降解。优选地,该主抗氧化剂选自胺类抗氧化剂、酚类抗氧化剂及其任何组合。
在本发明的一些实施方式中,主抗氧化剂优选为受阻酚类抗氧化剂。
主抗氧化剂的示例包括但不限于四[3-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate])、3-(3,5-二叔丁基-4-羟基苯基)丙酸十八烷基酯、3,3’-双(3,5-二叔丁基-4-羟基苯基)-N,N'-六亚甲基二丙酰胺及其任何组合。
可商购的主抗氧化剂的示例是例如得自Ciba的Irganox 1010;得自Ciba的Irganox L107;以及得自Ciba的Irganox L109。
在本发明的一些实施方式中,主抗氧化剂的量为基于该组合物总重量的0.04重量%至10重量%,优选地为0.05重量%至6重量%。
辅助抗氧化剂
本发明的辅助抗氧化剂不同于主抗氧化剂不同,与主抗氧化剂一起用于进一步去除氢过氧化物,从而使得氢过氧化物不会分解形成新的用于氧化的引发自由基。优选地,辅助抗氧化剂选自含磷抗氧化剂、含硫抗氧化剂及其任何组合。
在本发明的一些实施方式中,辅助抗氧化剂选自亚磷酸酯、膦酸酯及其任何组合。
辅助抗氧化剂的示例包括但不限于双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯、三(2,4-二叔丁基苯基)亚磷酸酯及其组合。
可商购的辅助抗氧化剂是例如得自BASF的Irgafos 168。
在本发明的一些实施方式中,辅助抗氧化剂的量为基于该组合物总重量的0.01重量%至2重量%,优选地为0.05重量%至0.5重量%。
其他任选存在的添加剂
在本发明的一些实施方式中,该发泡组合物还可任选地包含其他添加剂,例如至少一种蜡、至少一种粘合促进剂、至少一种填充剂、至少一种润滑剂、至少一种染料及其任何组合。
在本发明的一些实施方式中,该发泡组合物可任选地包含至少一种蜡。优选地,该蜡是熔化温度为90℃至100℃的微晶蜡。可商购蜡的示例是例如得自International Group的Microsere 5999A;以及得自Petrolite公司的BE SQUARE 185Amber Wax。
在本发明的一些实施方式中,该发泡组合物可任选地包括至少一种粘合促进剂。该粘合促进剂包括但不限于乙烯、丙烯酸酯和马来酸酐的三元共聚物。可商购粘合促进剂的示例是例如得自Arkema的Bondine HX 8290;以及得自Arkema France INC的LotaderBondine HX 8290。
在本发明的一些实施方式中,该发泡组合物可任选地包括至少一种填充剂。该填充剂包括但不限于二氧化硅、云母和滑石。可商购填充剂是例如得自Beijing LanningTalc factory的Talc 1250。
在本发明的一些实施方式中,该发泡组合物可任选地包括至少一种润滑剂。该润滑剂包括但不限于脂肪醇及其二元羧酸酯、短链醇的脂肪酸酯、脂肪酸、脂肪酸酰胺。可商购润滑剂是例如得自Changzhou Chemical Co.,LTD的硬脂酸。
在本发明的一些实施方式中,该发泡组合物可任选地包括至少一种染料。优选地,该染料是炭黑。可商购染料是例如得自Cabot公司的Monarch 580。
在优选的实施方式中,该发泡组合物包含:
(a)45重量%至70重量%的至少一种EVA共聚物;
(b)15重量%至30重量%的至少一种发泡剂;
(c)0.1重量%至10重量%的至少一种过氧化物化合物;
(d)0.001重量%至2重量%的至少一种多胺;
(e)0.1重量%至3重量%的至少一种交联促进剂;
(f)0.04重量%至10重量%的至少一种主抗氧化剂;以及
(g)0.01重量%至2重量%的至少一种辅助抗氧化剂;
所有组分的重量百分比合计为100重量%,并且交联促进剂的含量更优选为基于该组合物总重量的1重量%至2重量%。
本发明的发泡制品可通过在80℃至120℃的温度范围内,优选地在95℃至105℃的温度范围内固化该发泡组合物而制成。
在本发明的一些实施方式中,该发泡制品可通过以下步骤制备:
a)在15℃至55℃的温度下混合该发泡组合物的组分以形成均匀混合物;
b)通过在90℃至100℃的温度下进行挤出而使均匀混合物粒化,从而获得发泡颗粒;以及
c)在95℃至105℃的温度下通过注塑成型而由发泡颗粒形成发泡制品。
本发明的泡沫制品可通过在130℃至200℃的温度下加热该发泡制品而制备。在本发明的一些实施方式中,该发泡制品可加热10-120分钟,优选地为20-60分钟,最优选地为30-40分钟。
在本发明中,发泡制品的初始体积膨胀率(R)可通过以下步骤确定:
(a)测量发泡制品的体积(Vi);
(b)通过将发泡制品在130℃至200℃的温度下进行加热而获得泡沫制品;
(c)将泡沫制品冷却至室温;
(d)测量泡沫制品的体积(Vf);以及
(e)通过式R=Vf/Vi计算发泡制品的初始体积膨胀率(R)。
在本发明中,存储后发泡制品的体积膨胀率(Rs)可通过以下步骤确定:
(a)测量泡沫制品的体积(Vi);
(b)在40℃和50%RH的条件下将发泡制品存储6个月;
(c)通过将存储后的发泡制品在130℃至200℃的温度下进行加热而获得泡沫制品;
(d)将泡沫制品冷却至室温;
(e)测量泡沫制品的体积(Vs);以及
(f)通过式Rs=Vs/Vi计算存储后的发泡制品的体积膨胀率(Rs)。
在本发明中,存储后发泡制品的体积膨胀率变化(Rc)可通过以下步骤确定:
Rc=(Rs-R)/R;
其中Rc=体积膨胀率的变化;
Rs=存储后发泡制品的体积膨胀率;并且
R=发泡制品的初始体积膨胀率。
在150℃的温度下进行加热后,本发明的发泡制品的初始体积膨胀率(R)优选地等于或大于2400%。
在140℃的温度下进行加热后,本发明的发泡制品的初始体积膨胀率(R)优选地等于或大于750%。
在130℃的温度下进行加热后,本发明的发泡制品的初始体积膨胀率(R)优选地等于或大于360%。
在40℃和50%RH的条件下存储6个月后,本发明的发泡制品的体积膨胀率(Rs)优选地大于或等于初始体积膨胀率(R)。
本发明的发泡制品在40℃和50%RH的条件下存储6个月然后在140℃温度下进行加热时,发泡制品的体积膨胀率变化(Rc)优选地为至少5%、至少12%、至少22%或至少26%。
实施例
参考以下实施例将对本发明进行进一步的描述和说明。这些实施例旨在帮助本领域技术人员更好地理解和实践本发明,而并不旨在限制本发明的范围。除非另有说明,否则实施例中的所有数字均以重量计。
测试方法
发泡制品的初始体积膨胀率(R)
发泡制品的初始体积膨胀率(R)通过以下步骤获得:
(a)在35℃的温度下混合该发泡组合物的组分以形成均匀混合物;
(b)通过在95℃的温度下用挤出机(MTS 50,Nanjing DETENG Machinery Co.)使均匀混合物粒化而获得发泡颗粒;
(c)在95℃至105℃的温度下通过注塑成型将发泡颗粒制成厚度为3mm的板状发泡制品;
(d)通过水置换法测量发泡制品的体积(Vi);
(e)通过将发泡制品放置在烘烤温度为130℃至200℃的烘箱中并将发泡制品加热30分钟而获得泡沫制品;
(f)将泡沫制品在室温下冷却24小时;
(g)通过水置换法测量泡沫制品的体积(Vf);以及
(h)通过式R=Vf/Vi计算发泡制品的初始体积膨胀率(R)。
存储后发泡制品的体积膨胀率(Rs)
存储后发泡制品的体积膨胀率(Rs)通过以下步骤获得:
(a)通过水置换法测量发泡制品的体积(Vi);
(b)将发泡制品在40℃和50%RH的条件下存储6个月;
(c)通过将存储后发泡制品放置在烘烤温度为130℃至200℃的烘箱中并将发泡制品加热30分钟而获得泡沫制品;
(d)将泡沫制品在室温下冷却24小时;
(e)通过水置换法测量泡沫制品的体积(Vs);以及
(f)通过式Rs=Vs/Vi计算发泡制品的体积膨胀率(Rs)。
存储后发泡制品的体积膨胀率变化(Rc)
通过式Rc=(Rs-R)/R计算存储后发泡制品的体积膨胀率变化(Rc);
其中,Rc=体积膨胀率变化;
Rs=存储后发泡制品的体积膨胀率;并且
R=发泡制品的初始体积膨胀率。
实施例1-9
通过混合选自以下各项的组分,根据表1A和表1B制备发泡组合物样品:
EVA 250(Elvax 250,得自Dupont公司);
EVA 260(Elvax 260,得自Dupont公司);
EVA 460(Elvax 460,得自Dupont公司);
4,4′-氧代双(苯磺酰肼)(OBSH,得自IMCD);
三羟甲基丙烷三甲基丙烯酸酯(SR350,得自Sartomer);
过氧化二异丙苯(DCP40,得自Arkema);
4,4-二(叔丁基过氧化)戊酸正丁酯(Varox 231XL,得自Vanderbilt Chemicals);
改性多胺(Fujicure-FXR-1090FA,得自T&K Toka);
四[3-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(Irganox 1010,得自Ciba);
三(2,4-二叔丁基苯基)亚磷酸酯(Irgafos 168,得自BASF);
酚类抗氧化剂(Irganox L 109,得自Ciba);
酚类抗氧化剂(Irganox L107,得自Ciba);
乙烯、丙烯酸酯和马来酸酐的三元共聚物(Bondine HX 8290,得自Arkema);
蜡(Microsere 5999A,得自International Group);
硬脂酸(硬脂酸,得自Changzhou Chemical Co.,LTD);
滑石(Talc 1250,得自Beijing Lanning Talc factory);以及
炭黑(Monarch 580,得自Cabot公司)。
表1A.发泡组合物
表1B.发泡组合物
在表2A、2B、3A和3B中,报告了由实施例1至9中发泡组合物制成的发泡制品的性能。实施例1至4中获得的所有发泡制品在130℃至200℃的烘烤窗口均具有高的初始体积膨胀率(R),并且在40℃和50%RH的条件下储存6个月后显示出良好的稳定性。
如实施例5所示,当交联促进剂的含量高时,发泡制品与实施例1至4中的发泡制品相比在130℃至200℃的烘烤窗口没有充分膨胀。
如实施例6和7所示,当发泡组合物中仅存在过氧化物化合物或多胺时,由该发泡组合物制成的发泡制品与实施例1至4中获得的发泡制品相比在130℃至200℃的烘烤窗口膨胀程度较小。此外,在40℃和50%RH的条件下储存6个月后,实施例6和7中的发泡制品的体积膨胀率(Rs)小于初始体积膨胀率(R)。
如实施例8和9所示,当发泡组合物中仅存在主抗氧化剂或辅助抗氧化剂时,由该发泡组合物制成的发泡制品与实施例1至4中所获得的发泡制品相比在130℃至200℃的烘烤窗口膨胀程度较小。此外,在40℃和50%RH的条件下储存6个月后,实施例8和9中的发泡制品的体积膨胀率(Rs)小于初始体积膨胀率(R)。
表2A.发泡制品的体积膨胀率(R)
体积膨胀率(R) | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 |
130℃ | 400% | 360% | 400% | 360% | 150% | 150% |
140℃ | 800% | 900% | 750% | 850% | 720% | 320% |
150℃ | 2600% | 2500% | 2500% | 2400% | 500% | 1300% |
160℃ | 2800% | 2700% | 2700% | 2600% | 500% | 1500% |
170℃ | 2800% | 2700% | 2700% | 2600% | 320% | 1500% |
180℃ | 2800% | 2700% | 2700% | 2600% | 1200% | 1100% |
190℃ | 2400% | 2500% | 2400% | 2400% | 100% | 850% |
200℃ | 2200% | 2100% | 2100% | 2100% | 50% | 800% |
表2B.发泡制品的体积膨胀率(R)
体积膨胀率(R) | 实施例7 | 实施例8 | 实施例9 |
130℃ | 150% | 100% | 50% |
140℃ | 420% | 400% | 400% |
150℃ | 1400% | 1600% | 1600% |
160℃ | 1600% | 1800% | 1800% |
170℃ | 1600% | 1800% | 1800% |
180℃ | 1200% | 1800% | 1800% |
190℃ | 950% | 1050% | 1050% |
200℃ | 800% | 650% | 550% |
表3A.存储6个月后发泡制品的体积膨胀率(Rs)
表3B.存储6个月后发泡制品的体积膨胀率(Rs)
发现实施例1至4中的发泡制品在储存后的体积膨胀率(Rs)至少与初始体积膨胀率(R)相同,这表明在40℃和50%RH的条件下储存6个月后该发泡制品是稳定的。还发现,如表4中所示当实施例1至4中发泡制品在140℃的温度下加热时,存储后发泡制品的体积膨胀率(Rs)明显大于初始体积膨胀率(R)。例如,在实施例3中,储存后发泡制品的体积膨胀率变化(Rc)可达到26.7%。这表明,如果将本发明的发泡组合物制得的发泡制品在140℃的温度下加热,则该发泡制品可以保存更长的时间。
表4.存储6个月后发泡制品的体积膨胀率变化(Rc)
体积膨胀率变化(Rc) | 实施例1 | 实施例2 | 实施例3 | 实施例4 |
140℃ | 12.5% | 22.2% | 26.7% | 5.9% |
Claims (16)
1.一种发泡组合物,其包含:
(a)至少一种乙烯-乙酸乙烯酯共聚物;
(b)至少一种发泡剂;
(c)至少一种过氧化物化合物;
(d)至少一种胺,所述胺选自二乙基甲苯二胺、氯二氨基苯、二乙醇胺、二异丙醇胺、三乙醇胺、三丙醇胺、1,6-己二胺、改性多胺Fujicure-FXR-1090FA、及其任何组合;
(e)至少一种交联促进剂;
(f)至少一种主抗氧化剂,所述主抗氧化剂是酚类抗氧化剂;以及
(g)至少一种辅助抗氧化剂,所述辅助抗氧化剂选自含磷抗氧化剂、含硫抗氧化剂及其任何组合;
其中,
基于所述组合物的总重量,所述发泡剂的含量为15重量%至30重量%,
基于所述组合物的总重量,所述胺的含量为0.001重量%至0.5重量%,并且
基于所述组合物的总重量,所述交联促进剂的含量为0.1-3重量%。
2.根据权利要求1所述的发泡组合物,其中,所述发泡剂选自4,4′-氧代双(苯磺酰肼)、偶氮二甲酰胺、偶氮二甲酸二异丙酯及其任何组合。
3.根据权利要求1或2所述的发泡组合物,其中,所述过氧化物化合物是有机过氧化物化合物。
4.根据权利要求3所述的发泡组合物,其中,所述过氧化物化合物选自2,5-二甲基-2,5-二(叔丁基过氧)己烷、过氧化苯甲酸叔丁酯、过氧化苯甲酰、二(叔丁基过氧化异丙基)苯、过氧化二异丙苯、1,1-二-(叔丁基过氧基)-3,3,5-三甲基环己烷、4,4-双(叔丁基过氧化)戊酸丁酯及其任何组合。
5.根据权利要求1或2所述的发泡组合物,其中,所述交联促进剂选自三羟甲基丙烷三甲基丙烯酸酯、二乙基二硫代氨基甲酸锌、二(吗啉-4-基)二硫化物、四硫化双五亚甲基秋兰姆及其任何组合。
6.根据权利要求1或2所述的发泡组合物,其中,所述酚类抗氧化剂是受阻酚类抗氧化剂。
7.根据权利要求1或2所述的发泡组合物,还包括任选存在的添加剂,所述添加剂选自至少一种粘合促进剂、至少一种填充剂、至少一种润滑剂、至少一种蜡、至少一种染料及其任何组合。
8.根据权利要求1或2所述的发泡组合物,其包含:
(a)45重量%至70重量%的至少一种乙烯-乙酸乙烯酯共聚物;
(b)15重量%至30重量%的至少一种发泡剂;
(c)0.1重量%至10重量%的至少一种过氧化物化合物;
(d)0.001重量%至0.5重量%的至少一种胺;
(e)0.1重量%至3重量%的至少一种交联促进剂;
(f)0.04重量%至10重量%的至少一种主抗氧化剂;以及
(g)0.01重量%至2重量%的至少一种辅助抗氧化剂;
其中,所有组分的重量百分比合计为100重量%。
9.根据权利要求8所述的发泡组合物,其中,所述交联促进剂的含量为所述组合物总重量的1重量%至2重量%。
10.一种通过在80℃至120℃的温度下固化根据权利要求1至9中任一项所述的发泡组合物而制成的发泡制品。
11.根据权利要求10所述的发泡制品,其中,所述发泡制品是通过在95℃至105℃的温度下固化所述发泡组合物而制成的。
12.一种由根据权利要求1至9中任一项所述的发泡组合物通过以下步骤制备的发泡制品:
a)在15℃至55℃的温度下混合所述发泡组合物的组分以形成均匀混合物;
b)在90℃至100℃的温度下通过挤出而使所述均匀混合物粒化,从而获得发泡颗粒;以及
c)在95℃至105℃的温度下将发泡颗粒通过注塑成型形成所述发泡制品。
13.根据权利要求10至12中任一项所述的发泡制品,所述发泡制品在40℃和50%RH的条件下存储6个月并在140℃的温度下加热后,所述发泡制品的体积膨胀率变化Rc为至少5%。
14.一种由根据权利要求1至9中任一项所述的发泡组合物制成的泡沫制品。
15.一种由根据权利要求10至13中任一项所述的发泡制品制成的泡沫制品。
16.一种包括填充有根据权利要求14或15所述的泡沫制品的车辆部件的车辆。
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US4289856B1 (zh) * | 1978-11-14 | 1984-10-02 | ||
CN101293973A (zh) * | 2007-04-24 | 2008-10-29 | 日东电工株式会社 | 填充发泡用组合物、填充发泡部件以及填充用发泡体 |
CN101838416A (zh) * | 2010-02-05 | 2010-09-22 | 上海子元汽车零部件有限公司 | 可发性膨胀母粒、可发性膨胀材料及其制造方法 |
CN103717655A (zh) * | 2011-08-01 | 2014-04-09 | 汉高股份有限及两合公司 | 可热硬化的制剂 |
CN102807702A (zh) * | 2012-07-27 | 2012-12-05 | 苏州市兴吴工程塑胶有限公司 | 一种新型改性发泡eva塑料的配方 |
CN104419056A (zh) * | 2013-08-27 | 2015-03-18 | 三星Total株式会社 | 用于制备eva共聚物的组合物、eva共聚物及其制备方法 |
WO2017102996A1 (en) * | 2015-12-18 | 2017-06-22 | Sika Technology Ag | Heat expandable foam for low temperature cure |
Also Published As
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EP3728429A4 (en) | 2021-07-28 |
KR20200103058A (ko) | 2020-09-01 |
KR102570808B1 (ko) | 2023-08-28 |
US11643518B2 (en) | 2023-05-09 |
US20200317881A1 (en) | 2020-10-08 |
CN111511820A (zh) | 2020-08-07 |
WO2019119417A1 (en) | 2019-06-27 |
EP3728429A1 (en) | 2020-10-28 |
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