CN116515193A - 可回收交联聚合物发泡材及其运用 - Google Patents
可回收交联聚合物发泡材及其运用 Download PDFInfo
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- CN116515193A CN116515193A CN202211158039.7A CN202211158039A CN116515193A CN 116515193 A CN116515193 A CN 116515193A CN 202211158039 A CN202211158039 A CN 202211158039A CN 116515193 A CN116515193 A CN 116515193A
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- Prior art keywords
- linked polymer
- polymer foam
- recyclable
- cross
- foam according
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Links
- 229920006037 cross link polymer Polymers 0.000 title claims abstract description 46
- 239000006261 foam material Substances 0.000 title description 6
- 239000006260 foam Substances 0.000 claims abstract description 66
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 41
- 239000003999 initiator Substances 0.000 claims abstract description 27
- 239000002861 polymer material Substances 0.000 claims abstract description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 5
- 125000000732 arylene group Chemical group 0.000 claims abstract description 5
- 125000002993 cycloalkylene group Chemical group 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims description 74
- -1 polyethylene Polymers 0.000 claims description 55
- 239000000463 material Substances 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 38
- 239000000047 product Substances 0.000 claims description 33
- 150000003254 radicals Chemical class 0.000 claims description 25
- 238000004383 yellowing Methods 0.000 claims description 25
- 238000005187 foaming Methods 0.000 claims description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 20
- 239000005977 Ethylene Substances 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 150000002978 peroxides Chemical class 0.000 claims description 10
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 9
- 244000043261 Hevea brasiliensis Species 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
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- 229920003052 natural elastomer Polymers 0.000 claims description 8
- 229920001194 natural rubber Polymers 0.000 claims description 8
- 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 6
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 6
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 6
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 claims description 5
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- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 claims description 2
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 claims description 2
- YIFHBDOSSPGDOU-UHFFFAOYSA-N 1-propan-2-ylperoxybutane Chemical group CCCCOOC(C)C YIFHBDOSSPGDOU-UHFFFAOYSA-N 0.000 claims 1
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- LGZDNJBUAAXEMN-UHFFFAOYSA-N 1,2,2,3-tetramethyl-1-oxidopiperidin-1-ium Chemical compound CC1CCC[N+](C)([O-])C1(C)C LGZDNJBUAAXEMN-UHFFFAOYSA-N 0.000 description 6
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- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
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- 239000004711 α-olefin Substances 0.000 description 5
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- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 description 3
- JTQWEPYYUBACDU-UHFFFAOYSA-N 2-methyl-2-propylperoxypropane Chemical compound CCCOOC(C)(C)C JTQWEPYYUBACDU-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
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- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
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- 239000012948 isocyanate Substances 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
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Abstract
一种可回收交联聚合物发泡材,包括以下的反应产物:100质量份的聚合物材料,0.1~10质量份的交联剂以及0.1~5质量份的自由基起始剂。交联剂以下式表示:其中R为碳原子数2~10的亚烷基、碳原子数6~18的亚芳基或碳原子数6~18的亚环烷基。
Description
技术领域
本发明是关于可回收交联聚合物发泡材、使用其的可重复使用鞋类部件以及从其获得的回收材料(reversed material)。
背景技术
乙烯乙酸乙烯酯(ethylene vinyl acetate,EVA)共聚物发泡材是用于鞋类中底(midsole)的常用材料,因为它重量轻并且提供理想的缓冲性能。但是,它确实以缺乏耐用性而闻名。为了提高耐用性,EVA发泡材经过高度交联,使其无法回收,造成大量的废弃物。尽管热塑性聚氨酯(thermoplastic polyurethane,TPU)等替代原材料是可回收的,但存在原材料成本高、设备更换成本高等缺点。
尽管现有的EVA发泡材已经足以满足它们的预期目的,但它们不是在所有方面都完全令人满意的。特别是,对具有可回收性和适当特性的EVA发泡材仍有未满足的需求,以便在制鞋业和其他领域进一步利用。
发明内容
本发明实施例提供了一种可回收交联聚合物发泡材,包括以下的反应产物:100质量份的聚合物材料;0.1~10质量份的交联剂;以及0.1~5质量份的自由基起始剂,其中交联剂以下式表示:
其中R为碳原子数2~10的亚烷基、碳原子数6~18的亚芳基或碳原子数6~18的亚环烷基。
在一些实施例中,聚合物材料为乙烯类聚合物、聚烯烃聚合物、聚乙烯聚合物、丙烯聚合物、苯乙烯聚合物、乙烯丙烯二烯(ethylene-propylene-diene,EPDM)橡胶、天然橡胶(natural rubber,NR)、异丙烯橡胶(isopropylene rubber,IR)、其共聚物或其组合。
在一些实施例中,聚合物材料的乙酸乙烯酯含量(vinyl acetate content)为3-45质量%,熔融指数(melt index)为0.01-400g/10min。
在一些实施例中,交联剂包括氨基甲酸酯双四甲基哌啶氧化物(urethane bis-TEMPO(2,2,6,6-tetramethylpiperidinyloxy))。
在一些实施例中,氨基甲酸酯双四甲基哌啶氧化物包括4,4-二苯甲烷二异氰酸酯氨基甲酸酯双四甲基哌啶氧化物(4,4-diphenylmethane diisocyanate urethane bis-TEMPO)或4,4'-二异氰酸二环己基甲烷氨基甲酸酯双四甲基哌啶氧化物(4,4’-diisocyanato dicyclohexylmethane urethane bis-TEMPO)。
在一些实施例中,自由基起始剂包括过氧化物。
在一些实施例中,过氧化物为过氧化二异丙苯(dicumyl peroxide)或双-(三级丁基过氧化异丙基)苯过氧化物(bis-(tert-butylperoxy isopropyl)benzene peroxide,BIBP)。
在一些实施例中,可回收交联聚合物发泡材为化学发泡工艺的发泡产品。
在一些实施例中,化学发泡工艺包括使用发泡剂,其中发泡剂包括偶氮化合物(azo compound)或酰肼化合物(hydrazide compound)。
在一些实施例中,偶氮化合物为2,2’-偶氮双(2-氰基丁烷)(2,2’-azobis(2-cyanobutane))、2,2’-偶氮双(甲基丁腈)(2,2’-azobis(methylbutyronitrile))或偶氮二甲酰胺(azodicarbonamide)。
在一些实施例中,酰肼化合物为p,p’-氧双(苯磺酰肼)(p,p’-oxybis(benzenesulfonyl hydrazide))、对甲苯磺酰胺脲(p-toluene sulfonyl semicarbazide)或对甲苯磺酰肼(p-toluene sulfonyl hydrazide)。
在一些实施例中,可回收交联聚合物发泡材为物理发泡工艺的发泡产品。
在一些实施例中,自由基起始剂与交联剂的摩尔比为0.1~5。
在一些实施例中,对于100质量份的聚合物材料,自由基起始剂与交联剂的总和为0.5~15质量份。
在一些实施例中,可回收交联聚合物发泡材的密度在0.05g/cm3~0.8g/cm3的范围。
在一些实施例中,可回收交联聚合物发泡材的泡孔尺寸为30μm~1mm。
本发明实施例还提供了一种可重复使用的鞋类部件,包括如上述的可回收交联聚合物发泡材,其中可回收交联聚合物发泡材的黄化指数(yellow index)为-5~70。
在一些实施例中,可重复使用的鞋类部件包括内底(insole)、中底(midsole)或大底(outsole)。
本发明实施例更提供了一种回收材料(reversed material),从如上述的可重复使用的鞋类部件获得,其中回收材料的黄化指数为-5~95。
在一些实施例中,回收材料的黄化指数为-5~45。
附图说明
以下将配合所附附图详述本发明实施例。其中:
图1是未添加交联剂的聚合物组合物在交联工艺和加热回收工艺中的粘度测量示意图。
图2是添加交联剂的聚合物组合物在交联工艺和加热回收工艺中的粘度测量示意图。
具体实施方式
本发明的可回收聚合物组合物、聚合物发泡材、使用其的可重复使用的鞋类部件以及由此获得的回收材料在以下描述中详细描述。在以下详细描述中,出于解释的目的,阐述了许多具体细节和实施例以便提供对本发明的透彻理解。为了清楚地描述本发明,阐述了在以下详细描述中的特定组件和配置。然而,显而易见的是,这里阐述的示例性实施例仅用于说明的目的,并且本发明构思可以以各种形式实施而不限于这些示例性实施例。
目前,乙烯乙酸乙烯酯(ethylene vinyl acetate,EVA)经过交联的发泡材一般是不可回收的。此外,在加热回收的过程中,可能会出现黄化,这可能会限制回收材料进一步的应用。如果回收的发泡材料不是白色的,则所得产品只能是黑色或棕色等深色。为了解决上述问题,本案通过使用四甲基哌啶氧化物(2,2,6,6-tetramethylpiperidinyloxy,TEMPO)衍生物,将可热降解的氨基甲酸酯键(urethane linkage)引入EVA系统中,从而提供具有所需性能例如低黄化指数的可回收交联聚合物发泡材。
根据本发明的一些实施例,本案的可回收交联聚合物发泡材(例如,EVA发泡材)包括聚合物材料、交联剂(即,TEMPO衍生物)和自由基起始剂。在发泡过程中,通过使用特定的交联剂,以及控制自由基起始剂、交联剂和聚合物材料的比例,可以获得理想的性能。这导致了高交联效率和可回收性,以及聚合物及其回收材料意外的低黄化指数,为可染色基材、鞋类、运动器材和家具等的进一步应用提供了灵活性。
在一些其他实施例中,本发明提供的聚合物组合物也可以用作光伏模块(photovoltaic modules)中的封装材料(encapsulant)。封装材料透明度的降低可能导致光伏模块的电效率损失。通过调整封装材料的颜色,可以调节透光率和太阳能光伏转换效率。因此,黄化指数越低,太阳能光伏转换效率越高。
根据一些实施例,本发明提供了一种可回收交联聚合物发泡材。可回收交联聚合物发泡材包括以下的反应产物:100质量份的聚合物材料,0.1~10质量份的交联剂以及0.1~5质量份的自由基起始剂。交联剂以下式表示:
其中R为碳原子数2~10的亚烷基(alkylene)、碳原子数6~18的亚芳基(arylene)或碳原子数6~18的亚环烷基(cycloalkylene)。
根据本发明的一些实施例,聚合物材料可以是聚烯烃聚合物、丙烯聚合物、聚乙烯聚合物、苯乙烯聚合物、乙烯类聚合物例如乙烯乙酸乙烯酯(ethylene-vinyl acetate,EVA)、低密度聚乙烯(low-density polyethylene,LDPE)、线性低密度聚乙烯(linear-low-density polyethylene,LLDPE)、极低密度聚乙烯(very-low-density polyethylene,VLDPE)和高密度聚乙烯(high density polyethylene,HDPE)、二烯类橡胶,例如天然橡胶(natural rubber,NR)、异戊二烯橡胶(isoprene rubber,IR)、丁二烯橡胶(butadienerubber,BR)、1,2-丁二烯橡胶、苯乙烯-丁二烯橡胶(styrene-butadiene rubber,SBR)、丙烯腈-丁二烯橡胶(acrylonitrile-butadiene rubber,NBR)、氯丁橡胶(chloroprenerubber,CR)、丁基橡胶(butyl rubber,IIR)、乙烯-丙烯橡胶(ethylene propylenerubber,EPR)和三元乙丙橡胶(ethylene-propylene-diene rubber,EPDM)或其组合。上述聚烯烃聚合物、丙烯聚合物、聚乙烯聚合物、苯乙烯聚合物和乙烯类聚合物各包括其随机、嵌段和接枝共聚物。聚烯烃聚合物的例示包括烯烃嵌段共聚物(olefin blockcopolymers,OBC)。丙烯聚合物的实例包括丙烯乙烯共聚物。特别地,聚合物材料可以是三元乙丙橡胶(EPDM)、天然橡胶(NR)、异丙橡胶(isopropylene rubber,IR)或其组合。
在一些实施例中,乙烯类聚合物可以是LDPE。LDPE通常是高度分支的乙烯均聚物,可以通过高压工艺而制备(即高压LDPE)。适用于本案的LDPE可具有0.91至0.94g/cm3的密度。在一些实施例中,乙烯类聚合物是具有至少0.915g/cm3但小于0.94g/cm3或小于0.93g/cm3的密度的高压LDPE。本文提供的聚合物密度根据美国材料和试验协会(ASTMInternational,“ASTM”)方法D792测定。适用于本案的LDPE可具有小于40g/10min的熔融指数(melt index)或0.1-400g/10min、0.5-20g/10min、0.5-5g/10min、1-3g/10min的熔融指数或等于2g/10min的熔融指数。本文提供的熔融指数根据ASTM方法D1238测定。除非另有说明,否则熔融指数是在190℃和2.16kg下测定的。通常,LDPE具有较宽的分子量分布,从而导致较高的多分散指数(polydispersity index,PDI;重均分子量与数均分子量的比)。
在一些实施例中,乙烯类聚合物可以是LLDPE。LLDPE通常是乙烯类聚合物,具有不均匀分布的共聚单体(例如,α-烯烃单体),并且以短链分支为特征。例如,LLDPE可以是乙烯和α-烯烃单体的共聚物,例如上述那些。适用于本案的LLDPE可具有0.916-0.925g/cm3的密度。适用于本案的LLDPE可具有0.1-400g/10min、1-20g/10min或3-8g/10min的熔融指数。
在一些实施例中,乙烯类聚合物可以是VLDPE。VLDPE在本领域中也可称为超低密度聚乙烯(ultra-low-density polyethylene,ULDPE)。VLDPE通常是乙烯类聚合物,具有不均匀分布的共聚单体(例如,α-烯烃单体),并以短链分支为特征。例如,VLDPE可以是乙烯和α-烯烃单体的共聚物,例如一种或多种上述的α-烯烃单体。适用于本案的VLDPE可具有0.87-0.915g/cm3的密度。适用于本案的VLDPE可具有0.1-400g/10min、0.1-20g/10min或0.3-5g/10min的熔融指数。
在一些实施例中,乙烯类聚合物可以是HDPE。HDPE具有低分支度,因此具有更强的分子间作用力和抗张强度(tensile strength)。适用于本案的HDPE可具有0.941-0.965g/cm3的密度。适用于本案的HDPE可具有0.1-400g/10min、0.5-65g/10min或1-30g/10min的熔融指数。
在一些具体实施例中,乙烯乙酸乙烯酯聚合物可从USI Corporation购买,商品名为UE3312和UE629。适用于本案的乙烯乙酸乙烯酯聚合物具有3-45重量%的乙酸乙烯酯含量(vinyl acetate content)和0.01-400g/10min的熔融指数。
在一些具体实施例中,聚烯烃弹性体可从陶氏化学(Dow Chemical)购买,商品名为ENGAGETM8003和ENGAGETM8180。适用于本案的聚烯烃弹性体可具有0.857g/cm3-0.908g/cm3的密度。适用于本案的聚烯烃弹性体可具有0.1-400g/10min或0.1-10g/10min的熔融指数。在一些实施例中,烯烃嵌段共聚物的平均熔融指数在大于0.5g/10min且小于35g/10min的范围。熔融指数根据ASTM D1238在190℃、2.16kg下测定。
异氰酸酯化合物可以与四甲基哌啶氧化物化合物(TEMPO(2,2,6,6-tetramethylpiperidinyloxy)compound)组合使用以形成含有热可逆氨基甲酸酯键的TEMPO衍生物。合适的异氰酸酯化合物是每分子含有两个或两个以上-NCO基团的多官能异氰酸酯。这些本质上可以是脂族、脂环族、多环或芳香族,例如二异氰酸酯化合物或三异氰酸酯化合物。在一些实施例中,二异氰酸酯化合物可以是甲苯二异氰酸酯(toluenediisocyanate,TDI)、亚甲基二苯基二异氰酸酯(methylene diphenyl diisocyanate,MDI)、六亚甲基二异氰酸酯(hexamethylene diisocyanate,HDI)、4,4’-二异氰酸酯二环己基甲烷(4,4’-diisocyanato dicyclohexylmethane,HMDI)、二甲苯二异氰酸酯(xylenediisocyanate,XDI)、间四甲基二甲苯二异氰酸酯(meta-tetramethylxylylenediisocyanate,TMXDI)、氢化二甲苯二异氰酸酯(hydrogenated xylene diisocyanate,HXDI)、萘1,5-二异氰酸酯(naphthalene 1,5-diisocyanate,NDI)、对苯二异氰酸酯(p-phenylene diisocyanate,PPDI)、3,3'-二甲基二苯基-4,4’-二异氰酸酯(3,3’-dimethyldiphenyl-4,4’-diisocyanate,DDDI)、2,2,4-三甲基六亚甲基二异氰酸酯(2,2,4-trimethylhexamethylene diisocyanate,TMDI)、异佛尔酮二异氰酸酯(isophoronediisocyanate,IPDI)、4,4’-二环己基甲烷二异氰酸酯(4,4’-dicyclohexylmethanediisocyanate)、降冰片烷二异氰酸酯(norbornane diisocyanate,NDI)或4,4’-二芐基二异氰酸酯(4,4’-dibenzyl diisocyanate,DBDI)。
在一些其他实施例中,三异氰酸酯可以是三苯基甲烷-4,4’,4”-三异氰酸酯(triphenylmethane-4,4’,4”-triisocyanate)、1,6,11-十一烷三异氰酸酯(1,6,11-undecane triisocyanate)、1,3,6-六亚甲基三异氰酸酯(1,3,6-hexamethylenetriisocyanate)、1,8-二异氰酸酯-4-异氰酸甲基辛烷(1,8-diisocyanato-4-isocyanatomethyloctane)、2,5,7-三甲基-1,8-二异氰酸-5-异氰酸甲基辛烷(2,5,7-trimethyl-1,8-diisocyanato-5-isocyanato methyloctane)、赖氨酸三异氰酸酯(lysinetriisocyanate)、均三甲苯三异氰酸酯(mesitylene triisocyanate)、三甲基苯三异氰酸酯(trimethylbenzene triisocyanate)、苯三异氰酸酯(benzene triisocyanate)、三苯甲烷三异氰酸酯(triphenylmethane triisocyanate)、萘三异氰酸酯(naphthalenetriisocyanate)、二苯甲烷-2,4,4’-三异氰酸酯(diphenylmethane-2,4,4’-triisocyanate)、或3-甲基二苯基甲烷-4,6,4’-三异氰酸酯(3-methyldiphenylmethane-4,6,4’-triisocyanate)。
根据本发明的一个实施例,交联剂包括二异氰酸酯氨基甲酸酯双四甲基哌啶氧化物(diisocyanate urethane bis-TEMPO)。示例性二异氰酸酯氨基甲酸酯双四甲基哌啶氧化物包括亚甲基二苯基二异氰酸酯氨基甲酸酯双四甲基哌啶氧化物(methylene diphenyldiisocyanate urethane bis-TEMPO)或4,4’-二异氰酸酯二环己基甲烷氨基甲酸酯双四甲基哌啶氧化物(4,4’-diisocyanato dicyclohexylmethane urethane bis-TEMPO)。可回收交联聚合物也可以通过将羟基四甲基哌啶氧化物(hydroxy-tempo)接枝到热塑性聚合物的主链上形成接枝聚合物,然后将接枝聚合物与二异氰酸酯(在流动相中但不挥发)反应形成下一个结构来制备。
在一些具体实施例中,TEMPO可从Tokyo Chemical Industry购买,其可以原样使用。
合适的自由基起始剂包括α-过氧化新癸酸异丙苯酯(α-cumylperoxyneodecanoate)、乙酰基过氧化环己基磺酰(acetyl cyclohexylsulfonylperoxide)、过氧化苯甲酰(benzoyl peroxide)、4,4-二(三级丁基过氧化)戊酸丁酯(butyl4,4-di(tert-butylperoxy)valerate)、双(α-三级丁基-过氧化异丙基)苯(bis(alpha-t-butyl-peroxyisopropyl)benzene,BIBP)、氢过氧化异丙苯(cumyl hydroperoxide)、过氧化癸酰(decanoyl peroxide)、过氧化二异丙苯(dicumyl peroxide)、过氧化二(三级丁基)(di(tert-butyl)peroxide)、过氧化二(三级戊基)(di(tert-amyl)peroxide)、过氧化二(异丙基异丙苯)(di(isopropylcumyl)peroxide)、单过氧化氢二异丙基苯(diisopropylbenzene monohydroperoxide)、3,3-二(三级丁基过氧)丁酸乙酯(ethyl-3,3-di(tert-butylperoxy)butyrate)、3,3-二(三级戊基过氧)丁酸乙酯(ethyl-3,3-di(tert-amylperoxy)butyrate)、异丙基异丙苯过氧化异丙苯(isopropylcumylcumylperoxide)、过氧化月桂酰(lauroyl peroxide)、4,4-二(三级丁基过氧)戊酸正丁酯(n-butyl 4,4-di(tert-butylperoxy)valerate)、OO-三级丁基-O-异丙基单过氧化碳酸酯(OO-tert-butyl-O-isopropylmonoperoxy carbonate)、OO-三级丁基-O-(2-乙基己基)单过氧碳酸酯(OO-tert-butyl-O-(2-ethylhexyl)monoperoxy carbonate)、OO-三级戊基-O-(2-乙基己基)单过氧碳酸酯(OO-tert-amyl-O-(2-ethylhexyl)monoperoxy carbonate)、氢过氧化对薄荷烷(paramenthane hydroperoxide)、过氧化新戊酸三级戊酯(tert-amylperoxypivalate)、过氧化新癸酸三级戊酯(tert-amyl peroxyneodecanoate)、氢过氧化三级戊基(tert-amyl hydroperoxide)、过氧-2-乙基己酸三级戊酯(tert-amyl peroxy-2-ethylhexanoate)、过氧-3,5,5-三甲基己酸三级戊酯(tert-amyl peroxy-3,5,5-trimethylhexanoate)、氢过氧化三级丁酯(tert-butyl hydroperoxide)、过氧化异丙苯三级丁酯(tert-butyl cumyl peroxide)、过氧化苯甲酸三级丁酯(tert-butylperoxybenzoate)、过氧化乙酸三级丁酯(tert-butyl peroxyacetate)、过氧化异丁酸三级丁酯(tert-butyl peroxyisobutyrate)、过氧化马来酸三级丁酯(tert-butylperoxymaleate)、过氧化新戊酸三级丁酯(tert-butyl peroxypivalate)、过氧化新癸酸三级丁酯(tert-butyl peroxyneodecanoate)、过氧化异壬酸三级丁酯(tert-butylperoxyisononanoate)、过氧化-2-乙基己酸三级丁酯(tert-butyl peroxy-2-ethylhexanoate)、过氧化-3,5,5-三甲基己酸三级丁酯(tert-butyl peroxy-3,5,5-trimethylhexanoate)、1,1-二(三级丁基过氧)环己烷(1,1-di(tert-butylperoxy)cyclohexane)、1,1-二(三级丁基过氧)-3,3,5-三甲基环己烷(1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane)、1,1-二(三级-戊基过氧)环己烷(1,1-di(tert-amylperoxy)cyclohexane)、1,3-二(三级丁基过氧异丙基)苯(1,3-di(tert-butylperoxyisopropyl)benzene)、2,2-二(三级丁基过氧)丁烷(2,2-di(tert-butylperoxy)butane)、2,5-二甲基-2,5-二(2-乙基己酰基过氧)己烷(2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane)、2,5-二甲基-2,5-二(过氧化氢)己烷(2,5-dimethyl-2,5-di(hydroperoxy)hexane)、2,5-二甲基-2,5-二(过氧化苯甲酰)己烷(2,5-dimethyl-2,5-di(benzoylperoxy)hexane)、2,5-二甲基-2,5-二(三级丁基过氧)己烷(2,5-dimethyl-2,5-di(tert-butylperoxy)hexane)、2,5-二甲基-2,5-二(三级丁基过氧)己-3-炔(2,5-dimethyl-2,5-di(tert-butylperoxy)hex-3-yne)、2,2-双(4,4-二三级丁基过氧环己基)丙烷(2,2-bis(4,4-ditert-butylperoxycyclohexyl)propane)、3-羟基-1,1-二甲基丁基过氧新癸酸酯(3-hydroxy-1,1-dimethylbutylperoxyneodecanoate)、3,5,5-过氧化三甲基己酰(3,5,5-trimethylhexanoyl peroxide)、三级丁基过氧-2-乙基己基单碳酸酯(t-butyl peroxy-2-ethylhexyl monocarbonate)或其组合,但本发明不限于此。
根据本发明的实施例,自由基起始剂包括过氧化物,例如过氧化二异丙苯(dicumyl peroxide)或双-(三级丁基过氧化异丙基)苯过氧化物(bis-(tert-butylperoxyisopropyl)benzene peroxide,BIBP)。
根据本发明的一些实施例,自由基起始剂和交联剂的摩尔比可以在0.1-5的范围,例如,0.5-4.5、1-4、1-3、1-2.5或1-2的范围。特别地,自由基起始剂和交联剂的摩尔比高于0.9较为理想,以提供聚合物和回收材料合适的性能(例如黄化指数)以供进一步应用。在一些具体实施例中,自由基起始剂和交联剂的比例可以高于1.2。根据本发明的一些实施例,以100重量份的聚合物材料为基准,自由基起始剂和交联剂的总量可以为0.5-15重量份,较佳1-14重量份,2-12重量份,3-10重量份,或4至8重量份。特别地,自由基起始剂和交联剂的总量低于0.9会导致聚合物和回收材料的高黄化指数,这可能会限制进一步的应用。
可回收交联聚合物发泡材可以是化学或物理发泡工艺的发泡产品,其使用化学或物理发泡剂。这使得所得交联发泡材产品的重量减轻,并且可以表现出柔韧性、优异的抗撕裂性、抗压缩永久变形性(compression set resistance)、冲击吸收性、耐磨性和可设计性。化学发泡剂包括磺酰肼化合物(sulfonyl hydrazide compound)、偶氮化合物(azocompound)和亚硝基化合物(nitroso compound)。磺酰肼化合物的例子有:苯-1,3-二磺酰肼(benzene-1,3-disulfonyl hydrazide)、苯磺酰肼(benzene sulfonyl hydrazide)、对甲苯磺酰胺脲(p-toluene sulfonyl semicarbazide)、对甲苯磺酰肼(p-toluenesulfonylhydrazide)、对,对’-氧双(苯磺酰肼)(p,p’-oxybis(benzene sulfonyl hydrazide))、4,4’-氧基双(苯磺酰肼)(4,4’-oxybis(benzene sulfonyl hydrazide),OBSH)等。偶氮化合物的例子有偶氮二甲酰胺(azodicarbonamide)、偶氮双甲酰胺(azobisformamide)、偶氮双异丁腈(azobisisobutyronitrile)、重氮氨基苯(diazoaminobenzene)、2,2’-偶氮双(2-氰基丁烷)(2,2’-azobis(2-cyanobutane))、2,2’-偶氮双(甲基丁腈)(2,2’-azobis(methylbutyronitrile))、偶氮二羧酸钡(barium azodicarboxylate)等。亚硝基化合物的例子有N,N’-二亚硝基五亚甲基四胺(N,N’-dinitrosopentamethylenetetramine)、N,N’-二亚硝基-N,N’-二甲基对苯二甲酰胺(N,N’-dinitroso-N,N’-dimethylterephthalamide)等。
物理发泡剂的例示包括烃例如戊烷、丁烷和己烷,卤代烃例如氯甲烷和二氯甲烷,氟化烃例如三氯氟甲烷、二氯二氟甲烷、三氯三氟乙烷、氯二氟乙烷和氢氟烃,以及例如二氧化碳、氮气和空气等气体。
这些产品以各种粒径大小提供以控制气泡形成和发泡材密度。发泡剂的比例可以在很宽的范围内变化,并且尤其取决于发泡剂的类型、所用的聚合物混合物和要生产的发泡材料的所需密度。相对于可发泡热塑性混合物的总重量,发泡剂的比例可以在0.1和20wt.%之间,例如,它可以是5-15wt.%。有用的发泡剂可以包括可以商品名ADC(DONGINSEMICHEM)购买的发泡剂。
除了上述组分之外,可发泡热塑性混合物还可以包含一种或多种添加剂。可任选使用的添加剂的实例为防焦剂(scorch retardants)、抗氧化剂、加工助剂、填料、偶联剂、紫外线吸收剂或稳定剂、抗静电剂、成核剂、滑剂(slip agents)、增塑剂、润滑剂、粘度控制剂、增粘剂、防结块剂、表面活性剂、填充油(extender oil)、酸清除剂、阻燃剂、水树阻滞剂(water tree retardants)、电树阻滞剂(electrical tree retardants)、电压稳定剂、金属钝化剂或其组合。
根据本发明的一实施例,提供了一种可重复使用的鞋类部件。可重复使用的鞋类部件包括可回收交联聚合物发泡材,其中可回收交联聚合物发泡材的黄化指数可为-5~70,例如,它可为-2~70、-2~60、-2~55、-1~50、-1~45、-1~40、0~35、0~30、0~25、0~20、0~15、0~10、或0~5。特别地,可回收交联聚合物发泡材的黄化指数高于45将限制进一步应用的领域。
根据本发明的一实施例,提供了一种从可重复使用的鞋类部件获得的回收材料,其中回收材料的黄化指数可为-5~95,例如,可为-5~45、-2~45、0~45、2~45、4~45、5~45、0~40、2~40、4~40、5~40、0~35、2~35、4~35、5~35、0~30、2~30、4~30、5~30、0~25、2~25、4~25或5~25。特别地,可重复使用的鞋类部件的黄化指数低于45是理想的,以便在进一步的应用中为设计和操作提供更多选择。
根据本发明的一些实施例,可回收交联聚合物发泡材的密度为0.05g/cm3-0.8g/cm3。可回收交联聚合物发泡材的泡孔尺寸在30μm-1mm。
在一些实施例中,可重复使用的鞋类部件包括内底(insole)、中底(midsole)或大底(outsole)。
为使本发明的上述及其他目的、特征和优点更加明显易懂,以下举几个具体实施例进行详细说明。然而,它们不旨在以任何方式限制本发明。
评估聚合物组合物的性能
表1列出了在以下实施例中使用的材料。
表1
(I)黄化指数(yellow index,YI)
黄化指数根据标准化方法ASTM E313[D65/10],使用比色计(HunterLab,型号:UltraScan VIS)测定。YI在聚合物组合物的交联工艺和加热回收工艺之后测定。
实验例1
将100重量份的UE3312、6.46重量份的M交联剂、2.22重量份的DCP依次加入混合器(Brabender,型号:Plasti-Corder)中。加热至120℃后,以35rpm的转速继续混合工艺5分钟,直到聚合物组合物完全混合。接下来,将聚合物组合物置于模具(0.4mm厚)中并在2300psi下压缩。使用液压压缩机(Carver,型号:Monarch系列)进行加热和压缩。在180℃的温度下将聚合物组合物压缩15分钟。完成上述程序后,然后将聚合物组合物冷却至室温并相应地形成具有一致厚度的薄膜试样(film specimen)。
实验例2-13
实验例2-13以与实施例1中相同的方式进行,不同之处在于表2和表3中列出的聚合物材料、指定交联剂和自由基起始剂的成分和含量代替实施例1中所使用的,以获得薄膜试样。接着,对实验例1-13进行黄化指数(YIfilm)的测量,结果也显示于表2。
表2
注:
(i)m I/C指摩尔比(起始剂摩尔/交联剂摩尔)
(ii)YIfilm指薄膜试样的黄化指数
参照实验例1-3,其在制备过程中添加了相同类型的过氧化物(即过氧化二异丙苯)。据观察,具有较高m I/C的聚合物组合物的YIfilm值意外地低。在实验例4-5和实验例6-7中也可以观察到这种趋势,其在制备过程中添加的过氧化物类型分别是2,5-二甲基-2,5-二(三级丁基过氧)己烷和三级丁基过氧-2-乙基己基单碳酸酯。因此,可以采用较高的m I/C以获得较佳的YIfilm(即更低的YI值)。
表3
参照实验例8-9,其在制备过程中添加了相同类型的过氧化物(即过氧化二异丙苯)。据观察,具有较高m I/C的聚合物组合物的YIfilm值意外地低。在实验例10-11和实验例12-13中也可以观察到这种趋势,其在制备过程中添加的过氧化物类型分别是2,5-二甲基-2,5-二(三级丁基过氧)己烷和三级丁基过氧-2-乙基己基单碳酸酯。因此,可以采用较高的m I/C以获得较佳的YIfilm。
实验例14
将100重量份的UE3312、2.85重量份的M交联剂、1.67重量份的DCP依次加入混合器(Brabender,型号:Plasti-Corder)中。加热至120℃后,以35rpm的转速继续混合工艺5分钟,直到聚合物组合物完全混合。接下来,将聚合物组合物置于模具(0.4mm厚)中并在2300psi下压缩。使用液压压缩机(Carver,型号:Monarch系列)进行加热和压缩。在180℃的温度下将聚合物组合物压缩15分钟。完成上述程序后,然后将聚合物组合物冷却至室温并相应地形成具有一致厚度的薄膜试样。
实验例15-16
实验例15-16以与实验例14中相同的方式进行,不同之处在于表4中列出的聚合物材料、交联剂和自由基起始剂的成分和含量代替实验例14中所使用,以获得薄膜试样。接着,对实验例15-16进行黄化指数的测量,结果也显示于表4。
表4
注:
(i)m I/C指摩尔比(起始剂摩尔/交联剂摩尔)
(ii)I+C指起始剂和M交联剂或H交联剂的总和
(iii)YIfilm指薄膜试样的黄化指数
参照实验例14-16,观察到具有较低I+C的聚合物组合物倾向于提供较低的YIfilm值。因此,可以采用较低的I+C以获得较佳的YIfilm。
实验例17
将100重量份的UE3312、4.28重量份的M交联剂、2.78重量份的101XL45依次加入混合器(Brabender,型号:Plasti-Corder)中。加热至120℃后,以35rpm的转速继续混合工艺5分钟,直到聚合物组合物完全混合。接下来,将聚合物组合物置于模具(0.4mm厚)中并在2300psi下压缩。使用液压压缩机(Carver,型号:Monarch系列)进行加热和压缩。在180℃的温度下将聚合物组合物压缩15分钟。完成上述程序后,然后将聚合物组合物冷却至室温并相应地形成具有一致厚度的薄膜试样。
实验例18-22
实验例18-22以与实验例17中相同的方式进行,不同之处在于表5中列出的聚合材料、指定交联剂和自由基起始剂的成分和含量代替实验例17中所使用的,以获得薄膜试样。接着,将薄膜试样放入液压压缩机(Carver,型号:Monarch系列)上的模具(厚度为0.4mm)中,并在2300psi的压力下在230℃的温度下加热15分钟,从而检查薄膜试样的可逆性。对实验例17-22进行加热回收工艺后的黄化指数测定,结果显示于表5。
表5
参照实验例17-18,与通过添加M交联剂作为交联剂生产的聚合物组合物(实验例17)相比,具有相同m I/C或I+C,由添加H交联剂作为交联剂(实验例18)倾向于提供较佳的YIfilm。这种趋势在实验例19-22中也可以观察到,其中实验例20的YIfilm低于实验例19,实验例22的YIfilm低于实验例21。
(II)粘度
使用动态剪切流变仪(TA Instruments,型号:HR-1)根据以下程序和参数测定粘度:
1.调节试样(conditioning sample):
温度100℃,浸泡时间10s。
2.振荡温度斜坡(Oscillation temperature ramp):
起始温度100℃,
结束温度170℃,
升温速率:30℃/min,
应变0.5%
3.振荡时间:
温度170℃
持续时间:1800(秒)。
应变0.5%
4.振荡温度斜坡:
起始温度170℃,
结束温度230℃,
升温速率:30℃/min,
应变0.5%
5.振荡时间:
温度230℃
持续时间:900(秒)。
应变0.5%
实验例23
将100重量份的UE3312、4.28重量份的M交联剂和3.33重量份的DCP依次加入混合器(Brabender,型号:Plasti-Corder)中。加热至120℃后,以35rpm的转速继续混合工艺5分钟,直至完全混合。然后将聚合物组合物冷却至室温。
实验例24-29
实验例24-29以与实验例23相同的方式进行,不同之处在于表6中列出的聚合物材料、交联剂和自由基起始剂的成分和含量代替实施例23中所使用的,以获得聚合物组合物。接着,如图1和图2所示,在聚合物组合物的交联工艺和加热回收工艺之后,分别通过在170℃下将平行板之间的聚合物组合物加热30分钟,和通过在230℃下加热聚合物组合物15分钟来测定粘度。结果如表6所示。
表6
注:
(i)Vcrosslink指交联工艺的粘度,在170℃下30分钟测定
(ii)Vreverse指加热回收工艺的粘度,在230℃下15分钟测定
参照添加交联剂生产的发泡材产品(实验例23-28),Vcrosslink在25000-400000Pa.s的范围内。实验例23-28在230℃下测定15分钟的Vreverse在150-180000Pa.s的范围内,表明聚合物组合物是可回收的,无论在聚合物组合物的制备过程中添加的交联剂的类型。本文所使用的术语“可回收”是指聚合物组合物的粘度低于200000Pa.s。相比之下,不添加交联剂(实验例29)获得的发泡材产品的Vreverse超过200000Pa.s,表明聚合物组合物不可回收。
实验例30
将100重量份的UE629、3.42重量份的H交联剂和2.1重量份的DCP依次加入混合器(Brabender,型号:Plasti-Corder)中。加热至120℃后,以35rpm的转速继续混合工艺5分钟,直至完全混合。然后将聚合物组合物冷却至室温。
实验例31-35
实验例31-35以与实验例30中相同的方式进行,不同之处在于表7中列出的聚合物材料、交联剂和自由基起始剂的成分和含量代替实验例30中所使用的,以获得聚合物组合物。接着,在聚合物组合物的交联工艺和加热回收工艺之后,分别通过在170℃的温度下加热聚合物组合物30分钟,和在230℃的温度下加热聚合物组合物15分钟来测定粘度。结果如表7所示。
表7
参照实验例30-35,Vcrosslink在25000-400000Pa.s的范围。实验例30-34的Vreverse在1100-40000Pa.s的范围内,这表明只要添加交联剂,聚合物组合物则可交联和可回收,无论在聚合物组合物的制备过程中使用的聚合物材料的类型。然而,实验例35的Vreverse超过20000Pa.s,表明未添加交联剂制备的聚合物组合物不可回收。
可回收交联聚合物发泡材的制备
根据本发明的一些实施例,可以使用发泡工艺(例如物理或化学发泡工艺)将本聚合物发泡材制备成发泡材。
表8列出了本发明实施例中涉及的材料。
表8
化学发泡工艺
实验例36
将100重量份的UE659、3.42重量份的M交联剂、2重量份的DCP、1.9重量份的BA和0.5重量份的ZnO依次加入混合器(Brabender,型号:Plasti-Corder)中。加热至120℃后,以35rpm的转速继续混合工艺5分钟,直到聚合物组合物完全混合。接着,将聚合物组合物置于模具中(厚度为0.3mm)并在2300psi下压缩。使用液压压缩机(Carver,型号:Monarch系列)进行加热和压缩。聚合物组合物在约175℃的温度下放置在压机中12分钟。完成上述程序后,将聚合物组合物冷却至室温。
实验例37及实验例38
实验例37和实验例38以与实验例36相同的方式进行,不同之处在于表9中列出的聚合物材料、交联剂、自由基起始剂、发泡剂和添加剂的成分和含量代替了实验例36中所使用的,以得到发泡产品。接下来,测量发泡产品的密度和泡孔尺寸。通过电密度计(MIRAGE,型号:ED-120T)测量发泡材密度。通过显微镜(Nikon,型号:ECCIPSE CI)检查发泡材孔尺寸。最后,通过将发泡产品置于液压压缩机(Carver,型号:Monarch系列)上的模具(厚度为0.4mm)中,在230℃的温度和2300psi的压力下加热15分钟以形成热塑性回收材料,来检查发泡产品的再加工性。
实验例38中使用的聚合物材料为回收的UE659,其制备如下:将实验例37的发泡产品切成小块,并在230℃的温度下以20rpm的转速送入混合器中,然后以35rpm的转速持续10分钟。然后,将混合物冷却至温度以形成回收的UE659。
表9
注:
(i)m I/C指摩尔比(起始剂摩尔/交联剂摩尔)。
(ii)I+C指起始剂和M交联剂或H交联剂的总和。
添加交联剂制备的发泡产品(实验例36、37)显示出类似的发泡结构,其泡孔尺寸在100和220μm之间。此外,用回收聚合物材料制备的发泡产品(实验例38)显示出泡孔尺寸在200和300μm之间的发泡结构。实验例36和实验例37的发泡产品的密度在0.15g/cm3-0.23g/cm3的范围,这是中底(midsole)的典型密度范围。
此外,测量实验例36和实验例37的黄化指数(YI发泡材(YIfoam))。YIfoam是通过光谱和目测确定的。通过基于ASTM E313[D65/10]的标准化方法使用色度计(HunterLab,型号:UltraScan VIS)确定黄化指数。YI是经过发泡和加热回收后测定的。结果如表10所示。
表10
注:
YIfoam是指发泡产品的黄化指数
YIreversed film是指热塑性回收材料的黄化指数
从表10所示的结果可以看出,与添加M交联剂作为交联剂的发泡产品(实验例36)相比,添加H交联剂作为交联剂的发泡产品(实验例37)显示较佳的YIfoam,其回收材料显示较佳的YIreversed film。发泡产品和由其获得的热塑性回收材料的低黄化指数对于进一步应用的目的是更理想的。
在一些实施例中,以添加H交联剂作为交联剂的发泡产品(实验例37)为例,发泡过程可以在170℃至195℃的温度下进行6至15分钟。发泡后测得的YIfoam在27-29之间。加热回收后测得的YIreversed film在15.5-17.5之间。
此外,值得注意的是,用回收聚合物材料制备的发泡产品(实验例38)也显示出30.1的YIfoam,并且其回收材料显示出22.2的YIreversed film。这使得所得的发泡产品及其热塑性回收材料具有理想的白色。
物理发泡工艺
实验例39
100重量份的UE659、3.42重量份的H交联剂和2.0重量份的DCP依次加入混合器(Brabender,型号:Plasti-Corder)中。加热至120℃后,以35rpm的转速继续混合工艺5分钟,直至完全混合。然后将所得物置于模具中(厚度为0.4mm)并在2300psi下压缩。使用液压压缩机(Carver,型号:Monarch系列)进行加热和压缩。将所得物在约175℃的温度下压缩15分钟。完成上述程序后,将交联的试样冷却至室温。接着,将交联的试样放入超临界流体发泡系统的槽中,将系统温度调节到130℃以上(未达到熔融状态)。然后将氮气注入超临界流体发泡系统并与交联试样混合。接着,将系统压力调至150bar,使交联试样与氮气超临界流体形成单相溶液,并保持2小时。然后在1秒内将系统压力调至1.013bar,得到发泡产品。
实验例40
实验例40以与实验例39相同的方式进行,除了实验例39中使用的聚合物材料是回收的UE659。接下来,测量发泡产品的密度、泡孔尺寸和黄化指数(YIfoam)。通过电密度计(MIRAGE,型号:ED-120T)测量发泡材密度。通过显微镜(Nikon,型号:ECCIPSE CI)检查发泡材孔尺寸。最后,通过将发泡产品置于液压压缩机(Carver,型号:Monarch系列)上的模具(厚度为0.4mm)中,在230℃的温度和2300psi的压力下加热15分钟,检查发泡产品的可回收性。
实施例40中使用的聚合材料为回收的UE659,其制备如下:将实施例39的发泡产品切成小块,并在230℃的温度下以20rpm的转速送入混合器中,然后以35rpm的转速持续10分钟。然后,将混合物冷却至温度以形成回收的UE659。
表11
从表11所示的结果,值得注意的是,用回收的聚合物材料制备的发泡产品(实验例40)显示出27.3的YIfoam,而其回收材料显示出40.5的YIreversed film。YI值低于45可使所得发泡产品及其回收材料具有理想的白色。
实验例39的发泡产品显示出泡孔尺寸在100和150μm之间的发泡结构,而实验例40的发泡产品具有在200和400μm之间的泡孔尺寸。实验例39和实验例40的发泡产品的密度在0.15g/cm3-0.23g/cm3的范围,这是中底的典型密度范围。
根据本发明的一些实施例,当发泡材通过物理发泡工艺形成时,可以使用超临界流体或物理发泡剂进行发泡。超临界流体可以是二氧化碳、氮气或其组合。物理发泡剂可以是水、甲烷、乙烷、丁烷、丙烷、戊烷、己烷、乙烯、丙烯、甲醇、乙醇、丙酮、空气或其组合。
在本发明中,所得的可回收交联聚合物发泡材在环境和经济上是可持续的。在发泡工艺中(如物理或化学发泡工艺),通过应用特定类型的交联剂(其中特别优选H交联剂),并通过控制自由基起始剂、交联剂和聚合物材料之间的特定比例,可实现理想的物理性能,例如聚合物及其回收材料意外的低黄化指数,这为可染色基材、鞋类、运动器材和家具等的进一步应用提供了灵活性。
虽然已经通过示例并根据较佳实施例描述了本发明,但是应当理解,本发明不限于此。相反,它旨在涵盖各种修改和类似的配置(这对于本领域的技术人员来说是显而易见的)。因此,所附权利要求的范围应给予最广泛的解释,以涵盖所有此类修改和类似配置。
Claims (20)
1.一种可回收交联聚合物发泡材,包括以下的反应产物:
100质量份的聚合物材料;
0.1~10质量份的交联剂,其中该交联剂以下式表示:
其中R为碳原子数2~10的亚烷基、碳原子数6~18的亚芳基或碳原子数6~18的亚环烷基;以及
0.1~5质量份的自由基起始剂。
2.根据权利要求1的可回收交联聚合物发泡材,其中该聚合物材料为乙烯类聚合物、聚烯烃聚合物、聚乙烯聚合物、丙烯聚合物、苯乙烯聚合物、乙烯丙烯二烯(EPDM)橡胶、天然橡胶(NR)、异丙烯橡胶(IR)、其共聚物或其组合。
3.根据权利要求1的可回收交联聚合物发泡材,其中该聚合物材料的乙酸乙烯酯含量为3-45质量%,熔融指数为0.01-400g/10min。
4.根据权利要求1的可回收交联聚合物发泡材,其中该交联剂包括氨基甲酸酯双四甲基哌啶氧化物。
5.根据权利要求4的可回收交联聚合物发泡材,其中该氨基甲酸酯双四甲基哌啶氧化物包括4,4-二苯甲烷二异氰酸酯氨基甲酸酯双四甲基哌啶氧化物或4,4’-二异氰酸二环己基甲烷氨基甲酸酯双四甲基哌啶氧化物。
6.根据权利要求1的可回收交联聚合物发泡材,其中该自由基起始剂包括过氧化物。
7.根据权利要求6的可回收交联聚合物发泡材,其中该过氧化物为过氧化二异丙苯或双-(三级丁基过氧化异丙基)苯过氧化物(BIBP)。
8.根据权利要求1的可回收交联聚合物发泡材,其中该可回收交联聚合物发泡材为化学发泡工艺的发泡产品。
9.根据权利要求8的可回收交联聚合物发泡材,其中该化学发泡工艺包括使用发泡剂,其中该发泡剂包括偶氮化合物或酰肼化合物。
10.根据权利要求9的可回收交联聚合物发泡材,其中该偶氮化合物为2,2’-偶氮双(2-氰基丁烷))、2,2'-偶氮双(甲基丁腈))或偶氮二甲酰胺。
11.根据权利要求9的可回收交联聚合物发泡材,其中该酰肼化合物为p,p’-氧双(苯磺酰肼))、对甲苯磺酰胺脲或对甲苯磺酰肼。
12.根据权利要求1的可回收交联聚合物发泡材,其中该可回收交联聚合物发泡材为物理发泡工艺的发泡产品。
13.根据权利要求1的可回收交联聚合物发泡材,其中该自由基起始剂与该交联剂的摩尔比为0.1~5。
14.根据权利要求1的可回收交联聚合物发泡材,其中相对于100质量份的该聚合物材料,该自由基起始剂与该交联剂的总和为0.5~15质量份。
15.根据权利要求1的可回收交联聚合物发泡材,其中该可回收交联聚合物发泡材的密度在0.05g/cm3~0.8g/cm3的范围。
16.根据权利要求1的可回收交联聚合物发泡材,其中该可回收交联聚合物发泡材的泡孔尺寸为30μm~1mm。
17.一种可重复使用的鞋类部件,包括根据权利要求1的可回收交联聚合物发泡材,其中该可回收交联聚合物发泡材的黄化指数为-5~70。
18.根据权利要求17的可重复使用的鞋类部件,其中该可重复使用的鞋类部件包括内底、中底或大底。
19.一种回收材料,从根据权利要求17的可重复使用的鞋类部件获得,其中该回收材料的黄化指数为-5~95。
20.根据权利要求19的回收材料,其中该回收材料的黄化指数为-5~45。
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