TWI824566B - 可回收交聯聚合物發泡材及其運用 - Google Patents
可回收交聯聚合物發泡材及其運用 Download PDFInfo
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- TWI824566B TWI824566B TW111122434A TW111122434A TWI824566B TW I824566 B TWI824566 B TW I824566B TW 111122434 A TW111122434 A TW 111122434A TW 111122434 A TW111122434 A TW 111122434A TW I824566 B TWI824566 B TW I824566B
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- Taiwan
- Prior art keywords
- cross
- foam material
- linked polymer
- recyclable
- polymer foam
- Prior art date
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- 239000006260 foam Substances 0.000 title claims abstract description 34
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 38
- 239000003999 initiator Substances 0.000 claims abstract description 22
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims description 68
- -1 IR) Polymers 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 41
- 229920006037 cross link polymer Polymers 0.000 claims description 40
- 239000006261 foam material Substances 0.000 claims description 36
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- 150000003254 radicals Chemical class 0.000 claims description 25
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- 229920000573 polyethylene Polymers 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
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- 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 7
- 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 claims description 6
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- 229920001577 copolymer Polymers 0.000 claims description 4
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 4
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004156 Azodicarbonamide Substances 0.000 claims description 3
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- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 7
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- JUIBLDFFVYKUAC-UHFFFAOYSA-N [5-(2-ethylhexanoylperoxy)-2,5-dimethylhexan-2-yl] 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C(CC)CCCC JUIBLDFFVYKUAC-UHFFFAOYSA-N 0.000 description 2
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Abstract
一種可回收交聯聚合物發泡材,包括以下之反應產物:100質量份之聚合物材料,0.1~10質量份之交聯劑以及0.1~5質量份之自由基起始劑。交聯劑以下式表示:
Description
本發明是關於可回收交聯聚合物發泡材、使用其的可重複使用鞋類部件以及從其獲得的回收材料(reversed material)。
乙烯乙酸乙烯酯共聚物(ethylene vinyl acetate,EVA)發泡材是用於鞋類中底(midsole)的常用材料,因為它重量輕並且提供理想的緩衝性能。但是,它確實以缺乏耐用性而聞名。為了提高耐用性,EVA發泡材經過高度交聯,使其無法回收,造成大量的廢棄物。儘管熱塑性聚氨酯(thermoplastic polyurethane,TPU)等替代原材料是可回收的,但存在原材料成本高、設備更換成本高等缺點。
儘管現有的EVA發泡材已經足以滿足它們的預期目的,但它們不是在所有方面都完全令人滿意的。特別是,對具有可回收性和適當特性的EVA發泡材仍有未滿足的需求,以便在製鞋業和其他領域進一步利用。
本發明實施例提供了一種可回收交聯聚合物發泡材,包括以下之反應產物:100質量份之聚合物材料;0.1~10質量份之交聯劑;以及0.1~5質量份之自由基起始劑,其中交聯劑以下式表示:
其中R為碳原子數2~10的伸烷基、碳原子數6~18的亞芳基或碳原子數6~18的伸環烷基。
在一些實施例中,聚合物材料為乙烯類聚合物、聚烯烴聚合物、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)橡膠、天然橡膠(natural rubber,NR)、異丙烯橡膠(isopropylene rubber,IR)、其共聚物或其組合。
在一些實施例中,聚合物材料的乙酸乙烯酯含量(vinyl acetate content)為3-45質量%,熔融指數(melt index)為0.01-400g/10min。
在一些實施例中,交聯劑包括氨基甲酸酯雙四甲基哌啶氧化物(urethane bis-TEMPO(2,2,6,6-tetramethylpiperidinyloxy))。
在一些實施例中,氨基甲酸酯雙四甲基哌啶氧化物包括4,4’-二苯甲烷二異氰酸酯氨基甲酸酯雙四甲基哌啶氧化物(4,4’-diphenylmethane diisocyanate urethane bis-TEMPO)
或4,4'-二異氰酸二環己基甲烷氨基甲酸酯雙四甲基哌啶氧化物(4,4’-diisocyanato dicyclohexylmethane urethane bis-TEMPO)。
在一些實施例中,自由基起始劑包括過氧化物。
在一些實施例中,過氧化物為過氧化二異丙苯(dicumyl peroxide)或雙-(三級丁基過氧化異丙基)苯過氧化物(bis-(tert-butylperoxy isopropyl)benzene peroxide,BIBP)。
在一些實施例中,可回收交聯聚合物發泡材為化學發泡製程的發泡產品。
在一些實施例中,化學發泡製程包括使用發泡劑,其中發泡劑包括偶氮化合物(azo compound)或醯肼化合物(hydrazide compound)。
在一些實施例中,偶氮化合物為2,2’-偶氮雙(2-氰基丁烷)(2,2’-azobis(2-cyanobutane))、2,2’-偶氮雙(甲基丁腈)(2,2’-azobis(methylbutyronitrile))或偶氮二甲醯胺(azodicarbonamide)。
在一些實施例中,醯肼化合物為p,p’-氧雙(苯磺醯肼)(p,p’-oxybis(benzene sulfonyl hydrazide))、對甲苯磺醯胺脲(p-toluene sulfonyl semicarbazide)或對甲苯磺醯肼(p-toluene sulfonyl hydrazide)。
在一些實施例中,可回收交聯聚合物發泡材為物理發泡製程的發泡產品。
在一些實施例中,自由基起始劑與交聯劑的莫耳比為0.1~5。
在一些實施例中,對於100質量份的聚合物材料,自由基起始劑與交聯劑的總和為0.5~15質量份。
在一些實施例中,可回收交聯聚合物發泡材的密度在0.05g/cm3~0.8g/cm3的範圍。
在一些實施例中,可回收交聯聚合物發泡材的泡孔尺寸為30μm~1mm。
本發明實施例還提供了一種可重複使用的鞋類部件,包括如上述之可回收交聯聚合物發泡材,其中可回收交聯聚合物發泡材的黃化指數(yellow index)為-5~70。
在一些實施例中,可重複使用的鞋類部件包括內底(insole)、中底(midsole)或大底(outsole)。
本發明實施例更提供了一種回收材料(reversed material),從如上述之可重複使用的鞋類部件獲得,其中回收材料的黃化指數為-5~95。
在一些實施例中,回收材料的黃化指數為-5~45。
以下將配合所附圖式詳述本發明實施例。其中:
第1圖是未添加交聯劑的聚合物組合物在交聯製程和加熱回收製程中的黏度測量示意圖。
第2圖是添加交聯劑的聚合物組合物在交聯製程和加熱回收製程中的黏度測量示意圖。
本揭露的可回收聚合物組合物、聚合物發泡材、使用其的可重複使用的鞋類部件以及由此獲得的回收材料在以下描述中詳細描述。在以下詳細描述中,出於解釋的目的,闡述了許多具體細節和實施例以便提供對本揭露的透徹理解。為了清楚地描述本揭露,闡述了在以下詳細描述中的特定元件和配置。然而,顯而易見的是,這裡闡述的示例性實施例僅用於說明的目的,並且本發明構思可以以各種形式實施而不限於這些示例性實施例。
目前,乙烯-乙酸乙烯酯(ethylene vinyl acetate,EVA)經過交聯的發泡材一般是不可回收的。此外,在加熱回收的過程中,可能會出現黃化,這可能會限制回收材料進一步的應用。如果回收的發泡材料不是白色的,則所得產品只能是黑色或棕色等深色。為了解決上述問題,本案通過使用四甲基哌啶氧化物(2,2,6,6-tetramethylpiperidinyloxy,TEMPO)衍生物,將可熱降解的氨基甲酸酯鍵(urethane linkage)引入EVA系統中,從而提供具有所需性能例如低黃化指數的可回收交聯聚合物發泡材。
根據本揭露的一些實施例,本案的可回收交聯聚合物發泡材(例如,EVA發泡材)包括聚合物材料、交聯劑(即,TEMPO衍生物)和自由基起始劑。在發泡過程中,通過使用特定的交聯劑,以及控制自由基起始劑、交聯劑和聚合物材料的比例,可以獲得理想的性能。這導致了高交聯效率和可回收性,以及聚合物及其回收材料意外的低黃化指數,為可染色基材、鞋類、運動器材和家具等的進一步應用提供了靈活性。
在一些其他實施例中,本揭露提供的聚合物組合物也可以用作光伏模組(photovoltaic modules)中的封裝材料
(encapsulant)。封裝材料透明度的降低可能導致光伏模組的電效率損失。通過調整封裝材料的顏色,可以調節透光率和太陽能光伏轉換效率。因此,黃化指數越低,太陽能光伏轉換效率越高。
根據一些實施例,本揭露提供了一種可回收交聯聚合物發泡材。可回收交聯聚合物發泡材包括以下之反應產物:100質量份之聚合物材料,0.1~10質量份之交聯劑以及0.1~5質量份之自由基起始劑。交聯劑以下式表示:
其中R為碳原子數2~10的伸烷(alkylene)基、碳原子數6~18的亞芳(arylene)基或碳原子數6~18的伸環烷(cycloalkylene)基。
根據本揭露的一些實施例,聚合物材料可以是聚烯烴聚合物、丙烯聚合物、聚乙烯聚合物、苯乙烯聚合物、乙烯類聚合物例如乙烯-乙酸乙烯酯(ethylene-vinyl acetate,EVA)、低密度聚乙烯(low-density polyethylene,LDPE)、線性低密度聚乙烯(linear-low-density polyethylene,LLDPE)、極低密度聚乙烯(very-low-density polyethylene,VLDPE)和高密度聚乙烯(high density polyethylene,HDPE)、二烯類橡膠,例如天然橡膠(natural rubber,NR)、異戊二烯橡膠(isoprene rubber,IR)、丁二烯橡膠(butadiene rubber,BR)、1,2-丁二烯橡膠、苯乙烯-丁二烯橡膠(styrene-butadiene rubber,SBR)、丙烯腈-丁二烯橡膠(acrylonitrile-butadiene rubber,NBR)、氯丁橡膠(chloroprene rubber,CR)、丁基橡膠(butyl rubber,IIR)、乙
烯-丙烯橡膠(ethylene propylene rubber,EPR)和三元乙丙橡膠(ethylene-propylene-diene rubber,EPDM)或其組合。上述聚烯烴聚合物、丙烯聚合物、聚乙烯聚合物、苯乙烯聚合物和乙烯類聚合物各包括其隨機、嵌段和接枝共聚物。聚烯烴聚合物的例示包括烯烴嵌段共聚物(olefin block copolymers,OBC)。丙烯聚合物的實例包括丙烯乙烯共聚物。特別地,聚合物材料可以是三元乙丙橡膠(EPDM)橡膠、天然橡膠(NR)、異丙橡膠(isopropylene rubber,IR)或其組合。
在一些實施例中,乙烯類聚合物可以是LDPE。LDPE通常是高度分支的乙烯均聚物,可以通過高壓製程而製備(即高壓LDPE)。適用於本案的LDPE可具有0.91至0.94g/cm3的密度。在一些實施例中,乙烯類聚合物是具有至少0.915g/cm3但小於0.94g/cm3或小於0.93g/cm3的密度的高壓LDPE。本文提供的聚合物密度根據美國材料和試驗協會(ASTM International,“ASTM”)方法D792測定。適用於本案的LDPE可具有小於40g/10min的熔融指數(melt index)或0.1-400g/10min、0.5-20g/10min、0.5-5g/10min、1-3g/10min的熔融指數或等於2g/10min的熔融指數。本文提供的熔融指數根據ASTM方法D1238測定。除非另有說明,否則熔融指數是在190℃和2.16kg下測定的。通常,LDPE具有較寬的分子量分佈,從而導致較高的多分散指數(polydispersity index,PDI;重均分子量與數均分子量之比)。
在一些實施例中,乙烯類聚合物可以是LLDPE。LLDPE通常是乙烯類聚合物,具有不均勻分佈的共聚單體(例如,
α-烯烴單體),並且以短鏈分支為特徵。例如,LLDPE可以是乙烯和α-烯烴單體的共聚物,例如上述那些。適用於本案的LLDPE可具有0.916-0.925g/cm3的密度。適用於本案的LLDPE可具有0.1-400g/10min、1-20g/10min或3-8g/10min的熔融指數。
在一些實施例中,乙烯類聚合物可以是VLDPE。VLDPE在本領域中也可稱為超低密度聚乙烯(ultra-low-density polyethylene,ULDPE)。VLDPE通常是乙烯類聚合物,具有不均勻分佈的共聚單體(例如,α-烯烴單體),並以短鏈分支為特徵。例如,VLDPE可以是乙烯和α-烯烴單體的共聚物,例如一種或多種上述的α-烯烴單體。適用於本案的VLDPE可具有0.87-0.915g/cm3的密度。適用於本案的VLDPE可具有0.1-400g/10min、0.1-20g/10min或0.3-5g/10min的熔融指數。
在一些實施例中,乙烯類聚合物可以是HDPE。HDPE具有低分支度,因此具有更強的分子間作用力和抗張強度(tensile strength)。適用於本案的HDPE可具有0.941-0.965g/cm3的密度。適用於本案的HDPE可具有0.1-400g/10min、0.5-65g/10min或1-30g/10min的熔融指數。
在一些具體實施例中,乙烯-乙酸乙烯酯聚合物可從USI Corporation購買,商品名為UE3312和UE629。適用於本案的乙烯-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的熔融指數。
在一些具體實施例中,聚烯烴彈性體可從陶氏化學(Dow Chemical)購買,商品名為ENGAGETM 8003和ENGAGETM 8180。適用於本案的聚烯烴彈性體可具有
0.857g/cm3-0.908g/cm3的密度。適用於本案的聚烯烴彈性體可具有0.1-400g/10min或0.1-10g/10min的熔融指數。在一些實施例中,烯烴嵌段共聚物的平均熔融指數在大於0.5g/10min且小於35g/10min的範圍。熔融指數根據ASTM D1238在190℃、2.16kg下測定。
異氰酸酯化合物可以與四甲基哌啶氧化物化合物(TEMPO(2,2,6,6-tetramethylpiperidinyloxy)compound)組合使用以形成含有熱可逆氨基甲酸酯鍵的TEMPO衍生物。合適的異氰酸酯化合物是每分子含有兩個或兩個以上-NCO基團的多官能異氰酸酯。這些本質上可以是脂族、脂環族、多環或芳香族,例如二異氰酸酯化合物或三異氰酸酯化合物。在一些實施例中,二異氰酸酯化合物可以是甲苯二異氰酸酯(toluene diisocyanate,TDI)、亞甲基二苯基二異氰酸酯(methylene diphenyl diisocyanate,MDI)、六亞甲基二異氰酸酯(hexamethylene diisocyanate,HDI)、4,4’-二異氰酸酯二環己基甲烷(4,4’-diisocyanato dicyclohexylmethane,HMDI)、二甲苯二異氰酸酯(xylene diisocyanate,XDI)、間四甲基二甲苯二異氰酸酯(meta-tetramethylxylylene diisocyanate,TMXDI)、氫化二甲苯二異氰酸酯(hydrogenated xylene diisocyanate,HXDI)、萘1,5-二異氰酸酯(naphthalene 1,5-diisocyanate,NDI)、對苯二異氰酸酯(p-phenylene diisocyanate,PPDI)、3,3'-二甲基二苯基-4,4’-二異氰酸酯(3,3’-dimethyldiphenyl-4,4’-diisocyanate,DDDI)、2,2,4-三甲基六亞甲基二異氰酸酯(2,2,4-trimethylhexamethylene diisocyanate,TMDI)、異佛爾
酮二異氰酸酯(isophorone diisocyanate,IPDI)、4,4’-二環己基甲烷二異氰酸酯(4,4’-dicyclohexylmethane diisocyanate)、降冰片烷二異氰酸酯(norbornane diisocyanate,NDI)或4,4’-二芐基二異氰酸酯(4,4’-dibenzyl diisocyanate,DBDI)。
在一些其他實施例中,三異氰酸酯可以是三苯基甲烷-4,4’,4”-三異氰酸酯(triphenylmethane-4,4’,4”-triisocyanate)、1,6,11-十一烷三異氰酸酯(1,6,11-undecane triisocyanate)、1,3,6-六亞甲基三異氰酸酯(1,3,6-hexamethylene triisocyanate)、1,8-二異氰酸酯-4-異氰酸甲基辛烷(1,8-diisocyanato-4-isocyanatomethyloctane)、2,5,7-三甲基-1,8-二異氰酸-5-異氰酸甲基辛烷(2,5,7-trimethyl-1,8-diisocyanato-5-isocyanato methyloctane)、賴氨酸三異氰酸酯(lysine triisocyanate)、均三甲苯三異氰酸酯(mesitylene triisocyanate)、三甲基苯三異氰酸酯(trimethylbenzene triisocyanate)、苯三異氰酸酯(benzene triisocyanate)、三苯甲烷三異氰酸酯(triphenylmethane triisocyanate)、萘三異氰酸酯(naphthalene triisocyanate)、二苯甲烷-2,4,4’-三異氰酸酯(diphenylmethane-2,4,4’-triisocyanate)、或3-甲基二苯基甲烷-4,6,4’-三異氰酸酯(3-methyldiphenylmethane-4,6,4’-triisocyanate)。
根據本揭露的一個實施例,交聯劑包括二異氰酸酯氨基甲酸酯雙四甲基哌啶氧化物(diisocyanate urethane bis-TEMPO)。示例性二異氰酸酯氨基甲酸酯雙四甲基哌啶氧化物
包括亞甲基二苯基二異氰酸酯氨基甲酸酯雙四甲基哌啶氧化物(methylene diphenyl diisocyanate urethane bis-TEMPO)或4,4’-二異氰酸酯二環己基甲烷氨基甲酸酯雙四甲基哌啶氧化物(4,4’-diisocyanato dicyclohexylmethane urethane bis-TEMPO)。可回收交聯聚合物也可以通過將羥基四甲基哌啶氧化物(hydroxy-tempo)接枝到熱塑性聚合物的主鏈上形成接枝聚合物,然後將接枝聚合物與二異氰酸酯(在流動相中但不揮發)反應形成下一個結構來製備。
在一些具體實施例中,TEMPO可從Tokyo Chemical Industry購買,其可以原樣使用。
合適的自由基起始劑包括α-過氧化新癸酸異丙苯酯(α-cumyl peroxyneodecanoate)、乙醯基過氧化環己基磺醯(acetyl cyclohexylsulfonyl peroxide)、過氧化苯甲醯(benzoyl peroxide)、4,4-二(三級丁基過氧化)戊酸丁酯(butyl 4,4-di(tert-butylperoxy)valerate)、雙(α-三級丁基-過氧化異丙基)苯(bis(alpha-t-butyl-peroxyisopropyl)benzene,BIBP)、氫過氧化異丙苯(cumyl hydroperoxide)、過氧化癸醯(decanoyl peroxide)、過氧化二異丙苯(dicumyl peroxide)、過氧化二(三級丁基)(di(tert-butyl)peroxide)、過氧化二(三級戊基)(di(tert-amyl)peroxide)、過氧化二(異丙基異丙苯)(di(isopropylcumyl)peroxide)、單過氧化氫二異丙基苯(diisopropylbenzene monohydroperoxide)、3,3-二(三級丁基過氧)丁酸乙酯(ethyl-3,3-di(tert-butylperoxy)butyrate)、3,3-二(三級戊基過氧)丁酸乙酯
(ethyl-3,3-di(tert-amylperoxy)butyrate)、異丙基異丙苯過氧化異丙苯(isopropylcumyl cumylperoxide)、過氧化月桂醯(lauroyl peroxide)、4,4-二(三級丁基過氧)戊酸正丁酯(n-butyl 4,4-di(tert-butylperoxy)valerate)、OO-三級丁基-O-異丙基單過氧化碳酸酯(OO-tert-butyl-O-isopropylmonoperoxy carbonate)、OO-三級丁基-O-(2-乙基己基)單過氧碳酸酯(OO-tert-butyl-O-(2-ethylhexyl)monoperoxy carbonate)、OO-三級戊基-O-(2-乙基己基)單過氧碳酸酯(OO-tert-amyl-O-(2-ethylhexyl)monoperoxy carbonate)、氫過氧化對薄荷烷(paramenthane hydroperoxide)、過氧化新戊酸三級戊酯(tert-amyl peroxypivalate)、過氧化新癸酸三級戊酯(tert-amyl peroxyneodecanoate)、氫過氧化三級戊基(tert-amyl hydroperoxide)、過氧-2-乙基己酸三級戊酯(tert-amyl peroxy-2-ethylhexanoate)、過氧-3,5,5-三甲基己酸三級戊酯(tert-amyl peroxy-3,5,5-trimethylhexanoate)、氫過氧化三級丁酯(tert-butyl hydroperoxide)、過氧化異丙苯三級丁酯(tert-butyl cumyl peroxide)、過氧化苯甲酸三級丁酯(tert-butyl peroxybenzoate)、過氧化乙酸三級丁酯(tert-butyl peroxyacetate)、過氧化異丁酸三級丁酯(tert-butyl peroxyisobutyrate)、過氧化馬來酸三級丁酯(tert-butyl peroxymaleate)、過氧化新戊酸三級丁酯(tert-butyl peroxypivalate)、過氧化新癸酸三級丁酯(tert-butyl peroxyneodecanoate)、過氧化異壬酸三級丁酯(tert-butyl peroxyisononanoate)、過氧化-2-乙基己酸三級丁酯(tert-butyl
peroxy-2-ethylhexanoate)、過氧化-3,5,5-三甲基己酸三級丁酯(tert-butyl peroxy-3,5,5-trimethylhexanoate)、1,1-二(三級丁基過氧)環己烷(1,1-di(tert-butylperoxy)cyclohexane)、1,1-二(三級丁基過氧)-3,3,5-三甲基環己烷(1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane)、1,1-二(三級-戊基過氧)環己烷(1,1-di(tert-amylperoxy)cyclohexane)、1,3-二(三級丁基過氧異丙基)苯(1,3-di(tert-butylperoxyisopropyl)benzene)、2,2-二(三級丁基過氧)丁烷(2,2-di(tert-butylperoxy)butane)、2,5-二甲基-2,5-二(2-乙基己醯基過氧)己烷(2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane)、2,5-二甲基-2,5-二(過氧化氫)己烷(2,5-dimethyl-2,5-di(hydroperoxy)hexane)、2,5-二甲基-2,5-二(過氧化苯甲醯)己烷(2,5-dimethyl-2,5-di(benzoylperoxy)hexane)、2,5-二甲基-2,5-二(三級丁基過氧)己烷(2,5-dimethyl-2,5-di(tert-butylperoxy)hexane)、2,5-二甲基-2,5-二(三級丁基過氧)己-3-炔(2,5-dimethyl-2,5-di(tert-butylperoxy)hex-3-yne)、2,2-雙(4,4-二三級丁基過氧環己基)丙烷(2,2-bis(4,4-ditert-butylperoxycyclohexyl)propan)、3-羥基-1,1-二甲基丁基過氧新癸酸酯(3-hydroxy-1,1-dimethylbutylperoxyneodecanoate)、3,5,5-過氧化三甲基己醯(3,5,5-trimethylhexanoyl peroxide)、三級丁
基過氧-2-乙基己基單碳酸酯(t-butyl peroxy-2-ethylhexyl monocarbonate)或其組合,但本發明不限於此。
根據本揭露的實施例,自由基起始劑包括過氧化物,例如過氧化二異丙苯(dicumyl peroxide)或雙-(三級丁基過氧化異丙基)苯過氧化物(bis-(tert-butylperoxy isopropyl)benzene peroxide,BIBP)。
根據本揭露的一些實施例,自由基起始劑和交聯劑的莫耳比可以在0.1-5的範圍,例如,0.5-4.5、1-4、1-3、1-2.5或1-2的範圍。特別地,自由基起始劑和交聯劑的莫耳比高於0.9較為理想,以提供聚合物和回收材料合適的性能(例如黃化指數)以供進一步應用。在一些具體實施例中,自由基起始劑和交聯劑的比例可以高於1.2。根據本揭露的一些實施例,以100重量份的聚合物材料為基準,自由基起始劑和交聯劑的總量可以為0.5-15重量份,較佳1-14重量份,2-12重量份,3-10重量份,或4至8重量份。特別地,自由基起始劑和交聯劑的莫耳比低於0.9會導致聚合物和回收材料的高黃化指數,這可能會限制進一步的應用。
可回收交聯聚合物發泡材可以是化學或物理發泡製程的發泡產品,其使用化學或物理發泡劑。這使得所得交聯發泡材產品的重量減輕,並且可以表現出柔韌性、優異的抗撕裂性、抗壓縮永久變形性(compression set resistance)、衝擊吸收性、耐磨性和可設計性。化學發泡劑包括磺醯肼化合物(sulfonyl hydrazide compound)、偶氮(azo compound)化合物和亞硝基化合物(nitroso compound)。磺醯肼化合物的例子有:苯-1,3-二磺醯肼(benzene-1,3-disulfonyl hydrazide)、苯磺醯肼(benzene
sulfonyl hydrazide)、對甲苯磺醯胺脲(p-toluene sulfonyl semicarbazide)、對甲苯磺醯肼(p-toluenesulfonyl hydrazide)、對,對’-氧雙(苯磺醯肼)(p,p’-oxybis(benzene sulfonyl hydrazide))、4,4’-氧基雙(苯磺醯肼)(4,4’-oxybis(benzene sulfonyl hydrazide),OBSH)等。偶氮化合物的例子有偶氮二甲醯胺(azodicarbonamide)、偶氮雙甲醯胺(azobisformamide)、偶氮雙異丁腈(azobisisobutyronitrile)、重氮氨基苯(diazoaminobenzene)、2,2’-偶氮雙(2-氰基丁烷)(2,2’-azobis(2-cyanobutane))、2,2’-偶氮雙(甲基丁腈)(2,2’-azobis(methylbutyronitrile))、偶氮二羧酸鋇(barium azodicarboxylate)等。亞硝基化合物的例子有N,N’-二亞硝基五亞甲基四胺(N,N’-dinitrosopentamethylenetetramine)、N,N’-二亞硝基-N,N’-二甲基對苯二甲醯胺(N,N’-dinitroso-N,N’-dimethylterephthalamide)等。
物理發泡劑的例示包括烴例如戊烷、丁烷和己烷,鹵代烴例如氯甲烷和二氯甲烷,氟化烴例如三氯氟甲烷、二氯二氟甲烷、三氯三氟乙烷、氯二氟乙烷和氫氟烴,以及例如二氧化碳、氮氣和空氣等氣體。
這些產品以各種粒徑大小提供以控制氣泡形成和發泡材密度。發泡劑的比例可以在很寬的範圍內變化,並且尤其取決於發泡劑的類型、所用的聚合物混合物和要生產的發泡材料的所需密度。相對於可發泡熱塑性混合物的總重量,發泡劑的比例可以在0.1和20wt.%之間,例如,它可以是5-15wt.%。有用的發泡劑可以包括可以商品名ADC(DONGIN SEMICHEM)購買的發泡
劑。
除了上述組分之外,可發泡熱塑性混合物還可以包含一種或多種添加劑。可任選使用的添加劑的實例為防焦劑(scorch retardants)、抗氧化劑、加工助劑、填料、偶聯劑、紫外線吸收劑或穩定劑、抗靜電劑、成核劑、滑劑(slip agents)、增塑劑、潤滑劑、黏度控製劑、增黏劑、防結塊劑、表面活性劑、填充油(extender oil)、酸清除劑、阻燃劑、水樹阻滯劑(water tree retardants)、電樹阻滯劑(electrical tree retardants)、電壓穩定劑、金屬鈍化劑或其組合。
根據本揭露的一實施例,提供了一種可重複使用的鞋類部件。可重複使用的鞋類部件包括可回收交聯聚合物發泡材,其中可回收交聯聚合物發泡材的黃化指數可為-5~70,例如,它可為-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。特別地,可回收交聯聚合物發泡材的黃化指數高於45將限制進一步應用的領域。
根據本揭露的一實施例,提供了一種從可重複使用的鞋類部件獲得的回收材料,其中回收材料的黃化指數可為-5~95,例如,可為-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。特別地,可重複使用的鞋類部件的黃化指數低於45是理想的,以便在進一步的應用中為設計和操作提供更多選擇。
根據本揭露的一些實施例,可回收交聯聚合物發泡材的密度為0.05g/cm3-0.8g/cm3。可回收交聯聚合物發泡材的泡
孔尺寸在30μm-1mm。
在一些實施例中,可重複使用的鞋類部件包括內底(insole)、中底(midsole)或大底(outsole)。
為使本發明的上述及其他目的、特徵和優點更加明顯易懂,以下舉幾個具體實施例進行詳細說明。然而,它們不旨在以任何方式限制本發明。
評估聚合物組合物的性能
表1列出了在以下實施例中使用的材料。
(I)黃化指數(yellow index,YI)
黃化指數根據標準化方法ASTM E313[D65/10],使用比色計(HunterLab,型號:UltraScan VIS)測定。YI在聚合物組合物的交聯製程和加熱回收製程之後測定。
實驗例1
將100重量份的UE3312、6.46重量份的M交聯劑、2.22重量份的DCP依次加入混合器(Brabender,型號:Plasti-Corder)中。加熱至120℃後,以35rpm的轉速繼續混合製程5分鐘,直到聚合物組合物完全混合。接下來,將聚合物組合物置於模具(0.4mm厚)中並在2300psi下壓縮。使用液壓壓縮機(Carver,型號:Monarch系列)進行加熱和壓縮。在180℃的溫度下將聚合物組合物壓縮15分鐘。完成上述程序後,然後將聚合物組合物冷卻至室溫並相應地形成具有一致厚度的薄膜試樣(film specimen)。
實驗例2-13
實驗例2-13以與實施例1中相同的方式進行,不同之處在於表2和表3中列出的聚合物材料、指定交聯劑和自由基起始劑的成分和含量代替實施例1中所使用的,以獲得薄膜試樣。接著,對實驗例1-13進行黃化指數(YIfilm)的測量,結果也顯示於表2。
參照實驗例1-3,其在製備過程中添加了相同類型的過氧化物(即過氧化二異丙苯)。據觀察,具有較高m I/C的聚合物組合物的YIfilm值意外地低。在實驗例4-5和實驗例6-7中也可以觀察到這種趨勢,其在製備過程中添加的過氧化物類型分別是2,5-二甲基-2,5-二(三級丁基過氧)己烷和三級丁基過氧-2-乙基己基單碳酸酯。因此,可以採用較高的m I/C以獲得較佳的YIfilm(即更低的YI值)。
參照實驗例8-9,其在製備過程中添加了相同類型的過氧化物(即過氧化二異丙苯)。據觀察,具有較高m I/C的聚合物組合物的YIfilm值意外地低。在實驗例10-11和實驗例12-13中也可以觀察到這種趨勢,其在製備過程中添加的過氧化物類型分別是2,5-二甲基-2,5-二(三級丁基過氧)己烷和三級丁基過氧-2-乙基己基單碳酸酯。因此,可以採用較高的m I/C以獲得較佳的YIfilm。
實驗例14
將100重量份的UE3312、2.85重量份的H交聯劑、1.67重量份的DCP依次加入混合器(Brabender,型號:Plasti-Corder)中。加熱至120℃後,以35rpm的轉速繼續混合製程5分鐘,直到聚合物組合物完全混合。接下來,將聚合物組合物置於模具(0.4mm厚)中並在2300psi下壓縮。使用液壓壓縮機(Carver,型號:Monarch系列)進行加熱和壓縮。在180℃的溫度下將聚合物組合物壓縮15分鐘。完成上述程序後,然後將聚合物組合物冷卻至室溫並相應地形成具有一致厚度的薄膜試樣。
實驗例15-16
實驗例15-16以與實驗例14中相同的方式進行,不同之處在於表4中列出的聚合物材料、交聯劑和自由基起始劑的成分和含量代替實驗例14中所使用,以獲得薄膜試樣。接著,對實驗例15-16進行黃化指數的測量,結果也顯示於表4。
參照實驗例14-16,觀察到具有較低I+C的聚合物組合物傾向於提供較低的YIfilm值。因此,可以採用較低的I+C以獲得較佳的YIfilm。
實驗例17
將100重量份的UE3312、4.28重量份的M交聯劑、2.78重量份的101XL45依次加入混合器(Brabender,型號:Plasti-Corder)中。加熱至120℃後,以35rpm的轉速繼續混合製程5分鐘,直到聚合物組合物完全混合。接下來,將聚合物組合物置於模具(0.4mm厚)中並在2300psi下壓縮。使用液壓壓縮機
(Carver,型號:Monarch系列)進行加熱和壓縮。在180℃的溫度下將聚合物組合物壓縮15分鐘。完成上述程序後,然後將聚合物組合物冷卻至室溫並相應地形成具有一致厚度的薄膜試樣。
實驗例18-22
實驗例18-22以與實驗例17中相同的方式進行,不同之處在於表5中列出的聚合材料、指定交聯劑和自由基起始劑的成分和含量代替實驗例17中所使用的,以獲得薄膜試樣。接著,將薄膜試樣放入液壓壓縮機(Carver,型號:Monarch系列)上的模具(厚度為0.4mm)中,並在2300psi的壓力下在230℃的溫度下加熱15分鐘,從而檢查薄膜試樣的可逆性。對實驗例17-22進行加熱回收製程後的黃化指數測定,結果顯示於表5。
參照實驗例17-18,與通過添加M交聯劑作為交聯劑生產的聚合物組合物(實驗例17)相比,具有相同m I/C或I+C,由添加H交聯劑作為交聯劑(實驗例18)傾向於提供較佳的YIfilm。
這種趨勢在實驗例19-22中也可以觀察到,其中實驗例20的YIfilm低於實驗例19,實驗例22的YIfilm低於實驗例21。
(II)黏度
使用動態剪切流變儀(TA Instruments,型號:HR-1)根據以下程序和參數測定黏度:
1.調節試樣(conditioning sample):溫度100℃,浸泡時間10s。
2.振盪溫度斜坡(Oscillation temperature ramp):起始溫度100℃,結束溫度170℃,升溫速率:30℃/min,應變0.5%
3.振盪時間:溫度170℃持續時間:1800(秒)。應變0.5%
4.振盪溫度斜坡:起始溫度170℃,結束溫度230℃,升溫速率:30℃/min,應變0.5%
5.振盪時間:溫度230℃持續時間:900(秒)。
應變0.5%
實驗例23
將100重量份的UE3312、4.28重量份的M交聯劑和3.33重量份的DCP依次加入混合器(Brabender,型號:Plasti-Corder)中。加熱至120℃後,以35rpm的轉速繼續混合製程5分鐘,直至完全混合。然後將聚合物組合物冷卻至室溫。
實驗例24-29
實驗例24-29以與實驗例23相同的方式進行,不同之處在於表6中列出的聚合物材料、交聯劑和自由基起始劑的成分和含量代替實施例23中所使用的,以獲得聚合物組合物。接著,如第1圖和第2圖所示,在聚合物組合物的交聯製程和加熱回收製程之後,分別通過在170℃下將平行板之間的聚合物組合物加熱30分鐘,和通過在230℃下加熱聚合物組合物15分鐘來測定黏度。結果如表6所示。
參照添加交聯劑生產的聚合物組合物(實驗例23-28),Vcrosslink在25000-400000Pa.s的範圍內。實驗例23-28在230℃下測定15分鐘的Vreverse在150-180000Pa.s的範圍內,表明聚合物組合物是可回收的,無論在聚合物組合物的製備過程中添加的交聯劑的類型。本文所使用的術語「可回收」是指聚合物組合物的黏度低於200000Pa.s。相比之下,不添加交聯劑(實驗例29)獲得的聚合物組合物的Vreverse超過200000Pa.s,表明聚合物組合物不可回收。
實驗例30
將100重量份的UE629、3.42重量份的H交聯劑和2.1重量份的DCP依次加入混合器(Brabender,型號:Plasti-Corder)中。加熱至120℃後,以35rpm的轉速繼續混合製程5分鐘,直至完全混合。然後將聚合物組合物冷卻至室溫。
實驗例31-35
實驗例31-35以與實驗例30中相同的方式進行,不同之處在於表7中列出的聚合物材料、交聯劑和自由基起始劑的成分和含量代替實驗例30中所使用的,以獲得聚合物組合物。接著,
在聚合物組合物的交聯製程和加熱回收製程之後,分別通過在170℃的溫度下加熱聚合物組合物30分鐘,和在230℃的溫度下加熱聚合物組合物15分鐘來測定黏度。結果如表7所示。
參照實驗例30-35,Vcrosslink在25000-400000Pa.s的範圍。實驗例30-35的Vreverse在1100-40000Pa.s的範圍內,這表明只要添加交聯劑,聚合物組合物則可交聯和可回收,無論在聚合物組合物的製備過程中使用的聚合物材料的類型。然而,實驗例35的Vreverse超過20000Pa.s,表明其較難回收。
可回收交聯聚合物發泡材的製備
根據本揭露的一些實施例,可以使用發泡製程(例如物理或化學發泡製程)將本聚合物發泡材製備成發泡材。
表8列出了本發明實施例中涉及的材料。
化學發泡製程
實驗例36
將100重量份的UE659、3.42重量份的M交聯劑、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,型號:Plasti-Corder)中。加熱至120℃後,以35rpm的轉速繼續混合製程5分鐘,直到聚合物組合物完全混合。接著,將聚合物組合物置於模具中(厚度為0.3mm)並在2300psi下壓縮。使用液壓壓縮機(Carver,型號:Monarch系列)進行加熱和壓縮。聚合物組合物在約175℃的溫度下放置在壓機中12分鐘。完成上述程序後,將聚合物組合物冷卻至室溫。
實驗例37及實驗例38
實驗例37和實驗例38以與實驗例36相同的方式進行,不同之處在於表9中列出的聚合物材料、交聯劑、自由基起始劑、發泡劑和添加劑的成分和含量代替了實驗例36中所使用的,以得到發泡產品。接下來,測量發泡產品的密度和泡孔尺寸。藉由電密度計(MIRAGE,型號:ED-120T)測量發泡材密度。藉由顯微鏡(Nikon,型號:ECCIPSE CI)檢查發泡材孔尺寸。最後,通過將發泡產品置於液壓壓縮機(Carver,型號:Monarch系列)上的模具(厚度為0.4mm)中,在230℃的溫度和2300psi的壓力下加熱15分鐘以形成熱塑性回收材料,來檢查發泡產品的再加工性。
實驗例38中使用的聚合物材料為回收的UE659,其製備如下:將實驗例37的發泡產品切成小塊,並在230℃的溫度下以20rpm的轉速送入混合器中,然後以35rpm的轉速持續10分鐘。然後,將混合物冷卻至溫度以形成回收的UE659。
添加交聯劑製備的發泡產品(實驗例36、37)顯示出類似的發泡結構,其泡孔尺寸在100和220μm之間。此外,用回收聚合物材料製備的發泡產品(實驗例38)顯示出泡孔尺寸在200和300μm之間的發泡結構。實驗例36和實驗例37的發泡產品的密度在0.15g/cm3-0.23g/cm3的範圍,這是中底(midsole)的典型密度範圍。
此外,測量實驗例36和實驗例37的黃化指數(YI發泡材(YIfoam))。YIfoam是通過光譜和目測確定的。藉由基於ASTM E313[D65/10]的標準化方法使用色度計(HunterLab,型號:UltraScan VIS)確定黃化指數。YI是經過發泡和加熱回收後測定
的。結果如表10所示。
從表10所示的結果可以看出,與添加M交聯劑作為交聯劑的發泡產品(實驗例36)相比,添加H交聯劑作為交聯劑的發泡產品(實驗例37)顯示較佳的YIfoam,其回收材料顯示較佳的YIreversed film。發泡產品和由其獲得的熱塑性回收材料的低黃化指數對於進一步應用的目的是更理想的。
在一些實施例中,以添加H交聯劑作為交聯劑的發泡產品(實驗例37)為例,發泡過程可以在170℃至195℃的溫度下進行6至15分鐘。發泡後測得的YIfoam在27-29之間。加熱回收後測得的YIreversed film在15.5-17.5之間。
此外,值得注意的是,用回收聚合物材料製備的發泡產品(實驗例38)也顯示出30.1的YIfoam,並且其回收材料顯示出22.2的YIreversed film。這使得所得的發泡產品及其熱塑性回收材料具有理想的白色。
物理發泡製程
實驗例39
100重量份的UE659、3.42重量份的H交聯劑和2.0重量份的DCP依次加入混合器(Brabender,型號:Plasti-Corder)中。加熱至120℃後,以35rpm的轉速繼續混合製程5分鐘,直至完全混合。然後將所得物置於模具中(厚度為0.4mm)並在2300psi下壓縮。使用液壓壓縮機(Carver,型號:Monarch系列)進行加熱和壓縮。將所得物在約175℃的溫度下壓縮15分鐘。完成上述程序後,將交聯的試樣冷卻至室溫。接著,將交聯的試樣放入超臨界流體發泡系統的槽中,將系統溫度調節到130℃以上(未達到熔融狀態)。然後將氮氣注入超臨界流體發泡系統並與交聯試樣混合。接著,將系統壓力調至150bar,使交聯試樣與氮氣超臨界流體形成單相溶液,並保持2小時。然後在1秒內將系統壓力調至1.013bar,得到發泡產品。
實驗例40
實驗例40以與實驗例39相同的方式進行,除了實驗例39中使用的聚合物材料是回收的UE659。接下來,測量發泡產品的密度、泡孔尺寸和黃化指數(YIfoam)。藉由電密度計(MIRAGE,型號:ED-120T)測量發泡材密度。藉由顯微鏡(Nikon,型號:ECCIPSE CI)檢查發泡材孔尺寸。最後,藉由將發泡產品置於液壓壓縮機(Carver,型號:Monarch系列)上的模具(厚度為0.4mm)中,在230℃的溫度和2300psi的壓力下加熱15分鐘,檢查發泡產品的可回收性。
實施例40中使用的聚合材料為回收的UE659,其
製備如下:將實施例39的發泡產品切成小塊,並在230℃的溫度下以20rpm的轉速送入混合器中,然後以35rpm的轉速持續10分鐘。然後,將混合物冷卻至溫度以形成回收的UE659。
從表11所示的結果,值得注意的是,用回收的聚合物材料製備的發泡產品(實驗例40)顯示出27.3的YIfoam,而其回收材料顯示出40.5的YIreversed film。YI值低於45可使所得發泡產品及其回收材料具有理想的白色。
實驗例39的發泡產品顯示出泡孔尺寸在100和150μm之間的發泡結構,而實驗例40的發泡產品具有在200和400μm之間的泡孔尺寸。實驗例39和實驗例40的發泡產品的密度在0.15g/cm3-0.23g/cm3的範圍,這是中底的典型密度範圍。
根據本揭露的一些實施例,當發泡材通過物理發泡製程形成時,可以使用超臨界流體或物理發泡劑進行發泡。超臨界流體可以是二氧化碳、氮氣或其組合。物理發泡劑可以是水、甲烷、乙烷、丁烷、丙烷、戊烷、己烷、乙烯、丙烯、甲醇、乙醇、丙酮、空氣或其組合。
在本揭露中,所得的可回收交聯聚合物發泡材在環境和經濟上是可持續的。在發泡製程中(如物理或化學發泡製程),通過應用特定類型的交聯劑(其中特別優選H交聯劑),並通過控制自由基起始劑、交聯劑和聚合物材料之間的特定比例,可實現理想的物理性能,例如聚合物及其回收材料意外的低黃化指數,這為可染色基材、鞋類、運動器材和家具等的進一步應用提供了靈活性。
雖然已經通過示例並根據較佳實施例描述了本揭露,但是應當理解,本揭露不限於此。相反,它旨在涵蓋各種修改和類似的配置(這對於本領域的技術人員來說是顯而易見的)。因此,所附請求項的範圍應給予最廣泛的解釋,以涵蓋所有此類修改和類似配置。
Claims (17)
- 一種可回收交聯聚合物發泡材,包括以下之反應產物:100質量份之聚合物材料;0.1~10質量份之交聯劑,其中該交聯劑包括4,4’-二苯甲烷二異氰酸酯氨基甲酸酯雙四甲基哌啶氧化物(4,4’-diphenylmethane diisocyanate urethane bis-TEMPO)、4,4’-二異氰酸二環己基甲烷氨基甲酸酯雙四甲基哌啶氧化物(4,4’-diisocyanato dicyclohexylmethane urethane bis-TEMPO)、或其組合;以及0.1~5質量份之自由基起始劑,其中該自由基起始劑與該交聯劑的莫耳比為0.1~5。
- 如請求項1之可回收交聯聚合物發泡材,其中該聚合物材料為乙烯類聚合物、聚烯烴聚合物、乙烯丙烯二烯(ethylene-propylene-diene,EPDM)橡膠、天然橡膠(natural rubber,NR)、異丙烯橡膠(isopropylene rubber,IR)、其共聚物或其組合,其中乙烯類聚合物包含苯乙烯聚合物,聚烯烴聚合物包含聚乙烯聚合物、丙烯聚合物、或其組合。
- 如請求項1之可回收交聯聚合物發泡材,其中該聚合物材料的乙酸乙烯酯含量(vinyl acetate content)為3-45質量%,熔融指數(melt index)為0.01-400g/10min。
- 如請求項1之可回收交聯聚合物發泡材,其中該自由基起始劑包括過氧化物。
- 如請求項4之可回收交聯聚合物發泡材,其中該過 氧化物為過氧化二異丙苯(dicumyl peroxide)或雙-(三級丁基過氧化異丙基)苯過氧化物(bis-(tert-butylperoxy isopropyl)benzene peroxide,BIBP)。
- 如請求項1之可回收交聯聚合物發泡材,其中該可回收交聯聚合物發泡材為一化學發泡製程的一發泡產品。
- 如請求項6之可回收交聯聚合物發泡材,其中該化學發泡製程包括使用一發泡劑,其中該發泡劑包括偶氮化合物(azo compound)或醯肼化合物(hydrazide compound)。
- 如請求項7之可回收交聯聚合物發泡材,其中該偶氮化合物為2,2’-偶氮雙(2-氰基丁烷)(2,2’-azobis(2-cyanobutane))、2,2'-偶氮雙(甲基丁腈)(2,2’-azobis(methylbutyronitrile))或偶氮二甲醯胺(azodicarbonamide)。
- 如請求項7之可回收交聯聚合物發泡材,其中該醯肼化合物為p,p’-氧雙(苯磺醯肼)(p,p’-oxybis(benzene sulfonyl hydrazide))、對甲苯磺醯胺脲(p-toluene sulfonyl semicarbazide)或對甲苯磺醯肼(p-toluene sulfonyl hydrazide)。
- 如請求項1之可回收交聯聚合物發泡材,其中該可回收交聯聚合物發泡材為一物理發泡製程的一發泡產品。
- 如請求項1之可回收交聯聚合物發泡材,其中相對於100質量份的該聚合物材料,該自由基起始劑與該交聯劑的總和為0.5~15質量份。
- 如請求項1之可回收交聯聚合物發泡材,其中該可 回收交聯聚合物發泡材的密度在0.05g/cm3~0.8g/cm3的範圍。
- 如請求項1之可回收交聯聚合物發泡材,其中該可回收交聯聚合物發泡材的泡孔尺寸為30μm~1mm。
- 一種可重複使用的鞋類部件,包括如請求項1之可回收交聯聚合物發泡材,其中該可回收交聯聚合物發泡材的黃化指數(yellow index)為-5~70。
- 如請求項14之可重複使用的鞋類部件,其中該可重複使用的鞋類部件包括一內底(insole)、一中底(midsole)或一大底(outsole)。
- 一種回收材料(reversed material),從如請求項14之可重複使用的鞋類部件獲得,其中該回收材料的黃化指數為-5~95。
- 如請求項16之回收材料,其中該回收材料的黃化指數為-5~45。
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