CN110938229A - 发泡组合物及其发泡体 - Google Patents

发泡组合物及其发泡体 Download PDF

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Publication number
CN110938229A
CN110938229A CN201910880910.6A CN201910880910A CN110938229A CN 110938229 A CN110938229 A CN 110938229A CN 201910880910 A CN201910880910 A CN 201910880910A CN 110938229 A CN110938229 A CN 110938229A
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China
Prior art keywords
foaming
foaming composition
polyethylene
foam
copolymer
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汪毓杰
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SHAO SHUHUI
Fengda Composite Materials Co ltd
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SHAO SHUHUI
Fengda Composite Materials Co ltd
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Abstract

本发明提供一种发泡组合物及其发泡体，以该发泡组合物的总重为基准，其包含：5wt％至70wt％的回收聚乙烯醇缩丁醛；10wt％至70wt％的聚乙烯‑酯类共聚物；0.5wt％至3.5wt％的发泡剂；0.5wt％至3wt％的过氧化物交联剂；以及0.1wt％至2.5wt％的酰肼类交联剂。由该发泡组合物发泡成型的发泡体不仅不会散发醛类所产生的难闻气味，还具有良好机械性质，形变恢复能力佳。

Description

发泡组合物及其发泡体
技术领域
本发明涉及一种发泡组合物，及由该发泡组合物成型的发泡体。
背景技术
聚合物发泡材料由于内部含有大量气泡、不仅质轻、省料、热导率低、隔热性能好，还具有优良的缓冲性能、隔音性能以及比强度高等优点，因此广泛应用在工业、农业、军事、生活日用品和办公用品等各领域。
一般而言，聚合物发泡材料依其使用的原料不同，大致上可分为塑胶发泡材料和弹性体发泡材料；塑胶发泡材料具有加工塑形容易、颜色美观的优点，但其弹性不佳、止滑性差且回收不易；反之，弹性体发泡材料具有弹性佳及止滑性佳的优点，但其后加工的塑形不易、加工过程造成粉尘污染，且其产品有异味。
聚乙烯醇缩丁醛(polyvinyl butyral，PVB)因具有高透明度、高韧性和高弹性而广泛应用于汽车安全玻璃、航空航海、高层建筑以及太阳能光伏电池等领域。除此之外，聚乙烯醇缩丁醛还兼具加工塑形容易的优点，因此成为发泡材料的另一选择；然而，聚乙烯醇缩丁醛的价格昂贵，会造成发泡材料的生产成本大幅提高，便不利于产业开发。
为了解决上述问题，一些利用生产聚乙烯醇缩丁醛产品的边材或者聚乙烯醇缩丁醛产品的废弃物等废料作为聚乙烯醇缩丁醛原料的方法已被提出。例如，美国发明专利第7799840号(US 7799840 B2)提出以回收的聚乙烯醇缩丁醛、乙酸乙烯酯聚合物、发泡剂等成分作为阻尼材料组成物，并将所述阻尼材料组成物发泡制成的夹层结构放置于两面板之间，用来减少例如汽车车身板的振动，进而减少汽车产生的噪音。然而，由于聚乙烯醇缩丁醛是由聚乙烯醇和丁醛制备而来，回收得来的聚乙烯醇缩丁醛常具有丁醛或2-乙基-2-己烯醛残留的臭味，阻碍了聚乙烯醇缩丁醛产品在应用上的发展。
发明内容
有鉴于上述现有的发泡组合物存在技术缺陷，本发明的目的在于提供一种发泡组合物，其不仅能解决使用聚乙烯醇缩丁醛导致的生产成本提高的问题，还可以制得几乎不具有臭味的产品，进而更具商业产品的开发潜力。
本发明的另一目的在于提供一种发泡组合物，其制品具有良好机械性质，形变恢复能力佳。
为达成前述目的，本发明提供一种发泡组合物。以该发泡组合物的总重为基准，其包含：5重量百分比(wt％)至70wt％的回收聚乙烯醇缩丁醛；10wt％至70wt％的聚乙烯-酯类共聚物；0.5wt％至3.5wt％的发泡剂；0.5wt％至3wt％的过氧化物交联剂；以及0.1wt％至2.5wt％的酰肼类交联剂。
依据本发明，通过特定含量范围的酰肼类交联剂与回收聚乙烯醇缩丁醛中的丁醛或2-乙基-2-己烯醛(可由两个丁醛基缩合而得)在发泡过程中进行反应，因此可消耗掉大部份醛类所产生的难闻气味；并且，在发泡过程中，通过过氧化物交联剂和酰肼类交联剂将所述发泡组合物中的高分子聚合物主链(即聚乙烯醇缩丁醛、聚乙烯-酯类共聚物、热塑性聚烯烃等)彼此交联，形成三维网状结构，进而提升其制品的硬度、剪切模数、延伸性等机械性质；当其制品受冲击时能够通过重构(reconstructing)分子间交互作用、耗散(dissipating)所遭受的冲击能量，同时产生恢复形状的力而可保持初始形状。
依据本发明，该回收聚乙烯醇缩丁醛是制造车辆安全玻璃的PVB薄膜产品的边材或含有PVB薄膜产品的玻璃废弃物。具体而言，回收聚乙烯醇缩丁醛可由废弃的汽车安全玻璃中而得，但不限于此。另外，当该回收聚乙烯醇缩丁醛是源自制造车辆安全玻璃的PVB薄膜产品的边材时，其包含约100百万分率(ppm)的丁醛或其衍生物。
依据本发明，该酰肼类交联剂可与丁醛或2-乙基-2-己烯醛进行还原反应生成腙(hydrazine)，因此可消除醛类的气味。此外，该酰肼类交联剂可与聚乙烯醇缩丁醛或聚乙烯-酯类共聚物中的反应型羰基官能基进行交联反应。具体而言，该酰肼类交联剂可为分子中具有一个酰肼基的单酰肼化合物、分子中具有两个酰肼基的二酰肼化合物、或分子中具有超过两个酰肼基的多酰肼化合物。举例而言，单酰肼化合物可为月桂酰肼(laurylhydrazide)、水杨酸酰肼(salicylic acid hydrazide)、甲酰肼(formic hydrazide)、乙酰肼(acetic hydrazide)，但并非仅限于此；二酰肼化合物可为草酸二酰肼(oxalic aciddihydrazide)、琥珀酸二酰肼(succinic acid dihydrazide)、己二酸二酰肼(adipic aciddihydrazide)、壬二酸二酰肼(azelaic acid dihydrazide)、癸二酸二酰肼(sebacic aciddihydrazide)、马来酸二酰肼(maleic acid dihydrazide)，但并非仅限于此；多酰肼化合物可为聚丙烯酰肼(polyacrylic hydrazide)，但并非仅限于此。
该过氧化物交联剂受热时容易分解产生自由基，通过自由基夺取组成物中的聚合物成分(如聚乙烯醇缩丁醛、聚乙烯-酯类共聚物、热塑性聚烯烃等)主链上的氢原子，使聚合物成分主链上的部分碳原子成为活性基进而相互结合产生交联键结。依据本发明，该过氧化物交联剂可使用先前公知的。举例而言，该过氧化物交联剂可为过氧化二异丙苯(dicumyl peroxide)、2,5-二甲基-2,5-双(叔丁过氧)-3-己炔(2,5-dimethyl-2,5-di(tert-buytlperoxy)-3-hexyne)、2,5-二甲基-2,5-双(叔丁过氧基)己烷(2,5-dimethyl-2,5-di(tert-butyl peroxy)hexane)、1,1-二叔丁过氧基-3,3,5-三甲基环己烷(1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane)、2,5-二甲基-2,5-双(过氧叔丁基)己烷(2,5-dimethyl-2,5-di(tert-butyl peroxy)hexane)、或过氧化叔丁基异丙苯(tert-butyl cumyl peroxide)；也可以同时包含两种以上的过氧化物交联剂的混合物，例如过氧化二异丙苯和过氧化叔丁基异丙苯，但并非仅限于此。优选的，该过氧化物交联剂为过氧化二异丙苯。
依据本发明，该聚乙烯-酯类共聚物可为聚乙烯-醋酸乙烯酯共聚物(ethylene-vinyl acetate copolymer，EVA)、聚乙烯-丙烯酸甲酯共聚物(ethylene-methyl acrylatecopolymer，EMA)、聚乙烯-丙烯酸乙酯共聚物(ethylene-ethyl acrylate copolymer，EEA)、聚乙烯-丙烯酸丁酯共聚物(ethylene-butyl acrylate copolymer，EBA)或其组合，但并非仅限于此。优选的，该聚乙烯-酯类共聚物为EVA。其中，EVA中的醋酸乙烯酯单元的含量不同会影响EVA的性质；一般而言，当醋酸乙烯酯单元的含量越高时，EVA的回弹性、柔韧性、粘合性、透明性、溶解性、和耐冲击性等性质都会提高；当醋酸乙烯酯单元的含量越低时，EVA的刚性和耐磨性越佳。优选的，该聚乙烯-醋酸乙烯酯共聚物是由聚乙烯单体和醋酸乙烯酯单体所聚合而成，其中醋酸乙烯酯单体的含量为8wt％至35wt％。在一些实施例中，EVA可为回收的EVA材料。
在一些实施例中，该发泡组合物还可包括一热塑性聚烯烃；以该发泡组合物的总重为基准，该热塑性聚烯烃的含量为5wt％至20wt％。举例而言，该热塑性聚烯烃可为乙烯-丙烯共聚物(ethylene propylene copolymer)、乙烯-丙二烯-二烯三元共聚物(ethylenepropylene diene terpolymer)、乙烯-辛烯共聚物(ethylene octene copolymer)、乙烯-丁烯共聚物(ethylene butylene copolymer)、或其组合，但并非仅限于此。优选的，该热塑性聚烯烃的重量平均分子量为78,000至140,000。优选的，该热塑性聚烯烃为乙烯-辛烯共聚物，更优选地，在由乙烯单体和辛烯单体聚合而成的乙烯-辛烯共聚物中，辛烯单体的含量为20wt％至50wt％，其商购产品例如Solumer 891。
依据本发明，该发泡剂是热分解型发泡剂。举例而言，发泡剂的分解温度可介于120℃至200℃。该发泡剂可为偶氮二甲酰胺(azodicarbonamide，AC)、4,4’-氧代双苯磺酰肼(4,4'-oxybis(benzenesulfonyl hydrazide，OBSH)、对苯甲磺酰肼(p-toluenesulfonylhydrazide，TSH)、碳酸氢钠或其组合，但并非仅限于此。
在一些实施例中，该发泡组合物还可包括一种橡胶。以该发泡组合物的总重为基准，该橡胶的含量为1wt％至20wt％。优选的，该橡胶的门尼粘度(ML1+4，120℃)介于20至50。举例而言，该橡胶可为天然橡胶(natural rubber)、丁苯橡胶(styrene-butadienerubber，SBR)、聚丁二烯橡胶(polybutadiene rubber，BR)、乙丙橡胶(ethylene propylenerubber，EPR)、苯乙烯-异戊二烯-苯乙烯嵌段共聚物(styrene-isoprene-styrene blockcopolymer)、卤化丁基橡胶(halogenated isobutylene isoprene rubber)等，但并非仅限于此。其中，乙丙橡胶包括三元乙丙橡胶(ethylene propylene diene monomer，EPDM)；丁苯橡胶包括苯乙烯-丁二烯-苯乙烯嵌段共聚物(poly(styrene-butadiene-styrene)blockcopolymer)；卤化丁基橡胶可包括氯化丁基橡胶(chlorinated isobutylene isoprenerubber)或溴化丁基橡胶(brominated isobutylene isoprene rubber)；聚丁二烯橡胶可依其中所含的顺式丁二烯含量分成：顺式丁二烯含量为35摩尔(mole)％～40mole％的低顺式丁二烯橡胶、顺式丁二烯含量为96mole％～98mole％的高顺式丁二烯橡胶、及顺式丁二烯含量为98mole％以上的超顺式丁二烯橡胶。
在不影响本发明效果的范围内，所述发泡组合物还可依需求适当添加10wt％至29wt％的助剂。举例而言，助剂可包括发泡助剂、过氧化物交联助剂、增粘剂、增塑剂、润滑剂、填料或其组合，但并非仅限于此。
依据本发明，发泡助剂能用于降低发泡剂的分解温度、增加所述发泡组合物的流动性、防止腐蚀模具或改善泡沫均匀性等。举例而言，发泡助剂可为氧化锌、硬脂酸锌、邻苯二甲酸锌、碳酸锌等，但并非仅限于此。优选的，以该发泡组合物的总重为基准，该发泡助剂的含量为0.5wt％至1.5wt％。
就进一步增加交联密度的观点而言，所述发泡组合物可包括过氧化物交联助剂，以该发泡组合物的总重为基准，该过氧化物交联助剂的添加量为0.1wt％至1.0wt％。一般而言，过氧化物交联助剂是具有多官能基的反应型助剂，可对自由基的反应非常强烈，可产生更多的交联键结，提高过氧化物交联剂的交联效率。举例而言，该过氧化物交联助剂可为三羟甲基丙烷三丙烯酸酯(trimethylolpropane triacrylate)、1,3,5-三聚氰酸三烯丙基酯(1,3,5-triazin，TAC)、三烯丙基异氰脲酸酯(triallyl isocyanurate，TAIC)、N,N'-(1,3-亚苯基)双马来酰亚胺(N,N’-m-phenylene dimaleimide)，但并非仅限于此。
依据本发明，以该发泡组合物的总重为基准，该增粘剂的添加量可为5wt％至15wt％。举例而言，该增粘剂可为萜烯树脂(terpene resin)、萜酚树脂(terpene phenolicresin)、多萜树脂(polyterpene resin)、松香(rosin resin)、芳香烃增黏树脂、C5、C9的石油树脂等，但并非仅限于此。
依据本发明，以该发泡组合物的总重为基准，该增塑剂的添加量可为1.0wt％至3.0wt％。举例而言，该增塑剂可为三乙二醇二异辛酸酯(triethylene glycol bis(2-ethylhexanoate))、四乙二醇二庚酸酯(tetraethylene glycol diheptylate)、癸二酸二丁酯(dibutyl sebacate)、己二酸二己酯(dihexyl adipate)、己二酸二辛酸酯(dioctyladipate，DOA)等，但并非仅限于此。
依据本发明，以该发泡组合物的总重为基准，该润滑剂的添加量可为0.5wt％至1.5wt％。举例而言，该润滑剂可为硬脂酸(stearic acid)或硬脂酸锌(zinc stearate)，但并非仅限于此。
依据本发明，以该发泡组合物的总重为基准，该填料的添加量可为5.0wt％至17.0wt％。举例而言，该填料可为滑石粉、二氧化硅、碳酸镁、硅酸镁、碳酸钙、硫酸钡、黏土、云母、氢氧化镁、氢氧化铝等，但并非仅限于此。
优选的，以整体发泡组合物的总量为基准，该回收聚乙烯醇缩丁醛的含量为40wt％至60wt％；该聚乙烯-酯类共聚物的含量为10wt％至30wt％；该热塑性聚烯烃的含量为10wt％至15wt％；该发泡剂的含量为1.0wt％至2.0wt％；该过氧化物交联剂的含量为0.5wt％至1.5wt％；该酰肼类交联剂的含量为0.5wt％至1.5wt％；该橡胶的含量为5wt％至10wt％；该过氧化物交联助剂的含量为0.3wt％至1.0wt％；以及该发泡助剂的含量为0.5wt％至1.2wt％。
本发明另提供一种发泡体，其是由所述发泡组合物发泡成型而成。举例而言，发泡成型的方法可使用热压发泡成型、模压发泡成型或射出发泡成型等，但并非仅限于此。
所述发泡体可应用于吸震鞋垫、运动护具、医疗器材护垫、瑜珈垫、吸震隔音材料、或低弹吸震地垫等，但并非仅限于此。
具体实施方式
以下列举数种实施例及比较例说明本发明的实施方式，本领域技术人员可经由本说明书的内容轻易地了解本发明所能达成的优点与功效，并且在不背离本发明的精神下进行各种修饰与变更，以施行或应用本发明的内容。
原料
回收聚乙烯醇缩丁醛，其购自Protrade Asia Limited公司；
聚乙烯-醋酸乙烯酯，商品型号：UE629，其含有的VA单元为18wt％，购自USI公司；
回收聚乙烯-醋酸乙烯酯，回收自工厂内生产的聚乙烯-醋酸乙烯酯发泡后所产生的边角料；
热塑性聚烯烃：乙烯-辛烯二元共聚物，商品型号：Solumer 865，购自SK GlobalChemical公司；
橡胶：溴化丁基橡胶，商品型号：Bromobutyl 2211，购自ExxonMobil公司；
增粘剂：商品型号：Foral 85，购自Eastman公司；
发泡剂：偶氮二甲酰胺，商品型号：Celogen754A，购自Celchem LLC公司；
过氧化二异丙苯，商品型号：Luperox DC40，购自Arkema公司；
琥珀酸二酰肼，商品型号：SDH，购自Oakwood Chemical公司；
发泡助剂：氧化锌，购自Zinc Corp of America公司；
过氧化物交联助剂：三烯丙基异氰脲酸酯，商品型号：TAIC，购自MitsubishiInternational Polymer Trade公司；
润滑剂：硬脂酸，商品型号：Stearic Acid，购自炜创公司；
填料：碳酸钙，商品型号：轻质碳酸钙，购自益泰安公司；
填料：二氧化硅，商品型号：Ultrasil VN3，购自Evonik公司。
实施例1至4与比较例1至4：发泡组合物
实施例1：
首先将回收聚乙烯醇缩丁醛放置在捏合机中捏合10分钟；随后将聚乙烯-醋酸乙烯酯、琥珀酸二酰肼、碳酸钙、二氧化硅、氧化锌、三烯丙基异氰脲酸酯、硬脂酸加入捏合机中，并以120℃的温度进行12分钟的搅拌混合。在前述混合步骤完成前的最后2分钟时，将偶氮二甲酰胺和过氧化二异丙苯加入捏合机中混合2分钟，得到一混合物。将所述混合物转到双滚轮上并升温，再将所述混合物移至分散滚轮，得到一均匀的发泡组合物；该发泡组合物中各成分的配比如下：回收聚乙烯醇缩丁醛54.6wt％、聚乙烯-醋酸乙烯酯23.4wt％、琥珀酸二酰肼0.8wt％、碳酸钙13wt％、二氧化硅3.8wt％、氧化锌1.5wt％、三烯丙基异氰脲酸酯0.3wt％、硬脂酸0.5wt％、偶氮二甲酰胺1.4wt％、以及过氧化二异丙苯0.7wt％。
将该发泡组合物置于开炼机，以80℃的温度将混合均匀的发泡组合物进行混炼、塑化，再压延成厚度为1厘米的片状薄膜。
从所述片状薄膜中秤取150克放置于模具中，再将模具移至平板硫化机，以模压7公斤至8公斤、温度165℃至170℃的条件进行模压发泡成型10分钟至15分钟，最后得到发泡体1。
实施例2至4与比较例1至4：
根据下表1所示的配比配制实施例2至4的发泡组合物，且依照与制备发泡体1相同的步骤制备发泡体2至4；以及根据下表2所示的配比配制比较例1至4的发泡组合物，且依照与制备发泡体1相同的步骤制备发泡体7至10。其主要差异在于使用的发泡组合物的组成成份或其含量的差异。
实施例5
首先将回收聚乙烯醇缩丁醛放置在捏合机中捏合10分钟；随后将聚乙烯-醋酸乙烯酯、热塑性聚烯烃、橡胶、增粘剂、琥珀酸二酰肼、碳酸钙、二氧化硅、氧化锌、三烯丙基异氰脲酸酯、硬脂酸加入捏合机中，并以120℃的温度进行12分钟的搅拌混合。在前述混合步骤完成前的最后2分钟时，将偶氮二甲酰胺和过氧化二异丙苯加入捏合机中混合2分钟，得到一混合物。将所述混合物转到双滚轮上并升温，再将所述混合物移至分散滚轮，得到一均匀的发泡组合物；该发泡组合物中各成分的配比如下：回收聚乙烯醇缩丁醛47wt％、聚乙烯-醋酸乙烯酯8.4wt％、热塑性聚烯烃15wt％、橡胶6.7wt％、增粘剂6.7wt％、琥珀酸二酰肼0.8wt％、碳酸钙8.5wt％、二氧化硅2.2wt％、氧化锌1.5wt％、三烯丙基异氰脲酸酯0.4wt％、硬脂酸0.5wt％、偶氮二甲酰胺1.6wt％、以及过氧化二异丙苯0.7wt％。
将该发泡组合物置于开炼机，以80℃的温度将混合均匀的发泡组合物进行混炼、塑化，再压延成厚度为1厘米的片状薄膜。
从所述片状薄膜中秤取150克放置于模具中，再将模具移至平板硫化机，以模压7公斤至8公斤、温度165℃至170℃的条件进行模压发泡成型10分钟至15分钟，最后得到发泡体5。
实施例6与比较例5和6：
根据下表1所示的配比配制实施例6的发泡组合物，且依照与制备发泡体5相同的步骤制备发泡体6；以及根据下表2所示的配比配制比较例5和6的发泡组合物，且依照与制备发泡体5相同的步骤制备发泡体11和12。其主要差异在于使用的发泡组合物的组成成份或其含量的差异。
表1：实施例1至6的发泡组合物的配比。
Figure BDA0002205876270000091
表2：比较例1至6的发泡组合物的配比。
Figure BDA0002205876270000092
Figure BDA0002205876270000101
试验例：发泡体1至12的特性分析
本试验例是由如下所述的相同试验方法分析由实施例1至6、比较例1至6的发泡组合物所发泡成型的发泡体1至12的机械性质、发泡倍率、硬度、比重以及气味，其结果列于下表3和下表4所示。为确保特性分析的实验意义，各发泡组合物是以相同的方法形成各发泡体，且各发泡体亦是由相同的试验方法进行分析。由此可见，各发泡体的特性差异主要源自于各发泡组合物中组成差异所致。
试验方法：
流变测试(TS2)：依ASTM D5289标准试验法测量；
流变测试(TC90)：依ASTM D5289标准试验法测量；
最大转矩值(maximum torque，Mh)：依ASTM D5289标准试验法测量；
最小转矩值(minimum torque，Ml)：依ASTM D5289标准试验法测量；
发泡倍率(volumetric expansion factor)：以一个固定发泡制品试样的模具(长x宽x高＝140厘米x 100厘米x 15厘米)，在模具内底部加工一条长度为100厘米的小槽；当发泡体成型后，用游标尺量得此槽的长度尺寸(单位：厘米)，再将前述长度尺寸除以100，即为发泡倍率；
硬度(hardness，type C)：依ASTM D792-13标准试验法测量；
比重(specific gravity)：依ASTM D792-13标准试验法测量；
回弹率：依ASTM D2632-92标准试验法测量；
气味测试：使用嗅觉测定法进行评估，相同检测人员分别对发泡体1至12评估其气味。
表3：制作发泡体1至6所选用得发泡组合物的样品编号以及发泡体的特性分析结果。
Figure BDA0002205876270000111
表4：制作发泡体7至12所选用的发泡组合物的样品编号以及发泡体的特性分析结果。
Figure BDA0002205876270000112
如表3所示，由添加酰肼类交联剂的发泡组合物(即实施例1至6)发泡成型的发泡体1至6，并未散发醛类的臭味。反观表4所示的由比较例1至6成型的发泡体7至12，由于其所选用的发泡组合物中未添加酰肼类交联剂，致使发泡体7至12散发醛类的臭味。
此外，为进一步比较各组具有类似组成的发泡组合物的特性差异，以下将实施例1的发泡组合物所制得的发泡体1的实验结果与比较例1的发泡组合物所制得的发泡体7的实验结果相比，实施例2的发泡组合物所制得的发泡体2的实验结果与比较例2的发泡组合物所制得的发泡体8的实验结果相比，以此类推，由此确认发泡组合物中酰肼类交联剂的作用。
由表3和表4的流变测试(TS2)结果可知，当所述发泡组合物的成分主要差异为是否添加酰肼类交联剂时，添加酰肼类交联剂的发泡组合物(即实施例1)发泡成型的发泡体1，相比于未添加酰肼类交联剂的发泡组合物(即比较例1)发泡成型的发泡体7的TS2值约减少了43％，发泡体2相较发泡体8的TS2值约减少了30％、发泡体3相较发泡体9的TS2值约减少了57％、发泡体4相较发泡体10的TS2值约减少了10％；由此表示实施例1至4在初反应时流动性良好，能使组成成份均匀分散。另外，因实施例5和6的发泡组合物包含增粘剂和热塑性聚烯烃，且该增粘剂在模压发泡成型的170℃时为液态，因此延缓过氧化物交联剂的反应，而使得所述发泡组合物在初反应时的流动性更优选。
此外，由表3和表4的流变测试(TC90)结果可知，当所述发泡组合物发泡组合物的成分主要差异为是否添加酰肼类交联剂时，发泡体1的TC90值约低于发泡体7的TC90值约16％，发泡体2的TC90值约低于发泡体8的TC90值约11％，发泡体3的TC90值约低于发泡体9的TC90值约21％，发泡体4的TC90值约低于发泡体10的TC90值约9％，发泡体5的TC90值约低于发泡体11的TC90值约4％，以及发泡体6的TC90值约低于发泡体12的TC90值约5％；由此表示发泡体1至6需要达到完成90％反应的时间减少，即表示所述发泡组合物的反应速率提高。
由表3和表4中的最大转矩值的比较结果可知，当所述发泡组合物的成分主要差异为是否添加酰肼类交联剂时，发泡体1的Mh高于发泡体7的Mh，同样地，发泡体2的Mh高于发泡体8的Mh、发泡体3的Mh高于发泡体9的Mh、发泡体4的Mh高于发泡体10的Mh、发泡体5的Mh高于发泡体11的Mh、及发泡体6的Mh高于发泡体12的Mh；由此表示发泡体1至6具有优选的剪切模数、延伸性及交联密度，因此发泡体1至6具有更优选的机械性质。另外，发泡体1的硬度亦高于发泡体7的硬度，发泡体2的硬度高于发泡体8的硬度、发泡体3的硬度高于发泡体9的硬度、发泡体4的硬度高于发泡体10的硬度、发泡体5的硬度高于发泡体11的硬度、及发泡体6的硬度高于发泡体12的硬度；由此表示发泡体1至6具有优选的硬度，更可谓发泡体1至6具有相更优选的机械性质。
由表3和表4中的回弹率的比较结果可知，当所述发泡组合物的成分主要差异为是否添加酰肼类交联剂时，发泡体1的回弹率高于发泡体7的回弹率，发泡体2的回弹率高于发泡体8的回弹率、发泡体3的回弹率高于发泡体9的回弹率、发泡体4的回弹率高于发泡体10的回弹率、发泡体5的回弹率高于发泡体11的回弹率、及发泡体6的回弹率高于发泡体12的回弹率；由此表示发泡体1至6确实具有优选的形变恢复能力。
综合上述分析结果可知，本发明通过在发泡组合物中同时添加过氧化物交联剂和酰肼类交联剂的技术手段，不仅能消除发泡体的难闻气味，还有利于提升发泡体的机械性质，进而提升本发明的发泡组合物及其发泡体的应用价值。

Claims (13)

1.一种发泡组合物，以该发泡组合物的总重为基准，其包含：
5重量百分比至70重量百分比的回收聚乙烯醇缩丁醛；
10重量百分比至70重量百分比的聚乙烯-酯类共聚物；
0.5重量百分比至3.5重量百分比的发泡剂；
0.5重量百分比至3重量百分比的过氧化物交联剂；以及
0.1重量百分比至2.5重量百分比的酰肼类交联剂。
2.如权利要求1所述的发泡组合物，其中，该酰肼类交联剂为单酰肼化合物、二酰肼化合物或多酰肼化合物。
3.如权利要求2所述的发泡组合物，其中，该酰肼类交联剂为二酰肼化合物，该二酰肼化合物为琥珀酸二酰肼、己二酸二酰肼、
Figure FDA0002205876260000011
二酸二酰肼、癸二酸二酰肼或其组合。
4.如权利要求1所述的发泡组合物，其中，该过氧化物交联剂为过氧化二异丙苯、2,5-二甲基-2,5-双(叔丁过氧)-3-己炔、2,5-二甲基-2,5-双(叔丁过氧基)己烷、1,1-二叔丁过氧基-3,3,5-三甲基环己烷、2,5-二甲基-2,5-双(过氧叔丁基)己烷、过氧化叔丁基异丙苯或其组合。
5.如权利要求1所述的发泡组合物，其中，该聚乙烯-酯类共聚物为聚乙烯-醋酸乙烯酯共聚物、聚乙烯-丙烯酸甲酯共聚物、聚乙烯-丙烯酸乙酯共聚物、聚乙烯-丙烯酸丁酯共聚物或其组合。
6.如权利要求5所述的发泡组合物，其中，该聚乙烯-酯类共聚物为聚乙烯-醋酸乙烯酯共聚物，且该聚乙烯-醋酸乙烯酯共聚物是由聚乙烯单体和醋酸乙烯酯单体所聚合而成，其中醋酸乙烯酯单体的含量为8重量百分比至35重量百分比。
7.如权利要求1所述的发泡组合物，其中，该发泡剂为偶氮二甲酰胺、4,4’-氧代双苯磺酰肼、对苯甲磺酰肼、碳酸氢钠或其组合。
8.如权利要求1至7中任一项所述的发泡组合物，其中，该发泡组合物还包括5重量百分比至20重量百分比的热塑性聚烯烃。
9.如权利要求8所述的发泡组合物，其中，该热塑性聚烯烃为乙烯-丙烯共聚物、乙烯-丙二烯-二烯三元共聚物、乙烯-辛烯共聚物、乙烯-丁烯共聚物或其组合。
10.如权利要求1至7中任一项所述的发泡组合物，其中，该发泡组合物还包括1重量百分比至20重量百分比的橡胶。
11.如权利要求1至7中任一项所述的发泡组合物，其中该发泡组合物还包括10重量百分比至29重量百分比的助剂，该助剂选自下列群组中的至少一种：发泡助剂、过氧化物交联助剂、增粘剂、增塑剂、润滑剂、填料及其组合。
12.如权利要求11所述的发泡组合物，其中，该发泡助剂为氧化锌或硬脂酸锌；以及该过氧化物交联助剂为三羟甲基丙烷三丙烯酸酯、1,3,5-三聚氰酸三烯丙基酯、三烯丙基异氰脲酸酯、N,N'-(1,3-亚苯基)双马来酰亚胺或其组合。
13.一种发泡体，其是由如权利要求1至12中任一项所述的发泡组合物发泡成型而成。
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