CN113388185B - 一种eva发泡材料及其制备方法与应用 - Google Patents
一种eva发泡材料及其制备方法与应用 Download PDFInfo
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- CN113388185B CN113388185B CN202110690855.1A CN202110690855A CN113388185B CN 113388185 B CN113388185 B CN 113388185B CN 202110690855 A CN202110690855 A CN 202110690855A CN 113388185 B CN113388185 B CN 113388185B
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- 238000005187 foaming Methods 0.000 title claims abstract description 69
- 239000000463 material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 52
- 239000011347 resin Substances 0.000 claims abstract description 52
- 229920006124 polyolefin elastomer Polymers 0.000 claims abstract description 37
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 34
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 34
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000005977 Ethylene Substances 0.000 claims abstract description 26
- 229920001897 terpolymer Polymers 0.000 claims abstract description 26
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 25
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 19
- 239000004088 foaming agent Substances 0.000 claims abstract description 18
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 17
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 17
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 17
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008117 stearic acid Substances 0.000 claims abstract description 17
- 239000011787 zinc oxide Substances 0.000 claims abstract description 17
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims abstract description 17
- 241000209094 Oryza Species 0.000 claims description 24
- 235000007164 Oryza sativa Nutrition 0.000 claims description 24
- 235000009566 rice Nutrition 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 21
- DYAHQFWOVKZOOW-UHFFFAOYSA-N Sarin Chemical compound CC(C)OP(C)(F)=O DYAHQFWOVKZOOW-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 239000006260 foam Substances 0.000 claims description 11
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
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- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- 229920003314 Elvaloy® Polymers 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 229920000554 ionomer Polymers 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000005038 ethylene vinyl acetate Substances 0.000 abstract description 99
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 abstract description 92
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 abstract description 92
- 238000007788 roughening Methods 0.000 abstract description 9
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- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 15
- 230000001276 controlling effect Effects 0.000 description 12
- 239000004156 Azodicarbonamide Substances 0.000 description 7
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 7
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- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
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- 238000005299 abrasion Methods 0.000 description 1
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- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
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- 230000001681 protective effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
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Abstract
本发明公开一种EVA发泡材料及其制备方法与应用,其包括以下材料:乙烯‑乙酸乙烯酯(EVA)、液态环氧化聚丁二烯树脂、乙烯三元共聚物、沙林树脂、聚烯烃弹性体(POE)、选择性部分氢化SBS、发泡剂、交联剂、硬脂酸锌、氧化锌、硬脂酸、纳米碳酸钙混合而成;所述EVA发泡材料高硬度且易粘结、抗拉强度和抗撕强度优良,且可以免去打粗步骤直接刷胶,专用于鞋材发泡材料。
Description
技术领域
本发明涉及有机高分子材料技术领域,尤其涉及一种鞋材专用的高硬度易粘结贴合的EVA发泡材料及其制备方法。
技术背景
鞋是人们日常生活不可或缺的日用品,其消耗量巨大,然而生活中经常可以发现有人因为鞋底的粘结性能不足而导致的鞋底脱胶、开裂等现象,这极大的影响了鞋材的使用寿命及阻碍了鞋材的发展。目前,为了提高鞋底材料的粘结性,大多数采用的工艺为首先对大底和中底进行粗化处理即打粗然后再上胶,打粗能够增大接触面积,有利于粘结牢固;然而,打粗过程耗时耗力,人力成本高,且容易造成尘土飞扬,恶化工作环境,生产效率低下。因此,鞋材开发者把注意力转移到对EVA进行改性从而达到提高粘结性能的目的。申请号为CN 102002182A的中国专利申请公开了一种高粘着力EVA发泡运动鞋底配方及其制造方法,其通过将EVA与乙烯辛烯共聚物、乙烯-乙基丙烯酸酯共聚物以及乙烯-丙烯酸共聚物共混,从材料本身的分子结构出发,提高鞋底材料的极性,改变材料表面的致密性,使胶水更容易渗透到鞋材内部,同时韧性更强,以达到高粘着力的效果。目前,大多数的EVA发泡鞋底材料都较软,虽然穿着较为舒适,但是其拉伸强度和抗撕裂性等力学性能较差,且开发高硬度的EVA鞋材能够拓宽EVA鞋底材料的用途,如可以用于防护鞋、登山鞋等。申请号为CN102816376 A的中国专利申请公开了一种硬质EVA鞋底材料及其生产方法,其通过以EVA7350为基体树脂经交联固化得到一种硬质EVA鞋底材料。
但目前EVA鞋底材料无法同时具备高硬度易粘结的性能,往往硬度达到要求粘结性差,或者粘结性好但硬度不能达到要求。
发明内容
为了克服现有技术的不足,本发明采用EVA为主体树脂,液态环氧化聚丁二烯树脂、沙林树脂、选择性部分氢化SBS、聚烯烃弹性体(POE)为改性剂,乙烯三元共聚物为相容剂,再辅以发泡剂、交联剂等助剂,经过密炼、开炼、造粒、升温发泡、二次油压成型,得到一种高硬度易粘结贴合的EVA发泡鞋底。所述高硬度易粘结贴合的EVA发泡鞋底具有高硬度、优良的抗拉强度和抗撕强度,且可以免去打粗步骤直接刷胶,具有易于粘结贴合、粘结强度高、使用寿命长等特点。
为实现上述目的,本发明所采用的技术方案如下:
一种EVA发泡材料,按重量份数计,其包含如下组分:
在一些实施例中,所述EVA发泡鞋底由以下原料组成:乙烯-乙酸乙烯酯(EVA)、液态环氧化聚丁二烯树脂、乙烯三元共聚物、沙林树脂、聚烯烃弹性体(POE)、选择性部分氢化SBS、发泡剂、交联剂、硬脂酸锌、氧化锌、硬脂酸、纳米碳酸钙,其中各原料的重量份数如下:
进一步的是,其中各原料的重量份数优选如下:
本发明所述的EVA是乙烯-乙酸乙烯(醋酸乙烯)酯共聚物,它是由乙烯(E)和乙酸乙烯酯(VA)共聚而制得,英文名称为:Ethylene Vinyl Acetate,简称为EVA,或E/VAC。一般乙酸乙烯酯(VA)含量在5%~40%。与聚乙烯相比,EVA由于在分子链中引入了乙酸乙烯酯单体,从而降低了结晶度,提高了柔韧性、抗冲击性、填料相溶性和热密封性能。一般来说,EVA的性能主要取决于分子链上乙酸乙烯酯的含量。因构成组分比例可调从而符合不同的应用需要,乙酸乙烯酯(VA)的含量越高,其透明度,柔软度及坚韧度会相对提高。一般情况下,乙酸乙烯含量在5%以下的EVA,其主要产品是薄膜、电线电缆、LDPE改性剂、胶粘剂等;乙酸乙烯含量在5%~10%的EVA产品为弹性薄膜等;乙酸乙烯含量在20~28%的EVA,主要用于热熔粘合剂和涂层制品;乙酸乙烯含量在5%~40%,主要产品为薄膜(包括农用薄膜)和片材,注塑、模塑制品,发泡制品,热熔粘合剂等。本发明所述的EVA中VA含量优选为5-10%,更优选为8%。
本发明所述的液态环氧化聚丁二烯树脂又称聚丁二烯环氧树脂或2000#环氧树脂,其是由低分子量的聚丁二烯液体树脂经有机过氧化物氧化而制得。本发明所述的液态环氧化聚丁二烯树脂为琥珀色液体,分子量2000左右,密度0.9012g/cm3,环氧基含量(质量分数)7%~8%,羟基(质量分数)2%~3%,碘值180。
本发明所述的沙林树脂是乙烯-(甲基)丙烯酸锌盐、钠盐、锂盐等离子键聚合体,是杜邦利用独特的生产工艺聚合而成。杜邦沙林树脂的主要特性:1、优异的低温抗冲击韧性;2、出色的抗磨损、刮擦性能;3、出色的抗化学药品性能;4、透明、清澈、光泽柔和华贵;5、优异的熔融强度(熔融下拉伸不断裂);6、有多种牌号符合FDA相关标准;7、直接粘贴环氧树脂和聚丙烯表面作修饰保护;8、直接热贴合在金属、玻璃、天然纤维表面作修饰保护。
本发明所述的聚烯烃弹性体(POE)指的是熔融温度大于75度、拉伸强度大于15MPa的乙烯-辛烯共聚物。
本发明所述的乙烯三元共聚物指的是乙烯-甲基丙烯酸缩水甘油酯-丙烯酸酯三元共聚物,其具有极佳的相容性,极好的增韧效果;其中所述的丙烯酸酯优选丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸异辛酯中的任一种。本发明所述的乙烯三元共聚物优选杜邦TM PTW,乙烯-甲基丙烯酸缩水甘油酯-丙烯酸甲酯三元共聚物。
本发明所述的选择性部分氢化SBS具有高强度高硬度特性,其主链1,4丁二烯聚合不饱和双键不氢化;1,2丁二烯侧链双键氢化的一类SBS;其具体特征为苯乙烯含量大于60%,邵氏硬度大于70D,熔体流动速率大于2/10min(190℃、2.16kg)。
本发明所述的发泡剂是偶氮二甲酰胺(AC)发泡剂。
本发明所述的交联剂至少包括过氧化二异丙苯(DCP)、双叔丁基过氧化二异丙基苯(BIBP)中的至少一种。
所述EVA发泡材料具有高硬度易粘结特性,适用于EVA发泡鞋底材料。
另一方面,提供一种制备所述EVA发泡材料的方法,包括如下步骤:
步骤1:先将选择性部分氢化SBS、聚烯烃弹性体(POE)、沙林树脂按一定比例经过双螺杆混合,调整螺杆转速为10-30r/s,螺杆每段温150℃-190℃-200℃-200℃-200℃-200℃-190℃-190℃-180℃-170℃,混炼挤出造粒,得到改性备用料;
步骤2:将原料EVA、液态环氧化聚丁二烯树脂、乙烯三元共聚物、步骤1制备的改性备用材料、硬脂酸锌、氧化锌、硬脂酸、纳米碳酸钙混合进行密炼,调整密炼温度为90-100℃,保持4-6min,然后加入发泡剂、交联剂,继续密炼升温,出料温度为105-115℃,密炼结束后进行开炼、造粒,得到高硬度易粘结贴合的EVA料米;
步骤3:将准确称量的高硬度易粘结贴合的EVA料米加入到发泡模具中,经升温发泡,控制温度178-180度,时间280-290秒,然后将发泡材料放入油压模具中进行二次油压,温度178-180度,时间350-360秒,再将模具经水冷却340-350秒,打开模具得到高硬度易粘结贴合的EVA发泡鞋底。
与现有技术相比本发明的有异效果
(1)本发明采用低VA含量的EVA树脂作为主体树脂,通过将其与高熔点POE、选择性部分氢化SBS共混,获得高硬度、高尺寸稳定性的同时,提高了回弹率,并能保持较好的力学性能;沙林树脂的引入,与其他材料发生化学或物理反应,提高了材料的撕裂强度、抗冲击韧性、透光率、抗刮擦性能,改善了表面光泽度和粘结性能,提高了鞋材的剥离强度;液态环氧化聚丁二烯树脂中的环氧基能够与基材反应形成较一般物理相互作用更为强烈的化学键,从而提供优异的粘结性能;乙烯三元共聚物为增韧相容剂,其能够增加EVA、POE与液态环氧化聚丁二烯树脂、沙林树脂的相容性,而且其中的含有的酯基和环氧基反应形成的羟基,能够进一步提升材料的极性,提高免打粗情况下与鞋胶的粘结性,从而获得免打粗情况下优异的粘结性。
(2)本发明所述的高硬度易粘结贴合的EVA发泡材料制作的鞋底在生产过程中无需打粗即可以直接上胶、贴合,省去了鞋底刷胶贴合之前的打粗步骤,工艺简单、省时省力且免去了打粗带来的尘土飞扬。
具体实施方式
下面结合实施例对本发明作进一步的说明。
术语说明:本发明上下文中所用到的原料均从市场上购买,如沙林树脂从美国杜邦公司购买;本发明上下文提到的含量均为质量分数;
实施例1
一种高硬度易粘结贴合的EVA发泡鞋底,其特征在于,所述高硬度易粘结贴合的EVA发泡鞋底由以下原料组成:乙烯-乙酸乙烯酯(EVA)、液态环氧化聚丁二烯树脂、乙烯三元共聚物、沙林树脂、聚烯烃弹性体(POE)、选择性部分氢化材料、AC发泡剂、BIBP交联剂、硬脂酸锌、氧化锌、硬脂酸、纳米碳酸钙,其中各原料的重量份数如下:
所述高硬度易粘结贴合的EVA发泡鞋底的制备方法,包括如下步骤:
步骤1:高硬度易粘结贴合的EVA料米,先将选择性部分氢化SBS、聚烯烃弹性体(POE)、沙林树脂按一定比例经过双螺杆混合,调整螺杆转速为10-30r/s,螺杆每段温150℃-190℃-200℃-200℃-200℃-200℃-190℃-190℃-180℃-170℃,混炼挤出造粒,得到改性备用料。
步骤2:制备高硬度易粘结贴合的EVA料米,先将原料EVA、液态环氧化聚丁二烯树脂、乙烯三元共聚物、改性备用材料、硬脂酸锌、氧化锌、硬脂酸、纳米碳酸钙混合进行密炼,调整密炼温度为90-100℃,保持4-6min,然后加入发泡剂、交联剂,继续密炼升温,出料温度为105-115℃,密炼结束后进行开炼、造粒,得到高硬度易粘结贴合的EVA料米;
步骤3:将准确称量的高硬度易粘结贴合的EVA料米加入到发泡模具中,经升温发泡,控制温度178-180度,时间280-290秒,然后将发泡鞋底放入油压模具中进行二次油压,温度178-180度,时间350-360秒,再将模具经水冷却340-350秒,打开模具得到高硬度易粘结贴合的EVA发泡鞋底。
上述制备得到的高硬度易粘结贴合的EVA发泡鞋底,密度0.254g/cm3、邵氏硬度78C、回弹率46%、永久压缩歪度28%、尺寸收缩0.75%、撕裂强度18N/mm、延伸率222%、拉伸强度3.0MPa、剖层撕裂4.8N/mm、耐黄变测试5级。
实施例2
一种高硬度易粘结贴合的EVA发泡鞋底,其特征在于,所述高硬度易粘结贴合的EVA发泡鞋底由以下原料组成:乙烯-乙酸乙烯酯(EVA)、液态环氧化聚丁二烯树脂、乙烯三元共聚物、沙林树脂、聚烯烃弹性体(POE)、AC发泡剂、DCP交联剂、硬脂酸锌、氧化锌、硬脂酸、纳米碳酸钙,其中各原料的重量份数如下:
所述高硬度易粘结贴合的EVA发泡鞋底的制备方法,包括如下步骤:
步骤1:高硬度易粘结贴合的EVA料米,先将选择性部分氢化SBS、聚烯烃弹性体(POE)、沙林树脂按一定比例经过双螺杆混合,调整螺杆转速为10-30r/s,螺杆每段温150℃-190℃-200℃-200℃-200℃-200℃-190℃-190℃-180℃-170℃,混炼挤出造粒,得到改性备用料。
步骤2:制备高硬度易粘结贴合的EVA料米,先将原料EVA、液态环氧化聚丁二烯树脂、乙烯三元共聚物、改性备用材料、硬脂酸锌、氧化锌、硬脂酸、纳米碳酸钙混合进行密炼,调整密炼温度为90-100℃,保持4-6min,然后加入发泡剂、交联剂,继续密炼升温,出料温度为105-115℃,密炼结束后进行开炼、造粒,得到高硬度易粘结贴合的EVA料米;
步骤3:将准确称量的高硬度易粘结贴合的EVA料米加入到发泡模具中,经升温发泡,控制温度178-180度,时间280-290秒,然后将发泡鞋底放入油压模具中进行二次油压,温度178-180度,时间350-360秒,再将模具经水冷却340-350秒,打开模具得到高硬度易粘结贴合的EVA发泡鞋底。
上述制备得到的高硬度易粘结贴合的EVA发泡鞋底,密度0.262g/cm3、邵氏硬度85、回弹率42%、永久压缩歪度25%、尺寸收缩0.72%、撕裂强度20N/mm、延伸率202%、拉伸强度3.2MPa、剖层撕裂5.0N/mm、耐黄变测试5级。
实施例3
一种高硬度易粘结贴合的EVA发泡鞋底,其特征在于,所述高硬度易粘结贴合的EVA发泡鞋底由以下原料组成:乙烯-乙酸乙烯酯(EVA)、液态环氧化聚丁二烯树脂、乙烯三元共聚物、沙林树脂、聚烯烃弹性体(POE)、AC发泡剂、BIBP交联剂、硬脂酸锌、氧化锌、硬脂酸、纳米碳酸钙,其中各原料的重量份数如下:
所述高硬度易粘结贴合的EVA发泡鞋底的制备方法,包括如下步骤:
步骤1:高硬度易粘结贴合的EVA料米,先将选择性部分氢化SBS、聚烯烃弹性体(POE)、沙林树脂按一定比例经过双螺杆混合,调整螺杆转速为10-30r/s,螺杆每段温150℃-190℃-200℃-200℃-200℃-200℃-190℃-190℃-180℃-170℃,混炼挤出造粒,得到改性备用料。
步骤2:制备高硬度易粘结贴合的EVA料米,先将原料EVA、液态环氧化聚丁二烯树脂、乙烯三元共聚物、改性备用材料、硬脂酸锌、氧化锌、硬脂酸、纳米碳酸钙混合进行密炼,调整密炼温度为90-100℃,保持4-6min,然后加入发泡剂、交联剂,继续密炼升温,出料温度为105-115℃,密炼结束后进行开炼、造粒,得到高硬度易粘结贴合的EVA料米;
步骤3:将准确称量的高硬度易粘结贴合的EVA料米加入到发泡模具中,经升温发泡,控制温度178-180度,时间280-290秒,然后将发泡鞋底放入油压模具中进行二次油压,温度178-180度,时间350-360秒,再将模具经水冷却340-350秒,打开模具得到高硬度易粘结贴合的EVA发泡鞋底。
上述制备得到的高硬度易粘结贴合的EVA发泡鞋底,密度0.272g/cm3、邵氏硬度90、回弹率44%、永久压缩歪度24%、尺寸收缩0.71%、撕裂强度23N/mm、延伸率212%、拉伸强度3.5MPa、剖层撕裂5.1N/mm、耐黄变测试5级。
实施例4
一种高硬度易粘结贴合的EVA发泡鞋底,其特征在于,所述高硬度易粘结贴合的EVA发泡鞋底由以下原料组成:乙烯-乙酸乙烯酯(EVA)、液态环氧化聚丁二烯树脂、乙烯三元共聚物、沙林树脂、聚烯烃弹性体(POE)、AC发泡剂、BIBP交联剂、硬脂酸锌、氧化锌、硬脂酸、纳米碳酸钙,其中各原料的重量份数如下:
所述高硬度易粘结贴合的EVA发泡鞋底的制备方法,包括如下步骤:
步骤1:高硬度易粘结贴合的EVA料米,先将选择性部分氢化SBS、聚烯烃弹性体(POE)、沙林树脂按一定比例经过双螺杆混合,调整螺杆转速为10-30r/s,螺杆每段温150℃-190℃-200℃-200℃-200℃-200℃-190℃-190℃-180℃-170℃,混炼挤出造粒,得到改性备用料。
步骤2:制备高硬度易粘结贴合的EVA料米,先将原料EVA、液态环氧化聚丁二烯树脂、乙烯三元共聚物、改性备用材料、硬脂酸锌、氧化锌、硬脂酸、纳米碳酸钙混合进行密炼,调整密炼温度为90-100℃,保持4-6min,然后加入发泡剂、交联剂,继续密炼升温,出料温度为105-115℃,密炼结束后进行开炼、造粒,得到高硬度易粘结贴合的EVA料米;
步骤3:将准确称量的高硬度易粘结贴合的EVA料米加入到发泡模具中,经升温发泡,控制温度178-180度,时间280-290秒,然后将发泡鞋底放入油压模具中进行二次油压,温度178-180度,时间350-360秒,再将模具经水冷却340-350秒,打开模具得到高硬度易粘结贴合的EVA发泡鞋底。
上述制备得到的高硬度易粘结贴合的EVA发泡鞋底,密度0.278g/cm3、邵氏硬度90、回弹率41%、永久压缩歪度26%、尺寸收缩0.75%、撕裂强度24N/mm、延伸率208%、拉伸强度3.6MPa、剖层撕裂4.6N/mm、耐黄变测试5级。
实施例5
一种高硬度易粘结贴合的EVA发泡鞋底,其特征在于,所述高硬度易粘结贴合的EVA发泡鞋底由以下原料组成:乙烯-乙酸乙烯酯(EVA)、液态环氧化聚丁二烯树脂、乙烯三元共聚物、沙林树脂、聚烯烃弹性体(POE)、AC发泡剂、BIBP交联剂、硬脂酸锌、氧化锌、硬脂酸、纳米碳酸钙,其中各原料的重量份数如下:
所述高硬度易粘结贴合的EVA发泡鞋底的制备方法,包括如下步骤:
步骤1:高硬度易粘结贴合的EVA料米,先将选择性部分氢化SBS、聚烯烃弹性体(POE)、沙林树脂按一定比例经过双螺杆混合,调整螺杆转速为10-30r/s,螺杆每段温150℃-190℃-200℃-200℃-200℃-200℃-190℃-190℃-180℃-170℃,混炼挤出造粒,得到改性备用料。
步骤2:制备高硬度易粘结贴合的EVA料米,先将原料EVA、液态环氧化聚丁二烯树脂、乙烯三元共聚物、改性备用材料、硬脂酸锌、氧化锌、硬脂酸、纳米碳酸钙混合进行密炼,调整密炼温度为90-100℃,保持4-6min,然后加入发泡剂、交联剂,继续密炼升温,出料温度为105-115℃,密炼结束后进行开炼、造粒,得到高硬度易粘结贴合的EVA料米;
步骤3:将准确称量的高硬度易粘结贴合的EVA料米加入到发泡模具中,经升温发泡,控制温度178-180度,时间280-290秒,然后将发泡鞋底放入油压模具中进行二次油压,温度178-180度,时间350-360秒,再将模具经水冷却340-350秒,打开模具得到高硬度易粘结贴合的EVA发泡鞋底。
上述制备得到的高硬度易粘结贴合的EVA发泡鞋底,密度0.278g/cm3、邵氏硬度91、回弹率40%、永久压缩歪度30%、尺寸收缩0.77%、撕裂强度24N/mm、延伸率207%、拉伸强度3.3MPa、剖层撕裂4.2N/mm、耐黄变测试5级。
将上述实施例1-5的数据整理后,得到如下表1(注:邵氏硬度按照HG/T2489-93、GB2411-80测试,回弹率测试采用GT-7042-RE型冲击弹性试验机,永久压缩歪度按照HG/T2876-2009测试,尺寸收缩按照ISO 20873:2001测试,撕裂强度按照GB/T529-2008测试直形试片,延伸率和拉伸强度按照GB/T 528-2009测试,剖层撕裂按照GB/T3903.29-2008测试,耐黄变测试按照HG/T 3689-2001测试),粘合强度采用QB/T 2886-2007测试,测试结果如下:
表1:实施例1-5制备的防滑EVA鞋底的性能参数对照表
综上所述,按照本发明所述的高硬度易粘结贴合的EVA发泡鞋底的制备方法,能够制得具有高硬度、优良的抗拉强度和抗撕强度,且可以免去打粗步骤直接刷胶,具有易于粘结贴合、粘结强度高、使用寿命长等特点的EVA发泡鞋底。
以上所述实施方式,只是本发明的较佳实施方式,并非来限制本发明实施范围,故凡依本发明申请专利范围所述的构造、特征及原理所做的等效变化或修饰,均应包括本发明专利申请范围内。
Claims (9)
1. 一种EVA发泡材料,其特征在于,按重量份数计,其包含如下组分 :
EVA 45-60份
液态环氧化聚丁二烯树脂 5-10份
沙林树脂 2-5份
聚烯烃弹性体 10-20份
乙烯三元共聚物 5-15份
选择性部分氢化SBS 5-13份
发泡剂 2.8-3.4份
交联剂 1.6-1.8份
氧化锌 0.5-3份
硬脂酸锌 2.0-2.2份
硬脂酸 1.0-1.3份
纳米碳酸钙 2-3份;
所述乙烯三元共聚物为乙烯-甲基丙烯酸缩水甘油酯-丙烯酸酯三元共聚物;所述的选择性部分氢化SBS其主链1,4丁二烯聚合不饱和双键不氢化;1,2丁二烯侧链双键氢化的一类SBS;其具体特征为苯乙烯含量大于60%,邵氏硬度大于70D,熔体流动速率大于2g/10min。
2.一种EVA发泡材料,其特征在于,组成所述EVA发泡材料的各原料的重量份数如下 :
EVA 45-60份
液态环氧化聚丁二烯树脂 5-10份
沙林树脂 2-5份
聚烯烃弹性体 10-20份
乙烯三元共聚物 5-15份
选择性部分氢化SBS 5-13份
发泡剂 2.8-3.4份
交联剂 1.6-1.8份
氧化锌 0.5-3份
硬脂酸锌 2.0-2.2份
硬脂酸 1.0-1.3份
纳米碳酸钙 2-3份;
所述乙烯三元共聚物为乙烯-甲基丙烯酸缩水甘油酯-丙烯酸酯三元共聚物;所述的选择性部分氢化SBS其主链1,4丁二烯聚合不饱和双键不氢化;1,2丁二烯侧链双键氢化的一类SBS;其具体特征为苯乙烯含量大于60%,邵氏硬度大于70D,熔体流动速率大于2g/10min。
3. 根据权利要求1或2所述EVA发泡材料,其特征在于,组成所述EVA发泡材料的各原料的重量份数如下 :
EVA 50份
液态环氧化聚丁二烯树脂 8份
沙林树脂 3份
聚烯烃弹性体 14份
乙烯三元共聚物 12份
选择性部分氢化SBS 9份
发泡剂 3.2份
交联剂 1.8份
氧化锌 1.3份
硬脂酸锌 2.2份
硬脂酸 1.3份
纳米碳酸钙 2.8份。
4.根据权利要求1所述EVA发泡材料,其特征在于,所述的EVA中VA含量为5-10%。
5.根据权利要求1所述EVA发泡材料,其特征在于,所述沙林树脂为乙烯-(甲基)丙烯酸锌盐、钠盐或锂盐的离子键聚合体,所述的液态环氧化聚丁二烯树脂分子量2000左右,密度0.9012g/cm3,环氧基的含量为7%~8%,羟基的含量为2%~3%,碘值为180。
6.根据权利要求1所述EVA发泡材料,其特征在于,所述的聚烯烃弹性体为熔融温度大于75度、拉伸强度大于15MPa的乙烯-辛烯共聚物。
7. 根据权利要求1所述EVA发泡材料,其特征在于,所述的乙烯三元共聚物选自杜邦™Elvaloy®PTW,乙烯-甲基丙烯酸缩水甘油酯-丙烯酸甲酯三元共聚物。
8.权利要求1-7任一所述EVA发泡材料在发泡鞋底中的应用。
9. 一种制备权利要求1至7 任一所述EVA发泡材料的方法,其特征在于,包括如下步骤:
步骤1:先将选择性部分氢化SBS、聚烯烃弹性体、沙林树脂按比例经过双螺杆混合,调整螺杆转速为10-30r/s,螺杆每段温150℃-190℃-200℃-200℃-200℃-200℃-190℃-190℃-180℃-170℃,混炼挤出造粒,得到改性备用料;
步骤2:将原料 EVA、液态环氧化聚丁二烯树脂、乙烯三元共聚物、步骤1制备的改性备用材料、硬脂酸锌、氧化锌、硬脂酸、纳米碳酸钙混合进行密炼,调整密炼温度为90-100℃,保持 4-6min,然后加入发泡剂、交联剂,继续密炼升温,出料温度为105-115℃,密炼结束后进行开炼、造粒,得到高硬度易粘结贴合的EVA 料米;
步骤 3:将准确称量的高硬度易粘结贴合的EVA料米加入到发泡模具中,经升温发泡,控制温度178-180度,时间280-290秒,然后将发泡材料放入油压模具中进行二次油压,温度178-180度,时间350-360秒,再将模具经水冷却340-350秒,打开模具得到高硬度易粘结贴合的EVA发泡鞋底。
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