CN114426754A - 一种人造革用弹性体材料及其用于制备热塑性人造革面料的方法 - Google Patents
一种人造革用弹性体材料及其用于制备热塑性人造革面料的方法 Download PDFInfo
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- CN114426754A CN114426754A CN202010984722.0A CN202010984722A CN114426754A CN 114426754 A CN114426754 A CN 114426754A CN 202010984722 A CN202010984722 A CN 202010984722A CN 114426754 A CN114426754 A CN 114426754A
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- artificial leather
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- 239000002649 leather substitute Substances 0.000 title claims abstract description 61
- 239000004744 fabric Substances 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 35
- 229920001971 elastomer Polymers 0.000 title claims abstract description 30
- 239000000806 elastomer Substances 0.000 title claims abstract description 30
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 14
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 13
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims abstract description 21
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 19
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 239000004088 foaming agent Substances 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 239000011256 inorganic filler Substances 0.000 claims abstract description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 10
- 238000005187 foaming Methods 0.000 claims description 13
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000008187 granular material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 229920003184 Kraton D1100 SBS Polymers 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 238000004381 surface treatment Methods 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
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- -1 (2, 4-di-tert-butylphenyl) phosphite triester Chemical class 0.000 claims description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 2
- 239000004156 Azodicarbonamide Substances 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
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Abstract
本发明公开了一种人造革用弹性体材料及其用于制备热塑性人造革面料的方法。该人造革用弹性体材料是以热塑性弹性体材料(SEBS)为基料,加入EVA树脂或TPU树脂、少量无机填料,适量交联剂、发泡剂、促进剂、抗氧剂、润滑剂等助剂,制备的热塑性人造革面料手感好、耐低温性能优良,最低可耐‑60℃。
Description
技术领域
本发明涉及一种人造革用弹性体材料,具体涉及一种人造革用SEBS热塑性弹性体材料及制备热塑性人造革面料的方法,属于高分子复合材料技术领域。
背景技术
人造革是一种外观、手感似皮革并可代替其使用的塑料制品。通常以织物为底基,涂覆合成树脂及各种塑料添加制成。主要有PVC人造革、PU人造革和PU合成革三类。
上世纪八十年代,昂贵的皮衣皮料一般人消费不起,应市场需求,仿冒皮革的人造革一度流行起来,被广泛应用于制衣、制包。这样仿冒皮革的人造革衣服、包包一度充斥街头,满足了人们穿皮戴皮的愿望。与皮革相比,人造革易于老化磨损,因含有大量化学原料而对人身健康产生危害,而且用其制作的衣包因不耐用而逐渐失去市场,直至被其他原料取代。现有的PVC人造革虽然使用环保型增塑剂,但是还是含有增塑剂,而且低温发硬发脆;聚氨酯人造革低温性能、抗老化性能不好。中国专利“一种热塑型弹性体人造革及其制备方法”(申请号为201711259492.6)介绍了一种SEBS弹性体人造革的制备方法,但是其需要通过接枝材料作为相容剂,才能使SEBS弹性体材料与基布能较好贴合。
发明内容
针对现有技术中人造革材料存在的缺陷,本发明的第一个目的旨在提供一种热塑性弹性体人造革材料,该人造革用弹性体材料加工的面料具有优异的质感和触感及耐低温性能,不含任何增塑剂,安全无毒,符合绿色环保要求。
本发明的第二个目的旨在提供上述弹性体人造革材料制备方法,该方法操作简单、成本低,满足工业生产要求。
为了实现上述技术目的,本发明提供了一种人造革用弹性体材料,其原料包含以下质量份组分:SEBS 50~90份;树脂EVA或树脂TPU 10~50份;无机填料1~10份;交联剂0.1~1.0份;促进剂0.2~1.0份;发泡剂1.0~5.0份;抗氧剂0.2~1.0份;所述SEBS由线型苯乙烯-丁二烯-苯乙烯三嵌段共聚物氢化得到;
所述线型苯乙烯-丁二烯-苯乙烯三嵌段共聚物的分子量为4~10万,丁二烯的1,2-结构含量为50~70%,苯乙烯与丁二烯嵌段质量比为20~50:80~50。
本发明技术方案关键在于采用了一种特殊结构的SEBS,其1,2-结构含量高达68~70%,比现有技术常规SEBS的1,2-结构含量高35%左右,而且苯乙烯含量低、分子量低,这样的SEBS本身具有一定的极性,硬度低,赋予了人造革面料质感、手感好的特点。
作为一个优选的方案,SEBS乙烯基的氢化度≥97%。
本发明最优选的热塑性弹性体人造革材料由以下质量份组分原料组成:SEBS 80~90份;树脂EVA或TPU 10~20份;无机填料2~4份;交联剂0.5~1份;促进剂0.3~0.7份;发泡剂1~3份;抗氧剂0.3~0.5份。
作为一个优选的方案,所述树脂EVA的VA含量为15~30%。VA含量过高会引起材料表面发粘,VA含量过低是人造革弹性变差。
作为一个优选的方案,所述树脂TPU硬度为70~80A。TPU硬度过高会影响材料的硬度,TPU硬度越低价格越高,综合性价比一般选择硬度在70~80A,TPU树脂为常见的聚酯型或聚醚型TPU树脂。
作为一个优选的方案,所述无机填料为碳酸钙、滑石粉、白炭黑中至少一种。
作为一个优选的方案,所述交联剂为过氧化二异丙苯(DCP)、双叔丁基过氧化二异丙基苯(BIBP)中至少一种。
作为一个优选的方案,所述发泡剂为偶氮二甲酰胺、发泡剂H、ADC、DNTA、DAB、AIBN中至少一种。优选的发泡剂为能在185~200℃温度范围内释放小分子气体化合物的物质。
作为一个优选的方案,所述促进剂剂为氧化锌和/或硬脂酸锌。
作为一个优选的方案,所述抗氧剂由酚类抗氧剂和亚磷酸酯类抗氧剂按1:0.8~1.2组成。最优选的质量比为1:1。通过使用复合矿氧剂能够大大提高热塑性人造革面料的抗老化性能。
作为一个优选的方案,所述酚类抗氧剂为β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇酯,所述亚磷酸酯类抗氧剂为(2,4-二叔丁基苯基)亚磷酸三酯。
本发明还提供了一种人造革用弹性体材料用于制备热塑性人造革面料的方法,包括以下步骤:
1)将SEBS、树脂EVA或树脂TPU、促进剂、无机填料、抗氧剂混合挤压造粒;
2)将粒料与交联剂及发泡剂经过密炼后,挤压成片,片料与基布贴合,得到弹性体基布;
3)弹性体基布通过微发泡及表面处理,即得。
作为一个优选的方案,所述造粒的温度为185~200℃。
作为一个优选的方案,所述密炼的时间为3~5分钟。
作为一个优选的方案,所述发泡的温度为200~220℃,时间为300~400秒。
本发明的人造革用弹性体材料人造革面料的制备方法,包含如下步骤:
(1)将(SEBS)氢化苯乙烯-丁二烯-苯乙烯三嵌段共聚物、(EVA)乙烯-醋酸乙烯共聚物或聚氨酯(TPU)、无机填料、促进剂、抗氧剂称量好后,混合均匀后到双螺杆中造粒,造粒温度为185~200℃。
(2)将上述粒料加入称量好的交联剂、发泡剂加入到密炼机中密炼3~5分钟后进入双棍炼胶机成片,再通过牵引机送到三辊压延机与基布贴合;
(3)贴合好的弹性体基布,通过牵引机送到发泡炉进行微发泡,发泡温度为200~220℃,发泡时间为300~400秒;
(4)发泡后的人造革弹性体经过表面处理后进行性能检测,各项性能合格后即得到热塑性人造革面料。
相对现有技术,本发明技术方案带来的有益技术效果:
本发明使用特殊分子结构的氢化丁二烯苯乙烯共聚物为人造革基料,制备的人造革面料产品弹性好,具有类似CR、SBR或PU发泡材的柔软触感;加工更加简单,且不具异味或吐霜之困扰,不含任何增塑剂,耐低温性能优良,可发泡,表面可做成高光或哑光,边角废料可完全回收利用,可广泛应用于广泛应用于箱包面料、鞋面料、服装面料、沙发面料、汽车座椅面料等。
具体实施方式
以下实施例旨在进一步说明本发明内容,而不是限制本发明权利要求的保护范围。
下面先对本发明人造革材料组成物的基本组分加以说明,详情见表1。
表1
实施例1
SEBS氢化苯乙烯-丁二烯嵌段共聚物合成:
向经氮气净化的5L不锈钢聚合釜中加入3升非极性混合液,其中90%环己烷、10%的已烷(以占混合液的质量百分比计),4mmol四氢呋喃,聚合釜升温到40~50℃,加入引发剂正丁基锂36ml(正丁基锂浓度0.4M),搅拌3分钟,加入36克苯乙烯进行聚合,反应30分钟后,将8mL四甲基乙二胺和288克丁二烯一起混合均匀后加入到聚合釜进行聚合,聚合温度控制在55℃以下,反应120分钟,加入36克苯乙烯进行聚合,反应时间为30分钟,反应完成后加入基于聚合物重量计0.2(wt)%的抗氧剂1076和0.4(wt)%的抗氧剂168,搅拌5分钟,最后将产物加入蒸汽和水的的混合物中,溶剂被蒸发,聚合物则以固体状态离析出来。产品通过核磁共振碳谱测试1,2-结构为68.5%,GPC测试聚合物分子量,分子量49500(Mn)。
实施例2-5、对比例1-2
SEBS用于制备热塑性人造革料:
(1)将(SEBS)氢化苯乙烯-丁二烯-苯乙烯三嵌段共聚物、(EVA)乙烯-醋酸乙烯共聚物或聚氨酯(TPU)、无机填料、促进剂、抗氧剂称量好后,混合均匀后到双螺杆中造粒,造粒温度约为190℃。
(2)将上述粒料加入称量好的交联剂、发泡剂加入到密炼机中密炼4分钟后进入双棍炼胶机制成约0.12mm薄片,再通过牵引机送到三辊压延机与基布贴合;
(3)贴合好的弹性体基布,通过牵引机送到发泡炉进行微发泡,发泡温度约为210℃,发泡时间约为350秒;
(4)发泡后的人造革弹性体经过表面处理后进行性能检测,各项性能合格后即得到热塑性人造革面料。
表1实施例2-5
实施例2性能检测结果
实施例3性能检测结果
实施例4性能检测结果
实施例5性能检测结果
从实施例可知,实施例4和实施例5的性能优于实施例2和实施例3。说明配方加入TPU的效果比加入EVA的效果要好,因为TPU本身是一种热塑性弹性体,EVA性能更偏向于塑料。
对比例1加工流动性太差,无法在双螺杆机中造粒。对比例2加入32#白油后,虽然加工没有问题,但材料表面发粘,手感差,达不到人造革要求。
Claims (13)
1.一种人造革用弹性体材料,其特征在于:原料包含以下质量份组分:
SEBS 50~90份;
树脂EVA或树脂TPU 15~50份;
无机填料1~10份;
交联剂0.1~1.0份;
促进剂0.2~1.0份;
发泡剂1.0~5.0份;
抗氧剂0.2~1.0份;
所述SEBS由线型苯乙烯-丁二烯-苯乙烯三嵌段共聚物氢化得到;
所述线型苯乙烯-丁二烯-苯乙烯三嵌段共聚物的分子量为4~10万,丁二烯的1,2-结构含量为50~70%,苯乙烯与丁二烯嵌段质量比为20~50:80~50。
2.根据权利要求1所述的一种人造革用弹性体材料,其特征在于:所述树脂EVA的VA含量为15~30%。
3.根据权利要求1所述的一种人造革用弹性体材料,其特征在于:所述树脂TPU硬度为70~80A。
4.根据权利要求1所述的一种人造革用弹性体材料,其特征在于:所述无机填料为碳酸钙、滑石粉、白炭黑中至少一种。
5.根据权利要求1所述的一种人造革用弹性体材料,其特征在于:所述交联剂为过氧化二异丙苯、双叔丁基过氧化二异丙基苯中至少一种。
6.根据权利要求1所述的一种人造革用弹性体材料,其特征在于:所述发泡剂为偶氮二甲酰胺、发泡剂H、ADC、DNTA、DAB、AIBN中至少一种。
7.根据权利要求1所述的一种人造革用弹性体材料,其特征在于:所述促进剂剂为氧化锌和/或硬脂酸锌。
8.根据权利要求1所述的一种人造革用弹性体材料,其特征在于:所述抗氧剂由酚类抗氧剂和亚磷酸酯类抗氧剂按1:0.8~1.2组成。
9.根据权利要求8所述的一种人造革用弹性体材料,其特征在于:所述酚类抗氧剂为β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇酯,所述亚磷酸酯类抗氧剂为(2,4-二叔丁基苯基)亚磷酸三酯。
10.权利要求1~9任一项所述的一种人造革用弹性体材料用于制备热塑性人造革面料的方法,其特征在于:包括以下步骤:
1)将SEBS、树脂EVA或树脂TPU、促进剂、无机填料、抗氧剂混合挤压造粒;
2)将粒料与交联剂及发泡剂经过密炼后,挤压成片,片料与基布贴合,得到弹性体基布;
3)弹性体基布通过微发泡及表面处理,即得。
11.根据权利要求10所述的一种人造革用弹性体材料用于制备热塑性人造革面料的方法,其特征在于:所述造粒的温度为185~200℃。
12.根据权利要求10所述的一种人造革用弹性体材料用于制备热塑性人造革面料的方法,其特征在于:所述密炼的时间为3~5分钟。
13.根据权利要求10所述的一种人造革用弹性体材料用于制备热塑性人造革面料的方法,其特征在于:所述发泡的温度为200~220℃,时间为300~400秒。
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