CN112646265A - 一种耐低温eva超临界发泡复合材料及其制备方法 - Google Patents
一种耐低温eva超临界发泡复合材料及其制备方法 Download PDFInfo
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- 238000005187 foaming Methods 0.000 title claims abstract description 85
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- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 124
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 123
- -1 polysiloxane Polymers 0.000 claims abstract description 40
- 229920001971 elastomer Polymers 0.000 claims abstract description 15
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 15
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 15
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
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- 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 7
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- 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 5
- 229910021485 fumed silica Inorganic materials 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
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- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 4
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- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
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- 239000006260 foam Substances 0.000 abstract 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 95
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
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- AXWJKQDGIVWVEW-UHFFFAOYSA-N 2-(dimethylamino)butanedioic acid Chemical compound CN(C)C(C(O)=O)CC(O)=O AXWJKQDGIVWVEW-UHFFFAOYSA-N 0.000 description 1
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- 239000004088 foaming agent Substances 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开一种耐低温EVA超临界发泡复合材料及其制备方法，所述复合材料按重量计，包括以下成分：乙烯‑乙酸乙烯酯共聚物20~60份、弹性体10~50份，反应性聚硅氧烷10~40份、交联剂0.5~12份、成核剂0.5~1.5份和填充剂0~20份。本发明的耐低温EVA超临界发泡复合材料发泡效果好，发泡倍率高，泡孔均匀且大小可控。以该耐低温EVA超临界发泡复合材料作为中底材料所制作的鞋材可满足成品鞋对轻质、高回弹、低硬度和低压缩性能的要求，同时可解决鞋底材料在低温环境中发硬，易磨和低寿命等缺点，提高鞋的性能，制备工艺过程环保无污染，具有较大价值。
Description
技术领域
本发明涉及发泡鞋用材料领域，具体涉及的是一种耐低温EVA超临界发泡复合材料及其制备方法。
背景技术
在鞋材料中，中底是鞋子底部位于鞋垫和大底之间较厚的部分。中底的作用是提供稳定性、缓冲和回弹、吸收运动中产生的冲击力，在运动中提供保护和比较温和的脚感，是减震的主要角色。因此，中底是鞋材的核心部分。乙烯-醋酸乙烯共聚物（EVA）具有很好的可塑性、弹性和可加工性，并且发泡后的材料具有密度小、力学性能好、易着色等优点，是传统的中底材料。但在特殊的场合下（比如高频受压、低温等）要求有更好的回弹性，而通用EVA发泡材料的弹性不能满足要求，亟需开发出轻质、高弹EVA 发泡材料，以提高对回弹性能有特殊要求的鞋配件的弹性。目前一般通过橡塑改性技术引入非极性的弹性体可以有效地改善鞋底的弹性，然而其轻质性、低温、加工性能跟高端鞋材的性能需求仍有一定距离。同时，目前EVA发泡通常采用化学发泡的方法，而化学发泡一般采用化学交联剂和发泡剂，不仅使发泡EVA材料有残余气味，而且产生环保问题。因此，开发一种兼具轻质、高弹和耐低温等特性的EVA发泡鞋材，具有重要的应用价值和实际意义。
目前，已有部分涉及到了EVA超临界发泡的专利（丁尤权，丁星懿等，一种PLA/EVA超临界发泡复合材料及其制备方法，CN 111393812A；丁尤权，丁星懿等，一种TPU/EVA超临界发泡复合材料及其制备方法，CN110724375A；甘舸，乔志龙等，一种EVA/TPU超临界发泡复合鞋用材料及其制备方法，CN111763370A；甘舸，乔志龙等，一种EVA/PEBAX超临界发泡复合鞋用材料及其制备方法，CN111875872A等），然而，并没有涉及到以EVA为主体材质的耐低温鞋材的制备及性能，同时，以EVA为主材的超临界发泡仍有发泡效果不佳、发泡结构难以控制、发泡时间长等问题。
发明内容
基于以上情况，本发明的目的在于提供一种耐低温EVA超临界发泡复合材料及其制备方法，所述方法不仅工艺简单、环保，同时制作的EVA超临界发泡复合材料具备轻质、高弹、耐低温等性能，从而具有重要的应用价值和实际意义。
为了达成上述目的，本发明的解决方案是：
一种耐低温EVA超临界发泡复合材料，其组成（以重量份计）：乙烯-乙酸乙烯酯共聚物20~60份、弹性体10~50份，马来酸酐接枝改性剂5~20份、反应性聚硅氧烷10~20份、交联剂0.5~12份、成核剂0.5~1.5份和填充剂0~20份。
优选地，所述乙烯-乙酸乙烯酯共聚物为25~50份，所述弹性体为20~40份，所述马来酸酐接枝改性剂为8~20份、所述反应性聚硅氧烷为15~30份，所述交联剂为1~10份，所述成核剂为0.5~8份，所述填充剂为5~15份。
所述弹性体为有机硅橡胶、三元乙丙橡胶（EPDM）、乙烯辛烯共聚物（POE）和热塑性聚氨酯弹性体（TPU）中的一种或几种组合。
所述马来酸酐接枝改性剂为马来酸酐接枝聚乙烯、马来酸酐接枝聚丙烯和马来酸酐接枝EVA中的一种或几种的组合。
所述反应性聚硅氧烷为烯丙基封端聚二甲基硅氧烷、烯丙基封端聚甲基苯基硅氧烷、丙烯酸封端聚二甲基硅氧烷、丙烯酸封端聚甲基苯基硅氧烷、聚甲基乙烯基硅氧烷和聚甲基苯基乙烯基硅氧烷中的一种或几种的组合；所述的反应性聚硅氧烷分子量为500~100000 g/mol。
所述的交联剂为过氧化二异丙苯（DCP）、双叔丁基过氧异丙基苯（BIPB）、2, 5-二甲基-2, 5-双(过氧化叔丁基)己烷（DF-101）、过氧化(2-乙基己基)碳酸叔戊酯（TAEC）中一种或几种的组合。
所述成核剂为纳米碳酸钙、纳米氧化锌和纳米氧化铝中一种或几种的组合。
所述填充剂为滑石粉、硫酸钡、二氧化钛、贝母、高岭土、碳酸钙、硅微粉或气相二氧化硅中一种或几种的组合；
本发明还提供了所述的耐低温EVA超临界发泡复合材料的制备方法，包括以下步骤：
（1）称取相应量的各组分；
（2）将步骤（1）中称取好的EVA、弹性体、马来酸酐接枝改性剂、反应性聚硅氧烷和填充剂，在100~120℃温度下，通过密炼机混炼10~20min；然后加入交联剂和成核剂，在120~140℃温度下继续密炼至各组分混合均匀，获得EVA共混物；
（3）用压片机将步骤（2）中EVA共混物压制成片材，然后裁切成EVA共混物片材；
（4）将步骤（3）中的EVA共混物片材放入超临界发泡釜中发泡，气体饱和后泄压试片取出，裁样，即得所述耐低温EVA超临界发泡复合材料。
所述气体为超临界N2；所述发泡釜的压力为10-20MPa；所述发泡釜的温度为110-140℃；所述气体饱和的时间为2-5h；所述泄压的时间为10-30s。
采用上述技术方案后，本发明制备的耐低温EVA超临界发泡复合材料，具有以下有益效果：1）由于加入反应性聚硅氧烷，所制得的EVA复合材料具有良好的耐低温性能；2）在良好耐低温的前提下，加入了一定量的弹性体，与交联后的反应性聚硅氧烷构成交错的聚合物网络结构，可获得具备超高回弹、高韧性等高性能EVA发泡复合材料；3）采用超临界发泡的方法，制备得到的EVA发泡复合材料气孔均匀，孔径可控，材料无异味，制备过程环保；4）以该耐低温EVA超临界发泡复合材料作为中底材料所制作的鞋材可满足成品鞋对轻质、高回弹、低硬度和低压缩性能的要求，同时可解决鞋底材料在低温环境中发硬，易磨和低寿命等缺点，提高鞋的性能，制备工艺过程环保无污染，具有较大价值。具体实施方式
为了进一步解释本发明的技术方案，下面通过具体实施例来对本发明进行详细阐述。
实施例1
1. EVA共混物
VA含量为30%的EVA 25份、乙烯辛烯共聚物（POE）15份，马来酸酐接枝EVA 12份，分子量为2000 g/mol烯丙基封端聚二甲基硅氧烷15份，过氧化二异丙苯1份，纳米氧化锌1.5份和滑石粉10份。
2. 超临界发泡EVA复合材料的制备
1）以重量计，称取上述各组分；
2）将步骤1）中称取好的EVA、POE、马来酸酐接枝EVA、分子量为2000 g/mol烯丙基封端聚二甲基硅氧烷和滑石粉，在110℃温度下，通过密炼机混炼12min；然后加入过氧化二异丙苯和纳米氧化锌，在120℃温度下继续密炼至各组分混合均匀，获得EVA共混物；
3）用压片机将步骤2）中EVA共混物压制成片材，然后裁切成片；
4）将步骤3）中的EVA共混物片材放入超临界发泡釜中发泡，气体饱和后泄压试片取出，裁样，即得耐低温EVA超临界发泡复合材料。其中气体为超临界N2，发泡釜的压力为15MPa，发泡釜的温度为120℃，气体饱和的时间为2.5h，泄压的时间为15s。
实施例2
1. EVA共混物
VA含量为25%的EVA 30份、TPU 12份，马来酸酐接枝聚乙烯 15份，分子量为5000g/mol丙烯酸封端聚二甲基硅氧烷20份，双叔丁基过氧异丙基苯（BIPB）1.5份，纳米氧化铝1.5份和碳酸钙10份。
2. 超临界发泡EVA复合材料的制备
1）以重量计，称取上述各组分；
2）将步骤1）中称取好的EVA、TPU、马来酸酐接枝聚乙烯、分子量为5000 g/mol丙烯酸封端聚二甲基硅氧烷和碳酸钙，在120℃温度下，通过密炼机混炼15min；然后加入BIPB和纳米氧化铝，在140℃温度下继续密炼至各组分混合均匀，获得EVA共混物；
3）用压片机将步骤2）中EVA共混物压制成片材，然后裁切成片；
4）将步骤3）中的EVA共混物片材放入超临界发泡釜中发泡，气体饱和后泄压试片取出，裁样，即得所述一种耐低温EVA超临界发泡复合材料。其中气体为超临界N2，发泡釜的压力为18 MPa，发泡釜的温度为130℃，气体饱和的时间为3.5h，泄压的时间为20s。
实施例3
1. EVA共混物
VA含量为27.5%的EVA 35份、三元乙丙橡胶（EPDM）15份，马来酸酐接枝聚乙烯 20份，分子量为1000 g/mol丙烯酸封端聚甲基苯基硅氧烷20份，双叔丁基过氧异丙基苯（BIPB）1.5份，纳米碳酸钙2份和二氧化钛12份。
2. 超临界发泡EVA复合材料的制备
1）以重量计，称取上述各组分；
2）将步骤1）中称取好的EVA、EPDM、马来酸酐接枝聚乙烯、分子量为1000 g/mol丙烯酸封端聚甲基苯基硅氧烷和二氧化钛，在115℃温度下，通过密炼机混炼12 min；然后加入BIPB和纳米碳酸钙，在135℃温度下继续密炼至各组分混合均匀，获得EVA共混物；
3）用压片机将步骤2）中EVA共混物压制成片材，然后裁切成片；
4）将步骤3）中的EVA共混物片材放入超临界发泡釜中发泡，气体饱和后泄压试片取出，裁样，即得所述一种耐低温EVA超临界发泡复合材料。其中气体为超临界N2，发泡釜的压力为20 MPa，发泡釜的温度为140℃，气体饱和的时间为3 h，泄压的时间为18 s。
实施例4
1. EVA共混物
VA含量为32.5%的EVA 40份、甲基乙烯基硅橡胶12份，马来酸酐接枝聚丙烯 18份，分子量为10000 g/mol聚甲基苯基乙烯基硅氧烷18份，双叔丁基过氧异丙基苯（BIPB）1.5份，纳米氧化锌1.5份和气相二氧化硅10份。
2. 超临界发泡EVA复合材料的制备
1）以重量计，称取上述各组分；
2）将步骤1）中称取好的EVA、甲基乙烯基硅橡胶、马来酸酐接枝聚丙烯、分子量为10000 g/mol聚甲基苯基乙烯基硅氧烷和气相二氧化硅，在120℃温度下，通过密炼机混炼15 min；然后加入BIPB和纳米氧化锌，在140℃温度下继续密炼至各组分混合均匀，获得EVA共混物；
3）用压片机将步骤2）中EVA共混物压制成片材，然后裁切成片；
4）将步骤3）中的EVA共混物片材放入超临界发泡釜中发泡，气体饱和后泄压试片取出，裁样，即得所述一种耐低温EVA超临界发泡复合材料。其中气体为超临界N2，发泡釜的压力为18 MPa，发泡釜的温度为140℃，气体饱和的时间为4 h，泄压的时间为20 s。
实施例5
1. EVA共混物
VA含量为25%的EVA 35份、甲基乙烯基硅橡胶6份，TPU6份，马来酸酐接枝EVA 10份，马来酸酐接枝聚乙烯5份，分子量为10000 g/mol丙烯酸封端聚甲基苯基硅氧烷10份，分子量为5000 g/mol聚甲基苯基乙烯基硅氧烷5份，双叔丁基过氧异丙基苯（BIPB）2份，纳米氧化锌1.5份，气相二氧化硅5份，滑石粉5份和贝母5份。
2. 超临界发泡EVA复合材料的制备
1）以重量计，称取上述各组分；
2）将步骤1）中称取好的EVA、甲基乙烯基硅橡胶、TPU、马来酸酐接枝EVA、马来酸酐接枝聚乙烯、分子量为10000 g/mol丙烯酸封端聚甲基苯基硅氧烷、分子量为5000 g/mol聚甲基苯基乙烯基硅氧烷、气相二氧化硅、滑石粉和贝母，在120℃温度下，通过密炼机混炼20min；然后加入BIPB和纳米氧化锌，在135℃温度下继续密炼至各组分混合均匀，获得EVA共混物；
3）用压片机将步骤2）中EVA共混物压制成片材，然后裁切成片；
4）将步骤3）中的EVA共混物片材放入超临界发泡釜中发泡，气体饱和后泄压试片取出，裁样，即得所述一种耐低温EVA超临界发泡复合材料。其中气体为超临界N2，发泡釜的压力为20 MPa，发泡釜的温度为140℃，气体饱和的时间为4.5 h，泄压的时间为20 s。
3. 所得耐低温超临界EVA发泡复合材料性能
将所得耐低温超临界EVA发泡复合材料试片进行性能测试，其硬度为42（Type C），密度为0.14g/cm3，热收缩为0.6%，拉伸强度为2.5MPa，室温下断裂伸长率为300%、压缩歪变形为27%，在-25℃温度下断裂伸长率为250%，压缩歪变行为25%。
对比例1
1. EVA组合物
VA含量为25%的EVA 35份，POE 15份，TPU 6份，马来酸酐接枝EVA 10份，马来酸酐接枝聚乙烯5份，双叔丁基过氧异丙基苯（BIPB）2份，纳米氧化锌1.5份和滑石粉15份。
2. EVA组合物的制备
1）按重量计，称取上述各组分；
2）将步骤1中称取好的上述各组分混合均匀后，经密炼机120度下混炼15分钟，再经造粒机造粒后，得该EVA发泡组合物。
3. 所得EVA发泡鞋材性能
将上述制得的EVA发泡试片进行性能测试，其硬度为48（Type C），密度为0.18g/cm3，热收缩为0.6%，拉伸强度为2.2MPa，室温下断裂伸长率为270%、压缩歪变形为24%，在-25℃温度下断裂伸长率为120%，压缩歪变行为15%。
将实施例5和对比例1进行对比，可以看出，在EVA配方体系中引入了反应性的聚硅氧烷，可以与EVA发生交联。由于聚硅氧烷中Si-O链具有较大柔性和稳定性，使EVA具有更优异的弹性和耐低温性能。同时，采用超临界发泡的方法，使得EVA发泡气孔均匀，孔径可控，使材料更轻质，无异味，制备过程环保。因而，本发明中所述的超临界发泡EVA复合材料具有更良好的轻质性、弹性和耐低温性。
上述实施例并非限定本发明的产品形态和式样，任何所属技术领域的普通技术人员对其所做的适当变化或修饰，皆应视为不脱离本发明的专利范畴。
Claims (10)
1.一种耐低温EVA超临界发泡复合材料，其特征在于：其由以下重量份的原料制备而成：乙烯-乙酸乙烯酯共聚物20~60份、弹性体10~50份，马来酸酐接枝改性剂5~20份、反应性聚硅氧烷10~20份、交联剂0.5~12份、成核剂0.5~1.5份和填充剂0~20份。
2.根据权利要求1所述的一种耐低温EVA超临界发泡复合材料，其特征在于：所述乙烯-乙酸乙烯酯共聚物为25~50份，所述弹性体为20~40份，所述马来酸酐接枝改性剂为8~20份、所述反应性聚硅氧烷为15~30份，所述交联剂为1~10份，所述成核剂为0.5~8份，所述填充剂为5~15份。
3.根据权利要求1所述的一种耐低温EVA超临界发泡复合材料，其特征在于：所述乙烯-乙酸乙烯酯共聚物为乙酸乙烯含量在20~50%的乙烯-乙酸乙烯共聚物中的一种或几种的组合。
4.根据权利要求1所述的一种耐低温EVA超临界发泡复合材料，其特征在于：所述弹性体为有机硅橡胶、三元乙丙橡胶、乙烯辛烯共聚物和热塑性聚氨酯弹性体中的一种或几种组合。
5.根据权利要求1所述的一种耐低温EVA超临界发泡复合材料，其特征在于：所述马来酸酐接枝改性剂为马来酸酐接枝聚乙烯、马来酸酐接枝聚丙烯和马来酸酐接枝EVA中的一种或几种的组合。
6.根据权利要求1所述的一种耐低温EVA超临界发泡复合材料，其特征在于：所述反应性聚硅氧烷为烯丙基封端聚二甲基硅氧烷、烯丙基封端聚甲基苯基硅氧烷、丙烯酸封端聚二甲基硅氧烷、丙烯酸封端聚甲基苯基硅氧烷、聚甲基乙烯基硅氧烷和聚甲基苯基乙烯基硅氧烷中的一种或几种的组合，所述的反应性聚硅氧烷分子量为500~100000 g/mol。
7.根据权利要求1所述的一种耐低温EVA超临界发泡复合材料，其特征在于：所述的交联剂为过氧化二异丙苯、双叔丁基过氧异丙基苯、2, 5-二甲基-2, 5-双(过氧化叔丁基)己烷、过氧化(2-乙基己基)碳酸叔戊酯中一种或几种的组合。
8.根据权利要求1所述的一种耐低温EVA超临界发泡复合材料，其特征在于：所述成核剂为纳米碳酸钙、纳米氧化锌和纳米氧化铝中一种或几种的组合；所述填充剂为滑石粉、硫酸钡、二氧化钛、贝母、高岭土、碳酸钙、硅微粉或气相二氧化硅中一种或几种的组合。
9.如权利要求1-8任一项所述的一种耐低温EVA超临界发泡复合材料的制备方法，其特征在于：包括以下步骤：
（1）称取相应量的各组分；
（2）将步骤（1）中称取好的EVA、弹性体、马来酸酐接枝改性剂、反应性聚硅氧烷和填充剂，在100~120℃温度下，通过密炼机混炼10~20min；然后加入交联剂和成核剂，在120~140℃温度下继续密炼至各组分混合均匀，获得EVA共混物；
（3）用压片机将步骤（2）中EVA共混物压制成片材，然后裁切成EVA共混物片材；
（4）将步骤（3）中的EVA共混物片材放入超临界发泡釜中发泡，气体饱和后，泄压试片取出，裁样，即得所述耐低温EVA超临界发泡复合材料。
10.根据权利要求9所述的一种耐低温EVA超临界发泡复合材料的制备方法，其特征在于：所述气体为超临界N2,，所述发泡釜的压力为10-20MPa，所述发泡釜的温度为110-140℃；所述气体饱和的时间为2-5h，所述泄压的时间为10-30s。
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| CN113997464A (zh) * | 2021-11-01 | 2022-02-01 | 四川大学 | 一种利用废弃eva基材料制备复合再生泡沫材料的方法 |
| CN114957847A (zh) * | 2022-06-29 | 2022-08-30 | 福建嘉怡塑胶有限公司 | 一种eva超临界发泡鞋底及其制备方法 |
| CN115028921A (zh) * | 2022-06-22 | 2022-09-09 | 福建嘉怡塑胶有限公司 | 一种一次成型的环保型eva超临界发泡鞋底及其制备方法 |
| CN115058077A (zh) * | 2022-06-29 | 2022-09-16 | 福建嘉怡塑胶有限公司 | 一种eva超临界发泡一次成型鞋底及其制备方法 |
| CN115926260A (zh) * | 2022-12-28 | 2023-04-07 | 湖北格霖威新材料科技有限公司 | 一种可降解的高强度闭孔聚乳酸发泡材料的制备方法 |
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| CN115058077A (zh) * | 2022-06-29 | 2022-09-16 | 福建嘉怡塑胶有限公司 | 一种eva超临界发泡一次成型鞋底及其制备方法 |
| CN115926260A (zh) * | 2022-12-28 | 2023-04-07 | 湖北格霖威新材料科技有限公司 | 一种可降解的高强度闭孔聚乳酸发泡材料的制备方法 |
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