CN105968767B - 一种聚甲基乙撑碳酸酯发泡材料及其制备方法 - Google Patents
一种聚甲基乙撑碳酸酯发泡材料及其制备方法 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 56
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 title claims abstract description 47
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- 239000008187 granular material Substances 0.000 claims abstract description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 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 6
- 239000000155 melt Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
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- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 239000006260 foam Substances 0.000 abstract description 4
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- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical group NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 10
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 description 1
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- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
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- 229920002223 polystyrene Polymers 0.000 description 1
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Abstract
本发明涉及改性材料技术领域,更具体的,涉及一种聚甲基乙撑碳酸酯发泡材料及其制备方法。所述发泡材料由聚甲基乙撑碳酸酯基体、热塑性聚氨酯、发泡剂和助剂组成,各组分质量份数为聚甲基乙撑碳酸酯100份,热塑性聚氨酯10~70份,发泡剂2~20份,助剂1~5份。所述制备方法将各组分按配方计量后熔融共混,造粒或延压成片材后进行常压加热发泡,冷却定型后即得到所需产品。本发明的发泡材料具有良好的生物降解性、较高的发泡倍率、均匀而致密的泡孔结构以及良好的回弹性能。
Description
技术领域
本发明涉及改性材料技术领域,更具体的,涉及一种聚甲基乙撑碳酸酯发泡材料及其制备方法。
背景技术
泡沫塑料具有质轻、比强度高、能量吸收能力强、隔音隔热性能好等许多优点,在包装、运输、建筑、家具等领域获得了广泛应用。但是传统的泡沫材料如聚苯乙烯、聚乙烯和聚氯乙烯等均属于石油基塑料,不可降解;日益增大的使用量给环境带来了严重的负面影响,加剧了白色污染。
聚甲基乙撑碳酸酯以二氧化碳和环氧丙烷为原料进行合成,可以完全生物降解,是一种新型环境友好的环保材料。目前,聚甲基乙撑碳酸酯发泡材料的研究已取得一定进展。本研究组的专利(ZL200510033659.8)公开了一种全降解聚甲基乙撑碳酸酯发泡材料及其制备方法,但是纯聚甲基乙撑碳酸酯泡沫材料的力学性能差,特别是回弹性很差。在该发明专利的基础上,专利(ZL200510100342.1)发明了一种可生物降解聚甲基乙撑碳酸酯/乙烯乙烯醇共聚物复合发泡材料及其制备方法,专利(ZL201110204493.7)发明了一种以水为发泡剂的全降解聚甲基乙撑碳酸酯/淀粉复合发泡材料及其制备方法,这两项发明专利虽然在一定程度上提高了聚甲基乙撑碳酸酯泡沫材料的性能,但所制备的产品为开孔型发泡材料,回弹性能或力学性能较差。
发明内容
本发明要解决的技术问题在于克服上述缺陷,提供一种聚甲基乙撑碳酸酯发泡材料,所述发泡材料的发泡倍率高、孔隙均匀并且回弹性良好,是一种可生物降解的环境友好型的发泡新材料。
本发明的另一目的在于提供一种聚甲基乙撑碳酸酯发泡材料的制备方法。
本发明通过以下技术方案实现:
一种聚甲基乙撑碳酸酯发泡材料,由以下重量分数的组分制得:
聚甲基乙撑碳酸酯100份,
热塑性聚氨酯10~70份,
发泡剂2~20份,
助剂1~5份;
所述聚甲基乙撑碳酸酯的数均分子量20000~200000,初始分解温度220~300℃,拉伸强度为30~50MPa;200℃,2.16kg下的熔融指数为10~40g/10min。
发明人通过大量创造性的研究,采用特定性质的PPC和弹性体,以合适的配比组合提高了现有技术中PPC发泡材料的发泡倍率、泡孔结构和回弹性等性能,其主要因素在于PPC的性质以及发泡材料的改性。本发明中优选热塑性聚氨酯作为热塑性弹性体来提高发泡材料的柔韧性,从而在一定程度上提高发泡材料的回弹性能。然而,热塑性聚氨酯的使用给聚甲基乙撑碳酸酯的降解性能以及泡孔结构带来负面影响,造成泡孔均匀性差和发泡倍率低等问题,为此本发明采用了特定性质的PPC材料并严格控制发泡材料的组分配方,进而获得一种孔隙均匀且不易塌陷,具有更高的发泡倍率,且具有较好的回弹性的可生物降解的环境友好型的发泡新材料。
优选地,所述聚甲基乙撑碳酸酯的数均分子量20000~100000,初始分解温度220~300℃,拉伸强度为30~50MPa;200℃,2.16kg下的熔融指数为25~40g/10min。
优选地,所述聚甲基乙撑碳酸酯发泡材料由以下重量分数的组分制得:
聚甲基乙撑碳酸酯100份,
热塑性聚氨酯40~70份,
发泡剂5~15份,
助剂1~5份。
优选地,所述热塑性聚氨酯为聚酯型热塑性聚氨酯、聚醚型热塑性聚氨酯或聚碳酸酯型热塑性聚氨酯中的一种或几种混合物。进一步优选地,所述热塑性聚氨酯为聚酯型热塑性聚氨酯。
优选地,所述热塑性聚氨酯的邵氏硬度范围为50~90A。进一步优选地,所述热塑性聚氨酯邵氏硬度范围为80~90A。
优选地,所述发泡剂为偶氮二甲酰胺、N,N-二亚硝基五次甲基四胺、4,4’-氧代双苯磺酰肼或碳酸氢钠中的一种或多种混合物。
优选地,所述助剂为氧化锌、滑石粉、碳酸钙、二氧化硅或二氧化钛中的一种或多种混合物。
一种所述聚甲基乙撑碳酸酯发泡材料的制备方法,包括以下步骤:
S1. 将聚甲基乙撑碳酸酯和热塑性聚氨酯按配方计量后进行熔融共混,共混温度为180~200℃,共混时间为10~15分钟,混合均匀后造粒。
S2. 将步骤S1制备的复合粒料和发泡剂以及助剂按配方计量后进行熔融共混,共混温度为120~140℃,共混时间为10~15分钟,混合均匀后造粒或延压成片材,得到发泡材料。
S3. 将步骤S2制备的发泡材料进行加热发泡20~40分钟,温度保持在160~200℃,发泡完全后冷却定型得到所需产品。
与现在有技术相比,本发明具有以下有益效果:
本发明所述聚甲基乙撑碳酸酯发泡材料的孔隙均匀且不易塌陷,具有更高的发泡倍率,且具有较好的回弹性,是一种可生物降解的环境友好型的发泡新材料。
具体实施方式
下面结合具体实施例进一步说明本发明。除非特别说明,本发明实施例中采用的原料和方法为本领域常规市购的原料和常规使用的方法。
本发明采用的聚甲基乙撑碳酸酯的拉伸强度是依标准ASTM D638,在拉伸速度50mm/min,25℃,50%RH条件下测定的。熔融指数是依标准ASTM D1238,在200℃,2.16kg条件下测定。
实施例1
称取数均分子量为20000,初始分解温度220℃,拉伸强度(ASTM D638,拉伸速度50mm/min)30MPa,熔融指数(ASTM D1238,200℃,2.16kg)40g/10min的聚甲基乙撑碳酸酯100份、邵氏硬度为80A的聚酯型热塑性聚氨酯40份、偶氮二甲酰胺14份、滑石粉2份。
先将聚甲基乙撑碳酸酯和聚酯型热塑性聚氨酯加入混炼机进行熔融共混,转速为80转/分钟,共混温度为190℃,共混时间为15分钟;混合均匀后造粒,再加入偶氮二甲酰胺和滑石粉进行共混,转速为50转/分钟,共混温度为130℃,共混时间为10分钟,混合均匀后热压成型得到发泡材料。
将发泡材料放进模具中于200℃下加热发泡30分钟,发泡完全后冷却定型得到所需产品。
将得到的产品进行性能检测,检测结果如表1所示。测试方法如下:先将产品表皮切除并切割成相应的标准样品,按ASTM D3574标准测试样品密度,原始基体材料的密度与该密度的比值即为发泡倍率;按ASTM D3576标准测试样品平均泡孔直径;按ASTM D3574测试样品的钢球回弹率。
实施例2
称取数均分子量为100000,初始分解温度270℃,拉伸强度(ASTM D638,拉伸速度50mm/min)40MPa,熔融指数(ASTM D1238,200℃,2.16kg)25g/10min的聚甲基乙撑碳酸酯100份,邵氏硬度为90A的聚酯型热塑性聚氨酯的用量为50份,偶氮二甲酰胺的用量为10份,碳酸钙1份。
先将聚甲基乙撑碳酸酯和聚酯型热塑性聚氨酯加入混炼机进行熔融共混,转速为80转/分钟,共混温度为200℃,共混时间为15分钟;混合均匀后造粒,再加入偶氮二甲酰胺和滑石粉进行共混,转速为50转/分钟,共混温度为140℃,共混时间为10分钟,混合均匀后热压成型得到发泡材料。
将发泡材料放进模具中于180℃下加热发泡40分钟,发泡完全后冷却定型得到所需产品。
实施例3
称取数均分子量为50000,初始分解温度250℃,拉伸强度(ASTM D638,拉伸速度50mm/min)35MPa,熔融指数(ASTM D1238,200℃,2.16kg)35g/10min的聚甲基乙撑碳酸酯100份,邵氏硬度为90A的聚醚型热塑性聚氨酯70份,偶氮二甲酰胺的用量为7份,二氧化硅5份。
先将聚甲基乙撑碳酸酯和聚酯型热塑性聚氨酯加入混炼机进行熔融共混,转速为80转/分钟,共混温度为180℃,共混时间为10分钟;混合均匀后造粒,再加入偶氮二甲酰胺和滑石粉进行共混,转速为50转/分钟,共混温度为120℃,共混时间为15分钟,混合均匀后热压成型得到发泡材料。
将发泡材料放进模具中于170℃下加热发泡40分钟,发泡完全后冷却定型得到所需产品。
实施例4
本实施例的配方、制备工艺和性能检测与实施例1相似,不同之处在于:取数均分子量为200000,初始分解温度300℃,拉伸强度(ASTM D638,拉伸速度50mm/min)50MPa,熔融指数(ASTM D1238,200℃,2.16kg)10g/10min的聚甲基乙撑碳酸酯100份,邵氏硬度为50A采用聚碳酸酯型热塑性聚氨酯20份,偶氮二甲酰胺替换为N,N-二亚硝基五次甲基四胺,使用量变为16份。
实施例5
本实施例的配方、制备工艺和性能检测与实施例3相似,不同之处在于:取数均分子量为150000,玻璃化转变温度30℃,初始分解温度280℃,拉伸强度(ASTM D638,拉伸速度50mm/min)45MPa,熔融指数(ASTM D1238,200℃,2.16kg)15g/10min的聚甲基乙撑碳酸酯100份,邵氏硬度为90A的聚酯型热塑性聚氨酯的用量为10份,偶氮二甲酰胺替换为碳酸氢钠,使用量变为20份。
对比例1
本对比例的配方、制备工艺和性能检测与实施例1相似,不同之处在于:采用取数均分子量为8000,初始分解温度190℃,拉伸强度(ASTM D638,拉伸速度50mm/min)6MPa,熔融指数(ASTM D1238,200℃,2.16kg)60g/10min的聚甲基乙撑碳酸酯100份。
对比例2
本对比例的配方、制备工艺和性能检测与实施例1相似,不同之处在于:取数均分子量为250000,初始分解温度300℃,拉伸强度(ASTM D638,拉伸速度50mm/min)55MPa,熔融指数(ASTM D1238,200℃,2.16kg)5g/10min的聚甲基乙撑碳酸酯100份。
对比例3~4
本对比例的配方、制备工艺和性能检测与实施例1相似,不同之处在于:采用聚酯型热塑性聚氨酯的用量为0份和5份,采用的偶氮二甲酰胺均为12份。
表1 实验结果
从上述实施例和对比例的实验结果可知:
发泡剂添加量主要影响发泡材料的发泡倍率和孔隙直径,添加量越多,发泡倍率越大,孔隙直径也越大。热塑性聚氨酯添加量主要影响孔隙直径和钢球回弹率,添加量越多,孔隙直径越大,钢球回弹率也越大。在优选范围内,能同时获得发泡倍率较大,孔隙直径较小,并且钢球回弹率较大的发泡材料。
Claims (8)
1.一种聚甲基乙撑碳酸酯发泡材料,其特征在于,由以下重量份数的组分制得:
聚甲基乙撑碳酸酯100份,
热塑性聚氨酯10~70份,
发泡剂2~20份,
助剂1~5份;
所述聚甲基乙撑碳酸酯的数均分子量20000~200000,初始分解温度220~300℃,拉伸强度为30~50MPa;200℃、2.16kg下的熔融指数为10~40g/10min;
所述拉伸强度是依标准ASTM D638,在拉伸速度50mm/min、25℃、50%RH条件下测定的;所述熔融指数是依标准ASTM D1238,在200℃、2.16kg条件下测定。
2.根据权利要求1所述聚甲基乙撑碳酸酯发泡材料,其特征在于,由以下重量份数的组分制得:
聚甲基乙撑碳酸酯100份,
热塑性聚氨酯40~70份,
发泡剂5~15份,
助剂1~5份。
3.根据权利要求1所述聚甲基乙撑碳酸酯发泡材料,其特征在于,所述聚甲基乙撑碳酸酯的数均分子量20000~100000,初始分解温度220~300℃,拉伸强度为30~50MPa;200℃、2.16kg下的熔融指数为25~40g/10min;
所述拉伸强度是依标准ASTM D638,在拉伸速度50mm/min、25℃、50%RH条件下测定的;所述熔融指数是依标准ASTM D1238,在200℃、2.16kg条件下测定。
4.根据权利要求1所述聚甲基乙撑碳酸酯发泡材料,其特征在于,所述热塑性聚氨酯为聚酯型热塑性聚氨酯、聚醚型热塑性聚氨酯、聚碳酸酯型热塑性聚氨酯中的一种或几种混合物。
5.根据权利要求4所述聚甲基乙撑碳酸酯发泡材料,其特征在于,所述热塑性聚氨酯的邵氏硬度范围为50~90A。
6.根据权利要求1所述聚甲基乙撑碳酸酯发泡材料,其特征在于,所述发泡剂为偶氮二甲酰胺、N,N-二亚硝基五次甲基四胺、4,4’-氧代双苯磺酰肼或碳酸氢钠中的一种或多种混合物。
7.根据权利要求1所述聚甲基乙撑碳酸酯发泡材料,其特征在于,所述助剂为氧化锌、滑石粉、碳酸钙、二氧化硅或二氧化钛中的一种或多种混合物。
8.一种权利要求1~7任意一项所述聚甲基乙撑碳酸酯发泡材料的制备方法,其特征在于,包括以下步骤:
S1. 将聚甲基乙撑碳酸酯和热塑性聚氨酯按配方计量后进行熔融共混,共混温度为180~200℃,共混时间为10~15分钟,混合均匀后造粒;
S2. 将步骤S1制备的复合粒料和发泡剂以及助剂按配方计量后进行熔融共混,共混温度为120~140℃,共混时间为10~15分钟,混合均匀后造粒或延压成片材,得到发泡材料;
S3. 将步骤S2制备的发泡材料进行加热发泡20~40分钟,温度保持在160~200℃,发泡完全后冷却定型得到所需产品。
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