CN110563917B - 一种在线改性ppc树脂及其制备工艺 - Google Patents
一种在线改性ppc树脂及其制备工艺 Download PDFInfo
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- CN110563917B CN110563917B CN201911019341.2A CN201911019341A CN110563917B CN 110563917 B CN110563917 B CN 110563917B CN 201911019341 A CN201911019341 A CN 201911019341A CN 110563917 B CN110563917 B CN 110563917B
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Classifications
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Abstract
本发明涉及PPC树脂技术领域，具体涉及一种在线改性PPC树脂及其制备工艺，所述在线改性PPC树脂，其原料包括如下重量份数组分：多元醇100份、异氰酸酯15‑60份、小分子二醇2.4‑17份、催化剂0.1‑0.2份、羟基硅烷3‑10份、助剂1‑30份，所述多元醇为聚碳酸酯多元醇与其他多元醇的混合物，所述其他多元醇为聚己内酯多元醇、其他聚酯多元醇、山梨醇、有机硅多元醇中的至少一种。本发明具有生物降解性能优异、热稳定性和机械性能高、能耗低的优点。
Description
技术领域
本发明涉及PPC树脂技术领域，具体涉及一种在线改性PPC树脂及其制备工艺。
背景技术
社会经济的发展使人类对化石燃料的需求量不断增加，从而导致二氧化碳(CO2)的排放量日趋增大。众所周知，CO2是造成温室效应的主要气体之一，而全球变暖将带来非常严重的后果，如冰川消退、海平面上升、荒漠化等，直接威胁到人类社会的生存。与此同时，随着人类生活水平的不断提高，塑料制品的用量与日俱增。塑料给人们的生活带来便利的同时，被使用后的大量塑料废弃物也不断增加，大量不可降解的塑料废弃物造成“白色污染”，给我们赖以生存的自然环境造成了不可忽视的负面影响。
在综合考察温室效应和“白色污染”两大问题时，人们发现，CO2与环氧丙烷在催化剂的作用下，通过共聚反应生成了聚甲基乙撑碳酸酯(PPC)。PPC可以完全生物降解，能部分代替传统通用塑料使用，有助于解决传统石油基塑料所带来的“白色污染”问题。利用CO2作为原料来合成PPC，一方面可利用CO2，缓解了温室效应，减轻了塑料对石油资源的依赖；另一方面又可获得一种可全生物降解的材料，如果能够把工业生产排放的CO2制备成可降解的PPC，并广泛使用，将在一定程度上缓解温室效应，并且有利于减少“白色污染”。
PPC作为一种新型脂肪族聚酯，具有良好的降解性能和阻隔性能，PPC还具有透明和无毒等优点，因此PPC在食品包装、医用材料、胶黏剂以及工程塑料等方面具有较好的应用前景。PPC的分子链结构不对称，且柔性较好，属于完全非结晶塑料，它的玻璃化温度为35℃左右，拉伸强度较小(3-30MPa，与测试温度密切相关)，断裂伸长率极高(大于700％)，拉伸后具有较强的形变回复性，拉伸强度具有强烈的温敏性。但是，PPC的熔融加工温度在100℃以上，在170℃附近就出现热降解，热稳定性较差，同时PPC的机械性能相对较差。
中国专利申请CN1426430A公开了一种利用聚碳酸亚丙基酯软链段制备的热塑性聚氨酯弹性体(TPUs)，包括：a)作为软链段的聚(碳酸亚丙基酯)二醇(PTMC二醇)；b)二异氰酸酯；和c)至少一种二元醇，它与二异氰酸酯反应形成占组合物10－55％重量的硬链段，其中，硬链段定义为与二元醇反应的二异氰酸酯和未反应二元醇部分的总和。该弹性体比基于本领域公知的多元醇的相应TPUs更硬一点。该PTMC TPUs具有好的物理机械性能，包括比参照TPU更高一点的弹性模量。与聚醚TPUs相比，其耐磨性和压缩变定也非常好，其软化温度和热膨胀系数也比参照TPUs有改进。另外，利用PTMC多元醇，可以提高TPUs的透明度，甚至能够得到完全透明的材料。但是单纯地以PTMC多元醇为原料，制备得到的聚氨酯弹性体的热稳定性和机械性能有待进一步提高。
中国专利申请CN109694494A公开了一种可生物降解热塑性聚氨酯弹性体发泡珠粒及其制备方法，属于聚合物技术领域。所述的聚氨酯弹性体发泡珠粒，由下列质量份数的物质组成：生物基多元醇100-200份；异氰酸酯20-100份；小分子醇扩链剂10-100份；紫外线吸收剂0.1-10份；催化剂0.1-10份；物理发泡剂1-20份；其中，生物基多元醇为聚甲基乙撑碳酸酯二醇(PPC)、聚已内酯二醇(PCL)、聚乳酸PLA或聚乙交酯(PGA)中的两种或多种的组合。制得的发泡珠粒在保证原有的发泡倍率、强度和密度外，还能快速降解，可广泛用于包装等行业。同时，该专利申请还提供其制备方法，科学合理，简单易行。但是该发泡珠粒的生物降解性能有待进一步提高。
聚氨酯生产过程中也常常添加一些助剂来改善其制品性能和外观，或者改善其制备工艺，比如稳定剂、阻燃剂、防霉剂、抗氧剂或紫外线吸收剂。但是上述助剂都是在聚氨酯制备完成之后再将聚氨酯熔融和助剂进行复合，能耗较高。
中国专利CN102391458A公开了一种制备水性聚氨酯、助剂浆料和水性聚氨酯涂饰剂的方法，涂饰剂由水性聚氨酯和助剂浆料按比例制备而成。首先水性聚氨酯的制备是采用氢化异氰酸酯单体与聚酯多元醇、扩链剂等材料在催化剂作用下制备端基含异氰酸基团的预聚体，通过成盐剂与预聚体反应后加入去离子水分散成水性聚氨酯体系，最后在低温下加入扩链剂制备得到水性聚氨酯。其次，按照配比，将消泡剂、爽滑剂、分散剂和pH调节剂、溶剂、手感剂和偶联剂等组分混合均匀制备助剂浆料。再次通过水性聚氨酯和助剂浆料的复配制备医用PVC(聚氯乙烯)手套用水性聚氨酯涂饰剂，增加PVC手套的滑爽、易穿戴和透气性等性能。但是上述专利采用先制备聚氨酯再与助剂共混的方式，能耗较高。
因此，利用开发一种能解决上述技术问题的在线改性PPC树脂及其制备工艺是非常必要的。
发明内容
本发明的目的是克服现有技术的不足而提供一种生物降解性能优异、热稳定性和机械性能高、能耗低的在线改性PPC树脂及其制备工艺。
本发明是通过以下技术方案予以实现的：
一种在线改性PPC树脂，其原料包括如下重量份数组分：多元醇100份、异氰酸酯15-60份、小分子二醇2.4-17份、催化剂0.1-0.2份、羟基硅烷3-10份、助剂1-30份，所述多元醇为聚碳酸酯多元醇与其他多元醇的混合物，所述其他多元醇为聚己内酯多元醇、其他聚酯多元醇、山梨醇、有机硅多元醇中的至少一种。
本发明通过在改性PPC树脂原料中添加羟基硅烷，显著提高了改性PPC树脂的热稳定性，防止产生粘连现象。
优选地，所述聚碳酸酯多元醇和其他多元醇的摩尔比为12-15:1。
本发明通过限定在线改性PPC树脂各原料的重量份数及多元醇中不同醇的摩尔比，最终制得的在线改性PPC树脂不仅具有柔性，还具有刚性，机械力学性能明显提高。
优选地，所述助剂为聚乳酸、聚己二酸对苯二甲酸丁二酯、聚丁二酸丁二醇酯、碳酸钙、滑石粉、淀粉、纤维素、成核剂中的至少一种。
本发明采用助剂改性得到的改性PPC树脂，可以通过改变配方来满足下一步制品的性能要求，不需要再共混改性，直接可以使用。
优选地，所述聚碳酸酯多元醇为聚碳酸亚丙酯多元醇或者聚碳酸亚乙酯多元醇和聚碳酸亚丙酯多元醇的混合物。
更优选地，所述聚碳酸亚丙酯多元醇的分子量为1500-4000，官能度为2。
更优选地，所述聚碳酸亚乙酯多元醇和聚碳酸亚丙酯多元醇的质量比为1:4-6。
优选地，所述其他聚酯多元醇为聚己二酸乙二醇酯二醇、聚己二酸-1,4-丁二醇酯二醇、聚癸二酸二元醇酯二醇、聚苯二甲酸二元醇酯二醇中的至少一种。
更优选地，所述其他聚酯多元醇为聚己二酸乙二醇酯二醇和聚苯二甲酸二元醇酯二醇中的至少一种。
优选地，所述有机硅多元醇为有机硅氧烷二醇。
优选地，所述多元醇为聚碳酸酯多元醇和聚己内酯多元醇，聚碳酸酯多元醇和其他聚酯多元醇，聚碳酸酯多元醇和山梨醇，聚碳酸酯多元醇和有机硅多元醇，聚碳酸酯多元醇、聚己内酯多元醇和其他聚酯多元醇，聚碳酸酯多元醇、其他聚酯多元醇和山梨醇，聚碳酸酯多元醇、其他聚酯多元醇和有机硅多元醇，聚碳酸酯多元醇、聚己内酯多元醇、其他聚酯多元醇和山梨醇，聚碳酸酯多元醇、聚己内酯多元醇、其他聚酯多元醇、山梨醇和有机硅多元醇组合中的一种。
更优选地，所述其他多元醇为其他聚酯多元醇和山梨醇的混合物。
更优选地，所述其他聚酯多元醇和山梨醇的质量比为2-3:1。
优选地，所述异氰酸酯为4,4’-二苯甲烷二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯和六次甲基二异氰酸酯中的至少一种。
更优选地，所述异氰酸酯为4,4’-二苯甲烷二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯中的至少一种。
优选地，所述小分子二醇为乙二醇、1,4-丁二醇、丙二醇、1,4-环己二醇、新戊二醇中的至少一种。
更优选地，所述小分子二醇为1,4-丁二醇、丙二醇、1,4-环己二醇中的至少一种。
更优选地，所述小分子二醇为1,4-丁二醇、丙二醇、1,4-环己二醇的混合物。
更优选地，所述1,4-丁二醇、丙二醇、1,4-环己二醇的质量比为2-4:1:0.5-2。
优选地，所述催化剂包括锡类、铋类和钛酸丁酯中的至少一种。
更优选地，所述锡类包括辛酸亚锡、异辛酸亚锡、三丁基甲氧基锡、叔丁氧基锡、酚氧基锡、氯化锡、溴化锡、乙酰化锡中的至少一种。
更优选地，所述铋类包括硝酸铋、环烷酸铋中的至少一种。
更优选地，所述催化剂为锡类和钛酸丁酯的混合物。
更优选地，所述锡类和钛酸丁酯的质量比为1:2-3。
本发明还涉及上述在线改性PPC树脂的制备方法，包括如下步骤：
(1)将多元醇、异氰酸酯、小分子二醇、催化剂、羟基硅烷混合，得混合物A；
(2)将混合物A注入双螺杆挤出机进料口中，然后将助剂加入挤出机中间段，挤出，水下切粒，干燥，即得。
优选地，所述步骤(1)包括如下步骤：将多元醇、异氰酸酯、小分子二醇、催化剂、羟基硅烷同时加热到50-80℃，混合，得混合物A。
优选地，所述步骤(2)包括如下步骤：将混合物A通过浇注机注入双螺杆挤出机进料口中，360mm×15节，1-7节的温度130-170℃，8-15节的温度150-200℃，然后将助剂加入挤出机中间段6-8节，反应1.5-3分钟挤出，30-60℃水下切粒，干燥，即得。其中距离进料口最近的为第1节。
所述双螺杆挤出机为95型双螺杆挤出机，螺杆直径93.4mm，长径比为60:1。
更优选地，所述在线改性PPC树脂的制备方法，包括如下步骤：
(1)将多元醇、异氰酸酯、小分子二醇、催化剂、羟基硅烷同时加热到50-80℃，混合，得混合物A；
(2)将混合物A通过浇注机注入双螺杆挤出机进料口中，360mm×15节，1-7节的温度130-170℃，8-15节的温度150-200℃，然后将助剂加入挤出机中间段6-8节，反应1.5-3分钟挤出，30-60℃水下切粒，干燥，即得。
本发明的有益效果是：
本发明通过在改性PPC树脂原料中添加羟基硅烷，显著提高了改性PPC树脂的热稳定性、机械性能和生物可降解性能，防止产生粘连现象。
本发明通过限定在线改性PPC树脂各原料的重量份数及多元醇中聚碳酸酯多元醇与其它多元醇的混合多元醇的摩尔比，最终制得的在线改性PPC树脂不仅具有柔性，还具有刚性，机械力学性能和生物降解性能明显提高。尤其是当聚碳酸酯多元醇与其他聚酯多元醇、山梨醇联用作为多元醇时，并限定不同多元醇的配比，最终制得的在线改性PPC树脂力学性能明显提高。
本发明通过选用特定的多元醇、异氰酸酯、小分子二醇和催化剂，并限定各组分配比，尤其是通过限定小分子二醇为1,4-丁二醇、丙二醇、1,4-环己二醇的混合物，最终制得的PC树脂衍生物分子量可高达10万以上，耐高温性能高达120℃以上，即在此温度下仍然不产生板结粘连现象。
本发明中进一步限定了催化剂为锡类和钛酸丁酯的混合物，两者质量比对最终产品的性能具有显著影响。通过控制两种催化剂的质量比可以进一步控制改性PPC的合成反应，最终制备得到的产品机械性能、热稳定性、生物可降解性能均有明显提高。
本发明采用一步法制备在线改性PPC树脂，并且制备过程中不需要加入溶剂，制备简单，成本和能耗较低，并且加工性能优异，制备过程中不排放有害气体。
本发明在制备PPC树脂的过程中用助剂对其进行改性，改性更均匀，并且改性与制备一步完成，不需要先制备成PPC树脂后再熔融和助剂进行复合，能耗较低。本发明采用助剂改性得到的改性PPC树脂，可以通过改变配方来满足下一步制品的性能要求，不需要再共混改性，直接可以使用。
本发明在制备过程中，通过限定前后不同料筒的反应温度，1-7节的温度130-170℃，8-15节的温度150-200℃，制备得到的在线改性PPC树脂力学性能和生物降解性能显著提高。
以本发明制备得到的在线改性PPC树脂为原料制作的薄膜具有非常优异的断裂伸长率和撕裂强度，同时对氧气及水蒸气具有高阻隔性，而且可以堆肥实现完全生物降解，该材料与其它生物降解材料有良好的相容性等特殊性能，可广泛应用在包装、地膜、一次性用品等行业。
具体实施方式
下面结合具体实施例来进一步描述本发明，本发明的优点和特点将会随着描述而更为清楚。但这些实施例仅是范例性的，并不对本发明的范围构成任何限制。本领域技术人员应该理解的是，在不偏离本发明的精神和范围下可以对本发明技术方案的细节和形式进行修改或替换，但这些修改和替换均落入本发明的保护范围内。
本发明中的双螺杆挤出机如无特殊说明为95型双螺杆挤出机，螺杆直径93.4mm，长径比为60:1。
实施例1
一种在线改性PPC树脂，其原料包括如下重量份数组分：多元醇100份、4,4’-二苯甲烷二异氰酸酯15份、1,4-丁二醇2.4份、催化剂0.1份、羟基硅烷3份、聚乳酸1份，所述多元醇为聚碳酸亚丙酯二元醇(分子量1500)与聚己内酯二元醇(摩尔比为12:1)的混合物。
所述催化剂为辛酸亚锡和钛酸丁酯的混合物，两者质量比为1:2。
在线改性PPC树脂的制备方法，包括如下步骤：
(1)将多元醇、4,4’-二苯甲烷二异氰酸酯、1,4-丁二醇、催化剂、羟基硅烷同时加热到50℃，混合，得混合物A；
(2)将混合物A通过浇注机注入双螺杆挤出机进料口中，360mm×15节，1-7节的温度130℃，8-15节的温度150℃，然后将聚乳酸加入挤出机中间段第6节，反应1.5分钟挤出，30℃水下切粒，干燥，即得。
实施例2
一种在线改性PPC树脂，与实施例2的区别仅在于聚己内酯二元醇替换为聚己二酸乙二醇酯二醇和山梨醇的混合物，两者质量比为2:1，其余条件均相同。
实施例3
一种在线改性PPC树脂，其原料包括如下重量份数组分：多元醇100份、甲苯二异氰酸酯60份、丙二醇17份、催化剂0.2份、羟基硅烷10份、聚己二酸对苯二甲酸丁二酯15份，所述多元醇为聚碳酸酯多元醇与其他多元醇(摩尔比为15:1)的混合物。
所述聚碳酸酯多元醇为聚碳酸亚乙酯二元醇(分子量4000)和聚碳酸亚丙酯二元醇(分子量4000)(质量比为1:6)的混合物；所述其他多元醇为聚苯二甲酸二元醇酯二醇和山梨醇(质量比为3:1)的混合物；所述催化剂为三丁基甲氧基锡和钛酸丁酯的混合物，两者质量比为1:3。
在线改性PPC树脂的制备方法，包括如下步骤：
(1)将多元醇、甲苯二异氰酸酯、丙二醇、催化剂、羟基硅烷同时加热到80℃，混合，得混合物A；
(2)将混合物A通过浇注机注入双螺杆挤出机进料口中，360mm×15节，1-7节的温度170℃，8-15节的温度200℃，然后将聚己二酸对苯二甲酸丁二酯加入挤出机中间段第8节，反应3分钟挤出，60℃水下切粒，干燥，即得。
测试例1
实施例1-3的在线改性PPC树脂力学性能测试，具体测试方法参照GB/T31124-2014，试样为GB/T 1040.2-2006中的1A型。
结果如表1所示。
表1在线改性PPC树脂力学性能测试
| 拉伸强度/MPa | |
| 实施例1 | 33 |
| 实施例2 | 37 |
| 实施例3 | 39 |
测试例2
将实施例1的在线改性PPC树脂进行生物降解试验，参照GB/T 19277-2003。45天后生物分解百分率越高，说明其降解程度越好。结果如表2所示。
表2在线改性PPC树脂生物降解性能测试
| 45d后生物分解率/％ | 130d后生物分解率/％ | |
| 实施例1 | 72.5 | 90.3 |
本发明方案所公开的技术手段不仅限于上述技术手段所公开的技术手段，还包括由以上技术特征任意组合所组成的技术方案。以上所述是本发明的具体实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明的保护范围。
Claims (8)
1.一种改性PPC树脂，其原料由如下重量份数的组分组成：多元醇100份、异氰酸酯15-60份、小分子二醇2.4-17份、催化剂0.1-0.2份、羟基硅烷3-10份、助剂1-30份，所述多元醇为聚碳酸酯多元醇与其他多元醇的混合物，所述其他多元醇为其他聚酯多元醇和山梨醇的混合物；所述其他聚酯多元醇和山梨醇的质量比为2-3:1；
所述聚碳酸酯多元醇和其他多元醇的摩尔比为12-15:1；
所述助剂为聚乳酸、聚己二酸对苯二甲酸丁二酯、聚丁二酸丁二醇酯、碳酸钙、滑石粉、淀粉、纤维素、成核剂中的至少一种。
2.根据权利要求1所述的改性PPC树脂，其特征在于，所述聚碳酸酯多元醇为聚碳酸亚丙酯多元醇或者聚碳酸亚乙酯多元醇和聚碳酸亚丙酯多元醇的混合物；所述其他聚酯多元醇为聚己二酸乙二醇酯二醇、聚己二酸-1,4-丁二醇酯二醇、聚癸二酸二元醇酯二醇、聚苯二甲酸二元醇酯二醇中的至少一种。
3.根据权利要求2所述的改性PPC树脂，其特征在于，所述聚碳酸亚丙酯多元醇的分子量为1500-4000，官能度为2。
4.根据权利要求1所述的改性PPC树脂，其特征在于，所述异氰酸酯为4,4’-二苯甲烷二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯和六次甲基二异氰酸酯中的至少一种；所述小分子二醇为乙二醇、1,4-丁二醇、丙二醇、1,4-环己二醇、新戊二醇中的至少一种；所述催化剂包括锡类、铋类和钛酸丁酯中的至少一种。
5.根据权利要求1所述的改性PPC树脂，其特征在于，所述催化剂为锡类和钛酸丁酯的混合物，两者质量比为1:2-3。
6.一种权利要求1-5任一项所述改性PPC树脂的制备方法，其特征在于，包括如下步骤：
(1)将多元醇、异氰酸酯、小分子二醇、催化剂、羟基硅烷混合，得混合物A；
(2)将混合物A注入双螺杆挤出机进料口中，然后将助剂加入挤出机中间段，挤出，水下切粒，干燥，即得。
7.根据权利要求6所述的制备方法，其特征在于，所述步骤(1)包括如下步骤：将多元醇、异氰酸酯、小分子二醇、催化剂、羟基硅烷同时加热到50-80℃，混合，得混合物A。
8.根据权利要求6所述的制备方法，其特征在于，所述步骤(2)包括如下步骤：将混合物A通过浇注机注入双螺杆挤出机进料口中，360mm×15节，1-7节的温度130-170℃，8-15节的温度150-200℃，然后将助剂加入挤出机中间段6-8节，反应1.5-3分钟挤出，30-60℃水下切粒，干燥，即得。
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