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CN109971086A - 一种pvc易加工不透明高抗冲mbs及其制备方法 - Google Patents

一种pvc易加工不透明高抗冲mbs及其制备方法 Download PDF

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CN109971086A
CN109971086A CN201910113748.5A CN201910113748A CN109971086A CN 109971086 A CN109971086 A CN 109971086A CN 201910113748 A CN201910113748 A CN 201910113748A CN 109971086 A CN109971086 A CN 109971086A
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styrene
mbs
pvc
easy processing
monomer
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张效全
衣同刚
夏永全
赵洪刚
许铎
邹伯晓
刘�文
马晓敏
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Shandong Donglin New Materials Co Ltd
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Shandong Donglin New Materials Co Ltd
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Priority to CN201910113748.5A priority Critical patent/CN109971086A/zh
Publication of CN109971086A publication Critical patent/CN109971086A/zh
Priority to PCT/CN2019/125413 priority patent/WO2020164302A1/zh
Priority to DE112019000358.5T priority patent/DE112019000358B4/de
Priority to KR1020207021824A priority patent/KR102345094B1/ko
Priority to US16/968,830 priority patent/US11866537B2/en
Priority to MX2020008170A priority patent/MX2020008170A/es
Priority to RU2020126890A priority patent/RU2750936C1/ru
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Abstract

本发明公开了一种PVC易加工不透明高抗冲MBS及其制备方法，涉及PVC助剂生产制备技术领域，PVC易加工不透明高抗冲MBS为芯‑核‑壳三层结构，PVC易加工不透明高抗冲MBS由下列质量份数的各组分组成：芯层结构1‑20%，核层结构70‑85%，壳层结构5‑20%；芯层结构为半硬质的轻微交联的苯乙烯单体和丙烯酸酯类单体的共聚物，苯乙烯单体和丙烯酸酯类单体的比例为95/5‑5/95；核层结构为较软的玻璃化温度较低的轻度交联的丁二烯苯乙烯聚合物，丁二烯和苯乙烯的比例为100/0‑80/20；壳层结构为玻璃化温度较高的苯乙烯、丙烯酸丁酯和甲基丙烯酸甲酯的共聚物，其质量份数分别为0.2‑5%、0.2‑2%和13‑20%。本发明解决了现有不透明PVC制品用MBS产品存在的抗冲击强度不高及加工流动性差等问题。

Description

一种PVC易加工不透明高抗冲MBS及其制备方法
技术领域
本发明涉及PVC助剂生产制备技术领域，特别涉及一种PVC易加工不透明高抗冲MBS及其制备方法。
背景技术
PVC的增韧材料中，甲基丙烯酸甲酯-丁二烯-苯乙烯聚合物（MBS）是比较重要的一类，分为透明制品用和不透明制品用。用于不透明PVC制品的MBS，主要要求其抗冲击性能及加工时的流动性，优异的抗冲击性能与加工流动性是目前极力追求的目标。
MBS树脂是在粒子设计概念基础上合成的功能高分子材料，是通过乳液接枝聚合制得的三元聚合物，亚微观形态上具有典型的核壳结构，粒子的核心是经过轻度交联具有低剪切摸量的丁苯橡胶核，主要起到提高聚合物冲击韧性的作用；外壳是苯乙烯和甲基丙烯酸甲酯接枝形成的硬壳层，壳层中MMA 的主要作用是提高其与PVC 的相容性，使MBS 能够在PVC机体中均匀分散；St主要是提高MBS树脂的折光指数以使MBS拥有与PVC相近的折光指数，故MBS树脂是典型的粒子分散型增韧改性剂。
MBS与PVC两相之间是半相容的，即与PVC树脂具有较好的界面相容性，又能在PVC/MBS体系中保持粒子形状完整。MBS加入量少时，在PVC中分散性良好呈球状颗粒，形不成分散型“海-岛” 结构，起不到传递冲击能的作用，材料增韧效果差；随着MBS树脂加入量的增加，分散的颗粒逐渐聚结起来形成海岛结构，当材料受到外力冲击时, MBS树脂中的橡胶核作为应力集中点，使其产生形变，并在周围诱发银纹和剪切带，通过银纹和剪切带分散和吸收冲击能量，形成了材料从脆性断裂向韧性断裂的转变，从而达到增韧的目的。
甲基丙烯酸甲酯-丁二烯-苯乙烯聚合物（MBS）是一种典型的核壳结构，里面是较软的橡胶相，主要成分是丁二烯为主的丁二烯苯乙烯共聚物，外层是较硬的塑料相，主要成分是甲基丙烯酸甲酯和苯乙烯的共聚物，大量试验表明，此种结构的抗冲击强度并不是特别高。本发明在以前理论的基础上，提出一种芯-核-壳结构，这种结构的抗冲击强度较目前的核壳结构有了较大幅度的增加。
发明内容
根据现有技术中存在的技术缺陷，本发明所要解决的技术问题是：提供一种PVC易加工不透明高抗冲MBS及其制备方法，得到一种三层结构的聚合物，提高聚合物的抗冲击性能，解决现有不透明PVC制品用MBS产品存在的抗冲击强度不高及加工流动性差等问题。
为了实现本发明的技术目的，本发明一种PVC易加工不透明高抗冲MBS及其制备方法的技术方案是：
一种PVC易加工不透明高抗冲MBS，所述PVC易加工不透明高抗冲MBS为芯-核-壳三层结构，所述PVC易加工不透明高抗冲MBS由下列质量份数的各组分组成：芯层结构1-20%，核层结构70-85%，壳层结构5-20%；
所述芯层结构为半硬质的轻微交联的苯乙烯单体和丙烯酸酯类单体的共聚物，所述苯乙烯单体和所述丙烯酸酯类单体的比例为95/5-5/95；
所述苯乙烯类单体包括苯乙烯、甲基苯乙烯等；
所述丙烯酸酯类单体包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸-2-乙基己酯的一种或几种；
所述核层结构为较软的玻璃化温度较低的轻度交联的丁二烯苯乙烯聚合物，所述丁二烯和所述苯乙烯的比例为100/0-80/20；
所述壳层结构为玻璃化温度较高的苯乙烯、丙烯酸丁酯和甲基丙烯酸甲酯的共聚物，所述苯乙烯、所述丙烯酸丁酯和所述甲基丙烯酸甲酯的质量份数分别为0.2-5%、0.2-2%和13-20%。
作为本发明的进一步改进，所述芯层结构占比优选为1-15%，更优选为1-12%。
作为本发明的进一步改进，所述芯层结构中所述苯乙烯单体和所述丙烯酸酯类单体的比例优选为90/10-10/90，更优选为85/15-15/85。
作为本发明的进一步改进，所述核层结构占比优选为75-85%。
作为本发明的进一步改进，所述核层结构中所述丁二烯和所述苯乙烯的比例优选为100/0-85/15，更优选为100/0-90/10，最优选为100/0-95/5。
作为本发明的进一步改进，所述壳层结构占比优选为7-20%，更优选为9-19%。
作为本发明的进一步改进，所述PVC易加工不透明高抗冲MBS的制备具体步骤如下：
（1）在反应釜中加入配方量的水、乳化剂、无机盐、分子量调节剂、苯乙烯类单体和丙烯酸酯类单体、交联剂、引发剂，然后关闭反应釜盖，升温至反应温度进行反应，直至反应完毕；或单独用一反应釜反应，取配方量的反应好的乳液加入到MBS反应釜中作为芯层种子；
（2）向高压反应釜中加入配方量的水、乳化剂、无机盐溶液、分子量调节剂、交联剂、引发剂，然后关闭好反应釜盖并上紧螺栓，然后将丁二烯或丁二烯苯乙烯共聚物打入反应釜中；
（3）升温至70℃反应至反应完毕；
（4）再向反应釜中加入乳化剂、外层单体苯乙烯、丙烯酸丁酯和甲基丙烯酸甲酯的混合物，继续反应1-3h至反应完毕；
（5）出料，采用凝聚法将胶乳凝聚，通过离心机离心后采用沸腾流化床干燥，筛分、包装即得成品。
与现有技术相比，本发明的有益效果是：
本发明的一种PVC易加工不透明高抗冲MBS及其制备方法，PVC易加工不透明高抗冲MBS是由甲基丙烯酸甲酯、丁二烯、苯乙烯和丙烯酸酯合成，是一种特殊的三层结构的聚合物，三层结构为芯-核-壳结构，内部芯层结构为半硬质的轻微交联的苯乙烯单体和丙烯酸酯类单体的共聚物，占比为1-20%；中部核层结构为较软的玻璃化温度较低的轻度交联的丁二烯苯乙烯聚合物，占比为70-85%；外层壳层结构为玻璃化温度较高的苯乙烯、丙烯酸丁酯和甲基丙烯酸甲酯的共聚物，占比为5-20%。
本发明产品具有的芯-核-壳结构，其抗冲击强度较目前的核壳结构有大幅增加，当材料受到外力冲击时, MBS树脂中间层的橡胶核产生形变，并在周围诱发银纹和剪切带，并迅速传递到较硬的芯层，较硬的芯层会产生更大面积的银纹和剪切带，从而吸收更多的冲击能量，进而达到更高的增韧效果，提高聚合物的抗冲击性能。
具体实施方式
为对本发明有益效果作进一步阐述，进行了大量试验，特别说明的是，本发明试验旨在说明本发明技术的有益效果，绝不仅限于本发明的范围。
实施例1
（1）在反应釜中加入配方量的水、乳化剂、无机盐、分子量调节剂、苯乙烯单体和丙烯酸丁酯单体，其比例为95/5、交联剂、引发剂，然后关闭反应釜盖，升温至反应温度进行反应，直至反应完毕；或单独用一反应釜反应，取配方量的反应好的乳液加入到MBS反应釜中作为芯层种子，芯层占比为10%；
（2）向高压反应釜中加入配方量的水、乳化剂、无机盐溶液、10%的芯层种子、分子量调节剂、交联剂、引发剂，然后关闭好反应釜盖并上紧螺栓，然后将丁二烯和苯乙烯打入反应釜中，其中，丁二烯和苯乙烯比例为95/5，中间层占比为75%；
（3）升温至70℃反应至反应完毕；
（4）再向反应釜中加入乳化剂、外层单体苯乙烯、丙烯酸丁酯和甲基丙烯酸甲酯的混合物，三者的占比分别为2%、2%和11%，继续反应1-3h至反应完毕；
（5）出料，采用凝聚法将胶乳凝聚，通过离心机离心后采用沸腾流化床干燥，筛分、包装即得成品。
实施例2
将实施例1中步骤（1）芯层苯乙烯单体和丙烯酸丁酯单体比例变更为75/25，其余同实施例1。
实施例3
将实施例1中步骤（1）芯层苯乙烯单体和丙烯酸丁酯单体比例变更为50/50，其余同实施例1。
实施例4
将实施例1中步骤（1）芯层苯乙烯单体和丙烯酸丁酯单体比例变更为25/75，其余同实施例1。
实施例5
将实施例1中步骤（1）芯层苯乙烯单体和丙烯酸丁酯单体比例变更为5/95，其余同实施例1。
实施例6
将实施例1中步骤（2）中间层丁二烯和苯乙烯比例变更为80/20，其余同实施例1。
实施例7
将实施例1中步骤（2）中间层丁二烯和苯乙烯比例变更为90/10，其余同实施例1。
实施例8
将实施例1中步骤（2）中间层变更为纯丁二烯，其余同实施例1。
实施例9
将实施例1中步骤（1）芯层占比变更为3%，步骤（2）中间层占比变更为82%，其余同实施例1。
实施例10
将实施例2中步骤（1）芯层占比变更为3%，步骤（2）中间层占比变更为82%，其余同实施例2。
实施例11
将实施例3中步骤（1）芯层占比变更为3%，步骤（2）中间层占比变更为82%，其余同实施例3。
实施例12
将实施例4中步骤（1）芯层占比变更为3%，步骤（2）中间层占比变更为82%，其余同实施例4。
实施例13
将实施例5中步骤（1）芯层占比变更为3%，步骤（2）中间层占比变更为82%，其余同实施例5。
实施例14
将实施例1中步骤（1）芯层占比变更为15%，步骤（2）中间层占比变更为70%，其余同实施例1。
实施例15
将实施例2中步骤（1）芯层占比变更为15%，步骤（2）中间层占比变更为70%，其余同实施例2。
对比例1
实施例1中去掉芯层，其占比的部分用中间层补充，其余同实施例1。
对比例2
实施例2中去掉芯层，其占比的部分用中间层补充，其余同实施例2。
对比例3
实施例3中去掉芯层，其占比的部分用中间层补充，其余同实施例3。
对比例4
实施例4中去掉芯层，其占比的部分用中间层补充，其余同实施例4。
对比例5
实施例5中去掉芯层，其占比的部分用中间层补充，其余同实施例5。
对比例6
实施例6中去掉芯层，其占比的部分用中间层补充，其余同实施例6。
对比例7
实施例7中去掉芯层，其占比的部分用中间层补充，其余同实施例7。
对比例8
实施例8中去掉芯层，其占比的部分用中间层补充，其余同实施例8。
对比例9
实施例1中，芯层单体苯乙烯和丙烯酸丁酯单体，其比例变更为100/0，其余同实施例1。
对比例10
实施例1中，芯层单体苯乙烯和丙烯酸丁酯单体，其比例变更为0/100，其余同实施例1。
本发明实施例所得的PVC易加工不透明高抗冲MBS与对比例所得的产品的性能对比结果，如下表：
备注：
1、（1）加工时的流动性：
差 ◎ ◎◎ ◎◎◎ ◎◎◎◎ ◎◎◎◎◎ 好；
（2）下游产品的脆性：脆性越大，性能越差
脆 ● ●● ●●● ●●●●● ●●●●● 好；
2、表中用到的抗冲击强度的配方如下：PVC 为100份、有机锡为1.2份、轻钙为12份、DL-74为0.6份、DL-60为0.6份、硬脂酸钙为0.9份、二氧化钛为5份、MBS为8份。
本发明不仅适用于不透明MBS树脂，还可用于透明MBS树脂，以及用于工程塑料的MBS树脂，还可用于抗冲型ACR领域等。
以上所述，仅是本发明的较好实施例，并非对本发明作任何形式上的限制，任何未脱离本发明技术方案内容，依据本发明的技术实质对以上实例所作的任何简单修改、变换材料等同变化与修饰，均仍属于本发明技术方案的范围内。

Claims (7)

1.一种PVC易加工不透明高抗冲MBS，所述PVC易加工不透明高抗冲MBS为芯-核-壳三层结构，其特征在于：所述PVC易加工不透明高抗冲MBS由下列质量份数的各组分组成：芯层结构1-20%，核层结构70-85%，壳层结构5-20%；
所述芯层结构为半硬质的轻微交联的苯乙烯单体和丙烯酸酯类单体的共聚物，所述苯乙烯单体和所述丙烯酸酯类单体的比例为95/5-5/95；
所述苯乙烯类单体包括苯乙烯、甲基苯乙烯等；
所述丙烯酸酯类单体包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸-2-乙基己酯的一种或几种；
所述核层结构为较软的玻璃化温度较低的轻度交联的丁二烯苯乙烯聚合物，所述丁二烯和所述苯乙烯的比例为100/0-80/20；
所述壳层结构为玻璃化温度较高的苯乙烯、丙烯酸丁酯和甲基丙烯酸甲酯的共聚物，所述苯乙烯、所述丙烯酸丁酯和所述甲基丙烯酸甲酯的质量份数分别为0.2-5%、0.2-2%和13-20%。
2.根据权利要求1所述的一种PVC易加工不透明高抗冲MBS，其特征在于：所述芯层结构占比优选为1-15%，更优选为1-12%。
3.根据权利要求2所述的一种PVC易加工不透明高抗冲MBS，其特征在于：所述芯层结构中所述苯乙烯单体和所述丙烯酸酯类单体的比例优选为90/10-10/90，更优选为85/15-15/85。
4.根据权利要求3所述的一种PVC易加工不透明高抗冲MBS，其特征在于：所述核层结构占比优选为75-85%。
5.根据权利要求4所述的一种PVC易加工不透明高抗冲MBS，其特征在于：所述核层结构中所述丁二烯和所述苯乙烯的比例优选为100/0-85/15，更优选为100/0-90/10，最优选为100/0-95/5。
6.根据权利要求5所述的一种PVC易加工不透明高抗冲MBS，其特征在于：所述壳层结构占比优选为7-20%，更优选为9-19%。
7.根据权利要求1所述的一种PVC易加工不透明高抗冲MBS的制备方法，其特征在于：所述PVC易加工不透明高抗冲MBS的制备具体步骤如下：
（1）在反应釜中加入配方量的水、乳化剂、无机盐、分子量调节剂、苯乙烯类单体和丙烯酸酯类单体、交联剂、引发剂，然后关闭反应釜盖，升温至反应温度进行反应，直至反应完毕；或单独用一反应釜反应，取配方量的反应好的乳液加入到MBS反应釜中作为芯层种子；
（2）向高压反应釜中加入配方量的水、乳化剂、无机盐溶液、分子量调节剂、交联剂、引发剂，然后关闭好反应釜盖并上紧螺栓，然后将丁二烯或丁二烯苯乙烯共聚物打入反应釜中；
（3）升温至70℃反应至反应完毕；
（4）再向反应釜中加入乳化剂、外层单体苯乙烯、丙烯酸丁酯和甲基丙烯酸甲酯的混合物，继续反应1-3h至反应完毕；
（5）出料，采用凝聚法将胶乳凝聚，通过离心机离心后采用沸腾流化床干燥，筛分、包装即得成品。
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CN109971086A (zh) 2019-02-14 2019-07-05 山东东临新材料股份有限公司 一种pvc易加工不透明高抗冲mbs及其制备方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020164302A1 (zh) * 2019-02-14 2020-08-20 山东东临新材料股份有限公司 Pvc易加工不透明高抗冲mbs及其加工方法
KR20200106168A (ko) * 2019-02-14 2020-09-11 산둥 동린 뉴 머티리얼즈 코., 엘티디 Pvc가공이 용이한 불투명 고 항충격 mbs 및 그 제조 방법
KR102345094B1 (ko) 2019-02-14 2021-12-31 산둥 동린 뉴 머티리얼즈 코., 엘티디 Pvc가공이 용이한 불투명 고 항충격 mbs 및 그 제조 방법
US11866537B2 (en) 2019-02-14 2024-01-09 Shandong Donglin New Materials Co., Ltd Easy-to-process, opaque and high-impact methyl methacrylate-butadiene-styrene polymer for polyvinyl chloride and preparation method thereof

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DE112019000358B4 (de) 2023-02-16
DE112019000358T5 (de) 2021-10-14
RU2750936C1 (ru) 2021-07-06
KR20200106168A (ko) 2020-09-11
WO2020164302A1 (zh) 2020-08-20
MX2020008170A (es) 2020-09-25
US20210371569A1 (en) 2021-12-02
KR102345094B1 (ko) 2021-12-31

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