WO2020164302A1 - Pvc易加工不透明高抗冲mbs及其加工方法 - Google Patents

Pvc易加工不透明高抗冲mbs及其加工方法 Download PDF

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WO2020164302A1
WO2020164302A1 PCT/CN2019/125413 CN2019125413W WO2020164302A1 WO 2020164302 A1 WO2020164302 A1 WO 2020164302A1 CN 2019125413 W CN2019125413 W CN 2019125413W WO 2020164302 A1 WO2020164302 A1 WO 2020164302A1
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styrene
layer structure
pvc
impact
core layer
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PCT/CN2019/125413
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English (en)
French (fr)
Inventor
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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山东东临新材料股份有限公司
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Application filed by 山东东临新材料股份有限公司 filed Critical 山东东临新材料股份有限公司
Priority to KR1020207021824A priority Critical patent/KR102345094B1/ko
Priority to DE112019000358.5T priority patent/DE112019000358B4/de
Priority to US16/968,830 priority patent/US11866537B2/en
Priority to MX2020008170A priority patent/MX2020008170A/es
Priority to RU2020126890A priority patent/RU2750936C1/ru
Publication of WO2020164302A1 publication Critical patent/WO2020164302A1/zh

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Definitions

  • the invention relates to the technical field of PVC auxiliary agent production and preparation, in particular to a PVC easy-to-process opaque high-impact MBS and a preparation method thereof.
  • MBS methyl methacrylate-butadiene-styrene polymer
  • MBS resin is a functional polymer material synthesized on the basis of particle design concept. It is a ternary polymer prepared by emulsion graft polymerization. It has a typical core-shell structure in submicroscopic form, and the core of the particle is lightly cross-linked.
  • the styrene-butadiene rubber core with low shear modulus mainly plays a role in improving the impact toughness of the polymer;
  • the outer shell is a hard shell layer formed by grafting styrene and methyl methacrylate, and MMA (methyl methacrylate) in the shell layer
  • the main function of ester) is to improve its compatibility with PVC, so that MBS can be uniformly dispersed in the PVC body;
  • St mainly increases the refractive index of MBS resin so that MBS has a refractive index similar to that of PVC, so MBS resin is a typical The particle dispersion type toughening modifier.
  • the two phases of MBS and PVC are semi-compatible, that is, it has good interface compatibility with PVC resin, and it can keep the particle shape intact in the PVC/MBS system.
  • MBS metal-oxide-semiconductor
  • the amount of MBS added is small, it has good dispersibility in PVC and presents spherical particles, and does not form a dispersed "sea-island" structure, which does not play the role of transmitting impact energy, and the material has a poor toughening effect; with the increase of MBS resin addition , The dispersed particles gradually coalesce to form a sea-island structure.
  • the rubber core in the MBS resin acts as a stress concentration point, causing it to deform, and induce crazing and shear bands around it.
  • the shear band disperses and absorbs the impact energy, forming the transition of the material from brittle fracture to ductile fracture, so as to achieve the purpose of toughening.
  • Methyl methacrylate-butadiene-styrene polymer is a typical core-shell structure, with a softer rubber phase inside and the main component is butadiene-based butadiene styrene copolymer , The outer layer is a harder plastic phase, the main component is a copolymer of methyl methacrylate and styrene, a large number of tests have shown that the impact strength of this structure is not particularly high.
  • the present invention proposes a core-core-shell structure on the basis of previous theories, and the impact strength of this structure is greatly increased compared with the current core-shell structure.
  • the technical problem to be solved by the present invention is to provide a PVC easy-to-process opaque and high-impact MBS and a preparation method thereof to obtain a three-layer structure polymer to improve the resistance of the polymer Impact performance, to solve the problems of low impact strength and poor processing fluidity of MBS products for opaque PVC products.
  • the present invention provides a PVC easy-to-process opaque and high-impact MBS.
  • the PVC easy-to-process opaque and high-impact MBS has a core-core-shell three-layer structure.
  • Impact MBS consists of the following components in mass fraction: core layer structure 1-20%, core layer structure 70-85%, shell structure 5-20%;
  • the core layer structure is a semi-rigid slightly cross-linked copolymer of styrene monomer and acrylate monomer, and the ratio of the styrene monomer to the acrylate monomer is 95:5-5 :95;
  • the styrene monomer includes styrene or methyl styrene
  • the acrylic monomers include one or more of methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate;
  • the core layer structure is a slightly cross-linked butadiene styrene polymer with a softer glass transition temperature, and the ratio of the butadiene to the styrene is 100:0 to 80:20;
  • the shell structure is a copolymer of styrene, butyl acrylate and methyl methacrylate with a higher glass transition temperature, and the mass fractions of the styrene, the butyl acrylate and the methyl methacrylate are respectively It is 0.2 to 5%, 0.2 to 2% and 13 to 20%.
  • the core layer structure accounts for 1-15%.
  • the core layer structure accounts for 1-12%.
  • the ratio of the styrene monomer to the acrylic monomer in the core layer structure is 90:10-10:90.
  • the ratio of the styrene monomer and the acrylic monomer in the core layer structure is 85:15-15:85.
  • the core layer structure accounts for 75-85%.
  • the ratio of the butadiene to the styrene in the core layer structure is 100:0 to 85:15.
  • the ratio of the butadiene to the styrene in the core layer structure is 100:0 to 90:10.
  • the ratio of the butadiene to the styrene in the core layer structure is 100:0 to 95:5.
  • the shell structure accounts for 7-20%.
  • the shell structure accounts for 9-19%.
  • the latex is coagulated by a coagulation method, centrifuged in a centrifuge, dried in a boiling fluidized bed, sieved, and packaged to obtain the finished product.
  • the invention provides a PVC easy-to-process opaque and high-impact MBS and a preparation method thereof.
  • the PVC easy-to-process opaque and high-impact MBS is synthesized from methyl methacrylate, butadiene, styrene and acrylate, and is a special
  • the three-layer structure of the polymer, the three-layer structure is a core-core-shell structure, and the internal core layer structure is a semi-hard copolymer of slightly crosslinked styrene monomer and acrylic monomer, accounting for 1 ⁇ 20%;
  • the middle core layer structure is a softer, lightly cross-linked butadiene styrene polymer with a lower glass transition temperature, accounting for 70-85%;
  • the outer shell structure is a higher glass transition temperature
  • the copolymer of styrene, butyl acrylate and methyl methacrylate accounts for 5-20%.
  • the product of the present invention has a core-core-shell structure, and its impact strength is greatly increased compared with the current core-shell structure.
  • the rubber core of the MBS resin intermediate layer is deformed and causes silver streaks and Shear bands are quickly transferred to the harder core layer.
  • the harder core layer will produce a larger area of silver streaks and shear bands, thereby absorbing more impact energy, thereby achieving a higher toughening effect and improving The impact resistance of the polymer.
  • the latex is coagulated by a coagulation method, centrifuged in a centrifuge, dried in a boiling fluidized bed, sieved, and packaged to obtain the finished product.
  • Example 1 The ratio of styrene monomer and butyl acrylate monomer in the core layer of step (1) in Example 1 was changed to 75:25, and the rest was the same as in Example 1.
  • Example 1 The ratio of styrene monomer and butyl acrylate monomer in the core layer of step (1) in Example 1 was changed to 50:50, and the rest was the same as in Example 1.
  • Example 1 The ratio of styrene monomer and butyl acrylate monomer in the core layer of step (1) in Example 1 was changed to 25:75, and the rest was the same as in Example 1.
  • Example 1 The ratio of styrene monomer and butyl acrylate monomer in the core layer of step (1) in Example 1 was changed to 5:95, and the rest was the same as in Example 1.
  • Example 1 The ratio of butadiene and styrene in the intermediate layer of step (2) in Example 1 is changed to 90:10, and the rest is the same as in Example 1.
  • Example 1 the proportion of the core layer in step (1) was changed to 3%, and the proportion of the intermediate layer in step (2) was changed to 82%, and the rest was the same as in Example 1.
  • the proportion of the core layer in step (1) is changed to 3%, the proportion of the intermediate layer in step (2) is changed to 82% in Example 5, and the rest is the same as in Example 5.
  • the proportion of the core layer in step (1) is changed to 15%, the proportion of the intermediate layer in step (2) is changed to 70% in Example 2, and the rest is the same as in Example 2.
  • Example 1 the core layer was removed, and the proportion of the core layer was supplemented with an intermediate layer, and the rest was the same as in Example 1.
  • Example 2 the core layer was removed, and the proportion of the core layer was supplemented with an intermediate layer, and the rest was the same as in Example 2.
  • Example 3 the core layer was removed, and the proportion of the core layer was supplemented with an intermediate layer, and the rest was the same as in Example 3.
  • Example 4 the core layer was removed, and the proportion of the core layer was supplemented with an intermediate layer, and the rest was the same as in Example 4.
  • Example 5 the core layer was removed, and the proportion of the core layer was supplemented with an intermediate layer, and the rest was the same as in Example 5.
  • Example 6 the core layer was removed, and the proportion of the core layer was supplemented with an intermediate layer, and the rest was the same as in Example 6.
  • Example 7 the core layer was removed, and its proportion was supplemented with an intermediate layer, and the rest was the same as in Example 7.
  • Example 8 the core layer was removed, and the proportion of the core layer was supplemented with an intermediate layer, and the rest was the same as in Example 8.
  • Example 1 the ratio of the core layer monomer styrene and butyl acrylate monomer was changed to 100/0, and the rest was the same as in Example 1.
  • Example 1 the ratio of the core layer monomer styrene and butyl acrylate monomer was changed to 0/100, and the rest was the same as in Example 1.
  • the formula of impact strength used in the table is as follows: PVC is 100 parts, organotin is 1.2 parts, light calcium is 12 parts, DL-74 (polyethylene wax) is 0.6 parts, DL-60 (stearic acid) Pentaerythritol ester) is 0.6 parts, calcium stearate is 0.9 parts, titanium dioxide is 5 parts, and MBS is 8 parts.
  • the invention is not only suitable for opaque MBS resin, but also for transparent MBS resin, and MBS resin for engineering plastics, and can also be used in the field of impact-resistant ACR.

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Abstract

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，由下列质量分数的各组分组成：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；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；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。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
本申请要求于2019年02月14日提交中国专利局、申请号为201910113748.5、发明名称为“一种PVC易加工不透明高抗冲MBS及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
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模量的丁苯橡胶核，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(甲基丙烯酸甲酯)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，本发明提供了一种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由下列质量分数的各组分组成：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或甲基苯乙烯；
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-乙基己酯中的一种或几种；
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分数分别为0.2～5％、0.2～2％和13～20％。
优选的，所述芯层结构占比为1～15％。
优选的，所述芯层结构占比为1～12％。
优选的，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为90:10～10:90。
优选的，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为85:15～15:85。
优选的，所述核层结构占比为75～85％。
优选的，所述核层结构中所述丁二烯和所述苯乙烯的比例为100:0～85:15。
优选的，所述核层结构中所述丁二烯和所述苯乙烯的比例为100:0～90:10。
优选的，所述核层结构中所述丁二烯和所述苯乙烯的比例为100:0～95:5。
优选的，所述壳层结构占比为7～20％。
优选的，所述壳层结构占比为9～19％。
在本发明中，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、丙烯酸酯类单体、交联剂和引发剂，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：
本发明提供了一种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，如表1所示：
表1实施例和对比例的产品性能对比结果
Figure PCTCN2019125413-appb-000001
Figure PCTCN2019125413-appb-000002
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(聚乙烯蜡)为0.6份、DL-60(硬脂酸季戊四醇酯)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。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。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，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。对这些实施例的多种修改对本领域的专业技术人员来说是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下在其它实施例中实现。因此，本发明将不会被限制于 本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (12)

  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由下列质量分数的各组分组成：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或甲基苯乙烯；
    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-乙基己酯中的一种或几种；
    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分数分别为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，所述芯层结构占比为1～15％。
  3. 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，所述芯层结构占比为1～12％。
  4. 根据权利要求2或3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为90:10～10:90。
  5. 根据权利要求2或3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为85:15～15:85。
  6. 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，所述核层结构占比为75～85％。
  7. 根据权利要求6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为 100:0～85:15。
  8. 根据权利要求6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为100:0～90:10。
  9. 根据权利要求6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为100:0～95:5。
  10. 根据权利要求7、8或9所述的一种PVC易加工不透明高抗冲MBS，其特征在于，所述壳层结构占比为7～20％。
  11. 根据权利要求7、8或9所述的一种PVC易加工不透明高抗冲MBS，其特征在于，所述壳层结构占比为9～19％。
  12. 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。
PCT/CN2019/125413 2019-02-14 2019-12-14 Pvc易加工不透明高抗冲mbs及其加工方法 WO2020164302A1 (zh)

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