CN106336478A - Pvc树脂改性剂的制备方法 - Google Patents
Pvc树脂改性剂的制备方法 Download PDFInfo
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- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
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- 235000021317 phosphate Nutrition 0.000 claims 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
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- ACYXOHNDKRVKLH-UHFFFAOYSA-N 5-phenylpenta-2,4-dienenitrile prop-2-enoic acid Chemical compound OC(=O)C=C.N#CC=CC=CC1=CC=CC=C1 ACYXOHNDKRVKLH-UHFFFAOYSA-N 0.000 description 1
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- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
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Abstract
本发明公开了一种PVC树脂改性剂的制备方法,包括以下过程:采用两段乳液,在去离子水、乳化剂、引发剂、分子量调节剂的存在下,40℃-90℃进行共聚,共聚乳液经喷雾干燥,得PVC树脂改性剂;两段乳液中一个为重量份40‑80的丙烯酸酯和甲基丙烯酸酯,另一个为重量份20‑60的苯乙烯、丙烯腈和丙烯酸酯。它能显著提高PVC树脂的塑化加工性能,改善PVC树脂的加工流动性,和普通的加工型ACR相比,塑化时间明显缩短,用量仅为普通ACR加工助剂的30‑60%,主要用于要求塑化性能快和加工流动性好的管材和管件上。用其改性后的PVC树脂产品具有高的表面光泽度和抗拉强度强度和维卡软化点。
Description
技术领域
本发明涉及高分子化合物组合物技术领域,尤其是一种PVC树脂改性剂的制备方法。
背景技术
PVC是一种我国产量最大的通用型热塑性塑料之一,但同时也存在着很多缺点,例如热稳定性差,需添加PVC热稳定剂,韧性差,添加抗冲改性剂,润滑性差添加PVC内外润滑剂,加工性能差添加PVC加工改性剂。而在PVC型材和管材加工过程中,一般需要加入1-2份的加工改性剂,加入量少则会出现加工材料塑化不良,尺寸稳定性变差,材料便面光洁度变差。而由于PVC加工改性剂本身的材料比PVC价格贵,加入量大材料的成本就会相应增加。尤其在管件应用上,一般国内的管件添加剂(如碳酸钙)的量较大,为了改善PVC的塑化性能和加工流动性,国内大多数厂家一直在加入DOP、DBP等增塑剂,而这些液体增塑剂一方面不如固体好计量,即使加入增塑剂虽然改善了加工性能和流动性,但管件的维卡温度迅速降低,导致大多数厂家的维卡温度很少能达到国家标准,而且造成生产周期长,冷却慢等缺点,能耗也较大;致命的是,加入的增塑剂随着时间的延长会慢慢析出,降低了管件的性能。国外的管件生产厂家避免出现这种情况,为了改善PVC的塑化性能和加工流动性,只能大幅度降低添加剂的含量,大幅度增加了加工改性剂的含量,造成原料成本大幅度上升,一直以来,国内外研究人员为了改善PVC的塑化性能和加工流动性做了大量的工作,通过各种方法来改善性能或降低成本,虽然取得了一些效果,但未能从根本上改变。所以研制一种既能大幅度促进PVC塑化和改善PVC加工流动性,替代ACR加工改性剂和DOP等增塑剂的产品,长时间不析出,并且较大幅度改进PVC管件的维卡温度和表面光洁度,是人们非常期待的。
发明内容
本发明针对现有技术的不足,提出一种PVC树脂改性剂的制备方法,操作简单,对PVC树脂改性好。
为了实现上述发明目的,本发明提供以下技术方案:一种PVC树脂改性剂的制备方法,包括以下过程:采用两段乳液,在去离子水、乳化剂、引发剂、分子量调节剂的存在下,40℃-90℃进行共聚,共聚乳液经喷雾干燥,得PVC树脂改性剂;两段乳液中一个为重量份40-80的丙烯酸酯和甲基丙烯酸酯,另一个为重量份20-60的苯乙烯、丙烯腈和丙烯酸酯。
进一步地,乳化剂为烷基硫酸盐、烷基磷酸盐、烷基苯磺酸盐、聚氧乙烯烷基醚、聚氧乙烯烷基脂肪酸酯中的一种或多种;用量为两段乳液总重量的0.2-8%。
进一步地,乳化剂为阴离子乳化剂或阴离子乳化剂和非离子乳化剂的复配物,用量为两段乳液总重量的0.5%-5.0%;优选为1-7%;更优选为2-6%。
进一步地,引发剂为过硫酸盐、有机过氧化物、偶氮类化合物中的一种,或与亚硫酸盐、亚硫酸氢盐、硫代硫酸盐中的一种构成氧化还原引发剂体系;用量为两段乳液总重量的0.1-1%。
进一步地,分子量调节剂为C4-C20的烷基硫醇,用量为两段乳液总重量的0-2%;优选为0-1%;更优选为0-0.5%。
进一步地,丙烯酸酯为丙烯酸丁酯、丙烯酸乙酯、丙烯酸甲酯;甲基丙烯酸酯为甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯中的一种和多种。
进一步地,甲基丙烯酸酯和丙烯酸酯配比为30-70:70-30;优选为35-65:65-35;更优选为40-60:60-40;苯乙烯、丙烯腈和丙烯酸酯配比为50-70:10-20:10-30,优选为55-70:10-20:15-30。
进一步地,两段乳液的重量份比为50-75:25-50。
进一步地,具体制备过程为:
⑴、向搅拌的去离子水中,加入乳化剂、丙烯酸酯、甲基丙烯酸酯、分子量调节剂,通入氮气,升温至65℃,再加入引发剂,在65~85℃聚合;
⑵、在65℃下,向步骤⑴聚合物中加入苯乙烯、丙烯腈和丙烯酸酯的混合物,10分钟后加入引发剂,在65~85℃聚合;在85℃以上保温2小时,降温至40℃,过滤得PVC树脂改性剂乳液。
一种如上所述PVC树脂改性剂的制备方法得到的产品,特性粘度在3.0-10.0;优选为4.0-9.0;更优选为5.0-8.0。
与现有技术相比,本发明具有以下优点:
1.提供了一种能显著改善PVC加工性能的苯乙烯-丙烯腈-丙烯酸酯和甲基丙烯酸甲酯的共聚物,其塑化加工性能和加工流动性都非常优异,产出的PVC树脂产品具有高的表面光泽度,而且不影响产品的稳定性和冲击韧性。用较少的用量即可达到目前的效果,一般加料量为目前加料量的50-70%,较大的降低了成本,节约了资源。该产品特别适合于PVC管件,替代ACR加工改性剂和DOP等增塑剂的产品,长时间不析出,并且较大幅度改进PVC管件的维卡温度和表面光洁度。
2.采用前后两部分聚合工艺,前后两部分解决了塑化快慢的问题,后面还解决了物料加工过程中的流动性问题,和在后处理过程中的干燥的问题,这样,既解决了产品的塑化问题,加工流动性问题,又解决了产品的结块问题和运输问题。
3.制备工艺简单,生产成本低,产品使用方便。
具体实施方式
下面结合实施例对本发明进行详细描述,本部分的描述仅是示范性和解释性,不应对本发明的保护范围有任何的限制作用。
一种PVC树脂改性剂的制备方法,包括以下步骤:
a:在反应釜中,加入去离子水、开启搅拌,然后分别向反应釜中加入乳化剂,聚合用的丙烯酸酯和甲基丙烯酸酯、分子量调节剂,通入氮气,并向反应釜夹套通蒸汽升温、稳定在65℃后加入配方量的引发剂进行反应。控制温度在65~85℃聚合;
b.反应完后,温度稳定在65℃左右,在向反应釜中加入苯乙烯、丙烯腈和丙烯酸酯的混合物。10分钟后加入配方量的引发剂,进行聚合反应。控制温度在65~85℃聚合,反应完毕后,升温至85℃ 以上保温2小时。降温至40℃,过滤得共聚物乳液,聚合转化率为99.5%以上,特性粘度在3.0-10.0,备用;
c.喷雾、干燥:步骤b制备的共聚乳液经喷雾干燥,即可得到白色粉末状聚合物。
共聚单体包括步骤a中40-80重量份的丙烯酸酯和甲基丙烯酸酯,步骤b中20--60重量份的苯乙烯、丙烯腈及丙烯酸酯;优选50-75:25-50。步骤a单体占的比例越高,塑化越好,但后处理过程中越难干燥,步骤b占的比例越高,塑化越好,流动性也越好,后处理过程中越容易干燥。
采用的乳化剂是从烷基硫酸盐、烷基磷酸盐、烷基苯磺酸盐、聚氧乙烯烷基醚、聚氧乙烯烷基脂肪酸酯中选择出来的任意一种或其任意两种以上组合;总用量为聚合单体总重量的0.2-8%;或
乳化剂为阴离子乳化剂或阴离子乳化剂和非离子乳化剂的复配物。用量为聚合单体总重量的0.5%-8.0%;优选1-7%,更优选2-6%。
引发剂是从过硫酸盐、有机过氧化物、偶氮类化合物中选择出来的任意一种,或与从亚硫酸盐、亚硫酸氢盐、硫代硫酸盐中选择出来的任意一种所组成的氧化还原引发剂体系,总用量为聚合单体总重量的0.1-1%。
采用的丙烯酸酯为丙烯酸甲酯、丙烯酸丁酯、丙烯酸乙酯或这些单体的混合物;甲基丙烯酸酯是指甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯或这些单体的混合物。
采用的分子量调节剂是C4-C20的烷基硫醇,其总用量为聚合单体总重量的0-2%,优选0-1%,更优选0-0.5%。
采用上述制备方法得到的产品特性粘度在3.0-10.0;优选为4.0-9.0。
步骤a中,甲基丙烯酸酯和丙烯酸酯配比为30-70:70-30,优选35-65:65-35,更优选40-60:60-40。
步骤b中,苯乙烯、丙烯腈和丙烯酸酯配比为50-70:10-20::10-30,优选55-70:10-20:15-30,
各实施例的原料和产品性能结果如下表:
表1实施例1-7原料重量份 及产品性能指标
以上所述仅是本发明的优选实施方式,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,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种PVC树脂改性剂的制备方法,其特征在于:包括以下过程:采用两段乳液,在去离子水、乳化剂、引发剂、分子量调节剂的存在下,40℃-90℃进行共聚,共聚乳液经喷雾干燥,得PVC树脂改性剂;两段乳液中一个为重量份40-80的丙烯酸酯和甲基丙烯酸酯,另一个为重量份20-60的苯乙烯、丙烯腈和丙烯酸酯。
2.如权利要求1所述PVC树脂改性剂的制备方法,其特征在于:乳化剂为烷基硫酸盐、烷基磷酸盐、烷基苯磺酸盐、聚氧乙烯烷基醚、聚氧乙烯烷基脂肪酸酯中的一种或多种;用量为两段乳液总重量的0.2-8%。
3.如权利要求1所述PVC树脂改性剂的制备方法,其特征在于:乳化剂为阴离子乳化剂或阴离子乳化剂和非离子乳化剂的复配物,用量为两段乳液总重量的0.5%-5.0%;优选为1-7%;更优选为2-6%。
4.如权利要求1所述PVC树脂改性剂的制备方法,其特征在于:引发剂为过硫酸盐、有机过氧化物、偶氮类化合物中的一种,或与亚硫酸盐、亚硫酸氢盐、硫代硫酸盐中的一种构成氧化还原引发剂体系;用量为两段乳液总重量的0.1-1%。
5.如权利要求1所述PVC树脂改性剂的制备方法,其特征在于:分子量调节剂为C4-C20的烷基硫醇,用量为两段乳液总重量的0-2%;优选为0-1%;更优选为0-0.5%。
6.如权利要求1所述PVC树脂改性剂的制备方法,其特征在于:丙烯酸酯为丙烯酸丁酯、丙烯酸乙酯、丙烯酸甲酯;甲基丙烯酸酯为甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯中的一种和多种。
7.如权利要求1所述PVC树脂改性剂的制备方法,其特征在于:甲基丙烯酸酯和丙烯酸酯配比为30-70:70-30;优选为35-65:65-35;更优选为40-60:60-40;苯乙烯、丙烯腈和丙烯酸酯配比为50-70:10-20:10-30,优选为55-70:10-20:15-30。
8.如权利要求1所述PVC树脂改性剂的制备方法,其特征在于:两段乳液的重量份比为50-75:25-50。
9.如权利要求1所述PVC树脂改性剂的制备方法,其特征在于:具体制备过程为:
⑴、向搅拌的去离子水中,加入乳化剂、丙烯酸酯、甲基丙烯酸酯、分子量调节剂,通入氮气,升温至65℃,再加入引发剂,在65~85℃聚合;
⑵、在65℃下,向步骤⑴聚合物中加入苯乙烯、丙烯腈和丙烯酸酯的混合物,10分钟后加入引发剂,在65~85℃聚合;在85℃以上保温2小时,降温至40℃,过滤得PVC树脂改性剂乳液。
10.一种如权利要求1所述PVC树脂改性剂的制备方法得到的产品,其特征在于:特性粘度在3.0-10.0;优选为4.0-9.0;更优选为5.0-8.0。
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