CN109232785A - 阻燃型聚丙烯酸酯乳液及其制备方法 - Google Patents
阻燃型聚丙烯酸酯乳液及其制备方法 Download PDFInfo
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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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- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F220/10—Esters
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- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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Abstract
本发明公开了一种新型无卤阻燃型聚丙烯酸酯乳液及其制备方法,该方法包括以下步骤:(1)将丙烯酸酯单体、反应型阻燃单体、乳化剂与去离子水混合,并调节pH值至6.5‑7.5,搅拌;(2)升温至60‑70℃,并引发反应进行乳液种子聚合;(3)乳液种子聚合结束后,滴加剩余的30%‑60%的乳化剂,剩余的40‑50%去离子水和剩余的60%‑80%引发剂,控温70‑95℃,反应3‑9小时;及(4)升温至95‑110℃,熟化,调整pH值至8‑9,得到所述阻燃型聚丙烯酸酯乳液。该阻燃型聚丙烯酸乳液阻燃单体含量为5%‑15%可达到阻燃级别V0或者离火自熄级别。本发明制得的本体阻燃型聚丙烯酸酯乳液是通过将无卤阻燃单体和丙烯酸酯通过化学键的方式连接,因而具有良好的附着力,耐久性能好。
Description
技术领域
本发明涉及合成树脂技术领域,更特别涉及一种阻燃型聚丙烯酸酯乳液及其制备方法。
背景技术
随着丙烯酸酯类共聚物的研究发展与环保要求的日益提高,丙烯酸乳液被广泛用于涂料、印染和胶粘剂等领域。然而,丙烯酸酯为易燃聚合物,遇火易燃烧,给人们的生产和生活带来了巨大安全隐患。因此,人们对丙烯酸酯的阻燃性能提出了更高要求。目前对丙烯酸酯乳液的阻燃改性方法主要是添加阻燃剂对其进行阻燃改性,其阻燃效果较好,但是添加量一般较大,并且添加型阻燃剂与丙烯酸乳液的相容性一般较差,对乳液本身的性能及其制备产品的机械性能和外观有较大影响。例如,中国专利(CN201410555081.1)用含卤的反应型阻燃单体与丙烯酸酯单体乳液共聚,并加入锑类化合物搅拌均匀得到聚丙烯酸酯乳液。该阻燃型聚丙烯酸酯乳液阻燃剂用量为3-17%,达到阻燃V0或V1级。但该类型阻燃单位为卤素化合物,环保上限制较多,且存在发烟量大等卤锑阻燃剂固有问题。中国专利(201510574078.9)利用乙烯基硅烷与丙烯酸酯单体共聚制备硅烷共聚物,然后用硅烷共聚物的MHT进行表面改性,得到一种有机包覆MHT复合阻燃材料。该材料为无卤阻燃材料,但是阻燃剂添加量大,阻燃剂本身与基体无化学连接,相容性差。中国专利(CN201510547845.7)提供一种耐热阻燃改性丙烯酸乳液涂料,其通过加入溴化环氧树脂、硼酚醛树脂来提高涂层的阻燃性,此涂料耐热性和耐水性好,且阻燃效果好。但是溴化环氧树脂虽然其粘结性能好,但与丙烯酸树脂乳液本身也没有化学键结合,只是简单将溴化环氧树脂分散于涂料中,存在分布不均匀等缺点,仍然可以游离于成膜后的丙烯酸树脂表面,随着时间的推移阻燃性能会减弱。
发明内容
本发明要解决的是现有阻燃剂含卤锑,阻燃剂添加量大,阻燃剂和丙烯酸基材相容性差,粘结能力不够等技术问题,提供一种无卤阻燃型聚丙烯酸酯乳液及其制备方法。
为了实现上述目的,本发明采用了以下的技术方案:
在一方面,本发明提供了一种阻燃型聚丙烯酸酯乳液的制备方法,包括以下步骤:
(1)将丙烯酸酯单体、反应型阻燃单体、乳化剂与去离子水混合,并使用pH缓冲液调节pH值至6.5-7.5,搅拌,得到预乳化混合单体乳液;
(2)将所述预乳化混合单体乳液升温至60-70℃,搅拌,并添加引发剂引发反应,进行乳液种子聚合;
(3)乳液种子聚合结束后,滴加剩余的以重量计30%-60%的乳化剂,剩余的以重量计40-50%去离子水和剩余的以重量计60%-80%引发剂,控温70-95℃,反应3-9小时,其中,乳化剂、去离子水和引发剂各自分两次添加,在步骤(3)中添加的是总量的剩下的一部分;及
(4)将步骤(3)得到的反应液升温至95-110℃,熟化30-120min,调整pH值至8-9,得到所述阻燃型聚丙烯酸酯乳液。
优选地,丙烯酸酯单体选自甲基丙烯酸甲酯、丙烯酸甲酯、丙烯酸丁酯、丙烯酸乙酯、甲基丙烯酸羟乙酯、甲基丙烯酸缩水甘油酯和丙烯酸羟丙酯中的一种或几种。
优选地,反应型阻燃单体为多羟基膦酸酯,其具有以下式(I)结构式:
(I)
其中,R1、R2、R3和R4独立地选自甲基、乙基、丙基和环氧基;
R5为乙烯基、丙烯基或丁烯基。
优选地,乳化剂选自十二烷基苯磺酸盐、烯丙氧基脂肪醇氧乙烯醚硫酸盐和丙烯酰胺基异丙基磺酸钠中的一种或几种。
优选地,引发剂选自过硫酸铵、过硫酸钾、过硫酸钠、异丙苯过氧化氢和过氧化二苯甲酰中的一种或几种。
优选地,所述pH缓冲液为碳酸氢钠溶液、氨水和氢氧化钠中的一种或几种。
优选地,以所使用的原料的总重为基准,各成分的质量百分比如下:丙烯酸酯单体35%-50%,反应型阻燃单体5%-25%;乳化剂0.5%-3.0%,引发剂 0.5%-1.0%,pH缓冲液0.5%-2.0%,去离子水19%-58.5%。此处所提到的乳化剂、引发剂和去离子水指的是两个步骤中所添加量的和。
在本发明中,乳化剂、引发剂和去离子水分批加入可以提高乳液整体的分散性和反应效率,以保证所得乳液的性能和阻燃效果。
优选地,在步骤(1)中,搅拌速度为1000-1300 rmp/min;在步骤(2)中,搅拌速度为600-900 rmp/min。
优选地,在步骤(2)中,反应时间为1-6小时。
在另一方面,本发明还提供了一种上述方法制得的阻燃型聚丙烯酸酯乳液。
与现有技术相比,本发明具有以下优点:
本发明提供了一种阻燃型聚丙烯酸酯乳液及其制备方法,该乳液是通过将无卤阻燃单体和丙烯酸酯通过化学键连接,因而在提供阻燃性的同时,还具有良好的附着力,相容性和耐久性能。该阻燃型丙烯酸酯乳液在阻燃单体添加量为5-25%的条件下即达到了很好的阻燃效果,最终所得的阻燃型丙烯酸酯乳液按照阻燃测试标准可以达到UL94-V0级别或者离火自熄的级别。
具体实施方式
下面结合具体实施例对本发明作进一步说明,以使本领域的技术人员可以更好地理解本发明并能予以实施,但所举实施例不作为对本发明的限定。
实施例1
实施例1提供了一种阻燃型聚丙烯酸酯乳液,其由以下成分制成:甲基丙烯酸酯甲酯和丙烯酸丁酯混合单体(1:1)42.0kg、多羟基膦酸酯-1 (式I中,R1-R4均为甲基,R5为乙烯基)20.0kg、丙烯酰胺基异丙基磺酸钠3.0kg、过硫酸铵1.0kg、碳酸氢钠溶液2.0kg和去离子水32.0kg。
实施例1的阻燃型聚丙烯酸酯乳液的制备方法如下,将反应型阻燃剂单体多羟基膦酸酯-1、甲基丙烯酸酯甲酯和丙烯酸丁酯混合单体、19.2kg去离子水、碳酸氢钠溶液和1.2kg丙烯酰胺基异丙基磺酸钠混合,在1300rmp/min高速搅拌下进行预乳化3小时,得到乳白色预乳化混合单体乳液;然后当温度升到60-70℃时,调整转速为600-900rmp/min,添加0.2kg过硫酸铵,引发反应,进行乳液种子聚合;种子聚合完毕滴加剩余的1.8kg丙烯酰胺基异丙烯磺酸钠,剩余的12.8kg去离子水和剩余的0.8kg过硫酸铵,控温为80℃,反应6个小时后,升温至95℃熟化60min,调整pH值至8-9,冷却、过滤即得到无卤阻燃型聚丙烯酸酯乳液,记为样品1。
实施例2
实施例2提供了一种阻燃型聚丙烯酸酯乳液,其由以下成分制成:甲基丙烯酸酯甲酯和丙烯酸异辛酯 (2:1)40.0kg、多羟基膦酸酯-2(式I中,R1-R4均为乙基,R5为丙烯基)10.0kg、十二烷基苯磺酸盐2.0kg、过硫酸钾1.0kg、pH缓冲液 1.0kg和去离子水 46.0kg。
实施例2的阻燃聚丙烯酸酯乳液的制备方法如下:将反应型阻燃剂单体多羟基膦酸酯-2、甲基丙烯酸酯甲酯和丙烯酸异辛酯混合单体、27.6kg去离子水、氨水溶液和0.7kg十二烷基苯磺酸盐混合,在1200rmp/min高速搅拌下进行预乳化5小时,得到乳白色预乳化混合单体乳液;然后当温度升到60-70℃时,调整转速为900rmp/min,添加0.3kg过硫酸钾,引发反应,进行乳液种子聚合;种子聚合完毕滴加剩余的1.3kg十二烷基苯磺酸盐,剩余的18.4kg去离子水和剩余的0.7kg过硫酸钾,控温为80℃,反应6个小时后,升温至100℃熟化30min,调整pH值至8-9,冷却、过滤即得到无卤阻燃型聚丙烯酸酯乳液,记为样品2。
实施例3
实施例3提供了一种阻燃型聚丙烯酸酯乳液,其由以下成分制成:甲基丙烯酸酯甲酯和丙烯酸乙酯混合单体(2:3)45.0kg、多羟基膦酸酯-3 (式I中,R1-R2为甲基,R3-R4为乙基,R5为丙烯基)15.0kg、丙烯酰胺基异丙基磺酸钠3.0kg、过硫酸铵1.0kg、碳酸氢钠溶液 2.0kg和去离子水 34.0kg。
实施例3的阻燃聚丙烯酸酯乳液的制备方法如下:将反应型阻燃剂单体多羟基膦酸酯-3、甲基丙烯酸酯甲酯和丙烯酸乙酯混合单体、20.4kg去离子水、碳酸氢钠溶液和1.2kg丙烯酰胺基异丙基磺酸钠一起,在1300rmp/min高速搅拌下进行预乳化4小时,得到乳白色预乳化混合单体乳液;然后当温度升到60-70℃时,调整转速为900rmp/min,添加0.2kg过硫酸铵,引发反应,进行乳液种子聚合;种子聚合完毕滴加剩余的1.8kg丙烯酰胺基异丙基磺酸钠,13.6kg去离子水和剩余的0.8kg过硫酸铵,控温为80℃,反应6个小时后,升温至105℃熟化80min,调整pH值至8-9,冷却、过滤即得到无卤阻燃型聚丙烯酸酯乳液,记为样品3。
实施例4
实施例4提供了一种阻燃型聚丙烯酸酯乳液,按重量百分比计算,其由以下成分制成:甲基丙烯酸酯甲酯和丙烯酸乙酯混合单体(2:1)30.0kg、多羟基膦酸酯-4 (式I中,R1-R4均为丙基,R5为乙烯基)23.0kg、丙烯酰胺基异丙基磺酸钠和烯丙氧基脂肪醇氧乙烯醚硫酸盐(1:1)3.0kg、异丙苯过氧化氢1.0kg、氢氧化钠溶液2.0kg和去离子水 31.0kg。
实施例4的阻燃聚丙烯酸酯乳液的制备方法如下:将反应型阻燃剂单体多羟基膦酸酯-4、甲基丙烯酸酯甲酯和丙烯酸乙酯混合单体、18.6kg去离子水、氢氧化钠溶液和1.2kg丙烯酰胺基异丙基磺酸钠和烯丙氧基脂肪醇氧乙烯醚硫酸盐的混合物混合,在1000rmp/min高速搅拌下进行预乳化2小时,得到乳白色预乳化混合单体乳液;然后当温度升到70℃时,调整转速为900rmp/min,添加0.2kg异丙苯过氧化氢,引发反应,进行乳液种子聚合;种子聚合完毕滴加剩余的1.8kg丙烯酰胺基异丙烯磺酸钠和烯丙氧基脂肪醇氧乙烯醚硫酸盐的混合物,12.4kg的去离子水和剩余的0.8kg异丙苯过氧化氢,控温为80℃,反应4个小时后,升温至100℃熟化80min,调整pH值至8-9,冷却、过滤即得到无卤阻燃型聚丙烯酸酯乳液,记为样品4。
上述样品制成样片后进行阻燃测试结果如下,
实验组 | 测试标准 | 样品1 | 样品2 | 样品3 | 样品4 |
垂直燃烧 | UL94 | V0 | V2 | V1 | V0 |
氧指数 | GB/T2406.2 | 32 | 28 | 30 | 32 |
有焰燃烧/s | GB/T5454 | 0 | 13 | 9 | 2 |
综上可知,本发明的无卤阻燃型聚丙烯酸酯乳液制备方法简便,且有效地提高了阻燃效率。
以上所述实施例仅是为充分说明本发明而所举的较佳的实施例,本发明的保护范围不限于此。本技术领域的技术人员在本发明基础上所作的等同替代或变换,均在本发明的保护范围之内。本发明的保护范围以权利要求书为准。
Claims (10)
1.一种阻燃型聚丙烯酸酯乳液的制备方法,其特征在于,包括以下步骤:
(1)将丙烯酸酯单体、反应型阻燃单体、乳化剂与去离子水混合,并使用pH缓冲液调节pH值至6.5-7.5,搅拌,得到预乳化混合单体乳液;
(2)将所述预乳化混合单体乳液升温至60-70℃,搅拌,并添加引发剂引发反应,进行乳液种子聚合;
(3)乳液种子聚合结束后,滴加剩余的以重量计30%-60%的乳化剂,剩余的以重量计40-50%去离子水和剩余的以重量计60%-80%引发剂,控温70-95℃,反应3-9小时;及
(4)将步骤(3)得到的反应液升温至95-110℃,熟化30-120min,调整pH值至8-9,得到所述阻燃型聚丙烯酸酯乳液。
2.根据权利要求1所述的制备方法,其特征在于:所述丙烯酸酯单体选自甲基丙烯酸甲酯、丙烯酸甲酯、丙烯酸丁酯、丙烯酸乙酯、甲基丙烯酸羟乙酯、甲基丙烯酸缩水甘油酯和丙烯酸羟丙酯中的一种或几种。
3.根据权利要求1所述的制备方法,其特征在于:所述反应型阻燃单体为多羟基膦酸酯,具有以下式(I)结构式:
(I)
其中,R1、R2、R3和R4独立地选自甲基、乙基、丙基和环氧基;
R5为乙烯基、丙烯基或丁烯基。
4.根据权利要求1所述的制备方法,其特征在于:所述乳化剂选自十二烷基苯磺酸盐、烯丙氧基脂肪醇氧乙烯醚硫酸盐和丙烯酰胺基异丙基磺酸钠中的一种或几种。
5.根据权利要求1所述的制备方法,其特征在于:所述引发剂选自过硫酸铵、过硫酸钾、过硫酸钠、异丙苯过氧化氢和过氧化二苯甲酰中的一种或几种。
6.根据权利要求1所述的制备方法,其特征在于:所述pH缓冲液为碳酸氢钠溶液、氨水和氢氧化钠中的一种或几种。
7.根据权利要求1所述的制备方法,其特征在于,以所使用的原料的总重为基准,各成分质量百分比如下:丙烯酸酯单体35%-50%,反应型阻燃单体5%-25%;乳化剂0.5%-3.0%,引发剂 0.5%-1.0%,pH缓冲液0.5%-2.0%,去离子水19%-58.5%。
8.根据权利要求1所述的制备方法,其特征在于:在步骤(1)中,搅拌速度为1000-1300rmp/min;在步骤(2)中,搅拌速度为600-900 rmp/min。
9.根据权利要求1所述的制备方法,其特征在于:在步骤(2)中,反应时间为1-6小时。
10.一种根据权利要求1所述的方法制得的阻燃型聚丙烯酸酯乳液。
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