CN1005983B - 透明冲击改性的聚氯乙烯组合物 - Google Patents
透明冲击改性的聚氯乙烯组合物 Download PDFInfo
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Abstract
由ＰＶＣ和ＡＢＳ接枝共聚物组成的冲击改性的ＰＶＣ组合物，其中的ＡＢＳ接枝共聚物含６０－７０％（重量）苯乙烯－丁二烯橡胶和４０－３０％（重量）苯乙烯－丙烯腈（ＳＡＮ），其Ｓ／ＡＮ值约为３．８／１至４．２／１，此组合物具有优异的透明性和良好抗冲击性，优选的ＰＶＣ组合物中丁苯基质橡胶（ＳＢＲ）含７８－９５％（重量）丁二烯和２２－５％（重量）苯乙烯。
Description
本发明涉及一种透明冲击改性的树脂，具体说，涉及一种用于热塑性树脂的透明冲击改性剂，更具体地说，涉及一种用于透明的冲击改性的聚氯乙烯（PVC）组合物的冲击改性剂。
聚氯乙烯树脂是一种众所周知的热塑性模塑树脂，工业上得到广泛应用。通常，不加或加入少量增塑剂的PVC树脂是很脆的。为克服这一缺点，三十年来，一直采用橡胶类物质作其冲击改性剂。为此目的发展起来的典型冲击改性剂是以接枝共聚物为基础的，如美国专利3，073，798中所述。
PVC本身固有的清晰性和透明性是其得以广泛应用的另一种性质。但是，最初用于PVC的许多冲击改性剂会大大地降低其清晰性和透明性;为开发没有这种缺点的改良型冲击改性剂，人们已进行了很多工作。此后，发展了各种制备透明PVC冲击改性剂的方法，至今，许多这类改性剂已在市场上出售。最常用的方法是将冲击改性剂的表观折光指数与PVC的表观折光指数相匹配。如美国专利3，657，390指出要应用两种不同的接枝共聚物，其中一种的折光指数高于PVC，另一种则低于PVC，并按适当配比混合。美国专利3，636，138陈述了一种复杂的用两步法制备接枝共聚物的方法，每步中仔细地选择接枝单体，以调节所得到的复杂接枝共聚物的表观折光指数。在美国专利3，657，391中公开了一种透明冲击改性剂，是将折光指数与PVC相匹配的按严格配比混合的接枝单体组合物与具有折光指数与PVC相匹配的二烯烃-乙烯基芳烃橡胶基质进行接枝而制得的。
依照这些文献，对这些冲击改性剂折光指数的调整和匹配部分地取决于在接枝过程中所用的丙烯酸酯单体的种类。正如美国专利3，636，138中所指出的，将具有折光指数值在PVC一侧的橡胶基质与具有折光指数值在PVC另一侧的单体混合物互相接枝，以达到必要的匹配。丙烯酸烷基酯，尤其是甲基丙烯酸甲酯是为此目的常用的接枝单体。但是，据说丙烯酸酯单体，特别是甲基丙烯酸酯会降低对PVC的最佳粘合力，而且要牺牲另一些性能以达到必需的透明度。
早已知道，丙烯腈-丁二烯-苯乙烯（ABS）嵌段共聚物是PVC树脂的一种优良的冲击改性剂。但重要的是这些ABS树脂通常不能用在高透明和带彩色的冲击改性组合物中。据文献报导，若要使ABS组合物具有透明性，将会影响其冲击改性效果。
一种制备透明的ABS冲击改性剂的方法，尤其是用于PVC组合物中，将是对制备该组合物工艺的一个有用的改进。
本发明涉及一种以ABS接枝共聚物为基质的改良的冲击改性剂。此改性剂是将特定比例的苯乙烯和丙烯腈接枝到丁苯橡胶基质上。用本发明方法制得的冲击改性剂的PVC组合物显示了意想不到的清晰性和透明性，同时兼具良好的抗冲击性。
本发明的冲击改性剂用于ABS接枝共聚物树脂，是将特定比例的苯乙烯和丙烯腈接枝到特定的丁苯橡胶基质上制得的。
用本发明冲击改性剂的丁苯基质橡胶是常用的苯乙烯和丁二烯的共聚物，其内含78-95%（重量）丁二烯和22-5%（重量）苯乙烯。基质橡胶中还可含有2%（重量）以下附加的可共聚的交联单体（如：二乙烯基苯、三聚氰酸三烯丙酯等），如叔-十二烷基硫醇这样的链转移剂也常用于制备工艺中。二烯烃聚合物和共聚物橡胶是众所周知的，并已广泛地用于各种工业目的。可用任一种已知和通用方法制取基质橡胶。特别是用乳液聚合法制得的橡胶乳尤其适合后步的接枝聚合过程。用于制备冲击改性剂的这种基质橡胶颗粒大小不会明显影响透明度但先有技术中早已知道，大颗粒的基质橡胶通常对冲击改性有利，而较小颗粒的基质橡胶则会降低冲击改性组合物的增白效应。因而，特定颗粒大小的选择最终取决于是强调冲击性能，还是强调其白度。制取任意所需颗粒分布的基质橡胶以适应接枝物的要求，这在先有技术中是早已熟知的。
在100份（重量）的丁苯橡胶基质上接枝聚合42-67份，最好是47-61份（重量）的苯乙烯和丙烯腈单体混合物以制取本发明的冲击改性剂，因而此冲击改性剂是高橡胶含量的ABS接枝共聚物，其橡胶含量约为60-70%，最好为62-68%（重量），接枝单体含量相应为40-30%，最好为38-32%（重量）。
接枝单体混合物中，苯乙烯和丙烯腈的比例是3.5/1至4.5/1，最好是3.8/1至4.2/1。苯乙烯和丙烯腈（S/AN）的精确比例的选择取决于所用基质橡胶的折光指数和所要加入的接枝单体混合物量。例如，对某些应用，在某些合适的基质上，S/AN比可降到2.8/1，但这并非是最佳的比例，尤其是上述配方范围内的丁苯橡胶基质的折光指数系略低于PVC的折光指数。苯乙烯和丙烯腈的单体混合物中苯乙烯和丙烯腈之比约为4/1，更常用的范围是3.8/1至4.2/1，其折光指数略高于PVC。对于特定的基质，所选择的合适比例应是能使得到的表观折光指数基本上与PVC的表观折光指数相等。通常，本发明的接枝共聚物的表观折光指数是1.5500至1.5400，可用在大部分PVC树脂上。
将不同折光指数的基质和接枝单体组合起来以制备折光指数匹配适宜的物质的方法在先有技术中是已知的，并已作了描述。但是，正如美国专利3，363，138所指出，当用二烯烃基质接枝上苯乙烯和丙烯腈后将其作冲击改性剂加入到PVC组合物中时，所得组合物不是最佳的。但奇怪的是，用本发明的ABS冲击改性剂配制的PVC组合物却具有良好的抗冲击性能、优异的清晰性和透明性。
可采用制备ABS树脂的聚合工艺中常用的一般方法将苯乙烯/丙烯腈单体混合物接枝聚合到基质橡胶上，包括用乳液法、悬浮法和本体法。典型的方法是乳液接枝聚合法，制备时向基质胶乳中加入欲接枝的单体、一定量的表面活性剂、链转移剂和聚合用引发剂。引发剂可用常规的产生自由基的引发剂，包括过氧化物如过氧化二异丙苯;或采用偶氮类引发剂，如偶氮二异丁腈。另外，可在本方法中使用已知和通用的各种氧化还原类聚合反应催化剂，如对异丙基苯过氧化氢与硫酸亚铁和甲醛合次硫酸氢钠的混合物。本发明的用于制备冲击改性剂的接枝聚合法，以及后步的凝聚和分离均是已知和常用方法，因此，制取本发明冲击改性剂的技术很易为熟悉本技术的人员所掌握。
使用此种透明冲击改性组合物的PVC树脂是常用的PVC，包括含大于80%（重量）氯乙烯单体的共聚物。可用于制取此种氯乙烯共聚物的单体有偏卤乙烯、丙烯酸和甲基丙烯酸化合物、乙烯基醚和乙烯基酯。本发明可采用各种工业的模塑和挤出级PVC树脂，通过常规方法很容易制取透明冲击改性的PVC组合物。例如将100份（重量）PVC树脂和5至40份（重量）本发明的冲击改性剂熔融配料，组合物中可包括本领域制备透明冲击改性PVC树脂中的稳定剂、抗氧剂、润滑剂、调色剂、色料、染料等。调配该组合物可用常规设备来完成，包括：Banburg混炼机、热辊混炼机、配料挤出机等。还可将物料以粉状形式混合，此时可采用任何一种大功率搅拌机，以提供干粉组合物，继之，再用压延、辊炼、吹塑等法加工。
通过对下面实例的描述，将会更好地理解本发明的实质，但这些实例仅作说明而已，并不构成对本发明的限制。
实施例1-6
在丁苯橡胶基质上制备SAN接枝物
苯乙烯-丁二烯共聚物基质的制备是将150重量份数软水、0.05重量份过硫酸钾、0.1重量份焦磷酸四钠和13重量份十二烷基二苯基醚二磺酸钠（51%活性），加入到带有搅拌器的聚合釜中之后，再加入含有0.25重量份叔-十二烷基硫醇的苯乙烯和丁二烯，密封聚合釜，边搅拌边加热至50℃，在此温度下保持18小时，再在5小时内缓慢将温度升至65℃，冷却反应混合物，除去未反应的丁二烯，所得的subR胶乳再进行表征。此法也用于制取不同苯乙烯和丁二烯比例的subR胶乳。实施例1-6的每一种基质橡胶的配方和其表征归纳于表1。
实施例1-6中的每一种基质橡胶用以下配方接枝上SAN：
成份 重量份
软水 180.0
subR胶乳（固体） 65.0
甲醛合次硫酸氢钠 0.0750
EDTA（乙二胺四醋酸） 0.0225
六水硫酸亚铁 0.0075
叔-十二烷基硫醇 0.50
对异丙基苯过氧化氢 0.50
苯乙烯 28.0
丙烯腈 7.0
将水、胶乳和叔-十二烷基硫醇放入带有搅拌器、温度计、冷凝器和滴液漏斗的三口园底烧瓶中。之后，将溶于少量水中的甲醛合次硫酸氢钠、乙二胺四醋酸和硫酸亚铁加入反应釜中。混合物边搅拌，边加热至55℃。在60分钟内将苯乙烯、对异丙基苯过氧化氢和丙烯腈连续加到搅拌着的反应混合物中，并将反应器中的混合物保持在77℃下。如需要外加冷却，以除去因放热的聚合反应所释放的过量热量。将反应混合物再在77℃下再搅拌1小时，冷却并加入抗氧化剂。将混合物再搅拌一定时间，以后，用烯硫酸凝聚。用过滤法收集凝集的树脂，用软水洗涤，最后干燥。
将制得的每批聚合物制膜在23℃下用阿贝（Abbe）折光仪测定其折光指数，结果归纳于表Ⅰ。
表1
注：制法如上文所述，所有实例均用恒定的S/AN（4/1）比例，以得相同的转化率DVS：二乙烯苯
实施例7-12
透明的冲击改性的PVC
将PVC与实施例1-6中制得的冲击改性剂的混合物用双辊混炼机于325°F下混炼8分钟，共混物以片块压出、冷却，以后在350°F下用压模法压制成试片。
成份 重量份
PVC 100，00
硫醇锡稳定剂 2.00
丙烯酸加工助剂 2.00
润滑剂 1.3
调色剂 0.075
冲击改性剂 14
所用的PVC是K55挤出级PVC221树脂，HooKer化学公司生产。冲击改性的PVC组合物的冲击和光学性能列于表Ⅱ，用熔融压制法制得测光学性能的试样，试样厚0.070英寸（70密耳）。
表Ⅱ
注：Izod冲击强度＝英尺·磅/英寸，缺口23℃，1/4″试样于23℃;
ASTM D-256A
光学性能的测定按标准的Hunter实验室方法，
用Hunterlab Huntermeter仪测定。
实施例8-12表明了用本发明的ABS冲击改性剂改性的PVC组合物具有优异的透明性和清晰性。虽然从透射率值看，所有样品的透明度都是好的，但当组合物中苯乙烯量为15%时，其光雾度达最低值（实施例10）。作为透明度第二种度量的黄色指数值在实施例7、8中明显地增大了，因为两者的基质胶中所含苯乙烯量均超过22%（实施例8为25%，实施例7为30%）。要使透射率和透明度均好，这样的冲击改性剂应是含78-94%（重量）的丁二烯和5-20%（重量）的苯乙烯的丁苯橡胶。
很明显，与先有技术所说的完全不同，本发明的这些透明ABS冲击改性剂赋于PVC以优异的抗冲击性能。实施例7-12的组合物基本上有相同的橡胶含量，即65%（重量），但当其中苯乙烯含量较高时〔实施例7，30%（重量）〕，其冲击性能低。显然，欲将冲击性能、光的透射率和透明度最佳地结合起来，则其基质橡胶中的苯乙烯量应为5-20%（重量），丁二烯量应为78-94%（重量）。
对照例B的冲击改性剂是由丁二烯基质橡胶与足量的SAN接枝物共聚而制得，用以提供必要的折光指数匹配。用这种改性剂改性的PVC组合物的光学性质中其黄色指数明显增加，同时抗冲击性能明显下降。
实施例13-18
用实施例1-6方法，用实施例4的基质制取不同橡胶基质含量的冲击改性剂，然后用实施例7-12方法将其与PVC共混，该冲击改性剂与其相应的PVC共混物的组成和其抗冲击性能归纳于表Ⅲ。
表 Ⅲ
表Ⅲ（续）
注：Izod冲击强度＝英尺·磅/英寸，缺口，23℃，1/4″试样于23℃;
ASTM D-256A
光学性能的测定按标准的Hunter实验室方法，
用Hunterlab Huntermeter仪测定。
由实施例13-18显然可见，最佳的透明性和抗冲击性能是来自混有含约65%（重量）的丁苯橡胶基质（subR）的冲击改性剂（实施例15）。在橡胶含量低于65%时，如实施例13（55%）和实施例14（60%），其黄色指数增加，抗冲击性能明显降低。将橡胶基质增大至超过65%，特别是超过70%时（实施例16），光雾度明显增加，抗冲击性能和透射率有些下降。
显然，实施例17和18的折光指数可通过进一步增加接枝单体中S/AN比例来调节。但是，先有技术中已知要使冲击改性剂和PVC之间达到相容需要最低限量的丙烯腈，然而若进一步降低丙烯腈量则会增加光雾度，导致进一步降低透明性，同样实施例13和14中改性剂的折光指数也可通过降低S/AN比来调节。但是，正如先有技术中所指明并为实施例13-18中的黄色指数值所表明，增加丙烯腈量会进一步提高其黄色指数值。
实施例19
用实施例1-6方法制备的不用二乙烯苯交联单体的一种透明的冲击改性剂，采用如下配方：
CBR基质
苯乙烯 15.0重量份
丁二烯 85.0重量份
折光指数 1.5265
接枝共聚物
苯乙烯 28.0重量份
丙烯腈 7.0重量份
丁苯橡胶 65.0重量份
折光指数 1.5440
将上述冲击改性剂与PVC共混，并采用实施例7-12的物料和方法，所用配方和所得到的性能如下：
PVC 100
改性剂 14
Izod冲击强度 8.3
光透射率 83.86
光雾度 3.06
黄色指数 4.26
显然，用不加常用交联单体的丁苯基质胶组合物，也得到了满意的透明冲击改性剂。
本发明的透明冲击改性剂是一种接枝共聚物，它是由约42-67份，最好为47-61份（重量）的苯乙烯、丙烯腈混合单体（其S/AN值约3.8/1-4.2/1）接枝到100份（重量）的丁苯橡胶基质上，此基质胶含78-95%（重量）的丁二烯、22-5%（重量）的苯乙烯和不多于2%（重量）的可共聚的多官能度交联单体。因此，此改性剂实质上约含60-70%（重量）最好含62-68%subR基质胶和相应地约含40-30%最好含38-32%（重量）苯乙烯-丙烯腈接枝物。
显然，熟练掌握本技术的人员，可以对本发明的透明冲击改性剂的制备方法和配方作进一步的改进和变更，但这种改进和变更均不违背本发明的精神和范围，这些精神与范围在所附的权利要求书中作了明确的规定。
Claims (5)
1、一种透明冲击改性PVC组合物，包括PVC和接枝共聚物，此接枝共聚物实质上由约42-67份（重量）的苯乙烯和丙烯腈混合物接枝到100份（重量）的丁苯共聚物上而制得，其混合物中苯乙烯/丙烯腈的重量比为3.8/1至4.2/1，其共聚物是由78-95%（重量）丁二烯、22-5%（重量）苯乙烯和2%（重量）以下的可共聚的多官能度交联单体组成。
2、权利要求1所述的透明冲击改性PVC组合物，其中的接枝共聚物的折光指数在1.5500至1.5400范围内。
3、权利要求1所述的透明冲击改性PVC组合物，其中所述的接枝共聚物中每100份（重量）所述丁苯共聚物接枝上47-61份（重量）所述苯乙烯-丙烯腈混合物。
4、权利要求1所述的透明冲击改性PVC组合物，其中所述的苯乙烯-丁二烯共聚物是由78-95%（重量）丁二烯和22-5%（重量）苯乙烯组成的。
5、权利要求1所述的透明冲击改性PVC组合物，其中将47-61份（重量）的所述苯乙烯-丙烯腈混合物接枝到100份（重量）的所述丁苯共聚物上，且其中的苯乙烯/丙烯腈的重量比是4.0/1。
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| US3900529A (en) * | 1973-10-09 | 1975-08-19 | Monsanto Co | Rubber modified high nitrile polymers and polymer blends produced thereby |
| US3900528A (en) * | 1973-10-09 | 1975-08-19 | Monsanto Co | Process for impact modification of high nitrile polymers |
| JPS54140503A (en) * | 1978-04-24 | 1979-10-31 | Kureha Chemical Ind Co Ltd | Transparent resin composition for information disk |
| JPS57212246A (en) * | 1981-06-23 | 1982-12-27 | Kureha Chem Ind Co Ltd | Vinyl chloride resin composition |
| DE3217874A1 (de) * | 1982-05-12 | 1983-11-17 | Bayer Ag, 5090 Leverkusen | Pfropfkautschuke zur modifizierung thermoplastischer formmassen |
| JPS5984912A (ja) * | 1982-11-04 | 1984-05-16 | Mitsui Toatsu Chem Inc | ゴム変性耐衝撃性樹脂の連続的製造方法 |
| US4507435A (en) * | 1983-12-27 | 1985-03-26 | Mobil Oil Corporation | Blends of polyvinyl chloride and copolymers containing para-methyl styrene and acrylonitrile having improved clarity |
-
1986
- 1986-10-16 CA CA000520618A patent/CA1315906C/en not_active Expired - Fee Related
- 1986-10-23 DE DE8686114706T patent/DE3687509T2/de not_active Expired - Fee Related
- 1986-10-23 EP EP86114706A patent/EP0221456B1/en not_active Expired - Lifetime
- 1986-10-30 AU AU64532/86A patent/AU604219B2/en not_active Ceased
- 1986-11-03 KR KR1019860009241A patent/KR940003859B1/ko not_active IP Right Cessation
- 1986-11-04 JP JP61262594A patent/JPH0788415B2/ja not_active Expired - Lifetime
- 1986-11-04 AR AR86305782A patent/AR242812A1/es active
- 1986-11-04 BR BR8605428A patent/BR8605428A/pt not_active IP Right Cessation
- 1986-11-04 CN CN86107555.2A patent/CN1005983B/zh not_active Expired
-
1987
- 1987-02-27 US US07/020,283 patent/US4764563A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62106915A (ja) | 1987-05-18 |
| KR940003859B1 (ko) | 1994-05-04 |
| US4764563A (en) | 1988-08-16 |
| KR870005021A (ko) | 1987-06-04 |
| BR8605428A (pt) | 1987-08-11 |
| JPH0788415B2 (ja) | 1995-09-27 |
| AU604219B2 (en) | 1990-12-13 |
| CN86107555A (zh) | 1987-04-29 |
| EP0221456B1 (en) | 1993-01-13 |
| CA1315906C (en) | 1993-04-06 |
| EP0221456A3 (en) | 1990-01-03 |
| EP0221456A2 (en) | 1987-05-13 |
| DE3687509D1 (de) | 1993-02-25 |
| AR242812A1 (es) | 1993-05-31 |
| DE3687509T2 (de) | 1993-08-26 |
| AU6453286A (en) | 1987-05-07 |
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