CN105482344A - 提高树脂耐热性的耐热母粒及其制备方法和应用 - Google Patents
提高树脂耐热性的耐热母粒及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及化工助剂领域,提供一种用于提高树脂耐热性的耐热母粒及其制备方法和应用。本发明包括以下组分(重量份数):马来酸酐接枝PS/ASA合金100份、耐热剂80-100份、抗氧剂0.3-0.6份、润滑剂0.4-0.6份、分散剂0.5-1份和加工助剂0.5-1份;分散剂为硬脂酸锌和/或硬脂酸钙;马来酸酐接枝PS/ASA合金包括:聚苯乙烯(PS)粉50-70份、丙烯腈-苯乙烯-丙烯酸橡胶三元共聚物(ASA)粉30-50份、马来酸酐2-5份、过氧化物0.2-0.3份、分散剂0.2-0.3份和加工助剂0.5-1份;分散剂为活性磷酸钙。本发明过程简单,易操作,成本低,可有效提高树脂耐热性并保持树脂强度。
Description
技术领域
本发明涉及化工助剂领域,特别是涉及一种用于提高树脂耐热性的耐热母粒及其制备方法和应用。
背景技术
树脂是制造塑料的主要原料,力学性能优良,具有经济性、轻便性、长期使用稳定等特点。但很多应用场合中需要树脂材料能够具有一定的耐热性,由于树脂材料本身的结构和組成特点,在高于85℃的倩况下,树脂难以保持其刚性好和硬度髙的特点,因而需要通过共混改性的方法,将不同性能的聚合物以及填料进行共混,以得到聚合物高性能化、多功能化、精细化、发展新品种等目的。
目前,制备耐热树脂常用的有三种方法:
(1)用玻璃化转变温度高的树脂(如:聚碳酸酯等)与ABS树脂共混制得耐热ABS树脂,其中优点是提髙ABS耐热性能,热变形温度为105℃-115℃,同时提高了冲击性能,其缺点是成本太髙,且产品的流动性能下降;
(2)用具有梳状结构的苯乙烯-马来酸酐-丙烯酸酯三元共聚物与树脂共混制得耐热树脂,其优点是提高耐热温度的同时,使树脂具有高流动性,加工成型温度低,但其对树脂耐热温度的提高有限,即其产品的热变形温度提高不多,一般只能达到95℃~102℃,而且苯乙烯-马来酸酐-丙烯酸酯三元共聚物原料售价较高;
(3)用N-苯基马来酸亚胺(NPMI)共聚树脂与其他树脂共混得到耐热树脂,其优点是可以制得超耐热级树脂,热变形温度可达125℃~130℃,但但因其添加量大,一般添加量占产品质量百分比30%~40%,从而大大降低了材料的加工流动性和机械性能性能,尤其是冲击性能。
发明内容
本发明要解决的技术问题是提供一种过程简单,易操作,成本低,可有效提高树脂耐热性并保持树脂强度的耐热母粒及其制备方法。
为解决上述技术问题,本发明采用如下技术方案:
本发明提高树脂耐热性的耐热母粒,包括以下组分(重量份数):
马来酸酐接枝PS/ASA合金100份、耐热剂80-100份、抗氧剂0.3-0.6份、润滑剂0.4-0.6份、分散剂0.5-1份和加工助剂0.5-1份;所述分散剂为硬脂酸锌和/或硬脂酸钙;
其中马来酸酐接枝PS/ASA合金包括以下组分(重量份数):
聚苯乙烯(PS)粉50-70份、丙烯腈-苯乙烯-丙烯酸橡胶三元共聚物(ASA)粉30-50份、马来酸酐2-5份、过氧化物0.2-0.3份、分散剂0.2-0.3份和加工助剂0.5-1份;所述分散剂为活性磷酸钙。
本发明提高树脂耐热性的耐热母粒,进一步的,所述耐热剂为N-苯基马来酰胺、N-异丙基马来酰亚胺和聚十八烷基马来酰亚胺中的一种或几种。
本发明提高树脂耐热性的耐热母粒,进一步的,所述抗氧剂包括主抗氧剂和辅抗氧剂,所述主抗氧剂为β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇酯,所述辅抗氧剂为三(2.4-二叔丁基苯基)亚磷酸酯。
本发明提高树脂耐热性的耐热母粒,进一步的,所述润滑剂为季戊四醇硬脂酸酯。
本发明提高树脂耐热性的耐热母粒,进一步的,所述过氧化物为过氧化二异丙苯和/或过氧化二苯甲酰。
本发明提高树脂耐热性的耐热母粒,进一步的,所述聚苯乙烯(PS)粉的分子量为3-5万。
本发明提高树脂耐热性的耐热母粒,进一步的,所述丙烯腈-苯乙烯-丙烯酸橡胶三元共聚物(ASA)粉中胶含量不低于60%(质量百分数)。
本发明提高树脂耐热性的耐热母粒的制备方法,包括以下具体步骤:
(1)制备马来酸酐接枝PS/ASA合金:
按照以下组分(重量份数)进行备料:聚苯乙烯(PS)粉50-70份、丙烯腈-苯乙烯-丙烯酸橡胶三元共聚物(ASA)粉30-50份、马来酸酐2-5份、过氧化物0.2-0.3份、分散剂0.2-0.3份和加工助剂0.5-1份;所述分散剂为活性磷酸钙;
将以上各组分混合均匀,用双螺杆挤出机挤出,反应温度190-225℃,螺杆转速为300-350r/min,将挤出颗粒以三氯甲烷溶解,加入过量甲醇沉淀析出,将沉淀产物用甲醇清洗2-4次,过滤收集沉淀产物,干燥、备用;
(2)制备耐热母粒:
按照以下组分(重量份数)进行备料:马来酸酐接枝PS/ASA合金100份、耐热剂80-100份、抗氧剂0.3-0.6份、润滑剂0.4-0.6份、分散剂0.5-1份和加工助剂0.5-1份;所述分散剂为硬脂酸锌和/或硬脂酸钙;
将20-30%的耐热剂和上述其他组分混合均匀,投入双螺杆挤出机,剩余70-80%耐热剂从侧喂料口加入,进行挤出造粒,反应温度200-230℃,螺杆转速为200-300r/min。
本发明提高树脂耐热性的耐热母粒的制备方法,进一步的,步骤(1)中干燥的温度为100-105℃。
本发明利用耐热母粒提高树脂耐热性,将耐热母粒添加至树脂中共混,添加量为5-40%(质量百分数),所述树脂为丙烯腈-丁二烯-苯乙烯树脂、聚苯乙烯树脂、聚碳酸酯树脂、丙烯腈-苯乙烯共聚树脂和尼龙树脂中的一种或几种。
本发明提高树脂耐热性的耐热母粒与现有技术相比,具有如下有益效果:
本发明提高树脂耐热性的耐热母粒以马来酸酐接枝PS/ASA合金和耐热剂为主要原料,制得高性能耐热母粒,与丙烯腈-丁二烯-苯乙烯树脂(ABS)、聚苯乙烯树脂(PS)、聚碳酸酯树脂(PC)、丙烯腈-苯乙烯共聚树脂(SAN)和尼龙树脂(PA)等通用树脂均有优异的相容性,尤其是能够与ABS树脂可以任意比例互容,耐热母粒可与上述树脂中的一种或几种进行共混,形成种类繁多、性能易于调变、生产周期短的ABS合金树脂,实现ABS树脂的高性能化和多功能化。添加本发明耐热母粒的改性树脂产品,其中耐热母粒可添加的重量百分比在5-40%范围内均可行,制得树脂产品的热变形温度均在93.2-127.8℃内,均远高于未添加耐热母粒的树脂产品,悬臂梁缺口冲击强度在140.23-199.8J/m之间,拉伸强度和弯曲强度也没有明显降低,在保证了树脂产品强度的前提下提升了产品的热变形温度,使得树脂产品具有良好的耐热性和强度。
本发明提高树脂耐热性的耐热母粒与现有技术中的耐热剂如SMI相比,同等的用量,本发明耐热母粒可使树脂产品的热变形温度比使用SMI的树脂产品高出10℃以上,悬臂梁缺口冲击强度高出约45J/m,同时使拉伸强度、断裂伸长率以及弯曲强度等性能保持稳定;并且,欲升高至相同的热变形温度,SMI不仅用量需为本发明耐热母粒用量的2倍,且其树脂产品的悬臂梁缺口冲击强度仅为本发明树脂的1/2,本发明所述耐热母粒可有效提高树脂产品的热变形温度,提高树脂耐热性,同时保持较高的强度。
本发明耐热母粒同样适用于阻燃树脂中,溴系阻燃树脂的配方中添加20%的耐热母粒,树脂的阻燃等级不变,同时热变形温度可由78℃上升至95℃,而树脂的拉伸强度和弯曲强度也有小范围的提高,本发明耐热母粒可在不影响阻燃等级的前提下提升树脂的热变形温度。
众所周知,分子中含有苯环是很难实现接枝的,而聚苯乙烯PS与马来酸酐的结合通常是通过聚合反应实现的,聚合反应对所需的反应设备、原料和反应条件要求比较严苛,反应过程复杂、不易操作,且成本较高。本发明利用马来酸酐与PS/ASA合金进行共混接枝,马来酸酐与PS/ASA合金的接枝成功率高达0.6-0.8%,方法简单易操作,将原料按配比备料加入双螺杆挤出机进行共混挤出即可,制备过程中的影响因素较少,制备效果稳定,且成本较低,对设备和生产条件的要求较低,在实际生产过程中更加方便、经济。
本发明制备耐热母粒的方法选用活性磷酸钙为分散剂,避免了耐热剂在母粒中分散不均匀、挤出困难的情况,同时利用温度的控制和甲醇的多次清洗,清除了体系中残留的过氧化物和马来酸酐单体,避免了耐热母粒在制备过程中的分解,使得制备过程和效果保持稳定。
附图说明
图1为PS/ASA合金基料和耐热母粒的红外光图谱。
具体实施方式
制备实施例
本发明提高树脂耐热性的耐热母粒按照以下方法制备而成:
(1)制备马来酸酐接枝PS/ASA合金:
按照表1所示配比进行备料,其中分散剂为活性磷酸钙,过氧化物为过氧化二异丙苯和/或过氧化二苯甲酰,聚苯乙烯(PS)粉的分子量为3-5万,分子量过高不利于接枝,丙烯腈-苯乙烯-丙烯酸橡胶三元共聚物(ASA)粉中胶含量不低于60%(质量百分数),利于调节最终产品的冲击强度,加工助剂为乙撑双硬脂酰胺和硅油;
将以上各组分混合均匀,用双螺杆挤出机挤出,双螺杆挤出机的长径比为44:1,反应温度190-225℃,螺杆转速为300-350r/min,将挤出颗粒以三氯甲烷溶解,加入过量甲醇沉淀析出,将沉淀产物用甲醇清洗2-4次,除去残留的马来酸酐,过滤收集沉淀产物,在100-105℃下进行干燥,备用;
(2)制备耐热母粒:
按照表2所示配比进行备料,其中分散剂为硬脂酸锌和/或硬脂酸钙,耐热剂为N-苯基马来酰胺、N-异丙基马来酰亚胺和聚十八烷基马来酰亚胺中的一种或几种,抗氧剂包括主抗氧剂和辅抗氧剂,主抗氧剂为β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇酯(又名抗氧剂1076),辅抗氧剂为三(2.4-二叔丁基苯基)亚磷酸酯(又名抗氧剂168),润滑剂为季戊四醇硬脂酸酯,加工助剂为乙撑双硬脂酰胺和硅油;
将20-30%的耐热剂和上述其他组分混合均匀,投入双螺杆挤出机,双螺杆挤出机的长径比为44:1,剩余70-80%耐热剂从侧喂料口加入,进行挤出造粒,反应温度200-230℃,螺杆转速为200-300r/min。
表1马来酸酐接枝PS/ASA合金所需组分配比
表2耐热母粒制备所需组分配比
将上述制备实施例所得产品进行红外线检测,其中实施例3的PS/ASA合金基料和制得的耐热母粒的红外光谱图如图1所示,从红外光谱图中可以清楚的看到,与PS/ASA合金基料相比,耐热母粒在波数1787cm-1和1855cm-1处出现振动吸收峰,这是酸酐中羰基的特征吸收峰,说明马来酸酐已经成功接枝到PS/ASA合金基料上。
现采用滴定法测定材料接枝率,具体方法如下:
精确称取1.0g纯化后的接枝物溶于100mL丙酮中,加入10mL0.1mol/L的NaOH乙醇溶液,在磁力搅拌器上加热回流1h,使NaOH与接枝的马来酸酐充分反应;再用0.1%的甲基红乙醇溶液作指示剂,用0.1mol/L的HCl溶液(用无水碳酸钠标定过的)滴定未反应的NaOH,并按公式①计算马来酸酐与PS/ASA合金的接枝率(GD)计算所得结果如表3所示。
式中:V0:未接枝纯化后的ABS树脂作空白样时消耗的HCl体积,mL;
V1:接枝纯化后的样品消耗的HCl体积,mL;
C:HCl的摩尔浓度,mol/L;
M:马来酸酐的摩尔质量,g/mol;
W:称取的接枝物质量,g。
表3各制备实施例的接枝率结果汇总
(%) | 制备例1 | 制备例2 | 制备例3 | 制备例4 | 制备例5 | 制备例6 | 制备例7 |
接枝率 | 0.68 | 0.76 | 0.64 | 0.83 | 0.66 | 0.78 | 0.71 |
如表3所示,制备实施例1-7的接枝成功率均在0.6-0.8%之间,众所周知,分子中含有苯环是很难实现接枝的,而本发明所述制备方法以共混方式实现马来酸酐与PS/ASA合金的接枝率高达0.6-0.8%,可代替聚合反应,使得马来酸酐与PS/ASA合金的结合过程更加简单、易操作,并且降低了反应成本。
分析例1
将制备实施例1、2和5制得的耐热母粒与丙烯腈-丁二烯-苯乙烯树脂(ABS)和丙烯腈-苯乙烯共聚树脂(SAN)共混,将制得的树脂产品与添加了耐热剂N-苯基马来酰亚胺/苯乙烯共聚物(SMI)的树脂产品进行了对比,制作配方如表4所示,采用常规制备方法,制得的树脂产品的分析检测结果如表5所示。
表4分析例1树脂产品配方表
表5分析例1树脂产品分析检测结果
结合表4与表5分析可知,配方1与配方2除却添加的耐热母粒与耐热剂SMI不同外,其余成分组分及用量均完全相同,耐热母粒或耐热剂SMI的添加比例约为原料的20%(质量百分数),配方1制得的树脂产品与配方2制得产品相比,热变形温度高达106℃,远高于配方2的95.4℃,悬臂梁缺口冲击强度为163J/m,明显高于配方2,同时,拉伸强度、断裂伸长率以及弯曲强度均有一定程度的提高。而配方3与配方2相比,耐热剂SMI的添加量增加到了40%,制得树脂产品的热变形温度可以达到与配方1产品相同的水平,约106℃,但是此时树脂的悬臂梁缺口冲击强度为73.4J/m,尚不及配方1产品悬臂梁缺口冲击强度的一半,可知,与现有技术中的耐热剂如SMI相比,欲达到相同的热变形温度,本发明耐热母粒的用量约为SMI的一半,同时可有效避免耐热剂添加量的增加会造成的树脂强度下降的情况,当与SMI用量相同时,本发明耐热母粒可有效提高树脂的耐热性和强度。
分析例2
将制备实施例4、6和7制得的耐热母粒与溴系阻燃ABS共混,与为添加耐热母粒的溴系阻燃ABS对比,制作配方如表6所示,采用常规制备方法,制得的树脂产品的分析检测结果如表7所示。
表6分析例2树脂产品配方
表7分析例2树脂产品分析检测结果
结合表6与表7分析可知,本发明耐热母粒同样适用于阻燃树脂中,溴系阻燃树脂的配方中添加20%的耐热母粒,树脂的阻燃等级不变,同时热变形温度可由78℃上升至95℃,而树脂的拉伸强度和弯曲强度也有小范围的提高。说明本发明耐热母粒可在不影响阻燃等级的前提下提升树脂的热变形温度。
应用实施例
将上述制备实施例1-7所得产品与树脂共混,制成改性树脂,树脂为丙烯腈-丁二烯-苯乙烯树脂(ABS)、聚苯乙烯树脂(PS)、聚碳酸酯树脂(PC)、丙烯腈-苯乙烯共聚树脂(SAN)和尼龙树脂(PA)中的一种或几种,具体制备配方如表8所示,
表8树脂产品配方列表
按照表8所示配方制备的树脂产品,进行分析检测,检测结果如表9所示。
表9应用实施例树脂产品分析检测结果
对照 | 制备1 | 制备2 | 制备3 | 制备4 | 制备5 | 制备6 | 制备7 | |
热变形温度(℃) | 73.6 | 93.2 | 98.6 | 132.6 | 112.4 | 129.9 | 123.5 | 127.3 |
悬臂梁缺口冲击强度(J/m) | 221.62 | 199.80 | 152.42 | 186.36 | 172.64 | 169.23 | 185.3 | 140.23 |
拉伸强度(MPa) | 48.21 | 54.76 | 57.85 | 55.23 | 46.71 | 63.1 | 58.67 | 60.62 |
断裂伸长率(%) | 15.37 | 14.60 | 10.67 | 6.58 | 10.23 | 16.22 | 56.23 | 42.197 --> |
弯曲强度(MPa) | 72.49 | 86.79 | 89.53 | 87.80 | 76.52 | 95.24 | 91.63 | 90.52 |
洛氏硬度 | 102.1 | 111.6 | 116.2 | 114.0 | 108.9 | 114.6 | 122.4 | 116.6 |
如表9所示,本发明耐热母粒与丙烯腈-丁二烯-苯乙烯树脂(ABS)、聚苯乙烯树脂(PS)、聚碳酸酯树脂(PC)、丙烯腈-苯乙烯共聚树脂(SAN)和尼龙树脂(PA)等通用树脂均有优异的相容性,尤其是能够与ABS树脂可以任意比例互容,耐热母粒可与上述树脂中的一种或几种进行共混,形成种类繁多、性能易于调变、生产周期短的ABS合金树脂,实现ABS树脂的高性能化和多功能化。由表9可知,添加本发明耐热母粒的改性树脂产品,其中耐热母粒可添加的重量百分比在5-40%范围内均可行,制得树脂产品的热变形温度均在93.2-132.6℃内,均远高于未添加耐热母粒的对照组,悬臂梁缺口冲击强度在140.23-199.8J/m之间,拉伸强度和弯曲强度也没有明显降低,在保证了树脂产品强度的前提下提升了产品的热变形温度,使得树脂产品具有良好的耐热性和强度。
以上所述的实施例仅仅是对本发明的优选实施方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案作出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。
Claims (10)
1.提高树脂耐热性的耐热母粒,其特征在于:包括以下组分(重量份数):
马来酸酐接枝PS/ASA合金100份、耐热剂80-100份、抗氧剂0.3-0.6份、润滑剂0.4-0.6份、分散剂0.5-1份和加工助剂0.5-1份;所述分散剂为硬脂酸锌和/或硬脂酸钙;
其中马来酸酐接枝PS/ASA合金包括以下组分(重量份数):
聚苯乙烯(PS)粉50-70份、丙烯腈-苯乙烯-丙烯酸橡胶三元共聚物(ASA)粉30-50份、马来酸酐2-5份、过氧化物0.2-0.3份、分散剂0.2-0.3份和加工助剂0.5-1份;所述分散剂为活性磷酸钙。
2.根据权利要求1所述的提高树脂耐热性的耐热母粒,其特征在于:所述耐热剂为N-苯基马来酰胺、N-异丙基马来酰亚胺和聚十八烷基马来酰亚胺中的一种或几种。
3.根据权利要求1所述的提高树脂耐热性的耐热母粒,其特征在于:所述抗氧剂包括主抗氧剂和辅抗氧剂,所述主抗氧剂为β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇酯,所述辅抗氧剂为三(2.4-二叔丁基苯基)亚磷酸酯。
4.根据权利要求1所述的提高树脂耐热性的耐热母粒,其特征在于:所述润滑剂为季戊四醇硬脂酸酯。
5.根据权利要求1所述的提高树脂耐热性的耐热母粒,其特征在于:所述过氧化物为过氧化二异丙苯和/或过氧化二苯甲酰。
6.根据权利要求1所述的提高树脂耐热性的耐热母粒,其特征在于:所述聚苯乙烯(PS)粉的分子量为3-5万。
7.根据权利要求1所述的提高树脂耐热性的耐热母粒,其特征在于:所述丙烯腈-苯乙烯-丙烯酸橡胶三元共聚物(ASA)粉中胶含量不低于60%(质量百分数)。
8.制备权利要求1所述的提高树脂耐热性的耐热母粒的方法,其特征在于:包括以下具体步骤:
(1)制备马来酸酐接枝PS/ASA合金:
按照以下组分(重量份数)进行备料:聚苯乙烯(PS)粉50-70份、丙烯腈-苯乙烯-丙烯酸橡胶三元共聚物(ASA)粉30-50份、马来酸酐2-5份、过氧化物0.2-0.3份、分散剂0.2-0.3份和加工助剂0.5-1份;所述分散剂为活性磷酸钙;
将以上各组分混合均匀,用双螺杆挤出机挤出,反应温度190-225℃,螺杆转速为300-350r/min,将挤出颗粒以三氯甲烷溶解,加入过量甲醇沉淀析出,将沉淀产物用甲醇清洗2-4次,过滤收集沉淀产物,干燥、备用;
(2)制备耐热母粒:
按照以下组分(重量份数)进行备料:马来酸酐接枝PS/ASA合金100份、耐热剂80-100份、抗氧剂0.3-0.6份、润滑剂0.4-0.6份、分散剂0.5-1份和加工助剂0.5-1份;所述分散剂为硬脂酸锌和/或硬脂酸钙;
将20-30%的耐热剂和上述其他组分混合均匀,投入双螺杆挤出机,剩余70-80%耐热剂从侧喂料口加入,进行挤出造粒,反应温度200-230℃,螺杆转速为200-300r/min。
9.根据权利要求8所述的提高树脂耐热性的耐热母粒的制备方法,其特征在于:步骤(1)中干燥的温度为100-105℃。
10.将权利要求1所述的耐热母粒用于提高树脂耐热性,其特征在于:将耐热母粒添加至树脂中共混,添加量为5-40%(质量百分数),所述树脂为丙烯腈-丁二烯-苯乙烯树脂、聚苯乙烯树脂、聚碳酸酯树脂、丙烯腈-苯乙烯共聚树脂和尼龙树脂中的一种或几种。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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CN102643507A (zh) * | 2012-05-10 | 2012-08-22 | 金发科技股份有限公司 | 一种极高耐热阻燃abs组合物及其制备方法和应用 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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CN102643507A (zh) * | 2012-05-10 | 2012-08-22 | 金发科技股份有限公司 | 一种极高耐热阻燃abs组合物及其制备方法和应用 |
Non-Patent Citations (1)
Title |
---|
张玉龙 等: "《通用塑料改性技术》", 31 January 2007, 机械工业出版社 * |
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