CN114805765A - 建材用peat树脂及其制备方法 - Google Patents
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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Abstract
一种建材用PEAT树脂,其特征在于该PEAT树脂通过引入脂肪族二元酸取代部分对苯二甲酸,与乙二醇在一定的醇酸比进行酯化与缩聚制备得到。本发明还公开了一种建材用PEAT树脂的制备方法。用脂肪二元酸二酯单元取代了部分对苯二甲酸乙二醇酯单元,大幅降低聚酯中刚性苯环含量,使PEAT树脂具有高柔韧性、高黏结性和高特性黏度特性,这使得石粉可以较大比例与其混合,并可以实现共挤出加工成型,制造环保型聚酯塑胶建材,可取代PVC制备环保型建材。
Description
技术领域
本发明涉及一种应用于建材的树脂材料,本发明还涉及该树脂材料的制备方法,属于化学高分子材料技术领域。
背景技术
随着人们对环保的日益重视,发展和使用绿色环保材料,成为全世界的大趋势,这一方面,欧美走在了前列。目前PVC板材成为取代瓷砖、纯木地板的第三选择,在欧美比较流行,国内制造的PVC板材70%以上都是销往欧美和东南亚。但PVC降解表现为脱氯化氢气体,在燃烧时容易生成盐酸气体,还会生成含有氯气的混合物—二噁英,有致癌作用,对人体和环境有害,因此PVC材料在环保方面有缺陷,欧洲已经开始寻求替代PVC板材的环保材料,聚酯是潜在的选择。
普通PET聚酯由对苯二甲酸和乙二醇缩聚合成,分子链结构中苯环比例高,分子呈刚性,当与高比例石粉混合后,所得复合材料脆性大,无法在设备上牵引成型。若想成型,则普通PET和石粉混合比要大于1:0.5,这样的板材成本高且性能不能达标,不宜大规模应用;此外,普通PET熔点高,相比PVC能耗高,不经济。
目前市场上还未有专用的聚酯树脂,能看到相关或接近技术领域的专利文献可以参考如下:
申请号为200810019423.2的中国发明专利申请《一种用抗水解剂改性的聚酯纤维及其生产方法》(公开号为CN 101215730 A),该申请提供了一种全降解/无机纳米粒子复合材料及其制备方法。此方法通过脂肪族二元酸、脂肪族二元醇聚合得到的聚酯与无机纳米粒子复合,提高了聚酯的热稳定性和强度。
申请号为201410567429.9中国发明专利申请《一种板材用聚酯及其制备方法》(公开号为CN105585702A),该申请引入间苯二甲酸、二甘醇、亲水改性剂、多羟基化合物来制备可替代ABS的聚酯板材。
发明内容
本发明所要解决的第一个技术问题是针对上述的技术现状而另外提供一种板材用PEAT树脂。
本发明所要解决的第二个技术问题是提供一种能与高比例的石粉混合进而可取代PVC板材的建材用PEAT树脂。聚(对苯二甲酸乙二醇酯-co-己二酸乙二醇酯)
本发明所要解决的第三个技术问题是提供一种能与高比例的石粉混合进而可取代PVC板材的建材用PEAT树脂的制备方法。
本发明所要解决的第二个技术问题是针对上述的技术现状而另外提供一种板材用PEAT树脂的制备方法。
本发明解决上述第一个和第二个技术问题所采用的技术方案为:一种建材用PEAT树脂,其特征在于该PEAT树脂通过引入脂肪族二元酸取代部分对苯二甲酸,与乙二醇在一定的醇酸比进行酯化与缩聚制备得到。
进一步地,脂肪族二元酸和对苯二甲酸摩尔投料比为1:(1.5~8),优选为1:(2~5)。
进一步地,二元酸总摩尔量与乙二醇的摩尔量比为1:(1.1~1.6)。优选为1:(1.15~1.3)。
进一步地,二元酸为对C4-C8脂肪族二元酸的一种或两种,优选己二酸或丁二酸。
本发明解决上述第三个技术问题所采用的技术方案为:一种建材用PEAT树脂的制备方法,包括步骤:
(1)打浆:将对苯二甲酸、乙二醇、第三单体脂肪族二元酸,催化剂,稳定剂按比例加入反应釜中进行混合打浆10min,温度控制在60~100℃,加入惰性气体,控制压力为0.3Mpa,搅拌转速为20~40r/min。
(2)酯化:升温开始酯化,控制聚合釜内压力在0.1~0.4MPa,搅拌器的转速在50~120r/min,控制聚合釜内温度在180~250℃间梯度升温,对苯二甲酸、脂肪族二元酸与乙二醇的酯化温度不同,控制升温速率,调节好产物水溢出速度,防止过快造成釜内醇酸摩尔比失衡。通过出液率计算酯化效率,当转化率达到90~100%时酯化反应结束;
(3)卸压:待酯化水达到理论量的90%~95%,缓慢卸压至常压,稳定10min。
(4)预聚:设置好真空程控,1小时内从常压将至0.1Kpa以下,温度为250~260℃。
(5)终聚:控制温度为260~275℃,聚合1.5~2.5h,待电机功率达到设定功率后,结束聚合,出料,经冷却、切粒、干燥得到PEAT树脂切片。
进一步地,催化剂为锑系、钛系、铝系或锗系催化剂中的一种或两种复配,总加入量为PEAT质量的10~300ppm。
进一步地,稳定剂为磷酸、磷酸三甲酯、磷酸三乙酯或磷酸三苯酯的一种,加入的质量与PEAT树脂质量3~10ppm。
与现有技术相比,本发明的优点在于:PEAT树脂在分子结构上因用脂肪二元酸二酯单元取代了部分对苯二甲酸乙二醇酯单元,大幅降低聚酯中刚性苯环含量,使PEAT树脂具有良好的柔韧性,宏观表现具有一定的粘性,使其具有高柔韧性、高黏结性和高特性黏度特性,这使得石粉可以较大比例与其混合,石粉份数可达2~4的范围(PEAT树脂用量为1份),并可以实现共挤出加工成型,制造环保型聚酯塑胶建材,可取代PVC制备环保型建材。
具体实施方式
以下结合实施例对本发明作进一步详细描述。
实施例1,将对苯二甲酸1200g,己二酸400g,乙二醇760g,催化剂三氧化二锑0.45g,稳定剂磷酸(浓度3700ppm,下同)2.5g加入5L反应釜中,以惰性气体置换聚合釜内空气,0.3Mpa,70℃下搅拌10min,将物料混合均匀,控制聚合釜内压力在0.3MPa,搅拌器的转速在50r/min,聚合釜内温度在180~250℃间梯度升温,通过出液率计算酯化效率,当转化率达到93%时酯化反应结束,泄压。
将反应釜抽真空,控制好速度,1小时内从常压将至0.1Kpa以下,控制聚合釜内温度250~260℃,反应40min;然后控制反应釜压力在150Pa以下,控制聚合釜内温度265~270℃,反应2.5h;待搅拌电流到达设定值后进行出料、冷却、切粒得到PEAT树脂切片。
实施例2,将对苯二甲酸1500g,己二酸440g,乙二醇850g,乙二醇锑0.83g,稳定剂磷酸3.2g加入5L的反应釜中,以惰性气体置换聚合釜内空气,0.3Mpa,75℃下搅拌搅拌15min将物料混合均匀,升温酯化,控制聚合釜内压力在0.3MPa,搅拌器的转速在50min,聚合釜内温度在180~250℃间梯度升温,通过出液率计算酯化效率,当转化率达到92%时酯化反应结束,泄压。
将反应釜抽真空,控制好速度,1小时内从常压将至0.1Kpa以下,控制聚合釜内温度250~260℃,反应40min;然后控制反应釜压力在150Pa以下,控制聚合釜内温度265~270℃,反应2h;待搅拌电流到达设定值后进行出料、冷却、切粒得到建材用PEAT树脂切片。
实施例3,将对苯二甲酸1000g,己二酸200g,丁二酸50g,乙二醇640g,催化剂0.35g,稳定剂磷酸4g加入5L的反应釜中,以惰性气体置换聚合釜内空气,0.3Mpa,60℃下搅拌搅拌15min将物料混合均匀,升温酯化,控制聚合釜内压力在0.2MPa,搅拌器的转速在50r/min,聚合釜内温度在180~250℃间梯度升温,通过出液率计算酯化效率,当转化率达到90~100%时酯化反应结束,泄压。
将反应釜抽真空,控制好速度,1小时内从常压将至0.1Kpa以下,控制聚合釜内温度250~260℃,反应50min;然后控制反应釜压力在150Pa以下,控制聚合釜内温度265~270℃,反应2.5h;待搅拌电流到达设定值后进行出料、冷却、切粒得到建材用PEAT树脂切片。
上述实施例所制备建材用PEAT树脂基本参数如下:
实施例 | 特性黏度(dL/g) | 熔点(℃) | 端羧基(mmol/kg) | DEG% |
1 | 0.893 | 189 | 7.2 | 1.2 |
2 | 0.876 | 192 | 11.6 | 1.1 |
3 | 0.824 | 197 | 14.1 | 1.4 |
Claims (9)
1.一种建材用PEAT树脂,其特征在于该PEAT树脂通过引入脂肪族二元酸取代部分对苯二甲酸,与乙二醇在一定的醇酸比进行酯化与缩聚制备得到。
2.根据权利要求1所述的建材用PEAT树脂,其特征在于所述的脂肪族二元酸和对苯二甲酸摩尔投料比为1:1.5~1:8。
3.根据权利要求2所述的建材用PEAT树脂,其特征在于所述的脂肪族二元酸和对苯二甲酸摩尔投料比为1:2~1:5。
4.根据权利要求1所述的建材用PEAT树脂,其特征在于所述的脂肪族二元酸和对苯二甲酸总摩尔量与乙二醇的摩尔量比为1:1~1:1.6。
5.根据权利要求1所述的建材用PEAT树脂,其特征在于所述的脂肪族二元酸和对苯二甲酸总摩尔量与乙二醇的摩尔量比为1:1.15~1:1.3。
6.根据权利要求1所述的建材用PEAT树脂,其特征在于所述的脂肪族二元酸为对C4~C8脂肪族二元酸中的一种或两种。
7.一种权利要求1~6中任一一种权利要求所述的建材用PEAT树脂的制备方法,其特征在于包括如下步骤:
①打浆:将对苯二甲酸、乙二醇、第三单体脂肪族二元酸、催化剂、稳定剂按比例加入反应釜中进行混合打浆,温度控制在60~100℃,加入惰性气体;
②酯化:升温开始酯化,控制聚合釜内压力在0.1~0.4MPa,控制聚合釜内温度在180~250℃间梯度升温,当转化率达到90~100%时酯化反应结束;
③卸压:待酯化水达到理论量的90%~95%,缓慢卸压至常压,稳定。
④预聚:设置好真空程控,1小时内从常压将至0.1Kpa以下,温度为250~260℃;
⑤终聚:控制温度为260~275℃,聚合1.5~2.5h,待电机功率达到设定功率后,结束聚合,出料,经冷却、切粒、干燥得到PEAT树脂切片。
8.根据权利要求7所述的制备方法,其特征在于所述的催化剂为锑系、钛系、铝系或锗系催化剂中的一种或两种复配,总加入量为PEAT树脂总质量的10~300ppm。
9.根据权利要求7所述的制备方法,其特征在于所述稳定剂为磷酸、磷酸三甲酯、磷酸三乙酯或磷酸三苯酯中的一种,加入的质量为PEAT树脂总质量的3~10ppm。
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