CN113831517A - 抗菌及抗紫外聚酯的制备方法 - Google Patents
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 48
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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
-
- 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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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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Abstract
一种抗菌及抗紫外聚酯的制备方法,将对苯二甲酸、乙二醇、抗菌分散液、催化剂、稳定剂添加到反应釜中进行原位聚合反应,获得聚酯熔体,聚酯熔体经纺丝和加弹,加油加水后获得抗菌聚酯纤维,所述的抗菌分散液通过如下步骤制备:将纳米氧化锌、纳米二氧化钛和氟化物溶于分散介质中,滴加分散剂以及偶联剂,在超声分散及搅拌后,过滤、洗涤、干燥得到偶联剂接枝的无机纳米粒子;然后将偶联剂接枝的无机纳米粒子溶于分散介质中,加入抗菌醛类化合物,搅拌,使得抗菌醛类化合物包覆的无机纳米粒子,得到抗菌分散液。与现有技术相比,本发明具有成本低、抗菌及抗紫外性能长久的优点。
Description
技术领域
本发明涉及一种聚酯的制备方法,属于高分子材料技术领域。
背景技术
聚对苯二甲酸乙二醇酯(PET)广泛用于纤维纺织领域,但是人们的生存环境中散布着各种各样的细菌和霉菌,最常见的如金黄色葡萄球菌、大肠杆菌和白色念珠菌等。这些细菌容易附着在疏松多孔的织物上,可能引发交叉感染,危害人们身体健康。另一方面,太阳光中的紫外线除了会使皮肤晒黑之外,严重的还会导致皮肤老化甚至皮肤癌等。而纺织品和人们的日常生活息息相关,因此开发出具有抗菌、抗紫外的聚酯材料有着重要的意义。
见申请号为201610198226.6的中国发明专利申请公开《织物用聚合物基铈掺杂纳米氧化锌复合抗菌剂及其制备方法》(公开号为CN105648745A),该申请中以硝酸铈、醋酸锌为原料,通过共沉淀法制备稀土铈掺杂纳米氧化锌;然后以铈掺杂纳米氧化锌、二甲基二烯丙基氯化铵、烯丙基缩水甘油醚为原料,通过原位法制备聚合物基铈掺杂纳米氧化锌复合抗菌剂,将铈掺杂纳米氧化锌引入到含有阳离子和环氧基的聚合物基体中。但铈是一种稀土元素,价格比较昂贵,因此成本较高。
又见申请号为201710543759.8的中国发明专利申请公开《纳米氧化锌/银复合抗菌剂及其制备方法》(公开号为CN107142718A),该申请以纳米氧化锌、硅烷偶联剂KH-560为原料,制备环氧基化纳米氧化锌;之后以硝酸银、环氧基化纳米氧化锌、柠檬酸钠为原料,通过化学还原法制备纳米氧化锌/银复合抗菌剂。本发明将纳米氧化锌/银复合抗菌剂应用于棉织物的抗菌整理,通过ZnO和Ag的协同抗菌,提高本抗菌剂的广谱高效性。该申请使用了Ag,但是Ag在长期使用中会析出导致织物变色;另外纺织品中的 Ag+会透过皮肤进入人体内,而Ag的化合物大部分都不可溶,重金属在人体内积累,长期以往便危害人体健康;另外,Ag本身价格昂贵,生产成本比较高。类似的申请还可以参考申请号为202010057292.8的中国发明专利申请公开《一种纳米氧化锌包裹纳米银抗菌复合材料的制备方法》(公开号为CN111185170A)。
为降低成本,现有技术中还公开了一种非银的抗菌剂,见申请号为201710598161.9 的中国发明专利申请公开《氧化锌-季铵盐聚合物复合抗菌剂及其制备方法》(公开号为CN107401051A),但是此种方法采用的是抗菌后整理的方式,抗菌长久性一般。
发明内容
本发明所要解决的技术问题是针对上述的技术现状而提供一种成本低抗菌长久且成本较低的抗菌及抗紫外聚酯的制备方法。
本发明解决上述技术问题所采用的技术方案为:一种抗菌及抗紫外聚酯的制备方法,将对苯二甲酸、乙二醇、抗菌分散液、催化剂、稳定剂添加到反应釜中进行原位聚合反应,获得聚酯熔体,聚酯熔体经纺丝和加弹,加油加水后获得抗菌聚酯纤维,其特征在于所述的抗菌分散液通过如下步骤制备:
将纳米氧化锌、纳米二氧化钛和氟化物溶于分散介质中,滴加分散剂以及偶联剂,在超声分散及搅拌后,过滤、洗涤、干燥得到偶联剂接枝的无机纳米粒子;然后将偶联剂接枝的无机纳米粒子溶于分散介质中,加入抗菌醛类化合物,搅拌,使得抗菌醛类化合物包覆的无机纳米粒子,得到抗菌分散液;
前述的纳米氧化锌、纳米二氧化钛和氟化物的重量配比为0.5~3:1~4:1~3;
前述分散剂占偶联剂接枝的无机纳米粒子质量的1~2%;
前述偶联剂占偶联剂接枝的无机纳米粒子的质量百分含量为1~5%;
前述抗菌醛类化合物为偶联剂接枝纳米粒子的质量百分含量为6~12%。
作为优选,超声分散的温度为25~50℃,超声分散的时间为30~60min。搅拌速率为10~100rpm,优选的,为50~80rpm。
作为优选,纳米氧化锌、纳米二氧化钛的粒径为20-50nm。
抗菌醛类化合物包覆的无机纳米粒子于溶剂中,在超声分散和机械搅拌的双重作用下,以分散液的形式与PTA、EG进行原位聚合反应。
作为优选,所述的氟化物为含氟恶唑烷酮类。如:(S)-N-((3-(3-氟-4-(4-吗啉基)苯基)-2-氧代-5-恶唑烷基)甲基)乙酰胺。
作为优选,所述的抗菌醛类化合物为肉桂醛、柠檬醛或他们的衍生取代物中的至少一种。
作为优选,所述分散剂为白油、硅酮粉、硬脂酸钙、硬脂酸锌、乙烯基三乙氧基硅烷、甲基丙烯酰氧基丙基三甲氧基硅烷中的至少一种。
作为优选,所述的抗菌分散液中固含量的质量百分比浓度为10~30%。
作为优选,所述的偶联剂一端应含有-NH2氨基基团,另一端含有亲油的非极性基团。进一步,所述偶联剂为γ-氨丙基三乙氧基硅烷、γ-氨丙基三甲氧基硅烷、γ-氨丙基甲基二乙氧基硅烷、氨乙基氨丙基三甲氧基硅烷、氨乙基氨丙基甲基二甲氧基硅烷中的至少一种。
作为优选,所述偶联剂接枝的无机纳米粒子干燥时的温度应为50~80℃,时间为24 h。
作为优选,所述纳米氧化锌占制得的抗菌聚酯纤维的质量百分含量为0.5~3%,所述纳米二氧化钛占制得的抗菌聚酯纤维的质量百分含量为1~4%,所述氟化物占制得的抗菌聚酯纤维的质量百分含量为1-3%。
作为优选,所述的原位聚合反应包括酯化反应和缩聚反应,前述酯化反应温度为220~240℃,反应时间为1.5~2.5h,前述缩聚反应温度为265~280℃,反应时间为2~4h。
所述原位聚合法中聚酯PET的原料EG与PTA的摩尔比为1.1:1~1.5:1,优选的,控制在1.2:1~1.3:1。
所述稳定剂是磷酸、磷酸三甲酯、磷酸三苯酯、亚磷酸、亚磷酸三苯酯中的一种或两种以上组合物。
所述稳定剂占制得的抗菌聚酯树脂重量的50-500ppm,优选的,为100-300ppm。
所述催化剂为钛酸四丁酯、三氧化二锑、乙二醇锑、醋酸锑中的一种或两种以上组合物。
所述催化剂占制得的抗菌聚酯树脂重量的100-500ppm,优选的,为200-300ppm。抗菌聚酯树脂可以进一步通过熔融纺丝法制备成抗菌聚酯纤维,具体地,先通过原位聚合的方法制备成抗菌聚酯,然后将抗菌聚酯熔体通过熔体管道输送到纺丝箱体内,纺丝箱纺丝温度设为300℃,纺丝速度为2500-4500m/min,先纺出预取向纤维,采取内牵伸加捻加热加弹方法将预取向丝(POY)加工成低弹丝(DTY),加油加水,得到所述的抗菌及抗紫外聚酯纤维。
与现有技术相比,本发明的优点在于:纳米氧化锌(ZnO)因具有独特的小尺寸效应和表面效应使其化学活性高,具有稳定长久的抗菌作用和具有良好的抗紫外功能,纳米ZnO吸收紫外的效果更稳定且安全无毒。ZnO可以吸收波长280~380nm的紫外光,同时也有阻隔紫外光的功能。纳米ZnO不仅起到抗菌、抗紫外的作用,同时可以作为缩聚反应时的催化剂。
纳米二氧化钛(TiO2)具有一定的散射和吸收紫外光的能力,纳米TiO2存在光催化抗菌作用,但其也有禁带宽度大(3.2eV)、可见光响应效率低、光生电子和空穴易复合等缺陷,限制了其在抗菌方面的应用。将其与纳米ZnO复配能起到抗菌互补的作用,有效增强抗菌效率。
氟化物中的氟具有强的得电子能力,其表面容易积聚电荷,电荷能够吸附微小物质和细菌,在氟化物的吸附辅助作用下,纳米粒子的光催化和金属离子的双重抗菌作用得以进一步增强。
由于抗菌分散液是原位反应中加入的,而不是后整理添加的,因此,具有长久的抗菌和抗紫外功能,同时不含稀土或银等成本较高的金属离子,因此整体成本较低且对环境比较友好,符合环保要求。
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1,①纳米粒子分散液的制备
将聚酯树脂质量1%的纳米ZnO、2%的纳米TiO2和1%的含氟恶唑烷酮类氟化物溶于去离子水中,滴加无机纳米粒子质量1%的硬脂酸钙以及1%的γ-氨丙基三乙氧基硅烷,在30℃下及50rpm的搅拌速率下超声分散搅拌40min,经过滤、洗涤、干燥,得到偶联剂接枝的无机纳米粒子;然后以适量去离子水为溶剂,向偶联剂接枝的无机纳米粒子中加入其质量6%的肉桂醛,在50℃及60rpm的搅拌速率下超声分散搅拌30 min,即得到有机醛包覆的无机纳米粒子分散液。
②抗菌及抗紫外聚酯的制备
将PTA、EG、有机醛包覆的无机纳米粒子分散液(所加分散液中纳米ZnO占聚酯树脂质量的1%)、催化剂、稳定剂加入到反应釜中,搅拌升温到230℃,控制釜内压力达到240kPa,反应2h,当酯化率达到92%,结束酯化,泄除压力,排出酯化水;进行缩聚,启动真空泵使釜内压力保持在100Pa,反应温度控制在270℃,反应2.5h后将聚酯熔体通过熔体管道输送到纺丝箱体内进行纺丝加弹工艺。其中,PTA、EG的摩尔比为1:1.2,催化剂为三氧化二锑,加入量为聚酯树脂质量的240ppm,稳定剂为磷酸三苯酯,加入量为聚酯树脂质量的200ppm,纺丝箱纺丝温度设为300℃,纺丝速度为3000 m/min。
实施例2,①纳米粒子分散液的制备
将聚酯树脂质量2%的纳米ZnO、3%的纳米TiO2和2%的含氟恶唑烷酮类氟化物溶于乙二醇中,滴加无机纳米粒子质量2%的乙烯基三乙氧基硅烷以及2%的氨乙基氨丙基三甲氧基硅烷,在40℃下及60rpm的搅拌速率下超声分散搅拌50min,经过滤、洗涤、干燥,得到偶联剂接枝的无机纳米粒子;然后以适量乙二醇为溶剂,向偶联剂接枝的无机纳米粒子中加入其质量8%的柠檬醛,在60℃及80rpm的搅拌速率下超声分散搅拌50min,即得到有机醛包覆的无机纳米粒子分散液。
②抗菌及抗紫外聚酯的制备
将PTA、EG、有机醛包覆的无机纳米粒子分散液(所加分散液中纳米ZnO占聚酯树脂质量的1.5%)、催化剂、稳定剂加入到反应釜中,搅拌升温到240℃,控制釜内压力达到240kPa,反应2.5h,当酯化率达到92%,结束酯化,泄除压力,排出酯化水;进行缩聚,启动真空泵使釜内压力保持在100Pa,反应温度控制在275℃,反应3h后将聚酯熔体通过熔体管道输送到纺丝箱体内进行纺丝加弹工艺。其中,PTA、EG的摩尔比为1:1.3,催化剂为钛酸四丁酯,加入量为聚酯树脂质量的300ppm,稳定剂为亚磷酸,加入量为聚酯树脂质量的300ppm,纺丝箱纺丝温度设为350℃,纺丝速度为4000m/min。
表1.抗菌聚酯的抗菌测试
抗菌性能的测试对象包括:金黄色葡萄球菌ATCC 6538、大肠杆菌ATCC 25922、白色念珠菌ATCC 10231。抗菌性能检测方法:按照GB/T20944.3纺织品抗菌性能的评价,第3部分:振荡法,接触时间18h。
表2.不同波长下PET及样品的透过率
紫外透过率测试方法:制备长6cm,宽2cm,厚度为0.3mm的聚酯膜片,采用紫外课件分光光度仪测试膜片在280-400nm波段的紫外线透过率,测量三次取平均值作为测试结果。
Claims (10)
1.一种抗菌及抗紫外聚酯的制备方法,将对苯二甲酸、乙二醇、抗菌分散液、催化剂、稳定剂添加到反应釜中进行原位聚合反应,获得聚酯熔体,聚酯熔体经纺丝和加弹,加油加水后获得抗菌聚酯纤维,其特征在于所述的抗菌分散液通过如下步骤制备:将纳米氧化锌、纳米二氧化钛和氟化物溶于分散介质中,滴加分散剂以及偶联剂,在超声分散及搅拌后,过滤、洗涤、干燥得到偶联剂接枝的无机纳米粒子;然后将偶联剂接枝的无机纳米粒子溶于分散介质中,加入抗菌醛类化合物,搅拌,使得抗菌醛类化合物包覆的无机纳米粒子,得到抗菌分散液;
前述的纳米氧化锌、纳米二氧化钛和氟化物的重量配比为0.5~3:1~4:1~3;
前述分散剂占偶联剂接枝的无机纳米粒子质量的1~2%;
前述偶联剂占偶联剂接枝的无机纳米粒子的质量百分含量为1~5%;
前述抗菌醛类化合物为偶联剂接枝纳米粒子的质量百分含量为6~12%。
2.根据权利要求1所述的制备方法,其特征在于所述的氟化物为含氟恶唑烷酮类。
3.根据权利要求1所述的制备方法,其特征在于所述的抗菌醛类化合物为肉桂醛、柠檬醛或他们的衍生取代物中的至少一种。
4.根据权利要求1所述的制备方法,其特征在于所述分散剂为白油、硅酮粉、硬脂酸钙、硬脂酸锌、乙烯基三乙氧基硅烷、甲基丙烯酰氧基丙基三甲氧基硅烷中的至少一种。
5.根据权利要求1所述的制备方法,其特征在于所述的抗菌分散液中固含量的质量百分比浓度为10~30%。
6.根据权利要求1所述的制备方法,其特征在于所述的偶联剂一端应含有-NH2氨基基团,另一端含有亲油的非极性基团。
7.根据权利要求6所述的制备方法,其特征在于所述偶联剂为γ-氨丙基三乙氧基硅烷、γ-氨丙基三甲氧基硅烷、γ-氨丙基甲基二乙氧基硅烷、氨乙基氨丙基三甲氧基硅烷、氨乙基氨丙基甲基二甲氧基硅烷中的至少一种。
8.根据权利要求1所述的制备方法,其特征在于所述偶联剂接枝的无机纳米粒子干燥时的温度应为50~80℃,时间为24h。
9.根据权利要求1所述的制备方法,其特征在于所述纳米氧化锌占制得的抗菌聚酯纤维的质量百分含量为0.5~3%,所述纳米二氧化钛占制得的抗菌聚酯纤维的质量百分含量为1~4%,所述氟化物占制得的抗菌聚酯纤维的质量百分含量为1~3%。
10.根据权利要求1所述的制备方法,其特征在于所述的原位聚合反应包括酯化反应和缩聚反应,前述酯化反应温度为220~240℃,反应时间为1.5~2.5h,前述缩聚反应温度为265~280℃,反应时间为2~4h。
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