CN114621420A - 一种可生物降解的脂肪族-芳香族共聚酯及其合成方法 - Google Patents
一种可生物降解的脂肪族-芳香族共聚酯及其合成方法 Download PDFInfo
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- CN114621420A CN114621420A CN202011464404.8A CN202011464404A CN114621420A CN 114621420 A CN114621420 A CN 114621420A CN 202011464404 A CN202011464404 A CN 202011464404A CN 114621420 A CN114621420 A CN 114621420A
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- Prior art keywords
- acid
- aliphatic
- aromatic
- dicarboxylic acid
- copolyester
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- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 15
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- 238000000034 method Methods 0.000 claims abstract description 15
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004970 Chain extender Substances 0.000 claims abstract description 10
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- 238000005886 esterification reaction Methods 0.000 claims description 19
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 2
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- BTUDGPVTCYNYLK-UHFFFAOYSA-N 2,2-dimethylglutaric acid Chemical compound OC(=O)C(C)(C)CCC(O)=O BTUDGPVTCYNYLK-UHFFFAOYSA-N 0.000 claims 2
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Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
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- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G63/91—Polymers modified by chemical after-treatment
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- 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
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- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/26—Carbonates; Bicarbonates
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Abstract
本发明公开了一种可生物降解的脂肪族‑芳香族共聚酯及其制备方法,所述方法包括,原料芳香族二羧酸、脂肪族二羧酸、脂肪族二醇经过连续酯化后,加入醇胺类改性共聚单体并进行连续预缩聚,由此将叔胺基团接入脂肪族‑芳香族共聚酯分子链中,然后加入异氰酸酯扩链剂进行扩链反应使得所得产物共聚酯的分子量、熔融指数和特性粘度达到目标值。本发明所公开的脂肪族‑芳香族共聚酯的制备方法,相比较于现有技术,在扩链时异氰酸酯反应效率提高,异氰酸酯残留率降低。本发明所公开的可生物降解的脂肪族‑芳香族共聚酯具有较好的耐水解性,因此在农业地膜中具有广泛的应用前景。
Description
技术领域
本发明属于高分子材料合成领域,具体涉及一种可生物降解的脂肪族-芳香族共聚酯及其制备方法和应用。
背景技术
塑料在生活中无处不在,极大方便了人们的生活,然而近年来资源紧缺的同时,人们对塑料的过度依赖造成了更多的环境污染问题。大多数的高分子材料均是不可降解或难以降解的,近年来可生物降解塑料相关技术飞速发展,已有大量可生物降解塑料投入量产。常见的可生物降解塑料主要为可生物降解聚酯,如聚对苯二甲酸-己二酸-丁二醇酯、聚对苯二甲酸-丁二醇酯、聚乳酸、聚已内酯等。这些材料具有良好的延展性,成膜性能好,被广泛应用于食品包装、一次性餐具、一次性购物袋、堆肥袋、农用地膜等领域。
为了优化可生物降解聚酯的力学性能,如拉伸强度、断裂伸长率等,就必须通过加深缩聚程度、或者扩链使聚酯达到较高的分子量水平,并且尽量控制树脂产品的酸值,提高产品的耐水解性能。相比于加深缩聚程度,使用扩链剂能更快速有效的提高聚酯分子量,并且可以避免酸值升高、树脂颜色加深等问题。但如何提高扩链反应效率,增强扩链效果,减少游离扩链剂在树脂中的含量是一个需要解决的问题,特别是对于有毒的异氰酸酯类扩链剂。
农膜是农业生产中重要的生产资料之一,具有保水保墒、促进增收的效果。我国作为一个农业大国,是世界上农膜消耗最多、覆盖面积最大的国家。农膜覆盖技术在给我国农业生产带来巨大效率的同时,也给土壤带来严重的污染。可生物降解聚酯农膜能够在使用后一段时间内被土壤微生物降解掉,能够较好地解决传统农膜带来的污染问题。例如,中国专利文献CN104072953B介绍了PBAT/PGA/助剂的可控降解的农用地膜,发现农膜在170天后基本无明显农膜碎片。中国专利文献CN103087482A报导了由PBAT/PLA/淀粉/助剂组成的农膜,发现该农膜符合EN13432法规,能够完全降解。但是这种农膜一直在潮湿环境下使用,耐水解能力影响到它的使用寿命,如果在农作物成熟期,农膜出现水解破损,则会影响农作物产量。
发明内容
为了解决现有技术存在的问题,本发明提出了一种可生物降解的脂肪族-芳香族共聚酯,其共聚原料单体中,除了脂肪族二羧酸、芳香族二羧酸、脂肪族二醇等单体之外,还添加了如式(I)所示的醇胺类改性共聚单体:
其中,
R为OH、H;X、Y、Z为1-10的整数。
所述式(I)所示的醇胺类改性共聚单体优选为三乙醇胺、二乙醇单异丙醇胺、三异丙醇胺、N-丁基二乙醇胺等中的一种或多种。
所述醇胺类改性共聚单体与总的二羧酸(二元酸)的摩尔mol比为0.001:1-0.05:1;优选地,为0.003:1-0.02:1。
所述二羧酸为脂肪族二羧酸、芳香族二羧酸。
所述脂肪族二羧酸为己二酸、丁二酸、癸二酸、辛二酸、壬二酸、十三烷二酸、反丁烯二酸、2,2-二甲基戊二酸等中的一种或多种;优选地,为己二酸、丁二酸、癸二酸、十三烷二酸;进一步优选地,为己二酸、丁二酸、癸二酸。
所述芳香族二羧酸为对苯二甲酸、间苯二甲酸、2,6-萘二甲酸和1,5-萘二甲酸等中的一种或多种;优选地,为对苯二甲酸。
所述脂肪族二醇为1,4-丁二醇、乙二醇、1,3-丙二醇、1,5-戊二醇、1,6-己二醇等中的一种或多种;优选地,为1,4-丁二醇。
所述脂肪族二羧酸、芳香族二羧酸的摩尔mol比为65:35-45:55。
所述式(I)所示的醇胺类改性共聚单体可以在酯化阶段加入,也可以在预缩聚或缩聚阶段连续的加入反应物料中。
所述共聚原料单体中还可以添加其它常规共聚单体,如:酯环族二酸、芳香族二醇、脂环族二元醇、以及任选的常规多官能团支化剂共聚,所述多官能团支化剂为甘油、三羟甲基丙烷、季戊四醇等。
本发明还提出了一种可生物降解的脂肪族-芳香族共聚酯的连续生产方法,将脂肪族二醇、脂肪族二羧酸、芳香族二羧酸一起混合打浆,其中脂肪族二醇与总的二羧酸的摩尔mol比为(2.5-1.1):1,优选地,为(2.0-1.5):1,然后在
i)第一阶段中,将该混合物与钛催化剂一起进行连续酯化;
ii)第二阶段,将阶段i)中获得的酯化产物连续地进行预缩聚至根据GB-T 14190-2008的5.1.1.7.4的特性粘度为0.2-0.8dl/g;
iii)第三阶段,将由阶段ii)获得的产物连续地进行缩聚至根据GB-T 14190-2008的5.1.1.7.4的特性粘度为0.9-1.2dl/g;其中在阶段ii)和iii)之间,将稳定剂加入产物流中;
iv)第四阶段,使用异氰酸酯扩链剂连续扩链反应至根据GB-T 14190-2008的5.1.1.7.4的特性粘度为1.2-1.8dl/g;
其中,在阶段i)和ii)之间,将如式(I)所示的醇胺类改性共聚单体加入产物流中,式(I)所示的醇胺类改性共聚单体摩尔mol用量与二元酸摩尔mol用量的比为0.001:1-0.05:1;优选地,为0.003:1-0.01:1。
也可以选择在打浆阶段加入醇胺类单体,或者在阶段i)-阶段iii)中任意节点将醇胺类改性共聚单体加入产物流中。
所述总的二羧酸指脂肪族二羧酸与芳香族二羧酸。
所述醇胺类改性共聚单体优选为三乙醇胺、二乙醇单异丙醇胺、三异丙醇胺、N-丁基二乙醇胺等中的一种或多种。
所述脂肪族二羧酸为己二酸、丁二酸、癸二酸、辛二酸、壬二酸、十三烷二酸、反丁烯二酸、2,2-二甲基戊二酸等中的一种或多种;优选地,为己二酸、丁二酸、癸二酸、十三烷二酸;进一步优选地,为己二酸、丁二酸、癸二酸。
所述芳香族二羧酸为对苯二甲酸、间苯二甲酸、2,6-萘二甲酸和1,5-萘二甲酸等中的一种或多种;优选地,为对苯二甲酸。
所述脂肪族二醇为1,4-丁二醇、乙二醇、1,3-丙二醇、1,5-戊二醇、1,6-己二醇等中的一种或多种;优选地,为1,4-丁二醇。
所述脂肪族二羧酸、芳香族二羧酸的摩尔mol比为65:35-45:55。
阶段i)中,所述钛催化剂为钛酸正丁酯、钛酸四异丙酯等中的一种或几种;优选地,为钛酸正丁酯。
阶段i)中,所述钛催化剂的摩尔用量为共聚酯重量的0.01%-0.2%wt。
阶段i)中,酯化反应进行到直至酯化物的端羧基值小于200mol/t时结束。
在阶段i)或ii)或iii)还可以添加少量其它常规共聚单体,如:酯环族二酸、芳香族二醇、脂环族二元醇、呋喃二甲酸、聚乙二醇、异山梨醇,以及任选的常规多官能团支化剂共聚,所述多官能团支化剂为甘油、三羟甲基丙烷、季戊四醇、均苯四甲酸等。
本发明所述连续生产方法中,阶段ii)的预缩聚反应可以在中文专利文献CN100491439C所述的塔式反应器中连续地进行。
本发明所述连续生产方法中,所述稳定剂为磷酸、亚磷酸、磷酸三苯酯、磷酸三甲酯、亚磷酸三烷基酯、亚磷酸三苯基酯等中的一种或几种;优选地,为亚磷酸。
所述稳定剂的摩尔用量为共聚酯重量的0.01%-0.2%wt。
阶段iv)中,所述异氰酸酯扩链剂为六亚甲基二异氰酸酯、甲苯-2,4-二异氰酸酯,甲苯-2,6-二异氰酸酯,2,4'-二苯基甲烷二异氰酸酯,异佛尔酮二异氰酸酯等中的一种或多种;优选地,为六亚甲基二异氰酸酯(HDI)。
本发明所述方法中加入异氰酸酯扩链时,可以用静态混合器或者螺杆进行。
所述异氰酸酯扩链剂的摩尔用量为共聚酯重量的0.1%-0.5%wt。
阶段iv)中,所述扩链反应的温度为150-240℃;优选地,为180-230℃。
本发明还提供了由上述方法制备得到的可生物降解的脂肪族-芳香族共聚酯。
本发明还提供了所述可生物降解的脂肪族-芳香族共聚酯在农膜中的应用。
本发明还提供了一种可生物降解的农膜,特别适用于水稻种植(水稻栽培),其包含所述的可生物降解的脂肪族-芳香族共聚酯,配方包含:
1)65-95%wt的本发明所述的生物降解的脂肪族-芳香族共聚酯,基于组份1)和2)重量和计算;
2)5-35%wt的聚乳酸,基于组份1)和2)重量和计算;
3)5-30%wt的无机填料,基于组份1)和2)重量和计算;所述无机填料为碳酸钙或滑石粉;
4)0.1-0.6%wt的含有环氧基团且基于苯乙烯、丙烯酸酯和/或甲基丙烯酸酯的共聚物,基于组份1)和2)重量和计算。
本发明所述组分1)指生物降解的脂肪族-芳香族共聚酯。
本发明所述组分2)指聚乳酸。
聚酯合成时,聚酯产品的端羧基值(或酸值)是一个重要指标,因为端羧基在有水份存在的时候可以电离出少量的H+,会加速催化聚酯的水解,并进一步产生端羧基,从而降低聚酯分子量,使得聚酯树脂的力学性能迅速下降。本发明中式(I)所示的改性单体为含氮二元醇或三元醇单体,通过共缩聚反应引入聚合物分子链中,使分子主链中含有叔胺基团,叔胺基团可以吸收H+,抑制催化聚酯的水解。实验表明在经过一定量的醇胺类改性共聚单体改性后,树脂耐水解性能显著提高。
因为高粘度的聚酯通过缩聚进一步提高分子量比较困难,所以聚酯生产过程中,当粘度、分子量到达一定水平后,一般会通过扩链来提高树脂分子量。常用的扩链剂为异氰酸酯,异氰酸酯扩链之后常会在树脂中留有游离异氰酸酯,游离异氰酸酯有毒,限制了可降解树脂材料的在食品接触材料中的应用,而本发明公开的可降解生物聚酯,在异氰酸酯扩链时,叔胺可以催化异氰酸酯与羟基的反应,因此相同用量异氰酸酯扩链效果更好,扩链剂异氰酸酯的转化率更高,树脂中异氰酸酯残留更少。
本发明的有益效果在于:本发明公开的脂肪族-芳香族共聚酯的制备方法,在扩链时异氰酸酯反应效率提高,异氰酸酯残留率降低。且本发明制备的脂肪族-芳香族共聚酯具有较好的耐水解性。
具体实施方式
结合以下具体实施例,对本发明作进一步的详细说明。实施本发明的过程、条件、实验方法等,除以下专门提及的内容之外,均为本领域的普遍知识和公知常识,本发明没有特别限制内容。本发明的保护内容不局限于以下实施例。在不背离发明构思的精神和范围下,本领域技术人员能够想到的变化和优点都被包括在本发明中,并且以所附的权利要求书为保护范围。
1、特性粘度测量方法:根据GB-T 14190-2008的5.1.1.7.4部分的内容测量,按苯酚/1,2-二氯苯质量比为3:2,配成苯酚/1,2-二氯苯混合溶剂。将干燥后的产物脂肪族-芳香族共聚酯树脂溶于上述混合溶剂中,浓度为0.005g/mL。25±0.05℃的玻璃恒温水槽中用乌氏粘度计分别测纯溶剂的平均流经时间t0和树脂溶液流经时间t,按下式计算特性粘度[η]:
单位为克每百毫升(g/100mL)或克每分升(g/dl)
2、端羧基含量的测量方法:根据FZ/T50012-2006《聚酯中端羧基含量的测定滴定分析法》测量产物脂肪族-芳香族共聚酯树脂的端羧基含量。将苯酚和三氯甲烷按2:3(体积比)混合作为溶剂,用于溶解树脂,然后用酸碱滴定测端羧基含量,端羧基含量单位为mol/t。
3、分子量测量方法:用以氯仿为流动相的GPC进行测量。
参比例1
将28kg/h的对苯二甲酸、27kg/h的己二酸、37kg/h的1,4-丁二醇连续地加入到打浆釜中混合,然后将混合好的浆料连续地送入到酯化反应釜中。另一路连续加入8kg/h的1,4-丁二醇和0.03kg/h的钛酸四丁酯(TBOT)进入酯化反应釜中,在220℃的温度和-20KPa的压力下酯化,停留时间2h,水被蒸馏除去,所得酯化物的端羧基含量为160mol/t,将酯化物连续泵到预缩聚反应釜中,连续补加0.02kg/h的钛酸四丁酯进入预缩聚釜中,物料温度由220℃升至230℃,反应釜的压力从20KPa降低到1KPa,蒸出过量的丁二醇,当预聚物的特性粘度为0.6dL/g时,预聚物移料进入终聚反应釜中,并加入0.017kg/h亚磷酸,终聚反应釜的温度为245℃,压力为80Pa,停留时间为3h,对扩链前的聚酯树脂进行取样检测,然后聚酯产物连续进入双螺杆中,并连续加入树脂重量0.5%的六亚甲基二异氰酸酯,连续进行扩链反应。扩链后树脂产物进行取样检测。
参比例2
将28kg/h的对苯二甲酸、27kg/h的己二酸、37kg/h的1,4-丁二醇、0.05kg/h的甘油,连续地加入到打浆釜中混合,然后将混合好的浆料连续地送入到酯化反应釜中。另一路连续加入8kg/h的1,4-丁二醇和0.03kg/h的钛酸四丁酯(TBOT)进入酯化反应釜中,在220℃的温度和-15KPa的压力下酯化,停留时间2h,水被蒸馏除去,所得酯化物的端羧基含量为145mol/t,将酯化物连续泵到预缩聚反应釜中,连续补加0.02kg/h的钛酸四丁酯进入预缩聚釜中,物料温度由220℃升至230℃,反应釜的压力从20KPa降低到1KPa,蒸出过量的丁二醇,当预聚物的特性粘度为0.7dL/g时,预聚物移料进入终聚反应釜中,并加入0.02kg/h亚磷酸,终聚反应釜的温度为245℃,压力为80Pa,停留时间为2.5h,对扩链前的聚酯树脂进行取样检测,然后聚酯产物连续进入双螺杆中,并连续加入树脂重量0.5%的六亚甲基二异氰酸酯,连续进行扩链反应。扩链后树脂产物进行取样检测。
实施例1-5
将28kg/h的对苯二甲酸、27kg/h的己二酸、37kg/h的1,4-丁二醇连续地加入到打浆釜中混合,然后将混合好的浆料连续地送入到酯化反应釜中。另一路连续加入8kg/h的1,4-丁二醇和0.03kg/h的钛酸四丁酯(TBOT)进入酯化反应釜中,在220℃的温度和-20KPa的压力下酯化,水被蒸馏除去,酯化反应直至所得酯化物的端羧基含量都小于200mol/t,将酯化物连续泵到预缩聚反应釜中,连续补加0.02kg/h的钛酸四丁酯进入预缩聚釜中,并从另一路连续加入不同用量的醇胺类改性共聚单体,物料温度由220℃升至230℃,反应釜的压力从20KPa降低到1KPa,蒸出过量的丁二醇,当预聚物的特性粘度达到0.6dL/g时,预聚物连续移料进入终聚反应釜中,并加入0.017kg/h亚磷酸,终聚反应釜的温度为245℃,压力为80Pa,停留时间为3h,对扩链前的聚酯树脂进行取样检测,然后聚酯产物连续进入双螺杆中,并连续加入树脂重量0.5%的六亚甲基二异氰酸酯,连续进行扩链反应,双螺杆扩链温度220℃,停留时间2min,对扩链后树脂产物进行取样检测。加入不同含量醇胺类改性共聚单体制备的树脂和所制备树脂的性能对比如表1所示:
表1 0.5%wt用量六亚甲基二异氰酸酯(HDI)扩链后树脂制备和性能对比
*醇胺类改性共聚单体用量mol百分比基于总的二元酸用量,总的二元酸用量为100%mol
由表1结果可以发现,采用相同用量的异氰酸酯进行扩链后,本发明方案制备的树脂扩链效果更好,材料力学性能提高,端羧基含量更低。
实施例6
将参比例1-2、实施例1-5中所得的脂肪族-芳香族共聚酯树脂、以及其它市售可降解脂肪族-芳香族共聚酯树脂分别在吹膜机中吹制出5μm厚的薄膜,然后裁剪成面积为5cm×5cm的薄膜,放入湿热老化箱中,控制相对湿度95%,温度35℃,进行耐水解老化实验,观察薄膜树脂的分子量随时间变化,对比结果如下表2所示:
表2参比例1-2、实施例1-5及其他市售树脂分子量随时间的变化
C1200为BASF的ecoflex品牌的非改性PBAT产品的牌号,HT801T为蓝山屯河生产的非改性PBAT牌号,A400为金发科技生产的非改性PBAT牌号。
从表2中结果可知,本发明所提出的醇胺类改性共聚单体改性的可生物降解的脂肪族-芳香族聚酯具有优良的耐水解性能。湿热老化9个月过程中分子量降低显著低于对比例产品,说明本发明制得的脂肪族-芳香族共聚酯耐水解性明显提高。
参比例3-4和实施例7-12
将芳香族二羧酸、脂肪族二羧酸、脂肪族二醇连续地加入到打浆釜中混合,然后将混合好的浆料连续地送入到酯化反应釜中。另一路连续加入催化剂钛酸四丁酯(TBOT)(用单体脂肪族二醇为溶剂,配成溶液,浓度0.5%wt)进入酯化反应釜中,在220℃的温度和-20KPa的压力下酯化,进行酯化反应直至所得酯化物的端羧基含量都小于200mol/t,将酯化物连续泵到预缩聚反应釜中,连续补加催化剂钛酸四丁酯(TBOT)(用单体脂肪族二醇为溶剂,配成溶液,浓度1%wt)进入预缩聚釜中,并从另一路连续加入不同用量的醇胺类改性共聚单体,物料温度由220℃升至230℃,反应釜的压力从20KPa降低到1KPa,蒸出过量的丁二醇,当预聚物的特性粘度达到0.6dL/g时,预聚物连续移料进入终聚反应釜中,并加入亚磷酸进入产物流中,终聚反应釜的温度为245℃,压力为80Pa,停留时间为3h,对扩链前的聚酯树脂进行取样检测,然后聚酯产物连续进入双螺杆中,并连续加入六亚甲基二异氰酸酯,连续进行扩链反应,双螺杆扩链温度220℃,停留时间2min,对扩链后树脂产物进行取样检测。加入不同含量醇胺类改性共聚单体制备的树脂和所制备树脂的性能对比如表3所示:
表3六亚甲基二异氰酸酯(HDI)扩链的脂肪-芳香族共聚酯树脂制备和性能对比
二元酸总摩尔数为100%;
醇胺类改性共聚单体、以及改性单体:三羟甲基丙烷、异山梨醇、对苯二甲醇用量都是醇胺类改性共聚单体用量mol百分比基于总的二元酸用量,总的二元酸用量为100%mol;
HDI用量质量百分比基于扩链反应前总的树脂质量。
对比例3用1,3-丙二醇,按醇酸比2:1进行酯化;
对比例4、实施例7-12都用1,4-丁二醇,按醇酸比2:1进行酯化;
实施例13
将参比例3-4、实施例7-12中所得的脂肪族-芳香族共聚酯树脂在吹膜机中吹制出5μm厚的薄膜,裁剪成面积为5cm×5cm的薄膜,放入湿热老化箱中,控制相对湿度95%,温度35℃,进行耐水解老化实验,观察薄膜树脂的分子量随时间变化,对比结果如下表4所示:
表4参比例3-4、实施例7-12随时间的变化
从表4中结果可知,本发明所提出的醇胺类改性共聚单体改性的可生物降解的脂肪族-芳香族聚酯具有优良的耐水解性能。湿热老化9个月过程中分子量降低显著低于对比例产品,说明本发明制得的脂肪族-芳香族共聚酯耐水解性明显提高。
Claims (12)
2.如权利要求1所述的可生物降解的脂肪族-芳香族共聚酯,其特征在于,所述的醇胺类改性共聚单体为三乙醇胺、二乙醇单异丙醇胺、三异丙醇胺、N-丁基二乙醇胺等中的一种或多种;所述脂肪族二羧酸为己二酸、丁二酸、癸二酸、辛二酸、壬二酸、十三烷二酸、反丁烯二酸、2,2-二甲基戊二酸中的一种或多种;所述芳香族二羧酸为对苯二甲酸、间苯二甲酸、2,6-萘二甲酸和1,5-萘二甲酸中的一种或多种;所述脂肪族二醇为1,4-丁二醇、乙二醇、1,3-丙二醇、1,5-戊二醇、1,6-己二醇中的一种或多种。
3.如权利要求1所述的可生物降解的脂肪族-芳香族共聚酯,其特征在于,所述醇胺类改性共聚单体与总的二羧酸的摩尔比为0.001:1-0.05:1;所述脂肪族二羧酸、芳香族二羧酸的摩尔比为65:35-45:55。
4.一种可生物降解的脂肪族-芳香族共聚酯的制备方法,其特征在于,将脂肪族二醇、脂肪族二羧酸、芳香族二羧酸一起混合打浆,其中,所述脂肪族二醇与总的二羧酸的摩尔比为(2.5-1.1):1,然后在
i)第一阶段中,将该混合物与钛催化剂一起进行连续酯化;
ii)第二阶段,将所述阶段i)中获得的酯化产物连续地进行预缩聚至根据GB-T 14190-2008的5.1.1.7.4的特性粘度为0.2-0.8dl/g;
iii)第三阶段,将由所述阶段ii)获得的产物连续地进行缩聚至根据GB-T 14190-2008的5.1.1.7.4的特性粘度为0.9-1.2dl/g;其中,在阶段ii)和iii)之间,将稳定剂加入产物流中;
iv)第四阶段,使用异氰酸酯扩链剂连续扩链反应至根据GB-T 14190-2008的5.1.1.7.4的特性粘度为1.2-1.8dl/g;
其中,在阶段i)和ii)之间,将如式(Ⅰ)所示的醇胺类改性共聚单体加入产物流中,
其中,R为OH、H;X、Y、Z为1-10的整数。
5.如权利要求4所述的方法,其特征在于,所述的醇胺类改性共聚单体为三乙醇胺、二乙醇单异丙醇胺、三异丙醇胺、N-丁基二乙醇胺等中的一种或多种;所述脂肪族二羧酸为己二酸、丁二酸、癸二酸、辛二酸、壬二酸、十三烷二酸、反丁烯二酸、2,2-二甲基戊二酸中的一种或多种;所述芳香族二羧酸为对苯二甲酸、间苯二甲酸、2,6-萘二甲酸和1,5-萘二甲酸中的一种或多种;所述脂肪族二醇为1,4-丁二醇、乙二醇、1,3-丙二醇、1,5-戊二醇、1,6-己二醇中的一种或多种。
6.如权利要求4所述的方法,其特征在于,所述醇胺类改性共聚单体与总的二羧酸的摩尔比为0.001:1-0.05:1;所述脂肪族二羧酸和芳香族二羧酸的摩尔比为65:35-45:55。
7.如权利要求4所述的方法,其特征在于,阶段i)中,所述钛催化剂为钛酸正丁酯、钛酸四异丙酯中的一种或几种;阶段i)中,所述钛催化剂的用量为共聚酯的0.01-0.2%wt;阶段ii)的预缩聚反应在专利文献CN100491439C所述的塔式反应器中连续地进行。
8.如权利要求4所述的方法,其特征在于,所述稳定剂为磷酸、亚磷酸、磷酸三苯酯、磷酸三甲酯、亚磷酸三烷基酯、亚磷酸三苯基酯中的一种或几种;所述稳定剂的用量为共聚酯重量的0.01-0.2%wt;所述异氰酸酯扩链剂为六亚甲基二异氰酸酯、甲苯-2,4-二异氰酸酯、甲苯-2,6-二异氰酸酯、2,4'-二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯中的一种或多种。
9.如权利要求4-8之任一项所述方法制备得到的可生物降解的脂肪族-芳香族共聚酯。
10.如权利要求9所述的可生物降解的脂肪族-芳香族共聚酯在农膜中的应用。
11.一种可生物降解的农膜,其特征在于,包含如权利要求1-3之任一项所述的可生物降解的脂肪族-芳香族共聚酯,配方包含:
1)65-95%wt的本发明所述的生物降解的脂肪族-芳香族共聚酯,基于组份1)和2)重量和计算;
2)5-35%wt的聚乳酸,基于组份1)和2)重量和计算;
3)5-30%wt的无机填料,基于组份1)和2)重量和计算;
所述无机填料为碳酸钙或滑石粉;
4)0.1-0.6%wt的含有环氧基团且基于苯乙烯、丙烯酸酯和/或甲基丙烯酸酯的共聚物,
基于组份1)和2)重量和计算。
12.如权利要求11所述的农膜,其特征在于,所述农膜适用于水稻栽培中使用。
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CN115260470A (zh) * | 2022-03-23 | 2022-11-01 | 旭科新材料(山东)有限责任公司 | 用于制备聚酯薄膜材料的组合物、聚脂薄膜材料及其应用 |
CN115260470B (zh) * | 2022-03-23 | 2023-11-17 | 旭科新材料(山东)有限责任公司 | 用于制备聚酯薄膜材料的组合物、聚脂薄膜材料及其应用 |
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