WO2016165533A1 - 生物有机胍催化法合成聚丁二酸丁二醇酯的工艺方法 - Google Patents

生物有机胍催化法合成聚丁二酸丁二醇酯的工艺方法 Download PDF

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WO2016165533A1
WO2016165533A1 PCT/CN2016/076956 CN2016076956W WO2016165533A1 WO 2016165533 A1 WO2016165533 A1 WO 2016165533A1 CN 2016076956 W CN2016076956 W CN 2016076956W WO 2016165533 A1 WO2016165533 A1 WO 2016165533A1
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李弘�
张全兴
宋易婷
孙向前
黄伟
李爱民
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南京大学
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Priority to US15/263,307 priority patent/US9688811B2/en
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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
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/87—Non-metals or inter-compounds thereof
    • 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
    • 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
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
    • 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
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof

Definitions

  • the invention belongs to the technical field of environmentally friendly and biodegradable polymer synthesis, and particularly relates to a new synthetic process of polybutylene succinate.
  • PBS Polybutylene succinate
  • PBS is an aliphatic biodegradable material. Under natural conditions, PBS can be decomposed by various microorganisms or enzymes to form carbon dioxide and water. PBS has good ductility, elongation at break, heat resistance and impact resistance. PBS can be used for the blending modification of environmentally friendly and biodegradable material polylactic acid to improve the flexibility and ductility of polylactic acid products.
  • the catalysts reported in the literature are mostly heavy metal catalysts such as stannous octoate, stannous chloride, dibutyltin oxide, alkoxy fluorene, etc. (CN 103724599A, CN 102019202A). These metal catalysts have certain cells. Toxic, so the material will cause certain pollution to the environment after degradation.
  • the PBS product synthesized by the direct method reported in the literature has a weight average molecular weight (M w ) of 1.4 ⁇ 10 5 or less, and a PBS of M w ⁇ 1.4 ⁇ 10 5 .
  • the products are synthesized by medium molecular weight PBS chain extension method, and the chain extender (such as isocyanate) used has certain toxicity (Wang Yanliang et al., New Chemical Materials, 2011, 12, 43-45).
  • PBS with M w ⁇ 1.4 ⁇ 10 5 has important applications in high performance degradable plastic products.
  • the inventors have recently developed a high-molecular-weight M w ⁇ 1.4 ⁇ 10 5 polybutylene succinate using a non-toxic bioorganic ruthenium catalyst based on long-term research on the bio-organic oxime synthesis of environmentally friendly and biodegradable materials. New Technology.
  • the present invention is directed to a novel process for the synthesis of high molecular weight Mw ⁇ 1.7 x 10 5 PBS using a non-toxic bioorganic ruthenium catalyst.
  • the method for synthesizing PBS by the bioorganic ruthenium catalytic method of the invention comprises the following steps:
  • SA succinic acid
  • BDO 1,4-butanediol
  • BG bioorganic ruthenium catalyst
  • the catalytic system used in the present invention comprises:
  • Catalyst BG guanine (GN) or creatinine (CR);
  • CoCAT 1 titanium tetrabutoxide (TiOBu 4 ) or tetrabutoxy zirconium (TBOZ);
  • CoCAT 3 zinc oxide (ZO), zinc chloride (ZC) or zinc acetate (ZA).
  • the molar ratio of the raw materials SA and BDO is 1: (1 to 1.5).
  • the amount of BG in the quaternary catalyst is 0.01 ⁇ to 0.05 SA of the molar amount of SA;
  • the weight average molecular weight M w of the polybutylene succinate (PBS) of the process product of the present invention can be synthesized in a range of 1.4 ⁇ 10 5 to 1.7 ⁇ 10 5 according to actual needs and modulation of the catalyst composition.
  • the molecular weight of the polymer can be controlled and synthesized according to actual needs.
  • Succinic acid (SA, 59.05 g, 0.50 mol), 1,4-butanediol (BDO, 58.58 g, 0.65 mol) and creatinine (CR, 2.83 mg, 0.025 mmol) were added to the polymerization kettle in argon. Under atmospheric pressure, atmospheric pressure esterification reaction was carried out at 180 ° C for 3 h. Then, tetrabutoxyzirconium (TBOZ, 9.59 mg, 0.025 mmol), titanium dioxide (TDO, 2.00 mg, 0.025 mmol), zinc oxide (ZO, 10.17 mg, 0.125 mmol) were added to the reaction system, and the temperature was raised to 210 ° C.
  • TBOZ tetrabutoxyzirconium
  • the polycondensation reaction was carried out by pressing to 1.5 torr, and the reaction was carried out for 30 hours.
  • the polymer had a weight average molecular weight M w of 1.55 ⁇ 10 5 and a molecular weight distribution index of PDI of 1.55 by a GPC method.
  • Succinic acid (SA, 59.05 g, 0.50 mol), 1,4-butanediol (BDO, 67.59 g, 0.75 mol) and guanine (GN, 1.51 mg, 0.01 mmol) were added to the polymerization kettle. Under atmospheric pressure, the atmospheric pressure esterification reaction was carried out at 200 ° C for 2 h. Then, tetrabutoxytitanium (TiOBu 4 , 6.81 mg, 0.02 mmol), titanium dioxide (TDO, 0.96 mg, 0.012 mmol), zinc oxide (ZO, 2.44 mg, 0.03 mmol) were added to the reaction system, and the temperature was raised to 230 ° C.
  • TiOBu 4 tetrabutoxytitanium
  • TiOBu 4 6.81 mg, 0.02 mmol
  • TiOBu 4 6.81 mg, 0.02 mmol
  • TiO titanium dioxide
  • ZO zinc oxide
  • the polycondensation reaction was carried out under reduced pressure to 1.0 torr, and the reaction was carried out for 27 hours.
  • the polymer had a weight average molecular weight M w of 1.70 ⁇ 10 5 and a molecular weight distribution index of PDI 1.67 by a GPC method.
  • Succinic acid (SA, 59.05 g, 0.50 mol), 1,4-butanediol (BDO, 49.57 g, 0.55 mol) and guanine (GN, 0.755 mg, 0.005 mmol) were added to the polymerization kettle. Under atmospheric pressure, the atmospheric pressure esterification reaction was carried out at 200 ° C for 2 h. Then, tetrabutoxytitanium (TiOBu 4 , 1.702 mg, 0.005 mmol), titanium dioxide (TDO, 0.80 mg, 0.01 mmol), zinc chloride (ZC, 2.73 mg, 0.02 mmol) were added to the reaction system, and the temperature was raised to 230 ° C.
  • TiOBu 4 tetrabutoxytitanium
  • TiOBu 4 titanium dioxide
  • ZC zinc chloride
  • the pressure was reduced to 2.5 torr to carry out a polycondensation reaction, and the reaction was carried out for 20 hours.
  • the polymer had a weight average molecular weight M w of 1.61 ⁇ 10 5 and a molecular weight distribution index of PDI 1.69 by a GPC method.
  • TBOZ tetrabutoxyzirconium
  • TiO 2 titanium dioxide
  • ZA zinc acetate
  • the polycondensation reaction was carried out by pressing to 0.5 torr, and the reaction was carried out for 24 hours.
  • the polymer had a weight average molecular weight M w of 1.69 ⁇ 10 5 and a molecular weight distribution index of PDI 1.86 by a GPC method.
  • Succinic acid SA, 47.24g, 0.60mol
  • 1,4-butanediol BDO, 54.07g, 0.72mol
  • guanine GN, 2.27mg, 0.015mmol
  • TiOBu 4 tetrabutoxytitanium
  • TiOBu 4 11.51 mg, 0.03 mmol
  • TiO titanium dioxide
  • ZC zinc chloride
  • the pressure was reduced to 3.0 torr to carry out a polycondensation reaction, and the reaction was carried out for 23 hours.
  • the weight average molecular weight of the polymer was measured by the GPC method, M w 1.41 ⁇ 10 5 , and the molecular weight distribution index was PDI 1.91.
  • Succinic acid (SA, 59.05 g, 0.50 mol), 1,4-butanediol (BDO, 45.06 g, 0.50 mol) and creatinine (CR, 2.26 mg, 0.02 mmol) were added to the polymerization kettle in argon. Under atmospheric pressure, the atmospheric pressure esterification reaction was carried out at 190 ° C for 3 h. Then, tetrabutoxyzirconium (TBOZ, 11.51 mg, 0.03 mmol), titanium dioxide (TiO 2 , 2.56 mg, 0.032 mmol), zinc acetate (ZA, 16.51 mg, 0.09 mmol) were added to the reaction system, and the temperature was raised to 220 ° C.
  • TBOZ tetrabutoxyzirconium
  • TiO 2 titanium dioxide
  • ZA zinc acetate
  • the polycondensation reaction was carried out under reduced pressure to 2.5 torr, and the reaction was carried out for 25 hours.
  • the polymer had a weight average molecular weight M w of 1.58 ⁇ 10 5 and a molecular weight distribution index of PDI 1.74 by GPC method.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

一种生物有机胍催化合成聚丁二酸丁二醇酯的工艺方法。本发明的鲜明特点是：以人体内代谢生成的生物有机胍肌酐或鸟嘌呤为主催化剂组成高效四元催化体系，合成工艺包括：(1)将丁二酸、1,4-丁二醇和生物有机胍催化剂置于反应器中，常压下于180～200℃进行酯化反应2～3h，至无水馏出；(2)加入助催化剂，将反应体系绝对压力调至0.5～3torr，于210～230℃进行缩聚反应20～30h，得到产品。本发明的有益特点为：(1)采用四元催化体系，催化效率高，催化剂用量少；(2)本工艺大大降低了合成工艺过程中的降解副反应；(3)聚合物分子量可根据实际需要在1.4-1.7×105范围内受控合成。

Description

生物有机胍催化法合成聚丁二酸丁二醇酯的工艺方法 技术领域
本发明属于环境友好暨生物降解聚合物合成技术领域，特别涉及一种聚丁二酸丁二醇酯的合成新工艺。
背景技术
不可降解石油基塑料造成的环境污染已引起世界范围关注，研发环境友好暨生物降解材料替代不可降解石油基塑料已成为当今材料科学与生产界关注的焦点之一。聚丁二酸丁二醇酯(PBS)是一种脂肪族生物降解材料，PBS在自然条件下可被多种微生物或酶分解，最终生成二氧化碳和水。PBS具有良好的延展性、断裂伸长性、耐热性和抗冲击性。PBS可用于环境友好暨生物降解材料聚乳酸的共混改性，提高聚乳酸制品的柔顺性和延展性等。
关于PBS的合成文献报道的催化剂多为重金属催化剂如：辛酸亚锡、氯化亚锡、二丁基氧化锡、烷氧基锑等(CN 103724599A，CN 102019202A)，此类金属催化剂具有一定的细胞毒性，因此材料降解后会对环境造成一定的污染。另一方面，至今文献报道的直接法(以丁二醇、丁二酸为原料)合成的PBS产品重均分子量(Mw)在1.4×105以下，而Mw≥1.4×105的PBS产品均采用中分子量PBS扩链法合成，所用扩链剂(如异氰酸酯)具有一定的毒性(王衍亮等,化工新型材料,2011,12,43-45)。Mw≥1.4×105的PBS在高性能可降解塑料制品方面有重要用途。
发明人在利用生物有机胍合成环境友好暨生物降解材料方面长期研究的基础上，最近研发成功利用无毒生物有机胍催化剂合成高分子量Mw≥1.4×105聚丁二酸丁二醇酯的新工艺。
发明内容
本发明旨在采用无毒生物有机胍催化剂实现高分子量Mw≥1.7×105PBS合成的新工艺。
本发明所述的生物有机胍催化法合成PBS的工艺方法，包括如下步骤：
(1)将丁二酸(SA)、1,4-丁二醇(BDO)和生物有机胍主催化剂(BG)置于反应器中，常 压下于180～200℃进行酯化反应2～3h，至无水馏出；
(2)加入助催化剂1(CoCAT1)、加入助催化剂2(CoCAT2)及加入助催化剂3(CoCAT3)，将反应体系绝对压力调至0.5～3torr，于210～230℃进行缩聚反应20～30h，得到产品。
本发明所用催化体系包括：
(1)主催化剂BG：鸟嘌呤(GN)或肌酐(CR)；
(2)CoCAT1：四丁氧基钛(TiOBu4)或四丁氧基锆(TBOZ)；
(3)CoCAT2：二氧化钛(TDO)；
(4)CoCAT3：氧化锌(ZO)、氯化锌(ZC)或醋酸锌(ZA)。
原料SA和BDO的摩尔量比为1:(1～1.5)。
四元催化剂中BG用量为SA摩尔量的0.01‰～0.05‰；
BG:CoCAT1＝1.0：(1.0～2.0)；
BG:CoCAT2＝1.0：(1.0～2.0)；
BG:CoCAT3＝1.0：(2.0～5.0)。
本发明工艺产品聚丁二酸丁二醇酯(PBS)的重均分子量Mw可在1.4×105～1.7×105范围内根据实际需要和催化剂组成的调变合成。
本发明的优点和有益效果：
(1)采用四元催化体系，催化效率高，催化剂用量少；
(2)本工艺大大降低了合成工艺过程中的降解副反应；
(3)聚合物分子量可根据实际需要受控合成。
具体实施方式
实施例1
将丁二酸(SA,59.05g,0.50mol)、1,4-丁二醇(BDO,58.58g,0.65mol)和肌酐(CR,2.83mg,0.025mmol)，加入聚合反应釜中,在氩气保护下，180℃进行常压酯化反应，反应3h。然后往反应体系中加入四丁氧基锆(TBOZ,9.59mg,0.025mmol)、二氧化钛(TDO,2.00mg,0.025mmol),氧化锌(ZO,10.17mg,0.125mmol)，升温至210℃，减压至1.5torr进 行缩聚反应，反应30h。GPC法测得聚合物重均分子量Mw 1.55×105，分子量分布指数PDI 1.55。
实施例2
将丁二酸(SA,59.05g,0.50mol)、1,4-丁二醇(BDO,67.59g,0.75mol)和鸟嘌呤(GN,1.51mg,0.01mmol)，加入聚合反应釜中,在氩气保护下，200℃进行常压酯化反应，反应2h。然后往反应体系中加入四丁氧基钛(TiOBu4,6.81mg,0.02mmol)、二氧化钛(TDO,0.96mg,0.012mmol)，氧化锌(ZO,2.44mg,0.03mmol)，升温至230℃，减压至1.0torr进行缩聚反应，反应27h。GPC法测得聚合物重均分子量Mw 1.70×105，分子量分布指数PDI 1.67。
实施例3
将丁二酸(SA,59.05g,0.50mol)、1,4-丁二醇(BDO,49.57g,0.55mol)和鸟嘌呤(GN,0.755mg,0.005mmol)，加入聚合反应釜中,在氩气保护下，200℃进行常压酯化反应，反应2h。然后往反应体系中加入四丁氧基钛(TiOBu4,1.702mg,0.005mmol)、二氧化钛(TDO,0.80mg,0.01mmol)，氯化锌(ZC,2.73mg,0.02mmol)，升温至230℃，减压至2.5torr进行缩聚反应，反应20h。GPC法测得聚合物重均分子量Mw 1.61×105，分子量分布指数PDI 1.69。
实施例4
将丁二酸(SA,47.24g,0.40mol)、1,4-丁二醇(BDO,54.07g,0.60mol)和肌酐(CR,2.26mg,0.02mmol)，加入聚合反应釜中,在氩气保护下，190℃进行常压酯化反应，反应3h。往反应体系中加入四丁氧基锆(TBOZ,11.51mg,0.03mmol)、二氧化钛(TiO2,2.0mg,0.03mmol),醋酸锌(ZA,9.17mg,0.05mmol)，升温至230℃，减压至0.5torr进行缩聚反应，反应24h。GPC法测得聚合物重均分子量Mw 1.69×105，分子量分布指数PDI 1.86。
实施例5
将丁二酸(SA,47.24g,0.60mol)、1,4-丁二醇(BDO，54.07g,0.72mol)和鸟嘌呤(GN,2.27mg,0.015mmol)，加入聚合反应釜中,在氩气保护下，180℃进行常压酯化反应，反应3h。然后往反应体系中加入四丁氧基钛(TiOBu4,11.51mg,0.03mmol)、二氧化钛(TDO,2.16mg,0.027mmol),氯化锌(ZC,4.09mg,0.03mmol)，升温至220℃，减压至3.0torr进行缩聚反应，反应23h。GPC法测得聚合物重均分子量Mw 1.41×105，分子量分布指 数PDI 1.91。
实施例6
将丁二酸(SA,59.05g,0.50mol)、1,4-丁二醇(BDO,45.06g,0.50mol)和肌酐(CR,2.26mg,0.02mmol)，加入聚合反应釜中,在氩气保护下，190℃进行常压酯化反应，反应3h。然后往反应体系中加入四丁氧基锆(TBOZ，11.51mg,0.03mmol)、二氧化钛(TiO2,2.56mg,0.032mmol)，醋酸锌(ZA,16.51mg,0.09mmol)，升温至220℃，减压至2.5torr进行缩聚反应，反应25h。GPC法测得聚合物重均分子量Mw 1.58×105，分子量分布指数PDI 1.74。

Claims (3)

  1. 一种生物有机胍催化法合成高分子量Mw≥1.4×105聚丁二酸丁二醇酯(PBS)的工艺方法，合成工艺过程包括如下步骤：
    (1)将丁二酸(SA)、1,4-丁二醇(BDO)和生物有机胍主催化剂(BG)置于反应器中，常压下于180～200℃进行酯化反应2～3h，至无水馏出；
    (2)加入助催化剂CoCAT1、助催化剂CoCAT2及助催化剂CoCAT3，将反应体系绝对压力调至0.5～3torr，于210～230℃进行缩聚反应20～30h，得到产品。
  2. 根据权利要求1所述的方法，其特征在于：
    (1)所述的主催化剂生物有机胍(BG)为：鸟嘌呤(GN)或肌酐(CR)；
    (2)CoCAT1为：四丁氧基钛(TiOBu4)或四丁氧基锆(TBOZ)；
    (3)CoCAT2为：二氧化钛(TDO)；
    (4)CoCAT3为：氧化锌(ZO)、氯化锌(ZC)或醋酸锌(ZA)。
  3. 根据权利要求1或2所述的方法，其特征在于：
    (1)SA和BDO的摩尔量比为1:(1～1.5)；
    (2)四元催化剂中BG用量为SA摩尔量的0.01‰～0.05‰；
    BG:CoCAT1＝1.0：(1.0～2.0)；
    BG:CoCAT2＝1.0：(1.0～2.0)；
    BG:CoCAT3＝1.0：(2.0～5.0)。
PCT/CN2016/076956 2015-04-13 2016-03-22 生物有机胍催化法合成聚丁二酸丁二醇酯的工艺方法 WO2016165533A1 (zh)

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