WO2020150970A1 - 一种碱助催化烷基硫醚插入双(三)硫酯端基聚合物制备嵌段共聚物的聚合方法 - Google Patents

一种碱助催化烷基硫醚插入双(三)硫酯端基聚合物制备嵌段共聚物的聚合方法 Download PDF

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WO2020150970A1
WO2020150970A1 PCT/CN2019/073008 CN2019073008W WO2020150970A1 WO 2020150970 A1 WO2020150970 A1 WO 2020150970A1 CN 2019073008 W CN2019073008 W CN 2019073008W WO 2020150970 A1 WO2020150970 A1 WO 2020150970A1
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polymer
polymerization method
zero
template
sulfide
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PCT/CN2019/073008
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宗立率
希布莱德•范德扎赫
永井篤志
蹇锡高
王锦艳
唐慕
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大连理工大学
代尔夫特理工大学
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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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/06—Polythioethers from cyclic thioethers
    • 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
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers

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  • the invention belongs to the technical field of preparation of novel block polymer materials, and relates to a novel polymerization method, specifically a base-assisted alkyl sulfide insertion into a bis(tri)thioester end group polymer to prepare a block copolymer Polymerization method.
  • Polyalkyl sulfide is a kind of high molecular polymer with peculiar properties, which has good biocompatibility and chain flexibility.
  • the glass transition temperature is close to -50°C. It can be used as a blending resin element or as a copolymer component to improve the biocompatibility and amorphous form of commercial polymers.
  • the present invention adds organic weak bases such as 4-dimethylaminopyridine (DMAP) or 1,8-diazabicycloundec-7-ene (DBU) by analyzing the reaction mechanism. ), etc. as a co-catalyst (addition amount is 0.1-100eq, preferably 0.2-1.0eq), can effectively realize the insertion polymerization reaction, prepare high molecular weight homo(co)polymer, and the conversion rate of alkyl sulfide monomer reaches 80 %the above.
  • the polymerization method not only gives the possibility of high molecular weight polymerization reaction, but also polymerization efficiency and economy.
  • the present invention provides a novel method for preparing homo(co)polyalkyl sulfide.
  • This method can be carried out under mild reaction conditions (the reaction temperature is 40-90°C, and the requirements for water and oxygen are not harsh), and it has high atom availability and economy, which will expand the application of polyalkyl sulfide Range, and can be used in self-healing materials, smart materials, self-assembly, biopolymers, drug slow-release and other fields.
  • a base-assisted polymerization method for preparing a block copolymer by inserting an alkyl sulfide into a bis(tri)thioester end group polymer the steps are as follows:
  • the molar ratio of catalyst, organic base and organic solvent is 1:0.01 ⁇ 10:0.01 ⁇ 10:0.1 ⁇ 100; the number of moles of sulfide monomer depends on the molecular weight of the designed block copolymer, and it and the sulfide ester compound Or the molar ratio of the polymer is 10-1000:1, preferably 20-300:1; use liquid nitrogen and vacuum pump, perform three freezing and vacuum operations to completely remove the air in the reactor and then seal; heat up to 40-90°C After 6-72 hours of reaction, the reaction solution was settled in methanol, washed three times by centrifugation, and dried in a vacuum oven at 60°C for 24 hours to obtain a homo(co)polymer, which was retained for use;
  • the thioester end group template compound or polymer has the following general structural formula:
  • R 1 and R '2 are the same or different;
  • R 1 and R '2 are the same or different;
  • R 3 ⁇ R 10 are the same or different
  • M 1 and M 2 represent the structural units of the polymer, and the structures contained therein are independently selected without any related restrictions; one of M 1 and M 2 can be zero, but cannot be zero at the same time; one of M 1 and M 2 When zero is used, it is a homopolymer; when none is zero, it is a copolymer; in terms of categories, template polymers include common homopolymers or copolymers of styrene, acrylic, acrylamide, acetate and acrylonitrile Things etc.
  • the phase transfer catalyst has the following general structural formula:
  • the phase transfer catalyst includes but is not limited to the above structure.
  • the organic base contains the following structural formula:
  • the base catalyst includes the above three structure organic bases, but is not limited to these three structure organic bases.
  • the cyclic sulfide monomer may include the following general structural formula:
  • the cyclic sulfide monomer includes the above structure, but is not limited to the above structure, and its core structure is characterized by including a cyclic sulfide structure.
  • the organic solvents used include: chloroform, N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, etc., can be used alone or in two Or mix the above.
  • the chemical reagents are all commercially available except for cyclic sulfide monomers with special structures.
  • the catalyst system does not need a harsh anhydrous and oxygen-free environment during the reaction preparation stage, and only needs to vacuum the air in the system before the reaction.
  • the insertion reaction can be successfully carried out, and the monomer conversion rate is higher than 80%.
  • the prepared block copolymer has the characteristics of soft and hard double-segment, and the molecular weight can reach 20000 ⁇ 100000g/mol, the mechanical properties are obviously improved, the amorphous form of the polymer is obviously modified, and the glass transition temperature can be as low as -50 °C.
  • This invention transforms this type of insertion reaction from a chemical concept into an applicable technology.
  • Potential application areas include self-healing materials, smart materials, self-assembly, biopolymers, and sustained drug release.
  • Figure 1 is a comparison diagram of gel chromatograms of polymers before and after the insertion reaction, in which a template polystyrene; b insertion polymerization product without adding alkali cocatalyst; c insertion polymerization product adding alkali cocatalyst.
  • Fig. 2 is a comparison diagram of monomer conversion rate of polymerization reaction before and after insertion reaction (monomer conversion rate is detected by H-NMR of the reaction stock solution), in which a base cocatalyst is not added for insertion polymerization; b base cocatalyst is added for insertion polymerization product.
  • Figure 3 is a DSC comparison chart of polymerization reaction products before and after the insertion reaction, in which a template styrene; b insertion polymerization product (block polystyrene-alkyl sulfide).
  • Figure 4 is a TGA comparison diagram of polymerization reaction products before and after the insertion reaction, in which a template styrene; b insertion polymerization product (block polystyrene-alkyl sulfide).
  • the reaction solution was settled in methanol, washed three times by centrifugation, and dried in a vacuum oven at 60°C for 24 hours to obtain a pink viscous homopolymer PMCT.
  • the glass transition temperature (DSC) is -68°C
  • the number average molecular weight is 11.6KDa by GPC
  • the reaction conversion rate is 83%.
  • PBMA-co-BCT synthesis reaction formula add 0.5177g of template polymer B-PBMA containing thioester end groups, phase transfer catalyst tetra-tert-butyl nitrogen bromide TBNB 0.0074g, and organic Base Et 3 N 0.0240 g, sulfide monomer BCT 3.6480 g, organic solvent NMP 2 mL, after stirring evenly, use liquid nitrogen and a vacuum pump to perform three freezing and vacuum operations to completely remove the air in the reactor and then seal it.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

一种碱助催化烷基硫醚插入双(三)硫酯端基聚合物制备嵌段共聚物的聚合方法，通过加入有机碱为助催化剂，与已报道的相转移催化剂，如氯化四苯基膦、氯化四苯基胺等组成催化剂体系，催化含硫代酯端基的模板化合物或聚合物与含环硫醚单体进行插入聚合，得到高分子量均聚或嵌段共聚物。该聚合方法带来的有益效果是：对于模板化合物引发的插入反应，其单体转化率提高至80％以上；当模板聚合物的分子量高于2500g/mol时，也可成功进行插入聚合，且单体转化率高于80％。通过方法合成的该类嵌段合物具有特殊的相拓补结构，可大幅改善聚合物的无定形态，在自愈合材料、智能材料、自组装、生物高分子、药物缓释等领域具有广阔的应用前景。

Description

一种碱助催化烷基硫醚插入双(三)硫酯端基聚合物制备嵌段共聚物的聚合方法 技术领域
本发明属于新型嵌段高分子材料制备技术领域，涉及到一种新型的聚合方法，具体为一种碱助催化烷基硫醚插入双(三)硫酯端基聚合物制备嵌段共聚物的聚合方法。
背景技术
聚烷基硫醚是一类性能奇特的高分子聚合物，其具有良好的生物相容性和链柔顺性。玻璃化温度接近于-50℃，既可作为共混树脂基元，也可作为共聚组分，用于改善商用高分子的生物相容性和无定形态。
由于树脂共混无法精准调控多相树脂的相容性，以达到良好的改性效果。因此，多采用共聚的方法引入烷基硫醚结构单元，以改善聚合物的综合性能。Balzer等人采用阴离子共聚的方法，以烷基锂为催化剂制备苯乙烯-烷基硫醚嵌段共聚物(Macromolecules 2013,46(18),7406-7414.)。但是由于烷基锂价格昂贵，且过于活泼，反应需要在绝对无水无氧的低温下进行，给其应用带了一定的困难。Nagai等人曾报道了采用相转移催化剂——卤化四苯基膦作为催化剂，催化合成嵌段共聚苯乙烯和共聚乙烯胺，但是该报道仅将该聚合方法应用于分子量低于2500g/mol的齐聚物，所以产物分子量低于4000g/mol，单体转化率低于50％，未知其可否用于制备高分子量聚合物，不具备进一步应用的技术价值(Macromolecules 2007,40(23),8129-8131.)。发明人在使用Atsushi等人所述工艺制备高分子量烷基硫醚嵌段共聚物时发现，当齐聚物的分子量高于2500g/mol时，无论采用何种相转移催化剂、催化剂含量、反应温度和有机溶剂体系，由于端基含量低和包埋作用，均无法成功引发插入聚合，表明该聚合方法无法推 广应用于制备高分子量材料。
本发明在探索该研究的基础上，通过分析其反应机理，加入有机弱碱，如4-二甲氨基吡啶(DMAP)或1,8-二氮杂二环十一碳-7-烯(DBU)等作为助催化剂(添加量为0.1～100eq，优先0.2～1.0eq)，可有效地实现插入聚合反应，制备高分子量均(共)聚物，且烷基硫醚单体的转化率达80％以上。该聚合方法不仅赋予高分子量聚合反应发生的可能性，并且聚合反应效率和经济性。
发明内容
本发明提供了一种新型的均(共)聚烷基硫醚的制备方法。该方法既可以在温和的反应条件下(反应温度为40-90℃，对水和氧要求不苛刻)进行，又具有较高的原子利用性和经济性，将扩大聚烷基硫醚的应用范围，并可应用于自愈合材料、智能材料、自组装、生物高分子、药物缓释等领域。
本发明的技术方案：
一种碱助催化烷基硫醚插入双(三)硫酯端基聚合物制备嵌段共聚物的聚合方法，步骤如下：
向反应器中依次加入含硫代酯端基的模板化合物或聚合物、相转移催化剂、有机碱、环硫醚单体和有机溶剂，含硫代酯端基的模板化合物或聚合物、相转移催化剂、有机碱和有机溶剂的摩尔比为1：0.01～10：0.01～10：0.1～100；环硫醚单体的摩尔数视设计的嵌段共聚物的分子量而定，其与硫化酯化合物或聚合物的摩尔比为10～1000：1，优选20～300：1；使用液氮和真空泵，进行三次冷冻、真空操作以完全除净反应器中的空气后密封；升温至40-90℃反应6-72小时后，将反应溶液沉降于甲醇中，离心洗涤三次，置于真空烘箱中60℃干燥24h后，得到均(共)聚物，留用；
所述的硫代酯端基的模板化合物或聚合物具有以下的结构通式：
双硫酯模板化合物：
Figure PCTCN2019073008-appb-000001
三硫酯模板化合物：
Figure PCTCN2019073008-appb-000002
R 1和R′ 2相同或不同；
双硫酯模板聚合物：
Figure PCTCN2019073008-appb-000003
三硫酯模板聚合物：
Figure PCTCN2019073008-appb-000004
Figure PCTCN2019073008-appb-000005
R 1和R′ 2相同或不同；
R 3-R 10＝H，or C nH 2n+1，n＝n，2，3...
R 3～R 10相同或不同；
M 1与M 2结构代表聚合物的结构单元，独立选取其包含的结构，无任何关联限制；M 1与M 2其中之一可为零，但不可同时为零；M 1与M 2其一取零时则为均聚物；均不取零时则为共聚物；类别上，模板聚合物包含常见的苯乙烯类、丙烯酸酯类、丙烯酰胺、醋酸酯类和丙烯腈类均聚或共聚物等。
所述的相转移催化剂具有以下结构通式：
Figure PCTCN2019073008-appb-000006
所述的相转移催化剂包含但不仅限于上述结构。
所述的有机碱包含以下结构式：
Figure PCTCN2019073008-appb-000007
所述碱催化剂包含以上三种结构有机碱，但不限于这三种结构有机碱。
所述的环硫醚单体可包含以下结构通式：
Figure PCTCN2019073008-appb-000008
所述环硫醚单体包含以上结构，但不限于以上结构，其核心结构特征为包含环硫醚结构。
所使用的有机溶剂包含：氯仿、N-甲基吡咯烷酮、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、二甲基亚砜等，可以单独使用，也可以二种或以上混合使用。
所述的化学试剂除特殊结构环硫醚单体外，均为市售获得。
本发明的有益效果：
(1)催化剂体系在反应准备阶段无需苛刻的无水无氧环境，仅需在反应前真空抽去体系内空气即可。
(2)对于高分子量(>2500g/mol)的聚合物，插入反应可以成功进行，且单体转化率高于80％。
(3)制备的嵌段共聚物具有软硬段双链段特征，且分子量可达20000～100000g/mol，力学性能明显提升，聚合物的无定形态得到明显改性，玻璃化温度可低至-50℃。
(4)该发明将这类插入反应从化学概念转化为可应用的技术，潜在应用领域包含自愈合材料、智能材料、自组装、生物高分子、药物缓释等。
附图说明
图1是插入反应前后聚合物的凝胶色谱对比图，其中，a模板聚苯乙烯；b插入聚合产物不添加碱助催化剂；c插入聚合产物添加碱助催化剂。
图2是插入反应前后聚合反应单体转化率对比图(通过反应原液的H-NMR检测单体转化率)，其中，a插入聚合不添加碱助催化剂；b插入聚合产物添加碱助催化剂。
图3是插入反应前后聚合反应产物的DSC对比图，其中，a模板苯乙烯；b插入聚合产物(嵌段聚苯乙烯-烷基硫醚)。
图4是插入反应前后聚合反应产物的TGA对比图，其中，a模板苯乙烯；b插入聚合产物(嵌段聚苯乙烯-烷基硫醚)。
具体实施方式
以下结合附图和技术方案，进一步说明本发明的具体实施方式。
实施例1
如PMCT合成反应式，向10mL史莱克反应器中依次加入含硫代酯端基的模板化合物BMSE0.0122g、相转移催化剂四苯基氯化膦TPPC0.0381g、有机碱DMAP0.3660g、环硫醚单体0.8126ml、有机溶剂NMP0.2mL,搅拌均匀后，使用液氮和真空泵，进行三次冷冻、真空操作以完全除净反应器中的空气后密封。升温至70℃反应6小时后，将反应溶液沉降于甲醇中，离心洗涤三次，置于真空烘箱中60℃干燥24h后，得到粉红色粘稠状均聚物PMCT。其玻璃化温度(DSC)为-68℃，数均分子量经GPC检测为11.6KDa，反应转化率为83％。
Figure PCTCN2019073008-appb-000009
PMCT合成反应式
实施例2
如PS-co-MCT合成所示，向20mL史莱克反应器中依次加入含硫代酯内端基的模板聚苯乙烯(A-PS)0.48g,相转移催化剂四苯基溴化膦TPPB0.094g、有机碱DMAP0.0122g、环硫醚单体MCT 1.05mL、有机溶剂DMSO 4ML。使用液氮和真空泵，进行三次冷冻、真空操作以完全除净反应器中的空气后密封。升温至60℃反应12小时后，将反应溶液沉降于甲醇中，离心洗涤三次，置于真空烘箱中60℃干燥24h后，得到黄色共聚物PS-co-MCT。其玻璃化温度(DSC)为-40℃，数均分子量经GPC检测为15.2KDa，反应转化率为87％。
Figure PCTCN2019073008-appb-000010
PS-co-MCT合成反应式
实施例3
如PBMA-co-BCT合成反应式，向10mL史莱克反应器中依次加入含硫代酯端基的模板聚合物B-PBMA 0.5177g、相转移催化剂四叔丁基溴化氮TBNB0.0074g、有机碱Et 3N 0.0240g、环硫醚单体BCT 3.6480g、有机溶剂NMP 2mL,搅拌均匀后，使用液氮和真空泵，进行三次冷冻、真空操作以完全除净反应器中的空气后密封。升温至50℃反应48小时后，将反应溶液沉降于甲醇中，离心洗涤三次，置于真空烘箱中60℃干燥24h后，得到粉红色粘稠状共聚物PBMA-co-BCT。其玻璃化温度(DSC)为-39℃，数均分子量经GPC检测为19.8KDa，反应转化率为85％。
Figure PCTCN2019073008-appb-000011
PBMA-co-BCT合成反应式
实施例4
如PMMA-co-BA-co-FCT的反应式所示，向100mL反应器中依次加入含硫代酯端基的模板聚合物(聚甲基丙烯酸甲酯-丙烯酸丁酯共聚物,PMMA-co-BA,MMA:BA＝3:1,Mn＝37.0KDa,Tg＝63℃)3.70g、相转移催化剂四苯基碘化氮TPNI1.12g、有机碱DBU 1.52g、环硫醚单体12.36g、有机溶剂DMAc 20mL。使用液氮和真空泵，进行三次冷冻、真空操作以完全除净反应器中的空气后密封。升温至60℃反应72小时后，将反应溶液沉降于甲醇中，离心洗涤三次，置于真空烘箱中60℃干燥24h后，得到浅黄色共聚物PMMA-co-BA-co-FCT。其玻璃化温度(DSC)为-38℃，数均分子量经GPC检测为73.2KDa，反应转化率为83％。
Figure PCTCN2019073008-appb-000012
PMMA-co-BA-co-FCT的反应式
实施例5
如PS-co-MCT的反应式，向10mL史莱克反应器中依次加入含硫代酯端基 的模板聚合物B-PS 0.9342g、相转移催化剂四叔丁基氯化膦0.0324g、有机碱DBU 0.0430g、环硫醚单体MCT 1.8683g、有机溶剂NMP 4mL,搅拌均匀后，使用液氮和真空泵，进行三次冷冻、真空操作以完全除净反应器中的空气后密封。升温至50℃反应72小时后，将反应溶液沉降于甲醇中，离心洗涤三次，置于真空烘箱中60℃干燥24h后，得到粉红色粘稠状共聚物PBMA-co-BCT。其玻璃化温度(DSC)为-41℃，数均分子量经GPC检测为20.2KDa，反应转化率为81％。
Figure PCTCN2019073008-appb-000013
PS-co-MCT的反应式。

Claims (5)

  1. 一种碱助催化烷基硫醚插入双(三)硫酯端基聚合物制备嵌段共聚物的聚合方法，其特征在于，步骤如下：
    向反应器中依次加入含硫代酯端基的模板化合物或聚合物、相转移催化剂、有机碱、环硫醚单体和有机溶剂，含硫代酯端基的模板化合物或聚合物、相转移催化剂、有机碱和有机溶剂的摩尔比为1：0.01～10：0.01～10：0.1～100；环硫醚单体的摩尔数视设计的嵌段共聚物的分子量而定，其与硫化酯化合物或聚合物的摩尔比为10～1000：1；使用液氮和真空泵，进行三次冷冻、真空操作以完全除净反应器中的空气后密封；升温至40-90℃反应6-72小时后，将反应溶液沉降于甲醇中，离心洗涤三次，置于真空烘箱中60℃干燥24h后，得到均聚物或共聚物，留用；
    所述的硫代酯端基的模板化合物或聚合物具有以下的结构通式：
    双硫酯模板化合物：
    Figure PCTCN2019073008-appb-100001
    Figure PCTCN2019073008-appb-100002
    Figure PCTCN2019073008-appb-100003
    三硫酯模板化合物：
    Figure PCTCN2019073008-appb-100004
    Figure PCTCN2019073008-appb-100005
    R 1和R′ 2相同或不同；
    双硫酯模板聚合物：
    Figure PCTCN2019073008-appb-100006
    Figure PCTCN2019073008-appb-100007
    Figure PCTCN2019073008-appb-100008
    Figure PCTCN2019073008-appb-100009
    三硫酯模板聚合物：
    Figure PCTCN2019073008-appb-100010
    Figure PCTCN2019073008-appb-100011
    Figure PCTCN2019073008-appb-100012
    Figure PCTCN2019073008-appb-100013
    R 1和R′ 2相同或不同；
    R 3-R 10＝H，or C nH 2n+1，n＝1，2，3...
    R 3～R 10相同或不同；
    M 1与M 2相同或不同；
    所述的相转移催化剂具有以下结构通式：
    Figure PCTCN2019073008-appb-100014
    X＝F、Cl、Br、I
    Figure PCTCN2019073008-appb-100015
    R 11～R 14相同或不同；
    所述的有机碱包含以下结构式：
    Figure PCTCN2019073008-appb-100016
    所述的环硫醚单体包含以下结构通式：
    Figure PCTCN2019073008-appb-100017
    Figure PCTCN2019073008-appb-100018
    Figure PCTCN2019073008-appb-100019
  2. 根据权利要求1所述的聚合方法，其特征在于，所使用的有机溶剂为氯仿、N-甲基吡咯烷酮、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、二甲基亚砜中的一种或两种以上混合。
  3. 根据权利要求1或2所述的聚合方法，其特征在于，所述的环硫醚单体与硫化酯化合物或聚合物的摩尔比为20～300：1。
  4. 根据权利要求1或2所述的聚合方法，其特征在于，M 1与M 2结构代表聚合物的结构单元，独立选取其包含的结构，无任何关联限制；M 1与M 2其中之一可为零，但不可同时为零；M 1与M 2其一取零时则为均聚物；均不取零时则为共聚物。
  5. 根据权利要求3所述的聚合方法，其特征在于，M 1与M 2结构代表聚合物的结 构单元，独立选取其包含的结构，无任何关联限制；M 1与M 2其中之一可为零，但不可同时为零；M 1与M 2其一取零时则为均聚物；均不取零时则为共聚物。
PCT/CN2019/073008 2019-01-24 2019-01-24 一种碱助催化烷基硫醚插入双(三)硫酯端基聚合物制备嵌段共聚物的聚合方法 WO2020150970A1 (zh)

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