WO2022267271A1 - 一种杂化聚合物及其制备方法和应用 - Google Patents

一种杂化聚合物及其制备方法和应用 Download PDF

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WO2022267271A1
WO2022267271A1 PCT/CN2021/124669 CN2021124669W WO2022267271A1 WO 2022267271 A1 WO2022267271 A1 WO 2022267271A1 CN 2021124669 W CN2021124669 W CN 2021124669W WO 2022267271 A1 WO2022267271 A1 WO 2022267271A1
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hybrid polymer
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尹家福
杨俊升
殷盼超
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South China University of Technology SCUT
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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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/11—Homopolymers
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/144—Side-chains containing silicon
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/145—Side-chains containing sulfur
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/334—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing heteroatoms
    • C08G2261/3342—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing heteroatoms derived from cycloolefins containing heteroatoms
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]

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  • the invention relates to the technical field of polymer nanocomposite materials, in particular to a hybrid polymer and its preparation method and application.
  • Impact-resistant materials are special materials with high strength and excellent toughness, which can withstand instantaneous severe impacts and quickly dissipate energy, so as to effectively protect internal structures and equipment.
  • the most widely used impact-resistant materials in the industry are polymer materials such as polyethylene (PE), polyurethane (PU), and acrylonitrile-butadiene-styrene copolymer (ABS).
  • PE polyethylene
  • PU polyurethane
  • ABS acrylonitrile-butadiene-styrene copolymer
  • the impact effect requires ultra-high molecular weight, and as the molecular weight increases, the toughness of the system will decrease, and the viscosity coefficient of the system will increase accordingly, which will eventually lead to difficulties in molding and processing the material.
  • the recycling rate of ultra-high molecular weight polymers is low, and the environmental pollution problems caused by them cannot be underestimated.
  • the object of the present invention is to provide a hybrid polymer and its preparation method and application.
  • a hybrid polymer whose repeat unit structure is as follows:
  • the number average molecular weight of the hybrid polymer is 10000g/mol ⁇ 100000g/mol.
  • the preparation method of above-mentioned hybrid polymer comprises the following steps:
  • the preparation method of above-mentioned hybrid polymer comprises the following steps:
  • the molar ratio of trisilanol isooctyl-POSS to vinyltrichlorosilane in step 1) is 1:1.2 ⁇ 1:1.4.
  • the reaction in step 1) is carried out at 0°C to 5°C, and the reaction time is 15h to 25h.
  • the molar ratio of compound 1 and mercaptoethylamine hydrochloride in step 2) is 1:1.8 ⁇ 1:2.2.
  • the photoinitiator of step 2) is photoinitiator Igracure 2959.
  • the reaction in step 2) is carried out under ultraviolet light irradiation, and the reaction time is 10 minutes to 20 minutes.
  • the molar ratio of compound 2 and cis-5-norbornene-exo-2,3-dicarboxylic anhydride in step 3) is 1:1.8 ⁇ 1:2.2.
  • the reaction in step 3) is carried out at 130°C-140°C, and the reaction time is 30h-40h.
  • the catalyst in step 4) is [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]bis(2-bromopyridine)(phenylmethylene ) ruthenium dichloride, 1,3-bis(2,4,6-trimethylphenyl)-2-(imidazolidinylidene)(dichlorobenzylidene)(tricyclohexylphosphine)ruthenium at least one.
  • the catalyst in step 4) is Grubbs third-generation catalyst ([1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]bis(2-bromopyridine)( phenylmethylene) ruthenium dichloride).
  • the water and oxygen removal in step 4) adopts a cycle freezing and thawing method.
  • the polymerization reaction in step 4) is carried out at room temperature, and the reaction time is 0.5h-2h.
  • the hybrid polymer of the invention has the advantages of light weight, high strength, easy processing and molding, low cost, and environmental friendliness, and is suitable for large-scale popularization and application.
  • the impact resistance of the hybrid polymer of the present invention does not depend on high molecular weight, has good processability, is convenient for processing and molding, and is conducive to large-scale production and processing;
  • the hybrid polymer of the present invention can be reshaped through simple reprocessing operations when it becomes invalid due to impact, and the recycling rate is extremely high. It is a kind of resource-saving and environment-friendly polymer material.
  • Fig. 1 is the proton nuclear magnetic resonance spectrum figure of the compound 1 in the embodiment.
  • Fig. 2 is the proton nuclear magnetic resonance spectrum of compound 2 in the embodiment.
  • Fig. 3 is the proton nuclear magnetic resonance spectrogram of the monomer in the embodiment.
  • Fig. 4 is a comparison chart of the H NMR spectrum of the monomer and the hybrid polymer in the embodiment.
  • Fig. 5 is a comparison chart of gel permeation chromatograms of monomers and hybrid polymers in the examples.
  • Fig. 6 is a physical photo of the separated Hopkinson compression bar experimental device.
  • Fig. 7 is the stress-strain curve of the hybrid polymer in the embodiment after being impacted at different speeds.
  • Fig. 8 is a physical photo of the hybrid polymer in the embodiment after being impacted at different speeds.
  • Fig. 9 is the stress-strain curve of the hybrid polymer in the embodiment after multiple reprocessing.
  • a kind of hybrid polymer, its preparation method comprises the following steps:
  • the hybrid polymer exhibits excellent impact resistance at different strain rates.
  • the hybrid polymer can withstand a dynamic impact with a strain rate of 1000s -1 , and only the edge part will be damaged, and the middle part will be damaged.
  • the sample can still remain intact.
  • the strain rate reaches 1800s -1 , the specimen can no longer withstand the stress wave with such a high strain rate, so that the hybrid polymer completely fails after the impact .
  • the quantitative recovery of the sample can be achieved after simple reprocessing. Compared with the original sample, the impact resistance of the recovered sample has no obvious change, even after multiple impacts. The recovery situation is still the same.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

本发明公开了一种杂化聚合物及其制备方法和应用。本发明的杂化聚合物的重复单元结构如式（I）。本发明的杂化聚合物的制备方法包括以下步骤：1)进行三硅醇异辛基-POSS和乙烯基三氯硅烷的反应，得到化合物1；2)进行化合物1和巯基乙胺盐酸盐的反应，得到化合物2；3)进行化合物2和顺-5-降冰片烯-外-2,3-二甲酸酐的反应，得到单体；4)进行单体的聚合反应，即得杂化聚合物。本发明的杂化聚合物具有轻质高强、易于加工成型、低成本、环境友好等优点，适合大规模推广应用。

Description

一种杂化聚合物及其制备方法和应用 技术领域
本发明涉及聚合物纳米复合材料技术领域，具体涉及一种杂化聚合物及其制备方法和应用。
背景技术
抗冲击材料是一类兼具高强度和优异韧性的特殊材料，能够承受住瞬时的剧烈冲击快速将能量耗散，从而实现对内部的结构和设备进行有效保护。目前，工业上使用最为广泛的抗冲击材料为聚乙烯(PE)、聚氨酯(PU)、丙烯腈-丁二烯-苯乙烯共聚物(ABS)等聚合物材料，这些聚合物材料要想实现抗冲击效果需要具备超高的分子量，而随着分子量的增加体系的韧性会随之下降，体系的粘度系数也会相应增大，最终会导致材料成型加工困难。此外，超高分子量的聚合物的重复利用率低，带来的环境污染问题不容小觑。
因此，迫切需要开发一种轻质高强、易于加工成型、低成本、环境友好的抗冲击材料。
发明内容
本发明的目的在于提供一种杂化聚合物及其制备方法和应用。
本发明所采取的技术方案是：
一种杂化聚合物，其重复单元结构如下：
Figure PCTCN2021124669-appb-000001
优选的，所述杂化聚合物的数均分子量为10000g/mol～100000g/mol。
上述杂化聚合物的制备方法包括以下步骤：
1)进行三硅醇异辛基-POSS和乙烯基三氯硅烷的反应，得到化合物1；
2)进行化合物1和巯基乙胺盐酸盐的反应，得到化合物2；
3)进行化合物2和顺-5-降冰片烯-外-2,3-二甲酸酐的反应，得到单体；
4)进行单体的聚合反应，即得杂化聚合物。
优选的，上述杂化聚合物的制备方法包括以下步骤：
1)将三硅醇异辛基-POSS、三乙胺和乙烯基三氯硅烷分散在溶剂中，进行反应，得到化合物1；
2)将化合物1、光引发剂和巯基乙胺盐酸盐分散在溶剂中，进行反应，得到化合物2；
3)将化合物2和顺-5-降冰片烯-外-2,3-二甲酸酐分散在溶剂中，进行反应，得到单体；
4)将单体和催化剂分散在溶剂中，对反应体系除水除氧后进行聚合反应，即得杂化聚合物。
优选的，步骤1)所述三硅醇异辛基-POSS、乙烯基三氯硅烷的摩尔比为1:1.2～1:1.4。
优选的，步骤1)所述反应在0℃～5℃下进行，反应时间为15h～25h。
优选的，步骤2)所述化合物1、巯基乙胺盐酸盐的摩尔比为1:1.8～1:2.2。
优选的，步骤2)所光引发剂为光引发剂Igracure 2959。
优选的，步骤2)所述反应在紫外光照射下进行，反应时间为10min～20min。
优选的，步骤3)所述化合物2、顺-5-降冰片烯-外-2,3-二甲酸酐的摩尔比为1:1.8～1:2.2。
优选的，步骤3)所述反应在130℃～140℃下进行，反应时间为30h～40h。
优选的，步骤4)所述催化剂为[1,3-双(2,4,6-三甲基苯基)-2-咪唑烷亚基]双(2-溴吡啶)(苯基亚甲基)二氯化钌、1,3-双(2,4,6-三甲基苯基)-2-(咪唑烷亚基)(二氯苯亚甲基)(三环己基膦)钌中的至少一种。
进一步优选的，步骤4)所述催化剂为Grubbs三代催化剂([1,3-双(2,4,6-三甲基苯基)-2-咪唑烷亚基]双(2-溴吡啶)(苯基亚甲基)二氯化钌)。
优选的，步骤4)所述除水除氧采用循环冷冻解冻法。
优选的，步骤4)所述聚合反应在室温下进行，反应时间为0.5h～2h。
本发明的有益效果是：本发明的杂化聚合物具有轻质高强、易于加工成型、低成本、环境友好等优点，适合大规模推广应用。
具体来说：
1)本发明的杂化聚合物中的多级结构以及POSS的协同拓扑作用能够极大地提升其力学 强度，使其兼具高模量和优异韧性，在抗冲击材料领域具有广阔的应用前景；
2)本发明的杂化聚合物的抗冲击能力不依赖于高的分子量，具有很好的可加工性，便于加工成型，有利于大规模生产加工；
3)本发明的杂化聚合物在冲击致使其失效的情况下，通过简易的再加工操作就可以进行重塑，回收利用率极高，是一类资源节约、环境友好型高分子材料。
附图说明
图1为实施例中的化合物1的核磁共振氢谱图。
图2为实施例中的化合物2的核磁共振氢谱图。
图3为实施例中的单体的核磁共振氢谱图。
图4为实施例中的单体和杂化聚合物的核磁共振氢谱对比图。
图5为实施例中的单体和杂化聚合物的凝胶渗透色谱对比图。
图6为分离式霍普金森压杆实验装置的实物照片。
图7为实施例中的杂化聚合物在受到不同速率冲击后的应力-应变曲线。
图8为实施例中的杂化聚合物在受到不同速率冲击后的实物照片。
图9为实施例中的杂化聚合物进行多次再加工后的应力-应变曲线。
具体实施方式
下面结合具体实施例对本发明作进一步的解释和说明。
实施例：
一种杂化聚合物，其制备方法包括以下步骤：
1)将15.0g(12.67mmol)的三硅醇异辛基-POSS(美国Hybrid Plastics公司)、1.66g(16.47mmol)的三乙胺和150mL的无水四氢呋喃加入容积500mL的反应瓶中，搅拌至固体完全溶解，置于0℃的冰浴中，再将2.65g(16.46mmol)的乙烯基三氯硅烷用50mL的无水四氢呋喃分散后转移至滴液漏斗中，缓慢滴加进反应瓶中，滴加完后继续搅拌20h，过滤，取滤液旋干得到粗产物，再利用硅胶色谱柱对粗产物进行提纯，洗脱剂为纯石油醚(PE)，得到9.0g的化合物1(无色透明的粘稠液体，产率57％，核磁共振氢谱图如图1所示)；
2)将9.0g的(7.28mmol)的化合物1和34mg(0.15mmol)的光引发剂Igracure 2959加入80mL的四氢呋喃中，搅拌至固体完全溶解，再将1.66g(14.59mmol)的巯基乙胺盐酸盐分散在25mL的CH 3OH中，再将上述两种溶液混合均匀在紫外光反应器中光照15min，减压蒸馏除去溶剂，用浓度1mol/L的NaOH溶液洗涤2次，加入无水硫酸钠进行干燥，过滤，取滤液旋干，室温下真空干燥24h，得到7.6g的化合物2(淡黄色的粘稠液体，产率80％，核 磁共振氢谱图如图2所示)；
3)将9.8g(7.46mmol)的化合物2和2.45g(14.91mmol)的顺-5-降冰片烯-外-2,3-二甲酸酐加入350mL的甲苯中，升温至135℃，氮气氛围下反应36h，冷却至室温，减压蒸馏除去溶剂，得到粗产物，再利用硅胶色谱柱对粗产物进行提纯，洗脱剂为PE:EA(95:5，v/v)，得到7.1g的单体(无色透明的粘稠状液体，产率65％，核磁共振氢谱图如图3所示)，单体的整个合成路线如下：
Figure PCTCN2021124669-appb-000002
4)将1g步骤3)的单体和1.5mL的无水四氢呋喃加入Schlenk瓶(舒伦克瓶)，搅拌15min，通过循环冷冻解冻进行除水除氧，在氮气氛围下加入12mg的Grubbs三代催化剂([1,3-双(2,4,6-三甲基苯基)-2-咪唑烷亚基]双(2-溴吡啶)(苯基亚甲基)二氯化钌)，继续通过循环冷冻解 冻进行除水除氧，待反应体系解冻后25℃搅拌2h，反应结束后加入0.2mL的乙烯基乙醚继续搅拌0.5h淬灭反应，加入2.5mL的四氢呋喃稀释反应液，将稀释后的反应液缓慢滴加到75mL的甲醇中使产物沉淀出来，在11000r/min转速下离心5min，将离心得到的固体室温真空干燥24h，即得杂化聚合物，其重复单元结构为
Figure PCTCN2021124669-appb-000003
数均分子量为10000g/mol。
性能测试：
1)本实施例中的单体和杂化聚合物的核磁共振氢谱对比图如图4所示，凝胶渗透色谱(GPC)对比图如图5所示。
由图4可知：位于6.3ppm处的核磁峰在聚合反应完成之后消失，取而代之地，在5.5ppm处出现了一簇新的核磁信号，核磁共振氢谱的变化对应的是单体分子双键的断裂以及杂化聚合物主链上双键的形成。
由图5可知：与单体相比，杂化聚合物的保留时间明显减小，进一步证实了聚合反应的成功进行。
2)采用分离式霍普金森压杆实验装置(Split-Hopkinson pressure bar instrument，实物照片如图6所示，a为整机，b为样品台，c为样品台的局部放大图，d和e为测试样品)测试杂化聚合物在动态冲击条件下的力学行为，测试得到的杂化聚合物在受到不同速率冲击后的应力-应变曲线如图7所示，杂化聚合物在受到不同速率冲击后的实物照片如图8所示，杂化聚合物进行多次再加工后的应力-应变曲线如图9所示。
由图7～9可知：不同应变速率下杂化聚合物展现出了优异的抗冲击能力，杂化聚合物可以抵挡住应变速率为1000s -1的动态冲击，仅边缘部分会出现破损，中间部分的样品依然能够 保持完整，当应变率达到1800s -1时，试件不再能够承受住如此高应变率的应力波，以至于杂化聚合物在冲击之后完全失效，样品在1000s -1的应变速率下进行冲击后，经过简单的再加工就可以实现对样品的定量回收，回收后的样品与初始样品相比抗冲击能力无明显变化，即使在多次冲击后进行回收情况依然如此。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种杂化聚合物，其特征在于，其重复单元结构如下：
    Figure PCTCN2021124669-appb-100001
  2. 根据权利要求1所述的杂化聚合物，其特征在于：所述杂化聚合物的数均分子量为10000g/mol～100000g/mol。
  3. 权利要求1或2所述的杂化聚合物的制备方法，其特征在于，包括以下步骤：
    1)进行三硅醇异辛基-POSS和乙烯基三氯硅烷的反应，得到化合物1；
    2)进行化合物1和巯基乙胺盐酸盐的反应，得到化合物2；
    3)进行化合物2和顺-5-降冰片烯-外-2,3-二甲酸酐的反应，得到单体；
    4)进行单体的聚合反应，即得杂化聚合物。
  4. 根据权利要求3所述的制备方法，其特征在于：步骤1)所述三硅醇异辛基-POSS、乙烯基三氯硅烷的摩尔比为1:1.2～1:1.4。
  5. 根据权利要求3或4所述的制备方法，其特征在于：步骤1)所述反应在0℃～5℃下进行，反应时间为15h～25h。
  6. 根据权利要求3所述的制备方法，其特征在于：步骤2)所述化合物1、巯基乙胺盐酸盐的摩尔比为1:1.8～1:2.2。
  7. 根据权利要求3所述的制备方法，其特征在于：步骤3)所述化合物2、顺-5-降冰片烯-外-2,3-二甲酸酐的摩尔比为1:1.8～1:2.2。
  8. 根据权利要求3或7所述的制备方法，其特征在于：步骤3)所述反应在130℃～140℃下进行，反应时间为30h～40h。
  9. 根据权利要求3、4、6和7中任意一项所述的制备方法，其特征在于：步骤4)所述聚合 反应在室温下进行，反应时间为0.5h～2h。
  10. 一种抗冲击材料，其特征在于，其组成包括权利要求1或2所述的杂化聚合物。
PCT/CN2021/124669 2021-06-24 2021-10-19 一种杂化聚合物及其制备方法和应用 Ceased WO2022267271A1 (zh)

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