WO2019037369A1 - 一种聚氨酯聚合物及其制备方法和应用 - Google Patents

一种聚氨酯聚合物及其制备方法和应用 Download PDF

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WO2019037369A1
WO2019037369A1 PCT/CN2017/118900 CN2017118900W WO2019037369A1 WO 2019037369 A1 WO2019037369 A1 WO 2019037369A1 CN 2017118900 W CN2017118900 W CN 2017118900W WO 2019037369 A1 WO2019037369 A1 WO 2019037369A1
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polyurethane polymer
polymer
polyurethane
aminoimidazolidinone
compound
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French (fr)
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林木松
陈天生
付强
范圣平
彭磊
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广东电网有限责任公司电力科学研究院
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Priority to US16/088,078 priority Critical patent/US11053345B2/en
Publication of WO2019037369A1 publication Critical patent/WO2019037369A1/zh

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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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a polyurethane polymer and a preparation method and application thereof.
  • micro-cracks in polymer materials can weaken the function of materials because even small cracks can cause the function of materials such as ultraviolet light to fail, and on the other hand, because micro-cracks are difficult to detect, Therefore, as the use time prolongs, micro-cracks can spread into visible cracks, and structural and functional failures can have catastrophic consequences. Cracks in polymeric materials can also severely shorten the useful life of materials and cause significant waste (D.Y. Wu, S. Meure and D. Solomon, Prog. Polym. Sci., 2008, 33, 479).
  • Polyurethane has good adjustability, and a series of polymer materials such as rigid materials to soft materials can be obtained by adjusting the ratio of soft hardness segments, and thus has a wide application in modern society.
  • Polymer materials such as rigid materials to soft materials
  • the preparation of self-healing materials has received great attention (Hia et al., Polym Rev 2016, 56, 225.).
  • the DA reaction can be achieved by heating. Open loop to achieve a certain degree of self-healing effect (Chao Zeng et al. Macromolecules 2013, 46, 1794-1802).
  • the implementation of these self-repair processes requires the addition of a self-healing agent and the number of self-healing is less, or external stimuli such as heat, light, water, etc. are required to stimulate the healing process.
  • the present invention discloses the use of an aminoimidazolidinone compound in the preparation of a chain extender for a polyurethane polymer, which can be prepared repeatedly without any addition of a self-healing agent and without any external stimulation. Self-healing polyurethane polymer.
  • the present invention provides the use of aminoimidazolidinone compounds in the preparation of products of polyurethane polymers.
  • the present invention provides the use of aminoimidazolidinone compounds in the preparation of end products for polyurethane polymers.
  • aminoimidazolidinone compound is 1-(2-aminoethyl)-2-imidazolidinone.
  • the invention also discloses a polyurethane polymer obtained by polymerizing the following raw materials in molar parts:
  • Bifunctional isocyanate compound 3-6 Bifunctional isocyanate compound 3-6;
  • the aminoimidazolidinone compound is 1-(2-aminoethyl)-2-imidazolidinone.
  • the polymer diol comprises: polyether diol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetrahydrofuran, polyhexylene glycol neopentyl glycol ester and polytetrahydrofuran ether glycol
  • polyether diol, the polyethylene glycol, the polypropylene glycol, the polytetramethylene glycol or the polytetrahydrofuran have a molecular weight of from 400 to 10,000 Daltons.
  • the difunctional isocyanate compound comprises one or more of: hexamethylene diisocyanate, hexamethyl diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate. .
  • the polymer diol is polyethylene glycol.
  • the difunctional isocyanate compound is isophorone diisocyanate.
  • the invention also discloses a preparation method of a polyurethane polymer, comprising the following steps:
  • a catalyst is further added in the reaction of the polymer diol and the difunctional isocyanate compound, and the catalyst comprises one or more of triethylamine, organic hydrazine and dibutyltin dilaurate.
  • the aminoimidazolidinone compound of the step 2) is 1-(2-aminoethyl)-2-imidazolidinone.
  • the polymer diol of the step 1) comprises: polyether diol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetrahydrofuran, polyhexylene glycol neopentyl glycol ester and polytetrahydrofuran ether.
  • One or more of the diols, the polyether diol, the polyethylene glycol, the polypropylene glycol, the polytetramethylene glycol or the polytetrahydrofuran have a molecular weight of from 400 to 10,000 Daltons.
  • the difunctional isocyanate compound of the step 1) comprises: one of hexamethylene diisocyanate, hexamethyl diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate and isophorone diisocyanate. kind or more.
  • the polymer diol of step 1) is polyethylene glycol.
  • the polymer diol is specifically polytetrahydrofuran ether glycol having a molecular weight of 1000 g/mol, polypropylene glycol having a molecular weight of 1000 g/mol, polyethylene glycol having a molecular weight of 3000 g/mol, One or more of polytetramethylene glycol having a molecular weight of 2000 g/mol, polyethylene glycol having a molecular weight of 600 g/mol, and polyhexylene glycol neopentyl glycol ester having a molecular weight of 2000 g/mol.
  • the polymer diol is preferably dried and then reacted with a bifunctional isocyanate compound.
  • the difunctional isocyanate compound is more preferably one or more selected from the group consisting of diphenylmethane diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate. Most preferably, the difunctional isocyanate compound of step 1) is isophorone diisocyanate.
  • the catalyst is added in an amount of from 1 to 5% by weight based on the total amount of the polyurethane polymer.
  • the step 1) is carried out under the protection of an inert gas to prepare an isocyanate group-terminated prepolymer.
  • the inert gas is argon.
  • the polymer diol and the difunctional isocyanate compound are further reacted with a polymerization solution, and the polymerization solution includes one or more of N,N-dimethylformamide, tetrahydrofuran and acetone.
  • the polymerization solution is added in an amount of 10 to 40% by weight based on the total amount of the polyurethane polymer.
  • the reaction temperature is from 30 ° C to 100 ° C, and the reaction time is from 1 to 5 hours.
  • the reaction temperature is from 40 ° C to 80 ° C, and the reaction time is from 1 to 5 hours.
  • the reaction temperature is 70 ° C and the reaction time is 1.5 hours.
  • the aminoimidazolidinone compound reacts with the isocyanate group-terminated prepolymer at a temperature of 70 ° C for a reaction time of 1.5 hours; or at a temperature of 60 ° C for a period of 1.5 hours; or the temperature is 70 ° C, time is 1 h; or temperature is 50 ° C, time is 2 h.
  • step 2) reacting the aminoimidazolidinone compound with the isocyanate group-terminated prepolymer further comprises drying the reacted product.
  • the invention utilizes the characteristics of the aminoimidazolidinone compound and is used in the preparation of the end of the polyurethane polymer.
  • the aminoimidazolidinone compound contains a plurality of nitrogen and oxygen six-membered heterocyclic rings and an amino group, wherein nitrogen and oxygen are used.
  • the six-membered heterocyclic ring and the amino group can form a large amount of hydrogen bond with the polymer diol and the difunctional isocyanate compound, and the aminoimidazolidinone compound can be used as a polyurethane polymer prepared by preparing a terminal product of the polyurethane polymer, and the polyurethane polymer is polymerized.
  • the material has strong self-repairing ability and service life, and can achieve a certain degree of repair through the movement of the molecular chain in the event of damage, which can greatly improve the life span of the polyurethane polymer material.
  • the polyurethane polymer prepared by using the aminoimidazolidinone compound of the invention is a polyurethane polymer capable of achieving self-healing at room temperature without external stimulation, without any external stimulation, and the polyurethane The polymer can self-repair its mechanical damage multiple times without external stimulus in the temperature range of 0 °C - 100 °C and the humidity range of 0% - 100%.
  • Example 1 is a compression test curve of a polyurethane polymer of Example 1 before and after self-repair according to the present invention
  • Example 2 is a laser confocal diagram of the polyurethane polymer of Example 1 before self-repair according to the present invention
  • Example 3 is a laser confocal diagram of the polyurethane polymer of Example 1 after self-healing according to the present invention.
  • the invention provides a polyurethane elastomer and a preparation method and application thereof for solving the problem that the polyurethane polymer in the prior art has poor self-repairing effect, requires additional self-healing agent and requires external stimulation such as heat, light and water to stimulate healing. Technical flaws.
  • Embodiment 1 The present invention provides an embodiment.
  • the specific steps of Embodiment 1 are as follows:
  • FIG. 1 is a compression test curve of a polyurethane polymer of Example 1 before and after self-repair according to the present invention; wherein, curve 1 is a compression curve of the original sample, and curve 2 is a compression curve of the self-repair sample.
  • 2 is a laser confocal diagram of the polyurethane polymer of Example 1 before self-repair according to the present invention;
  • FIG. 3 is a laser confocal diagram of the self-repair of the polyurethane polymer of Example 1 provided by the present invention.
  • Example 1 the self-repairing experiment of Example 1 was carried out by cutting the dried polyurethane polymer with a scalpel and immediately touching the sections together, and the polyurethane polymer immediately became a whole which can withstand its own weight. After standing overnight, it was observed by a laser confocal microscope, and it was found that the crack was obviously shallow. The material was tested on a stretching machine, and it was found that the compressive strength recovered to 93.4%.
  • Embodiment 2 The present invention provides an embodiment.
  • the specific steps of Embodiment 2 are as follows:
  • Embodiment 3 The present invention provides an embodiment.
  • the specific steps of Embodiment 3 are as follows:
  • Embodiment 4 The present invention provides an embodiment.
  • the specific steps of Embodiment 4 are as follows:
  • Embodiment 5 The present invention provides an embodiment.
  • the specific steps of Embodiment 5 are as follows:
  • the self-repairing experiment proves that the dried polyurethane polymer is cut with a scalpel and the sections are brought into contact immediately.
  • the polyurethane polymer immediately becomes a whole that can withstand its own weight, and the compression strength at 40 ° C is restored to 96.3%. .
  • Embodiment 6 The present invention provides an embodiment.
  • the specific steps of Embodiment 6 are as follows:
  • the polyurethane polymers prepared in Examples 2 to 6 were similar to those in Example 1, and thus the recovery functions of the polyurethane polymers prepared in Examples 2 to 6 were similar to those of Example 1, and the present invention was prepared.
  • the polyurethane polymer has the highest compressive strength restored to 96% before compression.

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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)
  • Polyurethanes Or Polyureas (AREA)

Abstract

本发明属于高分子材料技术领域，尤其涉及一种聚氨酯聚合物及其制备方法和应用。本发明公开了氨基咪唑啉酮类化合物在制备聚氨酯聚合物的封端产品中的应用，氨基咪唑啉酮类化合物的应用能制备不需添加任何自愈合剂以及不需要任何外部刺激就能够多次重复自愈合的聚氨酯聚合物。同时，本发明还提供了一种聚氨酯聚合物及其制备方法，本发明的聚氨酯聚合物不需要任何外部刺激就能够实现多次重复自愈合，其压缩强度最高能恢复至压缩前的96％。

Description

一种聚氨酯聚合物及其制备方法和应用
本申请要求于2017年08月22日提交中国专利局、申请号为201710724492.2、发明名称为“一种聚氨酯聚合物及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及高分子材料技术领域，尤其涉及一种聚氨酯聚合物及其制备方法和应用。
背景技术
高分子材料在使用过程中由于处于长期受力的状态加之外界环境中光、热及紫外光的影响，容易在高分子材料中形成难以探测的微裂缝。一方面高分子材料中的微裂缝会弱化材料的功能，这是因为，即使是很小的裂缝也会使紫外光等穿透材料使材料的功能失效；另一方面，因为微裂缝难以探测，所以随着使用时间的延长微裂缝会蔓延成为肉眼可见的裂缝，结构和功能的失效可能会产生灾难性的后果。高分子材料的裂缝也会严重的缩短材料的使用寿命从而造成大量的浪费(D.Y.Wu,S.Meure and D.Solomon,Prog.Polym.Sci.,2008,33,479)。
聚氨酯具有良好的调节性，通过调节软硬度段的比例可以得到刚性材料到柔软材料等一系列的高分子材料，因而在现代社会中有着广泛的应用。受自然界生命体可以自行修复其受创伤口行为的启发，近年来，自修复材料的制备研究受到了极大的关注(Hia et al.,PolymRev 2016,56,225.)。科学家们基于包埋愈合剂(Trask et al.,J R Soc Interface 2007,4,363.)、引入动态共价键(Wei et al.,Adv Funct Mater 2015,25,1352.)或超分子化学(Nakahata et al.,Macromol Rapid Comm 2016,37,86.)等方法设计了很多种类的自修复材料，比如引入紫外光引发的动态二硫键构筑了自愈合的聚氨酯弹性体，在紫外光的照射下几乎可以达到原来的杨氏模量(Q.Shaobo et al.Adv.Mater.2015,27,7740–7745)；或者通过引入呋喃和马来酰亚胺的基团，通过加热可以实现D-A反应的开环从而达到一定程度的自愈合效果(Chao Zeng et al.Macromolecules 2013,46, 1794-1802)。但是这些自修复过程的实现均需要外加自愈剂且自愈合的次数较少，或者需要热、光、水等外部刺激才能激发愈合过程。
目前，能够在室温下不需添加任何自愈合剂以及不需要任何外部刺激就能够实现多次重复自愈合的聚氨酯聚合物还鲜有报导。
发明内容
有鉴于此，本发明公开了氨基咪唑啉酮类化合物在制备聚氨酯聚合物的扩链剂中的应用，这种应用能制备不需添加任何自愈合剂以及不需要任何外部刺激就能够多次重复自愈合的聚氨酯聚合物。
本发明提供了氨基咪唑啉酮类化合物在制备聚氨酯聚合物的产品中的应用。
本发明提供了氨基咪唑啉酮类化合物在制备聚氨酯聚合物的封端产品中的应用。
作为优选，根据权利要求2所述的应用，其特征在于，所述氨基咪唑啉酮类化合物为1-(2-氨基乙基)-2-咪唑啉酮。
本发明还公开了一种聚氨酯聚合物，按照摩尔份数计，包括以下原料聚合得到：
聚合物二元醇                 2-5；
双官能团异氰酸酯类化合物     3-6；
氨基咪唑啉酮类化合物         1-3。
作为优选，所述氨基咪唑啉酮类化合物为1-(2-氨基乙基)-2-咪唑啉酮。
作为优选，所述聚合物二元醇包括：聚醚二醇、聚乙二醇、聚丙二醇、聚丁二醇、聚四氢呋喃、聚己二醇新戊二醇酯和聚四氢呋喃醚二醇中的一种或几种，所述聚醚二醇、所述聚乙二醇、所述聚丙二醇、所述聚丁二醇或所述聚四氢呋喃的分子量为400-10000道尔顿。
作为优选，所述双官能团异氰酸酯类化合物包含：1，6-己二异氰酸酯、六甲基二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯和异佛尔酮二异氰酸酯中的一种或多种。
更为优选，所述聚合物二元醇为聚乙二醇。
更为优选，所述双官能团异氰酸酯类化合物为异佛尔酮二异氰酸酯。
本发明还公开了一种聚氨酯聚合物的制备方法，包括以下步骤：
1)聚合物二元醇和双官能团异氰酸酯类化合物进行反应制备异氰酸酯基团封端的预聚体；
2)将氨基咪唑啉酮类化合物与异氰酸酯基团封端的预聚体进行反应，得到聚氨酯聚合物。
作为优选，所述步骤1)中聚合物二元醇和双官能团异氰酸酯类化合物进行反应时还添加催化剂，所述催化剂包括三乙胺、有机铋和二月桂酸二丁基锡中的一种或多种。
作为优选，所述步骤2)的氨基咪唑啉酮类化合物为1-(2-氨基乙基)-2-咪唑啉酮。
作为优选，所述步骤1)的聚合物二元醇包括：聚醚二醇、聚乙二醇、聚丙二醇、聚丁二醇、聚四氢呋喃、聚己二醇新戊二醇酯和聚四氢呋喃醚二醇中的一种或几种，所述聚醚二醇、所述聚乙二醇、所述聚丙二醇、所述聚丁二醇或所述聚四氢呋喃的分子量为400-10000道尔顿。
作为优选，所述步骤1)的双官能团异氰酸酯类化合物包含：1,6-己二异氰酸酯、六甲基二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯和异佛尔酮二异氰酸酯中的一种或多种。
更为优选，所述步骤1)的聚合物二元醇为聚乙二醇。在本发明的具体实施例中，所述聚合物二元醇具体为分子量为1000g/mol的聚四氢呋喃醚二醇、分子量为1000g/mol的聚丙二醇、分子量为3000g/mol的聚乙二醇、分子量为2000g/mol的聚丁二醇、分子量为600g/mol的聚乙二醇和分子量为2000g/mol的聚己二醇新戊二醇酯中的一种或多种。所述聚合物二元醇优选经过干燥后再和双官能团异氰酸酯类化合物反应。
所述双官能团异氰酸酯类化合物更优选选自二苯甲烷二异氰酸酯、异佛尔酮二异氰酸酯和己二异氰酸酯中的一种或多种。最优选，所述步骤1)的双官能团异氰酸酯类化合物为异佛尔酮二异氰酸酯。
作为优选，所述催化剂添加量为聚氨酯聚合物总量的1-5wt％。
作为优选，所述步骤1)在惰性气体的保护下进行反应制备异氰酸酯基团 封端的预聚体。
更为优选，所述惰性气体为氩气。
作为优选，所述聚合物二元醇和双官能团异氰酸酯类化合物进行反应时还添加聚合溶液，所述聚合溶液包括N，N-二甲基甲酰胺、四氢呋喃和丙酮中的一种或多种，所述聚合溶液添加量为聚氨酯聚合物总量的10-40wt％。
作为优选，步骤1)聚合物二元醇和双官能团异氰酸酯类化合物进行反应时，反应温度为30℃-100℃，反应时间为1-5小时。
作为优选，步骤2)将氨基咪唑啉酮类化合物与异氰酸酯基团封端的预聚体进行反应时，反应温度为40℃-80℃，反应时间为1-5小时。
更为优选，步骤2)将氨基咪唑啉酮类化合物与异氰酸酯基团封端的预聚体进行反应时，反应温度为70℃，反应时间为1.5小时。
在本发明具体实施例中，氨基咪唑啉酮类化合物与异氰酸酯基团封端的预聚体反应的温度为70℃，反应时间为1.5小时；或温度为60℃，时间为1.5h；或温度为70℃，时间为1h；或温度为50℃，时间为2h。
作为优选，步骤2)将氨基咪唑啉酮类化合物与异氰酸酯基团封端的预聚体进行反应后还包括对所述反应后的产物进行烘干。
本发明利用氨基咪唑啉酮类化合物的特性，应用在制备聚氨酯聚合物的封端中，氨基咪唑啉酮类化合物含有较多的氮、氧的六元杂环和氨基，其中，氮、氧的六元杂环及氨基能与聚合物二元醇和双官能团异氰酸酯类化合物间形成大量的氢键，氨基咪唑啉酮类化合物作为制备聚氨酯聚合物的封端产品制备得到的聚氨酯聚合物，其聚氨酯聚合物具有较强的自修复能力和使用寿命，在出现损伤时能够通过分子链的运动实现一定程度的修复，能大大提高聚氨酯聚合物材料的寿命期限。本发明采用氨基咪唑啉酮类化合物制备得到的聚氨酯聚合物是一种不需要外加自愈合剂、不需要任何外部刺激，能在室温下能够实现重复自愈合的聚氨酯聚合物，而且，该聚氨酯聚合物在0℃-100℃的温度范围和0％-100％的湿度范围内无需外界刺激能多次自修复其机械损伤。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施 例或现有技术描述中所需要使用的附图作简单地介绍。
图1为本发明提供的实施例1的聚氨酯聚合物自修复前后的压缩测试曲线；
图2为本发明提供的实施例1的聚氨酯聚合物自修复前的激光共聚焦图；
图3为本发明提供的实施例1的聚氨酯聚合物自修复后的激光共聚焦图。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明提供了一种聚氨酯弹性体及其制备方法和应用，用于解决现有技术中聚氨酯聚合物自修复效果差、需要额外添加自愈剂且需要热、光、水等外部刺激才能激发愈合的技术缺陷。
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
其中，实施例中使用的试剂均为市售。
实施例1
本发明提供了一个实施例，实施例1具体步骤如下：
1)异氰酸酯基团封端的预聚体的制备：将5g的PTMG1000(聚四氢呋喃醚二醇，分子量为1000)在110℃条件下真空干燥2h后，冷却至40℃，加入10ml无水DMF(N,N-二甲基甲酰胺)，加入1.85g HDI(己二异氰酸酯)和700mg的催化剂DBTL(二月桂酸二丁基锡)在氩气的保护下于70℃反应3h，得到异氰酸酯基团封端的预聚体；
2)聚氨酯聚合物的制备：将异氰酸酯基团封端的预聚体冷却到40℃，加入含有260mg的1-(2-氨基乙基)-2-咪唑啉酮的DMF溶液(DMF溶解 1-(2-氨基乙基)-2-咪唑啉酮，DMF的用量为2mL)，升温至50℃继续反应2h后，将扩链后的反应物彻底烘干得到聚氨酯聚合物。
图1为本发明提供的实施例1的聚氨酯聚合物自修复前后的压缩测试曲线；其中，曲线1为原始样品的压缩曲线，曲线2为自修复样品的压缩曲线。图2为本发明提供的实施例1的聚氨酯聚合物自修复前的激光共聚焦图；图3为本发明提供的实施例1的聚氨酯聚合物自修复后的激光共聚焦图。请参照图1至图3，将实施例1自修复的实验：用手术刀将干燥后的聚氨酯聚合物切断，并且立刻将断面接触在一起，聚氨酯聚合物立刻成为一个可以承受自身重量的整体，放置一夜后用激光共聚焦显微镜观察，发现裂痕明显的变浅，将材料在拉伸机上进行实验，发现压缩强度恢复到原来的93.4％。
实施例2
本发明提供了一个实施例，实施例2具体步骤如下：
1)异氰酸酯基团封端的预聚体的制备：将10g PPG1000(聚丙二醇，分子量为1000)先于110℃条件下真空干燥2h后，冷却至40℃，加入10ml无水DMF(N,N-二甲基甲酰胺)，加入2.75g MDI(二苯甲烷二异氰酸酯)和1.4g的催化剂DBTL(二月桂酸二丁基锡)在氩气的保护下于80℃反应3h，得到异氰酸酯基团封端的预聚体；
2)聚氨酯聚合物的制备：将异氰酸酯基团封端的预聚体冷却到40℃，加入含有0.5g的1-(2-氨基乙基)-2-咪唑啉酮的DMF溶液(DMF溶解1-(2-氨基乙基)-2-咪唑啉酮，DMF的用量为4mL)，升温至50℃继续反应2h后，将扩链后的反应物彻底烘干得到聚氨酯聚合物。
自修复的实验证明：用手术刀将干燥后的聚氨酯聚合物切断，并且立刻将断面接触在一起，聚氨酯聚合物立刻成为一个可以承受自身重量的整体压缩强度恢复至以前的92.1％。
实施例3
本发明提供了一个实施例，实施例3具体步骤如下：
1)异氰酸酯基团封端的预聚体的制备：将15g PEG3000(聚乙二醇，分子 量为3000)先于110℃条件下真空干燥2h后，冷却至40℃，加入10ml无水四氢呋喃，加入1.47g IPDI(异佛尔酮二异氰酸酯)和2g的催化剂DBTL(二月桂酸二丁基锡)在氩气的保护下于70℃反应3h，得到异氰酸酯基团封端的预聚体；
2)聚氨酯聚合物的制备：将异氰酸酯基团封端的预聚体冷却到40℃后，加入含有150mg的1-(2-氨基乙基)-2-咪唑啉酮的四氢呋喃溶液(四氢呋喃溶液溶解1-(2-氨基乙基)-2-咪唑啉酮，四氢呋喃溶液的用量为5mL)，升温至70℃继续反应1h后，将扩链后的反应物彻底烘干得到聚氨酯聚合物。
自修复的实验证明：用手术刀将干燥后的聚氨酯聚合物切断，并且立刻将断面接触在一起，聚氨酯聚合物立刻成为一个可以承受自身重量的整体，压缩强度恢复至以前的92.9％。
实施例4
本发明提供了一个实施例，实施例4具体步骤如下：
1)异氰酸酯基团封端的预聚体的制备：将10g聚丁二醇(聚丁二醇的分子量为2000)先于110℃条件下真空干燥2h后，冷却至40℃，加入10ml无水丙酮，加入3.28g MDI(二苯甲烷二异氰酸酯)和2g的有机铋在氩气的保护下于80℃反应3h，得到异氰酸酯基团封端的预聚体；
2)聚氨酯聚合物的制备：将异氰酸酯基团封端的预聚体冷却到40℃后，加入含有260mg 1-(2-氨基乙基)-2-咪唑啉酮的丙酮溶液(丙酮溶液溶解1-(2-氨基乙基)-2-咪唑啉酮，丙酮溶液的用量为4mL)，升温至60℃继续反应1.5h后，将扩链后的反应物彻底烘干得到聚氨酯聚合物。
自修复的实验证明：用手术刀将干燥后的聚氨酯聚合物切断，并且立刻将断面接触在一起，聚氨酯聚合物立刻成为一个可以承受自身重量的整体，压缩强度恢复至以前88.9％。
实施例5
本发明提供了一个实施例，实施例5具体步骤如下：
1)异氰酸酯基团封端的预聚体的制备：将10g PEG(聚乙二醇，分子量为 600)先于110℃条件下真空干燥2h后，冷却至40℃，加入1.47g IPDI(异佛尔酮二异氰酸酯)和1.2g催化剂三乙胺在氩气的保护下于70℃反应3h，得到异氰酸酯基团封端的预聚体；
2)聚氨酯聚合物的制备：将异氰酸酯基团封端的预聚体冷却到40℃后，加入含有260mg 1-(2-氨基乙基)-2-咪唑啉酮的丙酮溶液(丙酮溶液溶解1-(2-氨基乙基)-2-咪唑啉酮，丙酮溶液的用量为4mL)，升温至70℃继续反应1.5h后，将扩链后的反应物彻底烘干得到聚氨酯聚合物。
自修复的实验证明：用手术刀将干燥后的聚氨酯聚合物切断，并且立刻将断面接触在一起，聚氨酯聚合物立刻成为一个可以承受自身重量的整体，40℃放置一夜压缩强度恢复至以前96.3％。
实施例6
本发明提供了一个实施例，实施例6具体步骤如下：
1)异氰酸酯基团封端的预聚体的制备：将5g聚己二醇新戊二醇酯(分子量为2000)、5g聚四氢呋喃醚二醇(分子量为2000)先于110℃条件下真空干燥2h后，冷却至40℃，加入1.47g IPDI(异佛尔酮二异氰酸酯)和700mg催化剂二月桂酸二丁基锡在氩气的保护下于90℃反应3h，得到异氰酸酯基团封端的预聚体；
2)聚氨酯聚合物的制备：将异氰酸酯基团封端的预聚体冷却到40℃后，加入含有260mg 1-(2-氨基乙基)-2-咪唑啉酮的丙酮溶液(丙酮溶液溶解1-(2-氨基乙基)-2-咪唑啉酮，丙酮溶液的用量为2mL)，升温至60℃继续反应1.5h后，将扩链后的反应物彻底烘干得到聚氨酯聚合物。
自修复的实验证明：用手术刀将干燥后的聚氨酯聚合物切断，并且立刻将断面接触在一起，聚氨酯聚合物立刻成为一个可以承受自身重量的整体，放置一夜后压缩强度恢复至以前90.4％。
实施例2至实施例6制备得到的聚氨酯聚合物与实施例1的类似，因此实施例2至实施例6制备得到的聚氨酯聚合物的恢复功能与实施例1的也相类似，本发明制备得到的聚氨酯聚合物压缩强度最高能恢复至压缩前的96％。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通 技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (10)

  1. 氨基咪唑啉酮类化合物在制备聚氨酯聚合物的封端产品中的应用。
  2. 根据权利要求1所述的应用，其特征在于，所述氨基咪唑啉酮类化合物为1-(2-氨基乙基)-2-咪唑啉酮。
  3. 一种聚氨酯聚合物，其特征在于，按照摩尔份数计，包括以下原料聚合得到：
    聚合物二元醇                 2-5；
    双官能团异氰酸酯类化合物     3-6；
    氨基咪唑啉酮类化合物         1-3。
  4. 根据权利要求3所述的聚氨酯聚合物，其特征在于，所述氨基咪唑啉酮类化合物为1-(2-氨基乙基)-2-咪唑啉酮。
  5. 根据权利要求3所述的聚氨酯聚合物，其特征在于，所述聚合物二元醇包括：聚醚二醇、聚乙二醇、聚丙二醇、聚丁二醇、聚四氢呋喃、聚己二醇新戊二醇酯和聚四氢呋喃醚二醇中的一种或几种，所述聚醚二醇、所述聚乙二醇、所述聚丙二醇、所述聚丁二醇或所述聚四氢呋喃的分子量均为400-10000道尔顿。
  6. 根据权利要求3所述的聚氨酯聚合物，其特征在于，所述双官能团异氰酸酯类化合物包含：1，6-己二异氰酸酯、六甲基二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯和异佛尔酮二异氰酸酯中的一种或多种。
  7. 一种聚氨酯聚合物的制备方法，其特征在于，包括以下步骤：
    1)聚合物二元醇和双官能团异氰酸酯类化合物进行反应制备异氰酸酯基团封端的预聚体；
    2)将氨基咪唑啉酮类化合物与异氰酸酯基团封端的预聚体进行反应，得到聚氨酯聚合物。
  8. 根据权利要求7所述的聚氨酯聚合物的制备方法，其特征在于，所述 步骤1)中聚合物二元醇和双官能团异氰酸酯类化合物进行反应时还添加催化剂，所述催化剂包括三乙胺、有机铋和二月桂酸二丁基锡中的一种或多种。
  9. 根据权利要求7所述的聚氨酯聚合物的制备方法，其特征在于，所述催化剂添加量为聚氨酯聚合物总量的1-5wt％。
  10. 根据权利要求7所述的聚氨酯聚合物的制备方法，其特征在于，所述聚合物二元醇和双官能团异氰酸酯类化合物进行反应时还添加聚合溶液，所述聚合溶液包括N，N-二甲基甲酰胺、四氢呋喃和丙酮中的一种或多种，所述聚合溶液添加量为聚氨酯聚合物总量的10-40wt％。
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