CN111363158A - Epoxy group-containing polysiloxane borane hyperbranched polymer and preparation method thereof - Google Patents
Epoxy group-containing polysiloxane borane hyperbranched polymer and preparation method thereof Download PDFInfo
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- CN111363158A CN111363158A CN202010346147.1A CN202010346147A CN111363158A CN 111363158 A CN111363158 A CN 111363158A CN 202010346147 A CN202010346147 A CN 202010346147A CN 111363158 A CN111363158 A CN 111363158A
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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
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/08—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing boron
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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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
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Abstract
The invention provides an epoxy group-containing polysiloxane borane hyperbranched polymer and a preparation method thereof, the polymer is prepared by a one-step method through the reaction of a boron hydroxyl compound and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, and the method has the advantages of controllable reaction conditions, simple process flow, high yield, easy realization of large-scale production and the like. Meanwhile, the polymer takes Si-O-B as a main chain structure, has the characteristics of high bond energy and good flexibility, can endow the polymer material with good mechanical and thermal stability, contains an epoxy group in a side chain structure, and can facilitate the forming processing and modification application of the polymer. The epoxy group-containing polysiloxane borane hyperbranched polymer provided by the invention can be widely applied to the fields of composite material matrix resin, heat-resistant coatings and the like, and has a wide application prospect.
Description
Technical Field
The invention relates to the technical field of hyperbranched polymers, in particular to a polysiloxane borane hyperbranched polymer containing epoxy groups and a preparation method thereof.
Background
The hyperbranched polymer is a high molecular material with a highly branched structure, has a compact structure, a small hydrodynamic radius of gyration, no chain entanglement among molecules and low viscosity, contains a large number of functional groups which can be further modified in the structure, has high chemical reaction activity and is easy to modify, so the hyperbranched polymer is widely applied to the fields of electronic communication, biomedicine, printing and dyeing industry, aerospace and the like. However, with the continuous development of scientific technology, higher requirements are also put forward on the thermal stability and the mechanical property of the hyperbranched polymer, so that the development of a functional hyperbranched polymer with good thermal stability and mechanical property has important research significance and practical application value.
In order to improve the thermal stability of polymer materials, there are generally several approaches: firstly, introducing a rigid or high-bond-energy group, designing a novel structural polymer, and improving energy required by damage; secondly, the regularity of molecular chains is improved, and the crystallinity of the polymer is improved; thirdly, improving the crosslinking degree of the polymer to generate the polymer with a three-dimensional network structure; and fourthly, compounding with other fillers with thermal stability. Among them, it is one of the hot spots of research to improve the thermal stability performance by the structural design of the Polymer, for example, it is reported that three bis-P-C bridged DOPO derivatives of ethyl, phenyl and naphthalene are synthesized and introduced into polylactic acid, and the addition of the novel DOPO derivative significantly improves the thermal stability of polylactic acid (Polymer Degradation and stability,2017,139,55-66), and the research shows that the structure of the Polymer itself has a large influence on the thermal stability performance, and the design of the structure is the key to improve the thermal stability performance.
Disclosure of Invention
One of the purposes of the invention is to provide an epoxy group-containing polysiloxane borane hyperbranched polymer, which has the structure:
wherein the content of the first and second substances,
R2a phenyl group, a p-methylbenzene group, a C1-5 alkyl group or a C3-6 cycloalkyl group.
The invention also aims to provide a preparation method of the epoxy group-containing polysiloxane borane hyperbranched polymer, which specifically comprises the following steps:
under the protection of inert gas, adding a boron-containing hydroxyl compound and an organic solvent into a three-neck flask provided with a condenser tube, a constant pressure dropping funnel and a thermometer, stirring to dissolve the boron-containing hydroxyl compound and the organic solvent, dropwise adding 3- (2, 3-epoxypropoxy) propyl trimethoxy silane through the constant pressure dropping funnel, reacting for a period of time at a certain temperature after dropwise adding is finished, and removing the solvent through filtering, washing and distilling to obtain the epoxy-containing polysiloxane borane hyperbranched polymer, wherein the equation of the reaction is as follows:
wherein the content of the first and second substances,
R2a phenyl group, a p-methylbenzene group, a C1-5 alkyl group or a C3-6 cycloalkyl group.
Wherein the molar ratio of the boron-containing hydroxyl compound to the 3- (2, 3-glycidoxy) propyl trimethoxy silane is 1-2: 1, the molar ratio of the organic solvent to the boron-containing hydroxyl compound is 20-35: 1, the reaction temperature is 60-140 ℃, and the reaction time is 6-13 h.
The organic solvent is one or a mixture of N, N-dimethylformamide, dichloroethane, chloroform and butyl ether;
based on the research background, the invention provides an epoxy group-containing polysiloxane borane hyperbranched polymer and a preparation method thereof, wherein the polymer is prepared by a 'one-step method' reaction of a boron hydroxyl compound and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, and the epoxy group-containing polysiloxane borane hyperbranched polymer has the following beneficial effects:
1. the method has the advantages of controllable reaction conditions, simple process flow, high yield and easy realization of large-scale production.
2. The polymer of the invention takes Si-O-B as a main chain structure, has the characteristics of high bond energy and good flexibility, can endow polymer materials with good mechanical and thermal stability, contains epoxy groups in a side chain structure, and can facilitate the molding processing and modification application of the polymer.
3. The epoxy group-containing polysiloxane borane hyperbranched polymer prepared by the invention has good thermal stability and mechanical properties, provides a feasible method for development, modification and functionalization of high-performance hyperbranched polymers, and widens the application field of hyperbranched polymers.
Detailed Description
The following will explain in detail the epoxy group-containing polysiloxane borane hyperbranched polymer and the preparation method thereof provided by the present invention with reference to the examples.
Example 1:
under the protection of inert gas, 60mL of butyl ether and 1.8304g (15mmol) of phenylboronic acid are sequentially added into a three-neck flask provided with a constant-pressure dropping funnel, a condensation pipe and a thermometer, the mixture is fully stirred to be dissolved, 2.22mL (9.8mmol) of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane is slowly and dropwise added into the three-neck flask through the constant-pressure dropping funnel, the temperature is raised to 140 ℃ after the dropwise addition is finished, the reaction is carried out for 6 hours, the obtained product is filtered, washed and distilled to remove the solvent, and the epoxy-containing polysiloxane borane hyperbranched polymer is obtained, wherein the structural formula of the polymer is as follows:
wherein the content of the first and second substances,
R2is a phenyl group.
Infrared spectrum:
(919cm-1)，-CH2-(2955cm-1)，Si-O(1050cm-1)，B-O(1350cm-1)，Ph(3020、1590cm-1)。
taking an amine compound as a curing agent, and curing and molding the synthesized polymer, wherein the thermal decomposition temperature of the obtained cured product is higher than 390 ℃; the bending strength, the tensile strength and the impact strength reach 150MPa, 98MPa and 55kJ/m2Has excellent thermal stability and mechanical property.
Example 2:
under the protection of inert gas, 30mL of dichloroethane and 1.2885g (15mmol) of cyclopropylboric acid are sequentially added into a three-neck flask provided with a constant-pressure dropping funnel, a condenser tube and a thermometer, the materials are fully stirred and dissolved, 2.22mL (9.8mmol) of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane is slowly and dropwise added into the three-neck flask through the constant-pressure dropping funnel, the temperature is raised to 70 ℃ after the dropwise addition is finished, the reaction is carried out for 10 hours, and the obtained product is filtered, washed and distilled to remove the solvent, so that the epoxy group-containing polysiloxane borane hyperbranched polymer is obtained, wherein the structural formula of the polymer is as follows:
wherein the content of the first and second substances,
infrared spectrum:
(903cm-1)，-CH2-(2991cm-1)，Si-O(1062cm-1)，B-O(1361cm-1)。
using diaminodiphenylmethane as curing agent, using the synthesized polymer to modify epoxy resin, and the thermal decomposition temperature of the obtained modified epoxy resin condensate is higher than 370 ℃; the bending strength, the tensile strength and the impact strength reach 141MPa, 86MPa and 42kJ/m2Has excellent thermal stability and mechanical property.
Example 3:
under the protection of inert gas, sequentially adding 30mL of dichloroethane and 1.02g (17mmol) of methylboronic acid into a three-neck flask provided with a constant-pressure dropping funnel, a condenser tube and a thermometer, fully stirring to dissolve the dichloroethane and the methylboronic acid, slowly and dropwise adding 2.22mL (9.8mmol) of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into the three-neck flask through the constant-pressure dropping funnel, heating to 75 ℃ after dropwise adding is finished, reacting for 8 hours, filtering, washing and distilling the obtained product to remove the solvent, thereby obtaining the epoxy-containing polysiloxane borane hyperbranched polymer, wherein the structural formula of the polymer is as follows:
wherein the content of the first and second substances,
R2＝CH3。
infrared spectrum:
(911cm-1)，CH3、-CH2-(2985cm-1)，Si-O(1062cm-1)，B-O(1357cm-1)。
using diaminodiphenylmethane as curing agent, using the synthesized polymer to modify epoxy resin, and the thermal decomposition temperature of the obtained modified epoxy resin condensate is higher than 365 ℃; the bending strength, the tensile strength and the impact strength reach 136MPa, 85MPa and 40kJ/m2Has excellent thermal stability and mechanical property.
Claims (6)
1. An epoxy group-containing polysiloxane borane hyperbranched polymer, which is characterized in that: the structural formula is as follows:
wherein the content of the first and second substances,
R2a phenyl group, a p-methylbenzene group, a C1-5 alkyl group or a C3-6 cycloalkyl group.
2. The method of claim 1, wherein the epoxy group-containing polysiloxane borane hyperbranched polymer is prepared by: the method comprises the following steps:
under the protection of inert gas, adding a boron-containing hydroxyl compound and an organic solvent into a three-neck flask provided with a condenser tube, a constant pressure dropping funnel and a thermometer, stirring to dissolve the boron-containing hydroxyl compound and the organic solvent, dropwise adding 3- (2, 3-epoxypropoxy) propyl trimethoxy silane through the constant pressure dropping funnel, reacting for a period of time at a certain temperature after dropwise adding is finished, and filtering, washing and distilling to remove the solvent to obtain the epoxy-containing polysiloxane borane hyperbranched polymer.
3. The method for preparing the epoxy group-containing polysiloxane borane hyperbranched polymer according to claim 2, wherein: the organic solvent is one or a mixture of N, N-dimethylformamide, dichloroethane, chloroform and butyl ether.
4. The method for preparing the epoxy group-containing polysiloxane borane hyperbranched polymer according to claim 2, wherein: the molar ratio of the organic solvent to the boron hydroxyl-containing compound is 20-35: 1.
5. The method for preparing the epoxy group-containing polysiloxane borane hyperbranched polymer according to claim 2, wherein: the molar ratio of the boron-containing hydroxyl compound to the 3- (2, 3-epoxypropoxy) propyl trimethoxy silane is 1-2: 1.
6. The method for preparing the epoxy group-containing polysiloxane borane hyperbranched polymer according to claim 2, wherein: after the 3- (2, 3-epoxypropoxy) propyl trimethoxy silane is dripped, the reaction temperature is 60-140 ℃, and the reaction time is 6-13 h.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113698611A (en) * | 2021-09-01 | 2021-11-26 | 福建师范大学 | Polymer with main chain of Si-O-B-O structure and method for toughening and modifying polylactic acid by using polymer |
| CN113801463A (en) * | 2021-09-06 | 2021-12-17 | 宁波葆尔新材料有限公司 | Anti-condensation material and preparation method thereof |
| CN114058926A (en) * | 2021-10-11 | 2022-02-18 | 铜陵精达新技术开发有限公司 | Material for generator conductor wire forming die and preparation method thereof |
| CN114245500A (en) * | 2022-02-09 | 2022-03-25 | 安徽蒯科砾工业加热技术有限公司 | Forming process of infrared heating pipe |
| CN114409691A (en) * | 2022-02-11 | 2022-04-29 | 安阳师范学院 | Preparation method of benzo-siloxaboron heterocyclic compound |
| CN114539642A (en) * | 2022-01-18 | 2022-05-27 | 宁波伏龙同步带有限公司 | High-performance double-sided tooth covering belt for robot and preparation method thereof |
| CN114790121A (en) * | 2022-05-12 | 2022-07-26 | 宁波金鼎紧固件有限公司 | Heat-resistant high-strength carbon/ceramic fastener and preparation method thereof |
| CN116396681A (en) * | 2023-03-29 | 2023-07-07 | 中科融志国际科技(北京)有限公司 | Anti-icing coating and fan blade |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113698611A (en) * | 2021-09-01 | 2021-11-26 | 福建师范大学 | Polymer with main chain of Si-O-B-O structure and method for toughening and modifying polylactic acid by using polymer |
| CN113801463A (en) * | 2021-09-06 | 2021-12-17 | 宁波葆尔新材料有限公司 | Anti-condensation material and preparation method thereof |
| CN114058926A (en) * | 2021-10-11 | 2022-02-18 | 铜陵精达新技术开发有限公司 | Material for generator conductor wire forming die and preparation method thereof |
| CN114539642A (en) * | 2022-01-18 | 2022-05-27 | 宁波伏龙同步带有限公司 | High-performance double-sided tooth covering belt for robot and preparation method thereof |
| CN114245500A (en) * | 2022-02-09 | 2022-03-25 | 安徽蒯科砾工业加热技术有限公司 | Forming process of infrared heating pipe |
| CN114409691A (en) * | 2022-02-11 | 2022-04-29 | 安阳师范学院 | Preparation method of benzo-siloxaboron heterocyclic compound |
| CN114790121A (en) * | 2022-05-12 | 2022-07-26 | 宁波金鼎紧固件有限公司 | Heat-resistant high-strength carbon/ceramic fastener and preparation method thereof |
| CN116396681A (en) * | 2023-03-29 | 2023-07-07 | 中科融志国际科技(北京)有限公司 | Anti-icing coating and fan blade |
| CN116396681B (en) * | 2023-03-29 | 2024-03-22 | 中科融志国际科技(北京)有限公司 | Anti-condensation anti-icing coating and fan blade |
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