CN112940349B - Combined toughening agent containing five-membered cyclic carbonate group, preparation method and application of combined toughening agent in epoxy toughening - Google Patents
Combined toughening agent containing five-membered cyclic carbonate group, preparation method and application of combined toughening agent in epoxy toughening Download PDFInfo
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Abstract
The invention discloses a combined toughening agent containing five-membered cyclic carbonate groups, a preparation method and application thereof in epoxy toughening. The composite toughening agent is a mixture consisting of a hydrolysis type aromatic cyclic carbonate mixture and an aliphatic cyclic carbonate according to the mass ratio of 1-10: 10, and is prepared by respectively synthesizing a hydrolysis type aromatic cyclic carbonate mixture and an aliphatic cyclic carbonate by taking carbon dioxide as a main reactant for synthesizing the cyclic carbonate and then mixing the two. The method is simple and easy to implement, safe and reliable, and environment-friendly because isocyanate is not used as a synthetic raw material of polyurethane in the whole preparation process. The combined toughening agent contains five-membered cyclic carbonate groups, a rigid benzene ring structure, a flexible carbon chain and a large amount of hydroxyl, and the combined toughening agent is introduced into an epoxy resin system, so that the impact strength of the epoxy resin can be obviously improved.
Description
Technical Field
The invention relates to a combined toughening agent containing five-membered cyclic carbonate groups and a preparation method thereof, in particular to an epoxy toughening agent prepared from carbon dioxide, belonging to the field of epoxy resin modification.
Background
Epoxy resins are thermosetting resins having excellent properties and are widely used as adhesives, coatings, potting materials, and the like. However, epoxy resins often need to be toughened and modified because of their low toughness and stress dissipation due to their large number of rigid benzene ring skeletons and high crosslinking density.
The epoxy resin is toughened and modified in many ways, wherein the toughness of the product can be effectively improved by introducing a polyurethane molecular chain into an epoxy resin system. The polyurethane structure has a flexible chain segment and a rigid chain segment, has good designability, and can meet different performance requirements by changing the proportion of the flexible chain segment and the rigid chain segment. The common approaches for toughening and modifying the epoxy resin by polyurethane include physical mixing and chemical bonding methods. However, in both methods, isocyanate is used as a raw material for polyurethane synthesis, and the isocyanate itself has high toxicity, and the synthesis thereof also uses phosgene with high toxicity. This therefore inevitably causes irreversible damage to the environment and to the laboratory operator, and the relevant patent documents are listed below:
CN109651922A discloses a waterborne polyurethane toughened waterborne epoxy resin anticorrosive paint and a preparation method thereof. In the method, polyisocyanate, oligomer polyol, hydrophilic monomer containing ethoxy, micromolecular chain extender and solvent are used as raw materials, polyurethane prepolymer with terminal isocyanate groups is firstly synthesized, and then water and amine chain extender are further added for reaction, so that the waterborne polyurethane is finally obtained. When the waterborne polyurethane is introduced into a waterborne epoxy resin system, the toughness of the waterborne epoxy resin system can be obviously improved.
CN105061710A discloses a preparation method of polyurethane liquid crystal for toughening epoxy resin. In the patent, p-hydroxybenzoic acid, thionyl chloride, hydroquinone and hexamethylene diisocyanate are selected as raw materials, N' -dimethylformamide is used as a solvent, and dibutyltin dilaurate is used as a catalyst to prepare light yellow polyurethane liquid crystal solid particles. Because the polyurethane liquid crystal has better compatibility with the epoxy resin, the toughness of the epoxy resin can be effectively improved after the polyurethane liquid crystal is introduced into an epoxy resin system.
CN104277449A discloses a preparation method of polyurethane modified epoxy resin. The method comprises the steps of utilizing isocyanate to react with hydroxyl in an epoxy resin structure, grafting a polyurethane chain segment onto the epoxy resin, and utilizing monohydric alcohol to carry out end capping on isocyanate at the end of the grafted polyurethane chain segment. The polyurethane chain segment is introduced into an epoxy resin system by the chemical bonding method, so that the motion power of the molecular chain segment is improved, and a better toughening effect can be achieved.
Although the polyurethane toughening agent synthesized by taking isocyanate as a raw material has excellent toughening modification effect on epoxy resin. However, most of the industrial synthesis of isocyanates uses the highly toxic phosgene method, and the isocyanates themselves are carcinogenic. This undoubtedly causes irreversible damage to the environment and to the operators, which also limits their industrial production to a certain extent. Therefore, on the basis of not using isocyanate as a polyurethane synthesis raw material, how to introduce a polyurethane molecular chain into an epoxy resin system so as to improve the toughness of the epoxy resin system has very important research and development significance.
Disclosure of Invention
In order to solve the problem that the prior polyurethane toughening agent needs to adopt toxic isocyanate in the preparation process, the invention aims to provide a combined toughening agent which can be introduced into a polyurethane chain segment by a non-isocyanate means. This type of toughener contains five-membered cyclic carbonate groups which can introduce urethane group-containing segments into the epoxy resin system by ring-opening reaction between the group and the amine, thus effectively avoiding the use of toxic isocyanates. And the toughening agent can form a strong hydrogen bonding effect with an epoxy resin matrix, so that the performance of the epoxy resin matrix is further improved.
The second purpose of the invention is to provide a preparation method of the combined toughening agent, which takes carbon dioxide as a main reactant for synthesizing five-membered cyclic carbonate, respectively synthesizes and obtains a hydrolysis type aromatic cyclic carbonate mixture and aliphatic cyclic carbonate, and then mixes the two to prepare the combined toughening agent containing the five-membered cyclic carbonate group. The method is simple and easy to implement, safe and reliable, and environment-friendly because isocyanate is not used as a synthetic raw material of polyurethane in the whole preparation process.
The invention also aims to provide the application of the combined toughening agent in epoxy toughening, and provide reliable basis for introducing polyurethane molecular chains into an epoxy resin system, avoiding the use of toxic isocyanate and preparing a novel toughening agent.
The invention is realized by the following technical scheme: a combined toughening agent containing five-membered cyclic carbonate groups is a mixture consisting of a hydrolytic aromatic cyclic carbonate mixture and aliphatic cyclic carbonate according to a mass ratio of 1-10: 10;
the hydrolysis type aromatic cyclic carbonate mixture contains the following components with structural formulas shown as I, II and III:
the aliphatic cyclic carbonate is a glycidyl ether cyclic carbonate containing a flexible aliphatic segment.
A preparation method of a combined toughening agent containing five-membered cyclic carbonate groups comprises the following steps:
(1) synthesis of hydrolysis type aromatic cyclic carbonate mixture: placing aromatic epoxy resin and a catalyst in a closed reaction kettle, continuously introducing carbon dioxide, and stirring and reacting for 8-24 hours under the conditions that the pressure of the carbon dioxide is 0.1-4 MPa and the temperature is 80-150 ℃; then adding distilled water into a closed reaction kettle, and reacting for 24-48 h at the temperature of 50-100 ℃; after the reaction is finished, cleaning and vacuum drying the obtained solid or transparent viscous liquid product to obtain a hydrolysis type aromatic cyclic carbonate mixture;
(2) synthesis of aliphatic cyclic carbonate: putting glycidyl ether and a catalyst in a closed reaction kettle, continuously introducing carbon dioxide, stirring and reacting for 8-60 hours under the conditions that the pressure of the carbon dioxide is 0.1-4 MPa and the temperature is 80-150 ℃, and obtaining aliphatic cyclic carbonate after the reaction is finished;
(3) preparing a combined toughening agent: and (3) mixing the hydrolysis type aromatic cyclic carbonate mixture prepared in the step (1) with the aliphatic cyclic carbonate prepared in the step (2) according to the mass ratio of 1-10: 10 to obtain a combined flexibilizer product containing five-membered cyclic carbonate groups.
In the step (1), the aromatic epoxy resin is one or two of bisphenol A type epoxy resin E51 and bisphenol F type epoxy resin F51.
In the step (1) or the step (2), the catalyst is one or more of tetrabutylammonium bromide, lithium bromide, zinc bromide or benzyltriethylammonium chloride.
In the step (1), the mass ratio of the aromatic epoxy resin to the catalyst is 100: 0.5-2.
In the step (1), the mass ratio of the aromatic epoxy resin to the distilled water is 10: 2-10.
In the step (1) or the step (2), the stirring speed is 200-700 r/min.
In the step (1), the cleaning solvent is one or more of water, methanol, ethanol, acetone, ethyl acetate, tetrahydrofuran, carbon dichloride or carbon trichloride.
In the step (1), the vacuum drying is carried out for 24-72 hours at the temperature of 100-150 ℃.
In the step (2), the glycidyl ether is one or more of ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether.
Further, in the above-mentioned case,
the number average molecular weight of the polyethylene glycol diglycidyl ether is 600-2000 g/mol;
the number average molecular weight of the polypropylene glycol diglycidyl ether is 500-2500 g/mol.
In the step (2), the mass ratio of the glycidyl ether to the catalyst is 100: 0.5-2.
On the basis, the infrared spectrum of the hydrolysis type aromatic cyclic carbonate mixture, the infrared spectrum of the reaction product of the hydrolysis type aromatic cyclic carbonate mixture and the hexamethylene diamine and the infrared spectrum of the reaction product of the combined toughening agent containing the five-membered cyclic carbonate group and the hexamethylene diamine all further prove that the combined toughening agent containing the five-membered cyclic carbonate group can achieve the similar toughening effect of the existing polyurethane toughening agent, and can be applied to epoxy toughening.
The application method of the combined toughening agent containing the five-membered cyclic carbonate group in epoxy toughening comprises the following steps: mixing epoxy resin and a combined toughening agent according to a mass ratio of 10: 1-10, then adding a catalyst, and mixing for 0.5-1.5 h at the temperature of 30-100 ℃; and then adding a curing agent, stirring uniformly, pouring into a mold, heating for curing, and standing at room temperature for 1-7 d after curing to obtain the modified epoxy resin.
In the epoxy toughening application, the epoxy resin is one or two of bisphenol A type epoxy resin E51 and bisphenol F type epoxy resin F51.
In the epoxy toughening application, the catalyst is one or more of triethylene diamine, triethylamine, benzyl dimethylamine or diazabicyclo.
In the epoxy toughening application, the mass ratio of the epoxy resin to the catalyst is 100: 0.5-2.
In the epoxy toughening application, the curing agent is one or more of ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, polyetheramine D230, polyetheramine D400, polyetheramine D1000, polyetheramine D2000, polyetheramine T403, diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
In the application of epoxy toughening, the heating curing adopts an intermittent mode, namely curing at room temperature for 1-12 h, curing at 50-80 ℃ for 5-12 h, and finally curing at 100-150 ℃ for 2-10 h.
Compared with the prior art, the invention has the outstanding technical effects that:
1. the combined flexibilizer containing the five-membered cyclic carbonate group provided by the invention can introduce a chain segment containing a carbamate group into an epoxy resin system through the ring-opening reaction of the cyclic carbonate group and amine, and effectively avoids the use of toxic isocyanate while improving the toughness of an epoxy resin matrix. In addition, the toughening agent can form a strong hydrogen bonding effect with an epoxy resin matrix, and the performance of the epoxy resin matrix is further effectively improved.
2. The ir spectrum further shows that in the product of the reaction of the combined toughener of the invention with hexamethylenediamine, the C = O stretching vibration peak of the cyclic carbonate group disappears completely, instead the C = O stretching peak of the-NHCOO-group appears, and it has a higher degree of hydrogen bonding than the C = O in the reaction product of a single aliphatic cyclic carbonate with hexamethylenediamine. Furthermore, in the invention, a five-membered cyclic carbonate-containing composite toughening agent consisting of a hydrolysis type aromatic cyclic carbonate mixture and an aliphatic cyclic carbonate according to a mass ratio of 1-10: 10 can form a strong hydrogen bonding effect with an epoxy resin matrix, so that the related performance of the epoxy resin matrix is effectively improved, and the epoxy resin matrix has good tensile strength, elongation at break and impact strength.
3. The method is simple, easy, safe and reliable, isocyanate is not adopted as a synthetic raw material of polyurethane in the whole preparation process, and the method is green and environment-friendly and is suitable for industrial production; and carbon dioxide, which is the main reactant causing the greenhouse effect, is used as the main reactant for synthesizing the cyclic carbonate, so that a new way can be provided for the rational utilization of the cyclic carbonate.
4. The prior art has proved that the introduction of polyurethane molecular chain into epoxy resin system can effectively improve the toughness of epoxy resin matrix. Modification experiments prove that the combined toughening agent (isocyanate is not used as a raw material for polyurethane synthesis) contains five-membered cyclic carbonate groups, a rigid benzene ring structure, a flexible carbon chain and a large amount of hydroxyl, and the combined toughening agent is introduced into an epoxy resin system, so that the impact strength of epoxy resin can be obviously improved, and the toughening effect similar to that of the conventional polyurethane toughening agent is achieved.
Drawings
FIG. 1 is an infrared spectrum of a mixture of hydrolysis-type aromatic cyclic carbonates in examples 1, 2 and 3 of the present invention.
FIG. 2 is an infrared spectrum of a reaction product of a hydrolyzable aromatic cyclic carbonate mixture and hexamethylenediamine in example 1, example 2 and example 3 of the present invention.
FIG. 3 is an infrared spectrum of the reaction product of the composite toughener containing five-membered cyclic carbonate groups and hexamethylene diamine in example 1 of the present invention.
Detailed Description
Example 1
A composite toughening agent containing five-membered cyclic carbonate groups is a mixture consisting of a hydrolytic aromatic cyclic carbonate mixture and aliphatic cyclic carbonate according to the mass ratio of 1: 10;
the hydrolysis type aromatic cyclic carbonate mixture contains the following components with structural formulas shown as I, II and III:
the aliphatic cyclic carbonate is polyethylene glycol diglycidyl ether type cyclic carbonate, and the number average molecular weight of the cyclic carbonate is 2000 g/mol.
Example 2
A composite toughening agent containing five-membered cyclic carbonate groups is a mixture consisting of a hydrolytic aromatic cyclic carbonate mixture and aliphatic cyclic carbonate according to the mass ratio of 1: 1;
the hydrolysis type aromatic cyclic carbonate mixture contains the following components with structural formulas shown as I, II and III:
the aliphatic cyclic carbonate is ethylene glycol diglycidyl ether cyclic carbonate.
Example 3
A composite toughening agent containing five-membered cyclic carbonate groups is a mixture consisting of a hydrolytic aromatic cyclic carbonate mixture and aliphatic cyclic carbonate according to the mass ratio of 1: 5;
the hydrolysis type aromatic cyclic carbonate mixture contains the following components with structural formulas shown as I, II and III:
the aliphatic cyclic carbonate is butanediol diglycidyl ether type cyclic carbonate.
Example 4
A composite toughening agent containing five-membered cyclic carbonate groups is a mixture consisting of a hydrolytic aromatic cyclic carbonate mixture and aliphatic cyclic carbonate according to the mass ratio of 1: 3;
the hydrolysis type aromatic cyclic carbonate mixture contains the following components with structural formulas shown as I, II and III:
the aliphatic cyclic carbonate is polypropylene glycol diglycidyl ether type cyclic carbonate, and the number average molecular weight thereof is 650 g/mol.
Example 5
A preparation method of a combined toughening agent containing five-membered cyclic carbonate groups comprises the following steps:
(1) synthesis of hydrolysis type aromatic cyclic carbonate mixture: placing bisphenol A type epoxy resin E51 and tetrabutylammonium bromide catalyst (mass ratio 100: 1) in a closed reaction kettle, continuously introducing carbon dioxide, and stirring and reacting for 15h under the conditions that the pressure of the carbon dioxide is 0.1MPa and the temperature is 80 ℃; then adding distilled water into a closed reaction kettle, and reacting for 48 hours at the temperature of 50 ℃; and after the reaction is finished, cleaning and vacuum drying the obtained transparent viscous liquid product to obtain the hydrolysis type aromatic cyclic carbonate mixture. The cyclic carbonate group content in the hydrolyzed aromatic cyclic carbonate is 1.49 mmol/g;
(2) synthesis of aliphatic cyclic carbonate: putting hexanediol diglycidyl ether and tetrabutylammonium bromide catalyst (the mass ratio is 100: 1) in a closed reaction kettle, continuously introducing carbon dioxide, stirring and reacting for 60 hours under the conditions that the pressure of the carbon dioxide is 0.5MPa and the temperature is 80 ℃, and obtaining hexanediol diglycidyl ether type cyclic carbonate after the reaction is finished;
(3) preparing a combined toughening agent: and (3) mixing the hydrolysis type aromatic cyclic carbonate mixture prepared in the step (1) with the hexanediol diglycidyl ether type cyclic carbonate prepared in the step (2) according to the mass ratio of 1: 8 to obtain a combined flexibilizer product containing five-membered cyclic carbonate groups.
Example 6
A preparation method of a combined toughening agent containing five-membered cyclic carbonate groups comprises the following steps:
(1) synthesis of hydrolysis type aromatic cyclic carbonate mixture: placing bisphenol F type epoxy resin F51 and lithium bromide (mass ratio is 100: 1.5) in a closed reaction kettle, continuously introducing carbon dioxide, and stirring and reacting for 8h under the conditions that the pressure of the carbon dioxide is 4MPa and the temperature is 150 ℃; adding distilled water into a closed reaction kettle (the mass ratio of the bisphenol F type epoxy resin to the distilled water is 10: 2), and reacting at 100 ℃ for 24 hours; and after the reaction is finished, cleaning and vacuum drying the obtained solid product to obtain the hydrolysis type aromatic cyclic carbonate mixture. The cyclic carbonate group content in the hydrolysis type aromatic cyclic carbonate ester is 3.89 mmol/g;
(2) synthesis of aliphatic cyclic carbonate: putting polypropylene glycol diglycidyl ether (with the number average molecular weight of 500 g/mol) and a zinc bromide catalyst (with the mass ratio of 100: 0.5) into a closed reaction kettle, continuously introducing carbon dioxide, stirring and reacting for 28 hours under the conditions that the pressure of the carbon dioxide is 4MPa and the temperature is 120 ℃, and obtaining polypropylene glycol diglycidyl ether cyclic carbonate (with the number average molecular weight of 600 g/mol) after the reaction is finished;
(3) preparing a combined toughening agent: and (3) mixing the hydrolysis type aromatic cyclic carbonate mixture prepared in the step (1) with the polypropylene glycol diglycidyl ether type cyclic carbonate prepared in the step (2) according to the mass ratio of 1: 5 to obtain a combined flexibilizer product containing five-membered cyclic carbonate groups.
Example 7
A preparation method of a combined toughening agent containing five-membered cyclic carbonate groups comprises the following steps:
(1) synthesis of hydrolysis type aromatic cyclic carbonate mixture: placing aromatic epoxy resin (bisphenol A epoxy resin E51, bisphenol F epoxy resin F51) and catalyst (lithium bromide and benzyltriethylammonium chloride) in a closed reaction kettle, continuously introducing carbon dioxide, and stirring and reacting for 15h under the conditions that the pressure of the carbon dioxide is 2MPa and the temperature is 120 ℃; adding distilled water into a closed reaction kettle (the mass ratio of the aromatic epoxy resin to the distilled water is 1: 1), and reacting at 80 ℃ for 35 h; and after the reaction is finished, cleaning and vacuum drying the obtained solid product to obtain the hydrolysis type aromatic cyclic carbonate mixture. The cyclic carbonate group content in the hydrolysis type aromatic cyclic carbonate ester is 3.54 mmol/g;
wherein the mass ratio of the bisphenol A type epoxy resin to the bisphenol F type epoxy resin is 1: 1;
the mass ratio of the lithium bromide to the benzyltriethylammonium chloride is 1: 1;
the mass ratio of the aromatic epoxy resin to the catalyst is 100: 2;
(2) synthesis of aliphatic cyclic carbonate: placing glycidyl ether (ethylene glycol diglycidyl ether and hexanediol diglycidyl ether) and tetrabutylammonium bromide catalyst in a closed reaction kettle, continuously introducing carbon dioxide, stirring and reacting for 30h under the conditions that the pressure of the carbon dioxide is 1MPa and the temperature is 150 ℃, and obtaining a mixture of ethylene glycol diglycidyl ether cyclic carbonate and hexanediol diglycidyl ether cyclic carbonate after the reaction is finished;
wherein the mass ratio of ethylene glycol diglycidyl ether to hexanediol diglycidyl ether is 2: 1;
the mass ratio of the glycidyl ether to the catalyst is 100: 1.5;
(3) preparing a combined toughening agent: and (2) mixing the hydrolysis type aromatic cyclic carbonate mixture prepared in the step (1) with two aliphatic cyclic carbonates (ethylene glycol diglycidyl ether type cyclic carbonate and hexanediol diglycidyl ether type cyclic carbonate) prepared in the step (2) according to the mass ratio of 1: 6 to obtain a combined flexibilizer product containing five-membered cyclic carbonate groups.
Example 8
A preparation method of a combined toughening agent containing five-membered cyclic carbonate groups comprises the following steps:
(1) synthesis of hydrolysis type aromatic cyclic carbonate mixture: placing bisphenol A type epoxy resin E51 and a catalyst (lithium bromide, benzyltriethylammonium chloride and zinc bromide) in a closed reaction kettle, continuously introducing carbon dioxide, and stirring and reacting for 15h under the conditions that the pressure of the carbon dioxide is 2MPa and the temperature is 120 ℃; adding distilled water into a sealed reaction kettle (the mass ratio of the aromatic epoxy resin to the distilled water is 10: 5), and reacting at 80 ℃ for 35 h; and after the reaction is finished, cleaning and vacuum-drying the obtained solid product to obtain the hydrolysis type aromatic cyclic carbonate mixture. The cyclic carbonate group content in the hydrolyzed aromatic cyclic carbonate ester was 3.49 mmol/g;
wherein the mass ratio of the lithium bromide to the benzyltriethylammonium chloride to the zinc bromide is 1: 1;
the mass ratio of the bisphenol A type epoxy resin E51 to the catalyst is 100: 2.
(2) Synthesis of aliphatic cyclic carbonate: placing glycidyl ether [ polyethylene glycol diglycidyl ether (number average molecular weight 600 g/mol), polypropylene glycol diglycidyl ether (number average molecular weight 2500 g/mol) ] and a lithium bromide catalyst in a closed reaction kettle, continuously introducing carbon dioxide, stirring and reacting for 48 hours under the conditions that the pressure of the carbon dioxide is 2MPa and the temperature is 100 ℃, and obtaining polyethylene glycol diglycidyl ether cyclic carbonate (number average molecular weight 700 g/mol) and polypropylene glycol diglycidyl ether cyclic carbonate (number average molecular weight 2600 g/mol) after the reaction is finished;
wherein the mass ratio of the polyethylene glycol diglycidyl ether to the polypropylene glycol diglycidyl ether is 1: 3;
the mass ratio of the glycidyl ether to the catalyst is 100: 1.5;
(3) preparing a combined toughening agent: and (2) mixing the hydrolysis type aromatic cyclic carbonate mixture prepared in the step (1) with the two aliphatic cyclic carbonates (polyethylene glycol diglycidyl ether type cyclic carbonate and polypropylene glycol diglycidyl ether type cyclic carbonate) prepared in the step (2) according to the mass ratio of 1: 1 to obtain a combined flexibilizer product containing five-membered cyclic carbonate groups.
Example 9
A preparation method of a combined toughening agent containing five-membered cyclic carbonate groups comprises the following steps:
(1) synthesis of hydrolysis type aromatic cyclic carbonate mixture: placing bisphenol F type epoxy resin F51 and a catalyst (tetrabutylammonium bromide, lithium bromide, zinc bromide and benzyltriethylammonium chloride) in a closed reaction kettle, continuously introducing carbon dioxide, and stirring (stirring speed of 200 r/min) to react for 50h under the conditions that the pressure of the carbon dioxide is 0.5MPa and the temperature is 100 ℃; adding distilled water into a closed reaction kettle (the mass ratio of the bisphenol F type epoxy resin to the distilled water is 10: 8), and reacting at the temperature of 70 ℃ for 40 h; after the reaction is finished, the obtained solid product is subjected to 2 times of cleaning (the solvent is water) and vacuum drying treatment at 100 ℃ to obtain the hydrolysis type aromatic cyclic carbonate mixture. The cyclic carbonate group content in the hydrolyzed aromatic cyclic carbonate is 3.87 mmol/g;
wherein the mass ratio of tetrabutylammonium bromide to lithium bromide to zinc bromide to benzyltriethylammonium chloride is 2: 1;
the mass ratio of the bisphenol F type epoxy resin F51 to the catalyst is 100: 2;
(2) synthesis of aliphatic cyclic carbonate: putting glycidyl ether [ ethylene glycol diglycidyl ether, butanediol diglycidyl ether and polypropylene glycol diglycidyl ether (the number average molecular weight is 1000 g/mol) ] and a catalyst (tetrabutylammonium bromide, lithium bromide, zinc bromide and benzyltriethylammonium chloride) into a closed reaction kettle, continuously introducing carbon dioxide, stirring (stirring speed is 500 r/min) to react for 25 hours under the conditions that the pressure of the carbon dioxide is 3MPa and the temperature is 130 ℃, and obtaining ethylene glycol diglycidyl ether type cyclic carbonate, butanediol diglycidyl ether type cyclic carbonate and polypropylene glycol diglycidyl ether type cyclic carbonate (the number average molecular weight is about 1100 g/mol) after the reaction is finished;
wherein the mass ratio of ethylene glycol diglycidyl ether, butanediol diglycidyl ether and polypropylene glycol diglycidyl ether is 1: 3;
the mass ratio of tetrabutylammonium bromide to lithium bromide to zinc bromide to benzyltriethylammonium chloride is 2: 1;
the mass ratio of the glycidyl ether to the catalyst is 100: 2;
(3) preparing a combined toughening agent: and (2) mixing the hydrolysis type aromatic cyclic carbonate mixture prepared in the step (1) with the three aliphatic cyclic carbonates (ethylene glycol diglycidyl ether type cyclic carbonate, butanediol diglycidyl ether type cyclic carbonate and polypropylene glycol diglycidyl ether type cyclic carbonate) prepared in the step (2) according to the mass ratio of 1: 7 to obtain the combined flexibilizer product containing the five-membered cyclic carbonate group.
Example 10
A preparation method of a combined toughening agent containing five-membered cyclic carbonate groups comprises the following steps:
(1) synthesis of hydrolysis type aromatic cyclic carbonate mixture: placing bisphenol A type epoxy resin E51 and tetrabutylammonium bromide catalyst (mass ratio is 100: 1) in a closed reaction kettle, continuously introducing carbon dioxide, and stirring (stirring speed of 700 r/min) to react for 10h under the conditions that the pressure of the carbon dioxide is 3MPa and the temperature is 140 ℃; adding distilled water into a closed reaction kettle (the mass ratio of the bisphenol A epoxy resin to the distilled water is 10: 6), and reacting at the temperature of 90 ℃ for 35 hours; after the reaction is finished, the obtained solid product is cleaned for 5 times (the solvents are water, methanol and ethanol) and dried in vacuum at 150 ℃ to obtain the hydrolysis type aromatic cyclic carbonate mixture. The cyclic carbonate group content in the hydrolyzed aromatic cyclic carbonate is 3.62 mmol/g;
(2) synthesis of aliphatic cyclic carbonate: putting ethylene glycol diglycidyl ether and a catalyst (tetrabutylammonium bromide, lithium bromide, zinc bromide and benzyltriethylammonium chloride) into a closed reaction kettle, continuously introducing carbon dioxide, stirring (stirring speed of 700 r/min) to react for 30 hours under the conditions that the pressure of the carbon dioxide is 1MPa and the temperature is 130 ℃, and obtaining ethylene glycol diglycidyl ether type cyclic carbonate after the reaction is finished;
wherein the mass ratio of tetrabutylammonium bromide, lithium bromide, zinc bromide and benzyltriethylammonium chloride is 1: 1;
the mass ratio of the ethylene glycol diglycidyl ether to the catalyst is 100: 1.5;
(3) preparing a combined toughening agent: and (3) mixing the hydrolysis type aromatic cyclic carbonate mixture prepared in the step (1) with the ethylene glycol diglycidyl ether type cyclic carbonate prepared in the step (2) according to the mass ratio of 1: 10 to obtain a combined flexibilizer product containing five-membered cyclic carbonate groups.
Example 11
(1) Synthesis of hydrolysis type aromatic cyclic carbonate mixture: placing bisphenol A epoxy resin E51 and tetrabutylammonium bromide catalyst (mass ratio 100: 1) in a reaction kettle, sealing the reaction kettle and checking airtightness; heating to 120 ℃, continuously introducing carbon dioxide, keeping the pressure at 1MPa, and reacting for 6 hours at the stirring speed of 300 r/min; adding distilled water into a closed reaction kettle (the mass ratio of the bisphenol A epoxy resin E51 to the distilled water is 10: 2), and reacting for 24h at 80 ℃; after the reaction is finished, washing the product for 5 times by using water, and then carrying out vacuum drying in a vacuum oven at 120 ℃ for 24 hours to obtain a hydrolysis type aromatic cyclic carbonate mixture;
(2) synthesis of aliphatic cyclic carbonate: placing polyethylene glycol diglycidyl ether (number average molecular weight of 600 g/mol) and tetrabutylammonium bromide catalyst (mass ratio of 100: 1) in a closed reaction kettle, continuously introducing carbon dioxide into the reaction kettle, and reacting for 24h under the conditions that the pressure of the carbon dioxide is 2MPa, the reaction temperature is 130 ℃ and the stirring speed is 200r/min to obtain polyethylene glycol diglycidyl ether type cyclic carbonate (number average molecular weight of 680 g/mol);
(3) preparing a combined toughening agent: and mixing the hydrolysis type aromatic cyclic carbonate mixture prepared in the two steps with polyethylene glycol diglycidyl ether type cyclic carbonate according to the mass ratio of 1: 2 to obtain a combined flexibilizer product containing five-membered cyclic carbonate groups.
In this example 11, the infrared spectrum of the hydrolysis-type aromatic cyclic carbonate mixture obtained in step (1) is shown in FIG. 1. In FIG. 1, 1795cm -1 C = O stretching vibration peak of five-membered cyclic carbonate group in the mixture, 3400cm -1 Is attributed to the hydroxyl group generated by the ring opening reaction of the epoxy group and water, and 915cm is arranged in the right partial diagram -1 The absorption peak of the epoxy group at (a) disappears completely. The infrared spectrogram analysis proves that the hydrolysis type aromatic cyclic carbonate is obtained. The cyclic carbonate group content in the hydrolyzed aromatic cyclic carbonate was 1.42 mmol/g.
Reacting the hydrolysis type aromatic cyclic carbonate mixture obtained in the step (1) with hexamethylene diamine, wherein the infrared spectrum of the corresponding reaction product is shown in figure 2. As can be seen from the figure, the cyclic carbonate is at 1795cm -1 The C = O stretching vibration peak of the five-membered cyclic carbonate group at (E) is completely disappeared, and it is replaced by-1710 cm -1 C = O stretching vibration peak of-NHCOO-appears. It was demonstrated that five-membered cyclic carbonates can react with amines to form urethane groups (characteristic functional groups of polyurethanes).
And (3) further reacting the combined flexibilizer containing the five-membered cyclic carbonate group obtained in the step (3) with hexamethylene diamine. FIG. 3 shows the IR spectrum of the reaction product of poly (ethylene glycol) diglycidyl ether cyclic carbonate, combined toughener and hexamethylenediamine. As can be seen from the figure, the C = O of the-NHCOO-group in the product of the reaction of the combination flexibilizer with hexamethylenediamine has a higher degree of hydrogen bonding than the C = O of the reaction product of the polyethylene glycol diglycidyl ether type cyclic carbonate with hexamethylenediamine.
Example 12
(1) Synthesis of hydrolysis type aromatic cyclic carbonate mixture: placing bisphenol A epoxy resin E51 and benzyltriethylammonium chloride catalyst (mass ratio 100: 1) in a reaction kettle, sealing the reaction kettle and checking airtightness; heating to 120 ℃, continuously introducing carbon dioxide, keeping the pressure at 1MPa, and reacting for 10 hours at the stirring speed of 300 r/min; adding distilled water into a closed reaction kettle (the mass ratio of the bisphenol A epoxy resin E51 to the distilled water is 10: 2), and reacting for 24h at 90 ℃; after the reaction is finished, washing the mixture for 4 times by using an acetone product, and then drying the mixture for 48 hours in a vacuum oven at the temperature of 120 ℃ in vacuum to obtain a hydrolysis type aromatic cyclic carbonate mixture.
(2) Synthesis of aliphatic cyclic carbonate: placing polyethylene glycol diglycidyl ether (with number average molecular weight of 600 g/mol) and tetrabutylammonium bromide (with mass ratio of 100: 1) in a closed reaction kettle, continuously introducing carbon dioxide into the reaction kettle, and reacting for 36h under the conditions of carbon dioxide pressure of 1MPa, reaction temperature of 130 ℃ and stirring speed of 200 r/min; after the reaction is finished, polyethylene glycol diglycidyl ether type cyclic carbonate (the number average molecular weight is about 680 g/mol) is obtained;
(3) preparing a combined toughening agent: and mixing the hydrolysis type aromatic cyclic carbonate mixture prepared in the two steps with polyethylene glycol diglycidyl ether type cyclic carbonate according to the mass ratio of 1: 2 to obtain a combined flexibilizer product containing five-membered cyclic carbonate groups.
In this example 12, the infrared spectrum of the hydrolysis-type aromatic cyclic carbonate mixture obtained in step (1) is shown in FIG. 1. In FIG. 1, 1795cm -1 C = O stretching vibration peak of five-membered cyclic carbonate group in the mixture, 3400cm -1 Is attributed to the hydroxyl group generated by the ring opening reaction of the epoxy group and water, and 915cm is arranged in the right partial diagram -1 The absorption peak of the epoxy group at (a) disappears completely. The infrared spectrogram analysis proves that the hydrolysis type aromatic cyclic carbonate is obtained. The cyclic carbonate group content in the hydrolyzed aromatic cyclic carbonate was 3.0 mmol/g.
And (2) reacting the hydrolysis type aromatic cyclic carbonate mixture obtained in the step (1) with hexamethylene diamine, wherein the infrared spectrum of the corresponding reaction product is shown in figure 2. As can be seen from the figure, the cyclic carbonate is at 1795cm -1 The C = O stretching vibration peak of the five-membered cyclic carbonate group at (E) is completely disappeared, and it is replaced by-1710 cm -1 C = O stretching vibration peak of-NHCOO-appears. Meanwhile, the absorption peak intensity of C = O of-NHCOO-in example 12 is stronger than that of C = O of-NHCOO-in example 11, indicating that it contains a higher cyclic carbonate content.
Example 13
(1) Synthesis of hydrolysis type aromatic cyclic carbonate mixture: placing bisphenol A epoxy resin E51 and benzyltriethylammonium chloride catalyst (mass ratio 100: 1) in a reaction kettle, sealing the reaction kettle and checking airtightness; heating to 150 ℃, continuously introducing carbon dioxide, keeping the pressure at 1MPa, and reacting for 12h at the stirring speed of 300 r/min; adding distilled water into a closed reaction kettle (the mass ratio of the bisphenol A epoxy resin E51 to the distilled water is 10: 2), and reacting for 24h at 90 ℃; after the reaction is finished, cleaning the product for 5 times by using ethyl acetate, and then carrying out vacuum drying in a vacuum oven at 120 ℃ for 48 hours to obtain a hydrolysis type aromatic cyclic carbonate mixture;
(2) synthesis of aliphatic cyclic carbonate: placing polyethylene glycol diglycidyl ether (number average molecular weight 600 g/mol) and lithium bromide (mass ratio 100: 2) in a closed reaction kettle, continuously introducing carbon dioxide into the reaction kettle, and reacting for 30h under the conditions that the pressure of the carbon dioxide is 1MPa, the reaction temperature is 125 ℃ and the stirring speed is 400 r/min; after the reaction is finished, polyethylene glycol diglycidyl ether type cyclic carbonate (the number average molecular weight is about 680 g/mol) is obtained;
(3) preparing a combined toughening agent: and mixing the hydrolysis type aromatic cyclic carbonate mixture prepared in the two steps with polyethylene glycol diglycidyl ether according to the mass ratio of 1: 2 to obtain a combined flexibilizer product containing five-membered cyclic carbonate groups.
In this example 13, the infrared spectrum of the hydrolysis-type aromatic cyclic carbonate mixture obtained in step (1) is shown in FIG. 1. In FIG. 1, 1795cm -1 C = O stretching vibration peak of five-membered cyclic carbonate group in the mixture, 3400cm -1 Is attributed to the hydroxyl group generated by the ring opening reaction of the epoxy group and water, and 915cm is arranged in the right partial diagram -1 The absorption peak of the epoxy group at (a) disappears completely. The infrared spectrogram analysis proves that the hydrolysis type aromatic cyclic carbonate is obtained. The cyclic carbonate group content in the hydrolyzed aromatic cyclic carbonate was 3.86 mmol/g.
And (2) reacting the hydrolysis type aromatic cyclic carbonate mixture obtained in the step (1) with hexamethylene diamine, wherein the infrared spectrum of the corresponding reaction product is shown in figure 2. As can be seen from the figure, the cyclic carbonate is at 1795cm -1 The C = O stretching vibration peak of the five-membered cyclic carbonate group at (E) is completely disappeared, and it is replaced by-1710 cm -1 C = O stretching vibration peak of-NHCOO-appears. Meanwhile, the absorption peak intensity of-NHCOO-C = O in example 13 is stronger than that of-NHCOO-C = O in examples 11 and 12, indicating that it contains a higher cyclic carbonate content.
Example 14 epoxy toughening experiment 1
The combined toughening agent containing the five-membered cyclic carbonate group prepared in the embodiment 5-8 is used for toughening bisphenol F epoxy resin F51. 100g of bisphenol F epoxy resin F51 was mixed with 20g of a composite toughening agent, and 1g of triethylamine was added as a catalyst, followed by stirring and mixing at 65 ℃. Adding propane diamine, stirring for 5min, pouring into a mold, curing at room temperature for 5h, curing at 80 deg.C for 12h, and post-curing at 100 deg.C for 2 h. The mechanical property test results of the bisphenol F type epoxy resin F51 after being placed at room temperature for 3 days are shown in the following table 1:
example 15 epoxy toughening experiment 2
The combined toughening agent containing the five-membered cyclic carbonate group prepared in examples 9-13 and comparative example is used for toughening bisphenol A epoxy resin E51. 100g of bisphenol A epoxy resin E51 and 30g of a combination toughening agent were mixed, 1g of triethylene diamine was added as a catalyst, and the mixture was stirred and mixed at 60 ℃. Then adding hexamethylene diamine, stirring for 1min, pouring into a mould, curing for 2h at room temperature, curing for 24h at 75 ℃, and finally curing for 2h at 100 ℃. The mechanical property test results (modification effect) are shown in table 2 below:
note: in comparative example, an epoxy resin was modified with only a cyclic carbonate of polyethylene glycol diglycidyl ether type (number average molecular weight of about 680 g/mol) synthesized in the same manner and under the same conditions as in example 13, and other preparation conditions were not changed.
As can be seen from tables 1 and 2, the combined toughening agent containing five-membered cyclic carbonate groups obtained by the invention is used for toughening bisphenol A type epoxy resin and bisphenol F type epoxy resin, and has good modification effect in the aspects of tensile strength, elongation at break and impact strength.
Example 16 comparative epoxy toughening experiment
The hydrolyzed aromatic cyclic carbonate mixture prepared in example 12 and polyethylene glycol diglycidyl ether cyclic carbonate (5 CC-pegdgge, number average molecular weight about 680 g/mol) were mixed at different mass ratios, and added to bisphenol a epoxy resin E51 to toughen it. The specific preparation process of the toughened epoxy resin comprises the following steps: firstly, 100g of bisphenol A epoxy resin E51 is mixed with combined toughening agents with different mass ratios, 1g of triethylene diamine is added as a catalyst, and the materials are stirred and mixed at the temperature of 60 ℃. Adding hexamethylenediamine, stirring for 1min, pouring into a mold, curing at room temperature for 2h, curing at 75 ℃ for 24h, and finally curing at 100 ℃ for 2 h. The mechanical property test results (modification effect) are shown in table 3 below:
injecting: in Table 3, when the amount of 5CC-PEGDGE used is 100g, the modified toughened epoxy resin has better elasticity and thus is not damaged by impact when subjected to an impact test.
As can be seen from Table 3, when only polyethylene glycol diglycidyl ether cyclic carbonate (5 CC-PEGDGE) is used for toughening epoxy resin, the mechanical property of the product is poor. However, the properties of the product, particularly impact strength, were improved after the hydrolysis-type aromatic cyclic carbonate mixture prepared in example 12 was added thereto. However, as the amount of 5CC-PEGDGE was continuously increased, the tensile strength of the product was severely decreased. In addition, further increases in the amount of the mixture of hydrolyzable aromatic cyclic carbonates also lead to a reduction in the overall properties of the product. This shows that the best toughening effect can be achieved only by properly selecting the dosage ratio of the hydrolysis type aromatic cyclic carbonate mixture and the 5 CC-PEGDGE.
Claims (10)
1. A combined toughener containing five-membered cyclic carbonate groups, characterized in that: the combined toughening agent is a mixture consisting of a hydrolytic aromatic cyclic carbonate mixture and an aliphatic cyclic carbonate according to the mass ratio of 1-10: 10;
the hydrolysis type aromatic cyclic carbonate mixture contains the following components with structural formulas shown as I, II and III:
the aliphatic cyclic carbonate is a glycidyl ether cyclic carbonate containing a flexible aliphatic segment.
2. The preparation method of the combined toughening agent containing the five-membered cyclic carbonate group according to claim 1, comprising the steps of:
(1) synthesis of hydrolysis type aromatic cyclic carbonate mixture: placing aromatic epoxy resin and a catalyst in a closed reaction kettle, continuously introducing carbon dioxide, and stirring and reacting for 8-24 hours under the conditions that the pressure of the carbon dioxide is 0.1-4 MPa and the temperature is 80-150 ℃; then adding distilled water into a closed reaction kettle, and reacting for 24-48 h at the temperature of 50-100 ℃; after the reaction is finished, cleaning and vacuum drying the obtained solid or transparent viscous liquid product to obtain a hydrolysis type aromatic cyclic carbonate mixture;
(2) synthesis of aliphatic cyclic carbonate: putting glycidyl ether and a catalyst in a closed reaction kettle, continuously introducing carbon dioxide, stirring and reacting for 8-60 hours under the conditions that the pressure of the carbon dioxide is 0.1-4 MPa and the temperature is 80-150 ℃, and obtaining aliphatic cyclic carbonate after the reaction is finished;
(3) preparing a combined toughening agent: and (3) mixing the hydrolysis type aromatic cyclic carbonate mixture prepared in the step (1) with the aliphatic cyclic carbonate prepared in the step (2) according to the mass ratio of 1-10: 10 to obtain a combined flexibilizer product containing five-membered cyclic carbonate groups.
3. The method for preparing the combined toughening agent containing the five-membered cyclic carbonate group according to claim 2, wherein: in the step (1), the aromatic epoxy resin is one or two of bisphenol A type epoxy resin E51 and bisphenol F type epoxy resin F51.
4. The method for preparing the combined toughening agent containing the five-membered cyclic carbonate group according to claim 2, wherein: in the step (1) or the step (2), the catalyst is one or more of tetrabutylammonium bromide, lithium bromide, zinc bromide or benzyltriethylammonium chloride.
5. The method for preparing the combined toughening agent containing the five-membered cyclic carbonate group according to claim 2, wherein: in the step (1), the mass ratio of the aromatic epoxy resin to the catalyst is 100: 0.5-2; the mass ratio of the aromatic epoxy resin to the distilled water is 10: 2-10.
6. The method for preparing the combined toughening agent containing the five-membered cyclic carbonate group according to claim 2, wherein: in the step (1), the cleaning solvent is one or more of water, methanol, ethanol, acetone, ethyl acetate, tetrahydrofuran, carbon dichloride or carbon trichloride.
7. The method for preparing the combined toughening agent containing the five-membered cyclic carbonate group according to claim 2, wherein: in the step (1), the vacuum drying is carried out for 24-72 hours at the temperature of 100-150 ℃.
8. The method for preparing the combined toughening agent containing the five-membered cyclic carbonate group according to claim 2, wherein: in the step (2), the glycidyl ether is one or more of ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether; the number average molecular weight of the polyethylene glycol diglycidyl ether is 600-2000 g/mol; the number average molecular weight of the polypropylene glycol diglycidyl ether is 500-2500 g/mol.
9. The method for preparing the combined toughening agent containing the five-membered cyclic carbonate group according to claim 2, wherein: in the step (2), the mass ratio of the glycidyl ether to the catalyst is 100: 0.5-2.
10. Use of a combined toughener containing five-membered cyclic carbonate groups according to claim 1 in epoxy toughening.
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