CN106893073B - Polyurethane modified bisphenol A epoxy resin and preparation method of cured product thereof - Google Patents
Polyurethane modified bisphenol A epoxy resin and preparation method of cured product thereof Download PDFInfo
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- 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
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
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- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
- C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
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- 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
- C08G18/58—Epoxy resins
- C08G18/581—Reaction products of epoxy resins with less than equivalent amounts of compounds containing active hydrogen added before or during the reaction with the isocyanate component
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- 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
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
- C08G59/502—Polyalkylene polyamines
Abstract
The invention discloses a preparation method of polyurethane modified bisphenol A epoxy resin and a condensate thereof, which comprises the following steps: s1, heating bisphenol A epoxy resin at 110 ℃ under a vacuum condition, stirring for 1-2h, and cooling to 50-60 ℃; s2, sequentially adding acetone and monohydric alcohol into S1, and stirring for 20-30 min; s3, mixing isocyanate and acetone to prepare solution A; s4, dropwise adding the solution A into the solution S2 at a rate of 10 drops/min, adding a catalyst after dropwise adding, heating the system to 80-90 ℃, and reacting for 2-4 hours to obtain modified epoxy resin; and S5, adding a curing agent into the modified epoxy resin of S4, and curing for 7 days at room temperature to obtain an epoxy resin cured product. The epoxy resin condensate prepared by the invention has high bonding strength, toughness and good impact resistance, and simultaneously has high peel strength, lap shear strength and creep resistance.
Description
Technical Field
The invention relates to the technical field of modified bisphenol A epoxy resin, in particular to polyurethane modified bisphenol A epoxy resin and a preparation method of a cured product thereof.
Background
The bisphenol A epoxy resin has the characteristics of good comprehensive mechanical property, high-strength adhesive force, small shrinkage rate, good thermal stability, excellent electrical insulation and the like, and is widely applied to the fields of machinery, electronics, electricity, aerospace and the like as a coating, an adhesive, a resin matrix of a composite material and the like. However, the cured epoxy resin has high crosslinking density and large internal stress, so that the cured epoxy resin has the defects of poor toughness, fatigue resistance, heat resistance, impact resistance and the like, and the performance requirements of many practical engineering technologies are difficult to meet, so that the application of the cured epoxy resin is limited to a certain extent.
Chinese patent document CN102924692A discloses a high-permeability polyurethane graft-modified epoxy resin interpenetrating network polymer grouting material and a preparation method thereof, the grouting material is composed of a component A and a component B, the component A is composed of 5-30 parts of isocyanate-terminated polyurethane prepolymer, 95-70 parts of epoxy resin and 10-30 parts of diluent Ӏ, a graft interpenetrating network structure is formed between polyurethane and epoxy resin, the component B is composed of 40-60 parts of curing agent, 10-30 parts of diluent Ӏ Ӏ and 0.5-2 parts of defoaming agent, and when in use, the grouting material can be obtained only by uniformly mixing the component A and the component B. The above method is helpful to form an interpenetrating network and a polymer grouting material with a high crosslinking degree by modifying an epoxy resin with polyurethane, however, the above polyurethane graft-modified epoxy resin interpenetrating network polymer grouting material has the following problems: the polyurethane is grafted and penetrated in the epoxy resin molecules, and the intermolecular distance is reduced due to mutual entanglement, the chain segment movement is limited, and the toughening effect is reduced; meanwhile, the collision among epoxy active groups is hindered, the reaction crosslinking is reduced, and the strength is correspondingly reduced.
Chinese patent document CN104277449A discloses a preparation method of polyurethane modified epoxy resin and a grouting material based on the same, wherein the epoxy resin is divided into two parts, wherein isocyanate and a catalyst are added into one part, the reaction is carried out for 1 to 3 hours in inert gas, then 5 to 10 weight parts of monohydric alcohol is added to continue the reaction for 1 to 3 hours, the temperature is reduced to 50 to 60 ℃, the other part of epoxy resin, a diluent, a plasticizer and an inorganic toughening agent are sequentially added to be uniformly mixed, and the polyurethane modified epoxy resin is obtained. Isocyanate and partial hydroxyl on epoxy resin react under certain conditions to obtain polyurethane grafted epoxy resin, the isocyanate units on the polyurethane grafted epoxy resin are blocked by monohydric alcohol, and polyurethane short branched chains are grafted on the epoxy resin, so that the intermolecular distance of the epoxy resin is increased, intermolecular force is reduced, the motion capability of chain segments is improved, and the effects of reducing the viscosity of slurry and toughening are achieved. However, the epoxy resin is added in two parts, the process is relatively complicated, in addition, the monohydric alcohol is added after the epoxy resin and the isocyanate react for a period of time, and the situation that the polyurethane and the epoxy resin are mutually entangled in a local area is unavoidable due to the high viscosity of the epoxy resin, so that the uniformity and the mechanical property of the modified epoxy resin are influenced.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a polyurethane modified bisphenol A epoxy resin and a preparation method of a cured product thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of polyurethane modified bisphenol A epoxy resin is characterized by comprising the following steps:
s1, heating 60-70 parts by weight of bisphenol A epoxy resin at 110 ℃ under a vacuum condition, stirring for 1-2h, and cooling to 50-60 ℃;
s2, sequentially adding 10-20 parts by weight of acetone and 5-10 parts by weight of monohydric alcohol into S1, and stirring for 20-30 min;
s3, mixing 10-20 parts by weight of isocyanate and 4-10 parts by weight of acetone to prepare solution A;
s4, dropwise adding the solution A into the solution S2 at a rate of 10 drops/min, adding 0.1-0.8 part by weight of catalyst after dropwise adding, heating the system to 80-90 ℃, reacting for 2-4h, cooling and cooling to obtain the polyurethane modified bisphenol A epoxy resin.
Preferably, the isocyanate is toluene diisocyanate or diphenylmethane diisocyanate.
Preferably, the monohydric alcohol is one or a mixture of n-butyl alcohol, tert-butyl alcohol, 2-ethylhexanol, n-octanol and 2-octanol.
Preferably, the catalyst is one or a mixture of dibutyltin dilaurate, triethylamine and stannous octoate.
Wherein the epoxy equivalent of the polyurethane modified bisphenol A epoxy resin in S4 is 195-130000 cps, and the viscosity at 25 ℃ is 8000-130000 cps.
The preparation method of the epoxy resin condensate is characterized by comprising the following steps:
s1, heating 60-70 parts by weight of bisphenol A epoxy resin at 110 ℃ under a vacuum condition, stirring for 1-2h, and cooling to 50-60 ℃;
s2, sequentially adding 10-20 parts by weight of acetone and 5-10 parts by weight of monohydric alcohol into S1, and stirring for 20-30 min;
s3, mixing 10-20 parts by weight of isocyanate and 4-10 parts by weight of acetone to prepare solution A;
s4, dropwise adding the solution A into the solution S2 at a rate of 10 drops/min, adding 0.1-0.8 part by weight of catalyst after dropwise adding, heating the system to 80-90 ℃, reacting for 2-4h, cooling and cooling to obtain polyurethane modified bisphenol A epoxy resin;
and S5, adding a curing agent into the polyurethane modified bisphenol A epoxy resin of S4, and curing at room temperature for 7 days to obtain an epoxy resin cured product, wherein the mass ratio of the polyurethane modified bisphenol A epoxy resin to the curing agent is 2: 1.
Preferably, the isocyanate is toluene diisocyanate or diphenylmethane diisocyanate.
Preferably, the monohydric alcohol is one or a mixture of n-butyl alcohol, tert-butyl alcohol, 2-ethylhexanol, n-octanol and 2-octanol.
Preferably, the catalyst is one or a mixture of dibutyltin dilaurate, triethylamine and stannous octoate.
Preferably, the curing agent is any one of aliphatic polyamine, polyamide, DICY or anhydride.
Compared with the prior art, the invention has the following beneficial effects: according to the preparation method of the polyurethane modified bisphenol A epoxy resin, monohydric alcohol is added before the reaction of the bisphenol A epoxy resin and isocyanate, and the hydroxyl on the monohydric alcohol and the hydroxyl of the bisphenol A epoxy resin have a competitive reaction, so that the generation of a bisphenol A epoxy resin grafted polyurethane long branched chain is avoided, the distance between epoxy resin molecules is increased, the intermolecular force is reduced, the motion capability of a chain segment is improved, and the toughening effect of the modified epoxy resin is improved; meanwhile, in the subsequent curing process, due to heat release, the combination of the monohydric alcohol and the isocyanate can be partially disconnected to participate in curing, so that the utilization rate of the isocyanate is improved, and the double effects of reaction toughening and reaction crosslinking are realized; the polyurethane modified bisphenol A epoxy resin prepared by the invention has high bonding strength, toughness and good impact resistance after being cured, and simultaneously has high peeling strength, lap shear strength and creep resistance.
Detailed Description
Example 1
S1, heating 60g of bisphenol A epoxy resin at 110 ℃ under a vacuum condition, stirring for 1h, and cooling to 50-55 ℃;
s2, sequentially adding 20g of acetone and 5g of n-butanol into S1, and stirring for 20 min;
s3, mixing 10g of toluene diisocyanate and 4.5g of acetone to prepare solution A;
s4, dropwise adding the solution A into the solution S2 at a rate of 10 drops/min, after dropwise adding, adding 0.5g of dibutyltin dilaurate, heating the system to 80-85 ℃, reacting for 2h, and cooling to obtain 100g of polyurethane modified bisphenol A epoxy resin;
s5, adding 50g of dimethylamine propylamine into the polyurethane modified bisphenol A epoxy resin in 100g S4, and curing for 7 days at room temperature to obtain an epoxy resin cured product.
Example 2
S1, taking 70g of bisphenol A epoxy resin, heating to 100-105 ℃ under a vacuum condition, stirring for 1.5h, and then cooling to 55-60 ℃;
s2, sequentially adding 10g of acetone and 5g of tert-butyl alcohol into S1, and stirring for 25 min;
s3, mixing 10g of diphenylmethane diisocyanate and 4.9g of acetone to prepare a solution A;
s4, dropwise adding the solution A into the solution S2 at a rate of 10 drops/min, after dropwise adding, adding 0.1g of triethylamine, heating the system to 85-90 ℃, reacting for 3h, cooling and cooling to obtain 100g of polyurethane modified bisphenol A epoxy resin;
s5, adding 50g of polyamide into 100g S4 of polyurethane modified bisphenol A epoxy resin, and curing for 7 days at room temperature to obtain an epoxy resin cured product.
Example 3
S1, taking 65g of bisphenol A epoxy resin, heating to 100-105 ℃ under a vacuum condition, stirring for 1.5h, and then cooling to 55-60 ℃;
s2, adding 10g of acetone and 7.5g of 2-ethylhexanol into S1 in sequence, and stirring for 30 min;
s3, mixing 10g of diphenylmethane diisocyanate and 6.7g of acetone to prepare a solution A;
s4, dropwise adding the solution A into the solution S2 at a rate of 10 drops/min, after dropwise adding, adding 0.8g of stannous octoate, heating the system to 85-90 ℃, reacting for 4 hours, and cooling to obtain 100g of polyurethane modified bisphenol A epoxy resin;
s5, adding 50g DICY into 100g S4 polyurethane modified bisphenol A epoxy resin, and curing at room temperature for 7 days to obtain epoxy resin cured product.
Example 4
S1, taking 60g of bisphenol A epoxy resin, heating to 100-105 ℃ under a vacuum condition, stirring for 1.5h, and then cooling to 55-60 ℃;
s2, adding 15g of acetone and 5g of n-octanol into S1 in sequence, and stirring for 30 min;
s3, mixing 10g of diphenylmethane diisocyanate and 9.9g of acetone to prepare a solution A;
s4, dropwise adding the solution A into the solution S2 at a rate of 10 drops/min, after dropwise adding, adding 0.1g of stannous octoate, heating the system to 85-90 ℃, reacting for 4 hours, and cooling to obtain 100g of polyurethane modified bisphenol A epoxy resin;
s5, adding 50g of acid anhydride into 100g of polyurethane modified bisphenol A epoxy resin in S4, and curing for 7 days at room temperature to obtain an epoxy resin cured product.
Example 5
S1, taking 60g of bisphenol A epoxy resin, heating to 100-105 ℃ under a vacuum condition, stirring for 2h, and then cooling to 55-60 ℃;
s2, sequentially adding 10g of acetone and 5g of 2-octanol into S1, and stirring for 30 min;
s3, mixing 20g of diphenylmethane diisocyanate and 4.9g of acetone to prepare a solution A;
s4, dropwise adding the solution A into the solution S2 at a rate of 10 drops/min, after dropwise adding, adding 0.1g of stannous octoate, heating the system to 85-90 ℃, reacting for 4 hours, and cooling to obtain 100g of polyurethane modified bisphenol A epoxy resin;
s5, adding 50g of acid anhydride into the polyurethane modified bisphenol A epoxy resin in 100g S4, and curing for 7 days at room temperature to obtain an epoxy resin cured product.
Example 6
S1, taking 60g of bisphenol A epoxy resin, heating to 100-105 ℃ under a vacuum condition, stirring for 1.5h, and then cooling to 55-60 ℃;
s2, sequentially adding 10g of acetone and 10g of 2-ethylhexanol into S1, and stirring for 30 min;
s3, mixing 15.2g of diphenylmethane diisocyanate and 4g of acetone to prepare a solution A;
s4, dropwise adding the solution A into the solution S2 at a rate of 10 drops/min, after dropwise adding, adding 0.8g of stannous octoate, heating the system to 85-90 ℃, reacting for 4 hours, and cooling to obtain 100g of polyurethane modified bisphenol A epoxy resin;
s5, adding 50g of acid anhydride into 100g of polyurethane modified bisphenol A epoxy resin in S4, and curing for 7 days at room temperature to obtain an epoxy resin cured product.
The cured epoxy resins prepared in examples 1 to 6 were subjected to adhesion strength test in accordance with ASTM D-1002, and the test results are shown in the following table.
The foregoing detailed description is given by way of example only, to better enable one of ordinary skill in the art to understand the patent, and is not to be construed as limiting the scope of what is encompassed by the patent; any equivalent alterations or modifications made according to the spirit of the disclosure of this patent are intended to be included in the scope of this patent.
Claims (10)
1. A preparation method of polyurethane modified bisphenol A epoxy resin is characterized by comprising the following steps:
s1, heating 60-70 parts by weight of bisphenol A epoxy resin at 110 ℃ under a vacuum condition, stirring for 1-2h, and cooling to 50-60 ℃;
s2, sequentially adding 10-20 parts by weight of acetone and 5-10 parts by weight of monohydric alcohol into S1, and stirring for 20-30 min;
s3, mixing 10-20 parts by weight of isocyanate and 4-10 parts by weight of acetone to prepare solution A;
s4, dropwise adding the solution A into the solution S2 at a rate of 10 drops/min, adding 0.1-0.8 part by weight of catalyst after dropwise adding, heating the system to 80-90 ℃, reacting for 2-4h, cooling and cooling to obtain the polyurethane modified bisphenol A epoxy resin.
2. The method of producing a urethane-modified bisphenol a epoxy resin according to claim 1, wherein said isocyanate is toluene diisocyanate or diphenylmethane diisocyanate.
3. The process for producing a urethane-modified bisphenol A epoxy resin according to claim 1, wherein said monohydric alcohol is one or a mixture of n-butanol, t-butanol, 2-ethylhexanol, n-octanol, and 2-octanol.
4. The method for preparing the urethane-modified bisphenol A epoxy resin according to claim 1, wherein the catalyst is one or a mixture of dibutyltin dilaurate, triethylamine and stannous octoate.
5. The method for preparing a urethane-modified bisphenol A epoxy resin as described in claim 1, wherein the urethane-modified bisphenol A epoxy resin in S4 has an epoxy equivalent of 195-130000 cps and a viscosity of 8000-130000cps at 25 ℃.
6. The preparation method of the epoxy resin condensate is characterized by comprising the following steps:
s1, heating 60-70 parts by weight of bisphenol A epoxy resin at 110 ℃ under a vacuum condition, stirring for 1-2h, and cooling to 50-60 ℃;
s2, sequentially adding 10-20 parts by weight of acetone and 5-10 parts by weight of monohydric alcohol into S1, and stirring for 20-30 min;
s3, mixing 10-20 parts by weight of isocyanate and 4-10 parts by weight of acetone to prepare solution A;
s4, dropwise adding the solution A into the solution S2 at a rate of 10 drops/min, adding 0.1-0.8 part by weight of catalyst after dropwise adding, heating the system to 80-90 ℃, reacting for 2-4h, cooling and cooling to obtain polyurethane modified bisphenol A epoxy resin;
and S5, adding a curing agent into the polyurethane modified bisphenol A epoxy resin of S4, and curing at room temperature for 7 days to obtain an epoxy resin cured product, wherein the mass ratio of the polyurethane modified bisphenol A epoxy resin to the curing agent is 2: 1.
7. The method for producing a cured epoxy resin according to claim 6, wherein the isocyanate is tolylene diisocyanate or diphenylmethane diisocyanate.
8. The method for producing an epoxy resin cured product according to claim 6, wherein the monohydric alcohol is one or a mixture of n-butanol, t-butanol, 2-ethylhexanol, n-octanol, and 2-octanol.
9. The method for producing an epoxy resin cured product according to claim 6, wherein the catalyst is one or a mixture of dibutyltin dilaurate, triethylamine and stannous octoate.
10. The method for producing a cured epoxy resin according to claim 6, wherein the curing agent is any one of aliphatic polyamine, polyamide, DICY and acid anhydride.
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| CN107840940B (en) * | 2017-10-25 | 2020-02-07 | 中南林业科技大学 | Preparation method of curing agent for epoxy powder coating |
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