CN107083025A - A kind of preparation method of carbon fiber Automobile Part rapid shaping fire resistant resin system - Google Patents
A kind of preparation method of carbon fiber Automobile Part rapid shaping fire resistant resin system Download PDFInfo
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- CN107083025A CN107083025A CN201710433658.5A CN201710433658A CN107083025A CN 107083025 A CN107083025 A CN 107083025A CN 201710433658 A CN201710433658 A CN 201710433658A CN 107083025 A CN107083025 A CN 107083025A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C08G59/5026—Amines cycloaliphatic
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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
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
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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
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The present invention relates to a kind of preparation method of carbon fiber Automobile Part rapid shaping fire resistant resin system, which solve that existing resin system hardening time length, shaping efficiency be low and injection temperature under gel time is short, the technical problem that viscosity build is too fast, the wellability to fiber preform body is poor, it comprises the following steps：High-active multiple amine and low activity aromatic amine are stirred to the curing agent component A for being mixed to form stable homogeneous, anionic initiator and low molecule epoxide are heated, prepare modified anion type catalyst, catalytic component B is uniformly mixing to obtain with chain-transferring agent, the epoxy resin of different epoxide numbers is uniformly mixing to obtain resin Composition E, it is well mixed with curing agent component A, catalytic component B under, prepares rapid shaping high-temperature-resistant epoxy resin system.The present invention can be used for the preparation field of carbon fiber Automobile Part.
Description
Technical field
The present invention relates to field of compound material, a kind of carbon fiber Automobile Part rapid shaping high temperature resistant tree is related in particular to
The preparation method of resin system.
Background technology
Carbon fibre composite will really be applied to the fields such as new-energy automobile, electronic apparatus, it is necessary to adapt to high yield certainly
The cost and speed of production of dynamic metaplasia production, this scale to composite, automation, rapid shaping technique propose higher
It is required that.RTM (Resin Transfer Molding, resin transfer molding) technique can realize semi-automatic or automatic metaplasia
Production, turns into the developing direction of future car CFRP moulding process by its advantage with short production cycle, and realizes RTM and be efficiently molded
Key be to develop the curing process of fast-curing resin system and its matching.
Current fast-curing epoxy resin system high-active multiple amine is used for curing agent more, but have the disadvantage resin system
Low viscosity plateau time is shorter, and fiber infiltration is not abundant enough.
A kind of resin system of Publication No. WO/2008/153542 International Patent Application Publication, it uses high activity fat
Cyclammonium makees curing agent, is prepared for RTM molding epoxy resin systems, and longer working life meets the work of large-scale composite material structural member
Skill requirement, but hardening time is long, shaping efficiency is low.
A kind of resin system of Publication No. WO/2015/014277 International Patent Application Publication, it uses high activity fat
Fat amine and Mannich modified firming agent, are prepared for quick-setting RTM molding epoxy resins system, and high solidification speed reduces multiple
Condensation material molding time, but gel time of the resin system under injection temperature is short, and viscosity build is too fast, to fiber preform
The wellability of body is poor.
The content of the invention
The present invention be exactly in order to solve that existing resin system hardening time length, shaping efficiency be low and injection temperature under gel
The technical problem that time is short, viscosity build is too fast, the wellability to fiber preform body is poor meets quick simultaneously there is provided a kind of
The preparation method of the high temperature resistant RTM epoxy-resin systems of solidification and the requirement of RTM moulding process.
Therefore, the present invention provides a kind of preparation method of carbon fiber Automobile Part rapid shaping fire resistant resin system, its
Comprise the following steps：(1) high-active multiple amine and low activity aromatic amine are stirred at 60~90 DEG C and is mixed to form stable homogeneous
Curing agent component A, the wherein mol ratio of high-active multiple amine and low activity aromatic amine is 15:(1~5)；(2) anion is drawn
Hair agent is heated to 70~100 DEG C of 3~6h of reaction with low molecule epoxide, prepares modified anion type catalyst, wherein living
The mol ratio for sprinkling hydrogen and epoxide group is 1:(0.8~1.3)；Then catalytic component B is uniformly mixing to obtain with chain-transferring agent, its
The mol ratio of middle modified anion type catalyst and chain-transferring agent is 1:(1~5)；(3) epoxy resin of different epoxide numbers is existed
Resin Composition E is uniformly mixing to obtain in 40~70 DEG C of reactor, is well mixed with curing agent component A, catalytic component B, is made
Standby rapid shaping high-temperature-resistant epoxy resin system, wherein component E, component A and component B mass ratio are 100:(16~24):(3
~6).
It is preferred that, high-active multiple amine hardener be Meng's alkane diamines, IPD, diamino-dicyclohexyl methane,
1,3~bis- aminomethyl cyclohexanes, N~aminoethyl piperazine, double (4~amino~3~methyl cyclohexyl) methane, fatty amines solidification
One or more of combinations in agent.
It is preferred that, low activity polyamine curing agent is diaminodiphenylsulfone, m-phenylene diamine (MPD), m-xylene diamine, diethyl first
One or more of combinations of phenylenediamine, diaminodiphenyl-methane.
It is preferred that, tertiary amine anion initiator be 4~dimethylamino naphthyridine, imidazole curing agent and its derivative, N, N~
Lupetazin, triethylamine, tripropyl amine (TPA), 2,4,6~tri- (dimethylamino methyl) phenol, triethylene diamine it is one or more of
Combination.
It is preferred that, low molecule epoxide is that n-butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl are sweet
Oily ether, the one or more to isobutyl glycidyl ether, diglycidyl ether.
It is preferred that, chain-transferring agent is glycerine, propane diols, ethylene glycol, butanediol, phenmethylol, diethylene glycol (DEG), phenol, ethyl
Phenol, ethyl mercaptan, the one or more of small carboxylic acid molecules' class compound.
It is preferred that, epoxy resin-base is bisphenol A epoxide resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, contracting
Water glyceramine epoxy resin, ethylene oxidic ester epoxy resin, cycloaliphatic epoxy resin, novolac epoxy resin it is one or more of
Combination.
Effect of the present invention is, resin system prepared by this method has longer working life, have at curing temperatures compared with
High reactivity, may be implemented in rapid curing in 5min, significantly shorten molding cycle, disclosure satisfy that automotive field is quickly made
Requirement of the technology to production efficiency is made, is embodied in：
(1) regulate and control the epoxide number of resin matrix with blending epoxy, make resin system that there is good reactivity, together
When meet requirement of the RTM techniques to low viscosity again, it is ensured that the good wellability of fiber preform, be advantageously implemented RTM quick
Injection.
(2) gradient for triggering resin with different activities polyamine curing agent solidifies, and utilizes high-active multiple amine curing exotherm
Trigger the curing reaction of low activity aromatic amine, improve curing efficiency, by solidification duration control within 5min, while aromatic amine
Introducing improve the heat resistance of resin.
(3) anionic initiator is modified with low molecule epoxide, reduces primary amine or secondary amine group low temperature
Lower reactivity, improves the latent stability under low temperature, introduces chain-transferring agent to triggering chain to carry out chain tra nsfer, realizes both associations
With catalysis, suppress early stage polymerisation, accelerate cured later.
Embodiment
More detailed description is done to the present invention below by way of specific embodiment：In embodiments, resin system curing degree
Obtained by differential scanning calorimetry (DSC) test；Resin system mechanical property is tried by the universal material of Instron companies of the U.S.
Machine test is tested to obtain；Resin stretched performance and bending property testing standard is according to GB/T 2567-2008；Glass transition temperature
(DMA) test is analyzed by dynamic thermomechanical to obtain.
Embodiment 1
(1) IPD and diethyl toluene diamine are stirred to the curing agent for being mixed to form stable homogeneous at 60 DEG C
The mol ratio of component, wherein IPD and diethyl toluene diamine is 15:1.
(2) 2-methylimidazole and n-butyl glycidyl ether are heated to 70 DEG C of reaction 6h, prepare modified anion type and urge
The mol ratio of agent, wherein active hydrogen and epoxide group is 1:0.8；The modified anion type catalyst and glycerine stirring is equal
Even to obtain catalytic component, the wherein mol ratio of modified anion type catalyst and chain-transferring agent is 1:1.
(3) it is 6 in mass ratio by bisphenol A type epoxy resin and novolac epoxy resin:4 ratio is in 40 DEG C of reactor
Resin Composition is uniformly mixing to obtain, resin Composition, curing agent component, catalytic component are well mixed, is prepared quick-setting
The mass ratio of RTM resin systems, wherein resin Composition, curing agent component and catalytic component is 100:16:6, by what is prepared
Resin system constant temperature 5min in 120 DEG C of vacuum ovens, cooling, obtains resin-cast body.
The curing degree of resin system is 95%, and 80 DEG C of gel times are 11.5min, the glass transition temperature of resin-cast body
Spend for 148 DEG C, tensile strength is 78MPa, stretch modulus is 2800MPa, and elongation at break is 5.5%, and bending strength is
120MPa, bending modulus is 2900MPa.
Embodiment 2
(1) IPD and 3,3- diaminodiphenylsulfones are stirred to the solidification for being mixed to form stable homogeneous at 90 DEG C
Agent component, the wherein mol ratio of IPD and 3,3- diaminodiphenylsulfone are 15:5.
(2) 2-ethyl-4-methylimidazole and phenyl glycidyl ether are heated to 100 DEG C of reaction 4h, prepare it is modified it is cloudy from
The mol ratio of subtype catalyst, wherein active hydrogen and epoxide group is 1:1.3.By the modified anion type catalyst and 1,4- fourths
Glycol is uniformly mixing to obtain catalytic component, and the wherein mol ratio of modified anion type catalyst and BDO is 1:5.
(3) it is 7 in mass ratio by bisphenol A type epoxy resin and bisphenol f type epoxy resin:Reaction of 3 ratio at 70 DEG C
Resin Composition is uniformly mixing to obtain in kettle, resin Composition, curing agent component, catalytic component are well mixed, is prepared quick solid
The RTM resin systems of change, the wherein mass ratio of resin Composition, curing agent component and catalytic component are 100:24:3, it will prepare
Good resin system constant temperature 5min in 120 DEG C of vacuum drying ovens, cooling obtains resin-cast body.
The curing degree of resin system is 96%, and 80 DEG C of gel times are 12min, the glass transition temperature of resin-cast body
For 150 DEG C, tensile strength is 80MPa, and stretch modulus is 2850MPa, and elongation at break is 5.0%, and bending strength is 115MPa,
Bending modulus is 2950MPa.
Embodiment 3
(1) Meng's alkane diamines and m-phenylene diamine (MPD) are stirred to the curing agent component for being mixed to form stable homogeneous at 70 DEG C, wherein
The mol ratio of Meng's alkane diamines and m-phenylene diamine (MPD) is 15:3.
(2) 2-methylimidazole and allyl glycidyl ether are heated to 80 DEG C of reaction 5h, prepare modified anion type and urge
The mol ratio of agent, wherein active hydrogen and epoxide group is 1:1.The modified anion type catalyst is stirred with butanediol
Obtained catalytic component, the wherein mol ratio of modified anion type catalyst and butanediol are 1:3.
(3) it is 7 in mass ratio by bisphenol A type epoxy resin and three-functionality-degree ethylene oxidic ester epoxy resin:3 ratio exists
Resin Composition is uniformly mixing to obtain in 60 DEG C of reactor, resin Composition, curing agent component, catalytic component are well mixed,
Quick-setting RTM resin systems are prepared, the wherein mass ratio of resin Composition, curing agent component and catalytic component is 100:
20:4, by the resin system prepared, constant temperature 5min, cooling in 120 DEG C of vacuum ovens, obtain resin-cast body.
The curing degree of resin system is 95%, and 80 DEG C of gel times are 12min, and the glass transition temperature of resin is 142
DEG C, tensile strength is 80MPa, and stretch modulus is 2800MPa, and elongation at break is 5.2%, and bending strength is 112MPa, bending
Modulus is 2900MPa.
Comparative example 1
The resin system is in addition to no addition chain-transferring agent component, and other resin Compositions are identical with embodiment 1.
(1) IPD and diethyl toluene diamine are stirred to the curing agent for being mixed to form stable homogeneous at 60 DEG C
The mol ratio of component, wherein IPD and diethyl toluene diamine is 15:1.
(2) 2-methylimidazole and n-butyl glycidyl ether are heated to 70 DEG C of reaction 6h, prepare modified anion type and urge
The mol ratio of agent, wherein active hydrogen and epoxide group is 1:0.8.
(3) it is 6 in mass ratio by bisphenol A type epoxy resin and novolac epoxy resin:4 ratio is in 40 DEG C of reactor
Resin Composition is uniformly mixing to obtain, resin Composition, curing agent component, catalytic component are well mixed, is prepared quick-setting
RTM resin systems, wherein resin Composition, curing agent component, the mass ratio of catalytic component are 100:16:3, by the tree prepared
Resin system constant temperature 5min in 120 DEG C of vacuum ovens, cooling, obtains resin-cast body.
The curing degree of resin system is 85%, and 80 DEG C of gel times are 11min, the glass transition temperature of resin-cast body
For 135 DEG C, tensile strength is 70MPa, and stretch modulus is 2700MPa, and elongation at break is 4.8%, and bending strength is 108MPa,
Bending modulus is 2800MPa.
Comparative example 2
The resin system is in addition to the fragrant amine component of no addition, and other resin Compositions are identical with embodiment 2.
(1) 2-ethyl-4-methylimidazole and phenyl glycidyl ether are heated to 100 DEG C of reaction 4h, prepare it is modified it is cloudy from
The mol ratio of subtype catalyst, wherein active hydrogen and epoxide group is 1:1.3.By the latency anionic catalyst and 1,4- fourths
Glycol is uniformly mixing to obtain catalytic component, and the wherein mol ratio of modified anion type catalyst and BDO is 1:5.
(2) it is 7 in mass ratio by bisphenol A type epoxy resin and bisphenol f type epoxy resin:Reaction of 3 ratio at 50 DEG C
Resin Composition is uniformly mixing to obtain in kettle, resin Composition, IPD, catalytic component are well mixed, is prepared quick
The RTM resin systems of solidification, wherein resin Composition, IPD, the mass ratio of catalytic component are 100:21:3, it will make
The resin system got ready constant temperature 5min in 120 DEG C of vacuum drying ovens, cooling, obtains resin-cast body.
The curing degree of resin system is 90%, and 80 DEG C of gel times are 11.5min, the glass transition temperature of resin-cast body
Spend for 140 DEG C, tensile strength is 70MPa, stretch modulus is 2750MPa, and elongation at break is 4.5%, and bending strength is
105MPa, bending modulus is 2800MPa.
As can be seen from the above Examples and Comparative Examples, effect of the invention is that shortening the hardening time of resin, carry
High shaping efficiency, and working life of the resin under injection temperature is extended, be conducive to the infiltration to fiber preform body.
Claims (7)
1. a kind of preparation method of carbon fiber Automobile Part rapid shaping fire resistant resin system, it is characterized in that including following step
Suddenly：
(1) high-active multiple amine and low activity aromatic amine are stirred to the curing agent group for being mixed to form stable homogeneous at 60~90 DEG C
Divide A, the mol ratio of wherein high-active multiple amine and low activity aromatic amine is 15:(1~5)；
(2) anionic initiator and low molecule epoxide are heated to 70~100 DEG C of 3~6h of reaction, prepare it is modified it is cloudy from
The mol ratio of subtype catalyst, wherein active hydrogen and epoxide group is 1:(0.8~1.3)；Then stirred with chain-transferring agent
Catalytic component B is obtained, the wherein mol ratio of modified anion type catalyst and chain-transferring agent is 1:(1~5)；
(3) epoxy resin of different epoxide numbers is uniformly mixing to obtain resin Composition E in 40~70 DEG C of reactor, with solidification
Agent component A, catalytic component B are well mixed, and prepare rapid shaping high-temperature-resistant epoxy resin system, wherein component E, component A with
Component B mass ratio is 100:(16~24):(3~6).
2. the preparation method of carbon fiber Automobile Part rapid shaping fire resistant resin system according to claim 1, it is special
Levy and be：Described high-active multiple amine hardener is Meng's alkane diamines, IPD, diamino-dicyclohexyl methane, 1,3
~bis- aminomethyl cyclohexanes, N~aminoethyl piperazine, double (4~amino~3~methyl cyclohexyl) methane, fatty amines curing agent
In one or more of combinations.
3. the preparation method of carbon fiber Automobile Part rapid shaping fire resistant resin system according to claim 1, it is special
Levy and be：Described low activity polyamine curing agent is diaminodiphenylsulfone, m-phenylene diamine (MPD), m-xylene diamine, diethyltoluene
One or more of combinations of diamines, diaminodiphenyl-methane.
4. the preparation method of carbon fiber Automobile Part rapid shaping fire resistant resin system according to claim 1, it is special
Levy and be：Described tertiary amine anion initiator is 4~dimethylamino naphthyridine, imidazole curing agent and its derivative, N, N~bis-
Methyl piperazine, triethylamine, tripropyl amine (TPA), 2,4,6~tri- (dimethylamino methyl) phenol, one or more of groups of triethylene diamine
Close.
5. the preparation method of carbon fiber Automobile Part rapid shaping fire resistant resin system according to claim 1, it is special
Levy and be：Described low molecule epoxide is n-butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl
Ether, the one or more to isobutyl glycidyl ether, diglycidyl ether.
6. the preparation method of carbon fiber Automobile Part rapid shaping fire resistant resin system according to claim 1, it is special
Levy and be：Described chain-transferring agent is glycerine, propane diols, ethylene glycol, butanediol, phenmethylol, diethylene glycol (DEG), phenol, ethylo benzene
Phenol, ethyl mercaptan, the one or more of small carboxylic acid molecules' class compound.
7. the preparation method of carbon fiber Automobile Part rapid shaping fire resistant resin system according to claim 1, it is special
Levy and be：Described epoxy resin-base is bisphenol A epoxide resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, shrink
Glyceramine epoxy resin, ethylene oxidic ester epoxy resin, cycloaliphatic epoxy resin, one or more of groups of novolac epoxy resin
Close.
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| CN110128628A (en) * | 2018-02-08 | 2019-08-16 | 艾普科模具材料（上海）有限公司 | A kind of preparation method of novel fire resistant epoxy mold resin |
| CN112194778A (en) * | 2020-09-28 | 2021-01-08 | 常州百思通复合材料有限公司 | Epoxy resin composition with unmatched epoxy groups and active hydrogen molar weight |
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| CN110128628A (en) * | 2018-02-08 | 2019-08-16 | 艾普科模具材料（上海）有限公司 | A kind of preparation method of novel fire resistant epoxy mold resin |
| CN112194778A (en) * | 2020-09-28 | 2021-01-08 | 常州百思通复合材料有限公司 | Epoxy resin composition with unmatched epoxy groups and active hydrogen molar weight |
| CN112194778B (en) * | 2020-09-28 | 2023-05-26 | 百思通新材料科技(武汉)有限公司 | Epoxy resin composition with unmatched molar quantity of epoxy groups and active hydrogen |
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| CN107083025B (en) | 2019-05-14 |
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