CN107501863A - A kind of rapid shaping toughened resin system preparation method - Google Patents
A kind of rapid shaping toughened resin system preparation method Download PDFInfo
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- CN107501863A CN107501863A CN201710776767.7A CN201710776767A CN107501863A CN 107501863 A CN107501863 A CN 107501863A CN 201710776767 A CN201710776767 A CN 201710776767A CN 107501863 A CN107501863 A CN 107501863A
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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
- C08G59/5006—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
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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
-
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention relates to a kind of rapid shaping toughened resin system preparation method, which solve that resin pot life obtained by existing method is shorter, fiber infiltration is insufficient, the technical problem of finished product not easy mold release, comprise the following steps：By high-active multiple amine with being reacted in epoxide, prepare modified amine curing agent, then medium activity curing agent is added, obtain curing agent component A, anionic initiator and chain-transferring agent are uniformly mixing to obtain catalytic component B, blending epoxy is uniformly mixing to obtain resin Composition E, resin Composition E is well mixed with curing agent component A, catalytic component B, rapid shaping RTM epoxy-resin systems are prepared, the present invention can be used for the preparation field of carbon fiber Automobile Part RTM rapid shaping toughened resin systems.
Description
Technical field
The present invention relates to field of compound material, relates in particular to a kind of rapid shaping toughened resin system preparation method.
Background technology
Lightweight Technology is one of key technology of China Automobile Industry, and the carbon fibre composite of high-strength light is automobile
Light-weighted ideal material.Realize scale application of the advanced composite material in automotive field, it is necessary to solve shaping efficiency
The problem of.Representative of the RTM rapid shapings as high efficiency, low cost composite technology is future car carbon fibre composite into
The developing direction of type technique.For same with thermosetting compound material, the solidification process of resin accounts for the major part of whole molding cycle,
Therefore it is the most important condition for realizing RTM rapid shapings to develop quick-setting resin system.
United States Patent (USP) (US20080197526) respectively preheats resin and curing agent, is then injected into high temperature (150 DEG C of ＞) mould
Being solidified in tool, hardening time is short, but because mold temperature is more than the glass transition temperature of resin, causes the demoulding difficult,
The easy buckling deformation of product.
International monopoly (WO2012177392) is used as curing agent and catalysis by the use of fatty amine and Mannich modified multicomponent amine respectively
Agent, RTM rapid shaping epoxy-resin systems are prepared for, high reaction activity shortens the molding time of composite, but shortcoming is
Gel time is short, and the working life of resin can not meet the requirement of RTM moulding process.
Therefore, rapid curing is realized using mold temperature or high activity amine hardener and accelerator etc. is improved, brings tree
Fat working life is shorter, fiber infiltration is insufficient, finished product not easy mold release the problem of.
The content of the invention
The present invention is exactly that resin pot life obtained by existing method is shorter, fiber infiltrates insufficient, finished product in order to solve
The not technical problem of easy mold release, there is provided a kind of to be beneficial to realize fast injection, extend resin pot life, improve cured later degree
Rapid shaping toughened resin system preparation method.
Therefore, the present invention provides a kind of rapid shaping tough epoxy resin system preparation method, it comprises the following steps：
(1) high-active multiple amine and epoxide are reacted into 1~4h in 40~70 DEG C of stirred tank, prepare modified amine curing agent,
Wherein the mol ratio of amino and epoxy radicals is 1:(0.2~0.5), medium activity curing agent is then added, be uniformly mixing to obtain solid
The quality parts ratio of agent component A, the modified amine curing agent and the medium activity curing agent is 1:(2~4)；(2) by the moon
Ionic initiator is uniformly mixing to obtain catalytic component B, the anionic initiator and the chain-transferring agent with chain-transferring agent
Mol ratio is 1:(1~3)；(3) blending epoxy is uniformly mixing to obtain resin Composition E in 40~70 DEG C of reactor,
The resin Composition E is well mixed with the curing agent component A, the catalytic component B, prepares rapid shaping RTM asphalt mixtures modified by epoxy resin
Resin system, the component E, component A and component B mass ratio are 100:(17~22):(3~6).
Preferably, high-active multiple amine hardener is ethylenediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, four ethene
One or more of combinations of five amine, polyethylene polyamine, divinyl propylamine, diethylamine, triethylamine.
Preferably, epoxide is bisphenol A epoxide resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, positive fourth
Base glycidol ether, allyl glycidyl ether, phenyl glycidyl ether, to isobutyl phenenyl glycidol ether, cresols shrink
The one or more of glycerin ether.
Preferably, medium activity curing agent is Meng's alkane diamines, IPD, diamino-dicyclohexyl methane, 1,3-
One or more of combinations of double aminomethyl cyclohexanes, N- aminoethyl piperazines, double (4- amino -3- methyl cyclohexyl) methane.
Preferably, anionic initiator be DMAP, imidazole curing agent and its derivative, N, N- dimethyl
One or more of combinations of piperazine, triethylamine, tripropyl amine (TPA), 2,4,6- tri- (dimethylamino methyl) phenol, triethylene diamine.
Preferably, 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.
Preferably, blending epoxy matrix is bisphenol A epoxide resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy tree
The combination of fat, cycloaliphatic epoxy resin, two kinds of liquid phenolic epoxy resin and the above.
Effect of the present invention is：
(1) regulate and control the epoxide number of resin matrix with blending epoxy, make resin matrix that there is good reactivity, together
When viscosity under injection temperature it is low, beneficial to fast injection is realized, there is good wellability to fiber preform.
(2) changed with the addition reaction of high-active multiple amine and epoxide, the active primary amine group of capping, regulation and control
Property curing agent low-temperature reactivity, extend resin pot life.Compounded simultaneously with medium activity curing agent, effectively realize staged
Efficiently solidification.
(3) using the anionic initiator with autohemagglutination catalytic effect as catalyst, accelerate the foundation of cross-linked network, improve
Crosslink density.Chain-transferring agent concerted catalysis is introduced, the length of regulation activity chain, it is rapid to avoid the viscosity brought due to rapid polymerization
Increasing problem, injection time is extended, while improve cured later degree.
Embodiment
More detailed description is done to the present invention below by way of specific embodiment：In embodiments, the gel of resin system
Time tests G ＇ and G ＇ ＇ by the plate rheometers of Haake MARS III and obtained；Resin system curing degree passes through differential scanning calorimetry
(DSC) test obtains；Glass transition temperature is analyzed (DMA) test by dynamic thermomechanical and obtained；Resin system mechanical property
Test to obtain by the universal testing machine of Instron companies of the U.S.；Resin stretched performance and bending property testing standard according to
According to GB/T 2567~2008.
Embodiment 1
(1) triethylene tetramine and bisphenol A epoxide resin are reacted into 4h under the conditions of 40 DEG C, prepares modified amine curing agent, its
The mol ratio of middle amino and epoxy radicals is 1:0.2, curing agent component then is uniformly mixing to obtain with IPD, wherein changing
Property amine hardener and IPD quality parts ratio be 1:2.
(2) 2~methylimidazole and butanediol are uniformly mixing to obtain catalytic component, wherein 2~methylimidazole and fourth two
The mol ratio of alcohol is 1:1.
(3) it is 7 according to mass ratio by bisphenol A epoxide resin and bisphenol F epoxy resin:Reactor of 3 ratio at 40 DEG C
In be uniformly mixing to obtain resin Composition, be well mixed with curing agent component, catalytic component, prepare rapid shaping RTM asphalt mixtures modified by epoxy resin
The mass ratio of resin system, wherein resin Composition, curing agent component and catalytic component is 100:22:3, the resinite that will be prepared
Constant temperature 3min in 115 DEG C of vacuum drying ovens is tied up to, obtains resin-cast body.
Embodiment 2
(1) polyethylene polyamine and n-butyl glycidyl ether are reacted into 1h under the conditions of 70 DEG C, prepare modified amine curing agent,
Wherein the mol ratio of amino and epoxy radicals is 1:0.5, curing agent component then is uniformly mixing to obtain with Meng's alkane diamines, wherein modified
The quality parts ratio of amine hardener and Meng's alkane diamines is 1:4.
(2) 2~phenylimidazole and glycerine are uniformly mixing to obtain catalytic component, wherein 2~phenylimidazole and the third three
The mol ratio of alcohol is 1:3.
(3) it is 8 according to mass ratio by bisphenol A epoxide resin and liquid phenolic epoxy resin:Reaction of 2 ratio at 70 DEG C
Resin Composition is uniformly mixing to obtain in kettle, is well mixed with curing agent component, catalytic component, prepares rapid shaping RTM epoxies
The mass ratio of resin system, wherein resin Composition, curing agent component and catalytic component is 100:17:6, the resin that will be prepared
System constant temperature 3min in 115 DEG C of vacuum drying ovens, obtains resin-cast body.
Embodiment 3
(1) ethylenediamine and bisphenol F epoxy resin are reacted into 2h under the conditions of 60 DEG C, prepares polyamine addition agent, wherein ammonia
The mol ratio of base and epoxy radicals is 1:0.3, then with 1,3~bis- aminomethyl cyclohexanes are uniformly mixing to obtain curing agent component, its
The quality parts ratio of middle modified amine curing agent and 1,3~bis- aminomethyl cyclohexanes is 1:3.
(2) 2~methylimidazole and phenmethylol are uniformly mixing to obtain catalytic component, wherein 2~methylimidazole and benzene first
The mol ratio of alcohol is 1:2.
(3) it is 6 according to mass ratio by bisphenol A epoxide resin and hydrogenated bisphenol A epoxy resin:4 ratio is anti-at 60 DEG C
Answer and resin Composition is uniformly mixing to obtain in kettle, be well mixed with curing agent component, catalytic component, prepare rapid shaping RTM rings
The mass ratio of epoxy resin system, wherein resin Composition, curing agent component and catalytic component is 100:20:4, the tree that will be prepared
Resin system constant temperature 3min in 115 DEG C of vacuum drying ovens, obtains resin-cast body.
Comparative example 1
The resin system is not complete by high-active multiple amine and epoxide pre-reaction, other resin Compositions and embodiment 1
It is exactly the same.
(1) triethylene tetramine and IPD are uniformly mixing to obtain curing agent component, wherein triethylene tetramine with
The quality parts ratio of intermediate temperature curing agent is 1:2.
(2) 2~methylimidazole and butanediol are uniformly mixing to obtain catalytic component, wherein 2~methylimidazole and fourth two
The mol ratio of alcohol is 1:1.
(3) it is 7 according to mass ratio by bisphenol A epoxide resin and bisphenol-type epoxy resin:Reactor of 3 ratio at 40 DEG C
In be uniformly mixing to obtain resin Composition, be well mixed with curing agent component, catalytic component, prepare rapid shaping RTM asphalt mixtures modified by epoxy resin
The mass ratio of resin system, wherein resin Composition, curing agent component and catalytic component is 100:22:3, the resinite that will be prepared
Constant temperature 3min in 115 DEG C of vacuum drying ovens is tied up to, obtains resin-cast body.
Comparative example 2
For the resin system in addition to no addition chain-transferring agent component, other resin Compositions are identical with embodiment 2.
(1) polyethylene polyamine and n-butyl glycidyl ether are reacted into 1h under the conditions of 80 DEG C, prepare modified amine curing agent,
Wherein the mol ratio of amino and epoxy radicals is 1:0.5, curing agent component then is uniformly mixing to obtain with Meng's alkane diamines, wherein modified
The quality parts ratio of amine hardener and Meng's alkane diamines is 1:4.
(2) it is 8 according to mass ratio by bisphenol A type epoxy resin and liquid phenolic epoxy resin:2 ratio is anti-at 70 DEG C
Answer and resin Composition is uniformly mixing to obtain in kettle, be well mixed with curing agent component, 2~methylimidazole, prepare rapid shaping RTM rings
The mass ratio of epoxy resin system, wherein resin Composition, curing agent component and catalytic component is 100:22:2, the tree that will be prepared
Resin system constant temperature 3min in 115 DEG C of vacuum drying ovens, obtains resin-cast body.
The effect of above-described embodiment and comparative example is as follows：
As can be seen from the table above, effect of the invention is as follows：(1) gel time of 80 DEG C of embodiment is considerably longer than pair
Ratio, illustrate that the present invention by regulating and controlling resin low-temperature reactivity, effectively extends resin pot life (2) embodiment at 115 DEG C
Gel time and curing degree approached with comparative example, illustrate the present invention by improve pyroreaction activity, realize efficiently solidification,
It ensure that the curing degree of resin；(3) invention significantly improves the glass transition temperature of resin after solidification and mechanical property.
Claims (7)
- A kind of 1. rapid shaping tough epoxy resin system preparation method, it is characterized in that comprising the following steps：(1) high-active multiple amine and epoxide are reacted into 1~4h in 40~70 DEG C of stirred tank, prepares modified amine solidification The mol ratio of agent, wherein amino and epoxy radicals is 1:(0.2~0.5), medium activity curing agent is then added, is uniformly mixing to obtain The quality parts ratio of curing agent component A, the modified amine curing agent and the medium activity curing agent is 1:(2~4)；(2) anionic initiator and chain-transferring agent are uniformly mixing to obtain catalytic component B, the anionic initiator with it is described The mol ratio of chain-transferring agent is 1:(1~3)；(3) blending epoxy is uniformly mixing to obtain to resin Composition E, the resin Composition E in 40~70 DEG C of reactor It is well mixed with the curing agent component A, the catalytic component B, prepares rapid shaping RTM epoxy-resin systems, described group The mass ratio for dividing E, component A and component B is 100:(17~22):(3~6).
- 2. rapid shaping tough epoxy resin system preparation method according to claim 1, it is characterised in that：The high activity is more First amine hardener is ethylenediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, TEPA, polyethylene polyamine, divinyl One or more of combinations of base propylamine, diethylamine, triethylamine.
- 3. rapid shaping tough epoxy resin system preparation method according to claim 1, it is characterised in that：The epoxy compound Thing is bisphenol A epoxide resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, n-butyl glycidyl ether, allyl glycidyl Glycerin ether, phenyl glycidyl ether, the one or more to isobutyl phenenyl glycidol ether, cresylglycidylether.
- 4. rapid shaping tough epoxy resin system preparation method according to claim 1, it is characterised in that：The medium activity Curing agent is Meng's alkane diamines, IPD, diamino-dicyclohexyl methane, 1,3~bis- aminomethyl cyclohexanes, N~ammonia second One or more of combinations of base piperazine, double (4~amino~3~methyl cyclohexyl) methane.
- 5. rapid shaping tough epoxy resin system preparation method according to claim 1, it is characterised in that：The anion draws Hair agent is 4~dimethylamino naphthyridine, imidazole curing agent and its derivative, N, N~lupetazin, triethylamine, tripropyl amine (TPA), 2, One or more of combinations of 4,6~tri- (dimethylamino methyl) phenol, triethylene diamine.
- 6. rapid shaping tough epoxy resin system preparation method according to claim 1, it is characterised in that：The chain-transferring agent For glycerine, propane diols, ethylene glycol, butanediol, phenmethylol, diethylene glycol (DEG), phenol, ethyl -phenol, ethyl mercaptan, small carboxylic acid molecules' class The one or more of compound.
- 7. rapid shaping tough epoxy resin system preparation method according to claim 1, it is characterised in that：It is described hybrid epoxidized Resin matrix is bisphenol A epoxide resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, cycloaliphatic epoxy resin, liquified phenol Two kinds of formaldehyde epoxy resin and the combination of the above.
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| CN201710776767.7A CN107501863A (en) | 2017-09-01 | 2017-09-01 | A kind of rapid shaping toughened resin system preparation method |
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| CN201710776767.7A CN107501863A (en) | 2017-09-01 | 2017-09-01 | A kind of rapid shaping toughened resin system preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171284A (en) * | 2020-01-07 | 2020-05-19 | 南宁珀源能源材料有限公司 | Epoxy modified aliphatic amine curing agent and application thereof in silicon ingot cutting fixing glue |
| CN111718474A (en) * | 2020-08-04 | 2020-09-29 | 中国工程物理研究院激光聚变研究中心 | High-toughness high-modulus polymer and preparation method thereof |
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| CN102558502A (en) * | 2012-02-01 | 2012-07-11 | 大连理工大学 | Epoxy resin with adjustable thermal degradation temperature and preparation method thereof |
| CN103619901A (en) * | 2011-06-24 | 2014-03-05 | 陶氏环球技术有限责任公司 | Thermosetting composition and process for preparing fiber-reinforced composites |
| CN105764985A (en) * | 2013-12-05 | 2016-07-13 | 三键有限公司 | Heat-curable resin composition |
| CN106674900A (en) * | 2016-12-21 | 2017-05-17 | 芜湖天道绿色新材料有限公司 | Fiber-enhanced epoxy resin composition for quickly forming automobile part and preparation method thereof |
| CN107083025A (en) * | 2017-06-09 | 2017-08-22 | 北京化工大学 | A kind of preparation method of carbon fiber Automobile Part rapid shaping fire resistant resin system |
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2017
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|---|---|---|---|---|
| CN102153833A (en) * | 2010-09-20 | 2011-08-17 | 青岛科技大学 | Carbon fiber (powder)/epoxy resin composite material used for rapid prototyping die |
| CN103619901A (en) * | 2011-06-24 | 2014-03-05 | 陶氏环球技术有限责任公司 | Thermosetting composition and process for preparing fiber-reinforced composites |
| CN102558502A (en) * | 2012-02-01 | 2012-07-11 | 大连理工大学 | Epoxy resin with adjustable thermal degradation temperature and preparation method thereof |
| CN105764985A (en) * | 2013-12-05 | 2016-07-13 | 三键有限公司 | Heat-curable resin composition |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171284A (en) * | 2020-01-07 | 2020-05-19 | 南宁珀源能源材料有限公司 | Epoxy modified aliphatic amine curing agent and application thereof in silicon ingot cutting fixing glue |
| CN111718474A (en) * | 2020-08-04 | 2020-09-29 | 中国工程物理研究院激光聚变研究中心 | High-toughness high-modulus polymer and preparation method thereof |
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Application publication date: 20171222 |