CN108148353A - A kind of composition epoxy resin - Google Patents
A kind of composition epoxy resin Download PDFInfo
- Publication number
- CN108148353A CN108148353A CN201711442358.XA CN201711442358A CN108148353A CN 108148353 A CN108148353 A CN 108148353A CN 201711442358 A CN201711442358 A CN 201711442358A CN 108148353 A CN108148353 A CN 108148353A
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- epoxy resin
- molecular weight
- anhydride
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
-
- 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
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention provides a kind of composition epoxy resin, and it is 100 that the composition epoxy resin, which includes weight ratio,：80~130：0.5~90 epoxy resin component, curing agent component and additive component.Wherein described epoxy resin component includes one or more epoxy resin that molecular weight is 100~10000.The additive component includes：With 0.1~3 part of antifoaming agent of weight ratio meter, 0.1 2 parts of coupling agents, 0.1~5 part of wetting agent and 5~100 parts of toughener.The curing agent component includes：With 100 parts of acid anhydride type curing agents of weight ratio meter and 0.5~30 part of accelerating agent.The advantages of composition epoxy resin provided by the invention is to possess excellent toughness, intensity and heat resistance.
Description
Technical field
The present invention relates to field of compound material, in particular to a kind of composition epoxy resin.
Background technology
Carrier of the pipeline as transmission, can convey liquid, gas etc..It is mainly widely used at present and is for metallic conduit
It is main, if steel, aluminium or alloying metal are as the main material for making pipeline.
In fiber winding pipe is used, the matrix used resin of winding layer composite material is thermosetting property or thermoplastic resin
Deng, such as epoxy resin, modified epoxy etc., main function binding material, play connection fiber, the work for transmitting stress
With.Its epoxy resin refers to the organic high molecular compound for containing two or more epoxy groups in molecule, adds in
After curing agent, cross-linking reaction can be generated and form insoluble, the insoluble polymer with the netted stereochemical structure of three-dimensional, therefore
Excellent physical mechanical property and chemical property are shown, and then epoxy resin is widely used in the base of winding layer composite material
Body resin.
In fiber winding pipe is used, the fibrous material of winding layer is divided into glass fibre, carbon fiber etc., wherein carbon fiber
The second generation high-performance composite materials after glass fibre, have density is small, light weight, intensity are high, corrosion-resistant, endurance,
The advantages such as coefficient of thermal expansion is low, gradually as the preferred fibrous material of winding pipeline.
Pipeline conveys the liquid or gas of high temperature according to the liquid of conveying, the characteristic of gas, some need, and some need is defeated
The gas with pressure is sent, some need conveying has liquid or gas of high moderate pressure etc. simultaneously, therefore pipeline is with bright
The attributes such as aobvious diameter, wall thickness, length.Using the pipeline of composite material, the continuity, again of metallic conduit can be solved
The disadvantages such as amount, toughness deficiency.
Invention content
For problems of the prior art, the present invention provides a kind of composition epoxy resin, is twined applied to fiber
Around pipeline.
The present invention provides a kind of composition epoxy resin, including：Weight ratio is 100：(80~130)：The ring of (0.5~90)
Oxygen resin components, curing agent component and additive component.It is 100~10000 that the epoxy resin component, which includes molecular weight,
One or more epoxy resin, when building form selection forms mixture by a variety of epoxy resin, mutual combination ratio
Example is not limited, it is only necessary to which each epoxy resin meets molecular weight requirement and total weight meets above-mentioned weight ratio requirement.
The curing agent component includes：With weight ratio meter, 100 parts of acid anhydride type curing agents, 0.5~30 part of accelerating agent；The additive group
Part includes：With weight ratio meter, 0.1~3 part of antifoaming agent：0.1-2 parts of coupling agents：0.1~5 part of wetting agent：5~100 parts of toughener.
In some embodiments, the molecular weight of the epoxy resin component is 100~10000.The epoxy resin ingredient
Include bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, novolac epoxy resin, alicyclic shrink
It is one or more mixed in glycerin ether epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin etc.
Close object.
Wherein preferably, the epoxy resin component includes the epoxy resin that molecular weight is 150-220, molecular weight 300-
Epoxy resin of 450 epoxy resin and molecular weight for 6000-10000, three of the above epoxy resin mass ratio in mixing
Meet (10~80)：(10~80)：(10~80), it is further preferred that the ring that it is 200 that the epoxy resin ingredient, which is molecular weight,
The mixture that oxygen resin, the epoxy resin that molecular weight is 400 and molecular weight are formed by 8000 epoxy resin.Because point
Son amount is 200 or so epoxy resin, has relatively low viscosity, higher heat resistance, poor toughness, molecular weight 400
The epoxy resin of left and right has medium viscosity, and medium heat resistance, medium toughness, molecular weight is 8000 or so ring
Oxygen resin has larger viscosity, medium heat resistance, higher toughness, therefore selects above three molecular weight segment
Epoxy resin formed mixture can obtain most suitable viscosity, heat-resisting and toughness.In epoxy resin component, above-mentioned three kinds
Epoxy resin weight ratio, molecular weight be 200 epoxy resin：Molecular weight is 400 epoxy resin：Molecular weight is 8000
The weight ratio of epoxy resin is：(10~80)：(10~80)：(10~80), wherein preferred weight ratio is (20~60)：(20
~80)：(20~60), wherein most preferred weight ratio is:(40-50)：(40~60)：(20~40).
The acid anhydride type curing agent includes：Methylnadic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, six
Hydrogen phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydro phthalic anhydride, methyl hexahydrophthalic anhydride, trimellitic anhydride, fat
It is one or more in race's acid anhydrides, fatty polyanhydride, when selection by it is a variety of form mixture when, the weight ratio between each component does not have
It is restricted, it is only necessary to which that the weight of whole mixt is met the requirements.The accelerating agent includes：Tertiary amine, boron class, imidazoles promote
One or more or described accelerating agents in agent include：2-ethyl-4-methylimidazole, 2-methylimidazole, 1- benzyl -2- methyl
It is one or more in imidazoles, when selection by it is a variety of forms mixture when, there is no limit only need for weight ratio between each component
The weight of whole mixt is wanted to meet the requirements.The weight ratio of anhydride curing agent and accelerating agent is 100 in curing agent component：
(0.5~30).Since the promotion principle and effect of the type of accelerating agent are different, the amount for using accelerating agent is also incomplete
Unanimously.The weight ratio of wherein preferred curing agent and accelerating agent is 100：(5~20), most preferred weight ratio are 100：(8~
15)。
The antifoaming agent includes：N-butyl alcohol, 1- octanols, tributyl phosphate, emulsification methyl-silicone oil, emulsification polymethylphenyl siloxane fluid,
One or more in organic phosphate or including：In low molecular weight alcohols, phosphoric acid ester, silicone emulsion class, compound class
It is one or more.When selection by it is a variety of forms mixture when, weight ratio between each component there is no limit, it is only necessary to it is whole to mix
The weight for closing object is met the requirements
The coupling agent includes：One or more mixtures in alicyclic acid chlorination chromium class, silanes, titanate ester,
Or including：In anilino- methylene triethoxysilane, propyl-triethoxysilicane, diethylenetriamine base triethoxy methyl silicane
It is one or more.When selection by it is a variety of forms mixture when, weight ratio between each component there is no limit, it is only necessary to integrally
The weight of mixture is met the requirements
The wetting agent includes：The polyamino and macromolecule acid esters of long-chain, high molecular weight poly-unsaturated acid ester, long-chain amine with
It is one or more in the salt of polycarboxylic acids, low molecular weight basic polyamide, anionic surfactant.When selection is by a variety of shapes
During resulting mixture, there is no limit for the weight ratio between each component, it is only necessary to which the weight of whole mixt is met the requirements
The toughener is liquid nbr carboxyl terminal, nbr carboxyl terminal, core shell rubbers, polyurethane rubber, different
In cyanate modified epoxy, dimer acid modified epoxy resin, phenoxy resin, polyethylene glycol, polypropylene glycol, polytetramethylene glycol etc.
It is one or more.When selection by it is a variety of forms mixture when, weight ratio between each component there is no limit, it is only necessary to integrally
The weight of mixture is met the requirements
In the additive component, preferred toughener composition is the toughener of core shell rubbers type.Wherein nucleocapsid
Rubber type can include the core by the core shell rubbers of polyvinyl chloride-type, the core shell rubbers of polymethyl acid type and acrylic type
It is one or more in shell rubber etc..Preferred performance in order to obtain, thus the grain size of core shell rubbers for less than 500 nanometers more
Favorably, better 300 nanometers hereinafter, most preferably less than 100 nanometers.When the grain size of core shell rubbers is 500 nanometers or more, toughening
Effect is bad.
In additive component, with weight ratio meter, 0.1~3 antifoaming agent：0.1~2 coupling agent：0.1~5 wetting agent：5~
100 toughener.Wherein most preferred weight ratio meter, 0.5~2 antifoaming agent：0.5~1 coupling agent：0.5~3 wetting agent：15~80
Toughener.
Summary, in whole system, epoxy resin component, curing agent component, additive component preferred weight ratio
It is 100：(80~130)：(0.5~90), preferred weight ratio are 100：(90~115)：(10~80), most preferred weight ratio
It is 100：(100~110)：(50~80).
Present invention has the advantage that：
It is excellent tough that the advantages of present invention provides a kind of composition epoxy resin, the composition epoxy resin is that it possesses
Property, intensity and high temperature resistance, there is excellent binding performance with fiber.
Specific embodiment
Purpose, technical scheme and advantage to make the embodiment of the present invention are clearer, below in conjunction with the embodiment of the present invention,
Technical solution in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is the one of the present invention
Section Example, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not doing
Go out all other embodiments obtained under the premise of creative work, shall fall within the protection scope of the present invention.
The present invention provides a kind of composition epoxy resins, are 100 comprising weight ratio：(80~130)：(0.5~90)
Epoxy resin component (A), curing agent component (B) and additive component (C).
Epoxy resin component (A) includes：With weight ratio meter, epoxy resin that 10~80 parts of molecular weight are 200,10~80 parts
Molecular weight be 400 epoxy resin, 10~80 parts of molecular weight be 8000 epoxy resin.Contain in epoxy resin component (A)
Each epoxy resin can be monofunctional epoxy resin or polyfunctional epoxy resin or more benzene ring structures epoxy resin or on
State the mixture of three kinds of epoxy resin.
Curing agent component (B) includes：Anhydride curing agent and accelerating agent, with weight ratio meter 100：0.5~30.It is wherein preferred
Anhydride curing agent is methylnadic anhydride or the mixture with other acid anhydrides, and preferred accelerating agent is 2- ethyl -4- methyl miaows
Azoles or the mixture with other accelerating agents.
Additive component (C) includes：Antifoaming agent, coupling agent, wetting agent and toughener.With weight ratio meter, 0.1~3 defoaming
Agent：0.1~2 coupling agent：0.1~5 wetting agent：5~100 toughener.
It carries out following three groups of embodiments to be implemented, and three groups of comparative examples is coordinated to be compared, each embodiment and comparative example
Composition design it is as shown in table 1, the Contrast on effect of the composition epoxy resin of preparation is as shown in table 2.
Table 1:Each embodiment and comparative example composition design table
Table 2:The Contrast on effect table of each embodiment and comparative example
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Tensile strength/MPa | 71.6 | 70.6 | 75.3 | 68.9 | 74.5 | 73.9 |
| Stretch modulus/MPa | 2780 | 2710 | 2876 | 2885 | 2760 | 2840 |
| Elongation at break/% | 3.0 | 2.7 | 3.5 | 3.0 | 2.1 | 2.2 |
| Tg/℃ | 194 | 197 | 218 | 165 | 173 | 202 |
It can be seen that by above-mentioned table 1, table 2：
1. the comparison of embodiment 3 and comparative example 1 has used the epoxy resin of 200 molecular weight and 200 molecular weight is not used
Epoxy resin, the performance that elongation at break improves 17%, Tg can improve 32%；
2. the comparison of embodiment 1 and comparative example 2 has used the epoxy resin of 8000 molecular weight and has increased in curing agent component
Accelerating agent number, the performance of Tg improves 12%, and elongation at break improves 43%；
3. in the epoxy resin for having used 400 molecular weight and 400 molecular weight are not used in the comparison of embodiment 3 and comparative example 3
Epoxy resin, wherein comparative example 3 epoxy resin component (A)：Curing agent component (B)：The weight ratio of additive component (C) is
70：103：1.3, Tg performance can improve 8%, and elongation at break improves 59%；
4. the comparison of embodiment 2 and comparative example 2 increases the epoxy resin of 8000 molecular weight and increases part of accelerating agent
Number, the performance of Tg improve 14%, and elongation at break improves 29%.
Epoxy resin, 400 molecules of 200 molecular weight are preferably used in the present invention simultaneously in epoxy resin component (A)
The epoxy resin of the epoxy resin of amount and 8000 molecular weight, for three kinds of epoxy resin with weight ratio meter, 40~50 one's share of expenses for a joint undertaking amounts are 200
Epoxy resin, the epoxy resin that 40~60 parts of molecular weight are 400, the epoxy resin that 20~40 parts of molecular weight are 8000.Curing agent
Anhydride curing agent ingredient and accelerating agent ingredient are used in component (B), with weight ratio meter：100 parts of anhydride curing agents：8~15 parts
Accelerating agent.And antifoaming agent, coupling agent, wetting agent, toughener ingredient are used in additive (C) component.With weight ratio meter,
0.1~3 antifoaming agent：0.1~2 coupling agent：0.1~5 wetting agent：5~100 toughener.Three components in whole system are with weight
Amount is than meter, 100 parts of epoxy resin components (A), 80~130 parts of curing agent components (B), and 0.5~90 part of additive component (C) can be with
Heat resistance is also improved while toughness is promoted.
It these are only the preferred embodiment of the present invention, be not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.Any modification for all within the spirits and principles of the present invention, being made,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of composition epoxy resin, which is characterized in that it is 100 that the composition epoxy resin, which includes weight ratio,：80~
130：0.5~90 epoxy resin component, curing agent component and additive component.
2. composition epoxy resin according to claim 1, which is characterized in that the epoxy resin component includes molecular weight
For 100~10000 one or more epoxy resin.
3. composition epoxy resin according to claim 2, which is characterized in that the epoxy resin ingredient includes bis-phenol
A types epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, novolac epoxy resin, cycloaliphatc glycidyl ether ring oxygen
It is one or more in resin, glycidyl ester type epoxy resin and glycidyl amine type epoxy resin.
4. composition epoxy resin according to claim 2, which is characterized in that the epoxy resin component includes molecular weight
The epoxy resin that the epoxy resin and molecular weight that epoxy resin, molecular weight for 150-220 are 300-450 are 6000-10000,
The epoxy that the epoxy resin and molecular weight that epoxy resin that molecular weight is 150-220, molecular weight are 300-450 are 6000-10000
The weight ratio of resin is (10~80)：(10~80)：(10~80).
5. composition epoxy resin according to claim 4, which is characterized in that the epoxy resin component includes molecular weight
The epoxy resin that the epoxy resin and molecular weight that epoxy resin, molecular weight for 200 are 400 are 8000, the molecular weight are 200
Epoxy resin, molecular weight be 400 epoxy resin and molecular weight be 8000 the weight ratio of epoxy resin be (20~60)：
(20~80)：(20~60).
6. composition epoxy resin according to claim 1, which is characterized in that the curing agent component includes：With weight
Than 100 parts of acid anhydride type curing agents of meter and 0.5~30 part of accelerating agent.
7. composition epoxy resin according to claim 6, which is characterized in that the acid anhydride type curing agent includes：Methyl
Carbic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,
It is one or more in methyl tetrahydro phthalic anhydride, methyl hexahydrophthalic anhydride, trimellitic anhydride, aliphatic anhydride and fatty polyanhydride；
The accelerating agent includes：One or more or described accelerating agents in tertiary amine, boron class and imidazoles accelerating agent include：
It is one or more in 2-ethyl-4-methylimidazole, 2-methylimidazole and 1 benzyl 2 methyl imidazole.
8. composition epoxy resin according to claim 1, which is characterized in that the additive component includes：With weight
Than counting 0.1~3 part of antifoaming agent, 0.1-2 parts of coupling agents, 0.1~5 part of wetting agent and 5~100 parts of toughener.
9. composition epoxy resin according to claim 8, which is characterized in that the antifoaming agent includes：N-butyl alcohol, 1- are pungent
Alcohol, tributyl phosphate, emulsification methyl-silicone oil, emulsification polymethylphenyl siloxane fluid and organic phosphate in it is one or more or including：
It is one or more in low molecular weight alcohols, phosphoric acid ester, silicone emulsion class and compound class；
The coupling agent includes：One or more mixtures or packet in alicyclic acid chlorination chromium class, silanes, titanate ester
It includes：In anilino- methylene triethoxysilane, propyl-triethoxysilicane and diethylenetriamine base triethoxy methyl silicane
It is one or more；
The wetting agent includes：The polyamino and macromolecule acid esters of long-chain, high molecular weight poly-unsaturated acid ester, long-chain amine and poly- carboxylic
It is one or more in the salt of acid, low molecular weight basic polyamide and anionic surfactant；
The toughener is liquid nbr carboxyl terminal, nbr carboxyl terminal, core shell rubbers, polyurethane rubber, isocyanic acid
Ester modified epoxy resin, dimer acid modified epoxy resin, phenoxy resin, polyethylene glycol, polypropylene glycol and polytetramethylene glycol one
Kind is a variety of.
10. according to the composition epoxy resin described in any one in claim 1-9, which is characterized in that the epoxy resin
Applied to fiber winding pipe.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711442358.XA CN108148353A (en) | 2017-12-27 | 2017-12-27 | A kind of composition epoxy resin |
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| CN201711442358.XA CN108148353A (en) | 2017-12-27 | 2017-12-27 | A kind of composition epoxy resin |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109809740A (en) * | 2019-01-26 | 2019-05-28 | 汉江弘源襄阳碳化硅特种陶瓷有限责任公司 | A kind of alkaline-resisting high temperature resistant thermosetting resin and its application |
| CN112778705A (en) * | 2020-12-31 | 2021-05-11 | 惠柏新材料科技（上海）股份有限公司 | Epoxy resin composition and preparation method and application thereof |
| CN113817289A (en) * | 2021-09-28 | 2021-12-21 | 江苏泰特尔新材料科技股份有限公司 | High-toughness transparent alicyclic epoxy resin composition |
| CN113897027A (en) * | 2021-09-28 | 2022-01-07 | 江苏泰特尔新材料科技股份有限公司 | High-toughness and high-heat-resistance alicyclic epoxy resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040802A (en) * | 2010-10-14 | 2011-05-04 | 天津联美化学工业有限公司 | Epoxy resin system and application thereof |
| CN104559062A (en) * | 2015-01-09 | 2015-04-29 | 江苏恒神纤维材料有限公司 | Thermosetting resin and preparation method thereof |
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2017
- 2017-12-27 CN CN201711442358.XA patent/CN108148353A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040802A (en) * | 2010-10-14 | 2011-05-04 | 天津联美化学工业有限公司 | Epoxy resin system and application thereof |
| CN104559062A (en) * | 2015-01-09 | 2015-04-29 | 江苏恒神纤维材料有限公司 | Thermosetting resin and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109809740A (en) * | 2019-01-26 | 2019-05-28 | 汉江弘源襄阳碳化硅特种陶瓷有限责任公司 | A kind of alkaline-resisting high temperature resistant thermosetting resin and its application |
| CN112778705A (en) * | 2020-12-31 | 2021-05-11 | 惠柏新材料科技（上海）股份有限公司 | Epoxy resin composition and preparation method and application thereof |
| CN113817289A (en) * | 2021-09-28 | 2021-12-21 | 江苏泰特尔新材料科技股份有限公司 | High-toughness transparent alicyclic epoxy resin composition |
| CN113897027A (en) * | 2021-09-28 | 2022-01-07 | 江苏泰特尔新材料科技股份有限公司 | High-toughness and high-heat-resistance alicyclic epoxy resin and preparation method thereof |
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