CN104388028A - High temperature resistant tough epoxy resin binder - Google Patents
High temperature resistant tough epoxy resin binder Download PDFInfo
- Publication number
- CN104388028A CN104388028A CN201410720235.8A CN201410720235A CN104388028A CN 104388028 A CN104388028 A CN 104388028A CN 201410720235 A CN201410720235 A CN 201410720235A CN 104388028 A CN104388028 A CN 104388028A
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- CN
- China
- Prior art keywords
- epoxy resin
- parts
- temperature
- high temperature
- resin binder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 49
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 49
- 239000011230 binding agent Substances 0.000 title abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 17
- 239000007822 coupling agent Substances 0.000 claims abstract description 10
- 229920001971 elastomer Polymers 0.000 claims abstract description 10
- 239000005060 rubber Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 8
- 150000004982 aromatic amines Chemical class 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical group CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005062 Polybutadiene Substances 0.000 claims description 4
- 229920002857 polybutadiene Polymers 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 6
- 239000004926 polymethyl methacrylate Substances 0.000 description 6
- 238000010008 shearing Methods 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- -1 alicyclic amine Chemical class 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000002419 bulk glass Substances 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
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- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a high temperature resistant tough epoxy resin binder. The high temperature resistant tough epoxy resin binder is prepared from 100 parts of epoxy resin, 20-60 parts of curing agent, 20-30 parts of shell-core rubber particles, 1-3 parts of coupling agent. The high temperature resistant tough epoxy resin binder has good high temperature resistance, and high shear strength, as well as certain impact toughness at normal temperature.
Description
Technical field
The present invention relates to epoxy resin binder technical field, particularly a kind of have the high epoxy resin binder of bond strength under normal temperature toughness, high temperature.
Background technology
Epoxy resin binder has excellent mechanical property, thermostability and corrosion resistance, and shortcoming is that toughness is poor.Along with the development of industrial technology, there are larger potential demand in all departments, especially in fields such as electronics embedding, space flight, boats and ships, automobile makings to toughness high-temperature-resistant epoxy resin tackiness agent.Usually require the high temperature of epoxy adhesive ability more than 200 DEG C, certain tough will be had simultaneously.
Though conventional bisphenol A type epoxy resin, bisphenol-s epoxy resin etc. have certain thermotolerance, but still can not meet some field high temperature resistant demand.And the fragility of epoxy resin is comparatively large, usually need toughness reinforcing rear use.The method the most frequently used to epoxy resin roughening adopts liquid nbr carboxyl terminal, and amino terminated butadiene acrylonitrile rubber etc. come epoxy resin toughened.But the partially compatible of liquid acrylonitrile butadiene rubber and epoxy resin can cause epoxy resin bulk glass transition temperature to decline, while toughness strengthens, the thermotolerance of epoxy resin also can decline, thus reduces the toughness reinforcing meaning of epoxy resin.
Document (Liu Lian and etc., Chinese patent discloses 201310674779) report a kind of high-temperature-resistant epoxy resin tackiness agent, by bisphenol A type epoxy resin, bisphenol f type epoxy resin, N, N-4, after the mixing of 4 '-ditane type bimaleimide resin, then by aliphatic amide or 4, one or more of 4 '-diaminodiphenylmethane are mixing cured.The performance data of its test not mentioned in document.
Document (magnifies brave etc., Chinese patent discloses 201310092792.5) report a kind of inorganic organic nano particle compound modification of epoxy resin tackiness agent, this linking agent has certain high temperature resistant bond strength, 250 DEG C of down cut intensity have 4 ~ 5MPa, its component is that every 70 ~ 80 parts of epoxy resin comprise 1 ~ 10 part of inorganic nano-particle and 1 ~ 10 part of organic nano particle, its claims epoxy resin refers to bisphenol A epoxide resin, novolac epoxy, bisphenol-s epoxy resin, 4, 5-oxepane-1, 2-dioctyl phthalate 2-glycidyl ester and 4, 4 '-diaminodiphenylmethane epoxy resin etc., several epoxy resin is all bifunctional based epoxy resin above, resistance to elevated temperatures has limitation, and last a kind of 4, ehter bond is not had in the middle of 4 '-diaminodiphenylmethane epoxy resin, toughness will be short of to some extent.Its solidifying agent is general one or more of aromatic amine, fatty amine and cycloaliphatic amines of being described as then.Fatty amine and alicyclic amine make solidifying agent, have larger negatively influencing to thermotolerance.
Summary of the invention
The object of this invention is to provide a kind of toughness high-temperature-resistant epoxy resin tackiness agent.This epoxy resin binder is made up of following component: epoxy resin 100 parts, 20 ~ 60 parts, solidifying agent, shell core rubber particles 20 ~ 30 parts, coupling agent 1 ~ 3 part.
Epoxy resin in the present invention adopts four glycidyl group-4,4 '-diaminodiphenyl oxide, four glycidyl group-3, one or both mixtures in 4 '-diaminodiphenyl oxide, this based epoxy resin has 4 functional groups, and cross-linking density is large, rigidity is strong, do not need inorganic nano-filler secondary to strengthen, connect two aromatic rings by ehter bond in this epoxy molecule structure, certain toughness can be provided.Epoxy resin kind in tackiness agent in document (magnify brave etc., Chinese patent discloses 201310092792.5) is different from the epoxy resin in the present invention, needs inorganic nano-filler to strengthen further.
Solidifying agent in the present invention is for be mixed by 20 ~ 40 parts of aromatic amines and 0 ~ 20 part of fatty amine, and wherein aromatic amine is diethyl toluene diamine or 3, and 3 '-two chloro-4,4 '-diaminodiphenylmethane or mixture.
Shell core rubber particles in the present invention is nano level polymethylmethacrylate (housing)-polyhutadiene (nucleome) particle or polymethylmethacrylate (housing)-polybutadiene styrene (nucleome) particle or its mixture.Shell core rubber particles content is higher, and higher than the organic nanometer granule content in the document claims such as (magnify brave, Chinese patent discloses 201310092792.5), therefore invention adhesives possesses good toughness.
Coupling agent in the present invention is γ-glycidyl ether oxygen propyl trimethoxy silicane.
The preparation method of this toughness high-temperature-resistant epoxy resin tackiness agent is: epoxy resin, shell core rubber particles and coupling agent are mixed by proportioning, on shredder, grinding makes main gel component 2 times, again main gel component and solidifying agent are mixed in proportion, under normal pressure, 130 DEG C of solidifications 4h or 150 DEG C of solidification 2h.What record at 200 DEG C is 12 ~ 15MPa with steel shearing resistance, and what record at 250 DEG C is 8 ~ 10MPa with steel shearing resistance, and the impact strength recorded at 23 DEG C is 25kJ/m
2.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated: in a kind of toughness high-temperature-resistant epoxy resin tackiness agent, containing epoxy resin 100 parts, 20 ~ 60 parts, solidifying agent, shell core rubber particles 20 ~ 30 parts, coupling agent 1 ~ 3 part.Its epoxy resin is one or both mixtures in four glycidyl group-4,4 '-diaminodiphenyl oxide, four glycidyl group-3,4 '-diaminodiphenyl oxide; Solidifying agent is for be mixed by 20 ~ 40 parts of aromatic amines and 0 ~ 20 part of fatty amine, and wherein aromatic amine is diethyl toluene diamine, 3, and 3 '-two chloro-4, the one of 4 '-diaminodiphenylmethane or its mixture; Shell core rubber particles is one or its mixture of nano level polymethylmethacrylate (housing)-polyhutadiene (nucleome) particle or polymethylmethacrylate (housing)-polybutadiene styrene (nucleome) particle; Coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane.
Example 1 (by weight): four glycidyl group-4,4 '-diaminodiphenyl oxide 100 parts, diethyl toluene diamine 35 parts, polymethylmethacrylate (housing)-20 parts, polyhutadiene (nucleome) particle, coupling agent 2 parts.By preparation method's preparation, obtain product.
Recording performance is: what record at 200 DEG C is 14.5MPa with steel shearing resistance, and what record at 250 DEG C is 8.8MPa with steel shearing resistance, and the impact strength recorded at 23 DEG C is 25kJ/m
2.
Example 2 (by weight): four glycidyl group-4,4 '-diaminodiphenyl oxide 100 parts, 3,3 '-two chloro-4,4 '-diaminodiphenylmethane 50 parts, triethylene tetramine 5 parts, polymethylmethacrylate (housing)-25 parts, polybutadiene styrene (nucleome) particle, coupling agent 2 parts.By preparation method's preparation, obtain product.Recording performance is: what record at 200 DEG C is 13.5MPa with steel shearing resistance, and what record at 250 DEG C is 8.2MPa with steel shearing resistance, and the impact strength recorded at 23 DEG C is 28kJ/m
2.
Claims (4)
1. a toughness high-temperature-resistant epoxy resin tackiness agent, is characterized in that: the composition formed by weight, and its component composition comprises:
Epoxy resin 100 parts
20 ~ 60 parts, solidifying agent
Shell core rubber particles 20 ~ 30 parts
Coupling agent 1 ~ 3 part
Its epoxy resin is one or both mixtures in four glycidyl group-4,4 '-diaminodiphenyl oxide, four glycidyl group-3,4 '-diaminodiphenyl oxide.
2. toughness high-temperature-resistant epoxy resin tackiness agent according to claim 1, it is characterized in that: solidifying agent is for be mixed by 20 ~ 40 parts of aromatic amines and 0 ~ 20 part of fatty amine, wherein aromatic amine is diethyl toluene diamine or 3,3 '-two chloro-4,4 '-diaminodiphenylmethane or its mixture.
3. toughness high-temperature-resistant epoxy resin tackiness agent according to claim 1, is characterized in that: its mesochite core rubber particles is nano level polymethylmethacrylate-polyhutadiene particle or polymethylmethacrylate-polybutadiene styrene particle or its mixture.
4. toughness high-temperature-resistant epoxy resin tackiness agent according to claim 1, is characterized in that: wherein coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane.
Priority Applications (1)
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CN201410720235.8A CN104388028A (en) | 2014-12-01 | 2014-12-01 | High temperature resistant tough epoxy resin binder |
Applications Claiming Priority (1)
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CN201410720235.8A CN104388028A (en) | 2014-12-01 | 2014-12-01 | High temperature resistant tough epoxy resin binder |
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CN104388028A true CN104388028A (en) | 2015-03-04 |
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CN201410720235.8A Pending CN104388028A (en) | 2014-12-01 | 2014-12-01 | High temperature resistant tough epoxy resin binder |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108977147A (en) * | 2018-06-29 | 2018-12-11 | 安徽尼古拉电子科技有限公司 | A kind of anti-aging epoxy resin-matrix packaging plastic and preparation method thereof |
CN109054709A (en) * | 2018-06-29 | 2018-12-21 | 安徽尼古拉电子科技有限公司 | A kind of microelectronic product corrosion-resistant packaging plastic and preparation method thereof |
CN112500820A (en) * | 2020-12-17 | 2021-03-16 | 陕西华达科技股份有限公司 | Novel high-temperature-resistant epoxy resin adhesive and preparation method and use method thereof |
CN116200156A (en) * | 2023-03-16 | 2023-06-02 | 北京智慧能源研究院 | Epoxy resin/metal insert epoxy composition interface adhesive and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030125423A1 (en) * | 2001-11-08 | 2003-07-03 | 3M Innovative Properties Company | High temperature epoxy adhesive films |
CN101547990A (en) * | 2006-10-06 | 2009-09-30 | 汉高股份及两合公司 | Pumpable epoxy paste adhesives resistant to wash-off |
CN103201102A (en) * | 2010-11-08 | 2013-07-10 | 东丽株式会社 | Epoxy resin composition for fiber reinforced composite material, prepreg, and fiber reinforced composite material |
CN103436212A (en) * | 2013-09-05 | 2013-12-11 | 中国电子科技集团公司第二十八研究所 | Room-temperature-curing structural adhesive for composite plates |
-
2014
- 2014-12-01 CN CN201410720235.8A patent/CN104388028A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030125423A1 (en) * | 2001-11-08 | 2003-07-03 | 3M Innovative Properties Company | High temperature epoxy adhesive films |
CN101547990A (en) * | 2006-10-06 | 2009-09-30 | 汉高股份及两合公司 | Pumpable epoxy paste adhesives resistant to wash-off |
CN103201102A (en) * | 2010-11-08 | 2013-07-10 | 东丽株式会社 | Epoxy resin composition for fiber reinforced composite material, prepreg, and fiber reinforced composite material |
CN103436212A (en) * | 2013-09-05 | 2013-12-11 | 中国电子科技集团公司第二十八研究所 | Room-temperature-curing structural adhesive for composite plates |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108977147A (en) * | 2018-06-29 | 2018-12-11 | 安徽尼古拉电子科技有限公司 | A kind of anti-aging epoxy resin-matrix packaging plastic and preparation method thereof |
CN109054709A (en) * | 2018-06-29 | 2018-12-21 | 安徽尼古拉电子科技有限公司 | A kind of microelectronic product corrosion-resistant packaging plastic and preparation method thereof |
CN112500820A (en) * | 2020-12-17 | 2021-03-16 | 陕西华达科技股份有限公司 | Novel high-temperature-resistant epoxy resin adhesive and preparation method and use method thereof |
CN116200156A (en) * | 2023-03-16 | 2023-06-02 | 北京智慧能源研究院 | Epoxy resin/metal insert epoxy composition interface adhesive and preparation method thereof |
CN116200156B (en) * | 2023-03-16 | 2023-10-24 | 北京智慧能源研究院 | Epoxy resin/metal insert epoxy composition interface adhesive and preparation method thereof |
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Application publication date: 20150304 |