CN106833464A - A kind of epoxy adhesive and its glass fiber reinforced plastics product being used under 196 DEG C of environment - Google Patents
A kind of epoxy adhesive and its glass fiber reinforced plastics product being used under 196 DEG C of environment Download PDFInfo
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- CN106833464A CN106833464A CN201611226932.3A CN201611226932A CN106833464A CN 106833464 A CN106833464 A CN 106833464A CN 201611226932 A CN201611226932 A CN 201611226932A CN 106833464 A CN106833464 A CN 106833464A
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- epoxy
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- epoxy adhesive
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on 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
- 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
-
- 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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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The present invention relates to adhesive preparing technical field, specially a kind of epoxy adhesive and its glass fiber reinforced plastics product being used under 196 DEG C of environment.The epoxy adhesive includes the raw material of following weight portion：100 parts of epoxy resin, 10~70 parts of phenolic resin, 1~5 part of coupling agent, 1~20 part of epoxide diluent.Described epoxy resin refers to the material containing two or more epoxy-functionals, is any one or a few the mixing in bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol aldehyde type epoxy resin, polyfunctional epoxy resin.Using epoxy adhesive of the present invention in normal temperature（25℃）Good mechanical property is respectively provided with during with 196 DEG C, obtained glass-reinforced plastic material also has good mechanical property.
Description
Technical field
The present invention relates to adhesive preparing technical field, specially a kind of epoxy adhesive under -196 DEG C of environment and
Its glass fiber reinforced plastics product.
Background technology
Ultralow-temperatureepoxy epoxy adhesive is a class adhesive still under conditions of ultralow temperature with adhesive property, and its glass
Glass steel part can tolerate of short duration high temperature, can meet liquid nitrogen (- 196 DEG C), liquid oxygen (- 183 DEG C), liquefied natural gas LNG (-
162 DEG C) etc. storage and transport vaccum storage tank, the requirement and basin and pipeline of the low temperature resistant equipment to material mechanical performance such as pipeline
Of short duration high temperature in welding, evacuation process, can be as this kind of refrigerated storage tank, the structural support of pipeline, it is also possible to as
The basin tank body of these low temperature liquid materials.And conventional ultralow temperature adhesive, generally with polyurethane or epoxy resin modification
Material is formulated, and the adhesive for polyurethane of some low temperature performance wells can also be used.What for example Beijing Aviation university developed is ultralow
Warm adhesive, more than 18MPa, at 140 DEG C, its adhesion strength still reaches its adhesion strength in -269 DEG C of temperature ranges
20MPa.But, existing adhesive formulated component is more, although low temperature environment can have preferable bond effect, but its
Hardening time is more long, it is still desirable to continue to research and develop.
Adhesive involved in the present invention preferable bin stability at normal temperatures, solidification temperature is moderate, curing rate compared with
Hurry up, be adapted to the manufacture craft requirement of existing glass-reinforced plastic material.
Adhesive involved in the present invention by the requirement of glass-reinforced plastic material manufacture craft solidify after, its interlaminar shear strength-
More than 35MPa at 196 DEG C, the ultralow temperature gluing agent prescription beyond Beijing Aviation university connects by about one time.
The content of the invention
The purpose of the present invention is directed to above-mentioned technical problem, there is provided a kind of epoxy gluing that can be used under -196 DEG C of environment
Agent and its glass fiber reinforced plastics product.The epoxy adhesive is respectively provided with good mechanical property in normal temperature (25 DEG C) and -196 DEG C, made
The mechanical property of the glass-reinforced plastic material for obtaining can reach following table requirement.
To achieve these goals, concrete technical scheme of the invention is：
A kind of epoxy adhesive under -196 DEG C of environment, including following weight portion raw material：100 parts of epoxy resin,
10~70 parts of phenolic resin, 1~5 part of coupling agent, 1~20 part of epoxide diluent.
Described epoxy resin refers to the material containing two or more epoxy-functionals, is bisphenol type epoxy tree
Any one or a few mixing in fat, bisphenol f type epoxy resin, phenol aldehyde type epoxy resin, polyfunctional epoxy resin.
The epoxide number of described epoxy resin is 0.3~0.9.
In parts by weight, described phenolic resin contains 10~90 parts of acid catalysis phenolic resin, 10~90 parts of base catalysis
Phenolic resin.
Phenol in the phenolic resin is any one in phenol, cresols, hydroquinones, resorcinol and p-tert-butylphenol
Plant or several mixtures.
Aldehyde in the phenolic resin is any one or a few the mixture in formaldehyde, acetaldehyde and butyraldehyde.
Described coupling agent is silane coupler, is any one or a few the mixture in KH550 and KH560.
Described epoxide diluent is the material containing one or two epoxy-functional, is butyl glycidyl ether, second
Hexanediol diglycidyl ether, phenyl glycidyl ether, neopentylglycol diglycidyl ether, benzyl glycidyl ether and 1,6- oneself two
Any one or a few mixture in alcohol diglycidyl ether.
The epoxy adhesive is used to prepare glass-reinforced plastic material, and its form is glass fiber, fiberglass woven cloth or glass felt.With
Weight/mass percentage composition meter, resin proportion is 25%~60% in the glass-reinforced plastic material.
The positive effect of the present invention is：
(1), the epoxy adhesive is respectively provided with good mechanical property in normal temperature (25 DEG C) and -196 DEG C.
(2), the mechanical property of obtained glass-reinforced plastic material can reach following table requirement.
The performance indications requirement of tubular glass Steel material：
The performance indications requirement of plate glass Steel material：
Specific embodiment
In order that goal of the invention of the invention, technical scheme and advantage become more apparent, with reference to specific embodiment party
The present invention is described in further detail for formula, but this scope for being interpreted as above-mentioned theme of the invention should not be only limitted into following realities
Apply example.
Embodiment 1, prepares the epoxy adhesive under -196 DEG C of environment：
In parts by weight, urged by 80 parts of E-44 bisphenol A epoxide resins, 20 parts of AG80 polyfunctional epoxy resins, 30 parts of acid
Change phenol formaldehyde resin, 5 parts of base catalysis phenol formaldehyde resins, 3 parts of KH560 silane couplers, 10 parts of 1,6-HDs two to shrink
Resin that glycerin ether epoxide diluent is well mixed is uniform to be coated on and weave cotton cloth through the alkali-free glass fibre of dewaxing treatment,
Wherein resin content is 40wt%.The adhesive plaster is uniform compactly on core tire, through 110 DEG C of 2h, 130 DEG C of 1h, 150 DEG C of 2h
After solidification, normal temperature is naturally cooled to.The test of glass-reinforced plastic material sample is taken, above-mentioned performance indications requirement can be reached.
Embodiment 2, prepares the epoxy adhesive under -196 DEG C of environment：
In parts by weight, by 80 parts of E-44 bisphenol A epoxide resins, 10 parts of F-44 phenol aldehyde type epoxy resins, 10 parts of Bisphenol F rings
Oxygen tree fat, 30 parts of acid catalysis phenol formaldehyde resins, 5 parts of base catalysis phenol formaldehyde resins, 3 parts of KH560 silane couplers, 10 parts of benzyls
The resin that base diglycidyl ether epoxy diluent is well mixed uniformly is coated on through the alkali-free glass fibre of dewaxing treatment
On weaving cotton cloth, resin content is 38%.Upper adhesive plaster is uniform compactly on core tire, through 110 DEG C of 2h, 130 DEG C of 1h, 150 DEG C
After 1h solidifications, normal temperature is naturally cooled to.The test of glass-reinforced plastic material sample is taken, above-mentioned performance indications requirement can be reached.
Embodiment 3：
In parts by weight, by 80 parts of E-44 bisphenol A epoxide resins, 10 parts of F-44 phenol aldehyde type epoxy resins, 10 parts of Bisphenol F rings
Oxygen tree fat, 40 parts of base catalysis phenol formaldehyde resins, 3 parts of KH560 silane couplers, 10 parts of benzyl glycidyl ether epoxide diluents
Viscosity rises quickly well mixed resin at room temperature, and made upper adhesive plaster bin stability is very poor, hardens quickly,
It is not used to make glass-reinforced plastic material.
Embodiment 4：
In parts by weight, by 100 parts of E-44 bisphenol A epoxide resins, 80 parts of acid catalysis phenol formaldehyde resins, 3 parts of KH560 silicon
The resin that alkane coupling agent, 10 parts of benzyl glycidyl ether epoxide diluents are well mixed, is uniformly coated on through at dewaxing
On the alkali-free glass fibre of reason is weaved cotton cloth, wherein resin content is 40wt%.Uniform compactly on core tire, the warp by the adhesive plaster
110 DEG C of 2h, 130 DEG C of 1h, after 150 DEG C of 2h solidifications, naturally cool to normal temperature.Take the test of glass-reinforced plastic material sample, compressive strength, interlayer
Shear strength project can not reach above-mentioned performance indications requirement, and remaining project can reach above-mentioned performance indications requirement.
Embodiment 5：
Calculated with one 25 cubes of tank car basin, if filled as interlayer using pearlife, the weight of pearlife used
Amount uses the further glass-reinforced plastic material for preparing of epoxy adhesive of the present invention more than 2 tons, and its weight is only 16 public
Jin.It is obvious during mitigation in weight.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of epoxy adhesive under -196 DEG C of environment, it is characterised in that the raw material including following weight portion：100 parts of rings
Oxygen tree fat, 10~70 parts of phenolic resin, 1~5 part of coupling agent, 1~20 part of epoxide diluent.
2. the epoxy adhesive under -196 DEG C of environment is used according to claim 1, it is characterised in that：Described epoxy resin
Refer to the material containing two or more epoxy-functionals, be bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenolic aldehyde
Any one or a few mixing in type epoxy resin, polyfunctional epoxy resin.
3. the epoxy adhesive under -196 DEG C of environment is used according to claim 1, it is characterised in that：Described epoxy resin
Epoxide number be 0.3~0.9.
4. the epoxy adhesive under -196 DEG C of environment is used according to claim 1, it is characterised in that：In parts by weight, institute
The phenolic resin stated contains 10~90 parts of acid catalysis phenolic resin, 10~90 parts of base catalysis phenolic resin.
5. the epoxy adhesive under -196 DEG C of environment is used according to claim 1, it is characterised in that：In the phenolic resin
Phenol be any one or a few the mixture in phenol, cresols, hydroquinones, resorcinol and p-tert-butylphenol.
6. the epoxy adhesive under -196 DEG C of environment is used according to claim 1, it is characterised in that：In the phenolic resin
Aldehyde be any one or a few the mixture in formaldehyde, acetaldehyde and butyraldehyde.
7. the epoxy adhesive under -196 DEG C of environment is used according to claim 1, it is characterised in that：Described coupling agent is
Silane coupler, is any one or a few the mixture in KH550 and KH560.
8. the epoxy adhesive under -196 DEG C of environment is used according to claim 1, it is characterised in that：Described epoxy dilution
Agent is the material containing one or two epoxy-functional, is butyl glycidyl ether, ethylene glycol diglycidylether, phenyl contracting
It is any in water glycerin ether, neopentylglycol diglycidyl ether, benzyl glycidyl ether and 1,6 hexanediol diglycidylether
The mixture of one or more.
9. the epoxy adhesive being used in described in any one claim in a kind of 1-8 according to claim under -196 DEG C of environment
Using, it is characterised in that the epoxy adhesive is used to prepare glass-reinforced plastic material, and its form is glass fiber, fiberglass woven cloth or glass
Glass felt.
10. the application of epoxy adhesive according to claim 9, it is characterised in that：In terms of weight/mass percentage composition, the glass
Resin proportion is 25%~60% in Steel material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611226932.3A CN106833464B (en) | 2016-12-27 | 2016-12-27 | Epoxy adhesive used in-196 ℃ environment and glass fiber reinforced plastic product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611226932.3A CN106833464B (en) | 2016-12-27 | 2016-12-27 | Epoxy adhesive used in-196 ℃ environment and glass fiber reinforced plastic product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106833464A true CN106833464A (en) | 2017-06-13 |
| CN106833464B CN106833464B (en) | 2020-04-21 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201611226932.3A Active CN106833464B (en) | 2016-12-27 | 2016-12-27 | Epoxy adhesive used in-196 ℃ environment and glass fiber reinforced plastic product thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102719210A (en) * | 2011-03-30 | 2012-10-10 | 中国科学院理化技术研究所 | Insulating heat-conducting adhesive for ultralow temperature |
| CN103102857A (en) * | 2012-11-29 | 2013-05-15 | 广州市尤特新材料有限公司 | High-temperature resistant adhesive for glass and preparation method thereof |
| CN103289313A (en) * | 2012-02-27 | 2013-09-11 | 河北华强科技开发有限公司 | Preparation method of improved glass fiber reinforced plastic material |
| CN103881056A (en) * | 2012-12-20 | 2014-06-25 | 陶氏环球技术有限公司 | Epoxy resin composition, method of making same, and articles thereof |
| CN104293229A (en) * | 2014-10-21 | 2015-01-21 | 济南圣泉集团股份有限公司 | Conductive adhesive and preparation method thereof |
| CN102942892B (en) * | 2012-11-28 | 2015-02-11 | 九江福莱克斯有限公司 | Epoxy phenolic resin adhesive and epoxy phenolic adhesive tape and laminated board manufactured by adhesive |
-
2016
- 2016-12-27 CN CN201611226932.3A patent/CN106833464B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102719210A (en) * | 2011-03-30 | 2012-10-10 | 中国科学院理化技术研究所 | Insulating heat-conducting adhesive for ultralow temperature |
| CN103289313A (en) * | 2012-02-27 | 2013-09-11 | 河北华强科技开发有限公司 | Preparation method of improved glass fiber reinforced plastic material |
| CN102942892B (en) * | 2012-11-28 | 2015-02-11 | 九江福莱克斯有限公司 | Epoxy phenolic resin adhesive and epoxy phenolic adhesive tape and laminated board manufactured by adhesive |
| CN103102857A (en) * | 2012-11-29 | 2013-05-15 | 广州市尤特新材料有限公司 | High-temperature resistant adhesive for glass and preparation method thereof |
| CN103881056A (en) * | 2012-12-20 | 2014-06-25 | 陶氏环球技术有限公司 | Epoxy resin composition, method of making same, and articles thereof |
| CN104293229A (en) * | 2014-10-21 | 2015-01-21 | 济南圣泉集团股份有限公司 | Conductive adhesive and preparation method thereof |
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| CN106833464B (en) | 2020-04-21 |
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