CN102977830B - Epoxy resin adhesive and preparation method and applications thereof - Google Patents
Epoxy resin adhesive and preparation method and applications thereof Download PDFInfo
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- CN102977830B CN102977830B CN201110264604.3A CN201110264604A CN102977830B CN 102977830 B CN102977830 B CN 102977830B CN 201110264604 A CN201110264604 A CN 201110264604A CN 102977830 B CN102977830 B CN 102977830B
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Abstract
The present invention relates to the field of composite materials, and concretely relates to an epoxy resin adhesive and a preparation method and applications thereof. The epoxy resin adhesive of the present invention comprises the following components: 60 to 100 parts by weight of epoxy resin, 20 to 60 parts of dicyandiamide, 10 to 40 parts by weight of amine terminated liquid butadiene acrylonitrile, 0.5 to 5 parts by weight of 2-ethyl -4-methylimidazole, and 5 to 30 parts by weight of white carbon black. The adhesive of the present invention has good adhesive performance, strong mechanical properties, so the adhesive is especially suitable to be used as an adhesive layer for composite sheets in vehicles.
Description
Technical field
The present invention relates to field of compound material, be specifically related to a kind of epoxy resin adhesive that is applicable to vehicle composite panel and its preparation method and application.
Background technology
In recent years, sizing agent industry has obtained developing rapidly.As human body, need enzyme, hormone and VITAMIN the same, almost anyone, any article all relate to sizing agent, and sizing agent has become the indispensable important materials of modern industrial society.
Epoxy resin adhesive belongs to thermosetting polymer sizing agent, formulated by epoxy resin, solidifying agent, promotor, thinner and filler etc.Therefore owing to containing polar group, and can add multiple polymers and additive modification, non-metallic material be had to good adhesiveproperties as pottery, timber, glass etc.
In addition, the metal construction of using at present matrix material to substitute on vehicle becomes study hotspot, and the adhesive property how solving between matrix material is the problem that is to be solved, about can be used for the binding agent of vehicle matrix material, also has no report.
Summary of the invention
The object of this invention is to provide a kind of adhesive property high, applicable to the epoxy resin adhesive of vehicle composite panel.
Epoxy resin adhesive of the present invention, comprises each composition of following weight parts:
Further, epoxy resin adhesive of the present invention, comprises each composition of following weight parts:
Wherein, described epoxy resin is that bisphenol A-type glycidyl ether based epoxy resin mixes with Racemic glycidol amine epoxy resin or glycidyl ester based epoxy resin.
In addition, the weight ratio that bisphenol A-type glycidyl ether based epoxy resin mixes with Racemic glycidol amine epoxy resin or glycidyl ester based epoxy resin is 8: 2～2: 8.In addition, bisphenol A-type glycidyl ether based epoxy resin is preferably 4: 1 with the weight ratio that Racemic glycidol amine epoxy resin or glycidyl ester based epoxy resin mix.
The present invention also provides a kind of method of preparing described sizing agent, and it comprises the steps:
(1) bisphenol A-type glycidyl ether based epoxy resin is mixed with Racemic glycidol amine epoxy resin or glycidyl ester based epoxy resin, stir, obtain epoxy resin;
(2) in epoxy resin, add amino terminated liquid nitrile rubber, white carbon black, then add the mixture of Dyhard RU 100 and 2-ethyl-4-methylimidazole, stir;
(3) vacuum removal bubble.
The present invention also provides the application of a kind of described sizing agent in vehicle matrix material.
Described being applied as is applied in described sizing agent between panel and core, solidifies 2 hours in 70～80 ℃ successively, and 135～150 ℃ solidify 3 hours, and 155～165 ℃ solidify 2 hours, form vehicle composite panel.
Wherein, described core is one or more in polyurethane foam, polyvinyl chloride foam, oak, Lignum paulowniae or glued board; Described panel is one or more in resin base fiber reinforced composite material plate, polydicyclopentadiene or macromole polyethylene.
Dyhard RU 100 is good thermic latent curing agent alive, and its micropowder is distributed in epoxy resin, good stability, and normal temperature can reach more than 6 months working life, and cured article has good performance.
Hold the miscible toughening modifying of amino liquid nitrile rubber and epoxy resin, in solidification process, separate out, form the two phase structure of " island model ", by active group, interact, on two-phase interface, form chemical bond and play toughening effect.After epoxy resin toughened by liquid rubber, the stripping strength of tackiness agent can be improved, and overall mechanical properties and thermal characteristics can not be reduced.
The present invention adds the toughness that amino terminated liquid nitrile rubber further improves sizing agent in epoxy resin composition matrix, improves its resistance to impact shock, and can reduce the cure shrinkage of sizing agent simultaneously.In addition, the present invention also further improves the physical strength of sizing agent by adding Dyhard RU 100 as solidifying agent.The plate of material making by sizing agent of the present invention is as sheet materials such as vehicle floor or side plates.
In addition, sizing agent adhesive property of the present invention is good, and mechanical property is strong, is particularly useful for the gluing layer as vehicle composite panel.
Embodiment
Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
The present invention, according to standard GB/T/T 7124-1986, adopts Shimadzu AGS-J trier, measures the tensile shear strength of sizing agent; According to standard GB/T/T528-1998, adopt Shimadzu AGS-J trier, measure the tensile strength of sizing agent; Press GB/T 1732-93, adopt QDI type paint film impact test device, measure the shock strength of sizing agent.
In addition, sizing agent of the present invention is applied between bottom surface and core, makes vehicle composite panel, according to standard GB/T/T2791-81, adopt the test of RGT-10 type microcomputer controlled electronic universal tester, measure stripping strength, the cohesive strength of composite panel.
Dyhard RU 100 used in the present invention is purchased from Xi'an chemical reagent factory product; 2-ethyl-4 methyl miaow file is purchased from Shanghai San'aisi Reagent Co., Ltd.; Amino terminated liquid nitrile rubber is purchased from ATBN U.S. Nuo Yu company; White carbon black is purchased from Shanghai Ba Yuan Chemical Co., Ltd..
Embodiment 1
By 64.0g bisphenol A-type glycidyl ether based epoxy resin E-51 (purchased from Wuxi Resin Factory of Blue Star New Chemical Material Co., Ltd., oxirane value is 0.48-0.54), 16.0g glycidyl ester based epoxy resin TDE-86 is (purchased from the brilliant eastern chemically composited Materials Co., Ltd in Tianjin, oxirane value is 0.88) mix, then add 16.0g amino terminated liquid nitrile rubber and 8.0g white carbon black, stir, the mixed solution that adds again 24.0g Dyhard RU 100 and 4.0g 2-ethyl-4-methylimidazole, continue to stir, be placed in vacuum drying oven and remove residual bubble, make sizing agent.
The tensile shear strength that records sizing agent is that 37.0Mpa, tensile strength are that 44.3Mpa, shock strength are 66kg/cm.
First using the resin base fiber reinforced composite material plate as panel and treat that as the polyvinyl chloride foam of core adhesive portion Bit Grinding is smooth; Then clean the surface of interface, sizing agent is evenly applied to the surface of interface, glue panel and material.According to following curing process, heat up so that sizing agent solidifies, program curing is 76 ℃ and solidifies 2 hours, and 140 ℃ solidify 3 hours, and 160 ℃ solidify 2 hours, obtain curing vehicle composite panel.
The stripping strength that records composite panel is 2.8KN/m, and vehicle composite panel interlayer cohesive strength reaches 98Mpa in addition.
Embodiment 2
By 48.0g bisphenol A-type glycidyl ether based epoxy resin E-51 (purchased from Wuxi Resin Factory of Blue Star New Chemical Material Co., Ltd., oxirane value is 0.48-0.54), 12.0g glycidyl ester based epoxy resin TDE-86 is (purchased from the brilliant eastern chemically composited Materials Co., Ltd in Tianjin, oxirane value is 0.88) mix, then add 10.0g amino terminated liquid nitrile rubber and 5.0g white carbon black, stir, the mixed solution that adds again 20.0g Dyhard RU 100 and 0.5g 2-ethyl-4-methylimidazole, continue to stir, be placed in vacuum drying oven and remove residual bubble, make sizing agent.
The tensile shear strength that records sizing agent is that 37.2Mpa, tensile strength are that 44.0Mpa, shock strength are 65.9kg/cm.
First using the polydicyclopentadiene plate as panel and treat that as the oak of core adhesive portion Bit Grinding is smooth; Then clean the surface of interface, sizing agent is evenly applied to the surface of interface, glue panel and core; According to following curing process, heat up so that sizing agent solidifies, program curing is 76 ℃ and solidifies 2 hours, and 140 ℃ solidify 3 hours, and 160 ℃ solidify 2 hours, obtain curing composite panel.
Recording stripping strength is that 2.9KN/m, vehicle composite panel interlayer cohesive strength reach 99Mpa.
Embodiment 3
By 67.0g bisphenol A-type glycidyl ether based epoxy resin E-51 (purchased from Wuxi Resin Factory of Blue Star New Chemical Material Co., Ltd., oxirane value is 0.48-0.54), 33.0g glycidyl ester based epoxy resin TDE-86 is (purchased from the brilliant eastern chemically composited Materials Co., Ltd in Tianjin, oxirane value is 0.88) mix, then add 40.0g amino terminated liquid nitrile rubber and 10.0g white carbon black, stir, the mixed solution that adds again 60.0g Dyhard RU 100 and 5.0g 2-ethyl-4-methylimidazole, continue to stir, be placed in vacuum drying oven and remove residual bubble, make sizing agent.
The tensile shear strength that records sizing agent is that 37.1Mpa, tensile strength are that 44.2Mpa, shock strength are 66.5kg/cm.
First using the macromole polyethylene board as panel and treat that as the polyurethane foam of core adhesive portion Bit Grinding is smooth; Then clean the surface of interface, sizing agent is evenly applied to interface, glue panel and core.According to following curing process, heat up so that sizing agent solidifies, program curing is 80 ℃ and solidifies 2 hours, and 150 ℃ solidify 3 hours, and 155 ℃ solidify 2 hours, obtain curing composite panel.
Record stripping strength 1.8KN/m, vehicle composite panel interlayer cohesive strength reaches 89Mpa.
Embodiment 4
By 45.0g bisphenol A-type glycidyl ether based epoxy resin E-51 (purchased from Wuxi Resin Factory of Blue Star New Chemical Material Co., Ltd., oxirane value is 0.48-0.54), 45.0g glycidyl ester based epoxy resin TDE-86 is (purchased from the brilliant eastern chemically composited Materials Co., Ltd in Tianjin, oxirane value is 0.88) mix, then add 20.0g amino terminated liquid nitrile rubber and 30.0g white carbon black, stir, the mixed solution that adds again 30.0g Dyhard RU 100 and 2.0g 2-ethyl-4-methylimidazole, continue to stir, be placed in vacuum drying oven and remove residual bubble, make sizing agent.
The tensile shear strength that records sizing agent is that 36.9Mpa, tensile strength are that 43.9Mpa, shock strength are 66kg/cm.
First using the polydicyclopentadiene plate as panel and treat that as the glued board of core adhesive portion Bit Grinding is smooth; Then the surface of clean interface, is evenly applied to interface by sizing agent, bonding panel and core; According to following curing process, heat up so that sizing agent solidifies, program curing is 70 ℃ and solidifies 2 hours, and 135 ℃ solidify 3 hours, and 155 ℃ solidify 2 hours, obtain curing composite panel.
Recording stripping strength is that 2.1KN/m, vehicle composite panel interlayer cohesive strength reach 91Mpa.
Embodiment 5
By 27.0g bisphenol A-type glycidyl ether based epoxy resin E-51 (purchased from Wuxi Resin Factory of Blue Star New Chemical Material Co., Ltd., oxirane value is 0.48-0.54), 53.0g Racemic glycidol amine epoxy resin JEh-012 is (purchased from Changhu Jiafa chemistry Co., Ltd., oxirane value is 0.80-0.85) mix, then add 30.0g amino terminated liquid nitrile rubber and 20.0g white carbon black, stir, the mixed solution that adds again 40.0g Dyhard RU 100 and 2.0g 2-ethyl-4-methylimidazole, continue to stir, be placed in and in vacuum drying oven, remove residual bubble, make sizing agent.
The tensile shear strength that records sizing agent is that 37.3Mpa, tensile strength are that 44.2Mpa, shock strength are 66.1kg/cm.
First using the macromole polyethylene board as panel and treat that as the Lignum paulowniae of core adhesive portion Bit Grinding is smooth; Then the surface of clean interface, is evenly applied to interface by sizing agent, glue panel and core; According to following curing process, heat up so that sizing agent solidifies, program curing is 76 ℃ and solidifies 2 hours, and 140 ℃ solidify 3 hours, and 160 ℃ solidify 2 hours, obtain curing composite panel.
Record stripping strength 2.7KN/m, vehicle composite panel interlayer cohesive strength reaches 95Mpa.
Embodiment 6
By 17.0g bisphenol A-type glycidyl ether based epoxy resin E-51 (purchased from Wuxi Resin Factory of Blue Star New Chemical Material Co., Ltd., oxirane value is 0.48-0.54), 68.0g Racemic glycidol amine epoxy resin JEh-012 is (purchased from Changhu Jiafa chemistry Co., Ltd., oxirane value is 0.80-0.85) mix, then add 20.0g amino terminated liquid nitrile rubber and 15.0g white carbon black, stir, the mixed solution that adds again 35.0g Dyhard RU 100 and 5.0g 2-ethyl-4-methylimidazole, continue to stir, be placed in and in vacuum drying oven, remove residual bubble, make sizing agent.
The tensile shear strength that records sizing agent is that 37.0Mpa, tensile strength are that 44.1Mpa, shock strength are 66.2kg/cm.
First using the macromole polyethylene board as panel and treat that as the oak of core adhesive portion Bit Grinding is smooth; Then the surface of clean interface, is evenly applied to interface by sizing agent, glue panel and core; According to following curing process, heat up so that sizing agent solidifies, program curing is 76 ℃ and solidifies 2 hours, and 140 ℃ solidify 3 hours, and 160 ℃ solidify 2 hours, obtain curing composite panel.
Recording stripping strength is that 2.6KN/m, vehicle composite panel interlayer cohesive strength reach 94Mpa.
Claims (7)
1. an epoxy resin adhesive, is characterized in that, comprises each composition of following weight parts:
Described epoxy resin is that bisphenol A-type glycidyl ether based epoxy resin mixes with Racemic glycidol amine epoxy resin or glycidyl ester based epoxy resin; Mixed weight is than being 8:2～2:8.
2. sizing agent according to claim 1, is characterized in that, comprises each composition of following weight parts:
3. sizing agent according to claim 1, is characterized in that, the weight ratio that bisphenol A-type glycidyl ether based epoxy resin mixes with Racemic glycidol amine epoxy resin or glycidyl ester based epoxy resin is 4:1.
4. a method of preparing sizing agent described in claim 1～3 any one, is characterized in that, comprises the steps:
(1) bisphenol A-type glycidyl ether based epoxy resin is mixed with Racemic glycidol amine epoxy resin or glycidyl ester based epoxy resin, stir, obtain epoxy resin;
(2) in epoxy resin, add amino terminated liquid nitrile rubber, white carbon black, then add the mixture of Dyhard RU 100 and 2-ethyl-4-methylimidazole, stir;
(3) vacuum removal bubble.
5. the application of sizing agent in vehicle matrix material described in claim 1～3 any one.
6. application according to claim 5, is characterized in that, described sizing agent is applied between panel and core, solidifies 2 hours in 70～80 ℃ successively, and 135～150 ℃ solidify 3 hours, and 155～165 ℃ solidify 2 hours, form vehicle composite panel.
7. application according to claim 6, is characterized in that, described core is one or more in polyurethane foam, polyvinyl chloride foam, oak, Lignum paulowniae or glued board; Described panel is one or more in resin base fiber reinforced composite material plate, polydicyclopentadiene or macromole polyethylene.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110264604.3A CN102977830B (en) | 2011-09-07 | 2011-09-07 | Epoxy resin adhesive and preparation method and applications thereof |
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| CN201110264604.3A CN102977830B (en) | 2011-09-07 | 2011-09-07 | Epoxy resin adhesive and preparation method and applications thereof |
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| CN102977830B true CN102977830B (en) | 2014-03-26 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865461B (en) * | 2014-04-08 | 2015-12-30 | 株洲时代新材料科技股份有限公司 | A kind of tackiness agent |
| FR3041317B1 (en) * | 2015-09-18 | 2017-10-06 | Peugeot Citroen Automobiles Sa | VEHICLE BODY WITH SHEET ELEMENTS ASSEMBLES BY COLLAGE |
| CN106753124A (en) * | 2016-12-07 | 2017-05-31 | 安徽艾蒂贝生物有限公司 | A kind of stone material special epoxy resin adhesive |
| CN106990204B (en) * | 2017-05-19 | 2023-09-26 | 云南中烟工业有限责任公司 | Pressure bin for cigarette smoking machine and sealing method thereof |
| CN109664314B (en) * | 2019-01-30 | 2022-04-29 | 合肥特尔卡机器人科技股份有限公司 | Preparation method of high-simulation robot |
| CN112142461B (en) * | 2019-06-28 | 2022-09-06 | 比亚迪股份有限公司 | Ceramic composition, ceramic, and preparation method and application thereof |
| CN110591623B (en) * | 2019-10-22 | 2022-09-02 | 惠州市亿铖达精细化工有限公司 | Fast-curing epoxy adhesive |
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| CN101821333A (en) * | 2007-07-26 | 2010-09-01 | 汉高公司 | Curable epoxy resin-based adhesive compositions |
| CN101925652A (en) * | 2008-01-30 | 2010-12-22 | Sika技术股份公司 | Wash-out resistant heat-curing epoxy resin adhesives |
| CN101415296A (en) * | 2008-11-24 | 2009-04-22 | 广东汕头超声电子股份有限公司覆铜板厂 | Structure for covering copper plate |
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Effective date of registration: 20200807 Address after: 101312 No.5, Anxiang street, Airport Industrial Zone, Shunyi District, Beijing Patentee after: BEIJING BLUESTAR CLEANING Co.,Ltd. Address before: 100176 No. 5 Xingye street, Beijing economic and Technological Development Zone Patentee before: BLUESTAR (BEIJING) CHEMICAL MACHINERY Co.,Ltd. |