CN104312508B - A kind of epoxy resin adhesive and preparation method thereof - Google Patents
A kind of epoxy resin adhesive and preparation method thereof Download PDFInfo
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- CN104312508B CN104312508B CN201410594264.4A CN201410594264A CN104312508B CN 104312508 B CN104312508 B CN 104312508B CN 201410594264 A CN201410594264 A CN 201410594264A CN 104312508 B CN104312508 B CN 104312508B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 73
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 73
- 239000000853 adhesive Substances 0.000 title claims abstract description 48
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 59
- 229920000570 polyether Polymers 0.000 claims abstract description 43
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 34
- -1 Sulfur alcohol compound Chemical class 0.000 claims abstract description 31
- 239000003085 diluting agent Substances 0.000 claims abstract description 24
- 150000002118 epoxides Chemical class 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 17
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 16
- 229920000768 polyamine Polymers 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 16
- 239000011593 sulfur Substances 0.000 claims abstract description 16
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001412 amines Chemical class 0.000 claims description 27
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 239000004814 polyurethane Substances 0.000 claims description 12
- 229920002635 polyurethane Polymers 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000002879 Lewis base Substances 0.000 claims description 7
- 150000007527 lewis bases Chemical class 0.000 claims description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 6
- 229960001124 trientine Drugs 0.000 claims description 6
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 3
- 238000007711 solidification Methods 0.000 abstract description 11
- 230000008023 solidification Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005520 cutting process Methods 0.000 abstract description 4
- 230000035939 shock Effects 0.000 abstract description 4
- 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 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 7
- 238000010008 shearing Methods 0.000 description 6
- 238000004513 sizing Methods 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 150000008431 aliphatic amides Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical group CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
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- Adhesives Or Adhesive Processes (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention relates to a kind of epoxy resin adhesive, to be mixed according to the weight ratio of 1:0.8-1 by component A and B component and make, component A comprises the material composition of following weight part: polyether glycol 376-470 part; Tolylene diisocyanate 80-100 part; Epoxy resin 4560-5700 part; Epoxide diluent 250-313 part; B component comprises the material composition of following weight part: aliphatic polyamine 20-40 part; Oxy-compound 40-50 part; Sulfur alcohol compound 8-15 part; Compound accelerant 5-10 part; Composite solidifying agent 55-70 part; Wherein, described polyether glycol is selected from least one in polyethers 3050, polyethers 3010 and polyethers 2070; Described epoxy resin is selected from least one in E51 type epoxy resin and E44 type epoxy resin; Described sulfur alcohol compound is tetramethylolmethane mercaptopropionic acid ester.Epoxy resin adhesive provided by the present invention under cryogenic (lower than at-5 DEG C) is non-crystallizable, and solidification effect is good, has good shock-resistant and cutting performance after solidification.
Description
Technical field
The present invention relates to sizing agent field, concrete, relate to a kind of epoxy resin adhesive and preparation method thereof
Background technology
The basal component of epoxy resin adhesive is epoxy resin and solidifying agent, and it all has good stickiness to multiple material, and Application Areas is extensive.
The preparation method of bisphenol A type epoxy resin is generally epoxy resin to mix with sulphur oxygen solidifying agent and obtains, in the practical application of bisphenol A epoxy, it is poor that it solidifies rear toughness at normal temperatures, when running into the situation needing to solidify under low temperature (less than 0 DEG C) condition, the state of cure of bisphenol A type epoxy resin is often difficult to the requirement of the standard that reaches more.This may be because bisphenol A type epoxy resin easily crystallization occurs at low temperatures, thus have impact on the carrying out of solidification.Also do not occur under cryogenic that (less than 0 DEG C) crystallization does not occur and obtains the bisphenol A epoxy of good solidification effect in the market.
Summary of the invention
First object of the present invention is that providing a kind of can avoid under cryogenic crystallization occurring thus the epoxy resin adhesive of acquisition good solidification effect.
Second object of the present invention is the preparation method providing a kind of epoxy resin adhesive.
For reaching first object of the present invention, the invention provides a kind of epoxy resin adhesive, being mixed by component A and B component and make, wherein,
Component A comprises the material composition of following weight part:
B component comprises the material composition of following weight part:
Wherein, described polyether glycol is selected from least one in polyethers 3050, polyethers 3010 and polyethers 2070; Described epoxy resin is selected from least one in E51 type epoxy resin and E44 type epoxy resin; Described sulfur alcohol compound is tetramethylolmethane mercaptopropionic acid ester.
Preferably, described epoxide diluent is selected from least one in 660 type epoxide diluents and 2013 type epoxide diluents; Described aliphatic polyamine is selected from least one in diethylenetriamine and triethylene tetramine; Described oxy-compound is selected from least one in dihydroxyphenyl propane, Bisphenol F, end hydroxy polyether, hydroxyl telechelic polyester; Described composite solidifying agent comprises modified amine curing agent.
Preferably, described compound accelerant to be contacted with the Lewis base of 5-7 weight part by the sulfhydryl compound of 3-5 weight part and makes.
Preferably, also comprise the silane coupling agent of 1-3 weight part in described B component, described silane coupling agent is selected from least one in KH-550 silane coupling agent and KH-560 silane coupling agent.
Preferably, the altax P-30 of 1-3 weight part is also comprised in composite solidifying agent
In order to realize second object of the present invention, the invention provides a kind of method of epoxy resin adhesive, comprising the following steps:
(1) polyether glycol and tolylene diisocyanate are carried out first and contact to obtain adhesive for polyurethane;
(2) epoxy resin, adhesive for polyurethane and epoxide diluent are carried out second and contact to obtain component A;
(3) aliphatic polyamine, oxy-compound and sulfur alcohol compound are carried out the 3rd and contact to obtain modified amine curing agent;
(4) modified amine curing agent, compound accelerant and composite solidifying agent are carried out the 4th and contact to obtain B component;
(5) component A and B component are mixed acquisition epoxy resin adhesive.
Preferably, described second contact comprises: add adhesive for polyurethane after first epoxy resin being heated to 75-85 DEG C and at 75-85 DEG C, react 3.5-4.5h to obtain modified mixture, again described modified mixture is cooled to not higher than 40 DEG C, adds epoxide diluent and stir to obtain component A.
Preferably, described 3rd contact comprises aliphatic polyamine, oxy-compound and sulfur alcohol compound is reacted 2.5-3.5h at 68-72 DEG C.
Preferably, described 4th contact comprise modified amine curing agent and compound accelerant are reacted 1.8-2.2h at 45-55 DEG C after obtain mixture B1, then add in described mixture B1 composite solidifying agent stir 0.4-0.6h to obtain B component.
Preferably, described 4th contact also comprises and adds silane coupling agent.
Epoxy resin adhesive provided by the present invention under cryogenic (lower than at-5 DEG C) is non-crystallizable, and solidification effect is good, has good shock-resistant and cutting performance after solidification.
Other features and advantages of the present invention are described in detail in embodiment part subsequently
Embodiment
Below will be described in detail the specific embodiment of the present invention.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
On the one hand, the invention provides a kind of epoxy resin adhesive, mixed by component A and B component and make, wherein,
Component A comprises the material composition of following weight part:
B component comprises the material composition of following weight part:
Wherein, described polyether glycol is selected from least one in polyethers 3050, polyethers 3010 and polyethers 2070; Described epoxy resin is selected from least one in E51 type epoxy resin and E44 type epoxy resin; Described sulfur alcohol compound is tetramethylolmethane mercaptopropionic acid ester.
One of the present invention preferred embodiment in, described polyether glycol is made up of polyethers 3050 and polyethers 3010, and the weight ratio of the two is 1:1.
The epoxy resin adhesive that the application provides has good shock-resistant and cutting performance in actual applications, the anti-crystallization of product is strong, what is particularly worth mentioning is that, when using epoxy resin adhesive provided by the present invention at lower than the temperature of-5 DEG C, can not there is crystallization in component A, thus be conducive at cold operation at low temperatures, at low temperatures after solidification, sizing agent still can keep excellent shock-resistant and cutting performance, is better than other like products.
Described epoxide diluent is selected from least one in 660 type epoxide diluents and 2013 type epoxide diluents; Described aliphatic polyamine is selected from least one in diethylenetriamine and triethylene tetramine; Described oxy-compound is selected from least one in dihydroxyphenyl propane, Bisphenol F, end hydroxy polyether and hydroxyl telechelic polyester; Described composite solidifying agent is modified amine curing agent.
Preferably, described polyether glycol is that polyethers 3010 and polyethers 3050, described epoxy resin are E51 type epoxy resin, described thio-alcohol chemical combination is tetramethylolmethane mercaptopropionic acid ester; Described epoxide diluent is 660 type epoxide diluents and 2013 type epoxide diluents; Described aliphatic polyamine is triethylene tetramine; Described oxy-compound is dihydroxyphenyl propane.According to the sizing agent of above-mentioned preferred ingredient gained, can preserve at low temperatures, operation, the reactive behavior of B component is higher, can ensure still can react with component A at low temperatures.
In method provided by the present invention, it is active that the acting as of described compound accelerant improves solidifying agent, one of the present invention preferred embodiment in, described compound accelerant to be contacted with the Lewis base of 5-7 weight part by the sulfhydryl compound of 3-5 weight part and makes.Described sulfhydryl compound can at least one in selected from mercapto acetic acid, thiohydracrylic acid and single Thiomalic acid, and preferably, described sulfhydryl compound is Thiovanic acid.
In the present invention, the silane coupling agent of 1-3 weight part is also preferably included in described B component, described silane coupling agent is selected from least one in KH-550 silane coupling agent (γ-aminopropyl triethoxysilane) and KH-560 silane coupling agent (γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane).Preferably, described silane coupling agent is KH-550 silane coupling agent.
In the present invention, also comprise the promotor of 1-3 weight part in described composite solidifying agent, concrete, described composite solidifying agent can be mixed by modified amine curing agent and promotor.
In the present invention, described modified amine curing agent is add that other functional groups (as epoxy-functional) to carry out the material of modification acquisition to it by addition reaction on aliphatic amide, optionally, modified amine curing agent of the present invention is modified amine curing agent 1008.Described modified amine curing agent 1008 is that natural long chain replaces pnenolic aldehyde amine hardener, by addition reaction, aliphatic amide adds that on slightly acidic phenolic hydroxyl group and phenyl ring, double bond C15 long-chain obtains.
One of the present invention preferred embodiment in, described promotor is DMP-30, and the weight ratio of modified amine curing agent and promotor is 100:1-3.
Adopt technique scheme, the present invention obtains a kind of epoxy resin adhesive for polyurethane of excellent performance, can carry out under cryogenic operating and solidifying, avoid the conventional bisphenol A epoxide resin defect that the solidification effect that causes of crystallization is bad at low temperatures, be widely used in temperature district and north mining lower, the fields such as piling, have easy and simple to handle, with low cost, avoid indirect heating, save energy, replicability advantages of higher.
Present invention also offers a kind of method preparing epoxy resin adhesive, comprise the following steps:
(1) polyether glycol and tolylene diisocyanate are carried out first and contact to obtain adhesive for polyurethane;
(2) epoxy resin, adhesive for polyurethane and epoxide diluent are carried out second and contact to obtain component A;
(3) aliphatic polyamine, oxy-compound and sulfur alcohol compound are carried out the 3rd and contact to obtain modified amine curing agent;
(4) modified amine curing agent, compound accelerant and composite solidifying agent are carried out the 4th and contact to obtain B component;
(5) component A and B component are mixed acquisition epoxy resin adhesive.
Wherein, in step (1), described first contact specifically can comprise: added to by polyether glycol in reaction unit, then add toluene and vulcabond, the two mixed and be heated to 75-85 DEG C, reaction 2.5-3.5h.Preferably, the temperature of reaction is 80 DEG C, and the time of reaction is 3h.
In method provided by the present invention, described second contact comprises: add adhesive for polyurethane reaction 3.5-4.5h after first epoxy resin being heated to 75-85 DEG C and obtain modified mixture, again described modified mixture is cooled to not higher than 40 DEG C, add epoxide diluent stir obtain component A.Preferably, the condition of the second contact for react 4h at 80 DEG C.
After the second contact obtains component A, for subsequent use under component A can being stored in the condition of-5-40 DEG C.
According to method provided by the present invention, the condition of described 3rd contact comprises reacts aliphatic polyamine, oxy-compound and sulfur alcohol compound to 2.5-3.5h at 68-72 DEG C.
Wherein, in the 3rd contact, having no particular limits the order of addition of aliphatic polyamine, oxy-compound and sulfur alcohol compound can for simultaneously or add successively.As long as three can be made to contact and mix.
According to method provided by the present invention, described 4th contact comprise modified amine curing agent and compound accelerant are reacted 1.8-2.2h at 45-55 DEG C after obtain mixture B1, then in described mixture B1, add composite solidifying agent at 15-30 DEG C, stir 0.4-0.6h to obtain B component.
Method provided by the present invention also comprises and prepares compound accelerant, and acting as of compound accelerant improves solidifying agent reactive behavior, and preferably, the preparation method of described compound accelerant can for react sulfhydryl compound and Lewis base to 0.5-1h at 60 DEG C.
When also comprising altax P-30 in described composite solidifying agent, method provided by the present invention also comprises and modified amine curing agent and promotor are stirred 0.5-1h at 15-30 DEG C obtains composite solidifying agent.
Of the present invention one preferred embodiment in, described 4th contact also comprises and adds silane coupling agent, described silane coupling agent can with composite solidifying agent simultaneously or add to successively in reaction unit and contact with described mixture B1, at 15-30 DEG C, stir 0.4-0.6h obtain B component.
Method provided by the present invention has no particular limits for method component A and B component mixed, and can carry out according to the working method of this area routine.It should be noted that, because method provided by the present invention is improved for component A and B component, therefore, operating process of the present invention and solidification process can carry out at a lower temperature, such as, can to carry out at-5-0 DEG C and the crystallization that component A can not occur affects the solidification of sizing agent.
In method provided by the present invention, the reaction unit used for preparation process has no particular limits, and can be the reaction unit of this area routine, and such as, described reaction unit can be reactor.
Further illustrate the content of one's duty invention by the following examples.If do not specialize, the conventional means that technique means used in embodiment is well known to those skilled in the art.The all ingredients used in following examples and instrument all can obtain by buying commercially available prod.
Embodiment 1-14
The present embodiment is for illustration of the preparation method of epoxy resin adhesive provided by the present invention.Epoxy resin adhesive 1-7 is prepared by following steps according to the adding proportion given by table 1.
(1) preparation of adhesive for polyurethane: joined in reactor by polyether glycol and add tolylene diisocyanate again, reacts 3h after the two being stirred, frequently stirs in reaction process at 80 DEG C.
(2) preparation of component A: epoxy resin is added in reactor and be heated to 80 DEG C, add adhesive for polyurethane prepared by step (1), the two is stirred react 4h at 80 DEG C after and be cooled to 35 DEG C, add epoxide diluent and the acquisition component A that stirs.
(3) preparation of modified amine curing agent: aliphatic polyamine, oxy-compound and sulfur alcohol compound are mixed in a kettle. post-heating to 70 DEG C reaction 3h to obtain modified amine curing agent.
(4) preparation of compound accelerant: sulfhydryl compound is joined in reactor to react at 60 DEG C with Lewis base and obtain compound accelerant in 1 hour.
(5) preparation of B component: in a kettle. modified amine curing agent and compound accelerant are reacted 2h at 50 DEG C.Add silane coupling agent and composite solidifying agent (composite solidifying agent modified amine curing agent 1008 (purchased from Shanghai Mei Dong biomaterial limited-liability company) is reacted 1h with altax P-30 according to the weight ratio of 100:1 at 20 DEG C obtain) again at 20 DEG C, to stir 0.5h obtain B component.
(6) curing schedule: component A and B component are obtained epoxy resin adhesive 1-7 according to the weight ratio stirring and evenly mixing after fixing of 1:1 at-5 DEG C.
Table 1
In above-described embodiment, the concrete selection mode of raw material is as follows:
In embodiment 1-7, polyether glycol is that polyethers 3010 is mixed according to the ratio of 1:1 with polyethers 3050; Epoxy resin is E51 type epoxy resin; Epoxide diluent is 660 type epoxide diluents; Aliphatic polyamine is triethylene tetramine; Oxy-compound is end hydroxy polyether; Sulfur alcohol compound is tetramethylolmethane mercaptopropionic acid ester; Compound accelerant is reacted by 4 weight part Thiovanic acids and 5 weight part Lewis bases to be made; Silane coupling agent is KH-550 silane coupling agent; Composite solidifying agent modified amine curing agent 1008 is reacted 1h with altax P-30 according to the weight ratio of 100:1 at 20 DEG C obtain.
Embodiment 8, according to the material choice mode identical with embodiment 1, unlike, the kind of polyether glycol is polyethers 3050, obtains epoxy resin adhesive 8.
Embodiment 9, according to the material choice mode identical with embodiment 1, unlike, the kind of polyether glycol is polyethers 2070, obtains epoxy resin adhesive 9.
Embodiment 10, according to the material choice mode identical with embodiment 1, unlike, the kind of epoxy resin is E44 type epoxy resin, obtains epoxy resin adhesive 10.
Embodiment 11, according to the material choice mode identical with embodiment 1, unlike, the kind of aliphatic polyamine is diethylenetriamine, and the kind of oxy-compound is dihydroxyphenyl propane, obtains epoxy resin adhesive 11.
Embodiment 12, according to the material choice mode identical with embodiment 1, unlike, composite solidifying agent is modified amine curing agent 1008, obtains epoxy resin adhesive 12.
Embodiment 13, according to the material choice mode identical with embodiment 1, unlike, do not add silane coupling agent, obtain epoxy resin adhesive 13.
Embodiment 14, according to the material choice mode identical with embodiment 1, unlike, the weight ratio of component A and B component is 1:0.8, obtains epoxy resin adhesive 14.
Comparative example 1
According to the proportioning identical with example 1, unlike, do not add polyether glycol and tolylene diisocyanate, replace sulfur alcohol compound with thiourea and obtain epoxy resin adhesive 15.Epoxy resin adhesive 15 is component A crystallization at-5 DEG C, can not operate, can only at 15 DEG C by A, B two component mixing.
Test case 1-13
According to the detection method of GB/T6329 and GB/T7124, the shearing resistance of the sizing agent 1-15 that embodiment 1-14 and comparative example 1 obtain and tensile strength are detected, the results are shown in table 2.
Table 2
| Test case | Shearing resistance (Mpa) | Tensile strength (Mpa) |
| 1 | 2.3 | 3 |
| 2 | 2.3 | 3 |
| 3 | 2.2 | 2.8 |
| 4 | 2.3 | 2.9 |
| 5 | 2.1 | 3 |
| 6 | 2.2 | 2.8 |
| 7 | 1.9 | 2.9 |
| 8 | 2.3 | 2.7 |
| 9 | 1.9 | 2.7 |
| 10 | 2 | 2.5 |
| 11 | 2 | 2.7 |
| 12 | 1.8 | 2.4 |
| 13 | 1.7 | 2.4 |
| 14 | 2.2 | 3 |
| 15 | Nothing | Nothing |
The result of the result of test case 1-14 and test case 15 is carried out contrast can find out, when the epoxy resin adhesive prepared according to method provided by the present invention solidifies at-5 DEG C, shearing resistance, tensile strength is significantly better than other test cases.
The result of the result of test case 1-7 and test case 8-12 is carried out contrast can find out, when in the sizing agent that the present invention provides more: polyether glycol is polyethers 3010; Epoxy resin is E51 type epoxy resin; Epoxide diluent is 660 type epoxide diluents; Aliphatic polyamine is triethylene tetramine; Oxy-compound is end hydroxy polyether; Sulfur alcohol compound is tetramethylolmethane mercaptopropionic acid ester; Compound accelerant is reacted by 4 weight part Thiovanic acids and 5 weight part Lewis bases to be made; Silane coupling agent is KH-550 silane coupling agent; Composite solidifying agent by 100 part by weight modified amine hardener 1008 and 1-3 weight part altax P-30 react make time, after it solidifies at low temperatures, shearing resistance and tensile strength better.
The result of the result of test case 1 and test case 13 is carried out contrast can find out, when the raw material of epoxy resin provided by the present invention comprises coupling agent, after it solidifies at low temperatures, shearing resistance and tensile strength better.
The result of the result of test case 1 and test case 12 is carried out contrast can find out, when the composite solidifying agent in epoxy resin provided by the present invention is prepared from by modified amine curing agent and promotor, its solidify rear shearing resistance at low temperatures and tensile strength better.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (9)
1. an epoxy resin adhesive, to be mixed according to the weight ratio of 1:0.8-1 by component A and B component and makes, it is characterized in that,
Component A comprises the material composition of following weight part:
B component comprises the material composition of following weight part:
Wherein, described polyether glycol is selected from least one in polyethers 3050, polyethers 3010 and polyethers 2070; Described epoxy resin is selected from least one in E51 type epoxy resin and E44 type epoxy resin; Described sulfur alcohol compound is tetramethylolmethane mercaptopropionic acid ester;
Described composite solidifying agent comprises modified amine curing agent; Described compound accelerant to be contacted with the Lewis base of 5-7 weight part by the sulfhydryl compound of 3-5 weight part and makes.
2. epoxy resin adhesive according to claim 1, is characterized in that, described epoxide diluent is selected from least one in 660 type epoxide diluents and 2013 type epoxide diluents; Described aliphatic polyamine is selected from least one in diethylenetriamine and triethylene tetramine; Described oxy-compound is selected from least one in dihydroxyphenyl propane, Bisphenol F, end hydroxy polyether, hydroxyl telechelic polyester.
3. epoxy resin adhesive according to claim 2, is characterized in that, also comprises the silane coupling agent of 1-3 weight part in described B component, and described silane coupling agent is selected from least one in KH-550 silane coupling agent and KH-560 silane coupling agent.
4. according to the epoxy resin adhesive in claim 1-3 described in any one, it is characterized in that, in composite solidifying agent, also comprise the altax P-30 of 1-3 weight part.
5. prepare the method for the epoxy resin adhesive in claim 1-4 described in any one, comprise the following steps:
(1) polyether glycol and tolylene diisocyanate are carried out first and contact to obtain adhesive for polyurethane;
(2) epoxy resin, adhesive for polyurethane and epoxide diluent are carried out second and contact to obtain component A;
(3) aliphatic polyamine, oxy-compound and sulfur alcohol compound are carried out the 3rd and contact to obtain modified amine curing agent;
(4) modified amine curing agent, compound accelerant and composite solidifying agent are carried out the 4th and contact to obtain B component;
(5) component A and B component are mixed to obtain epoxy resin adhesive.
6. method according to claim 5, it is characterized in that, described second contact comprises: add adhesive for polyurethane after first epoxy resin being heated to 75-85 DEG C and at 75-85 DEG C, react 3.5-4.5h to obtain modified mixture, again described modified mixture is cooled to not higher than 40 DEG C, adds epoxide diluent and stir to obtain component A.
7. the method according to claim 5 or 6, is characterized in that, described 3rd contact comprises reacts aliphatic polyamine, oxy-compound and sulfur alcohol compound to 2.5-3.5h at 68-72 DEG C.
8. method according to claim 7, it is characterized in that, described 4th contact comprise modified amine curing agent and compound accelerant are reacted 1.8-2.2h at 45-55 DEG C after obtain mixture B1, then add in described mixture B1 composite solidifying agent stir 0.4-0.6h to obtain B component.
9. the method according to claim 5 or 8, is characterized in that, described 4th contact also comprises and adds silane coupling agent.
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| CN104774529A (en) * | 2015-03-24 | 2015-07-15 | 牛无畏 | Quick-drying epoxy coating |
| CN107151307A (en) * | 2017-04-24 | 2017-09-12 | 苏州金枪新材料股份有限公司 | A kind of organic silicon modified polyurethane sealant |
| CN107033822B (en) * | 2017-05-19 | 2020-06-30 | 江苏三木化工股份有限公司 | Solvent-free two-component epoxy resin adhesive as well as preparation method and application thereof |
| CN107828367A (en) * | 2017-10-31 | 2018-03-23 | 梁军普 | A kind of band water band oil adhesive blocking glue and preparation method thereof |
| CN111253896B (en) * | 2020-03-05 | 2021-03-19 | 深圳市凯恩应用化学技术有限公司 | Epoxy adhesive and preparation method and application thereof |
| CN111909649B (en) * | 2020-07-24 | 2022-06-21 | 中国乐凯集团有限公司 | Adhesive, solar cell back sheet and solar cell |
| CN113322038A (en) * | 2021-06-28 | 2021-08-31 | 中国兵器工业第五九研究所 | Normal-temperature curing modified epoxy resin adhesive and preparation method thereof |
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| US5972423A (en) * | 1998-08-03 | 1999-10-26 | Lord Corporation | Primerless substrate repair with polyepoxide and polythiol |
| JP4715010B2 (en) * | 2001-03-27 | 2011-07-06 | 味の素株式会社 | Curable epoxy resin composition, adhesive, and sealant |
| EP1916269A1 (en) * | 2006-10-24 | 2008-04-30 | Sika Technology AG | Blocked polyurethane prepolymers and heat curing epoxy resin compositions |
| CN103184022B (en) * | 2011-12-30 | 2017-09-19 | 汉高股份有限及两合公司 | Temporary bonding adhesive composition in being prepared for silicon chip |
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Denomination of invention: Epoxy resin adhesive and preparation method and applications thereof Effective date of registration: 20200427 Granted publication date: 20160120 Pledgee: All bondholders Pledgor: SUZHOU JINQIANG NEW MATERIALS Co.,Ltd. Registration number: Y2020320010024 |
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