CN118027872A - Detachable silane modified polyether composition and preparation method and application thereof - Google Patents
Detachable silane modified polyether composition and preparation method and application thereof Download PDFInfo
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- CN118027872A CN118027872A CN202410261908.1A CN202410261908A CN118027872A CN 118027872 A CN118027872 A CN 118027872A CN 202410261908 A CN202410261908 A CN 202410261908A CN 118027872 A CN118027872 A CN 118027872A
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- modified polyether
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- 239000004526 silane-modified polyether Substances 0.000 title claims abstract description 74
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 83
- 239000000945 filler Substances 0.000 claims abstract description 40
- 239000004014 plasticizer Substances 0.000 claims abstract description 32
- 239000003822 epoxy resin Substances 0.000 claims abstract description 19
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229920005862 polyol Polymers 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 4
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 3
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 3
- 125000003320 C2-C6 alkenyloxy group Chemical group 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- -1 polyol ester Chemical class 0.000 claims description 3
- 239000000565 sealant Substances 0.000 claims description 3
- 125000005591 trimellitate group Chemical group 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 abstract description 16
- 230000001070 adhesive effect Effects 0.000 abstract description 16
- 239000003292 glue Substances 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 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 4
- 239000000376 reactant Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- UVDDHYAAWVNATK-VGKOASNMSA-L (z)-4-[dibutyl-[(z)-4-oxopent-2-en-2-yl]oxystannyl]oxypent-3-en-2-one Chemical compound CC(=O)\C=C(C)/O[Sn](CCCC)(CCCC)O\C(C)=C/C(C)=O UVDDHYAAWVNATK-VGKOASNMSA-L 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- LGROXJWYRXANBB-UHFFFAOYSA-N trimethoxy(propan-2-yl)silane Chemical group CO[Si](OC)(OC)C(C)C LGROXJWYRXANBB-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 229910018173 Al—Al Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- IFPXKNMATMDMFY-UHFFFAOYSA-J [Sn+4].C(C)C(CC(C(=O)[O-])S)CCCC.C(C)C(CC(C(=O)[O-])S)CCCC.C(C)C(CC(C(=O)[O-])S)CCCC.C(C)C(CC(C(=O)[O-])S)CCCC Chemical compound [Sn+4].C(C)C(CC(C(=O)[O-])S)CCCC.C(C)C(CC(C(=O)[O-])S)CCCC.C(C)C(CC(C(=O)[O-])S)CCCC.C(C)C(CC(C(=O)[O-])S)CCCC IFPXKNMATMDMFY-UHFFFAOYSA-J 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a detachable silane modified polyether composition, a preparation method and application thereof, and relates to the technical field of silane modified polyether glue, wherein a component A in the detachable silane modified polyether composition comprises 30-100 parts of epoxy resin, 1-30 parts of first plasticizer, 0-10 parts of cross-linking agent, 1-30 parts of first filler and 0-10 parts of catalyst; the component B comprises 30-100 parts of silane modified polyether, 0-5 parts of antioxidant, 0-50 parts of second filler, 1-30 parts of second plasticizer, 1-20 parts of accelerator and 0-10 parts of cross-linking agent; the sum of the dosage of the cross-linking agent in the component A and the dosage of the cross-linking agent in the component B is 2-10 parts, and the sum of the dosage of the first filler and the second filler is 30-60 parts; the structural formula of the cross-linking agent is shown as formula I. The invention solves the problem that the prior silane modified polyether adhesive is difficult to detach and recycle after being bonded.
Description
Technical Field
The invention relates to the technical field of silane modified polyether glue, in particular to a detachable silane modified polyether composition, a preparation method and application thereof.
Background
The silane modified polyether adhesive (MS adhesive) is an adhesive type with unique performance and numerous varieties, can be used for designing products with various performances according to different raw material formulas of the MS adhesive, and is applied to various fields in daily life, such as the fields of industry and agriculture, aerospace, automobiles, electronics, biomedical treatment and the like. In the industries of new energy automobiles, electronics and the like, MS glue plays an important role in fixing, heat conduction, insulation and other special functions for some key components. In recent years, on the premise of higher and higher requirements of high environmental protection, low energy consumption and resource recycling in China, the recycling of MS glue and the disassembly and recycling of adhered components become an extremely important research direction.
The MS glue is widely applied to fixing batteries and electronic products in a power system of a new energy automobile, the existing MS glue has higher bonding strength to components after bonding is completed, and when the components are required to be removed, the cross-linked network structure existing in the MS glue cannot be broken through simple post-treatment, so that the bonding strength between the components cannot be effectively removed.
The traditional method for disassembling the adhered components is to destroy the adhered interfaces or the adhesive layers by mechanical force or heating by adding the thermal expansion microspheres into the adhesive layers, so that the adhered components are disassembled, but the adhered components are easily damaged, or MS adhesive remains on the components. For the fields of complex production process, high production cost and reusability of components after disassembly and cleaning, the disassembly and recycling of adhered components are more important. The components are difficult to disassemble and recycle after being bonded by MS glue.
Therefore, there is a need to develop a detachable silane-modified polyether composition, a preparation method and application thereof to solve the above problems.
Disclosure of Invention
The invention aims to provide a detachable silane modified polyether composition, a preparation method and application thereof, and solves the problem that the existing silane modified polyether adhesive is difficult to detach and recycle after being bonded.
In order to achieve the above object, in a first aspect, the present invention provides a detachable silane-modified polyether composition comprising an a component and a B component, in parts by weight,
The component A comprises 30-100 parts of epoxy resin, 1-30 parts of first plasticizer, 0-10 parts of cross-linking agent, 1-30 parts of first filler and 0-10 parts of catalyst;
The component B comprises 30-100 parts of silane modified polyether, 0-5 parts of antioxidant, 0-50 parts of second filler, 1-30 parts of second plasticizer, 1-20 parts of accelerator and 0-10 parts of cross-linking agent;
The sum of the amounts of the cross-linking agent in the component A and the cross-linking agent in the component B is 2-10 parts, and the sum of the amounts of the first filler and the second filler is 30-60 parts;
The structural formula of the cross-linking agent is as follows:
wherein, the R1 group is selected from any one of C1-C6 alkoxy, C2-C6 alkenyloxy, C3-C6 epoxy, C2-C6 ester, C2-C6 alkenyl and hydrosilyl; n is any integer from 1 to 8.
Optionally, the preparation method of the cross-linking agent comprises the following steps: adding trimethoxysilane with substituent R1 and water into a container, dropwise adding a condensation catalyst into the container under stirring, heating to 60-100 ℃ for reaction for 1-3h, distilling under reduced pressure to remove low-boiling substances for 1-3h, adding bis- [3- (triethoxysilyl) propyl ] -disulfide into the container, and continuously reacting under reduced pressure for 1-3h to obtain the cross-linking agent.
Alternatively, the cross-linking agent has a structural formula selected from
Wherein n is not less than 4.
Optionally, the cross-linking agent in the component a is a first cross-linking agent, and the structure of the first cross-linking agent is shown in formula II:
Wherein n is greater than or equal to 4.
Optionally, the crosslinking agent in the component B is a second crosslinking agent and/or a third crosslinking agent, the structure of the second crosslinking agent is shown in formula III, and the structure of the third crosslinking agent is shown in formula IV:
Wherein n is greater than or equal to 4;
Wherein n is greater than or equal to 4.
Optionally, the silane-modified polyether comprises a first silane-modified polyether and a second silane-modified polyether, wherein the weight ratio of the first silane-modified polyether to the second silane-modified polyether is 1 (1-2).
Optionally, the component A comprises 50-90 parts of the epoxy resin, 5-20 parts of the first plasticizer, 1-5 parts of the cross-linking agent, 1-20 parts of the first filler, 1-5 parts of the catalyst and 0-3 parts of the color paste;
The component B comprises 40-80 parts of the silane modified polyether, 0-3 parts of the antioxidant, 1-20 parts of the second filler, 5-20 parts of the second plasticizer, 1-10 parts of the accelerator, 1-2 parts of the cross-linking agent and 0-3 parts of the water remover.
Optionally, the viscosity of the epoxy resin at 25 ℃ is 100-200000 mPa-s, and the viscosity of the first plasticizer and the second plasticizer at 25 ℃ is 100-200000 mPa-s.
Optionally, the first filler and the second filler are one or more of calcium carbonate, aluminum oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, and silicon dioxide.
Optionally, the first plasticizer and the second plasticizer are one or more of butadiene, polyether polyol, phthalate, aliphatic dibasic acid ester, trimellitate, polyol ester, citrate, phosphate, polyester, epoxy fatty acid.
In a second aspect, the invention provides a method for preparing a detachable silane-modified polyether composition, comprising the steps of:
And (3) preparation of the component A: heating the first filler to 80-110 ℃ for vacuum dehydration, and cooling to finish pretreatment of the first filler; preparing raw materials according to a proportion, adding the raw materials required by the component A into a stirrer, vacuumizing, and uniformly stirring to obtain the component A;
And (3) preparation of a component B: heating the second filler to 80-110 ℃ for vacuum dehydration, and cooling to complete pretreatment of the second filler; preparing raw materials according to the proportion, adding the raw materials required by the component B into a stirrer, vacuumizing, and uniformly stirring to obtain the component B.
In a third aspect, the invention provides an application of a detachable silane modified polyether composition, wherein the component A and the component B are uniformly mixed according to a volume ratio of 2:1 and then used as sealant.
The beneficial effects of the invention include:
1. The invention synthesizes the silicon ether cross-linking agent with disulfide bonds, and the cross-linking agent has good compatibility with the system provided by the invention, and can greatly reduce the tolerance to corresponding solvents so as to achieve the effect of debonding.
2. According to the invention, the flowability and toughness of the detachable silane-modified polyether composition are balanced by compounding the two silane-modified polyethers with different viscosities, and the mechanical properties of the detachable silane-modified polyether composition can be adjusted by selecting the mass ratio of the two silane-modified polyethers with different viscosities, so that the requirements of different base materials and use scenes can be met.
3. The preparation method of the detachable silane modified polyether composition is simple in operation, mild in condition and suitable for large-scale industrial production.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a detachable silane modified polyether composition, which comprises an A component and a B component in parts by weight,
The component A comprises 30-100 parts of epoxy resin, 1-30 parts of first plasticizer, 0-10 parts of cross-linking agent, 1-30 parts of first filler and 0-10 parts of catalyst;
The component B comprises 30-100 parts of silane modified polyether, 0-5 parts of antioxidant, 0-50 parts of second filler, 1-30 parts of second plasticizer, 1-20 parts of accelerator and 0-10 parts of cross-linking agent;
The sum of the amounts of the cross-linking agent in the component A and the cross-linking agent in the component B is 2-10 parts, and the sum of the amounts of the first filler and the second filler is 30-60 parts;
The structural formula of the cross-linking agent is as follows:
wherein, the R1 group is selected from any one of C1-C6 alkoxy, C2-C6 alkenyloxy, C3-C6 epoxy, C2-C6 ester, C2-C6 alkenyl and hydrosilyl; n is any integer from 1 to 8.
In some embodiments of the present invention, the method for preparing the crosslinking agent includes the steps of: adding trimethoxysilane with substituent R1 and water into a container, dropwise adding a condensation catalyst into the container under stirring, heating to 60-100 ℃ for reaction for 1-3h, distilling under reduced pressure to remove low-boiling substances for 1-3h, adding bis- [3- (triethoxysilyl) propyl ] -disulfide into the container, and continuously reacting under reduced pressure for 1-3h to obtain the cross-linking agent.
In some embodiments of the invention, the cross-linking agent has a formula selected from the group consisting of
Wherein n is not less than 4.
In some embodiments of the present invention, the crosslinking agent in the component a is a first crosslinking agent, and the structure of the first crosslinking agent is shown in formula II:
Wherein n is greater than or equal to 4.
In some embodiments of the present invention, the crosslinking agent in the B component is a second crosslinking agent and/or a third crosslinking agent, where the structure of the second crosslinking agent is shown in formula III, and the structure of the third crosslinking agent is shown in formula IV:
Wherein n is greater than or equal to 4;
Wherein n is greater than or equal to 4.
In some embodiments of the invention, the silane-modified polyether comprises a first silane-modified polyether and a second silane-modified polyether, wherein the weight ratio of the first silane-modified polyether to the second silane-modified polyether is 1 (1-2).
In some embodiments of the present invention, the A component further comprises 0-5 parts of color paste.
In some embodiments of the invention, the B component further comprises 0-5 parts of a water scavenger.
Some embodiments of the present invention, the A component comprises 50-90 parts of the epoxy resin, 5-20 parts of the first plasticizer, 1-5 parts of the cross-linking agent, 1-20 parts of the first filler, 1-5 parts of the catalyst and 0-3 parts of the color paste;
The component B comprises 40-80 parts of the silane modified polyether, 0-3 parts of the antioxidant, 1-20 parts of the second filler, 5-20 parts of the second plasticizer, 1-10 parts of the accelerator, 1-2 parts of the cross-linking agent and 0-3 parts of the water remover.
In some embodiments of the invention, the epoxy resin is at least one of a bisphenol a type epoxy resin and a bisphenol F type epoxy resin. Specifically, the epoxy resin is bisphenol A type epoxy resin.
In some embodiments of the invention, the viscosity of the epoxy resin is 100-200000 mPas at 25 ℃; specifically, the viscosity of the epoxy resin is 2000-100000 mPa.s at 25 ℃; more specifically, the viscosity of the epoxy resin is 5000-20000 mPas at 25 ℃.
In some embodiments of the invention, the first filler and the second filler are one or more of calcium carbonate, aluminum oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, and silicon dioxide.
Some embodiments of the invention, the first plasticizer and the second plasticizer have a viscosity of 100 to 200000 mPa-s at 25 ℃; specifically, the viscosity of the first plasticizer and the second plasticizer at 25 ℃ is 200-10000 mPa.s; more specifically, the viscosity of the first plasticizer and the second plasticizer at 25 ℃ is 300-6000 mpa·s.
In some embodiments of the invention, the first plasticizer and the second plasticizer are one or more of butadiene, polyether polyol, phthalate, aliphatic dibasic acid ester, trimellitate, polyol ester, citrate, phosphate, polyester, epoxy fatty acid.
In some embodiments of the invention, the cross-linking agent is an epoxysilane.
Some embodiments of the invention, the catalyst is a tin-based catalyst; specifically, the catalyst is one or more of tributyltin oxide (TBTO), dibutyl tin chloride (DBTC), di-n-octyl-bis (2-ethylhexyl thioglycolate) tin (DOTE), dibutyl tin bis (acetylacetonate) and dioctyl tin dilaurate.
In the embodiment of the invention, the epoxy resin is bisphenol A type epoxy resin purchased from Nanya new materials; the first plasticizer and the second plasticizer are polyether polyols with molecular weight of 4000 and are purchased from Lanxingdong; the catalyst is dibutyl tin bis (acetylacetonate), purchased from the eastern chemical industry; the cross-linking agent in the A component in the comparative example 1 and the comparative example 3 is 3-glycidoxypropyl trimethoxysilane (KH-560) which is purchased from Zhejiang Wo Xingman new materials technology Co., ltd; the water scavenger vinyl trimethoxysilane is A-171, and is purchased from Zhejiang Wo Xingman new material science and technology Co., ltd; the silane-modified polyethers were purchased from brillouin chemistry, including 6000 viscosity and 45000 viscosity silane-modified (capped) polyethers.
In some embodiments of the present invention, the method for preparing the crosslinking agent includes the steps of: adding trimethoxysilane with substituent R1 and water into a three-neck flask with a thermometer, dropwise adding a condensation catalyst (1% of the total mass of reactants) under stirring, heating to 80 ℃ for reaction for 2h, distilling under reduced pressure to remove low-boiling substances for 2h, adding bis- [3- (triethoxysilyl) propyl ] -disulfide, and continuously reacting under reduced pressure for 2h to obtain the cross-linking agent with the structure shown in the formula I.
The invention creatively synthesizes the silicon ether cross-linking agent with disulfide bonds, the cross-linking agent has good compatibility in the system, and introduces a large number of amino groups, alkoxy groups, epoxy groups and other active groups, and can be adapted to different base materials to generate chemical bond connection with the surface groups of the base materials, thereby obviously improving the adhesive force of the organosilicon composition and the subsequent disassembly effect under corresponding reducing solution.
The invention also provides a preparation method of the detachable silane modified polyether composition, which comprises the following steps:
And (3) preparation of the component A: heating the first filler to 80-110 ℃ for vacuum dehydration for 2-3h, and vacuum cooling to room temperature to finish pretreatment of the first filler; preparing raw materials according to a proportion, adding the raw materials required by the component A into a stirrer, vacuumizing, and uniformly stirring to obtain the component A;
And (3) preparation of a component B: heating the second filler to 80-110 ℃ for vacuum dehydration for 2-3h, and vacuum cooling to room temperature to finish pretreatment of the second filler; preparing raw materials according to the proportion, adding the raw materials required by the component B into a stirrer, vacuumizing, and uniformly stirring to obtain the component B.
The invention also provides an application of the detachable silane modified polyether composition, which comprises the following steps: and uniformly mixing the component A and the component B according to the volume ratio of 2:1, and using the mixture as sealant.
The parts in examples and comparative examples are parts by weight and the values in tables 1 and 2 are parts by weight.
Example 1
This example provides a removable silane-modified polyether composition whose raw materials for the a and B components are shown in table 1 and prepared by the following method:
and (3) a component A:
The preparation method of the first cross-linking agent comprises the following steps: 1mol of N- (2-aminoethyl-3-aminopropyl) trimethoxysilane and 0.1mol of water are added into a three-neck flask with a thermometer, tetrabutyl titanate (1% of the total mass of reactants) is dropwise added under the condition of magnetic stirring, the temperature is raised to 80 ℃ for reaction for 2 hours, low-boiling substances are removed by reduced pressure distillation for 2 hours, and 0.05mol of bis- [3- (triethoxysilyl) propyl ] -disulfide is added for continuous reaction for 2 hours under the condition of reduced pressure, so that the first cross-linking agent with the structure of formula II is prepared, wherein n=5.
Wherein n=5; the bis- [3- (triethoxysilyl) propyl ] -disulphide used has a CAS number 56706-10-6 and the N- (2-aminoethyl-3-aminopropyl) trimethoxysilane has a CAS number 1760-24-3.
The preparation method of the component A comprises the following steps: dehydrating calcium carbonate with the D50 particle size of 2 mu m and silicon dioxide with the D50 of 0.1 mu m at 110 ℃ for 3 hours, and then cooling to room temperature to finish pretreatment of the calcium carbonate and the silicon dioxide; 31 parts of bisphenol A epoxy resin with viscosity of 8000 mPas, 40 parts of bisphenol A epoxy resin with viscosity of 15000 mPas and 12 parts of polyether polyol with molecular weight of 4000 are added into a planetary mixer for dispersion; adding 7 parts of pretreated calcium carbonate, 6 parts of pretreated silicon dioxide, 0.5 part of black color paste and 1 part of first cross-linking agent into a planetary mixer for dispersion; then adding 2.5 parts of di (acetylacetonate) dibutyl tin into a planetary stirrer for dispersion, and then stirring the components in vacuum uniformly to obtain the component A.
The preparation method of the second crosslinking agent comprises the following steps: 1mol of gamma-glycidoxypropyl trimethoxysilane and 0.1mol of water are added into a three-neck flask with a thermometer, tetrabutyl titanate (1% of the total mass of reactants) is dropwise added under the condition of magnetic stirring, the temperature is raised to 80 ℃ for reaction for 2 hours, low-boiling substances are removed by reduced pressure distillation for 2 hours, and then 0.05mol of bis- [3- (triethoxysilyl) propyl ] -disulfide is added for continuous reaction for 2 hours under the condition of reduced pressure, so that the second cross-linking agent with the structure of formula III is prepared, wherein n=5.
Wherein n=5; the gamma-glycidoxypropyl trimethoxysilane used had a CAS number of 2530-83-8.
The preparation method of the component B comprises the following steps: dehydrating calcium carbonate with the D50 of 2 mu m and silicon dioxide with the D50 of 0.1 mu m at 110 ℃ for 3 hours, and cooling to room temperature for pretreatment; 30 parts of an MS resin (silane-modified polyether) having a viscosity of 6000 mPas, 35.5 parts of a silane-modified polyether having a viscosity of 45000 mPas and 15 parts of a polyether polyol having a molecular weight of 4000 are added to a planetary mixer to be dispersed; adding 6 parts of pretreated calcium carbonate and 6 parts of pretreated silicon dioxide into a planetary mixer for dispersion; and then adding 1 part of a second cross-linking agent, 0.5 part of an antioxidant, 5 parts of an accelerator and 1 part of a water scavenger into a planetary mixer for dispersion, and then uniformly stirring the components in vacuum to obtain a component B.
Example 2
This example provides a removable silane-modified polyether composition having the raw materials of the a and B components shown in table 1, the embodiment being the same as example 1 except that: the amount of the second crosslinking agent added in the component B was 2 parts, and the amount of the MS resin (silane-modified polyether) having a viscosity of 45000 mPas added was 34.5 parts.
Example 3
This example provides a removable silane-modified polyether composition having the raw materials of the a and B components shown in table 1, the embodiment being the same as example 1 except that: the amount of the second crosslinking agent added in the component B was 3 parts, and the amount of the MS resin (silane-modified polyether) having a viscosity of 45000 mPas added was 33.5 parts.
Example 4
This example provides a removable silane-modified polyether composition having the raw materials of the a and B components shown in table 1, the embodiment being the same as example 2 except that: the cross-linking agent in the component B is a third cross-linking agent.
The preparation method of the third crosslinking agent comprises the following steps: adding 0.1mol of gamma-aminopropyl triethoxysilane and 0.1mol of water into a three-neck flask, dropwise adding tetrabutyl titanate (1% of the total mass of reactants) under the condition of magnetic stirring, heating to 80 ℃ for reaction for 2 hours, distilling under reduced pressure to remove low-boiling substances for 2 hours, and adding 0.05mol of bis- [3- (triethoxysilane) propyl ] -disulfide for continuous reaction under reduced pressure for 2 hours to prepare the third cross-linking agent with the structure of formula IV, wherein n=5.
Wherein n=5; the gamma-aminopropyl triethoxysilane used has a CAS number of 13822-56-5.
Comparative example 1
This comparative example provides a detachable silane-modified polyether composition whose raw materials of the a and B components are shown in table 2, and the embodiment is the same as example 2 except that: the cross-linking agent in the component A is 3-glycidoxypropyl trimethoxysilane (CAS number: 2530-83-8), and the structural formula is as follows:
Comparative example 2
This comparative example provides a detachable silane-modified polyether composition whose raw materials of the a and B components are shown in table 2, and the embodiment is the same as example 2 except that: the cross-linking agent in the component B is isopropyl trimethoxysilane (CAS number: 4420-74-0), and the structural formula is as follows:
Comparative example 3
This comparative example provides a detachable silane-modified polyether composition whose raw materials of the a and B components are shown in table 2, and the embodiment is the same as example 2 except that: the cross-linking agent in the component A is 3-glycidoxypropyl trimethoxy silane, and the cross-linking agent in the component B is isopropyl trimethoxy silane.
Performance testing
The components A and B prepared in examples 1 to 4 and comparative examples 1 to 3, respectively, having a thickness of 1mm, were sandwiched between two cleaned aluminum die-cast plates in a mass ratio of 1: 2A uniformly mixed detachable silane-modified polyether composition, according to a bonding size of 12.5X25X0.2 mm, was prepared into groups of Al-Al, and left at room temperature of 25℃for 7 days to cure the crosslinking agent, one group was designated as a first adhesion test body as an initial state, and the other group was placed in a reducing solution (the reducing solution consisting of a reducing substance and a solvent, and in the present example, 0.1mol/L of N-tributylphosphine and N, N-dimethylformamide) and designated as a second adhesion test body. The tensile shear adhesive strength of the first adhesive test article was measured according to the method defined in GB-T7124-2008 "measurement of tensile shear strength of adhesive (rigid material to rigid material)". In addition, the adhesive face of the second adhesive test body was observed, and the cohesive failure rate (the ratio of the adhesive area of the cohesive-damaged silicone rubber to the area of the adhesive portion) of the second adhesive test body was observed, and the test results are shown in tables 1 and 2. When peeling occurs without adhesion, the peeling was evaluated as "peeling".
TABLE 1
TABLE 2
As can be seen from the test results in tables 1 and 2, the initial tensile shear strength of the detachable silane-modified polyether compositions of examples 1 to 4 is not lower than 5.32MPa, the failure mode is cohesive failure, the tensile shear strength is greatly reduced after the composition is immersed in a reducing solvent for 4 hours, and is lower than 0.83MPa, and the failure mode is interfacial peeling; the silane-modified polyether compositions of comparative examples 1 to 3 had an initial tensile shear strength of not less than 7.65MPa, a failure mode of cohesive failure, a tensile shear strength of more than 3.58MPa after soaking in a reducing solvent for 4 hours, and a failure mode of cohesive failure or partial interfacial peeling, and as can be seen from the above data, the detachable silane-modified polyether composition of the present application had an tensile shear strength of not less than 5.32MPa, and the adhesion test body was peeled off without damaging the components of the detachable silane-modified polyether composition in the reducing solvent.
While embodiments of the present invention have been described in detail hereinabove, it will be apparent to those skilled in the art that various modifications and variations can be made to these embodiments. It is to be understood that such modifications and variations are within the scope and spirit of the present invention as set forth in the following claims. Moreover, the invention described herein is capable of other embodiments and of being practiced or of being carried out in various ways.
Claims (12)
1. The detachable silane modified polyether composition is characterized by comprising a component A and a component B, wherein the component A comprises, by weight, 30-100 parts of epoxy resin, 1-30 parts of a first plasticizer, 0-10 parts of a crosslinking agent, 1-30 parts of a first filler and 0-10 parts of a catalyst;
The component B comprises 30-100 parts of silane modified polyether, 0-5 parts of antioxidant, 0-50 parts of second filler, 1-30 parts of second plasticizer, 1-20 parts of accelerator and 0-10 parts of cross-linking agent;
The sum of the amounts of the cross-linking agent in the component A and the cross-linking agent in the component B is 2-10 parts, and the sum of the amounts of the first filler and the second filler is 30-60 parts;
The structural formula of the cross-linking agent is as follows:
wherein, the R1 group is selected from any one of C1-C6 alkoxy, C2-C6 alkenyloxy, C3-C6 epoxy, C2-C6 ester, C2-C6 alkenyl and hydrosilyl; n is any integer from 1 to 8.
2. The detachable silane-modified polyether composition of claim 1, wherein said crosslinking agent is prepared by a process comprising the steps of: adding trimethoxysilane with substituent R1 and water into a container, dropwise adding a condensation catalyst into the container under stirring, heating to 60-100 ℃ for reaction for 1-3h, distilling under reduced pressure to remove low-boiling substances for 1-3h, adding bis- [3- (triethoxysilyl) propyl ] -disulfide into the container, and continuously reacting under reduced pressure for 1-3h to obtain the cross-linking agent.
3. The removable silane-modified polyether composition of claim 1, wherein said cross-linking agent has a structural formula selected from the group consisting of
Wherein n is not less than 4.
4. The removable silane-modified polyether composition of claim 1, wherein said crosslinking agent in component a is a first crosslinking agent having a structure according to formula II:
Wherein n is greater than or equal to 4.
5. The detachable silane-modified polyether composition according to claim 1, wherein the crosslinking agent in the component B is a second crosslinking agent and/or a third crosslinking agent, the structure of the second crosslinking agent is shown in formula III, and the structure of the third crosslinking agent is shown in formula IV:
Wherein n is greater than or equal to 4;
Wherein n is greater than or equal to 4.
6. The removable silane-modified polyether composition of claim 1, wherein said silane-modified polyether comprises a first silane-modified polyether and a second silane-modified polyether, said first silane-modified polyether and said second silane-modified polyether being present in a weight ratio of 1 (1-2).
7. The removable silane-modified polyether composition according to claim 1, wherein said a component comprises 50 to 90 parts of said epoxy resin, 5 to 20 parts of said first plasticizer, 1 to 5 parts of said crosslinking agent, 1 to 20 parts of said first filler, 1 to 5 parts of said catalyst and 0 to 3 parts of said color paste;
The component B comprises 40-80 parts of the silane modified polyether, 0-3 parts of the antioxidant, 1-20 parts of the second filler, 5-20 parts of the second plasticizer, 1-10 parts of the accelerator, 1-2 parts of the cross-linking agent and 0-3 parts of the water remover.
8. The detachable silane-modified polyether composition according to claim 1, wherein the viscosity of said epoxy resin at 25 ℃ is 100 to 200000 mPa-s and the viscosity of said first plasticizer and said second plasticizer at 25 ℃ is 100 to 200000 mPa-s.
9. The removable silane-modified polyether composition of claim 1, wherein said first filler and said second filler are one or more of calcium carbonate, aluminum oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, and silicon dioxide.
10. The removable silane-modified polyether composition of claim 1, wherein said first plasticizer and said second plasticizer are one or more of butadiene, polyether polyol, phthalate, aliphatic dibasic acid ester, trimellitate, polyol ester, citrate, phosphate, polyester, epoxy fatty acid.
11. A method of preparing the removable silane-modified polyether composition of any of claims 1-10, comprising the steps of:
And (3) preparation of the component A: heating the first filler to 80-110 ℃ for vacuum dehydration, and cooling to finish pretreatment of the first filler; preparing raw materials according to a proportion, adding the raw materials required by the component A into a stirrer, vacuumizing, and uniformly stirring to obtain the component A;
And (3) preparation of a component B: heating the second filler to 80-110 ℃ for vacuum dehydration, and cooling to complete pretreatment of the second filler; preparing raw materials according to the proportion, adding the raw materials required by the component B into a stirrer, vacuumizing, and uniformly stirring to obtain the component B.
12. Use of a detachable silane-modified polyether composition according to any of claims 1-10, characterized in that said a-component and said B-component are homogeneously mixed in a volume ratio of 2:1 for use as a sealant.
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