CN115466595A - Bi-component modified silicone rubber adhesive for bonding automobile cabin door and preparation method and bonding process thereof - Google Patents
Bi-component modified silicone rubber adhesive for bonding automobile cabin door and preparation method and bonding process thereof Download PDFInfo
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- CN115466595A CN115466595A CN202211383084.2A CN202211383084A CN115466595A CN 115466595 A CN115466595 A CN 115466595A CN 202211383084 A CN202211383084 A CN 202211383084A CN 115466595 A CN115466595 A CN 115466595A
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- component
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- silicone rubber
- bonding
- modified silicone
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 38
- 239000000853 adhesive Substances 0.000 title claims abstract description 36
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 36
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title description 8
- 239000004432 silane-modified polyurethane Substances 0.000 claims abstract description 18
- -1 polysiloxane Polymers 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004014 plasticizer Substances 0.000 claims abstract description 14
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 11
- 239000012459 cleaning agent Substances 0.000 claims abstract description 10
- 239000002250 absorbent Substances 0.000 claims abstract description 9
- 230000002745 absorbent Effects 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 9
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 8
- 239000000049 pigment Substances 0.000 claims abstract description 8
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 8
- 238000004026 adhesive bonding Methods 0.000 claims abstract description 7
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 239000000945 filler Substances 0.000 claims abstract description 7
- 239000002516 radical scavenger Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 25
- 239000002994 raw material Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 14
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 230000003213 activating effect Effects 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 claims description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 3
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical group [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000003017 thermal stabilizer Substances 0.000 claims description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 2
- 229920003169 water-soluble polymer Polymers 0.000 claims description 2
- 102100035474 DNA polymerase kappa Human genes 0.000 claims 1
- 101710108091 DNA polymerase kappa Proteins 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 229910000831 Steel Inorganic materials 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010959 steel Substances 0.000 abstract description 4
- 239000000919 ceramic Substances 0.000 abstract description 2
- 239000011521 glass Substances 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract 1
- 238000004070 electrodeposition Methods 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010422 painting Methods 0.000 description 9
- 239000000565 sealant Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 238000011056 performance test Methods 0.000 description 7
- 239000003973 paint Substances 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 2
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- YKGYQYOQRGPFTO-UHFFFAOYSA-N bis(8-methylnonyl) hexanedioate Chemical compound CC(C)CCCCCCCOC(=O)CCCCC(=O)OCCCCCCCC(C)C YKGYQYOQRGPFTO-UHFFFAOYSA-N 0.000 description 2
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000004587 polysulfide sealant Substances 0.000 description 2
- 239000004588 polyurethane sealant Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000004806 diisononylester Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000008036 rubber plasticizer Substances 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a bi-component modified silicone rubber adhesive for bonding automobile doors and a bonding process thereof. The modified silicone rubber consists of the following components: polysiloxane, silane modified polyurethane, a plasticizer, a filler, a pigment, a thixotropic agent, an ultraviolet absorbent, a heat stabilizer, a cross-linking agent, a water scavenger, an adhesion promoter and a catalyst; the bonding process adopts a surface active agent and a cleaning agent for activation and cleaning, and then the non-woven fabric is used for wiping and gluing. According to the invention, the silane modified polyurethane is added to modify the common silicone rubber, so that the obtained modified silicone rubber has extremely low TVOC content, is ecological and environment-friendly, realizes quick bonding, and has good flexibility, cohesiveness, high temperature resistance and electrocoating performance. The adhesive can be firmly bonded to materials such as steel, aluminum, glass, plastics, ceramics and the like, and can be widely used in the fields of automobiles, high-speed trains, mechanical equipment and the like.
Description
Technical Field
The invention belongs to the technical field of silicone rubber adhesives, and particularly relates to a bi-component modified silicone rubber adhesive for bonding automobile doors, and a preparation method and a bonding process thereof.
Background
The automobile skin and the framework are connected by a traditional welding method, welding spots are not smooth in appearance no matter how the welding spots are polished and coated with putty, and attractiveness is affected. In addition, as the weight reduction of automobiles progresses, aluminum materials and light materials are used in large quantities instead of steel materials, and welding of steel materials and aluminum materials and the like becomes difficult, and thus cabin door adhesive glue is growing in popularity.
After the cabin door is bonded, the cabin door needs to be initially fixed within 1 hour and needs to be repaired; the adhesive has initial adhesion after 2 hours, and needs to be cohesively damaged; the single-component glue is moisture-absorbing and curing, is slow in curing, cannot meet the bonding requirement of the cabin door, and can meet the use requirement only by selecting the double-component glue. The two-component glue can be selected from the following materials: polysulfide sealant, epoxy sealant, acrylic sealant, polyurethane sealant, MS (SPU) sealant and silicone rubber sealant. From the experimental result, the polysulfide sealant and the acrylic sealant do not meet the environmental protection requirement; the toughness and the peeling strength of the epoxy sealant are poor, and the epoxy sealant does not meet the requirement of cabin door bonding toughness; the initial adhesion of the polyurethane sealant is poor, cohesive failure cannot be achieved, and subsequent process construction cannot be carried out; the MS (SPU) sealant has excellent performance after being bonded, but the electrophoretic performance of the MS (SPU) sealant is poor; after the silicon rubber is bonded, various performances are excellent, but the paint has a shrinkage cavity phenomenon and is not high in strength.
Therefore, it is necessary to develop a novel silicone rubber adhesive for bonding automobile doors, which has no shrinkage cavities and high strength.
Disclosure of Invention
The invention aims to provide a bi-component modified silicone rubber adhesive for bonding an automobile door, and simultaneously provides a preparation method of the bi-component modified silicone rubber adhesive, which is the second invention aim of the invention.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
the bi-component modified silicone rubber adhesive for bonding the automobile cabin door is prepared from a component A and a component B, wherein the component A comprises the following raw materials in parts by weight:
polysiloxane resin: 30-55 parts of (by weight),
silane-modified polyurethane: 3-20 parts of (by weight),
plasticizer: 3-20 parts of (by weight),
filling: 25-40 parts of (by weight),
thermal stabilizer: 0.1 to 2 portions of the raw materials,
ultraviolet light absorber: 0.1-2 parts;
the component B comprises the following raw materials in parts by weight:
a crosslinking agent: 5-10 parts of (A) a water-soluble polymer,
thixotropic agent: 1-2 parts of (A) a solvent,
pigment: 1-2 parts of (A) a solvent,
and (3) water removal agent: 0.1-1 part of (by weight),
an adhesion promoter: 0.1-1 part of (by weight),
catalyst: 0.1-1 part.
Preferably, in the component A, the polysiloxane is alpha, omega-dihydroxy polysiloxane, and the silane modified polyurethane is T-920R jm102 silane modified polyurethane.
Further preferably, in the component A, the plasticizer is one or a mixture of two of phthalic acid \8206, diisodecyl phthalate (DIDP) or phthalic acid \8206anddiisononyl phthalate (DINP); the filler is one or the mixture of calcium carbonate and calcium oxide.
Further preferably, in the component a, the heat stabilizer is a ferrocene-based heat stabilizer, preferably acetyl ferrocene, vinyl ferrocene, ethynyl ferrocene, ferrocenyl methyl alcohol; the ultraviolet resistant absorbent is benzotriazole ultraviolet absorbent, preferably German Basff ultraviolet absorbent Tinuvin326, tinuvin327 and Tinuvin329.
Preferably, in the component B, the cross-linking agent is one or a mixture of more than two of tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane or propyltrimethoxysilane; the thixotropic agent is silicon dioxide or argil; the pigment is carbon black or titanium dioxide.
Further preferably, in the component B, the water removing agent is calcium oxide or vinyl trimethoxy silane, the adhesion promoter is one or a mixture of more than two of gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxy silane and N- (beta-aminoethyl) -gamma-aminopropyl trimethoxy silane, and the catalyst is dibutyltin dilaurate or dibutyltin diacetate.
Preferably, the preparation method of the bi-component modified silicone rubber adhesive for bonding the car door comprises the following steps:
(1) Heating the raw materials of the component A to 50-100 ℃ under vacuum, and stirring and mixing for 1-3h at a stirring speed of 500-800r/min to obtain a component A;
(2) Taking the raw materials of the component B, stirring and mixing the raw materials for 1-3h at the speed of 500-800r/min under the vacuum condition to obtain the component B;
(3) And mixing the component A and the component B according to the mass ratio of (10-15) to 1 to obtain the bi-component modified silicone rubber adhesive.
The invention also discloses an automobile cabin door bonding process, which comprises the following steps:
1) Mixing an activating agent with deionized water, spraying the mixture on the metal surface of the automobile cabin door, and staying for 3-5min;
2) Cleaning with a cleaning agent, wiping with non-woven fabric, and gluing after 3-5min, wherein the glue is the bi-component modified silicone rubber adhesive.
Preferably, the activating agent is one or a mixture of more than two of methylsulfonyl chloride, sulfonyl chloride and phosphoric acid; the cleaning agent is an alcohol solution; the mass and dosage ratio of the activating agent, the deionized water and the cleaning agent is as follows: activating agent: 1-20 parts of deionized water: 100 parts of cleaning agent: 200-400 parts.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the common silicon rubber, the bi-component modified silicon rubber has the advantages that by controlling the technical parameters such as the type and content of polysiloxane and silane modified polyurethane, the type and content of plasticizer, the type and content of filler, the type and content of activator and the like, the prepared product has extremely low TVOC content, is ecological and environment-friendly, can realize quick bonding, has good flexibility, cohesiveness, high temperature resistance and electrophoretic painting performance, and is a practical ideal adhesive for bonding the car doors;
2. the invention adopts diisodecyl phthalate (DIDP) or diisononyl phthalate (DINP) without silicone oil, successfully solves the shrinkage cavity phenomenon of the common silicone rubber after painting;
3. the activating cleaning agent can be suitable for surface treatment before gluing of any metal material, ensures that an automobile cabin door and the adhesive are easier to combine after treatment, can be suitable for firmly bonding materials such as steel, aluminum, glass, plastic, ceramic and the like, is widely applied to the fields of automobiles, high-speed trains, mechanical equipment and the like, and has simple and universal bonding process.
Detailed description of the preferred embodiment
The invention is further described with reference to specific examples, but the scope of the invention is not limited to the examples, which are set forth in the claims.
It should be noted that the components or the parts of the raw materials in the present invention are all in parts by mass.
Example 1:
the bi-component modified silicone rubber adhesive for bonding the automobile door comprises a component A and a component B, wherein the component A comprises the following components in parts by weight: 30 parts of alpha, omega-dihydroxy polysiloxane, 3 parts of T-920R jm102 silane modified polyurethane, 3 parts of phthalic acid \8206, diisodecyl ester (DIDP) (plasticizer), 25 parts of calcium carbonate (filler), 0.1 part of acetyl ferrocene (heat stabilizer), and 0.1 part of German Pasteur Tinuvin326 (ultraviolet-resistant absorbent); and B component: 5 parts of tetraethoxysilane (cross-linking agent), 1 part of silicon dioxide (thixotropic agent), 1 part of carbon black (pigment), 0.1 part of calcium oxide (water removal agent), 0.1 part of gamma-aminopropyltriethoxysilane (adhesion promoter) and 0.1 part of dibutyltin dilaurate (catalyst).
Preparing a component A: weighing the raw materials according to the composition of the component A, putting the raw materials into a stirring kettle, heating to 50 ℃, starting stirring under a vacuum condition, stirring at the speed of 500r/min for 1h, dehydrating, and cooling to room temperature to obtain the product.
Preparing a component B: weighing the raw materials according to the composition of the component B, mixing under a vacuum condition, starting stirring at a stirring speed of 500r/min for 1h to obtain the finished product. And compounding the component A and the component B according to the mass ratio of 10.
The activating and cleaning method comprises the following specific steps: firstly weighing 1 part of methylsulfonyl chloride and 100 parts of deionized water, uniformly mixing, wiping the mixture on a metal surface by using non-woven fabric, cleaning by using 200 parts of alcohol solution after 3 minutes, wiping by using the non-woven fabric, and gluing after 3 minutes.
Example 2:
the bi-component modified silicone rubber adhesive for bonding the automobile cabin door comprises a component A and a component B, wherein the component A comprises the following components in parts by weight: 40 parts of alpha, omega-dihydroxy polysiloxane, 10 parts of T-920R jm102 silane modified polyurethane, 10 parts of phthalic acid \8206, diisononyl ester (DINP) (plasticizer), 32 parts of calcium oxide (filler), 1 part of vinyl ferrocene (heat stabilizer) and 1 part of German BASF Tinuvin327 (ultraviolet-resistant absorbent); and the component B comprises: 3 parts of methyltrimethoxysilane, 4 parts of methyltriethoxysilane (crosslinking agent), 1.5 parts of argil (thixotropic agent), 1.5 parts of titanium dioxide (pigment), 0.5 part of vinyltrimethoxysilane (water removal agent), 0.5 part of gamma-glycidoxypropyltrimethoxysilane (adhesion promoter) and 0.5 part of dibutyltin diacetate (catalyst).
Preparing a component A: weighing the raw materials according to the composition of the component A, putting the raw materials into a stirring kettle, heating to 75 ℃, starting stirring under a vacuum condition, wherein the stirring speed is 650r/min, the stirring time is 2 hours, dehydrating, and cooling to room temperature to obtain the composition.
Preparing a component B: weighing the raw materials according to the composition of the component B, mixing under vacuum condition, starting stirring at the stirring speed of 650r/min for 2h to obtain the final product. And (3) compounding the component A and the component B according to the mass ratio of 12.
The activating and cleaning method comprises the following specific steps: firstly weighing 10 parts of sulfonyl chloride and 100 parts of deionized water, uniformly mixing, wiping the mixture on the surface of a metal by using non-woven fabric, cleaning the metal surface by using 300 parts of alcohol solution after 4 minutes, wiping the metal surface by using the non-woven fabric, and gluing the metal surface after 4 minutes.
Example 3:
the bi-component modified silicone rubber adhesive for bonding the automobile cabin door comprises a component A and a component B, wherein the component A comprises the following components in parts by weight: 55 parts of alpha, omega-dihydroxy polysiloxane, 20 parts of T-920R jm102 silane modified polyurethane, 20 parts of phthalic acid \8206, diisodecyl ester (DIDP) (plasticizer), 40 parts of calcium carbonate (filler), 2 parts of ethynyl ferrocene (heat stabilizer) and 2 parts of German basf Tinuvin329 (ultraviolet-resistant absorbent); and the component B comprises: 5 parts of dimethyldimethoxysilane, 5 parts of propyltrimethoxysilane (crosslinker), 2 parts of silicon dioxide (thixotropic agent), 2 parts of carbon black (pigment), 1 part of calcium oxide (water scavenger), 1 part of N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane (adhesion promoter) and 1 part of dibutyltin dilaurate (catalyst).
Preparing a component A: weighing the raw materials according to the composition of the component A, putting the raw materials into a stirring kettle, heating the mixture to 100 ℃, starting stirring under a vacuum condition with the stirring speed of 800r/min and the stirring time of 3h, dehydrating, and cooling the mixture to room temperature to obtain the finished product.
Preparing a component B: weighing the raw materials according to the composition of the component B, mixing under vacuum condition, starting stirring at the stirring speed of 800r/min for 3h to obtain the final product. And compounding the component A and the component B according to a mass ratio of 15.
The activating and cleaning method comprises the following specific steps: firstly weighing 20 parts of phosphoric acid and 100 parts of deionized water, uniformly mixing, wiping the mixture on the surface of a metal by using a non-woven fabric, cleaning the metal surface by using 400 parts of an alcohol solution after 5 minutes, wiping the metal surface by using the non-woven fabric, and gluing the metal surface after 5 minutes.
Comparative example 1:
the adhesive composition and preparation method of this example are different from example 1 in that T-920R jm102 silane-modified polyurethane is not added to the A component.
The rest of the process was the same as in example 1.
Comparative example 2:
the adhesive composition and the preparation method of the present example are different from those of example 1 in that the plasticizer used in the component a is methyl silicone oil.
The rest is the same as in example 1.
Comparative example 3:
the adhesive component and the preparation method of the embodiment are different from the embodiment 1 in that T-920R jm102 silane modified polyurethane is not added into the component A; the plasticizer is methyl silicone oil.
The rest is the same as in example 1.
In other embodiments, when the silicone rubber adhesive is prepared, the heating temperature in the step (1) can be selected within the range of 50-100 ℃, the stirring speed in the steps (1) and (2) is 500-800r/min, and the stirring time is 1-3 h.
Performance test
The modified silicone rubber adhesives prepared in examples 1 to 3 and comparative examples 1 to 3 were tested for initial set time, elongation, hardness, shear strength, electrophoretic properties, and painting properties, respectively. The initial fixing time test method comprises the steps of initially fixing the adhesive without touching hands; the standard of the elongation performance test is GB/T528; the hardness performance test is based on the standard GB/T531.1; the shear strength performance test is based on the standard GB/T7124; the electrophoresis performance test method is that the adhesive does not crack, differentiate and change at the temperature of 200 ℃ for 50 min; the paint performance test method is to observe whether the shrinkage cavity phenomenon exists after painting.
The test results are shown in table 1 below.
Table 1 statistical table for various performance tests of modified silicone rubber adhesive
| Initial fixed time (min) | Elongation (%) | Hardness (Shao A) | Shear strength (MPa) | Electrophoretic Performance (200 ℃ for 50 min) | Paint performance | |
| Comparative example 1 | 30 | 150 | 35 | 1.6 | Not good | Without shrinkage cavity |
| Comparative example 2 | 24 | 160 | 36 | 1.7 | Good effect | With a reduced bore |
| Comparative example 3 | 30 | 135 | 33 | 1.5 | Not good | With a reduced bore |
| Example 1 | 22 | 180 | 38 | 1.8 | Good effect | Without shrinkage cavity |
| Example 2 | 25 | 220 | 42 | 2.2 | Is good | Without shrinkage cavity |
| Example 3 | 27 | 250 | 48 | 2.5 | Is good | Without shrinkage cavity |
As can be seen from the test results, examples 1, 2 and 3 all had good initial set time, elongation, hardness and shear strength. In addition, since the silane-modified polyurethane was added in each of examples 1, 2 and 3, the electrophoretic properties were good at 200 ℃ for 50 min. Secondly, the plasticizers used in examples 1, 2 and 3 were phthalate \8206, diisodecyl phthalate (DIDP) or phthalate \8206anddiisononyl phthalate (DINP) and did not contain a silicone oil component, so that they were excellent in painting performance and free from cratering after painting. In comparative example 1, the electrophoretic properties were not good because no silane-modified polyurethane was added. In comparative example 2, since the plasticizer used was methyl silicone oil, it had a crater phenomenon after painting. In comparative example 3, since the silane-modified polyurethane was not added and the plasticizer used was methyl silicone oil, the electrophoretic properties were not good and the paint was shrunk after painting. Through comparison test results, the modified silicone rubber obtained by modifying the common silicone rubber by adding the silane modified polyurethane can realize quick bonding, and has good flexibility, cohesiveness, high temperature resistance and electrophoretic painting performance. In addition, the common silicon rubber plasticizer contains methyl silicone oil or dimethyl silicone oil, and the shrinkage cavity phenomenon can occur when the paint is sprayed.
Claims (9)
1. The bi-component modified silicone rubber adhesive for bonding the automobile cabin door is prepared from a component A and a component B, and is characterized in that the component A is prepared from the following raw materials in parts by weight:
polysiloxane resin: 30-55 parts of (by weight),
silane-modified polyurethane: 3-20 parts of (by weight),
plasticizer: 3-20 parts of (by weight),
filling: 25-40 parts of (by weight),
thermal stabilizer: 0.1 to 2 portions of the raw materials,
ultraviolet absorber: 0.1-2 parts;
the component B comprises the following raw materials in parts by weight:
a crosslinking agent: 5-10 parts of (A) a water-soluble polymer,
thixotropic agent: 1-2 parts of (A) a solvent,
pigment: 1-2 parts of (A) a solvent,
water removal agent: 0.1-1 part of (A) to obtain,
an adhesion promoter: 0.1-1 part of (by weight),
catalyst: 0.1-1 part.
2. The two-component modified silicone rubber adhesive for bonding automobile doors according to claim 1, wherein in the component A, the polysiloxane is α, ω -dihydroxy polysiloxane; the silane modified polyurethane is T-920R jm102 silane modified polyurethane.
3. The bi-component modified silicone rubber adhesive for bonding the automobile door as claimed in claim 1, wherein in the component A, the plasticizer is one or a mixture of two of phthalic acid \8206, diisodecyl phthalate (DIDP) or phthalic acid \8206anddiisononyl phthalate (DINP); the filler is one or the mixture of calcium carbonate and calcium oxide.
4. The bi-component modified silicone rubber for bonding the car doors according to claim 1, wherein in the component A, the heat stabilizer is a ferrocene heat stabilizer; the ultraviolet-resistant absorbent is a benzotriazole ultraviolet absorbent.
5. The bi-component modified silicone rubber adhesive for bonding the car doors according to claim 1, wherein in the component B, the cross-linking agent is one or a mixture of more than two of tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane or propyltrimethoxysilane; the thixotropic agent is silicon dioxide or argil; the pigment is carbon black or titanium dioxide.
6. The two-component modified silicone rubber adhesive for bonding automobile doors as claimed in claim 1, wherein in the component B, the water scavenger is calcium oxide or vinyl trimethoxysilane, the adhesion promoter is one or a mixture of more than two of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, and the catalyst is dibutyltin dilaurate or dibutyltin diacetate.
7. The method for preparing the two-component modified silicone rubber adhesive for bonding the doors of the automobiles according to any one of claims 1 to 6, comprising the steps of:
(1) Heating the raw materials of the component A to 50-100 ℃ under vacuum, and stirring and mixing for 1-3h at a stirring speed of 500-800r/min to obtain the component A;
(2) Taking the raw materials of the component B, and stirring and mixing the raw materials for 1-3h at the speed of 500-800r/min under the vacuum condition to obtain the component B;
(3) And mixing the component A and the component B according to the mass ratio of (10-15) to 1 to obtain the bi-component modified silicone rubber adhesive.
8. An automobile cabin door bonding process is characterized by comprising the following steps:
1) Mixing an activating agent with deionized water, spraying the mixture on the metal surface of the automobile cabin door, and staying for 3-5min;
2) Cleaning with a cleaning agent, wiping with non-woven fabric, and gluing after 3-5min, wherein the glue is the bi-component modified silicone rubber adhesive in any one of claims 1-7.
9. The car door bonding process according to claim 8, wherein the activating agent is one or a mixture of more than two of methylsulfonyl chloride, sulfonyl chloride and phosphoric acid; the cleaning agent is an alcohol solution; the mass and dosage ratio of the activating agent, the deionized water and the cleaning agent is as follows: activating agent: 1-20 parts of deionized water: 100 parts of a cleaning agent: 200-400 parts.
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