CN117903747A - Bi-component dealcoholized silicone adhesive for bonding low-surface-energy substrate and preparation method thereof - Google Patents
Bi-component dealcoholized silicone adhesive for bonding low-surface-energy substrate and preparation method thereof Download PDFInfo
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- CN117903747A CN117903747A CN202410076101.0A CN202410076101A CN117903747A CN 117903747 A CN117903747 A CN 117903747A CN 202410076101 A CN202410076101 A CN 202410076101A CN 117903747 A CN117903747 A CN 117903747A
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- 239000013464 silicone adhesive Substances 0.000 title claims abstract description 131
- 239000000758 substrate Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 82
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 109
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 95
- 230000001070 adhesive effect Effects 0.000 claims abstract description 91
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 90
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 79
- 239000000853 adhesive Substances 0.000 claims abstract description 78
- 229910000077 silane Inorganic materials 0.000 claims abstract description 22
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 18
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000006229 carbon black Substances 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 83
- 238000002156 mixing Methods 0.000 claims description 15
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000004593 Epoxy Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 9
- BUZRAOJSFRKWPD-UHFFFAOYSA-N isocyanatosilane Chemical compound [SiH3]N=C=O BUZRAOJSFRKWPD-UHFFFAOYSA-N 0.000 claims description 9
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 9
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical group [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 6
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- BOTMPGMIDPRZGP-UHFFFAOYSA-N triethoxy(isocyanatomethyl)silane Chemical compound CCO[Si](OCC)(OCC)CN=C=O BOTMPGMIDPRZGP-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 5
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 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 2
- SZMZIUKGERWEQD-UHFFFAOYSA-N 1-isocyanatopropyl(trimethoxy)silane Chemical compound O=C=NC(CC)[Si](OC)(OC)OC SZMZIUKGERWEQD-UHFFFAOYSA-N 0.000 claims description 2
- NNTRMVRTACZZIO-UHFFFAOYSA-N 3-isocyanatopropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCN=C=O NNTRMVRTACZZIO-UHFFFAOYSA-N 0.000 claims description 2
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 claims description 2
- PJIFJEUHCQYNHO-UHFFFAOYSA-N diethoxy-(3-isocyanatopropyl)-methylsilane Chemical compound CCO[Si](C)(OCC)CCCN=C=O PJIFJEUHCQYNHO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 2
- AMVXVPUHCLLJRE-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)hexane-1,6-diamine Chemical compound CO[Si](OC)(OC)CCCNCCCCCCN AMVXVPUHCLLJRE-UHFFFAOYSA-N 0.000 claims description 2
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 17
- 125000003277 amino group Chemical group 0.000 abstract description 7
- 125000003700 epoxy group Chemical group 0.000 abstract description 7
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 34
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 25
- 238000004132 cross linking Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- VUUUWEJVDQMBLC-UHFFFAOYSA-N [O].[Si].[B] Chemical compound [O].[Si].[B] VUUUWEJVDQMBLC-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- SFMJNHNUOVADRW-UHFFFAOYSA-N n-[5-[9-[4-(methanesulfonamido)phenyl]-2-oxobenzo[h][1,6]naphthyridin-1-yl]-2-methylphenyl]prop-2-enamide Chemical compound C1=C(NC(=O)C=C)C(C)=CC=C1N1C(=O)C=CC2=C1C1=CC(C=3C=CC(NS(C)(=O)=O)=CC=3)=CC=C1N=C2 SFMJNHNUOVADRW-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The application discloses a double-component dealcoholized silicone adhesive for bonding a low-surface-energy substrate and a preparation method thereof, wherein the double-component dealcoholized silicone adhesive for bonding the low-surface-energy substrate comprises an A component and a B component, and the A component comprises the following raw materials in parts by weight: 100 parts of hydroxyl-terminated polydimethylsiloxane, 60-100 parts of calcium carbonate and 0-10 parts of white carbon black; the component B comprises the following raw materials in parts by weight: 100 parts of black paste, 80-120 parts of methoxy-terminated polydimethylsiloxane, 30-50 parts of AIES adhesive cross-linking agents and 5-10 parts of catalysts, wherein the AIES adhesive cross-linking agents are silane cross-linking agents at least comprising amino groups, ureido groups, hydroxyl groups, epoxy groups and alkoxy groups. The various active groups in AIES adhesive cross-linking agents can be cooperatively connected with the surfaces of the silicone adhesive and the base material to form a bridge for connecting the silicone adhesive and the low-surface-energy base material, so that the silicone adhesive also has good adhesive property on the low-surface base material.
Description
Technical Field
The application relates to the field of bi-component silicone adhesive, in particular to bi-component dealcoholized silicone adhesive for bonding a low-surface-energy substrate and a preparation method thereof.
Background
The automobile lamp is an indispensable component in the use process of an automobile, and mainly has the effects of lighting and signal reminding, and the lamp shade material of the automobile lamp is mainly PP and PMMA, so that the automobile lamp is used as an adhesive sealant for bonding and sealing the automobile lamp, and good bonding performance between the automobile lamp and an automobile body is required to be maintained, so that the lighting and indication effects of the automobile lamp are not affected. The organic silicon sealant is widely applied to the bonding process of automobile lamps due to the characteristics of excellent bonding property, excellent temperature resistance, ultraviolet resistance, weather resistance and the like.
However, most of the car light materials are added with recycled reclaimed materials in the preparation process due to the double consideration of environmental protection and cost reduction, but the reclaimed materials have complex composition components, the formed surface performance is more complex, the surface energy is low, and the conventional dealcoholized silicone adhesive is difficult to form good bonding effect on the materials with low surface energy, so that the research on the silicone adhesive bonded by the low surface materials is attracting attention gradually. However, at present, for some silicone adhesives used for bonding low surface materials, most of the products are single-component silicone adhesives, and various tackifiers are added to achieve the bonding effect, but the silicone adhesives are difficult to quickly cure, so that the service efficiency is affected.
Disclosure of Invention
The application provides a bi-component dealcoholized silicone adhesive for bonding a low-surface-energy substrate and a preparation method thereof, aiming at solving the problems that the existing dealcoholized silicone adhesive has poor bonding effect on a low-surface-energy material and has low bonding effect.
In a first aspect, the application provides a dual-component dealcoholized silicone adhesive for bonding a low-surface-energy substrate, which comprises an A component and a B component, wherein the A component and the B component respectively comprise the following raw materials in parts by weight:
And (3) a component A:
100 parts of hydroxyl-terminated polydimethylsiloxane;
60-100 parts of calcium carbonate;
0-10 parts of white carbon black;
and the component B comprises the following components:
100 parts of black paste;
80-120 parts of methoxy-terminated polydimethylsiloxane;
AIES parts of bonding cross-linking agent;
5-10 parts of a catalyst;
the AIES adhesive cross-linking agent is a silane cross-linking agent at least comprising amino, ureido, hydroxyl, epoxy and alkoxy.
Preferably, the black paste comprises the following raw materials in percentage by mass: carbon black and methyl silicone oil of (3.5-4.5).
Preferably, the viscosity of the methoxy-terminated polydimethylsiloxane is 1000-30000 cp.
Preferably, the catalyst is dibutyltin dilaurate.
Preferably, the calcium carbonate is nano calcium carbonate.
Preferably, the white carbon black is fumed silica, and the specific surface area is 100-400 m 2/g.
By adopting the technical scheme, the double-component dealcoholized silicone adhesive is adopted, and in the use process, the component A and the component B are mixed according to a certain mass ratio, wherein the hydroxyl-terminated polydimethylsiloxane in the component A and the methoxy-terminated polydimethylsiloxane in the component B undergo dealcoholization condensation reaction, so that the silicone adhesive is cured, and compared with the single-component dealcoholized silicone adhesive, the double-component dealcoholized silicone adhesive has a faster curing rate and can improve the working efficiency.
For the low surface energy substrate, a AIES bonding cross-linking agent is also added, and the AIES bonding cross-linking agent is a silane cross-linking agent at least comprising amino, ureido, hydroxyl, epoxy and alkoxy. The amino group, the hydroxyl group, the ureido group and the epoxy group are active groups, and specifically, on one hand, the active groups can improve the polarity of a silicone adhesive system, the van der Waals force and the hydrogen bond acting force of the silicone adhesive and the surface of the low-surface-energy substrate are improved, and the adhesive property of the bi-component silicone adhesive on the surface of the low-surface-energy substrate is further improved; on the other hand, the polar groups have stronger reactivity, and the mutual synergistic action among the polar groups can further promote the silicone adhesive to form a covalent bond on the surface of the substrate, wherein the epoxy groups also provide active groups for crosslinking and curing, so that active crosslinking points in the two-component silicone adhesive are increased, the AIES adhesive crosslinking agent can form stronger connection between the silicone adhesive and the surface of the low-surface-energy substrate, and can serve as a connecting bridge between the two, so that the adhesive property of the two-component silicone adhesive on the low-surface-energy substrate is enhanced.
And AIES the bonding cross-linking agent also contains an alkoxy group, the alkoxy group can react with moisture in the air, and is hydrolyzed to form a silicon hydroxyl group, and the silicon hydroxyl group can form tight connection with a low-surface substrate, so that the bonding property between the silicone adhesive and the substrate is improved. Through the coordination effect between AIES bonding cross-linking agent and other polydimethylsiloxane in the system, the bi-component silicone adhesive can have good bonding performance on the surface of the low-surface-energy substrate.
Preferably, the AIES bonding cross-linking agent comprises the following raw materials in parts by weight:
90-130 parts of aminosilane;
40-60 parts of isocyanatosilane;
100-140 parts of alkoxy silane crosslinking agent;
50-70 parts of epoxy silane.
Preferably, the aminosilane comprises one or a combination of several of 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, N-aminoethyl-3-aminopropyl triethoxysilane, N-aminoethyl-3-aminopropyl trimethoxysilane, [3- (6-aminohexylamino) propyl ] trimethoxysilane;
The isocyanatosilane comprises one or a combination of a plurality of 3-isocyanatopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, 1-isocyanatopropyl trimethoxysilane, 1-isocyanatomethyl triethoxysilane, 3-isocyanatopropyl methyl dimethoxy silane and 3-isocyanatopropyl methyl diethoxy silane;
The alkoxy silane crosslinking agent comprises one or a combination of a plurality of methyl trimethoxy silane and vinyl trimethoxy silane; the epoxy silane comprises one or a combination of more of epoxy butyl trimethoxy silane, 3- (2, 3-epoxy propoxy) propyl trimethoxy silane and 3- (2, 3-epoxy propoxy) propyl triethoxy silane.
Through the technical scheme, active groups among the silane crosslinking agents react mutually to crosslink, amino silane can form ureido with isocyanate silane, and can react with epoxy groups to generate hydroxyl, so that the silane crosslinking agent simultaneously containing amino, ureido, hydroxyl, alkoxy and epoxy groups is finally formed, the obtained AIES adhesive crosslinking agent can be simultaneously connected with a low-surface-energy substrate and silicone adhesive, and the adhesive property between the silicone adhesive and the low-surface-energy substrate is enhanced.
Preferably, the AIES adhesive cross-linking agent is prepared according to the following method: adding isocyanatosilane into aminosilane under nitrogen atmosphere, adjusting the temperature to 60-100 ℃, stirring and refluxing for 3-3.5 h, then continuously adding alkoxy silane crosslinking agent and epoxy silane, adjusting the temperature to 40-70 ℃, stirring and refluxing for 70-72 h, and obtaining AIES adhesive crosslinking agent.
By adopting the technical scheme, firstly, isocyanate silane is added into amino silane, the activity of amino is high, a large amount of active hydrogen is contained, the isocyanate group and the active hydrogen in the amino group are extremely easy to react, the isocyanate group and the active hydrogen in the amino group can react and connect under a mild reaction condition to form an ureido, then an alkoxy silane cross-linking agent and epoxy silane are continuously added into the system, the amino group and the epoxy group in the compound react to form a hydroxyl group, meanwhile, the alkoxy silane also participates in the reaction to a certain extent, and then the four silanes can react and cross-link with each other to form AIES adhesive cross-linking agent, and the obtained AIES adhesive cross-linking agent contains a large amount of polar groups, so that the adhesive force of the surface of a low-surface-energy substrate can be changed, and the adhesive becomes a bridge for connecting between silicone adhesive and the low-surface-energy substrate.
Preferably, the hydroxyl-terminated polydimethylsiloxane is composed of hydroxyl-terminated polydimethylsiloxane with different viscosities, and the mass ratio of the hydroxyl-terminated polydimethylsiloxane with different viscosities is as follows:
0-15% of hydroxyl-terminated polydimethylsiloxane with the concentration of 50-200 cp;
10 to 15 percent of hydroxyl-terminated polydimethylsiloxane with 1000 to 2000 cp;
25-45% of 4500-5500 cp hydroxyl-terminated polydimethylsiloxane;
20000-80000 cp hydroxyl-terminated polydimethylsiloxane 40-55%.
By adopting the technical scheme, the hydroxyl-terminated polydimethylsiloxane adopted in the component A is compounded by the hydroxyl-terminated polydimethylsiloxane with different viscosities, so that on one hand, the compounding of the hydroxyl-terminated polydimethylsiloxane with different viscosities can promote the dispersity of calcium carbonate and white carbon black in the component A in a system, and further improve the stability of a colloid system; on the other hand, through the reasonable matching use between different viscosities of the hydroxyl-terminated polydimethylsiloxane, the viscosity of the silicone adhesive can be adjusted, the influence on the workability due to the fact that the viscosity is too high or too low in a system is prevented, the quality of the silicone adhesive can be well enhanced by adjusting the viscosity of the silicone adhesive system, and the bi-component silicone adhesive with excellent performance and good bonding performance is obtained.
Preferably, the hydroxyl-terminated polydimethylsiloxane with the viscosity of 50-200 cp is subjected to modification treatment; the modified hydroxyl-terminated polydimethylsiloxane contains boron-silicon chain segments.
By adopting the technical scheme, the AIES bonding cross-linking agent in the silicone adhesive system can enhance the bonding performance between the two-component silicone adhesive and the surface of the low-surface substrate. In order to further improve the crosslinking density of the silicone adhesive system, and further improve the mechanical property of the silicone adhesive and the interconnection between the silicone adhesive and the low-surface base material, a boron-silicon chain segment is further introduced into the system, the boron-silicon chain segment can be favorable for forming dynamic crosslinking by bonding the polydimethylsiloxane and the AIES crosslinking agent, and the crosslinking density of the silicone adhesive is improved, wherein the specific empty orbit of the outermost layer of the boron atom can contain lone pair electrons in oxygen atoms, and further the boron atom can form dynamic coordination bonds with the polydimethylsiloxane and the oxygen atoms in the AIES bonding crosslinking agent, so that the crosslinking density of the material can be improved, the mechanical property of the silicone adhesive is enhanced, oxygen-containing groups on the low-surface energy surface can be connected to a certain extent, the mutual coordination is formed, and the adhesion between the silicone adhesive and the low-surface energy base material is enhanced.
Preferably, the raw materials in the modification treatment process comprise the following components in percentage by mass: (0.1 to 0.9) a hydroxyl-terminated polydimethylsiloxane and boric acid.
Preferably, the modification treatment process is specifically as follows:
mixing boric acid and hydroxyl-terminated polydimethylsiloxane after grinding and drying treatment, adding the mixture into a reactor, stirring the mixture at room temperature for reaction for 1 to 1.5 hours, then raising the temperature to 180 to 190 ℃, continuously stirring the mixture, adjusting the pressure of the reactor to be-0.09 to-0.1 MPa, reacting the mixture for 2 to 4 hours, and cooling the mixture to obtain the modified hydroxyl-terminated polydimethylsiloxane.
By adopting the technical scheme, the hydroxyl contained in the boric acid and the hydroxyl contained in the hydroxyl-terminated polydimethylsiloxane are condensed to obtain the boron-silicon chain segment in the main chain, and the main chain is crosslinked with each other in the reaction process to form the compound with the boron-oxygen-silicon and the silicon chain segment, wherein the dynamic bond of the boron-oxygen-silicon is used as a crosslinking point, the formed boron-silicon chain segment is connected with the silicon chain segment in the original polydimethylsiloxane, and the introduction of the boron-silicon chain segment in the system is beneficial to the improvement of the crosslinking density and the enhancement of the mechanical property of the silicone adhesive, and meanwhile, the adhesive property between the two-component silicone adhesive and the low-surface-energy substrate is improved to a certain extent.
In a second aspect, the application also provides a preparation method of the low-surface-energy bonding bi-component dealcoholized silicone adhesive, which comprises the following steps:
and (3) preparation of the component A: mixing hydroxyl-terminated polydimethylsiloxane, calcium carbonate and white carbon black, regulating the temperature to 60-100 ℃, and stirring and dispersing for 90-180 min under the vacuum pressure of-0.08 to-0.1 MPa to obtain a component A;
and (3) preparation of a component B: mixing black paste, methoxy end-capped polydimethylsiloxane, AIES bonding cross-linking agent and catalyst, regulating vacuum pressure to-0.08 to-0.1 MPa, stirring and dispersing for 90-180 min at room temperature to obtain a component B;
preparation of dealcoholized silicone adhesive: mixing the obtained component A and the component B in proportion to obtain the bi-component dealcoholized silicone adhesive for bonding the low-surface-energy substrate; the mass ratio of the component A to the component B is (6-10): 1.
In summary, the application has the following beneficial effects:
1. The AIES adhesive cross-linking agent added in the application is a silane cross-linking agent at least comprising amino, ureido, hydroxyl, epoxy and alkoxy, can be used as a bridge between the two-component silicone adhesive and the low-surface-energy substrate, and the addition of a large number of active groups can improve the polarity of the two-component silicone adhesive and the reactivity with the surface of the low-surface-energy substrate, so that the adhesive force between the two-component silicone adhesive and the substrate is improved. The AIES adhesive cross-linking agent can be added to improve the adhesiveness between the silicone adhesive and the low-surface-energy substrate and the curing speed of the reaction, so that the bi-component dealcoholized silicone adhesive with excellent adhesive property and high adhesive effect speed is obtained.
2. The hydroxyl-terminated polydimethylsiloxane adopted in the component A is prepared by compounding hydroxyl-terminated polydimethylsiloxanes with different viscosities, so that the stability of a colloid system can be improved. Meanwhile, part of hydroxyl-terminated polydimethylsiloxane can be introduced into a borosilicate chain segment, so that the crosslinking density of the system is increased, the bonding performance is improved, and the mechanical property of the material is improved.
Detailed Description
Preparation example of AIES adhesive crosslinking agent
Preparation example 1-1, AIES adhesive cross-linking agent, is prepared according to the following method:
50g of isocyanatosilane (including 20g of 3-isocyanatopropyl trimethoxysilane and 30g of 1-isocyanatomethyl triethoxysilane) was added to 120g of aminosilane (including 50g of 3-aminopropyl trimethoxysilane and 70g N-aminoethyl-3-aminopropyl trimethoxysilane) under nitrogen atmosphere, the temperature was adjusted to 85 ℃, the reaction was stirred and refluxed for 3 hours, and then 130g of alkoxysilane crosslinking agent (including 90g of methyltrimethoxysilane and 40g of vinyltrimethoxysilane) and 60g of 3- (2, 3-epoxypropoxy) propyl trimethoxysilane were further added, the temperature was adjusted to 60 ℃, and the reaction was stirred and refluxed for 72 hours to obtain AIES adhesive crosslinking agent.
Preparation examples 1-2 to 1-11, a AIES adhesive crosslinking agent, differ from preparation example 1-1 in the proportions and types of the raw materials used, and are shown in Table I and Table II:
TABLE one formulation table of preparation examples 1-1 to 1-3
Table II preparation examples 1-1, preparation examples 1-4 and preparation examples 1-11
Preparation examples 1-12, a AIES adhesive cross-linking agent, were prepared as follows:
130g of alkoxysilane crosslinking agent (comprising 90g of methyltrimethoxysilane and 40g of vinyltrimethoxysilane) and 60g of 3- (2, 3-glycidoxy) propyltrimethoxysilane were added to 120g of aminosilane (comprising 50g of 3-aminopropyl trimethoxysilane and 70g N-aminoethyl-3-aminopropyl trimethoxysilane) under nitrogen atmosphere, the temperature was adjusted to 70 ℃, and the mixture was stirred and refluxed for 72 hours to obtain AIES adhesive crosslinking agent.
Preparation examples 1-13, a AIES adhesive cross-linking agent, were prepared as follows:
50g of isocyanatosilane (comprising 20g of 3-isocyanatopropyl trimethoxysilane and 30g of 1-isocyanatomethyl triethoxysilane) was added to 120g of aminosilane (comprising 50g of 3-aminopropyl trimethoxysilane and 70g N-aminoethyl-3-aminopropyl trimethoxysilane) under nitrogen atmosphere, the temperature was adjusted to 85 ℃, the reaction was stirred and refluxed for 3 hours, then 60g of 3- (2, 3-epoxypropoxy) propyl trimethoxysilane was continuously added, the temperature was adjusted to 60 ℃, and the reaction was stirred and refluxed for 72 hours to obtain AIES adhesive cross-linking agent.
Preparation examples 1-14, a AIES adhesive cross-linking agent, were prepared as follows:
50g of isocyanatosilane (comprising 20g of 3-isocyanatopropyl trimethoxysilane and 30g of 1-isocyanatomethyl triethoxysilane) was added to 120g of aminosilane (comprising 50g of 3-aminopropyl trimethoxysilane and 70g N-aminoethyl-3-aminopropyl trimethoxysilane) under nitrogen atmosphere, the temperature was adjusted to 85 ℃, the reaction was stirred and refluxed for 3 hours, then 130g of alkoxysilane crosslinking agent (comprising 90g of methyltrimethoxysilane and 40g of vinyltrimethoxysilane) was further added, the temperature was adjusted to 60 ℃, and the reaction was stirred and refluxed for 72 hours, to obtain AIES adhesive crosslinking agent.
Preparation examples 1-15, a AIES adhesive cross-linking agent, were prepared as follows:
60g of 3- (2, 3-glycidoxy) propyl trimethoxy silane is added to 120g of amino silane (comprising 50g of 3-aminopropyl trimethoxy silane and 70g N-aminoethyl-3-aminopropyl trimethoxy silane) under nitrogen atmosphere, the temperature is adjusted to 75 ℃, and stirring reflux reaction is carried out for 72 hours, so as to obtain the AIES adhesive cross-linking agent.
Modification treatment of hydroxyl-terminated polydimethylsiloxane
Preparation example 2-1, a modified hydroxyl-terminated polydimethylsiloxane, was modified by the following method:
Mixing and adding 0.5g of boric acid and 100g of hydroxyl-terminated polydimethylsiloxane (with average viscosity of 100 cp) subjected to grinding and drying treatment into a reactor, stirring and reacting for 1h at room temperature, then raising the temperature to 180 ℃, adjusting the pressure of the reactor to-0.1 MPa, continuing stirring and reacting for 3h, and cooling to obtain the modified hydroxyl-terminated polydimethylsiloxane.
Preparation example 2-2, a modified hydroxyl-terminated polydimethylsiloxane, differed from preparation example 2-1 only in that boric acid was added in an amount of 0.1g.
Preparation example 2-3, a modified hydroxyl-terminated polydimethylsiloxane, differed from preparation example 2-1 only in that boric acid was added in an amount of 0.9g.
Preparation examples 2-4, a modified hydroxyl-terminated polydimethylsiloxane, differed from preparation example 2-1 only in that boric acid was added in an amount of 0.05g.
Preparation examples 2 to 5, a modified terminal hydroxyl polydimethylsiloxane, differed from preparation example 2 to 1 only in that boric acid was added in an amount of 1.5g.
Examples
Example 1 a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was prepared as follows: and (3) preparation of the component A: mixing 100g of hydroxyl-terminated polydimethylsiloxane, 80g of nano calcium carbonate (with the average particle size of 30 nm) and 5g of white carbon black (fumed silica with the specific surface area of 170m 2/g), regulating the temperature to 70 ℃, and stirring and dispersing for 120min under the vacuum pressure of-0.09 MPa to obtain a component A;
Wherein the hydroxyl-terminated polydimethylsiloxane is obtained by mixing 5g of hydroxyl-terminated polydimethylsiloxane with the viscosity of 150cp, 10g of hydroxyl-terminated polydimethylsiloxane with the viscosity of 1500cp, 40g of hydroxyl-terminated polydimethylsiloxane with the viscosity of 5000cp and 45g of hydroxyl-terminated polydimethylsiloxane with the viscosity of 20000 cp.
And (3) preparation of a component B: mixing 100g of black paste, 100g of methoxy-terminated polydimethylsiloxane (comprising methoxy-terminated polydimethylsiloxane with the viscosity of 11000cp and methoxy-terminated polydimethylsiloxane with the viscosity of 22000cp in a mass ratio of 7:3), AIES bonding crosslinking agent prepared in preparation example 1-1 and 7g of dibutyltin dilaurate, regulating the vacuum pressure to be-0.09 MPa, and stirring and dispersing for 120min at room temperature to obtain a component B;
Wherein the black paste is obtained by mixing carbon black (the specific surface area is 120m 2/g) and methyl silicone oil (the viscosity is 350 cp) with the mass ratio of 1:4.
Preparation of dealcoholized silicone adhesive: and mixing the obtained component A and the component B according to the mass ratio of 8:1 to obtain the double-component dealcoholized silicone adhesive for bonding the low-surface-energy substrate.
Examples 2 to 9 differ from example 1 only in the parts by mass of the raw materials used, specifically as shown in table three:
Table III the formulation tables of examples 1 to 9
Wherein the viscosity ratio of the hydroxyl-terminated polydimethylsiloxane used in examples 2 to 9 was the same as that in example 1; the AIES adhesive cross-linking agents prepared in preparation example 1-1 were used in examples 2 to 9.
The black paste used in examples 2 to 7 was the same as in example 1; the mass ratio of the black paste carbon black to the methyl silicone oil adopted in the example 8 is 1:3.5; the mass ratio of the black paste carbon black to the methyl silicone oil adopted in the example 9 is 1:4.5.
Examples 10 to 13 differ from example 1 only in the viscosity ratio of the hydroxyl-terminated polydimethylsiloxane added to the a component, and specifically, the following table four shows:
table four viscosity ratios of hydroxyl-terminated polydimethylsiloxanes in example 1, example 10 to example 13
Example 14, a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion, was different from example 1 only in that no white carbon black was added to the a component.
Example 15 a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that AIES adhesive cross-linking agent obtained in preparation example 1-1 was replaced with AIES adhesive cross-linking agent obtained in preparation example 1-2 in the same amount.
Example 16 a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that AIES adhesive cross-linking agent prepared in preparation example 1-1 was replaced with AIES adhesive cross-linking agent prepared in preparation example 1-3 in the same amount.
Example 17 a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that AIES adhesive cross-linking agent obtained in preparation example 1-1 was replaced with AIES adhesive cross-linking agent obtained in preparation example 1-4 in the same amount.
Example 18 a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that AIES adhesive cross-linking agent prepared in preparation example 1-1 was replaced with AIES adhesive cross-linking agent prepared in preparation example 1-5 in the same amount.
Example 19 a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that AIES adhesive cross-linking agent obtained in preparation example 1-1 was replaced with AIES adhesive cross-linking agent obtained in preparation example 1-6 in the same amount.
Example 20 a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that AIES adhesive cross-linking agent obtained in preparation example 1-1 was replaced with AIES adhesive cross-linking agent obtained in preparation example 1-7 in the same amount.
Example 21 a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that the modified terminal hydroxy polydimethylsiloxane obtained in preparation example 2-1 was used in place of the terminal hydroxy polydimethylsiloxane having a viscosity of 150 cp.
Example 22a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that the modified terminal hydroxy polydimethylsiloxane obtained in preparation example 2-2 was used in place of the terminal hydroxy polydimethylsiloxane having a viscosity of 150 cp.
Example 23 a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that the modified terminal hydroxy polydimethylsiloxane obtained in preparation examples 2 to 3 was used in place of the terminal hydroxy polydimethylsiloxane having a viscosity of 150 cp.
Example 24 a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that the modified terminal hydroxy polydimethylsiloxane obtained in preparation examples 2 to 4 was used in place of the terminal hydroxy polydimethylsiloxane having a viscosity of 150 cp.
Example 25 a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that the modified terminal hydroxy polydimethylsiloxane obtained in preparation examples 2 to 5 was used in place of the terminal hydroxy polydimethylsiloxane having a viscosity of 150 cp.
Example 26 a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that AIES adhesive cross-linking agent prepared in preparation example 1-1 was replaced with AIES adhesive cross-linking agent prepared in preparation example 1-8 in the same amount.
Example 27 a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that AIES adhesive cross-linking agent obtained in preparation example 1-1 was replaced with AIES adhesive cross-linking agent obtained in preparation example 1-9 in the same amount.
Example 28 a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that AIES adhesive cross-linking agent obtained in preparation example 1-1 was replaced with AIES adhesive cross-linking agent obtained in preparation example 1-10 in the same amount.
Example 29 a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that AIES adhesive cross-linking agent obtained in preparation example 1-1 was replaced with AIES adhesive cross-linking agent obtained in preparation example 1-11 in the same amount.
Example 30 a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that 100g of hydroxyl-terminated polydimethylsiloxane having a viscosity of 5000cp was used instead of the hydroxyl-terminated polydimethylsiloxane obtained by mixing different viscosities in the component of example 1A.
Example 31A two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that 100g of hydroxyl-terminated polydimethylsiloxane having a viscosity of 20000cp was used instead of the hydroxyl-terminated polydimethylsiloxane obtained by mixing different viscosities in the component of example 1A.
Example 32, a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion, was different from example 1 only in that the mass ratio of the a component to the B component was 6:1.
Example 33, a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion, was different from example 1 only in that the mass ratio of the a component to the B component was 10:1.
Comparative example
Comparative example 1, a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion, was different from example 1 only in that the amount of AIES adhesive cross-linking agent prepared in preparation example 1-1 was 25g.
Comparative example 2, a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion, was different from example 1 only in that the amount of AIES adhesive cross-linking agent prepared in preparation example 1-1 was 55g.
Comparative example 3a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that AIES adhesive crosslinking agent prepared in preparation example 1-1 was not added to the B component.
Comparative example 4a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that AIES adhesive cross-linking agent obtained in preparation example 1-1 was replaced with AIES adhesive cross-linking agent obtained in preparation example 1-12 in the same amount.
Comparative example 5a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that AIES adhesive cross-linking agent obtained in preparation example 1-1 was replaced with AIES adhesive cross-linking agent obtained in preparation example 1-13 in the same amount.
Comparative example 6a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that AIES adhesive cross-linking agent obtained in preparation example 1-1 was replaced with AIES adhesive cross-linking agent obtained in preparation example 1-14 in the same amount.
Comparative example 7 a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that AIES adhesive cross-linking agent obtained in preparation example 1-1 was replaced with AIES adhesive cross-linking agent obtained in preparation example 1-15 in the same amount.
Comparative example 8 a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that AIES adhesive cross-linking agent obtained in preparation example 1-1 was replaced with an equal amount of aminosilane (including 18g of 3-aminopropyl trimethoxysilane and 27g N-aminoethyl-3-aminopropyl trimethoxysilane).
Comparative example 9 a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that AIES adhesive crosslinking agent obtained in preparation example 1-1 was replaced with an equivalent amount of isocyanate silane (including 18g of 3-isocyanatopropyl trimethoxysilane and 27g of 1-isocyanatomethyl triethoxysilane).
Comparative example 10, a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion, differing from example 1 only in that the AIES adhesive cross-linking agent obtained in preparation example 1-1 was replaced with an aminosilane (containing 11.98g of 3-aminopropyl trimethoxysilane and 16.77g N-aminoethyl-3-aminopropyl trimethoxysilane) and an alkoxysilane cross-linking agent (containing 11.25g of methyltrimethoxysilane and 5g of vinyltrimethoxysilane).
Comparative example 11 a two-component dealcoholized silicone adhesive for low surface energy substrate adhesion was different from example 1 only in that the AIES adhesive cross-linking agent obtained in preparation example 1-1 was replaced with an equivalent amount of 3- (2, 3-glycidoxy) propyltrimethoxysilane.
Performance test
1. And (3) surface dry time detection: according to GB/T13477.5-2002 section 5 of the test method for building sealing materials: measurement of tack free time the tack free time of the two-component dealcoholized silicone adhesive obtained in examples and comparative examples was measured.
2. Tensile property detection: the two-component dealcoholized silicone adhesives obtained in examples and comparative examples were tested for tensile strength and elongation at break according to the relevant description in GB/T528-2009 "measurement of tensile stress Strain Properties of vulcanized rubber or thermoplastic rubber".
The test results of the above tests are shown in Table five.
3. And (3) detecting the bonding shear strength: the two-component dealcoholized silicone adhesives obtained in examples and comparative examples were tested for adhesive shear strength after 3h curing and 72h curing according to the relevant description in GB/T7124-2008 "measurement of adhesive tensile shear strength (rigid Material vs. rigid Material)", wherein the materials of the samples were PC and PMMA with low surface tension, specifically, the surface tension of the samples was 30-32 dyn/cm.
After the shear strength test is carried out, taking a substrate sample piece with relatively less residual adhesive in the two separated substrate sample pieces, counting the area of the silicone adhesive remained on the surface of the substrate, marking as S Residue (C) , and then obtaining the cohesive failure rate after calculation, wherein the calculation formula is as follows:
Wherein S Adhesive tape represents the total bonding area of the silicone adhesive on the substrate wafer.
The test results are shown in Table six.
Table five results of test of surface drying time and tensile properties of two-component dealcoholized silicone adhesive
Note that: "/" indicates that the formulation was not normally cured.
Table six results of adhesive shear strength test of two-component dealcoholized silicone adhesive
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Note that: "/" indicates that the formulation was not normally cured.
From tables five and six, in combination with examples 1, 2 to 9, 14 and 32 to 33, it can be seen that the two-component dealcoholized silicone adhesive obtained in the above examples has little change in the surface dry time, tensile strength and elongation at break, and shear strength and cohesive failure rate of the surface of the substrate having different low surface energy in different curing times, compared with example 1, and no significant difference in curing speed, mechanical properties and adhesion property to the substrate having low surface energy, compared with example 1. The reason for this is probably that the above-mentioned examples mainly change the amounts of the raw materials and the proportions of the two components A, B within the required range, which means that the change of the raw material proportions of the two components A, B and the proportion of the two components A, B in the silicone adhesive within the required range has no obvious influence on the curing speed and the bonding strength of the obtained two-component dealcoholized silicone adhesive, and can achieve good performance characteristics.
In combination with examples 1, 10 to 13 and 30 and 31, it can be seen that the two-component dealcoholized silicone adhesives obtained in examples 10 to 13 have less variation in the tack time, tensile strength and elongation at break, and the shear strength and cohesive failure rate of the surface of the substrate having different low surface energies within different curing times than those of example 1, and that examples 30 and 31 have relatively prolonged tack times, and the shear strength and cohesive failure rate are reduced as compared with example 1, indicating that the curing speed, mechanical properties, and adhesion properties of the substrates having low surface energies of examples 10 to 13 are not significantly different as compared with example 1, and that examples 30 and 31 have reduced curing speeds and adhesion strengths as compared with example 1. The reason for this is probably that the difference between examples 10 to 13 is only that the ratio of the different viscosities of the hydroxyl-terminated polydimethylsiloxanes in the a-component was adjusted within the required range, and the properties of the final silicone adhesive were not greatly affected, but that the hydroxyl-terminated polydimethylsiloxanes of only one viscosity were used in examples 30 and 31, and that the stability of the resulting colloidal system was lowered, both with a smaller viscosity and a larger viscosity, and the curing speed and the adhesive properties of the final silicone adhesive were lowered.
In combination with examples 1 and 15 to 20, it can be seen that the surface drying time, tensile strength and elongation at break of the two-component dealcoholized silicone adhesive obtained in examples 15 to 20 and the shear strength and cohesive failure rate of the surface of the substrate having different low surface energies within different curing times are less varied than those of example 1, and no significant difference is observed in curing speed, mechanical properties and adhesion performance to the substrate having low surface energies in examples 15 to 20 as compared with example 1. The reason for this is probably that the difference between examples 15 to 20 and example 1 is only that the proportion of raw materials in the required range was adjusted during the preparation of AIES adhesive cross-linking agent added thereto, which means that the change of the proportion of raw materials in the required range during the preparation of AIES adhesive cross-linking agent has no obvious influence on the performance of the finally obtained silicone adhesive.
In combination with examples 1 and 21-25, it can be seen that the two-component dealcoholized silicone adhesives obtained in examples 21-25 have substantially the same tack coat time as in example 1, and have increased tensile strength and elongation at break and shear strength and cohesive failure rate of the surface of the substrate having different low surface energies at different curing times as compared with example 1, indicating that the mechanical properties of examples 21-25 and the adhesion properties to the substrate having low surface energies are enhanced as compared with example 1. The reason for this is probably that the difference between examples 21 to 25 and example 1 is only that a borosilicate segment is introduced into the hydroxyl-terminated polydimethylsiloxane added in the a component, and the borosilicate segment is a dynamic chain, and can form chemical connection with the active groups in the system and oxygen atoms on the surface with low surface energy, so that the crosslinking density of the silicone adhesive and the adhesiveness with the low-surface substrate are increased.
In combination with examples 1 and 26-29, it can be seen that the tensile strength and elongation at break of examples 26-29 are increased as compared to example 1, and the shear strength and cohesive failure rate of the surface of the low surface energy substrate are decreased as compared to example 1 during different curing times, wherein the decrease in examples 26 and 28 is more pronounced, indicating a decrease in the cure rate of examples 26, and the mechanical properties and adhesion properties of examples 26-29 are decreased as compared to example 1. The reason for this is probably that the difference between examples 26 to 29 is that the amount of isocyanate silane and alkoxysilane crosslinking agent added in the preparation of AIES adhesive crosslinking agent is changed within the required range, wherein the amount of isocyanate silane added in example 26 is reduced, the urea group content in the system is reduced, the memory is reduced, the adhesive property of silicone adhesive is reduced, the amount of alkoxysilane crosslinking agent added in example 28 is reduced, the alkoxy group can react with water vapor to obtain silicon hydroxyl group to improve the adhesive property with the substrate surface, the reduction of the alkoxy group can correspondingly reduce the adhesive property of the obtained silicone adhesive, and the alkoxy group can also accelerate the crosslinking curing of the silicone adhesive.
In combination with examples 1 and comparative examples 1 to 3, it can be seen that the surface drying time of comparative examples 1 to 3 is prolonged, the tensile strength and elongation at break and the shear strength and cohesive failure rate of the surfaces of the substrates with different low surface energies are reduced compared with those of example 1 in comparative examples 1 to 3, wherein the silicone adhesive of comparative example 3 cannot be cured, possibly because the amounts of AIES bonding cross-linking agent added are different in comparative examples 1 to 3 compared with example 1, wherein the addition amount of AIES bonding cross-linking agent in comparative example 1 is reduced, on the one hand, the crosslinking density inside the silicone adhesive is reduced, the mechanical properties are reduced, and on the other hand, the mutual coordination among various polar groups in the bonding cross-linking agent is absent, the bonding performance of the obtained silicone adhesive is reduced, the content of active groups in the system is greatly reduced, the bonding performance of the surfaces with low surface energies is not cured, and the cross-linking agent is not significantly cured, and the cross-linking agent is not cured, so that the cross-linking layer of the cross-linking agent cannot be cured, and the cross-linking material is difficult to form; the amount of AIES adhesive cross-linking agent added in comparative example 2 was excessive, and excessive cross-linking in the system resulted in a decrease in the properties of the material.
In combination with example 1, comparative examples 4 to 6, comparative example 7 and comparative examples 8 to 11, it can be seen that the tensile strength and elongation at break and the shear strength and cohesive failure rate of the surfaces of the substrates having different low surface energies at different curing times are all reduced compared with example 1, wherein the performance degradation of comparative examples 5, 7 and 8 to 11 is remarkable and the curing is difficult. The reason for this is probably that the types of reactive groups contained in the AIES adhesive cross-linking agent used in the above comparative examples were adjusted to different degrees, wherein the AIES adhesive cross-linking agents used in comparative examples 4 to 6 all lack one type of polar group, specifically, the isocyanate group is lacking in comparative example 4, so that the curing speed of comparative example 4 is lowered, and at the same time, the urea group is lacking, and the adhesive strength of the system is lowered; in comparative example 5, the alkoxy group is absent, the alkoxy group can provide a connecting site on the surface of the low-surface substrate for the silicone adhesive or is an important group for crosslinking and curing the silicone adhesive, and the adhesive property of the silicone adhesive is obviously reduced, the silicone adhesive is difficult to crosslink and cure, and the adhesive cannot play a role in adhesion; the lack of epoxy groups in comparative example 6, which can provide reactive groups for crosslinking curing, reduced crosslinking density in the system, and a corresponding decrease in performance. The silicone adhesive is difficult to cure because of the lack of alkoxy groups in comparative example 7, and the lack of three groups in comparative examples 10-13, the types of active groups can reduce various properties of the obtained silicone adhesive differently, and the curing speed is very slow and the strength is very low when only amino groups or alkoxy groups exist, and the silicone adhesive can not be crosslinked and cured simply even when the amino groups or the alkoxy groups are absent, so that the corresponding adhesive effect is achieved.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (10)
1. The double-component dealcoholized silicone adhesive for bonding low-surface-energy substrates is characterized by comprising an A component and a B component, wherein the A component and the B component respectively comprise the following raw materials in parts by weight:
And (3) a component A:
100 parts of hydroxyl-terminated polydimethylsiloxane;
60-100 parts of calcium carbonate;
0-10 parts of white carbon black;
and the component B comprises the following components:
100 parts of black paste;
80-120 parts of methoxy-terminated polydimethylsiloxane;
AIES parts of bonding cross-linking agent;
5-10 parts of a catalyst;
the AIES adhesive cross-linking agent is a silane cross-linking agent at least comprising amino, ureido, hydroxyl, epoxy and alkoxy.
2. The two-component dealcoholized silicone adhesive for bonding a low-surface-energy substrate according to claim 1, wherein the AIES bonding crosslinking agent comprises the following raw materials in parts by mass:
90-130 parts of aminosilane;
40-60 parts of isocyanatosilane;
100-140 parts of alkoxy silane crosslinking agent;
50-70 parts of epoxy silane.
3. The two-component dealcoholized silicone adhesive for low-surface-energy substrate adhesion according to claim 2, wherein the aminosilane comprises one or a combination of several of 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, N-aminoethyl-3-aminopropyl triethoxysilane, N-aminoethyl-3-aminopropyl trimethoxysilane, [3- (6-aminohexylamino) propyl ] trimethoxysilane; the isocyanatosilane comprises one or a combination of a plurality of 3-isocyanatopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, 1-isocyanatopropyl trimethoxysilane, 1-isocyanatomethyl triethoxysilane, 3-isocyanatopropyl methyl dimethoxy silane and 3-isocyanatopropyl methyl diethoxy silane; the alkoxy silane crosslinking agent comprises one or a combination of a plurality of methyl trimethoxy silane and vinyl trimethoxy silane; the epoxy silane comprises one or a combination of more of epoxy butyl trimethoxy silane, 3- (2, 3-epoxy propoxy) propyl trimethoxy silane and 3- (2, 3-epoxy propoxy) propyl triethoxy silane.
4. The two-component dealcoholized silicone adhesive for bonding a low-surface-energy substrate according to claim 2, wherein the AIES bonding crosslinking agent is prepared according to the following method: adding isocyanatosilane into aminosilane under nitrogen atmosphere, adjusting the temperature to 60-100 ℃, stirring and refluxing for 3-3.5 h, then continuously adding alkoxy silane crosslinking agent and epoxy silane, adjusting the temperature to 40-70 ℃, stirring and refluxing for 70-72 h, and obtaining AIES adhesive crosslinking agent.
5. The two-component dealcoholized silicone adhesive for low surface energy substrate adhesion according to claim 1, wherein the hydroxyl-terminated polydimethyl siloxane is composed of hydroxyl-terminated polydimethyl siloxanes of different viscosities, wherein the mass ratio of the hydroxyl-terminated polydimethyl siloxanes of different viscosities is as follows:
5-15% of hydroxyl-terminated polydimethylsiloxane with the concentration of 50-200 cp;
10 to 15 percent of hydroxyl-terminated polydimethylsiloxane with 1000 to 2000 cp;
25-45% of 4500-5500 cp hydroxyl-terminated polydimethylsiloxane;
20000-80000 cp hydroxyl-terminated polydimethylsiloxane 40-55%.
6. The two-component dealcoholized silicone adhesive for low-surface-energy substrate adhesion according to claim 5, wherein the hydroxyl-terminated polydimethylsiloxane having a viscosity of 50 to 200cp is modified; the modified hydroxyl-terminated polydimethylsiloxane contains boron-silicon chain segments.
7. The two-component dealcoholized silicone adhesive for low-surface-energy substrate adhesion according to claim 6, wherein the raw materials in the modification treatment process comprise 100 mass ratio: (0.1 to 0.9) a hydroxyl-terminated polydimethylsiloxane and boric acid.
8. The two-component dealcoholized silicone adhesive for bonding a low-surface-energy substrate according to claim 1, wherein the raw materials of the black paste comprise the following components in mass ratio of 1: carbon black and methyl silicone oil of (3.5-4.5).
9. The two-component dealcoholized silicone adhesive for low-surface-energy substrate adhesion according to claim 1, wherein the viscosity of the methoxy-terminated polydimethylsiloxane is 1000 to 30000cp.
10. A method for preparing the two-component dealcoholized silicone adhesive for bonding a low-surface-energy substrate according to any one of claims 1 to 9, comprising the steps of:
and (3) preparation of the component A: mixing hydroxyl-terminated polydimethylsiloxane, calcium carbonate and white carbon black, regulating the temperature to 60-100 ℃, and stirring and dispersing for 90-180 min under the vacuum pressure of-0.08 to-0.1 MPa to obtain a component A;
and (3) preparation of a component B: mixing black paste, methoxy end-capped polydimethylsiloxane, AIES bonding cross-linking agent and catalyst, regulating vacuum pressure to-0.08 to-0.1 MPa, stirring and dispersing for 90-180 min at room temperature to obtain a component B;
Preparation of dealcoholized silicone adhesive: mixing the obtained component A and the component B in proportion to obtain the bi-component dealcoholized silicone adhesive for bonding the low-surface-energy substrate; the mass ratio of the component A to the component B is (6-10): 1.
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| CN202410076101.0A CN117903747A (en) | 2024-01-18 | 2024-01-18 | Bi-component dealcoholized silicone adhesive for bonding low-surface-energy substrate and preparation method thereof |
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