CN115305045A - High-temperature-resistant ultraviolet curing adhesive and preparation method thereof - Google Patents
High-temperature-resistant ultraviolet curing adhesive and preparation method thereof Download PDFInfo
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- CN115305045A CN115305045A CN202211061723.3A CN202211061723A CN115305045A CN 115305045 A CN115305045 A CN 115305045A CN 202211061723 A CN202211061723 A CN 202211061723A CN 115305045 A CN115305045 A CN 115305045A
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 91
- 239000000853 adhesive Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000005416 organic matter Substances 0.000 claims abstract description 43
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 37
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 33
- 239000003112 inhibitor Substances 0.000 claims abstract description 33
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 30
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 229910021389 graphene Inorganic materials 0.000 claims description 68
- 238000003756 stirring Methods 0.000 claims description 46
- -1 hydrotalcite modified aluminum dihydrogen phosphate Chemical class 0.000 claims description 44
- 238000010438 heat treatment Methods 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 229960001545 hydrotalcite Drugs 0.000 claims description 21
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 21
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 16
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 15
- 239000013067 intermediate product Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 13
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 9
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 9
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 9
- HHRKFGMMAHZWIM-UHFFFAOYSA-N ethenoxyboronic acid Chemical compound OB(O)OC=C HHRKFGMMAHZWIM-UHFFFAOYSA-N 0.000 claims description 9
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
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- AYLIBFFGMZIILD-UHFFFAOYSA-N 4,4,4-trifluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCC(F)(F)F AYLIBFFGMZIILD-UHFFFAOYSA-N 0.000 claims description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 3
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- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 2
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 claims description 2
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 claims description 2
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
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- 238000004132 cross linking Methods 0.000 claims 3
- 239000003999 initiator Substances 0.000 claims 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims 1
- SEEVRZDUPHZSOX-WPWMEQJKSA-N [(e)-1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate Chemical compound C=1C=C2N(CC)C3=CC=C(C(\C)=N\OC(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C SEEVRZDUPHZSOX-WPWMEQJKSA-N 0.000 claims 1
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- 238000001035 drying Methods 0.000 description 24
- 239000002244 precipitate Substances 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 20
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- 238000005406 washing Methods 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
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- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 13
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 12
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 12
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- 239000003063 flame retardant Substances 0.000 description 12
- 229910052731 fluorine Inorganic materials 0.000 description 12
- 239000011737 fluorine Substances 0.000 description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 10
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 9
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 description 8
- JEHFRMABGJJCPF-UHFFFAOYSA-N 2-methylprop-2-enoyl isocyanate Chemical compound CC(=C)C(=O)N=C=O JEHFRMABGJJCPF-UHFFFAOYSA-N 0.000 description 8
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 8
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- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 8
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
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- 238000012360 testing method Methods 0.000 description 7
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 5
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- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- ALPIESLRVWNLAX-UHFFFAOYSA-N hexane-1,1-dithiol Chemical compound CCCCCC(S)S ALPIESLRVWNLAX-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- JRWNODXPDGNUPO-UHFFFAOYSA-N oxolane;prop-2-enoic acid Chemical compound C1CCOC1.OC(=O)C=C JRWNODXPDGNUPO-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- NCNISYUOWMIOPI-UHFFFAOYSA-N propane-1,1-dithiol Chemical compound CCC(S)S NCNISYUOWMIOPI-UHFFFAOYSA-N 0.000 description 1
- UWHMFGKZAYHMDJ-UHFFFAOYSA-N propane-1,2,3-trithiol Chemical compound SCC(S)CS UWHMFGKZAYHMDJ-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- 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
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/327—Aluminium phosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention relates to the technical field of adhesives, in particular to a high-temperature-resistant ultraviolet curing adhesive and a preparation method thereof. The high-temperature-resistant ultraviolet curing adhesive comprises urethane acrylate, an acrylic monomer, a photoinitiator, a defoaming agent, a polymerization inhibitor, a sulfhydryl organic matter and modified graphene oxide. The invention also provides a preparation method of the composition. Compared with the prior art, the high-temperature-resistant ultraviolet curing adhesive prepared by the invention has the advantages of ultraviolet curing, simple operation, long applicable period, good flame retardance, high temperature resistance and the like.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a high-temperature-resistant ultraviolet curing adhesive and a preparation method thereof.
Background
A Flexible Printed Circuit (FPC) is also called a Flexible Printed circuit board, or a Flexible Printed circuit board. The flexible printed circuit board is a printed circuit board having good flexibility and made of a flexible film such as polyester or polyimide as an insulating base film. The foldable folding umbrella has the outstanding advantages of light weight, thin thickness, flexible structure, flexibility, curling, folding and the like, is widely applied to the fields of electronics, automobiles, aerospace, mobile phones, digital cameras, notebooks, medical treatment, military affairs and the like, and has wide market and application backgrounds. The performance of a Flexible Copper Clad Laminate (FCCL) as a core substrate will directly determine the performance of the FPC.
The adhesive is an important component in the FCCL, directly influences the performance of the FCCL, and is required to have the characteristics of good bonding strength, temperature resistance, weather resistance, flexibility resistance, good flame retardant property and the like.
The currently commonly used adhesives are classified into epoxy resins, polyacrylates, polyurethanes, polyesters, nitrile rubbers, polyimides and the like; the polyacrylate adhesive is an adhesive with wide applicability, has the advantages of good flexibility, cohesiveness, dielectricity, chemical stability, low curing temperature, process operation and the like, but has poor high temperature resistance and flame resistance, and the use of the adhesive is seriously influenced.
The high-temperature-resistant adhesives commonly used in recent years comprise epoxy resin high-temperature-resistant adhesives, phenolic resin high-temperature-resistant adhesives, organic silicon high-temperature-resistant adhesives, heterocyclic high-temperature-resistant adhesives and inorganic high-temperature-resistant adhesives; wherein the epoxy resin high temperature resistant adhesive has the defects of heating requirement, easy degradation at high temperature and the like in the curing process; the phenolic resin high-temperature-resistant adhesive has the defects of large brittleness, poor toughness and the like; the organic silicon high-temperature-resistant adhesive needs to be dried at high temperature, and has the defects of long curing time, poor solvent resistance and the like; the heterocyclic high-temperature-resistant adhesive has the defects of high raw material cost, complex process, difficult application and the like; the inorganic high-temperature-resistant adhesive has the defects of low cohesive strength, high brittleness and the like.
CN112574711A discloses a high-identification high-temperature-resistant ultraviolet curing adhesive and a preparation method thereof, and relates to the field of adhesives. The adhesive comprises a self-made organic silicon modified polyurethane acrylic oligomer and a self-made photochromic paste, wherein the self-made organic silicon modified polyurethane acrylic oligomer is obtained by reacting HDI tripolymer, hydroxypropyl polymethylphenyl siloxane, polyester glycol and hydroxyethyl acrylate; the self-made photochromic paste has a wavelength of 200-400nm and an illumination intensity of more than or equal to 300mw/cm 2 The self-made photochromic material comprises a shell at least containing 2-methoxy-1-methyl ethyl acetate and diazonium salt and a photochromic compound coated in the shell. The adhesive has excellent high-temperature resistance, meets the high-temperature resistance standard, changes in color before and after curing, can identify the curing condition of the adhesive, and realizes full-automatic and efficient effects; but does not improve the flame retardant properties of the adhesive and its high temperature performanceMechanical properties under high humidity conditions.
Disclosure of Invention
In order to achieve the purpose, the invention provides a high-temperature-resistant ultraviolet curing adhesive and a preparation method thereof.
A high-temperature resistant ultraviolet curing adhesive comprises the following raw materials: the coating comprises urethane acrylate, acrylic acid monomers, a photoinitiator, a defoaming agent, a polymerization inhibitor, a sulfhydryl organic substance and graphene oxide.
Preferably, the high-temperature resistant ultraviolet curing adhesive comprises the following raw materials in parts by weight: 40-60 parts of urethane acrylate, 10-15 parts of acrylic monomer, 2-9 parts of photoinitiator, 0.1-0.5 part of defoaming agent, 0.1-0.2 part of polymerization inhibitor, 0.5-5 parts of sulfhydryl organic matter and 5-8 parts of graphene oxide.
The acrylic monomer is one or a mixture of more than two of tetrahydrofuran acrylate, pentaerythritol triacrylate, isoprene tetraacrylate, methacryloyl isocyanate, bisphenol-A-dimethacrylate, neopentyl glycol diacrylate, ethylene glycol dimethacrylate, 2,2-diallyl bisphenol A, methyl acrylate, ethyl methacrylate, butyl methacrylate, 2- (2-ethoxyethoxy) ethyl acrylate, tetrahydrofurfuryl methacrylate, lauric acid acrylate, isooctyl acrylate, 2-phenoxyethyl acrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, propoxylated neopentyl glycol diacrylate and pentaethoxy pentaerythritol tetraacrylate.
The sulfhydryl organic matter is one or a mixture of more than two of monothiol organic matter, dithiol organic matter, trithiol organic matter and tetrathiol organic matter; the monothiol organic matter is one or a mixture of more than two of thioglycolic acid, 3-mercaptopropionic acid, 4-mercaptobutyric acid, mercaptoisobutyric acid and omega-mercaptohexanoic acid; the dithiol organic matter is one or a mixture of more than two of 2,2- (1,2-ethanediylbisproxo) bisethanethiol, ethanedithiol, propanedithiol, 2,3-butanedithiol, hexanedithiol, decanedithiol and s-triazine dithiol; the trithiol organic matter is one or a mixture of more than two of trimethylolpropane tris (3-mercaptopropionate), propane-1,2,3-trithiol and 1,3,5-triazine-2,4,6-trithiol; the tetrathiol organic matter is one or a mixture of pentaerythritol tetra (3-mercaptopropionate) ester and pentaerythritol tetra (3-mercaptobutyrate) ester.
The defoaming agent is one or a mixture of more than two of a defoaming agent F681, diethylene glycol monomethyl ether and a polysiloxane emulsion defoaming agent N-10.
The polymerization inhibitor is one or a mixture of more than two of p-benzoquinone, 4-methoxyphenol and hydroquinone.
The photoinitiator is one or two mixtures of 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, benzoin dimethyl ether, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl ] ethanone 1- (O-acetyloxime), 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl phenylpropanone, phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-hydroxy-2-methyl-1-phenyl acetone, 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone, alpha-dimethyl benzil ketal, isopropyl thioxanthone, benzophenone, benzoin ethyl ether, benzoin dimethyl ether and benzoin butyl ether.
According to the invention, the graphene oxide is introduced to improve the flame retardant and high temperature resistance of the adhesive, but the graphene oxide is fragile, easy to break, easy to crush, poor in cohesive strength, easy to crack, poor in compatibility and the like, and further influences the curing, peeling strength, water resistance and the like of the adhesive in the application process.
Further preferably, the high-temperature resistant ultraviolet curing adhesive comprises the following raw materials in parts by weight: 40-60 parts of urethane acrylate (BR-7432 GB), 10-15 parts of acrylic monomer, 2-9 parts of photoinitiator, 0.1-0.5 part of defoaming agent, 0.1-0.2 part of polymerization inhibitor, 0.5-5 parts of sulfhydryl organic matter and 5-8 parts of modified graphene oxide.
The preparation method of the modified graphene oxide comprises the following steps:
step 1, adding 5-8 parts by weight of graphene oxide into 80-100 parts by weight of mixed solution, stirring at a rotating speed of 100-300r/min for 10-30min, then adding 0.5-1.5 parts by weight of methacryloyl chloride, heating to 50-60 ℃, reacting at 100-300r/min for 20-24h, cooling to room temperature after the reaction is finished, adding 0-4 ℃ water with equal mass, standing for 5-10min, adjusting the pH to 2-3 by using 0.5-1mol/L hydrochloric acid, finally standing for 20-24h, centrifuging, taking precipitate, and drying to obtain the methacrylic-based graphene oxide; the mixed solution is formed by mixing 1-5wt% of sodium hydroxide aqueous solution and absolute ethyl alcohol according to the volume ratio of (1-2) to 1;
step 2, adding 1-4.8 parts by weight of aluminum hydroxide into 30-50 parts by weight of 75-85wt% phosphoric acid, heating to 70-90 ℃, reacting for 30-90min at 100-300r/min, then adding 1-3 parts by weight of hydrotalcite, keeping the temperature for continuous reaction for 1-3h, and after the reaction is finished, centrifuging, taking precipitate, washing and drying to obtain hydrotalcite modified aluminum dihydrogen phosphate;
step 3, adding 5-8 parts by weight of methyl propenyl graphene oxide into 80-100 parts by weight of toluene, stirring for 5-20min at the rotating speed of 100-300r/min, adding 1-2 parts by weight of organic matter, then adding 0.1-0.8 part by weight of ammonium persulfate and 0.01-0.05 part by weight of 4-methoxyphenol, heating to 60-80 ℃, stirring and reacting for 1-3h at the rotating speed of 100-300r/min, and after the reaction is finished, centrifuging to take precipitate, washing and drying to obtain an intermediate product;
and 4, adding the intermediate product obtained in the step 3, 1-3 parts by weight of hydrotalcite modified aluminum dihydrogen phosphate and 0.1-1 part by weight of glycidyl ether into 50-100 parts by weight of acetone, uniformly mixing, then adding 0.1-0.6 part by weight of tetramethylammonium chloride, heating to 70-90 ℃ in a nitrogen atmosphere, reacting for 1-2h, centrifuging after the reaction is finished, taking the precipitate, washing and drying to obtain the modified graphene oxide.
The organic matter is one or a mixture of two of tributyl methacrylate, vinyl tri-tert-butyl peroxide silane and trans-2- (4-biphenyl) vinyl boric acid. Preferably, the organic matter is prepared from vinyl tri-tert-butyl peroxysilane and trans-2- (4-biphenyl) vinyl boric acid according to the mass ratio of (1-3): (1-3) mixing.
According to the invention, graphene oxide is introduced, methacryloyl chloride is adopted to perform methyl propenyl modification on the graphene oxide, and finally water at 4 ℃ is adopted for standing treatment, so that the agglomeration phenomenon of the graphene oxide is improved, and the high temperature resistance and flame retardant property of the adhesive are improved; however, graphene oxide is fragile, easy to break, crush, poor in cohesive strength, easy to crack and the like, and further influences curing, peeling strength, water resistance and the like of the adhesive in the application process.
On the basis, the polymerization reaction of the trifluoro butyl methacrylate and the trans-2- (4-biphenyl) vinyl boric acid on the methyl propenyl graphene oxide in the ammonium persulfate is adopted to prepare the graphene oxide containing the boron, the fluorine and the carbon elements, the carbon forming rate is high, the carbon layer is compact, the boron, the fluorine and the carbon are synergistic, the flame retardance and the high temperature resistance of the adhesive are improved, the prepared graphene oxide containing the boron, the fluorine and the carbon elements is highly crosslinked to form a compact network structure, and the brittleness of the graphene oxide is improved. The method is characterized in that the graphene oxide containing the elements of boron, fluorine and carbon is treated by using glycidyl ether, the graphene oxide containing the elements of boron, fluorine and carbon is highly crosslinked by using the glycidyl ether, cracks generated by the fracture of the graphene oxide can be timely compensated by the hydrotalcite, and the flame retardant and high temperature resistance performance is improved by the synergistic effect of the hydrotalcite and the graphene oxide. Under the high temperature condition, the aluminum dihydrogen phosphate has the adhesion effect on inorganic materials, and the adhesive is prevented from generating cracks under the high temperature condition to influence the mechanical property, the flame retardance and the appearance of the adhesive.
The invention also discloses a preparation method of the high-temperature-resistant ultraviolet curing adhesive.
A preparation method of a high-temperature-resistant ultraviolet curing adhesive comprises the following steps: adding an acrylic monomer and a photoinitiator into a stirring kettle, stirring for 1-6min at 500-700r/min under a vacuum and dark state, heating to 50-70 ℃ for reaction for 20-60min, cooling to room temperature, sequentially adding urethane acrylate, a defoaming agent, a polymerization inhibitor, a sulfhydryl organic matter and modified graphene oxide, stirring for 1-2min at a rotating speed of 600-900r/min, dispersing for 2-4 times, and finally vacuumizing and defoaming for 3-5min to obtain the high-temperature-resistant ultraviolet curing adhesive.
The invention has the beneficial effects that:
1. the high-temperature-resistant ultraviolet curing adhesive is prepared from the raw materials of urethane acrylate, an acrylic monomer, a photoinitiator, a defoaming agent, a polymerization inhibitor, a sulfydryl organic matter and graphene oxide, can be cured by ultraviolet light, is simple to operate, has a long service life, and has good flame retardance and high temperature resistance.
2. The invention discloses modified graphene oxide, which is subjected to methyl propenyl modification by adopting methacryloyl chloride, and finally subjected to standing treatment by adopting water at 4 ℃ to improve the agglomeration phenomenon of the graphene oxide, wherein the polymerization reaction of methyl propenyl graphene oxide in ammonium persulfate is carried out by adopting tributyl methacrylate and trans-2- (4-biphenyl) vinyl boric acid to prepare the graphene oxide containing boron, fluorine and carbon elements, the graphene oxide has the advantages of high carbon forming rate, compact carbon layer, boron, fluorine and carbon synergistic effect, and the flame retardance and high temperature resistance of an adhesive are improved.
Detailed Description
Sources of materials used in the various examples:
urethane acrylate, grade: ETERCURE, cat number: 6145-100, viscosity: 75000 (cps, at60 ℃) purchased from Guangzhou City Krestan chemical Co., ltd.
Graphene oxide, fineness: 1-3nm, number of layers: 2-5 layers, purchased from Hangzhou Zhi Ti purification technologies, inc.
Hydrotalcite, type: FM300, 200 mesh, purchased from Biotechnology, inc., located in Shanghai, shuwatsu.
Example 1
A high-temperature-resistant ultraviolet curing adhesive comprises the following raw materials in parts by weight: 50 parts of urethane acrylate, 12 parts of acrylic monomer, 4 parts of photoinitiator, 0.3 part of defoaming agent, 0.2 part of polymerization inhibitor, 3 parts of sulfhydryl organic matter and 8 parts of graphene oxide.
The acrylic acid monomer is composed of pentaerythritol triacrylate, methacryloyl isocyanate and bisphenol-A-dimethacrylate according to a mass ratio of 2.
The mercapto organic matter consists of 3-mercaptopropionic acid, 1,3,5-triazine-2,4,6-trithiol in a mass ratio of 1:2.
The defoaming agent is diethylene glycol monomethyl ether.
The polymerization inhibitor is p-benzoquinone.
The photoinitiator is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.
A preparation method of a high-temperature-resistant ultraviolet curing adhesive comprises the following steps: adding an acrylic monomer and a photoinitiator into a stirring kettle, stirring for 5min at 600r/min under a vacuum and dark state, heating to 60 ℃ for reaction for 30min, cooling to room temperature, sequentially adding urethane acrylate, a defoaming agent, a polymerization inhibitor, a sulfhydryl organic substance and graphene oxide, stirring for 2min at a rotation speed of 900r/min, dispersing for 3 times, and finally vacuumizing and defoaming for 4min to obtain the high-temperature-resistant ultraviolet curing adhesive.
Example 2
A high-temperature-resistant ultraviolet curing adhesive comprises the following raw materials in parts by weight: 50 parts of urethane acrylate, 12 parts of acrylic acid monomer, 4 parts of photoinitiator, 0.3 part of defoamer, 0.2 part of polymerization inhibitor, 3 parts of mercapto organic matter and 8 parts of modified graphene oxide.
The acrylic acid monomer comprises pentaerythritol triacrylate, methacryloyl isocyanate and bisphenol-A-dimethacrylate in a mass ratio of 2.
The mercapto organic matter consists of 3-mercaptopropionic acid, 1,3,5-triazine-2,4,6-trithiol in a mass ratio of 1:2.
The defoaming agent is diethylene glycol monomethyl ether.
The polymerization inhibitor is p-benzoquinone.
The photoinitiator is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.
The preparation method of the modified graphene oxide comprises the following steps: adding 5 parts by weight of graphene oxide into 80 parts by weight of mixed solution, stirring for 10min at the rotating speed of 150r/min, then adding 1 part by weight of methacryloyl chloride, heating to 55 ℃, reacting for 24h at the speed of 150r/min, cooling to room temperature after the reaction is finished, adding equal mass of 4 ℃ water, standing for 10min, adjusting the pH to 3 by adopting 1mol/L hydrochloric acid, standing for 24h, centrifuging, taking precipitate, and drying to obtain modified graphene oxide; the mixed solution is formed by mixing 5wt% of sodium hydroxide aqueous solution and absolute ethyl alcohol according to the volume ratio of 1:1.
A preparation method of a high-temperature-resistant ultraviolet curing adhesive comprises the following steps: adding an acrylic monomer and a photoinitiator into a stirring kettle, stirring for 5min at 600r/min under a vacuum and dark state, heating to 60 ℃ for reaction for 30min, cooling to room temperature, sequentially adding urethane acrylate, a defoaming agent, a polymerization inhibitor, a sulfhydryl organic substance and modified graphene oxide, stirring for 2min at a rotation speed of 900r/min, dispersing for 3 times, and finally vacuumizing and defoaming for 4min to obtain the high-temperature-resistant ultraviolet curing adhesive.
Example 3
A high-temperature-resistant ultraviolet curing adhesive comprises the following raw materials in parts by weight: 50 parts of urethane acrylate, 12 parts of acrylic monomer, 4 parts of photoinitiator, 0.3 part of defoaming agent, 0.2 part of polymerization inhibitor, 3 parts of sulfhydryl organic matter and 8 parts of modified graphene oxide.
The acrylic acid monomer is composed of pentaerythritol triacrylate, methacryloyl isocyanate and bisphenol-A-dimethacrylate according to a mass ratio of 2.
The mercapto organic matter consists of 3-mercaptopropionic acid, 1,3,5-triazine-2,4,6-trithiol in a mass ratio of 1:2.
The defoaming agent is diethylene glycol monomethyl ether.
The polymerization inhibitor is p-benzoquinone.
The photoinitiator is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.
The preparation method of the modified graphene oxide comprises the following steps:
step 1, adding 5 parts by weight of graphene oxide into 80 parts by weight of mixed solution, stirring for 10min at a rotating speed of 150r/min, then adding 1 part by weight of methacryloyl chloride, heating to 55 ℃, reacting for 24h at 150r/min, cooling to room temperature after the reaction is finished, adding equal mass of 4 ℃ water, standing for 10min, adjusting the pH to 3 by using 1mol/L hydrochloric acid, standing for 24h, centrifuging, taking precipitate, and drying to obtain the methyl propenyl graphene oxide; the mixed solution is formed by mixing 5wt% of sodium hydroxide aqueous solution and absolute ethyl alcohol according to the volume ratio of 1:1;
and 2, adding 5 parts by weight of methyl propenyl graphene oxide into 100 parts by weight of toluene, stirring for 10min at the rotating speed of 150r/min, adding 1.8 parts by weight of organic matter, then adding 0.8 part by weight of ammonium persulfate and 0.05 part by weight of 4-methoxyphenol, heating to 70 ℃, stirring and reacting for 1h at the rotating speed of 150r/min, centrifuging after the reaction is finished, taking precipitate, washing and drying to obtain the modified graphene oxide.
The organic matter is vinyl tri-tert-butyl peroxide silane.
A preparation method of a high-temperature-resistant ultraviolet curing adhesive comprises the following steps: adding an acrylic monomer and a photoinitiator into a stirring kettle, stirring for 5min at 600r/min under a vacuum and dark state, heating to 60 ℃ for reaction for 30min, cooling to room temperature, sequentially adding urethane acrylate, a defoaming agent, a polymerization inhibitor, a sulfhydryl organic substance and modified graphene oxide, stirring for 2min at a rotation speed of 900r/min, dispersing for 3 times, and finally vacuumizing and defoaming for 4min to obtain the high-temperature-resistant ultraviolet curing adhesive.
Example 4
A high-temperature-resistant ultraviolet curing adhesive comprises the following raw materials in parts by weight: 50 parts of urethane acrylate, 12 parts of acrylic acid monomer, 4 parts of photoinitiator, 0.3 part of defoamer, 0.2 part of polymerization inhibitor, 3 parts of mercapto organic matter and 8 parts of modified graphene oxide.
The acrylic acid monomer comprises pentaerythritol triacrylate, methacryloyl isocyanate and bisphenol-A-dimethacrylate in a mass ratio of 2.
The mercapto organic matter consists of 3-mercaptopropionic acid, 1,3,5-triazine-2,4,6-trithiol in a mass ratio of 1:2.
The defoaming agent is diethylene glycol monomethyl ether.
The polymerization inhibitor is p-benzoquinone.
The photoinitiator is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.
The preparation method of the modified graphene oxide comprises the following steps:
step 1, adding 5 parts by weight of graphene oxide into 80 parts by weight of mixed solution, stirring for 10min at a rotating speed of 150r/min, then adding 1 part by weight of methacryloyl chloride, heating to 55 ℃, reacting for 24h at 150r/min, cooling to room temperature after the reaction is finished, adding equal mass of 4 ℃ water, standing for 10min, adjusting the pH to 3 by using 1mol/L hydrochloric acid, standing for 24h, centrifuging, taking precipitate, and drying to obtain the methyl propenyl graphene oxide; the mixed solution is formed by mixing 5wt% of sodium hydroxide aqueous solution and absolute ethyl alcohol according to the volume ratio of 1:1;
step 2, adding 4.8 parts by weight of aluminum hydroxide into 50 parts by weight of 85wt% phosphoric acid, heating to 80 ℃, reacting for 90min at 150r/min, then adding 1.5 parts by weight of hydrotalcite, keeping the temperature, continuously reacting for 2h, centrifuging after the reaction is finished, taking precipitate, washing and drying to obtain hydrotalcite modified aluminum dihydrogen phosphate;
step 3, adding 5 parts by weight of methyl propenyl graphene oxide into 100 parts by weight of toluene, stirring for 10min at the rotating speed of 150r/min, adding 1.8 parts by weight of organic matter, then adding 0.8 part by weight of ammonium persulfate and 0.05 part by weight of 4-methoxyphenol, heating to 70 ℃, stirring and reacting for 1h at the rotating speed of 150r/min, centrifuging after the reaction is finished, taking precipitate, washing and drying to obtain an intermediate product;
and 4, adding the intermediate product obtained in the step 3, 1.5 parts by weight of hydrotalcite modified aluminum dihydrogen phosphate and 0.5 part by weight of glycidyl ether into 80 parts by weight of acetone, uniformly mixing, then adding 0.5 part by weight of tetramethylammonium chloride, heating to 80 ℃ in a nitrogen atmosphere, reacting for 1h, centrifuging after the reaction is finished, taking the precipitate, washing and drying to obtain the modified graphene oxide.
The organic matter is prepared from vinyl tri-tert-butyl peroxysilane and trans-2- (4-biphenyl) vinyl boric acid according to the mass ratio of 1:3, and mixing.
A preparation method of a high-temperature-resistant ultraviolet curing adhesive comprises the following steps: adding an acrylic monomer and a photoinitiator into a stirring kettle, stirring for 5min at 600r/min under a vacuum and dark state, heating to 60 ℃ for reaction for 30min, cooling to room temperature, sequentially adding urethane acrylate, a defoaming agent, a polymerization inhibitor, a sulfhydryl organic substance and modified graphene oxide, stirring for 2min at a rotation speed of 900r/min, dispersing for 3 times, and finally vacuumizing and defoaming for 4min to obtain the high-temperature-resistant ultraviolet curing adhesive.
Example 5
A high-temperature-resistant ultraviolet curing adhesive comprises the following raw materials in parts by weight: 50 parts of urethane acrylate, 12 parts of acrylic monomer, 4 parts of photoinitiator, 0.3 part of defoaming agent, 0.2 part of polymerization inhibitor, 3 parts of sulfhydryl organic matter and 8 parts of modified graphene oxide.
The acrylic acid monomer is composed of pentaerythritol triacrylate, methacryloyl isocyanate and bisphenol-A-dimethacrylate according to a mass ratio of 2.
The mercapto organic compound is prepared from 3-mercaptopropionic acid, 1,3,5-triazine-2,4,6-trithiol according to the mass ratio of 1:2.
The defoaming agent is diethylene glycol monomethyl ether.
The polymerization inhibitor is p-benzoquinone.
The photoinitiator was 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.
The preparation method of the modified graphene oxide comprises the following steps:
step 1, adding 5 parts by weight of graphene oxide into 80 parts by weight of mixed solution, stirring for 10min at the rotating speed of 150r/min, then adding 1 part by weight of methacryloyl chloride, heating to 55 ℃, reacting for 24h at the speed of 150r/min, cooling to room temperature after the reaction is finished, adding equal-mass 4 ℃ water, standing for 10min, adjusting the pH to 3 by using 1mol/L hydrochloric acid, standing for 24h, centrifuging, taking precipitate, and drying to obtain the methyl propenyl graphene oxide; the mixed solution is formed by mixing 5wt% of sodium hydroxide aqueous solution and absolute ethyl alcohol according to the volume ratio of 1:1.
Step 2, adding 4.8 parts by weight of aluminum hydroxide into 50 parts by weight of 85wt% phosphoric acid, heating to 80 ℃, reacting for 90min at 150r/min, then adding 1.5 parts by weight of hydrotalcite, keeping the temperature, continuously reacting for 2h, centrifuging after the reaction is finished, taking precipitate, washing and drying to obtain hydrotalcite modified aluminum dihydrogen phosphate;
step 3, adding 5 parts by weight of methyl propenyl graphene oxide into 100 parts by weight of methylbenzene, stirring for 10min at the rotating speed of 150r/min, adding 1.8 parts by weight of organic matter, then adding 0.8 part by weight of ammonium persulfate and 0.05 part by weight of 4-methoxyphenol, heating to 70 ℃, stirring and reacting for 1h at the rotating speed of 150r/min, centrifuging after the reaction is finished, taking precipitate, washing and drying to obtain an intermediate product;
and 4, adding the intermediate product obtained in the step 3, 1.5 parts by weight of hydrotalcite modified aluminum dihydrogen phosphate and 0.5 part by weight of glycidyl ether into 80 parts by weight of acetone, uniformly mixing, then adding 0.5 part by weight of tetramethylammonium chloride, heating to 80 ℃ in a nitrogen atmosphere, reacting for 1h, centrifuging after the reaction is finished, taking the precipitate, washing and drying to obtain the modified graphene oxide.
The organic matter is vinyl tri-tert-butyl peroxide silane.
A preparation method of a high-temperature-resistant ultraviolet curing adhesive comprises the following steps: adding an acrylic monomer and a photoinitiator into a stirring kettle, stirring for 5min at 600r/min under a vacuum and dark state, heating to 60 ℃ for reaction for 30min, cooling to room temperature, sequentially adding urethane acrylate, a defoaming agent, a polymerization inhibitor, a sulfhydryl organic substance and modified graphene oxide, stirring for 2min at a rotation speed of 900r/min, dispersing for 3 times, and finally vacuumizing and defoaming for 4min to obtain the high-temperature-resistant ultraviolet curing adhesive.
Example 6
A high-temperature-resistant ultraviolet curing adhesive comprises the following raw materials in parts by weight: 50 parts of urethane acrylate, 12 parts of acrylic monomer, 4 parts of photoinitiator, 0.3 part of defoaming agent, 0.2 part of polymerization inhibitor, 3 parts of sulfhydryl organic matter and 8 parts of modified graphene oxide.
The acrylic acid monomer comprises pentaerythritol triacrylate, methacryloyl isocyanate and bisphenol-A-dimethacrylate in a mass ratio of 2.
The mercapto organic compound is prepared from 3-mercaptopropionic acid, 1,3,5-triazine-2,4,6-trithiol according to the mass ratio of 1:2.
The defoaming agent is diethylene glycol monomethyl ether.
The polymerization inhibitor is p-benzoquinone.
The photoinitiator is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.
The preparation method of the modified graphene oxide comprises the following steps:
step 1, adding 5 parts by weight of graphene oxide into 80 parts by weight of mixed solution, stirring for 10min at a rotating speed of 150r/min, then adding 1 part by weight of methacryloyl chloride, heating to 55 ℃, reacting for 24h at 150r/min, cooling to room temperature after the reaction is finished, adding equal mass of 4 ℃ water, standing for 10min, adjusting the pH to 3 by using 1mol/L hydrochloric acid, standing for 24h, centrifuging, taking precipitate, and drying to obtain the methyl propenyl graphene oxide; the mixed solution is formed by mixing 5wt% of sodium hydroxide aqueous solution and absolute ethyl alcohol according to the volume ratio of 1:1;
step 2, adding 4.8 parts by weight of aluminum hydroxide into 50 parts by weight of 85wt% phosphoric acid, heating to 80 ℃, reacting for 90min at a speed of 150r/min, then adding 1.5 parts by weight of hydrotalcite, keeping the temperature, continuously reacting for 2h, and after the reaction is finished, centrifuging, taking precipitate, washing and drying to obtain hydrotalcite modified aluminum dihydrogen phosphate;
step 3, adding 5 parts by weight of methyl propenyl graphene oxide into 100 parts by weight of toluene, stirring for 10min at the rotating speed of 150r/min, adding 1.8 parts by weight of organic matter, then adding 0.8 part by weight of ammonium persulfate and 0.05 part by weight of 4-methoxyphenol, heating to 70 ℃, stirring and reacting for 1h at the rotating speed of 150r/min, centrifuging after the reaction is finished, taking precipitate, washing and drying to obtain an intermediate product;
and 4, adding the intermediate product obtained in the step 3, 1.5 parts by weight of hydrotalcite modified aluminum dihydrogen phosphate and 0.5 part by weight of glycidyl ether into 80 parts by weight of acetone, uniformly mixing, then adding 0.5 part by weight of tetramethylammonium chloride, heating to 80 ℃ in a nitrogen atmosphere, reacting for 1h, centrifuging after the reaction is finished, taking the precipitate, washing and drying to obtain the modified graphene oxide.
The organic matter is trans-2- (4-biphenyl) vinyl boric acid.
A preparation method of a high-temperature-resistant ultraviolet curing adhesive comprises the following steps: adding an acrylic monomer and a photoinitiator into a stirring kettle, stirring for 5min at 600r/min under a vacuum and dark state, heating to 60 ℃ for reaction for 30min, cooling to room temperature, sequentially adding urethane acrylate, a defoaming agent, a polymerization inhibitor, a sulfhydryl organic substance and modified graphene oxide, stirring for 2min at a rotation speed of 900r/min, dispersing for 3 times, and finally vacuumizing and defoaming for 4min to obtain the high-temperature-resistant ultraviolet curing adhesive.
Example 7
A high-temperature-resistant ultraviolet curing adhesive comprises the following raw materials in parts by weight: 50 parts of urethane acrylate, 12 parts of acrylic monomer, 4 parts of photoinitiator, 0.3 part of defoaming agent, 0.2 part of polymerization inhibitor, 3 parts of sulfhydryl organic matter and 8 parts of modified graphene oxide.
The acrylic acid monomer is composed of pentaerythritol triacrylate, methacryloyl isocyanate and bisphenol-A-dimethacrylate according to a mass ratio of 2.
The mercapto organic matter consists of 3-mercaptopropionic acid, 1,3,5-triazine-2,4,6-trithiol in a mass ratio of 1:2.
The defoaming agent is diethylene glycol monomethyl ether.
The polymerization inhibitor is p-benzoquinone.
The photoinitiator is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.
The preparation method of the modified graphene oxide comprises the following steps:
step 1, adding 5 parts by weight of graphene oxide into 80 parts by weight of mixed solution, stirring for 10min at the rotating speed of 150r/min, then adding 1 part by weight of methacryloyl chloride, heating to 55 ℃, reacting for 24h at the speed of 150r/min, cooling to room temperature after the reaction is finished, adding equal-mass 4 ℃ water, standing for 10min, adjusting the pH to 3 by using 1mol/L hydrochloric acid, standing for 24h, centrifuging, taking precipitate, and drying to obtain the methyl propenyl graphene oxide; the mixed solution is prepared by mixing 5wt% of sodium hydroxide aqueous solution and absolute ethyl alcohol according to the volume ratio of 1:1.
Step 2, adding 5 parts by weight of methyl propenyl graphene oxide into 100 parts by weight of toluene, stirring for 10min at the rotating speed of 150r/min, adding 1.8 parts by weight of organic matter, then adding 0.8 part by weight of ammonium persulfate and 0.05 part by weight of 4-methoxyphenol, heating to 70 ℃, stirring and reacting for 1h at the rotating speed of 150r/min, centrifuging after the reaction is finished, taking precipitate, washing and drying to obtain an intermediate product;
and 3, adding the intermediate product obtained in the step 2 and 0.5 part by weight of glycidyl ether into 80 parts by weight of acetone, uniformly mixing, then adding 0.5 part by weight of tetramethylammonium chloride, heating to 80 ℃ in a nitrogen atmosphere, reacting for 1h, centrifuging after the reaction is finished, taking the precipitate, washing and drying to obtain the modified graphene oxide.
The organic matter is vinyl tri-tert-butyl peroxide silane.
A preparation method of a high-temperature-resistant ultraviolet curing adhesive comprises the following steps: adding an acrylic monomer and a photoinitiator into a stirring kettle, stirring for 5min at 600r/min under a vacuum and dark state, heating to 60 ℃ for reaction for 30min, cooling to room temperature, sequentially adding urethane acrylate, a defoaming agent, a polymerization inhibitor, a sulfhydryl organic substance and modified graphene oxide, stirring for 2min at a rotation speed of 900r/min, dispersing for 3 times, and finally vacuumizing and defoaming for 4min to obtain the high-temperature-resistant ultraviolet curing adhesive.
Test example 1
The flame retardant property is as follows:
coating the high-temperature-resistant ultraviolet curing adhesive prepared in each embodiment on one surface of a polyimide film, wherein the thickness of the adhesive is 0.3mm, treating the adhesive in a 110 ℃ drying oven for 20min, and preliminarily compounding the adhesive surface of the polyimide film with a prepreg film and a copper foil by a 110 ℃ plastic packaging machine; then putting the mixture into a pressure compounding machine at the temperature of 180 ℃ and the pressure of 40Kgf/cm 2 And processing for 40min to obtain the FPC base material.
And (3) carrying out flame retardant performance test on the prepared FPC by referring to a polyimide film copper-clad plate for a GB/T13555-2017 flexible printed circuit. The VTM test is carried out according to UL 94-2006 test Standard for flammability of Plastic materials in Equipment and devices, and is classified into three grades, namely VTM-0, VTM-1 and VTM-2.
TABLE 1 flame retardancy test results
As can be seen from table 1, the flame retardant performance of example 4 is better than that of examples 1-3 and 7, the flame retardant performance of the adhesive is significantly improved by adding the self-made modified graphene oxide in example 4 to reach VTM-0, the graphene oxide is subjected to methacryl modification by using methacryloyl chloride, and finally the graphene oxide is subjected to standing treatment by using water at 4 ℃ to improve the agglomeration phenomenon of the graphene oxide, trifluorobutyl methacrylate and trans-2- (4-biphenyl) vinyl boric acid are used to perform polymerization reaction on the methacryl graphene oxide in ammonium persulfate to prepare the graphene oxide containing boron, fluorine and carbon elements, the graphene oxide has high char formation rate, compact carbon layers, boron, fluorine and carbon synergistic effect, the flame retardant performance and the high temperature resistance of the adhesive are improved, the graphene oxide containing boron, fluorine and carbon elements is treated by using glycidyl ether, the hydrotalcite modified aluminum dihydrogen phosphate, the graphene oxide containing boron, fluorine and carbon elements is highly cross-linked by using glycidyl ether, and the hydrotalcite can timely compensate for the synergistic crack generated by the fracture of the graphene oxide, and the flame retardant performance of the hydrotalcite is improved.
Test example 2
Mechanical properties: the initial tensile shear strength and the tensile shear strength after aging for two weeks at a temperature of 85 ℃ and a humidity of 85% were tested with reference to GB/T7124-2008 "determination of tensile shear strength of adhesive".
The test method comprises the following steps: the test piece was a rectangular steel plate having dimensions of 100 mm. Times.25 mm. Times.1.6 mm, and a length of the bonded portion at one end thereof was 12.5mm. And (3) alternately polishing the surface of the bonding part of the sample by using coarse sand paper and then using fine sand paper at an angle of 45 degrees, cleaning the bonding part of the sample by using acetone for a plurality of times after polishing, cleaning the bonding part of the sample by using absolute ethyl alcohol, and drying the sample. And uniformly coating the prepared high-temperature-resistant ultraviolet curing adhesive on the surface of the bonding part of the sample, superposing and bonding the two samples, ensuring the two samples to be accurately aligned through a clamp, and controlling the thickness of an adhesive layer to be 0.2cm. And (3) curing the bonded sample in ultraviolet light. And (3) symmetrically clamping the sample during a tensile test, wherein the distance from the clamping position to the bonding end is 50mm, and the gasket is used for clamping to ensure that the tensile force acts in the bonding surface. The tensile testing machine is loaded at a constant speed, and the damage time is controlled to be about 75 s.
TABLE 2 tensile shear Strength Retention test results
| Retention ratio of tensile shear strength/%) | |
| Example 1 | 72.5 |
| Example 2 | 76.3 |
| Example 3 | 81.7 |
| Example 4 | 91.4 |
| Example 5 | 88.2 |
| Example 6 | 89.7 |
| Example 7 | 85.1 |
As can be seen from table 2, the tensile shear strength of the adhesive prepared in example 4 after aging for two weeks at 85 ℃ and 85% humidity is better than that of examples 1 to 3, in example 2, methacryl chloride is used to perform methacryl modification on graphene oxide, and finally water at 4 ℃ is used for standing treatment, so that the agglomeration phenomenon of graphene oxide is improved, and the high temperature resistance and flame retardant property of the adhesive are improved, but graphene oxide is fragile and easy to break, crush, has poor cohesive strength, and is easy to crack. In example 3, trifluorobutyl methacrylate and trans-2- (4-biphenyl) vinyl boric acid are used to perform a polymerization reaction on methacrylic graphene oxide on ammonium persulfate, and the graphene oxide containing boron, fluorine and carbon elements is highly crosslinked to form a dense network structure, so that the brittleness of the graphene oxide is improved, and the tensile shear strength of the adhesive is further improved.
The tensile shear strength of the adhesive prepared in example 4 after aging for two weeks at 85 ℃ and 85% humidity is greater than that of examples 5-6, methacrylic chloride is used for carrying out methacrylic modification on graphene oxide, and finally standing treatment is carried out by using water at 4 ℃ to improve the agglomeration phenomenon of graphene oxide, but the graphene oxide is fragile and easy to break, crush, poor in cohesive strength, easy to crack and the like. Under the high temperature condition, the aluminum dihydrogen phosphate has the adhesive effect on inorganic materials, and the adhesive is prevented from generating cracks under the high temperature condition to influence the mechanical property, the flame retardance and the appearance of the adhesive.
Claims (9)
1. The high-temperature-resistant ultraviolet curing adhesive is characterized by comprising the following raw materials: the preparation method comprises the following steps of (1) preparing urethane acrylate, an acrylic monomer, a photoinitiator, a defoaming agent, a polymerization inhibitor, a sulfhydryl organic matter and modified graphene oxide; the modified graphene oxide is prepared by heating and modifying graphene oxide by adopting methacryloyl chloride and carrying out heating and crosslinking treatment on hydrotalcite modified aluminum dihydrogen phosphate.
2. The high-temperature resistant UV-curable adhesive according to claim 1, wherein the thiol organic compound is one or a mixture of two or more of monothiol organic compound, dithiol organic compound, trithiol organic compound and tetrathiol organic compound.
3. The high-temperature-resistant ultraviolet-curable adhesive according to claim 1, wherein the defoaming agent is one or a mixture of two or more of defoaming agent F681, diethylene glycol monomethyl ether and polysiloxane emulsion defoaming agent N-10.
4. The high-temperature-resistant ultraviolet-curable adhesive according to claim 1, wherein the polymerization inhibitor is one or a mixture of more than two of p-benzoquinone, 4-methoxyphenol and hydroquinone.
5. The high temperature resistant UV curable adhesive of claim 1, wherein the photoinitiator is one or a mixture of 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, benzoin bis-methyl ether, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyloxime), 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone, phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-hydroxy-2-methyl-1-phenyl acetone, 2-methyl-1- (4-methylthiophenyl) -2-morpholin-1-one, α -dimethyl benzil ketal, isopropyl thioxanthone, benzophenone, benzoin ethyl ether, benzoin bis-methyl ether, and benzoin butyl ether.
6. The high-temperature-resistant ultraviolet-curable adhesive according to claim 1, wherein the preparation method of the modified graphene oxide comprises the following steps:
(1) Heating and modifying the graphene oxide by adopting methacryloyl chloride to prepare methacrylic-based graphene oxide;
(2) Carrying out heating reaction on methyl propenyl graphene oxide and an organic matter under the action of an initiator and a polymerization inhibitor to prepare an intermediate product;
(3) Heating and crosslinking the intermediate product and the hydrotalcite modified aluminum dihydrogen phosphate by using glycidyl ether to prepare the modified graphene oxide.
7. The high-temperature-resistant ultraviolet-curable adhesive according to claim 6, wherein the organic substance is one or a mixture of two of trifluorobutyl methacrylate, vinyl tri-tert-butylperoxysilane and trans-2- (4-biphenyl) vinyl boric acid.
8. The method for preparing the high-temperature resistant ultraviolet curing adhesive according to any one of claims 1 to 7, comprising the following steps: adding an acrylic monomer and a photoinitiator into a stirring kettle, stirring in a vacuum and dark state, heating for reaction, cooling to room temperature, sequentially adding urethane acrylate, a defoaming agent, a polymerization inhibitor, a sulfhydryl organic matter and modified graphene oxide, stirring, dispersing, and finally vacuumizing for defoaming to obtain the high-temperature-resistant ultraviolet curing adhesive.
9. The modified graphene oxide is characterized by being prepared by the following method:
(1) Heating and modifying graphene oxide by adopting methacryloyl chloride to prepare methacrylic-based graphene oxide;
(2) Carrying out heating reaction on methyl propenyl graphene oxide and an organic matter under the action of an initiator and a polymerization inhibitor to prepare an intermediate product;
(3) Heating and crosslinking the intermediate product and the hydrotalcite modified aluminum dihydrogen phosphate by using glycidyl ether to prepare the modified graphene oxide.
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| CN104910333A (en) * | 2015-06-24 | 2015-09-16 | 深圳职业技术学院 | Modified graphene oxide polymer composite material and preparation method thereof |
| CN112574711A (en) * | 2020-12-29 | 2021-03-30 | 烟台信友新材料有限公司 | High-identification-degree high-temperature-resistant ultraviolet curing adhesive and preparation method thereof |
| CN113716557A (en) * | 2021-09-13 | 2021-11-30 | 长春工业大学 | Preparation method of modified graphene oxide and method for preparing epoxy resin composite material by using modified graphene oxide |
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| CN104910333A (en) * | 2015-06-24 | 2015-09-16 | 深圳职业技术学院 | Modified graphene oxide polymer composite material and preparation method thereof |
| CN112574711A (en) * | 2020-12-29 | 2021-03-30 | 烟台信友新材料有限公司 | High-identification-degree high-temperature-resistant ultraviolet curing adhesive and preparation method thereof |
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