CN117143558A - High-specific gravity high-weather-resistance ultraviolet deep-curing adhesive and preparation method thereof - Google Patents
High-specific gravity high-weather-resistance ultraviolet deep-curing adhesive and preparation method thereof Download PDFInfo
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- CN117143558A CN117143558A CN202311395136.2A CN202311395136A CN117143558A CN 117143558 A CN117143558 A CN 117143558A CN 202311395136 A CN202311395136 A CN 202311395136A CN 117143558 A CN117143558 A CN 117143558A
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- 230000005484 gravity Effects 0.000 title claims abstract description 37
- 239000000853 adhesive Substances 0.000 title claims abstract description 30
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 78
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 56
- -1 modified acrylic ester Chemical class 0.000 claims abstract description 44
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000003112 inhibitor Substances 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 239000004814 polyurethane Substances 0.000 claims abstract description 6
- 229920002635 polyurethane Polymers 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 57
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000004530 micro-emulsion Substances 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 28
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 18
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 12
- 238000010907 mechanical stirring Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- 238000002834 transmittance Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 6
- 229920005603 alternating copolymer Polymers 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000011976 maleic acid Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000003828 vacuum filtration Methods 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- GCGKIXNNTHZMPM-UHFFFAOYSA-N C1(=CC=CC=C1)P(C1=CC=CC=C1)=O.CC1=C(C(=O)C2=CC=CC=C2)C(=CC(=C1)C)C Chemical compound C1(=CC=CC=C1)P(C1=CC=CC=C1)=O.CC1=C(C(=O)C2=CC=CC=C2)C(=CC(=C1)C)C GCGKIXNNTHZMPM-UHFFFAOYSA-N 0.000 claims description 3
- BDAHDQGVJHDLHQ-UHFFFAOYSA-N [2-(1-hydroxycyclohexyl)phenyl]-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C1(O)CCCCC1 BDAHDQGVJHDLHQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000593 microemulsion method Methods 0.000 claims description 3
- 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
- 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
- 238000007738 vacuum evaporation Methods 0.000 claims description 2
- XVZXOLOFWKSDSR-UHFFFAOYSA-N Cc1cc(C)c([C]=O)c(C)c1 Chemical group Cc1cc(C)c([C]=O)c(C)c1 XVZXOLOFWKSDSR-UHFFFAOYSA-N 0.000 claims 1
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical compound O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 239000000945 filler Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 16
- 239000004568 cement Substances 0.000 description 14
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 230000008439 repair process Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910021485 fumed silica Inorganic materials 0.000 description 6
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 3
- 229940119545 isobornyl methacrylate Drugs 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- FZSHSWCZYDDOCK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;oxolane Chemical compound C1CCOC1.CC(=C)C(O)=O FZSHSWCZYDDOCK-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 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 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OZTGTXHZVGBUBD-UHFFFAOYSA-N 1-(1-hydroxycyclohexyl)-2-phenylethanone Chemical compound C=1C=CC=CC=1CC(=O)C1(O)CCCCC1 OZTGTXHZVGBUBD-UHFFFAOYSA-N 0.000 description 1
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000011282 treatment 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
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a high specific gravity and high weather-resistant ultraviolet deep curing adhesive and a preparation method thereof, and relates to the field of adhesives. The adhesive consists of the following raw materials in parts by weight: 15-30 parts of self-made organosilicon modified acrylic ester containing bisphenol fluorene structure, 10-15 parts of polyfunctional polyurethane acrylic ester prepolymer, 20-30 parts of acrylic monomer, 0.5-5 parts of photoinitiator, 0.01-0.1 part of polymerization inhibitor, 0.5-5 parts of silane coupling agent, 0-3 parts of anti-settling agent and 50-70 parts of self-made spherical barium sulfate. According to the invention, the self-made organosilicon modified acrylic ester containing bisphenol fluorene structure and the self-made spherical barium sulfate filler are added into the adhesive, so that the high specific gravity adhesive based on the invention can be rapidly subjected to deep curing under ultraviolet light, and has excellent flexibility and weather resistance.
Description
Technical Field
The invention relates to the field of adhesives, in particular to a high-specific gravity and high-weather-resistance ultraviolet deep curing adhesive and a preparation method thereof.
Background
The unbalance is a state that each rotor is inevitably subjected to, and specifically, the unbalance refers to a state in which the rotor is in a state in which the rotor center of mass is unevenly and non-coincident with the shaft center line due to processing, material unevenness, and the like, and the rotor rotates to generate centrifugal force, and acts on the rotor bearing in a vibration or vibration force manner. In the processing production, unbalance cannot be thoroughly eliminated, and the unbalance amount of the rotor is only required to be reduced to be within an allowable range, so that the use is not influenced.
The motor rotor and the cooling fan belong to the rotating body, in order to solve the balance, a balanced cement weighting mode is adopted at present, cement of A, B components is manually mixed, a certain weight of cement is weighed and is adhered to the position of the motor rotor or the cooling fan, which needs to be balanced, and then the cement is hardened by heating, so that the purpose of dynamic balance of the rotor is achieved. For example, CN108504043a discloses a balancing cement for a motor rotor, which includes a cement a and a cement B, and the cement a and the cement B are used together.
However, the viscosity of the bi-component balanced cement is high and is semi-solid, manual mixing can be only relied on, mechanical automation cannot be realized, secondary glue supplementing is needed if unbalance is caused after the cement is hardened, the efficiency is low, and a large amount of labor cost is consumed. In addition, the bi-component balance cement in the current market has the phenomena of cement falling, cracking, easy weight deviation due to shrinkage and moisture absorption after the cement is hardened after being used for a period of time, and the service lives of the motor and the cooling fan are reduced.
Disclosure of Invention
The invention discloses a high-specific-gravity high-weather-resistance ultraviolet deep-curing adhesive and a preparation method thereof. The adhesive disclosed by the invention is single-component, has low viscosity, can be used for automatic dispensing, can be rapidly cured under ultraviolet light, and has the advantages of high curing depth, excellent flexibility and weather resistance, and wide application range.
In order to achieve the technical effects, the invention discloses a high specific gravity and high weather-resistant ultraviolet deep curing adhesive which can be cured under the irradiation of ultraviolet light with the wavelength of 200-420 nm and comprises the following raw materials in parts by weight:
15-30 parts of self-made organosilicon modified acrylic ester containing bisphenol fluorene structure; 10-15 parts of polyfunctional polyurethane acrylic ester prepolymer; 20-30 parts of acrylic acid monomer; 0.5-5 parts of photoinitiator; 0.01 to 0.1 portion of polymerization inhibitor; 0.5-5 parts of silane coupling agent; 50-70 parts of self-made spherical barium sulfate; 0-3 parts of anti-settling agent;
wherein the self-made organosilicon modified acrylic ester containing bisphenol fluorene structure has the structure shown in the following formula I,
i is a kind of
Wherein R in formula I 1 Is that，R 2 is-C m H 2m -, wherein m is 4-8.
Further, the self-made organosilicon modified acrylic ester containing bisphenol fluorene structure is prepared according to the following steps:
weighing 60g of epoxy acrylate, putting the epoxy acrylate into a reaction device, adding 30-60 g of toluene, slowly heating to 100-120 ℃, adding 0.3-0.8 g of dibutyl tin dilaurate as a catalyst for reaction, gradually dropwise adding 40-70 g of organosilicon oligomer containing bisphenol fluorene structure in the mechanical stirring process, keeping the temperature of 90-110 ℃, stirring for 4-6 h under the condition of the rotating speed of 300-500 r/min, stopping stirring when the system temperature is reduced to 50 ℃, vacuumizing, and evaporating the solvent under reduced pressure to obtain transparent viscous liquid, namely the self-made organosilicon modified acrylate containing bisphenol fluorene structure.
Further, the epoxy acrylate has a structure shown in a formula II, the organosilicon oligomer containing bisphenol fluorene structure has a structure shown in a formula III,
II (II)
Formula III
Wherein R is 3 Is that。
Further, the organosilicon oligomer containing bisphenol fluorene structure is prepared according to the following steps:
150g of 9, 9-bis [ (2, 3-glycidoxy) phenyl ] fluorene is weighed, put into a reaction device, 50-80 g of toluene is added, the temperature is slowly heated to 90-110 ℃, 0.5-0.8 g of dibutyl tin dilaurate is added as a catalyst for reaction, 20-30 g of hydroxyl-terminated polydimethylsiloxane is gradually dripped in the mechanical stirring process, the temperature of 90-110 ℃ is kept, stirring is carried out for 4-6 h under the condition of the rotating speed of 300-500 r/min, when the system temperature is reduced to 50 ℃, stirring is stopped, and the solvent is removed by vacuum evaporation under reduced pressure, so that the transparent viscous liquid is the organosilicon oligomer containing bisphenol fluorene structure.
Further, the 9, 9-bis [ (2, 3-glycidoxy) phenyl ] fluorene has a structure as shown in formula IV.
IV (IV)
The hydroxyl-terminated polydimethylsiloxane has a structure as shown in formula IIV.
IIV (IIV)
Furthermore, the transmittance of the self-made organosilicon modified acrylic ester containing bisphenol fluorene structure is 95% -98%, and the refractive index is 1.57-1.60.
The polyfunctional polyurethane acrylic ester prepolymer is one or more than two of CN975 of a sand-lime corporation, 6146-100 of a Changxing chemical material limited company, 6147 of a Changxing chemical material limited company, 4312 of a RAHN company and 4316 of a RAHN company in any proportion;
the acrylic monomer is one or a mixture of more than one of isobornyl acrylate, isobornyl methacrylate, isooctyl acrylate, isooctyl methacrylate, isodecyl acrylate, tetrahydrofuran methacrylate, tricyclodecane dimethanol diacrylate, 1, 6-hexanediol diacrylate and tricyclopropane trimethacrylate.
The photoinitiator is selected from one or a mixture of any of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl benzophenone, bis (2, 4, 6-trimethylbenzoyl) phenyl phosphorus oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone, alpha' -dimethylbenzoyl ketal, isopropyl thioxanthone, benzophenone and 2,4, 6-trimethylbenzoyl benzene-diphenyl phosphine oxide.
The polymerization inhibitor is one or a mixture of more than one of hydroquinone, p-hydroxyanisole and 2, 6-di-tert-butyl p-cresol.
The silane coupling agent is one or a mixture of more than one of KH551, KH172, KH560 and KH 570.
The anti-settling agent is one or a mixture of any of fumed silica, bentonite, polyolefin wax and modified hydrogenated castor oil.
The spherical barium sulfate is prepared by a double microemulsion method according to the following steps:
1) Preparing microemulsion
6.00 g TritonX-100, 4.8 ml n-hexanol and 40 ml cyclohexane were added to 100ml of BaCl 2 Aqueous solution (0.1 mol.L) −1 ) Ultrasonic treating at 35deg.C for 30min to obtain uniform transparent BaCl 2 A microemulsion.
50ml of 0.2mol.L −1 Na of (2) 2 SO 4 Adding the aqueous solution into 50ml of 0.5-1.5g/L PSMA (polystyrene-maleic acid alternating copolymer) aqueous solution, placing into ultrasonic wave for 30min, then dropwise adding hydrochloric acid or sodium hydroxide aqueous solution, regulating pH value to 5-7, adding 4.8 ml n-hexanol and 40 ml cyclohexane, placing into ultrasonic wave at 35deg.C for 30min, and making into uniform transparent Na 2 SO 4 A microemulsion.
2) Preparation of silane modified spherical barium sulfate
50ml of BaCl under ultrasound conditions 2 The microemulsion was slowly added dropwise to Na 2 SO 4 And (3) in the microemulsion, after the dripping is finished, carrying out constant-temperature reaction for 2 hours, and standing at room temperature for 24 hours. Adding 3-8g of silane coupling agent, performing ultrasonic dispersion for 3 hours at 90 ℃, and after the reaction is finished, performing vacuum filtration on the product while the product is hot, cleaning 3 times with 50-200 ml of acetone, and then cleaning 3 times with 50-200 ml of absolute ethyl alcohol. And drying for 12 hours in a baking oven at 105 ℃, cooling and grinding to obtain white barium sulfate powder.
Further, the silane coupling agent is one or a mixture of any of KH551, KH172, KH560 and KH 570.
Further, the density of the spherical barium sulfate is 4.3-4.5 g/cm 3 The particle diameter is 5-12 mu m, the specific surface area is 0.8-1.2 m 2 /g。
The invention also discloses a preparation method of the high specific gravity and high weather-resistant ultraviolet deep curing adhesive, which is prepared by the following steps:
15 to 30 parts of self-made organosilicon modified acrylic ester containing bisphenol fluorene structure, 10 to 15 parts of polyfunctional polyurethane acrylic ester prepolymer, 20 to 30 parts of acrylic monomer, 0.5 to 5 parts of photoinitiator, 0.01 to 0.1 part of polymerization inhibitor and 0.5 to 5 parts of silane coupling agent are added into a stirring kettle, and revolution is carried out for 30 to 50r/min under the vacuum light-proof state, and stirring is carried out for 30min under the condition of rotation of 600 to 1000 r/min; adding 50-70 parts of self-made spherical barium sulfate, revolving for 30-50 r/min under vacuum light-proof state, and stirring for 30min under rotation for 300-800 r/min; adding 0-3 parts of anti-settling agent, revolving for 30-50 r/min under vacuum light-proof state, and stirring for 30min under rotation for 300-800 r/min to obtain the high specific gravity and high weather-proof ultraviolet deep curing adhesive.
Further, the prepared high specific gravity and high weather-resistant ultraviolet deep curing adhesive has the specific gravity of 2.2-3.1 g/cm 3 。
The beneficial effects of the invention include:
(1) According to the invention, the raw materials containing bisphenol fluorene structures are subjected to organosilicon and acrylic acid modification by a two-step copolymerization modification method, epoxy groups are replaced, and the acrylic ester containing the organosilicon long chain and the bisphenol fluorene structures is prepared.
(2) According to the invention, the self-made organosilicon modified acrylic ester containing bisphenol fluorene structure with high light transmittance is added into the adhesive, so that the ultraviolet light transmittance of the adhesive under the condition of high filler filling is improved, and the specific gravity of a solidified product of the adhesive is greater than 2.2g/cm 3 Still having a depth of cure greater than 3 mm. Meanwhile, the organic silicon long chain in the polymer improves the flexibility and moisture resistance of the cured product; the bisphenol fluorene structure improves the heat resistance of the cured product.
(3) The invention prepares the silane modified spherical barium sulfate by a double microemulsion method, and the spherical structure and the barium sulfate with high specific gravity make the adhesive possible to realize ultraviolet deep curing while achieving high specific gravity. Meanwhile, the specific surface area of the filler can be reduced by silane modification, and the filling rate of the filler in the adhesive is further improved.
(4) The invention is single-component, has low viscosity, can be used for automatic dispensing, replaces the traditional double-component balance daub, saves the cost and improves the production line efficiency.
Detailed Description
In order to make the purposes, technical schemes and advantages of the embodiments of the present invention more clear, the technical schemes in the embodiments of the present invention are clearly and completely described. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Adding 25 parts of self-made organosilicon modified acrylic ester containing bisphenol fluorene structure, 10 parts of 6146-100 parts of Changxing chemical material, 20 parts of isobornyl acrylate, 2.8 parts of 2-hydroxy-2-methyl-1-phenylpropionyl, 0.05 part of hydroquinone and 3 parts of KH551 into a stirring kettle, and stirring for 30min under the conditions of revolution of 50r/min and autorotation of 800r/min under the vacuum light-shielding state; 60 parts of self-made spherical barium sulfate is added, and the mixture is subjected to revolution for 30r/min and rotation for 400r/min under the vacuum light-proof state and stirred for 30min; 2 parts of fumed silica is added, revolution is carried out for 30r/min under the vacuum light-proof state, and stirring is carried out for 30min under the condition of rotation of 600r/min, so that the high-specific gravity and high-weather-resistance ultraviolet deep curing balance repair composition is obtained.
The self-made organosilicon modified acrylic ester containing bisphenol fluorene structure is prepared according to the following steps:
weighing 60g of epoxy acrylate, putting the epoxy acrylate into a reaction device, adding 60g of toluene, slowly heating to 100 ℃, adding 0.8g of dibutyl tin dilaurate as a catalyst for reaction, gradually dropwise adding 60g of organosilicon oligomer containing bisphenol fluorene structures in the mechanical stirring process, keeping the temperature at 90 ℃, stirring for 6 hours under the condition of the rotating speed of 3400r/min, stopping stirring when the system temperature is reduced to 50 ℃, vacuumizing and decompressing to evaporate the solvent to obtain transparent viscous liquid, namely the self-made organosilicon modified acrylate containing bisphenol fluorene structures.
The transmittance of the self-made organosilicon modified acrylic ester containing bisphenol fluorene structure is 95%, and the refractive index is 1.58.
The epoxy acrylate has the following formula structure,
the organosilicon oligomer containing bisphenol fluorene structure is prepared according to the following steps:
150g of 9, 9-bis [ (2, 3-glycidoxy) phenyl ] fluorene is weighed, placed into a reaction device, added with 60g of toluene, slowly heated to 90 ℃, added with 0.6g of dibutyl tin dilaurate as a catalyst for reaction, gradually dropwise added with 20g of hydroxyl-terminated polydimethylsiloxane in the mechanical stirring process, kept at 90 ℃ and stirred for 4 hours under the condition of 300r/min of rotating speed, when the temperature of the system is reduced to 50 ℃, stirring is stopped, and the solvent is distilled off under vacuum pumping and reduced pressure to obtain transparent viscous liquid, namely the organosilicon oligomer containing bisphenol fluorene structure.
The spherical barium sulfate is prepared according to the following steps:
1) Preparing microemulsion
6.00 g TritonX-100, 4.8ml of n-hexanol and 40 ml cyclohexane were added to 100ml BaCl 2 Aqueous solution (0.1 mol.L) −1 ) Ultrasonic treating at 35deg.C for 30min to obtain uniform transparent BaCl 2 A microemulsion.
50ml of 0.2mol.L −1 Na of (2) 2 SO 4 Adding the aqueous solution into 50ml of 0.5g/L PSMA (alternating copolymer of polystyrene-maleic acid) aqueous solution, placing into ultrasonic wave for 30min, then regulating pH value of the solution to 5 by dripping aqueous solution of hydrochloric acid or sodium hydroxide, adding 4.8 ml n-hexanol and 40 ml cyclohexane, placing into ultrasonic wave at 35 deg.C for 30min, and making into uniform transparent Na 2 SO 4 A microemulsion.
2) Preparation of silane modified spherical barium sulfate
50ml of BaCl under ultrasound conditions 2 The microemulsion was slowly added dropwise to Na 2 SO 4 And (3) in the microemulsion, after the dripping is finished, carrying out constant-temperature reaction for 2 hours, and standing at room temperature for 24 hours. KH5515g is added, ultrasonic dispersion is carried out for 3 hours at 90 ℃, after the reaction is finished, the product is filtered in vacuum while the product is hot, and is washed 3 times with 120ml of acetone and then 3 times with 100ml of absolute ethyl alcohol. And drying for 12 hours in a baking oven at 105 ℃, cooling and grinding to obtain white barium sulfate powder.
The density of the spherical barium sulfate is 4.38g/cm 3 The particle diameter is 5-10 mu m, and the specific surface area is 1.1m 2 /g。
Example 2
Adding 20 parts of self-made organosilicon modified acrylic ester containing bisphenol fluorene structure, 15 parts of 6147 of Changxing chemical material, 25 parts of isobornyl methacrylate, 3 parts of 1-hydroxycyclohexyl benzyl ketone, 0.08 part of p-hydroxyanisole and 2.5 parts of KH172 into a stirring kettle, and stirring for 30min under the conditions of revolution of 50r/min and rotation of 1000r/min in a vacuum light-proof state; adding 65 parts of self-made spherical barium sulfate, revolving for 30r/min under a vacuum light-proof state, and stirring for 30min under the condition of rotation 400 r/min; adding 2.5 parts of polyolefin wax, and stirring for 30min under the conditions of revolution of 300r/min and rotation of 400r/min in a vacuum light-proof state to obtain the high-specific gravity and high-weather-resistant ultraviolet deep-curing balance repair composition.
The self-made organosilicon modified acrylic ester containing bisphenol fluorene structure is prepared according to the following steps:
weighing 60g of epoxy acrylate, putting the epoxy acrylate into a reaction device, adding 40g of toluene, slowly heating to 120 ℃, adding 0.3g of dibutyl tin dilaurate as a catalyst for reaction, gradually dropwise adding 45g of organosilicon oligomer containing bisphenol fluorene structures in the mechanical stirring process, keeping the temperature of 100 ℃, stirring for 5 hours under the condition of the rotating speed of 400r/min, stopping stirring when the temperature of the system is reduced to 50 ℃, vacuumizing and decompressing to evaporate the solvent to obtain transparent viscous liquid, namely the self-made organosilicon modified acrylate containing bisphenol fluorene structures.
The transmittance of the self-made organosilicon modified acrylic ester containing bisphenol fluorene structure is 97%, and the refractive index is 1.59.
The epoxy acrylate has the following formula structure,
the organosilicon oligomer containing bisphenol fluorene structure is prepared according to the following steps:
150g of 9, 9-bis [ (2, 3-glycidoxy) phenyl ] fluorene is weighed, placed into a reaction device, 50g of toluene is added, the mixture is slowly heated to 110 ℃, 0.7g of dibutyl tin dilaurate is added as a catalyst for reaction, 25g of hydroxyl-terminated polydimethylsiloxane is gradually dripped in the process of mechanical stirring, the temperature of 110 ℃ is kept, stirring is carried out for 5 hours under the condition of 400r/min of rotating speed, when the temperature of the system is reduced to 50 ℃, stirring is stopped, and the solvent is distilled off under vacuum pumping and reduced pressure to obtain transparent viscous liquid, namely the organosilicon oligomer containing bisphenol fluorene structure.
The spherical barium sulfate is prepared according to the following steps:
1) Preparing microemulsion
6.00 g TritonX-100, 4.8 ml n-hexanol and 40 ml cyclohexane were added to 100ml of BaCl 2 Aqueous solution (0.1 mol.L) −1 ) Ultrasonic treating at 35deg.C for 30min to obtain uniform transparent BaCl 2 A microemulsion.
50ml of 0.2mol.L −1 Na of (2) 2 SO 4 Adding the aqueous solution into 50ml of 1.0 g/L PSMA (alternating copolymer of polystyrene-maleic acid) aqueous solution, placing into ultrasonic wave for 30min, then regulating pH value of the solution to 6 by dripping aqueous solution of hydrochloric acid or sodium hydroxide, adding 4.8 ml n-hexanol and 40 ml cyclohexane, placing into ultrasonic wave at 35 deg.C for 30min, and making into uniform transparent Na 2 SO 4 A microemulsion.
2) Preparation of silane modified spherical barium sulfate
50ml of BaCl under ultrasound conditions 2 The microemulsion was slowly added dropwise to Na 2 SO 4 And (3) in the microemulsion, after the dripping is finished, carrying out constant-temperature reaction for 2 hours, and standing at room temperature for 24 hours. Adding 172 g of KH, dispersing for 3h at 90 ℃ by ultrasonic, and after the reaction is finished, carrying out vacuum filtration on the product while the product is hot, washing with 150ml of acetone for 3 times, and then washing with 150ml of absolute ethyl alcohol for 3 times. And drying for 12 hours in a baking oven at 105 ℃, cooling and grinding to obtain white barium sulfate powder.
The density of the spherical barium sulfate is 4.42g/cm 3 The particle diameter is 6-10 mu m, and the specific surface area is 0.95m 2 /g。
Example 3
22 parts of self-made organosilicon modified acrylic ester containing bisphenol fluorene structure, 13 parts of RAHN (r-methyl-phenyl-n-phenylene) company 4312, 28 parts of tetrahydrofuran methacrylate, 3 parts of bis (2, 4, 6-trimethylbenzoyl) phenyl-phosphorus oxide, 0.07 part of 2, 6-di-tert-butyl-p-cresol and 2.8 parts of KH560 are added into a stirring kettle, and the mixture is stirred for 30min under the conditions of revolution of 50r/min and rotation of 800r/min under the vacuum light-proof state; 70 parts of self-made spherical barium sulfate is added, and the mixture is subjected to revolution for 30r/min and rotation for 500r/min under the vacuum light-proof state and stirred for 30min; adding 3 parts of modified hydrogenated castor oil, and stirring for 30min under the conditions of revolution 35 r/min and rotation 400r/min in a vacuum light-proof state to obtain the high specific gravity and high weather-proof ultraviolet deep curing balance repair composition.
The self-made organosilicon modified acrylic ester containing bisphenol fluorene structure is prepared according to the following steps:
weighing 60g of epoxy acrylate, putting the epoxy acrylate into a reaction device, adding 60g of toluene, slowly heating to 120 ℃, adding 0.8g of dibutyl tin dilaurate as a catalyst for reaction, gradually dropwise adding 60g of organosilicon oligomer containing bisphenol fluorene structures in the mechanical stirring process, keeping the temperature of 100 ℃, stirring for 5 hours under the condition of 500r/min, stopping stirring when the temperature of the system is reduced to 50 ℃, vacuumizing and decompressing, and evaporating the solvent to obtain transparent viscous liquid, namely self-made organosilicon modified acrylate containing bisphenol fluorene structures.
The transmittance of the self-made organosilicon modified acrylic ester containing bisphenol fluorene structure is 96%, and the refractive index is 1.59.
The epoxy acrylate has the following formula structure,
the organosilicon oligomer containing bisphenol fluorene structure is prepared according to the following steps:
150g of 9, 9-bis [ (2, 3-glycidoxy) phenyl ] fluorene is weighed, put into a reaction device, added with 70g of toluene, slowly heated to 105 ℃, added with 0.6g of dibutyl tin dilaurate as a catalyst for reaction, gradually dropwise added with 22g of hydroxyl-terminated polydimethylsiloxane in the mechanical stirring process, kept at 105 ℃ and stirred for 5 hours under the condition of 400r/min of rotating speed, when the temperature of the system is reduced to 50 ℃, stirring is stopped, and the solvent is distilled off under vacuum pumping and reduced pressure to obtain transparent viscous liquid, namely the organosilicon oligomer containing bisphenol fluorene structure.
The spherical barium sulfate is prepared according to the following steps:
1) Preparing microemulsion
6.00 g TritonX-100, 4.8 ml n-hexanol and 40 ml cyclohexane were added to 100ml of BaCl 2 Aqueous solution (0.1 mol.L) −1 ) Ultrasonic treating at 35deg.C for 30min to obtain uniform transparent BaCl 2 A microemulsion.
50ml of 0.2mol.L −1 Na of (2) 2 SO 4 Adding the aqueous solution into 50ml of 1.2 g/L PSMA (polystyrene-maleic acid alternating copolymer) aqueous solution, ultrasonic treating for 30min, and dripping hydrochloric acid or sodium hydroxide waterAdjusting pH to 6.5, adding 4.8. 4.8 ml n-hexanol and 40. 40 ml cyclohexane, and ultrasonic treating at 35deg.C for 30min to obtain uniform transparent Na 2 SO 4 A microemulsion.
2) Preparation of silane modified spherical barium sulfate
50ml of BaCl under ultrasound conditions 2 The microemulsion was slowly added dropwise to Na 2 SO 4 And (3) in the microemulsion, after the dripping is finished, carrying out constant-temperature reaction for 2 hours, and standing at room temperature for 24 hours. Adding 560 g of KH, performing ultrasonic dispersion at 90 ℃ for 3 hours, and after the reaction is finished, performing vacuum filtration on the product while the product is hot, cleaning the product with 180ml of acetone for 3 times, and then cleaning the product with 180ml of absolute ethyl alcohol for 3 times. And drying for 12 hours in a baking oven at 105 ℃, cooling and grinding to obtain white barium sulfate powder.
The density of the spherical barium sulfate is 4.4 g/cm 3 The particle diameter is 6-12 mu m, the specific surface area is 0.98m 2 /g。
Example 4
15 parts of self-made organosilicon modified acrylic ester containing bisphenol fluorene structure, 15 parts of 4316 of RAHN company, 30 parts of 1, 6-hexanediol diacrylate, 3 parts of 2,4, 6-trimethylbenzoyl benzene-diphenyl phosphine oxide, 0.05 part of hydroquinone and 3 parts of KH570 are added into a stirring kettle, and the mixture is stirred for 30min under the conditions of revolution of 50r/min and autorotation of 8000r/min under the vacuum light-shielding state; 50 parts of self-made spherical barium sulfate is added, revolution is carried out for 40 r/min under the vacuum light-proof state, and stirring is carried out for 30min under the condition of rotation of 500 r/min; adding 1.5 parts of fumed silica, and stirring for 30min under the conditions of revolution of 30r/min and rotation of 400r/min in a vacuum light-proof state to obtain the high-specific gravity and high-weather-resistant ultraviolet deep-curing balance repair composition.
The self-made organosilicon modified acrylic ester containing bisphenol fluorene structure is prepared according to the following steps:
weighing 60g of epoxy acrylate, putting the epoxy acrylate into a reaction device, adding 40g of toluene, slowly heating to 110 ℃, adding 0.6g of dibutyl tin dilaurate as a catalyst for reaction, gradually dropwise adding 45g of organosilicon oligomer containing bisphenol fluorene structures in the mechanical stirring process, keeping the temperature of 110 ℃, stirring for 5 hours at the rotating speed of 400r/min, stopping stirring when the temperature of the system is reduced to 50 ℃, vacuumizing and decompressing, and evaporating the solvent to obtain transparent viscous liquid, namely self-made organosilicon modified acrylate containing bisphenol fluorene structures.
The transmittance of the self-made organosilicon modified acrylic ester containing bisphenol fluorene structure is 98%, and the refractive index is 1.60.
The epoxy acrylate has the following formula structure,
the organosilicon oligomer containing bisphenol fluorene structure is prepared according to the following steps:
100g of 9, 9-bis [ (2, 3-glycidoxy) phenyl ] fluorene is weighed, placed into a reaction device, 45g of toluene is added, the mixture is slowly heated to 100 ℃,0.5 g of dibutyl tin dilaurate is added as a catalyst for reaction, 18g of hydroxyl-terminated polydimethylsiloxane is gradually dripped in the process of mechanical stirring, the temperature of 100 ℃ is kept, stirring is carried out for 4.5 hours under the condition of the rotating speed of 450r/min, when the temperature of the system is reduced to 50 ℃, stirring is stopped, and the solvent is distilled off under reduced pressure by vacuumizing to obtain transparent viscous liquid, namely the organic silicon oligomer containing bisphenol fluorene structure.
The spherical barium sulfate is prepared according to the following steps:
1) Preparing microemulsion
6.00 g TritonX-100, 4.8 ml n-hexanol and 40 ml cyclohexane were added to 100ml of BaCl 2 Aqueous solution (0.1 mol.L) −1 ) Ultrasonic treating at 35deg.C for 30min to obtain uniform transparent BaCl 2 A microemulsion.
50ml of 0.2mol.L −1 Na of (2) 2 SO 4 Adding the aqueous solution into 50ml of 1.5g/L PSMA (alternating copolymer of polystyrene-maleic acid) aqueous solution, placing into ultrasonic wave for 30min, then regulating pH value of the solution to 7 by dripping aqueous solution of hydrochloric acid or sodium hydroxide, adding 4.8 ml n-hexanol and 40 ml cyclohexane, placing into ultrasonic wave at 35 deg.C for 30min, and making into uniform transparent Na 2 SO 4 A microemulsion.
2) Preparation of silane modified spherical barium sulfate
50ml of BaCl under ultrasound conditions 2 The microemulsion was slowly added dropwise to Na 2 SO 4 And (3) in the microemulsion, after the dripping is finished, carrying out constant-temperature reaction for 2 hours, and standing at room temperature for 24 hours. 8g of silane coupling agent is added, ultrasonic dispersion is carried out for 3 hours at 90 ℃, after the reaction is finished, the product is filtered in vacuum while the product is hot, and is washed with 200ml of acetone for 3 times and then with 200ml of absolute ethyl alcohol for 3 times. And drying for 12 hours in a baking oven at 105 ℃, cooling and grinding to obtain white barium sulfate powder.
The density of the spherical barium sulfate is 4.5g/cm 3 The particle diameter is 7-11 mu m, the specific surface area is 0.85 and 0.85 m 2 /g。
Comparative example 1
Adding 6146-100 parts of Changxing chemical material, 20 parts of isobornyl acrylate, 2.8 parts of 2-hydroxy-2-methyl-1-phenylpropion, 0.05 part of hydroquinone and 3 parts of KH551 into a stirring kettle, and stirring for 30min under the conditions of revolution of 50r/min and rotation of 800r/min under the vacuum light-proof state; 60 parts of spherical silicon dioxide is added, revolution is carried out for 30r/min under the vacuum light-proof state, and stirring is carried out for 30min under the condition of rotation of 400 r/min; 2 parts of fumed silica is added, revolution is carried out for 30r/min under the vacuum light-proof state, and stirring is carried out for 30min under the rotation condition of 600r/min, so that the high-specific gravity high-weather-resistance ultraviolet deep curing balance repairing composition is obtained.
Comparative example 2
Adding 6147 parts of Changxing chemical material, 25 parts of isobornyl methacrylate, 3 parts of 1-hydroxycyclohexyl benzophenone, 0.08 part of para-hydroxyanisole and 2.5 parts of KH172 into a stirring kettle, and stirring for 30min under the conditions of revolution of 50r/min and rotation of 1000r/min under the vacuum light-proof state; adding 65 parts of spherical silicon dioxide, revolving for 30r/min under a vacuum light-shielding state, and stirring for 30min under the condition of rotation of 400 r/min; adding 2.5 parts of polyolefin wax, and stirring for 30min under the conditions of revolution 300r/min and rotation 400r/min in a vacuum light-proof state to obtain the high specific gravity and high weather-proof ultraviolet deep curing balance repair composition.
Comparative example 3
Adding 25 parts of self-made organosilicon modified acrylic ester containing bisphenol fluorene structure, 10 parts of 6146-100 parts of Changxing chemical material, 20 parts of isobornyl acrylate, 2.8 parts of 2-hydroxy-2-methyl-1-phenylpropionyl, 0.05 part of hydroquinone and 3 parts of KH551 into a stirring kettle, and stirring for 30min under the conditions of revolution of 50r/min and autorotation of 800r/min under the vacuum light-shielding state; 60 parts of common non-spherical barium sulfate is added, and the mixture is stirred for 30min under the condition of revolution of 30r/min and rotation of 400r/min under the vacuum light-proof state; 2 parts of fumed silica is added, revolution is carried out for 30r/min under the vacuum light-proof state, and stirring is carried out for 30min under the condition of rotation of 600r/min, so that the high-specific gravity and high-weather-resistance ultraviolet deep curing balance repair composition is obtained.
The self-made organosilicon modified acrylic ester containing bisphenol fluorene structure is prepared according to the preparation method of example 1.
Comparative example 4
Adding 6146-100 parts of Changxing chemical material, 20 parts of isobornyl acrylate, 2.8 parts of 2-hydroxy-2-methyl-1-phenylpropion, 0.05 part of hydroquinone and 3 parts of KH551 into a stirring kettle, and stirring for 30min under the conditions of revolution of 50r/min and rotation of 800r/min under the vacuum light-proof state; 60 parts of spherical barium sulfate is added, revolution is carried out for 30r/min under the vacuum light-proof state, and stirring is carried out for 30min under the condition of rotation of 400 r/min; 2 parts of fumed silica is added, revolution is carried out for 30r/min under the vacuum light-proof state, and stirring is carried out for 30min under the condition of rotation of 600r/min, so that the high-specific gravity and high-weather-resistance ultraviolet deep curing balance repair composition is obtained.
The spherical barium sulfate was prepared according to the preparation method of example 1.
The beneficial effects of the invention are further illustrated below in conjunction with experimental data:
1. materials and methods:
1.1 experimental detection:
specific gravity (density) test: the specific gravity (density) was measured using a fully automatic solid-liquid densitometer.
Curing depth test: the prepared composition is uniformly filled in a prefabricated square flat bottom groove, and then is placed in an LED curing oven with the wavelength of 365nm for irradiation according to the specified light intensity.
Viscosity test: the test was performed using a BROOKFIELD DV2T cone-plate viscometer.
Elastic modulus and glass transition temperature (Tg) test instrument: and (5) DMA.
Double 85 test: the cured bonding sample is placed into a high-low temperature alternating damp-heat test box and set at 85 ℃ and 85% humidity.
Glue curing conditions: LED 365nm 500mw/cm 2 ×10S。
1.2 Test material: comparative examples 1 to 4, examples 1 to 4.
The experiment is consistent with other operations except different experimental treatments.
2. Results and analysis:
conclusion(s)
The specific gravity and the curing depth of the present invention are significantly higher than those of comparative examples 1 and 2, compared with those of comparative examples 1 and 2 in the table. Compared with the glass transition temperature (Tg), the elastic modulus and the double 85 strength retention data of the comparative example 1, the comparative example 2 and the invention in the table, the Tg and the double 85 strength retention of the invention are obviously improved, the elastic modulus is lower, and the heat resistance, the moisture resistance and the flexibility are better than those of the comparative example. The viscosity of the present invention was lower and showed better process operability for the comparative examples, as compared to the viscosity data of comparative example 1, comparative example 2 and the present invention in the table. The spherical barium sulfate prepared from comparative example 3 in the table compared to the cure depth data of example 1 allows the uv light balanced repair composition of the present invention to achieve a higher cure depth than the conventional non-spherical barium sulfate. The use of spherical barium sulfate allows the ultraviolet light balance repair composition of the present invention to obtain a higher specific gravity than spherical silica from comparative example 4 compared to comparative example 1 specific gravity data. From this, it can be seen that the composition of the present invention is suitable for the balance repair of motors, cooling fans, and the like.
The foregoing is only illustrative of the present invention and is not to be construed as limiting the invention, but rather as various modifications, alternatives, improvements, etc. may be made within the spirit and principles of the invention.
Claims (8)
1. The high specific gravity and high weather resistance ultraviolet deep curing adhesive is characterized by comprising the following raw materials in parts by weight:
15-30 parts of self-made organosilicon modified acrylic ester containing bisphenol fluorene structure;
10-15 parts of polyfunctional polyurethane acrylic ester prepolymer;
20-30 parts of acrylic acid monomer;
0.5-5 parts of photoinitiator;
0.01 to 0.1 portion of polymerization inhibitor;
0.5-5 parts of silane coupling agent;
0-3 parts of anti-settling agent;
50-70 parts of self-made spherical barium sulfate;
wherein the self-made organosilicon modified acrylic ester containing bisphenol fluorene structure has the structure shown in the following formula I,
i is a kind of
Wherein R in formula I 1 Is that，
R 2 is-C m H 2m -, wherein m is 4-8.
2. The high specific gravity and high weather resistance ultraviolet deep curing adhesive according to claim 1, wherein the self-made organosilicon modified acrylic ester containing bisphenol fluorene structure is prepared by the following steps:
weighing 60g of epoxy acrylate, putting the epoxy acrylate into a reaction device, adding 30-60 g of toluene, slowly heating to 100-120 ℃, adding 0.3-0.8 g of dibutyl tin dilaurate as a catalyst for reaction, gradually dropwise adding 40-70 g of organosilicon oligomer containing bisphenol fluorene structure in the mechanical stirring process, keeping the temperature of 90-110 ℃, stirring for 4-6 h under the condition of the rotating speed of 300-500 r/min, stopping stirring when the system temperature is reduced to 50 ℃, vacuumizing, and evaporating the solvent under reduced pressure to obtain transparent viscous liquid, namely the self-made organosilicon modified acrylate containing bisphenol fluorene structure;
the epoxy acrylate has a structure shown in a formula II, the organosilicon oligomer containing bisphenol fluorene structure has a structure shown in a formula III,
II (II)
Formula III
Wherein R is 3 Is that；
The organosilicon oligomer containing bisphenol fluorene structure is prepared according to the following steps:
150g of 9, 9-bis [ (2, 3-glycidoxy) phenyl ] fluorene is weighed, put into a reaction device, 50-80 g of toluene is added, the mixture is slowly heated to 90-110 ℃, 0.5-0.8 g of dibutyl tin dilaurate is added as a catalyst for reaction, 20-30 g of hydroxyl-terminated polydimethylsiloxane is gradually dripped in the mechanical stirring process, the temperature of 90-110 ℃ is kept, stirring is carried out for 4-6 h under the condition of the rotating speed of 300-500 r/min, when the system temperature is reduced to 50 ℃, stirring is stopped, and the solvent is removed by vacuum evaporation under reduced pressure to obtain transparent viscous liquid, namely the organosilicon oligomer containing bisphenol fluorene structure;
the 9, 9-bis [ (2, 3-glycidoxy) phenyl ] fluorene has a structure as shown in formula IV;
IV (IV)
The hydroxyl-terminated polydimethylsiloxane has a structure as shown in formula IIV;
formula IIV.
3. The high specific gravity and high weather resistance ultraviolet deep curing adhesive according to claim 2, wherein the light transmittance of the self-made organosilicon modified acrylic ester containing bisphenol fluorene structure is 95% -98%, and the refractive index is 1.57-1.60.
4. The high specific gravity and high weather resistance ultraviolet deep curing adhesive according to claim 1, wherein the spherical barium sulfate is prepared by a double microemulsion method according to the following steps:
1) Preparing microemulsion
6.00 g TritonX-100, 4.8 ml n-hexanol and 40 ml cyclohexane were added to 100ml at a concentration of 0.1 mol.L −1 BaCl of (F) 2 Adding into water solution, ultrasonic treating at 35deg.C for 30min to obtain uniform transparent BaCl 2 A microemulsion;
50ml of 0.2mol.L −1 Na of (2) 2 SO 4 Adding the aqueous solution into 50ml of 0.5-1.5g/L polystyrene-maleic acid alternating copolymer aqueous solution, placing into ultrasonic wave for 30min, then regulating pH value of the solution to 5-7 by dripping hydrochloric acid or sodium hydroxide aqueous solution, adding 4.8 ml n-hexanol and 40 ml cyclohexane, placing into ultrasonic wave at 35 ℃ for 30min, and preparing into uniform transparent Na 2 SO 4 A microemulsion;
2) Preparation of silane modified spherical barium sulfate
50ml of BaCl under ultrasound conditions 2 The microemulsion was slowly added dropwise to Na 2 SO 4 In the microemulsion, after the dripping is finished, the microemulsion reacts for 2 hours at constant temperature and then stands for 24 hours at room temperature; adding 3-8g of silane coupling agent, performing ultrasonic dispersion at 90 ℃ for 3 hours, and after the reaction is finished, performing vacuum filtration on the product while the product is hot, and cleaning with 50-200 ml of acetone for 3 timesWashing with 50-200 ml absolute ethyl alcohol for 3 times; drying for 12 hours in a baking oven at 105 ℃, cooling and grinding to obtain white barium sulfate powder;
the silane coupling agent is one or a mixture of more than one of KH551, KH172, KH560 and KH 570.
5. The deep curing adhesive with high specific gravity and high weather resistance according to claim 4, wherein the density of the spherical barium sulfate is 4.3-4.5 g/cm 3 The particle diameter is 5-12 mu m, the specific surface area is 0.8-1.2 m 2 /g。
6. The high specific gravity and high weather resistance ultraviolet deep curing adhesive according to claim 1, wherein the photoinitiator is selected from one or a mixture of any of 2-hydroxy-2-methyl-1-phenylpropion, 1-hydroxycyclohexyl benzophenone, bis 2,4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholin-1-propanone, alpha' -dimethylbenzoyl ketal, isopropylthioxanthone, benzophenone and 2,4, 6-trimethylbenzoyl benzene-diphenyl phosphine oxide.
7. The high specific gravity and high weather resistance ultraviolet light deep curing adhesive according to claim 1, wherein the specific gravity of the high specific gravity and high weather resistance ultraviolet light deep curing adhesive is 2.2-3.1 g/cm 3 。
8. The method for preparing the high specific gravity and high weather resistance ultraviolet light deep curing adhesive according to any one of claims 1 to 7, which is characterized by comprising the following steps:
15 to 30 parts of self-made organosilicon modified acrylic ester containing bisphenol fluorene structure, 10 to 15 parts of polyfunctional polyurethane acrylic ester prepolymer, 20 to 30 parts of acrylic monomer, 0.5 to 5 parts of photoinitiator, 0.01 to 0.1 part of polymerization inhibitor and 0.5 to 5 parts of silane coupling agent are added into a stirring kettle, and revolution is carried out for 30 to 50r/min under the vacuum light-proof state, and stirring is carried out for 30min under the condition of rotation of 600 to 1000 r/min; adding 50-70 parts of self-made spherical barium sulfate, revolving for 30-50 r/min under vacuum light-proof state, and stirring for 30min under rotation for 300-800 r/min; adding 0-3 parts of anti-settling agent, revolving for 30-50 r/min under vacuum light-proof state, and stirring for 30min under rotation for 300-800 r/min to obtain the high specific gravity and high weather-resistant ultraviolet deep curing adhesive.
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| CN202311395136.2A CN117143558B (en) | 2023-10-26 | 2023-10-26 | High-specific gravity high-weather-resistance ultraviolet deep-curing adhesive and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017092650A1 (en) * | 2015-11-30 | 2017-06-08 | 深圳市联深化学技术有限公司 | Bisphenol fluorene acrylic resin and preparation method therefor, quantum dot-coloured photosensitive resin composition, preparation method therefor and use thereof |
| CN111363481A (en) * | 2019-12-23 | 2020-07-03 | 烟台信友新材料有限公司 | Low-shrinkage, low-modulus and heat-resistant UV-heat dual-curing adhesive and preparation method thereof |
| CN113249039A (en) * | 2021-06-16 | 2021-08-13 | 广西向东电子科技有限公司 | Optical adhesive |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017092650A1 (en) * | 2015-11-30 | 2017-06-08 | 深圳市联深化学技术有限公司 | Bisphenol fluorene acrylic resin and preparation method therefor, quantum dot-coloured photosensitive resin composition, preparation method therefor and use thereof |
| CN111363481A (en) * | 2019-12-23 | 2020-07-03 | 烟台信友新材料有限公司 | Low-shrinkage, low-modulus and heat-resistant UV-heat dual-curing adhesive and preparation method thereof |
| CN113249039A (en) * | 2021-06-16 | 2021-08-13 | 广西向东电子科技有限公司 | Optical adhesive |
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