CN108299493B - Silicon-containing acrylate monomer and preparation method and application thereof - Google Patents
Silicon-containing acrylate monomer and preparation method and application thereof Download PDFInfo
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- CN108299493B CN108299493B CN201610541153.6A CN201610541153A CN108299493B CN 108299493 B CN108299493 B CN 108299493B CN 201610541153 A CN201610541153 A CN 201610541153A CN 108299493 B CN108299493 B CN 108299493B
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- 239000000178 monomer Substances 0.000 title claims abstract description 57
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 52
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 48
- 239000010703 silicon Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 32
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 31
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 30
- 238000006467 substitution reaction Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 21
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 21
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 18
- 239000005049 silicon tetrachloride Substances 0.000 claims description 18
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 15
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 10
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 claims description 9
- 229940044119 2-tert-butylhydroquinone Drugs 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 4
- 238000000576 coating method Methods 0.000 abstract description 9
- 239000011521 glass Substances 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 150000007529 inorganic bases Chemical class 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 238000007689 inspection Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000000047 product Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 14
- 238000000926 separation method Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- -1 ethyl (methyl) silicate Chemical compound 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000006228 supernatant Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000012295 chemical reaction liquid Substances 0.000 description 9
- 230000003472 neutralizing effect Effects 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 3
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- FXSGDOZPBLGOIN-UHFFFAOYSA-N trihydroxy(methoxy)silane Chemical compound CO[Si](O)(O)O FXSGDOZPBLGOIN-UHFFFAOYSA-N 0.000 description 3
- 239000010963 304 stainless steel Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 2
- FYTPGBJPTDQJCG-UHFFFAOYSA-N Trichloro(chloromethyl)silane Chemical compound ClC[Si](Cl)(Cl)Cl FYTPGBJPTDQJCG-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 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 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000004590 silicone sealant Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/025—Silicon compounds without C-silicon linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
Abstract
The invention discloses a silicon-containing acrylate monomer and a preparation method and application thereof, wherein the structural formula of the silicon-containing acrylate monomer is shown as the formula (I):
in the formula (I), R1Is CH3Or H, R2Is CH3Or
Description
Technical Field
The invention relates to the technical field of preparation of acrylate monomers, in particular to a silicon-containing acrylate monomer and a preparation method and application thereof.
Background
The organic silicon polymer is a novel material with excellent performance and unique function, and has wide application.
In 1941, scientists in the united states developed a method for directly synthesizing methylchlorosilane under the catalysis of copper powder. The development to the present is that the production scale is continuously enlarged, and a set of unique chemical system is formed; among them, the synthesis of methylchlorosilanes is the backbone of this system.
During the synthesis of methyl chlorosilane by a direct method, the aim is to produce dimethyl dichlorosilane, and simultaneously produce methyl trichlorosilane and silicon tetrachloride, wherein the methyl trichlorosilane and the silicon tetrachloride account for about 5-15% of the total amount of monomers. The two-branch chlorosilane can be used for preparing a silane cross-linking agent, methyl silicone resin, methyl phenyl silicone resin, a waterproof agent, ethyl (methyl) silicate and the like. But because the market application of dimethyldichlorosilane and downstream products of silicone oil, crude rubber, silicone rubber, sealant and the like is expanded, the application of methyltrichlorosilane and silicon tetrachloride in the market is limited, and more backlog is caused; meanwhile, the hydrogen chloride is easy to react with moisture in the air to generate hydrogen chloride, so that the environmental pollution is caused. How to effectively utilize methyltrichlorosilane and silicon tetrachloride is a problem which must be considered when a production plant is operated for a long period.
At present, the white carbon black is mainly prepared by using methyltrichlorosilane or silicon tetrachloride at home and abroad or is converted into other useful monosilane; some domestic enterprises also can use methyltrichlorosilane to prepare products such as silane cross-linking agents, methyl silicone resin, waterproofing agents and the like.
The invention patent application publication No. CN104558003A discloses a method for preparing chloromethyl trichlorosilane by liquid phase chlorination reaction, which uses a mixture of benzoyl peroxide and ferric chloride as a catalyst, uses methyltrichlorosilane as a raw material, uniformly introduces chlorine into the mixture, and controls the chlorine introduction amount to ensure that the conversion rate of the methyltrichlorosilane can reach 70-80%, the selectivity of the chloromethyl trichlorosilane is obviously improved to 95%, and the total content of the polychlorinated methyl trichlorosilane is less than 5%.
The invention patent application publication No. CN101906111A discloses a method for preparing methyl silicic acid and industrial hydrochloric acid by hydrolyzing methyl trichlorosilane, which comprises the steps of firstly adding 10-13 parts of dilute hydrochloric acid with the concentration of 14-16% into a reaction kettle, starting stirring, then dropwise adding 1 part of methyl trichlorosilane into the kettle to obtain solid methyl silicic acid and hydrochloric acid liquid, and separating the solid methyl silicic acid from the hydrochloric acid liquid; and then, by adopting the same method, dropwise adding methyl trichlorosilane into hydrochloric acid twice, and controlling the reaction temperature during dropwise adding. The method changes the byproduct hydrochloric acid into high-concentration industrial hydrochloric acid, and greatly reduces the emission.
The invention patent application publication No. CN102249246A discloses a method for preparing precipitated silica, which comprises the following steps: 1) at room temperature, 170 parts by weight of silicon tetrachloride solution is dripped into 720-4000 parts by weight of water, and the temperature is controlled to be 20-50 ℃ to prepare silica sol; diluting water glass to the weight percentage concentration of 1-15% to prepare a water glass dilute solution; 2) adding silica sol into 3000-5000 parts by weight of the dilute sodium silicate solution, and reacting for 1-5 hours at 50-100 ℃; then adjusting the pH value to 5-10 by using the silicon tetrachloride solution; 3) then adding a flocculating agent, aging for 20-60 min, and cooling to below 50 ℃; then filtering, washing the precipitate, drying and crushing. The method effectively utilizes the silicon tetrachloride which is a byproduct in the production of the polycrystalline silicon, reduces the environmental pollution, saves energy and reduces emission; hydrochloric acid generated by hydrolyzing the silicon tetrachloride is directly utilized, acid does not need to be added, and the cost of the white carbon black is greatly reduced.
Since the advent of violet light curing coatings, the coatings have been widely used due to their high hardness, solvent resistance, high efficiency and energy saving. However, when applied to glass, metal, etc., the coating composition has the disadvantages of poor adhesion, weak tensile strength, weak impact resistance, etc., and thus cannot be widely applied.
Disclosure of Invention
The invention provides a silicon-containing acrylate monomer and a preparation method and application thereof, and the silicon-containing acrylate monomer has the characteristics of good adhesion to inorganic base materials such as glass, metal and the like, high hardness, collision resistance and good impact resistance.
A silicon-containing acrylate monomer has a structural formula shown in formula (I):
in the formula (I), R1Is CH3Or H, R2Is CH3Or
n is 2,3 or 4.
The monomer has an organic-inorganic chemical hybrid structure, and can be cured and crosslinked in a UV (ultraviolet) light curing and moisture-heat curing mode; the acrylate structure in the monomer structure can be subjected to UV curing under the initiation of a photoinitiator, and the silicate structure can be subjected to crosslinking through hydrolysis.
The UV crosslinking of the acrylate provides good hardness and solvent resistance of the coating, and also provides high efficiency during production; the silicate in the monomer structure is cured by moisture and coatedSiO is introduced into the layer2And the inorganic particles improve the adhesive force of the coating on inorganic base materials such as glass, metal and the like, provide the scratch resistance of the coating, and have the characteristics of high strength and impact resistance of a nano composite material. At the same time because of SiO2The coating is generated for post reaction, is uniformly distributed, has nanometer size, and cannot easily cause coating defects like silica sol.
Preferably, R is1Is CH3，R2Is composed of
n is 2.
Preferably, R is1Is CH3，R2Is CH3(ii) a n is 2; the silicon-containing acrylate monomer with the structural formula is the lowest in preparation cost and is suitable for practical popularization and application.
The invention also provides a preparation method of the silicon-containing acrylate monomer, which comprises the following steps: dropwise adding methyl trichlorosilane or silicon tetrachloride into the compound shown in the formula (II), heating, and carrying out substitution reaction to obtain a silicon-containing acrylate monomer shown in the formula (I);
the reaction equation of the above preparation method is as follows:
in the formula, R3Is CH3Or Cl, m is 3 or 4; when R is3Is CH3R in the reaction product2Is CH3M is 3;
when R is3R in the reaction product when Cl is used2Is composed of
m is 4.
Preferably, the molar ratio of the compound shown in the formula (II) to the methyltrichlorosilane is 3.05-3.15: 1; the molar ratio of the compound shown in the formula (II) to the silicon tetrachloride is 4.05-4.20: 1.
Preferably, the dripping time is 30-240 min; more preferably, 30 to 60 min.
Preferably, the temperature of the substitution reaction is 90-110 ℃; more preferably, it is 100 to 110 ℃.
Preferably, the time of the substitution reaction is 60-240 min; more preferably, 120 to 240 min.
Experiments show that the dripping time is 30-45 min, the temperature of the substitution reaction is 100-110 ℃, the time is 180-240 min, and the yield and the purity of the obtained product are optimal.
During the substitution reaction, the polymerization inhibitor can protect the double bond of acrylic acid. Preferably, a polymerization inhibitor is further added to the reaction system, and the polymerization inhibitor is at least one of hydroquinone, p-benzoquinone, methylhydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone and 2, 5-di-tert-butylhydroquinone. More preferably, the polymerization inhibitor is at least one of 2-tertiary butyl hydroquinone and 2, 5-di-tertiary butyl hydroquinone.
The invention also provides application of the silicon-containing acrylate monomer in preparation of a violet light photocureable coating.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the silicon-containing acrylate monomer is prepared from methyl trichlorosilane or silicon tetrachloride, and the monomer has the characteristics of good adhesion to inorganic substrates such as glass and metal, high hardness, collision resistance and good impact resistance through inspection.
(2) The preparation method of the silicon-containing acrylate monomer is simple and convenient and is easy to operate.
Detailed Description
Example 1
A preparation method of a silicon-containing acrylate monomer comprises the following specific steps:
396.5kg of 2-hydroxyethyl methacrylate, 0.04kg of 2-tert-butylhydroquinone and 0.035kg of 2, 5-di-tert-butylhydroquinone are taken and put into a reaction kettle, and in the stirring process, the molar ratio of the 2-hydroxyethyl methacrylate to the methyltrichlorosilane is 3.05: 1, dripping methyl trichlorosilane into a reaction kettle for 30 min; after the dropwise addition is finished, heating to 110 ℃, and preserving the temperature for 120min to carry out substitution reaction; in the processes of dripping and heat preservation, air is introduced below the liquid level of the liquid to drive hydrogen chloride generated by substitution reaction; the generated hydrogen chloride is introduced into the sodium hydroxide aqueous solution through a reflux condenser pipe to be absorbed; after the reaction is finished, cooling to room temperature, neutralizing the reaction liquid with sodium hydroxide ethanol solution until the pH value is 8, standing for liquid separation, and taking supernatant to obtain a finished product silicon-containing acrylate monomer, namely methyl tri (2-hydroxyethyl methacrylate) silane.
The structural formula of the silicon-containing acrylate monomer is as follows:
example 2
A preparation method of a silicon-containing acrylate monomer comprises the following specific steps:
396.5kg of methacrylic acid-2-hydroxyethyl ester, 0.04kg of 2-tert-butylhydroquinone and 0.035kg of hydroquinone are put into a reaction kettle, and during stirring, the molar ratio of the methacrylic acid-2-hydroxyethyl ester to the methyltrichlorosilane is 3.05: 1, dripping methyl trichlorosilane into a reaction kettle for 60 min; after the dropwise addition is finished, heating to 100 ℃, and preserving the temperature for 240min to carry out substitution reaction; in the processes of dripping and heat preservation, air is introduced below the liquid level of the liquid to drive hydrogen chloride generated by substitution reaction; the generated hydrogen chloride is introduced into the sodium hydroxide aqueous solution through a reflux condenser pipe to be absorbed; after the reaction is finished, cooling to room temperature, neutralizing the reaction liquid with sodium hydroxide ethanol solution until the pH value is 8, standing for liquid separation, and taking supernatant to obtain a finished product silicon-containing acrylate monomer, namely methyl tri (2-hydroxyethyl methacrylate) silane.
The structural formula of the silicon-containing acrylate monomer is as follows:
example 3
A preparation method of a silicon-containing acrylate monomer comprises the following specific steps:
396.5kg of 2-hydroxyethyl methacrylate, 0.04kg of 2-tert-butylhydroquinone and 0.035kg of 2, 5-di-tert-butylhydroquinone are taken and put into a reaction kettle, and in the stirring process, the molar ratio of the 2-hydroxyethyl methacrylate to the methyltrichlorosilane is 3.05: 1, dripping methyl trichlorosilane into a reaction kettle for 60 min; after the dropwise addition is finished, heating to 80 ℃, and preserving the temperature for 360min to carry out substitution reaction; in the processes of dripping and heat preservation, air is introduced below the liquid level of the liquid to drive hydrogen chloride generated by substitution reaction; the generated hydrogen chloride is introduced into the sodium hydroxide aqueous solution through a reflux condenser pipe to be absorbed; after the reaction is finished, cooling to room temperature, neutralizing the reaction liquid with sodium hydroxide ethanol solution until the pH value is 8, standing for liquid separation, and taking supernatant to obtain a finished product silicon-containing acrylate monomer, namely methyl tri (2-hydroxyethyl methacrylate) silane.
The structural formula of the silicon-containing acrylate monomer is as follows:
example 4
A preparation method of a silicon-containing acrylate monomer comprises the following specific steps:
396.5kg of 2-hydroxyethyl methacrylate, 0.04kg of hydroquinone and 0.035kg of 2, 5-di-tert-butylhydroquinone are put into a reaction kettle, and during stirring, the molar ratio of the 2-hydroxyethyl methacrylate to the methyltrichlorosilane is 3.05: 1, dripping methyl trichlorosilane into a reaction kettle for 120 min; after the dropwise addition is finished, heating to 90 ℃, and preserving the temperature for 240min to carry out substitution reaction; in the processes of dripping and heat preservation, air is introduced below the liquid level of the liquid to drive hydrogen chloride generated by substitution reaction; the generated hydrogen chloride is introduced into the sodium hydroxide aqueous solution through a reflux condenser pipe to be absorbed; after the reaction is finished, cooling to room temperature, neutralizing the reaction liquid with sodium hydroxide ethanol solution until the pH value is 8, standing for liquid separation, and taking supernatant to obtain a finished product silicon-containing acrylate monomer, namely methyl tri (2-hydroxyethyl methacrylate) silane.
The structural formula of the silicon-containing acrylate monomer is as follows:
example 5
A preparation method of a silicon-containing acrylate monomer comprises the following specific steps:
396.5kg of 2-hydroxyethyl methacrylate, 0.04kg of 2-tert-butylhydroquinone and 0.035kg of 2, 5-di-tert-butylhydroquinone are taken and put into a reaction kettle, and in the stirring process, the molar ratio of the 2-hydroxyethyl methacrylate to the methyltrichlorosilane is 3.05: 1, dripping methyl trichlorosilane into a reaction kettle for 240 min; after the dropwise addition is finished, heating to 65 ℃, and preserving the temperature for 480min to perform substitution reaction; in the processes of dripping and heat preservation, air is introduced below the liquid level of the liquid to drive hydrogen chloride generated by substitution reaction; the generated hydrogen chloride is introduced into the sodium hydroxide aqueous solution through a reflux condenser pipe to be absorbed; after the reaction is finished, cooling to room temperature, neutralizing the reaction liquid with sodium hydroxide ethanol solution until the pH value is 8, standing for liquid separation, and taking supernatant to obtain a finished product silicon-containing acrylate monomer, namely methyl tri (2-hydroxyethyl methacrylate) silane.
The structural formula of the silicon-containing acrylate monomer is as follows:
example 6
A preparation method of a silicon-containing acrylate monomer comprises the following specific steps:
396.5kg of 2-hydroxyethyl methacrylate, 0.04kg of 2-tert-butylhydroquinone and 0.035kg of 2, 5-di-tert-butylhydroquinone are taken and put into a reaction kettle, and in the stirring process, the molar ratio of the 2-hydroxyethyl methacrylate to the methyltrichlorosilane is 3.05: 1, dripping methyl trichlorosilane into a reaction kettle for 240 min; after the dropwise addition is finished, heating to 110 ℃, and preserving the heat for 60min to carry out substitution reaction; in the processes of dripping and heat preservation, air is introduced below the liquid level of the liquid to drive hydrogen chloride generated by substitution reaction; the generated hydrogen chloride is introduced into the sodium hydroxide aqueous solution through a reflux condenser pipe to be absorbed; after the reaction is finished, cooling to room temperature, neutralizing the reaction liquid with sodium hydroxide ethanol solution until the pH value is 8, standing for liquid separation, and taking supernatant to obtain a finished product silicon-containing acrylate monomer, namely methyl tri (2-hydroxyethyl methacrylate) silane.
The structural formula of the silicon-containing acrylate monomer is as follows:
example 7
A preparation method of a silicon-containing acrylate monomer comprises the following specific steps:
526.5kg of 2-hydroxyethyl methacrylate, 0.05kg of hydroquinone and 0.055kg of 2, 5-di-tert-butylhydroquinone are put into a reaction kettle, and in the stirring process, the molar ratio of 2-hydroxyethyl methacrylate to silicon tetrachloride is 4.05: 1, dripping silicon tetrachloride into a reaction kettle for 30 min; after the dropwise addition is finished, heating to 110 ℃, and preserving the temperature for 120min to carry out substitution reaction; in the processes of dripping and heat preservation, air is introduced below the liquid level of the liquid to drive hydrogen chloride generated by substitution reaction; the generated hydrogen chloride is introduced into the sodium hydroxide aqueous solution through a reflux condenser pipe to be absorbed; after the reaction is finished, cooling to room temperature, neutralizing the reaction liquid with sodium hydroxide ethanol solution until the pH value is 8, standing for liquid separation, and taking supernatant to obtain a finished product silicon-containing acrylate monomer, namely the tetra (2-hydroxyethyl methacrylate) silane.
The structural formula of the silicon-containing acrylate monomer is as follows:
example 8
A preparation method of a silicon-containing acrylate monomer comprises the following specific steps:
439.2kg of acrylic acid-4-hydroxybutyl ester and 0.088kg of hydroquinone are put into a reaction kettle, and in the stirring process, the molar ratio of the acrylic acid-4-hydroxybutyl ester to the methyltrichlorosilane is 3.05: 1, dripping methyl trichlorosilane into a reaction kettle for 30 min; after the dropwise addition is finished, heating to 110 ℃, and preserving the temperature for 120min to carry out substitution reaction; in the processes of dripping and heat preservation, air is introduced below the liquid level of the liquid to drive hydrogen chloride generated by substitution reaction; the generated hydrogen chloride is introduced into the sodium hydroxide aqueous solution through a reflux condenser pipe to be absorbed; after the reaction is finished, cooling to room temperature, neutralizing the reaction liquid with sodium hydroxide ethanol solution until the pH value is 8, standing for liquid separation, and taking supernatant to obtain a finished product silicon-containing acrylate monomer, namely methyl tri (4-hydroxybutylacrylate) silane.
The structural formula of the silicon-containing acrylate monomer is as follows:
example 9
A preparation method of a silicon-containing acrylate monomer comprises the following specific steps:
583.2kg of acrylic acid-4-hydroxybutyl ester and 0.1166kg of hydroquinone are put into a reaction kettle, and in the stirring process, the molar ratio of acrylic acid-4-hydroxybutyl ester to silicon tetrachloride is 4.05: 1, dripping silicon tetrachloride into a reaction kettle for 30 min; after the dropwise addition is finished, heating to 110 ℃, and preserving the temperature for 120min to carry out substitution reaction; in the processes of dripping and heat preservation, air is introduced below the liquid level of the liquid to drive hydrogen chloride generated by substitution reaction; the generated hydrogen chloride is introduced into the sodium hydroxide aqueous solution through a reflux condenser pipe to be absorbed; after the reaction is finished, cooling to room temperature, neutralizing the reaction liquid with sodium hydroxide ethanol solution until the pH value is 8, standing for liquid separation, and taking supernatant to obtain a finished product silicon-containing acrylate monomer, namely tetra (4-hydroxybutylacrylate) silane.
The structural formula of the silicon-containing acrylate monomer is as follows:
application of silicon-containing acrylate monomer and determination of index
(1) The results of measurement of solution appearance and product yield after liquid separation of the supernatants obtained in the above examples are shown in table 1.
TABLE 1 appearance of solutions and yields after separation for the different examples
(2) The monomers prepared in each of the above examples were compared with trifunctional monomers such as trimethylolpropane triacrylate TMPTA (comparative 1), pentaerythritol triacrylate (comparative 2), ethoxylated trimethylolpropane triacrylate TMP3EOTA (comparative 3), propoxylated trimethylolpropane triacrylate TMP3POTA (comparative 4) in terms of adhesion, hardness, and impact resistance to glass, 304 stainless steel, and cast aluminum (as shown in table 2).
The formulations tested were:
the construction conditions are that the several formulas are respectively sprayed on glass, 304 stainless steel, cast aluminum and tinplate, and then dried at 60 DEG CBaking for 4 min, and heating with high-pressure mercury lamp at 900mj/cm2Is cured. And testing the performances of hardness, adhesion, impact resistance and the like after the paint film is cured.
TABLE 2 comparison of the products obtained in the different examples with different trifunctional acrylates in respect of pencil hardness, adhesion, impact resistance, etc
In the above table 2, the results of the different examples are compared with the results of the different trifunctional acrylates in terms of pencil hardness, adhesion, impact resistance, etc., wherein the results of the examples are products having the same structure, and the yield of the individual examples after the reaction is not high due to the different reaction conditions. The actual test performed is example 1.
And (4) conclusion: the silicon-containing acrylate monomers of examples 1, 7, 8 and 9 are significantly superior to conventional multifunctional acrylate monomers in terms of adhesion and impact resistance of inorganic substrates such as glass, and have the characteristic of high hardness of the latter.
Claims (2)
1. A preparation method of a silicon-containing acrylate monomer is disclosed, wherein the structural formula of the silicon-containing acrylate monomer is shown as the formula (I):
in the formula (I), R1Is CH3Or H, R2Is CH3Or
n is 2,3 or 4;
the preparation method of the silicon-containing acrylate monomer comprises the following steps: dropwise adding methyl trichlorosilane or silicon tetrachloride into the compound shown in the formula (II), heating, and carrying out substitution reaction to obtain a silicon-containing acrylate monomer shown in the formula (I);
the molar ratio of the compound shown in the formula (II) to the methyltrichlorosilane is 3.05-3.15: 1; the molar ratio of the compound shown in the formula (II) to the silicon tetrachloride is 4.05-4.20: 1; the dripping time is 30-60 min; the temperature of the substitution reaction is 100-110 ℃; the time of the substitution reaction is 120-240 min; in the processes of dripping and heat preservation, air is introduced below the liquid level of the liquid to drive hydrogen chloride generated by substitution reaction; and a polymerization inhibitor is also added into the reaction system, and the polymerization inhibitor is at least one of hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone and 2, 5-di-tert-butylhydroquinone.
2. The method of claim 1, wherein R is selected from the group consisting of1Is CH3，R2Is composed of
n is 2.
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| JPS6053514A (en) * | 1983-09-02 | 1985-03-27 | Hitachi Chem Co Ltd | Resin composition |
| JPH05255349A (en) * | 1992-03-13 | 1993-10-05 | Nippon Shokubai Co Ltd | Production of reactive organosilicon compound |
| US5437896A (en) * | 1993-07-06 | 1995-08-01 | U.S. Philips Corporation | Method of preparing a composite material of silica network and chains of a polyhydroxy compound and a liquid crystal display device incorporating such composite material |
| CN103232782A (en) * | 2013-04-23 | 2013-08-07 | 广东信翼新材料股份有限公司 | Environmentally-friendly solvent-free acrylic ester conformal coating |
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| US5385988A (en) * | 1991-09-24 | 1995-01-31 | Mitsubishi Rayon Co., Ltd. | Composite composition having high transparency and process for producing same |
| JPH10245247A (en) * | 1997-03-06 | 1998-09-14 | Nippon Sheet Glass Co Ltd | Laminated glass |
| CN102850536B (en) * | 2012-09-18 | 2014-04-02 | 江苏柏鹤涂料有限公司 | Silicon-containing acrylate-polyester resin, and finish coat and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS6053514A (en) * | 1983-09-02 | 1985-03-27 | Hitachi Chem Co Ltd | Resin composition |
| JPH05255349A (en) * | 1992-03-13 | 1993-10-05 | Nippon Shokubai Co Ltd | Production of reactive organosilicon compound |
| US5437896A (en) * | 1993-07-06 | 1995-08-01 | U.S. Philips Corporation | Method of preparing a composite material of silica network and chains of a polyhydroxy compound and a liquid crystal display device incorporating such composite material |
| CN103232782A (en) * | 2013-04-23 | 2013-08-07 | 广东信翼新材料股份有限公司 | Environmentally-friendly solvent-free acrylic ester conformal coating |
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