CN117285423A - Multifunctional acrylic ester and application thereof - Google Patents
Multifunctional acrylic ester and application thereof Download PDFInfo
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- CN117285423A CN117285423A CN202311241755.6A CN202311241755A CN117285423A CN 117285423 A CN117285423 A CN 117285423A CN 202311241755 A CN202311241755 A CN 202311241755A CN 117285423 A CN117285423 A CN 117285423A
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- acrylic ester
- resin
- monomer
- acrylate
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- -1 acrylic ester Chemical class 0.000 title claims abstract description 25
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 6
- 229920005862 polyol Polymers 0.000 claims abstract description 5
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical group C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 40
- 239000011347 resin Substances 0.000 claims description 29
- 229920005989 resin Polymers 0.000 claims description 29
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000006185 dispersion Substances 0.000 claims description 25
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 24
- 238000004321 preservation Methods 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 17
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 11
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical group C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 239000004922 lacquer Substances 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- WDFFWUVELIFAOP-UHFFFAOYSA-N 2,6-difluoro-4-nitroaniline Chemical compound NC1=C(F)C=C([N+]([O-])=O)C=C1F WDFFWUVELIFAOP-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 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 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical group CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 11
- 238000000576 coating method Methods 0.000 abstract description 11
- 239000000853 adhesive Substances 0.000 abstract description 9
- 230000001070 adhesive effect Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
- 239000004925 Acrylic resin Substances 0.000 abstract description 8
- 229920000178 Acrylic resin Polymers 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000003848 UV Light-Curing Methods 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000003973 paint Substances 0.000 description 24
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 21
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 14
- 238000005240 physical vapour deposition Methods 0.000 description 10
- 238000010907 mechanical stirring Methods 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000010276 construction Methods 0.000 description 4
- 238000011534 incubation Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 2
- 241000208227 Toxicodendron vernicifluum Species 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002633 protecting effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/593—Dicarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/60—Maleic acid esters; Fumaric acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/105—Esters of polyhydric alcohols or polyhydric phenols of pentaalcohols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the field of materials, and particularly relates to polyfunctional acrylic ester and application thereof. The multi-functionality acrylic ester is prepared by the following method: is obtained by ring-opening reaction of polyol acrylic ester and maleic anhydride at 100-110 ℃. According to the invention, the acrylic resin and the UV component are grafted through the preparation of the polyfunctional acrylic ester, the acrylic resin can provide adhesion to a metal coating, and the UV component provides feasibility of UV curing and crosslinking. Meanwhile, double bonds with different activities provide a technical scheme of multiple crosslinking for crosslinking, so that the adhesive force is greatly improved.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to polyfunctional acrylic ester and application thereof.
Background
PVD technology has wide application in 3C field, and PVD lacquer has color adding and coating protecting effects, and solvent PVD lacquer has UV resin, monomer, color concentrate, assistant and solvent in 70-80% ratio, so that great amount of solvent has serious VOC problem. With the increasing environmental awareness, there is a need to replace solvent-based systems in existing PVD with aqueous systems.
At present, the traditional PVD intermediate paint adopts a UV curing mode, which brings challenges to coloring, and cannot meet the requirement of darkening, because the darkening needs high energy to reach the bottom of a paint film, but the high energy brings the problem of interlayer adhesion between the top paint and the intermediate paint, thereby influencing the performance of a system.
The prior art CN 104003875A discloses a 6-functionality aliphatic epoxy acrylate, a preparation method and application thereof. Firstly, succinic anhydride reacts with pentaerythritol triacrylate under the action of a catalyst and a polymerization inhibitor to prepare a 3-functionality acrylic ester intermediate (I) containing 1 carboxyl, and the intermediate (I) reacts with neopentyl glycol diglycidyl ether under the action of the catalyst and the polymerization inhibitor to prepare the 6-functionality aliphatic epoxy acrylic ester. After the prepared 6-functionality UV light-cured aliphatic epoxy acrylate is cured, the prepared UV light-cured aliphatic epoxy acrylate has the advantages of high hardness, wear resistance, scratch resistance, heat resistance, weather resistance and the like, and can be applied to raw materials of UV coating, printing ink and adhesive. However, phthalic anhydride, succinic anhydride, methyl hexahydrophthalic anhydride and hexahydrophthalic anhydride adopted by the adhesive do not have double bonds and cannot provide double bonds with different activities, so that good interlayer adhesive force cannot be provided; tetrahydrophthalic anhydride, although bearing a double bond, is extremely low in activity and large in steric hindrance, does not substantially participate in crosslinking, and also does not provide good interlayer adhesion.
Disclosure of Invention
The present invention provides a multi-functional acrylate, which provides different curing speeds by utilizing the difference of double bond activities of the multi-functional acrylate, thereby providing excellent interlayer adhesion.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a multifunctional acrylate prepared by the method comprising: is obtained by ring-opening reaction of polyol acrylic ester and maleic anhydride at 100-110 ℃.
In one preferred embodiment, the polyol acrylate is pentaerythritol triacrylate.
In one preferred embodiment, a catalyst is added to the ring-opening reaction, wherein the catalyst is triphenylphosphine, benzyl triethyl ammonium bromide, triethylamine or tetrabutylammonium bromide; from the viewpoints of reaction rate and yellowing, triphenylphosphine is preferred.
The method comprises the steps of adopting pentaerythritol triacrylate and maleic anhydride to carry out ring-opening reaction at 100-110 ℃ under the catalysis of triphenylphosphine, and generating the polyfunctional acrylate with carboxyl and double bonds. The compound has two parts of double bonds, the activity of the double bonds on pentaerythritol triacrylate is higher, and the compound can be rapidly cured during ultraviolet light curing, thereby providing high performance for the intermediate paint. The double bonds introduced on maleic anhydride have lower relative reactivity, and the part of double bonds on the surface of the intermediate paint are difficult to cure due to oxygen polymerization inhibition when the intermediate paint is cured, and after finishing the spraying of the finishing paint, the uncured double bonds on the surface of the intermediate paint can be crosslinked with the double bonds in the finishing paint, so that the interlayer adhesive force between the intermediate paint and the finishing paint is better.
The synthetic route of the polyfunctional acrylate is as follows:
the invention also discloses a UV resin, which comprises 90-150 parts of high TG monomer with double bonds and 450-750 parts of polyfunctional acrylate.
In one preferred embodiment, the UV resin comprises 90-150 parts of high TG monomer with double bonds, 335-410 parts of acrylic ester, 4-6 parts of phosphate, 450-750 parts of polyfunctional acrylic ester and 5-10 parts of catalyst.
In one preferred embodiment, the UV resin comprises 90-150 parts of double bond high TG monomer, 120-140 parts of methyl methacrylate, 35-45 parts of methoxy polyethylene glycol methacrylate, 90-110 parts of glycidyl methacrylate, 90-110 parts of hydroxypropyl acrylate, 4-6 parts of 2-hydroxyethyl methacrylate phosphate, 450-750 parts of polyfunctional acrylate and 5-10 parts of triphenylphosphine.
In the resin, the addition amount of the high TG monomer with double bonds is less than 90 parts, the adhesive force is poor, and the yellowing cannot pass due to the excessively high content; too low an amount of methoxypolyethylene glycol methacrylate to provide water-based properties, too high an amount would result in water-resistant deviation of the resin; too low an amount of GMA to be added cannot graft enough UV components, too high an amount affects the water resistance; too low an amount of HPA added is insufficient in heat curing crosslinking density, and too high hydroxyl residues affect water resistance; too low an amount of 2-hydroxyethyl methacrylate phosphate added may affect adhesion, too high may result in too hydrophilic properties, affecting water resistance. The addition amount of each component is strictly controlled according to the structural design of the resin, and the structure and the performance of the excessive or insufficient resin are adversely affected.
The invention adopts the idea of free radical polymerization, uses methoxy polyethylene glycol methacrylate as a nonionic hydrophilic monomer, uses a high TG monomer with double bonds to provide adhesion to metal, uses HPA and GMA as crosslinking monomers, and improves the boiling resistance and chemical resistance of a paint film by crosslinking with a curing agent in the paint. The intermediate grafts the UV component to the molecular chain of the resin by reaction with the epoxy groups on the GMA.
In one preferred embodiment, the high TG monomer with double bonds has a TG value of 70-110 ℃.
In one preferred embodiment, the high TG monomer with double bond is one or more of styrene, isobornyl acrylate, and isobornyl methacrylate. Styrene is preferred from the viewpoints of adhesion and cost.
In one preferred embodiment, the methoxypolyethylene glycol methacrylate is EM3105.
The structural formula of the EM3105 is:
in one preferred embodiment, the 2-hydroxyethyl methacrylate phosphate is PM1510.
The structural formula of PM1510 is:
the preparation method of the UV resin comprises the following steps:
s1, mixing styrene, MMA, EM3105, GMA, HPA, PM151 and an initiator according to parts by weight to obtain a mixed monomer;
s2, slowly dropwise adding the mixed monomer at 75-85 ℃, and preserving heat for 2-3 hours after the dropwise adding is finished; then adding an initiator, and continuing to keep the temperature for 3-5 hours;
and S3, adding polyfunctional acrylic ester and triphenylphosphine after heat preservation is finished, heating to 100-110 ℃ and preserving heat for 4-5 hours to react until the acid ester is less than 2.
The synthetic route of the UV resin is as follows:
the invention also claims a UV resin dispersion obtained by dispersing a UV resin in deionized water and removing the solvent.
The invention also claims a UV-cured PVD lacquer comprising: 80-120 parts of UV resin dispersoid, 10-20 parts of curing agent, 2-3 parts of initiator, 2-5 parts of auxiliary agent, 3-5 parts of solvent and 20-40 parts of water.
In one preferred embodiment, the curing agent is an aliphatic polyisocyanate, preferably HDI.
In one preferred embodiment, the initiator is azobisisobutyronitrile.
In one preferred embodiment, the auxiliary agent is a wetting agent, filler or pigment.
In one preferred embodiment, the solvent is ethylene glycol butyl ether.
The invention is further explained below:
according to the invention, the acrylic resin and the UV component are grafted through the preparation of the polyfunctional acrylic ester, the acrylic resin can provide adhesion to a metal coating, and the UV component provides feasibility of UV curing and crosslinking. Meanwhile, double bonds with different activities provide a technical scheme of multiple crosslinking for crosslinking, so that the adhesive force is greatly improved. On the other hand, the invention grafts the phosphate and the acrylic resin, thereby further improving the good adhesive force and water resistance of the resin; and a proper hydrophilic component is grafted on the main chain of the resin, so that the resin is water-borne, and the VOC content of a coating system is reduced.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) According to the invention, the polyfunctional acrylic ester is synthesized, the difference of double bond activity in the polyfunctional acrylic ester is utilized, the high-functional double bond provides a faster curing speed and physical properties of the coating, the double bond activity introduced by maleic anhydride is relatively low, especially, the part of double bonds on the surface of the Chinese lacquer are difficult to crosslink due to oxygen polymerization inhibition, and the part of double bonds can crosslink with the double bonds in the finish after the finish is sprayed, so that excellent interlayer adhesive force is provided, and the full test of the coating can be ensured.
(2) The double bond density of the resin can be effectively adjusted by adjusting the addition amount of the polyfunctional acrylic ester; the paint films with different crosslinking densities are obtained, and the water resistance of different requirements is met;
(3) The adhesion promoter phosphate is used in the formula of the traditional Chinese paint, and the adhesion promoter PM1510 is introduced into a molecular main chain in a grafting way, so that the water resistance is effectively improved.
Detailed Description
Example 1
(1) 1mol of pentaerythritol triacrylate and 1mol of maleic anhydride are added into a three-neck flask with a mechanical stirrer and a thermometer, the temperature is slowly raised to 80 ℃, the temperature is kept until the materials are completely dissolved, 4.3 g of triphenylphosphine is then added, the temperature is slowly raised to 105 ℃, and the reaction is continued until the acid ester is less than 66, thus obtaining an intermediate 1.
Example 2
(1) 1mol of HPA and 1mol of maleic anhydride are added into a three-neck flask with a mechanical stirrer and a thermometer, the temperature is slowly raised to 80 ℃, the temperature is kept until the materials are completely dissolved, 3.5 g of triphenylphosphine is added, the temperature is slowly raised to 105 ℃, and the reaction is continued until the acid ester is less than 244, thus obtaining an intermediate 2.
Example 3
(1) 1mol of pentaerythritol triacrylate and 1mol of butyric anhydride are added into a three-neck flask with mechanical stirring and a thermometer, the temperature is slowly raised to 80 ℃, the temperature is kept until the materials are completely dissolved, 4.3 g of triphenylphosphine is added, the temperature is slowly raised to 105 ℃, and the reaction is continued until the acid ester is less than 66, thus obtaining an intermediate 3.
Example 4
(1) 1mol of dipentaerythritol pentaacrylate and 1mol of maleic anhydride are added into a three-neck flask with a mechanical stirrer and a thermometer, the temperature is slowly raised to 80 ℃, the temperature is kept until the materials are completely dissolved, then 4.3 g of triphenylphosphine is added, the temperature is slowly raised to 105 ℃, and the reaction is continued until the acid ester is less than 40, thus obtaining an intermediate 4.
Example 5
(1) 480 g of butyl ester is added into a three-neck flask with mechanical stirring and a thermometer, and the temperature is slowly raised to 80 ℃;
(2) 120 g of styrene, 140 g of MMA,30 g of EM3105,5 g of PM1510, 100 g of GMA,100 g of HPA and 5 g of AIBN are added into a dropping tank to be uniformly dispersed until the AIBN is completely dissolved;
(3) After the temperature of the materials in the three-neck flask is raised to 80 ℃, dropwise adding the monomers for 4 hours, and preserving heat for 3 hours after the dropwise adding is finished;
(4) Adding 0.2 g of AIBN and 20 g of butyl ester after the heat preservation is finished, taking 10 minutes, and preserving the heat for 4 hours after the addition is finished;
(5) After the heat preservation is finished, 600 g of intermediate (intermediate 1-4) and 3 g of triphenylphosphine are added, the temperature is slowly raised to 105 ℃ and the heat preservation is carried out for 4 hours to react until the acid ester is less than 3;
(6) After the heat preservation is finished, 1100 g of water is added for dispersion, and the solvent is extracted to obtain micro-permeable dispersoid 1-4 with the solid content of 50%;
comparative example 1
(1) 480 g of butyl ester is added into a three-neck flask with mechanical stirring and a thermometer, and the temperature is slowly raised to 80 ℃;
(2) 120 g of styrene, 130 g of MMA,40 g of EM3105,5 g of PM1510, 100 g of GMA,100 g of HPA and 5 g of AIBN are added into a dropping tank to be uniformly dispersed until the AIBN is completely dissolved;
(3) After the temperature of the materials in the three-neck flask is raised to 80 ℃, dropwise adding the monomers for 4 hours, and preserving heat for 3 hours after the dropwise adding is finished;
(4) Adding 0.2 g of AIBN and 20 g of butyl ester after the heat preservation is finished, taking 10 minutes, and preserving the heat for 4 hours after the addition is finished;
(5) After the heat preservation is finished, 600 g of intermediate 2, 3 g of triphenylphosphine and 1100 g of deionized water are added for uniform dispersion, and the solvent is extracted to obtain milky white dispersion 5 with the solid content of 50%;
comparative example 2
(1) 480 g of butyl ester is added into a three-neck flask with mechanical stirring and a thermometer, and the temperature is slowly raised to 80 ℃;
(2) 120 g of styrene, 140 g of MMA,30 g of EM3105, 100 g of GMA,100 g of HPA and 5 g of AIBN are added into a dropping tank to be uniformly dispersed until the AIBN is completely dissolved;
(3) After the temperature of the materials in the three-neck flask is raised to 80 ℃, dropwise adding the monomers for 4 hours, and preserving heat for 3 hours after the dropwise adding is finished;
(4) Adding 0.2 g of AIBN and 20 g of butyl ester after the heat preservation is finished, taking 10 minutes, and preserving the heat for 4 hours after the addition is finished;
(5) After the heat preservation is finished, 600 g of intermediate 2 and 3 g of triphenylphosphine are added, the temperature is slowly raised to 105 ℃ and the heat preservation is carried out for 4 hours to react until the acid ester is less than 3;
(6) After the heat preservation is finished, 1100 g of water is added for dispersion, and the solvent is extracted to obtain micro-permeable dispersion 6 with the solid content of 50 percent;
PVD (physical vapor deposition) intermediate paint is prepared from the dispersion, and the formula, construction process and performance test are shown in Table 1:
table 1 formulation, construction process and performance test
Dispersion 1 could pass the full set of tests; dispersion 2 has low crosslinking density, so that the medium paint has low crosslinking density and is difficult to resist the erosion of moisture, and the water resistance, vibration abrasion resistance and chemical resistance cannot pass; the main reason that the dispersion 3 cannot pass the whole set of test is that the intermediate 3 only has PETA grafted double bonds, and the activity of the double bonds is not different, so that the interlayer adhesion of the intermediate paint and the finishing paint is poor, the finishing paint is removed during the high-temperature high-humidity and water boiling resistance test, and the chemical resistance and vibration abrasion resistance are further affected; dispersion 4 resulted in intermediate hardness being too high due to the grafted dipentaerythritol pentaacrylate in intermediate 4, resulting in deviation of adhesion to the coating; dispersion 5 showed microphase separation due to failure of intermediate 2 to graft with the backbone of the acrylic resin, resulting in non-uniform distribution of the UV and acrylate resin phases after curing of the lacquer, reflecting the appearance of the paint film as hazy. The poor water resistance of the phase region of the acrylic resin in the paint film of the Chinese lacquer caused by microphase separation reflects that the high temperature, high humidity and water boiling resistance of the test result are not passed, and meanwhile, chemicals resistance and vibration abrasion resistance are not passed; dispersion 6 had poor adhesion of the resin to the coating due to the ungrafted PM1510 in the resin; formulation No. 7 has an initial adhesion OK of the coating because PM1510 is not grafted to the molecular backbone, but has poor water and chemical resistance properties because small PM1510 is not crosslinked with the resin during the water resistance test.
Comparative example 3
(1) 480 g of butyl ester is added into a three-neck flask with mechanical stirring and a thermometer, and the temperature is slowly raised to 80 ℃;
(2) 120 g of styrene, 140 g of MMA,30 g of EM3105,5 g of PM1510, 100 g of GMA,100 g of HPA and 5 g of AIBN are added into a dropping tank to be uniformly dispersed until the AIBN is completely dissolved;
(3) After the temperature of the materials in the three-neck flask is raised to 80 ℃, dropwise adding the monomers for 4 hours, and preserving heat for 3 hours after the dropwise adding is finished;
(4) Adding 0.2 g of AIBN and 20 g of butyl ester after the heat preservation is finished, taking 10 minutes, and preserving the heat for 4 hours after the addition is finished;
(5) After the heat preservation is finished, 300 g of intermediate 1 and 3 g of triphenylphosphine are added, the temperature is slowly raised to 105 ℃ and the heat preservation is carried out for 4 hours to react until the acid ester is less than 3;
(6) After the end of the incubation, 800 g of water was added for dispersion, and the solvent was withdrawn to obtain a micro-permeable dispersion 7 having a solid content of 50%.
Comparative example 4
(1) 480 g of butyl ester is added into a three-neck flask with mechanical stirring and a thermometer, and the temperature is slowly raised to 80 ℃;
(2) 120 g of styrene, 140 g of MMA,30 g of EM3105,5 g of PM1510, 100 g of GMA,100 g of HPA and 5 g of AIBN are added into a dropping tank to be uniformly dispersed until the AIBN is completely dissolved;
(3) After the temperature of the materials in the three-neck flask is raised to 80 ℃, dropwise adding the monomers for 4 hours, and preserving heat for 3 hours after the dropwise adding is finished;
(4) Adding 0.2 g of AIBN and 20 g of butyl ester after the heat preservation is finished, taking 10 minutes, and preserving the heat for 4 hours after the addition is finished;
(5) After the heat preservation is finished, 450 g of intermediate 1 and 3 g of triphenylphosphine are added, the temperature is slowly raised to 105 ℃ and the heat preservation is carried out for 4 hours to react until the acid ester is less than 3;
(6) After the end of the incubation, 950 g of water was added for dispersion and the solvent was withdrawn to give a micro-permeable dispersion 8 having a solids content of 50%.
Comparative example 5
(1) 480 g of butyl ester is added into a three-neck flask with mechanical stirring and a thermometer, and the temperature is slowly raised to 80 ℃;
(2) 120 g of styrene, 140 g of MMA,30 g of EM3105,5 g of PM1510, 100 g of GMA,100 g of HPA and 5 g of AIBN are added into a dropping tank to be uniformly dispersed until the AIBN is completely dissolved;
(3) After the temperature of the materials in the three-neck flask is raised to 80 ℃, dropwise adding the monomers for 4 hours, and preserving heat for 3 hours after the dropwise adding is finished;
(4) Adding 0.2 g of AIBN and 20 g of butyl ester after the heat preservation is finished, taking 10 minutes, and preserving the heat for 4 hours after the addition is finished;
(5) After the heat preservation is finished, 750 g of intermediate 1 and 3 g of triphenylphosphine are added, the temperature is slowly raised to 105 ℃ and the heat preservation is carried out for 4 hours to react until the acid ester is less than 3;
(6) After the end of the incubation, 1250 g of water were added for dispersion and the solvent was withdrawn to give a slightly permeable dispersion 9 with a solids content of 50%.
Comparative example 6
(1) 480 g of butyl ester is added into a three-neck flask with mechanical stirring and a thermometer, and the temperature is slowly raised to 80 ℃;
(2) 120 g of styrene, 140 g of MMA,30 g of EM3105,5 g of PM1510, 100 g of GMA,100 g of HPA and 5 g of AIBN are added into a dropping tank to be uniformly dispersed until the AIBN is completely dissolved;
(3) After the temperature of the materials in the three-neck flask is raised to 80 ℃, dropwise adding the monomers for 4 hours, and preserving heat for 3 hours after the dropwise adding is finished;
(4) Adding 0.2 g of AIBN and 20 g of butyl ester after the heat preservation is finished, taking 10 minutes, and preserving the heat for 4 hours after the addition is finished;
(5) After the heat preservation is finished, 900 g of intermediate 1 and 3 g of triphenylphosphine are added, the temperature is slowly raised to 105 ℃ and the heat preservation is carried out for 4 hours to react until the acid ester is less than 3;
(6) After the end of the incubation, 1400 g of water was added for dispersion and the solvent was withdrawn to give a micro-permeable dispersion 10 with a solids content of 50%.
PVD (physical vapor deposition) intermediate paint is prepared from the dispersion, and the formula, construction process and performance test are shown in Table 2:
table 2 formulation, construction process and performance test
Dispersion 7, due to the too low content of intermediate 1, results in too low a crosslinking density, making it water-resistant, chemical-resistant and shock-resistant; dispersion 10, due to the intermediate content being too high, has too high a crosslink density, which results in poor adhesion to the coating, and likewise fails the complete test. The amount of intermediate 1 added is 450-750 parts.
All cited references, patents and patent applications in the above applications are incorporated herein by reference in their entirety in a consistent manner. In the event of an inconsistency or contradiction between the incorporated references and the present application, the information in the foregoing description shall prevail. The previous description of the disclosure, provided to enable one of ordinary skill in the art to practice the disclosure, is not to be construed as limiting the scope of the disclosure, which is defined by the appended claims and all equivalents thereof.
Claims (10)
1. A multifunctional acrylate, characterized by being prepared by the following method: is obtained by ring-opening reaction of polyol acrylic ester and maleic anhydride at 100-110 ℃.
2. The multi-functionality acrylate of claim 1 wherein the polyol acrylate is pentaerythritol triacrylate; preferably, a catalyst is added in the ring-opening reaction, wherein the catalyst is triphenylphosphine, benzyl triethyl ammonium bromide, triethylamine or tetrabutyl ammonium bromide; preferably triphenylphosphine.
3. The UV resin is characterized in that the raw materials comprise 90-150 parts of high TG monomer with double bonds and 450-750 parts of polyfunctional acrylate.
4. The UV resin according to claim 3, wherein the raw materials comprise 90-150 parts of high TG monomer with double bonds, 335-410 parts of acrylic ester, 4-6 parts of phosphate, 450-750 parts of polyfunctional acrylic ester and 5-10 parts of catalyst.
5. The UV resin according to claim 3, wherein the TG value of the high TG monomer with double bond is 70 to 110 ℃; preferably, the high TG monomer with double bond is one or more of styrene, isobornyl acrylate and isobornyl methacrylate, preferably styrene.
6. The UV resin according to claim 3, wherein the raw materials comprise 90-150 parts of double bond high TG monomer, 120-140 parts of methyl methacrylate, 35-45 parts of methoxy polyethylene glycol methacrylate, 90-110 parts of glycidyl methacrylate, 90-110 parts of hydroxypropyl acrylate, 4-6 parts of 2-hydroxyethyl methacrylate phosphate, 450-750 parts of polyfunctional acrylate and 5-10 parts of triphenylphosphine.
7. The method for producing a UV resin according to any one of claims 3 to 6, comprising the steps of:
s1, mixing styrene, MMA, EM3105, GMA, HPA, PM151 and an initiator according to parts by weight to obtain a mixed monomer;
s2, slowly dropwise adding the mixed monomer at 75-85 ℃, and preserving heat for 2-3 hours after the dropwise adding is finished; then adding an initiator, and continuing to keep the temperature for 3-5 hours;
and S3, adding polyfunctional acrylic ester and triphenylphosphine after heat preservation is finished, heating to 100-110 ℃ and preserving heat for 4-5 hours to react until the acid ester is less than 2.
8. A UV resin dispersion obtained by dispersing the UV resin according to any one of claims 3 to 6 in deionized water and removing the solvent.
9. A UV-cured PVD lacquer, comprising: 80-120 parts of UV resin dispersoid, 10-20 parts of curing agent, 2-3 parts of initiator, 2-5 parts of auxiliary agent, 3-5 parts of solvent and 20-40 parts of water.
10. The UV-cured PVD lacquer according to claim 9, wherein the curing agent is an aliphatic polyisocyanate; the initiator is azodiisobutyronitrile; the solvent is ethylene glycol butyl ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311241755.6A CN117285423A (en) | 2023-09-25 | 2023-09-25 | Multifunctional acrylic ester and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311241755.6A CN117285423A (en) | 2023-09-25 | 2023-09-25 | Multifunctional acrylic ester and application thereof |
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| CN117285423A true CN117285423A (en) | 2023-12-26 |
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| CN202311241755.6A Pending CN117285423A (en) | 2023-09-25 | 2023-09-25 | Multifunctional acrylic ester and application thereof |
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| Country | Link |
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| CN (1) | CN117285423A (en) |
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- 2023-09-25 CN CN202311241755.6A patent/CN117285423A/en active Pending
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