CN104003874A - New aliphatic epoxy acrylate with functionality of 4, and preparation method and application thereof - Google Patents
New aliphatic epoxy acrylate with functionality of 4, and preparation method and application thereof Download PDFInfo
- Publication number
- CN104003874A CN104003874A CN201410172932.4A CN201410172932A CN104003874A CN 104003874 A CN104003874 A CN 104003874A CN 201410172932 A CN201410172932 A CN 201410172932A CN 104003874 A CN104003874 A CN 104003874A
- Authority
- CN
- China
- Prior art keywords
- functionality
- aliphatic epoxy
- acrylate
- epoxy acrylate
- stopper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
-
- 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
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to the material field, and relates to a new aliphatic epoxy acrylate with the functionality of 4, and a preparation method and an application thereof. The method comprises the following steps: reacting succinic anhydride with hydroxyethyl(propyl) (meth)acrylate under the action of a catalyst and a polymerization inhibitor to prepare a one carboxyl group-containing acrylate intermediate (I) with the functionality of 1, and reacting the intermediate (I) with pentaerythritol glycidyl ether under the action of the catalyst and the polymerization inhibitor to prepare the aliphatic epoxy acrylate with the functionality of 4. The UV light-cured aliphatic epoxy acrylate with the functionality of 4 has the advantages of high hardness, excellent wear resistance, excellent scrape resistance, excellent heat resistance, excellent weatherability and the like, and can be applied in UV coatings, printing inks and adhesives as a raw material.
Description
Technical field
The invention belongs to Material Field, relate to a kind of 4 functionality aliphatic epoxy acrylate and preparation method thereof and application.
Background technology
Along with developing rapidly and the strict restriction of legislations of environmental protection to solvent of science and technology, UV photocuring macromolecular material is more and more subject to people's attention.UV photo-curing material have quick solidifying, energy consumption low, pollute less, the premium properties such as efficiency height, thereby be widely used in the fields such as coating, printing and electronic industry, development in recent years is rapid.Epoxy acrylate (epoxy acrylate, EA) be to be made through esterification by ring opening by compound and acrylic or methacrylic acid containing epoxide group, it is a kind of important photocuring oligopolymer, there is the premium propertiess such as low stimulation, curing speed are fast, high transparent, hardness height, be widely used in the fields such as light-curable ink, coating, tackiness agent, at the U.S., Japan, countries in Europe, be widely used.In recent years, along with the rise of UV-curing technology in China, novel photo-curing material is more and more wider as the raw material purposes of UV coating, ink, tackiness agent, and usage quantity is increasing year by year.
Summary of the invention
The object of the invention is the above-mentioned deficiency for prior art, a kind of 4 functionality aliphatic epoxy acrylate are provided.
Another object of the present invention is to provide the preparation method of this 4 functionality aliphatic epoxy acrylate.
Another object of the present invention is to provide the application of this 4 functionality aliphatic epoxy acrylate.
Object of the present invention can be achieved through the following technical solutions:
4 functionality aliphatic epoxy acrylate, prepare by the following method: first by Succinic anhydried (CASNO.108-30-5, Chinese another name: succinyl oxide, molecular formula: C
4h
4o
3molecular weight 100.07) under catalyzer, stopper effect, react the 1 functionality acrylate intermediate (I) making containing 1 carboxyl with (methyl) vinylformic acid hydroxyl second (third) ester, intermediate (I) and tetramethylolmethane glycidyl ether (CAS:3126-63-4, molecular formula: C
17h
28o
8, molecular weight: 360.3994) make 4 functionality aliphatic epoxy acrylate (aliphatic epoxy four acrylic acid esters) under the effect of catalyzer, stopper.Described (methyl) vinylformic acid hydroxyl second (third) ester is selected from any one in hydroxyethyl methylacrylate, Rocryl 410, Hydroxyethyl acrylate or Propylene glycol monoacrylate.
Wherein,
Take Hydroxyethyl acrylate as example, and the first step reaction formula is:
The 1 functionality acrylate intermediate (I) containing 1 carboxyl is preferably prepared by following steps: (methyl) vinylformic acid hydroxyl second (third) ester and Succinic anhydried are under catalyst action, in reactor, in 60 ℃-120 ℃, react 1-6 hour, then be cooled to below 50 ℃, make the 1 functionality acrylate intermediate (I) containing 1 carboxyl; Wherein, preferred 1:(0.8～1.5 of mol ratio of (methyl) vinylformic acid hydroxyl second (third) ester and Succinic anhydried).Under reaction conditions of the present invention, Succinic anhydried open loop generates 1 carboxyl, and when reaction system acid number drops to constantly, Succinic anhydried carries out ring-opening reaction completely and generates carboxyl, and transformation efficiency is more than 99.9%.
One or both in the preferred Louis's bases of described the first step catalysts, quaternary ammonium salt, quaternary phosphine salt or two or more arbitrary proportion miscellany; Further preferably from triethylamine, N, N-dimethyl benzylamine, N, one or both in N-diethyl benzylamine, triphenyl phosphorus, tributyl phosphorus, benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, tetramethyl ammonium chloride, etamon chloride, tetrabutylammonium chloride, 4 bromide, tetraethylammonium bromide, Tetrabutyl amonium bromide, tri-phenyl-ethyl phosphonium bromide, four butyl phosphonium bromides or two or more arbitrary proportion miscellany; Catalyst levels is the 0.1wt%-2wt% of (methyl) vinylformic acid hydroxyl second (third) ester and Succinic anhydried total mass.The preferred MEHQ of stopper or Resorcinol, its consumption is 100-5000ppm.
Second step reaction formula:
4 described functionality aliphatic epoxy acrylate are preferably prepared by following steps: tetramethylolmethane glycidyl ether and the prepared 1 functionality acrylate intermediate (I) that contains 1 carboxyl, under catalyzer, stopper effect, make 4 described functionality aliphatic epoxy acrylate in 60 ℃-120 ℃ reactions 1-10 hour; Wherein, the mol ratio of described tetramethylolmethane glycidyl ether and Succinic anhydried is (0.22～0.3): 1.
4 described functionality aliphatic epoxy acrylate are further preferably prepared by following steps: tetramethylolmethane glycidyl ether and the prepared 1 functionality acrylate intermediate (I) that contains 1 carboxyl, under catalyzer, stopper effect, make 4 described functionality aliphatic epoxy acrylate in 70 ℃-110 ℃ reactions 3-9 hour; Wherein, the mol ratio of described tetramethylolmethane glycidyl ether and Succinic anhydried is (0.24～0.27): 1.
Wherein stopper can be MEHQ or Resorcinol, and its consumption is 100-5000ppm.
Described second step catalysts is triethylamine, N, N-dimethyl benzylamine, N, N-diethyl benzylamine, triphenyl phosphorus, Louis's bases such as tributyl phosphorus, or benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, tetramethyl ammonium chloride, etamon chloride, tetrabutylammonium chloride, 4 bromide, tetraethylammonium bromide, the quaternary ammonium salts such as Tetrabutyl amonium bromide, or tri-phenyl-ethyl phosphonium bromide, one or both in the quaternary phosphine salts such as four butyl phosphonium bromides or two or more arbitrary proportion miscellany, catalyst levels is the 0.1wt%-2wt% of tetramethylolmethane glycidyl ether and intermediate (I) total mass.
After the first step reaction finishes, without intermediate is carried out to purifying, directly add tetramethylolmethane glycidyl ether, and add catalyzer and stopper reacts.Wherein, to add the amount of catalyzer to take the total mass of reactant Succinic anhydried and (methyl) vinylformic acid hydroxyl second (third) ester be benchmark for the first step reaction; It is benchmark that the amount of second step catalysts (amount of the catalyzer of adding while comprising catalyzer that the first step reaction adds and second step reaction) be take the total mass of reactant Succinic anhydried, (methyl) vinylformic acid hydroxyl second (third) ester and tetramethylolmethane glycidyl ether.The stopper adding in the first step reaction is also the same with catalyzer, will enter into second reaction and play a role, and the consumption of second step reaction stopper is the first step reaction add-on of stopper and the amount sum of the stopper that second step is added.
The application of 4 functionality aliphatic epoxy acrylate of the present invention in preparation UV coating, ink or tackiness agent.
Beneficial effect:
The present invention discloses a kind of 4 new functionality UV photocuring aliphatic epoxy acrylate and preparation method thereof.After this 4 functionality UV photocuring aliphatic epoxy acrylate is solidified, have that hardness is high, wear-resisting, scratch resistance, heat-resisting, weathering resistance etc. are good, can be in the raw material application as UV coating, ink, tackiness agent.
Embodiment
Embodiment 1:
The first step drops into 2000 grams of Succinic anhydrieds (CAS NO.108-30-5, molecular formula: C in 8L reactor
4h
4o
3, molecular weight 100.07), 15 grams of benzyltriethylammoinium chlorides, 1.5 grams of MEHQ, 2420 grams of Hydroxyethyl acrylates (CAS No.:818 ?61 ?1, molecular formula: C
5h
8o
3molecular weight 116.12, content is by 96%), start stirring, be warming up to 70 ℃, be incubated 1 hour, be warmed up to again 80 ℃ of insulations 1 hour, then be warming up to 100 ℃ of insulations 3 hours, react constant to acid number, then be cooled to below 50 ℃, make containing 4436.5 grams, 1 functionality acrylate intermediate (I) of 1 carboxyl.Without carrying out separation and purification, directly carry out second step reaction.
Second step then drops into 1800 grams of tetramethylolmethane glycidyl ethers ((CAS:3126-63-4, molecular formula: C in 8L reactor
17h
28o
8360.3994), 5 grams of benzyltriethylammoinium chlorides, 1 gram of MEHQ molecular weight:, be warming up to 70 ℃, be incubated 1 hour, be warmed up to again 80 ℃ of insulations 1 hour, be warmed up to again 90 ℃ of insulations 1 hour, be warming up to again 100 ℃ of insulations 1 hour, be warming up to again 110 ℃ of insulations 5 hours, react constant to acid number, then be cooled to 50 ℃ and obtain crude product with bottom discharge, overanxious through 200 mesh filter screens (gauze), obtain 6117 grams of clear thick liquids, 4 functionality aliphatic epoxy acrylate (aliphatic epoxy four acrylic acid esters) C
53h
76o
32, structure is suc as formula shown in (II).
1H?NMR(400MHz,CD
3OD,δppm)：2.84‐2.86(16H,m,4CH
2CH
2),3.40(4H,m,4CH
2),3.58(4H,brs,4OH),3.65(4H,m,4CH
2),4.11(4H,m,4CH
2),4.14(4H,m,4CH),4.31‐4.38(20H,m,4CH
2,4CH
2CH
2),5.59(4H,d,4CH＝CH
2),5.80(8H,s,4CH
2),6.05(4H,m,4CH＝CH
2),6.27(4H,m,4CH＝CH
2)
13C?NMR(100MHz,CD
3OD,δppm)：29.5(8CH
2),44.8(1C),61.8(4CH
2),62.2(4CH
2),65.5(4CH
2),68.7(4CH),71.0(4CH
2),73.6(4CH
2),128.2(4CH),131.3(4CH
2),166.5(4CO),173.1(8CO)
Embodiment 2:
The first step drops into 2000 grams of Succinic anhydrieds (CAS NO.108-30-5, molecular formula: C in 8L reactor
4h
4o
3, molecular weight 100.07), 10 grams of benzyltriethylammoinium chlorides, 5 grams of tetramethyl ammonium chlorides, 1.5 grams of MEHQ, 2425 grams of Hydroxyethyl acrylates (CAS No.:818 ?61 ?1, molecular formula: C
4h
4o
3, molecular weight 116.12, content is by 96%), start stirring, be warming up to 70 ℃, be incubated 1 hour, then be warmed up to 80 ℃ of insulations 1 hour, be warming up to again 100 ℃ of insulations 3 hours, react constant to acid number, be then cooled to below 50 ℃, make containing 4441.5 grams, 1 functionality acrylate intermediate (I) of 1 carboxyl.Without carrying out separation and purification, directly carry out second step reaction.
Second step then drops into 1800 grams of tetramethylolmethane glycidyl ethers (CAS:3126-63-4, molecular formula: C in 8L reactor
17h
28o
8360.3994), 6.5 grams of triethylamines, 1 gram of Resorcinol molecular weight:, be warming up to 70 ℃, be incubated 1 hour, be warmed up to again 80 ℃ of insulations 1 hour, be warmed up to again 90 ℃ of insulations 1 hour, be warming up to again 100 ℃ of insulations 1 hour, be warming up to again 110 ℃ of insulations 5 hours, react constant to acid number, then be cooled to 50 ℃ and obtain crude product with bottom discharge, overanxious through 200 mesh filter screens (gauze), obtain 6124 grams of clear thick liquids, 4 functionality aliphatic epoxy acrylate (aliphatic epoxy four acrylic acid esters) C
53h
76o
32, structure is suc as formula shown in (II).
Embodiment 3
Starting material
4 functionality aliphatic epoxy acrylate of UV resin: embodiment 1 preparation; 3 functionality aliphatic urethane acrylates (F5301, profit field, Jiangsu science and technology).
UV monomer: ditrimethylolpropane tetraacrylate (Di-TMPTA, profit field, Jiangsu); 1,6 hexanediol diacrylate (HDDA, profit field, Jiangsu); Isobornyl acrylate (IBOA, profit field, Jiangsu).
Light trigger: 1173, Nanjing Wa Li Chemical Industry Science Co., Ltd.
Auxiliary agent: Tego432, Tego92, German enlightening is high.
Mixed solvent: N-BUTYL ACETATE, toluene, mibk are in mass ratio for 1:1:1 mixes.
Instrument and equipment
LT-1002 type uv cure machine, blue sky Te Deng Development Co., Ltd; QFZ type paint film adhesion determinator, Tianjin Ke Lian material-testing machine factory; RCA paper tape wear resistant instrument, Shanghai modern environment project institute; Water-bath; Cold cycling equipment.The preparation of coating
The UV resin that takes certain mass, then adds UV monomer, light trigger, auxiliary agent, stirs, and is mixed with coating.The proportioning of coating is in Table l.
Table 1: the proportioning of coating
The preparation of filming is with curing
Select the ABS plastic sheet material of 10cm * 10cm, first at its surface spraying one deck thermoplastic acrylic resin white primer, 60 ℃ of baking 3h, again at its surface spraying UV finish paint, coating thickness is about 20 μ m, on photo solidification machine, solidifies, and makes cured film reach surface drying, with referring to that touching dry method characterizes, and records set time.
Performance test
Set time: experiment adopts and refers to touch dry method, touches coating surface to point, and is clamminess if do not felt, thinks that coating surface is curing.
Pencil hardness: measure with reference to the GB6739-86 pencil hardness method of filming.
Sticking power: measure with reference to GB/T1720-88 film adhesive assay method.Be divided into 7 grades, 1 grade of the best, 7 grades are the poorest.
Wear resistance: RCA test, 175g, 500 ± 50 times.
Water boiling resistance: with reference to standard GB/T/T1733 < < paint film water tolerance assay method > >.
Cold-hot circulation:
(1) scope and explanation: plastic paint is because of damp and hot circulation or losses of plasticizer, or both there will be the trend of cracking while having concurrently, adopt to be alternately exposed in climate cabinet and refrigerated tank and can measure the degree whether paint film ftractures and ftracture.
(2) instrument: 1. damp heat box, 2. refrigerated tank, 3. color measurement instrument, 4. draws lattice device.
(3) measuring method: 1. test piece is put into relative temperature 100%, temperature and be the hot case 24h of incubator of 38 ℃.The placement of model should become with vertical direction 0-30 degree angle, and requires plate plate mutually not contact in process of the test.2. after 24h, immediately model is moved to 20h in the refrigerated tank of (23 ± 1.5) ℃, should not surpass 30S transfer time at most.3. take out model, at room temperature place 4h, 48h is a circulation so altogether, during can carry out stage evaluation.4. carry out altogether 15 circulations, then model outward appearance, color, sticking power are tested.
(4) result represents: filming should be without cracking, variable color, loss of adhesion or other defect.
(5) reference standard: USS AAMA615-02 < < is for industry standard, performance requriements and the test method > > of high-performance organic coating on plastic material.
(1)
Result and discussion, the impact of resin on film performance
UV resin is the main body of UV coating, the salient features of having filmed after its performance has determined to solidify substantially.This experiment adopts 3 functionality aliphatic epoxy acrylate and 4 functionality aliphatic urethane acrylate resins to form different ingredients, and various composition consumptions are in Table 1, and film performance is in Table 2.
Table 2:4 official aliphatic epoxy acrylate and the impact of the different proportionings of 3 official's aliphatic urethane acrylate on coating property
Reference:
(1) Yu Yingying. coatings industry is complete works of by the method for inspection and instrument. Beijing: Chemical Industry Press, 2007:525.
Attached light trigger 1173 explanations:
Manufacturer: Nanjing Wa Li Chemical Industry Science Co., Ltd
Chemical name: 2-hydroxy-2-methyl-1-phenyl-1-acetone
English name: 2-Hydroxy-2-methyl-1-phenyl-propan-1-one
CAS?NO：7473-98-5
Molecular formula: C10H12O
Molecular weight: 164.2
Chemical structural formula:
Technical indicator:
Outward appearance: colourless to light yellow transparent liquid
Purity: >=99.0%
Boiling point: 80-81 ℃ (degree Celsius)
Transmittance: 425nm >=99.0%; 500nm >=99.3%
Fugitive constituent :≤0.2%
Ash :≤0.10%
Application:
1173 are applicable to vinylformic acid photocuring varnish system, as varnish of timber, metal, paper, plastics etc. etc.1173 special recommendations needs stand the UV-of long-term Exposure to Sunlight and resistance to xanthochromia coating material solidified in, owing to 1173 being liquid, be highly susceptible to blend, so be applicable to and the composite use of other light trigger, suggestion addition is 1-4%w/w.
Claims (10)
1. 4 functionality aliphatic epoxy acrylate, it is characterized in that 4 described functionality aliphatic epoxy acrylate are prepared by the following method to the first step reaction: first reacted with (methyl) acrylate hydroxyl second (third) ester under catalyzer, stopper effect by Succinic anhydried and make the 1 functionality acrylate intermediate (I) that contains 1 carboxyl; Second step reaction: intermediate (I) makes 4 functionality aliphatic epoxy acrylate with tetramethylolmethane glycidyl ether under the effect of catalyzer, stopper; Wherein, described (methyl) vinylformic acid hydroxyl second (third) ester is selected from any one in hydroxyethyl methylacrylate, Rocryl 410, Hydroxyethyl acrylate or Propylene glycol monoacrylate.
2. 4 functionality aliphatic epoxy acrylate according to claim 1, it is characterized in that (methyl) acrylate hydroxyl second (third) ester and Succinic anhydried are under catalyzer and stopper effect, in reactor, in 60 ℃-120 ℃, react 1-6 hour, then be cooled to below 50 ℃, make the 1 functionality acrylate intermediate (I) containing 1 carboxyl; Wherein, described (methyl) acrylate hydroxyl second (third) ester and the mol ratio of Succinic anhydried are 1:(0.8～1.5).
3. 4 functionality aliphatic epoxy acrylate according to claim 1, it is characterized in that tetramethylolmethane glycidyl ether and the described 1 functionality acrylate intermediate (I) containing 1 carboxyl, under catalyzer and stopper effect, make 4 described functionality aliphatic epoxy acrylate in 60 ℃-120 ℃ reactions 1-10 hour; Wherein, the mol ratio that described tetramethylolmethane glycidyl ether reacts the Succinic anhydried adding with the first step is (0.22～0.30): 1.
4. according to 4 functionality aliphatic epoxy acrylate described in any one in claim 1～3, it is characterized in that described catalyzer is selected from one or both or the two or more arbitrary proportion miscellany in Louis's bases, quaternary ammonium salt, quaternary phosphine salt; Preferably from triethylamine, N, N-dimethyl benzylamine, N, one or both in N-diethyl benzylamine, triphenyl phosphorus, tributyl phosphorus, benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, tetramethyl ammonium chloride, etamon chloride, tetrabutylammonium chloride, 4 bromide, tetraethylammonium bromide, Tetrabutyl amonium bromide, tri-phenyl-ethyl phosphonium bromide, four butyl phosphonium bromides or two or more arbitrary proportion miscellany; Catalyst levels is the 0.1wt%-2wt% of reactant total mass; Described stopper is MEHQ or Resorcinol, and its consumption is 100-5000ppm.
5. the preparation method of 4 functionality aliphatic epoxy acrylate claimed in claim 1, it is characterized in that comprising following steps and first by Succinic anhydried, under catalyzer, stopper effect, reacted the 1 functionality acrylate intermediate (I) making containing 1 carboxyl with (methyl) acrylate hydroxyl second (third) ester, intermediate (I) makes 4 functionality aliphatic epoxy acrylate with tetramethylolmethane glycidyl ether under the effect of catalyzer, stopper.
6. the preparation method of 4 functionality aliphatic epoxy acrylate according to claim 5, it is characterized in that (methyl) vinylformic acid hydroxyl second (third) ester and Succinic anhydried are under catalyzer and stopper effect, in reactor, in 60 ℃-120 ℃, react 1-6 hour, then be cooled to below 50 ℃, make the 1 functionality acrylate intermediate (I) containing 1 carboxyl; Wherein, described (methyl) vinylformic acid hydroxyl second (third) ester and the mol ratio of Succinic anhydried are 1:(0.8～1.5).
7. the preparation method of 4 functionality aliphatic epoxy acrylate according to claim 5, it is characterized in that tetramethylolmethane glycidyl ether and the described 1 functionality acrylate intermediate (I) containing 1 carboxyl, under catalyzer and stopper effect, make 4 described functionality aliphatic epoxy acrylate in 60 ℃-120 ℃ reactions 1-10 hour; Wherein, the mol ratio that described tetramethylolmethane glycidyl ether reacts the Succinic anhydried adding with the first step is (0.22～0.30): 1.
8. the preparation method of 4 functionality aliphatic epoxy acrylate according to claim 7, it is characterized in that the first step reaction finish after without the separation and purification of carrying out intermediate (I), directly add tetramethylolmethane glycidyl ether, and add catalyzer and stopper carries out second step reaction.
9. according to the preparation method of 4 functionality aliphatic epoxy acrylate described in any one in claim 5～8, it is characterized in that described catalyzer is selected from one or both or the two or more arbitrary proportion miscellany in Louis's bases, quaternary ammonium salt, quaternary phosphine salt; Preferably from triethylamine, N, N-dimethyl benzylamine, N, one or both in N-diethyl benzylamine, triphenyl phosphorus, tributyl phosphorus, benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, tetramethyl ammonium chloride, etamon chloride, tetrabutylammonium chloride, 4 bromide, tetraethylammonium bromide, Tetrabutyl amonium bromide, tri-phenyl-ethyl phosphonium bromide, four butyl phosphonium bromides or two or more arbitrary proportion miscellany; Catalyst levels is the 0.1wt%-2wt% of reactant total mass; Described stopper is MEHQ or Resorcinol, and its consumption is 100-5000ppm.
10. the application of 4 functionality aliphatic epoxy acrylate claimed in claim 1 in preparation UV coating, ink or tackiness agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410172932.4A CN104003874B (en) | 2014-04-25 | 2014-04-25 | A kind of 4 functionality aliphatic epoxy acrylate newly and preparation method thereof and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410172932.4A CN104003874B (en) | 2014-04-25 | 2014-04-25 | A kind of 4 functionality aliphatic epoxy acrylate newly and preparation method thereof and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104003874A true CN104003874A (en) | 2014-08-27 |
| CN104003874B CN104003874B (en) | 2016-04-27 |
Family
ID=51364811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410172932.4A Active CN104003874B (en) | 2014-04-25 | 2014-04-25 | A kind of 4 functionality aliphatic epoxy acrylate newly and preparation method thereof and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104003874B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753694A (en) * | 2016-03-31 | 2016-07-13 | 江苏博砚电子科技有限公司 | Polycarboxyl functionalization acrylate for color resistor and preparation method thereof |
| CN105820063A (en) * | 2016-04-15 | 2016-08-03 | 江苏利田科技股份有限公司 | 4-functionality polyurethane acrylic ester based on anhydrous citric acid as well as preparation method and application of 4-functionality polyurethane acrylic ester |
| CN108395522A (en) * | 2018-03-29 | 2018-08-14 | 广州市嵩达新材料科技有限公司 | A kind of epoxy acrylic resin of tetra functional and its preparation method and application |
| CN112175489A (en) * | 2020-09-04 | 2021-01-05 | 江苏利田科技股份有限公司 | Hybrid epoxy acrylate UV coating with high surface hardness |
| CN112409574A (en) * | 2020-11-24 | 2021-02-26 | 广东立邦长润发科技材料有限公司 | Ultraviolet light curing bright white resin and preparation method thereof |
| CN113215825A (en) * | 2021-04-29 | 2021-08-06 | 江苏利田科技股份有限公司 | Fabric crease-resistant UV finishing agent and preparation method thereof |
| TWI781508B (en) * | 2020-10-30 | 2022-10-21 | 財團法人工業技術研究院 | Resin and ink |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1643083A (en) * | 2002-03-22 | 2005-07-20 | 日本油脂Basf涂料株式会社 | UV-curable coating composition and coated articles |
| CN101570592A (en) * | 2008-04-30 | 2009-11-04 | 北京化工大学 | Polyether type hyperbranched epoxy resin and preparation method thereof |
| CN102660387A (en) * | 2012-04-12 | 2012-09-12 | 广州市博兴化工科技有限公司 | Acrylic acid ester modified epoxy soybean oil, its preparation method and application thereof |
-
2014
- 2014-04-25 CN CN201410172932.4A patent/CN104003874B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1643083A (en) * | 2002-03-22 | 2005-07-20 | 日本油脂Basf涂料株式会社 | UV-curable coating composition and coated articles |
| CN101570592A (en) * | 2008-04-30 | 2009-11-04 | 北京化工大学 | Polyether type hyperbranched epoxy resin and preparation method thereof |
| CN102660387A (en) * | 2012-04-12 | 2012-09-12 | 广州市博兴化工科技有限公司 | Acrylic acid ester modified epoxy soybean oil, its preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| DONG KOOK KIM ET AL.: "《Synthesis and properties of photocurable epoxy modified acrylates using half-ester acrylates》", 《POLYMER (KOREA)》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753694A (en) * | 2016-03-31 | 2016-07-13 | 江苏博砚电子科技有限公司 | Polycarboxyl functionalization acrylate for color resistor and preparation method thereof |
| CN105753694B (en) * | 2016-03-31 | 2018-08-03 | 江苏博砚电子科技有限公司 | A kind of how carboxy-functionalized acrylate and preparation method thereof for chromatic photoresist |
| CN105820063A (en) * | 2016-04-15 | 2016-08-03 | 江苏利田科技股份有限公司 | 4-functionality polyurethane acrylic ester based on anhydrous citric acid as well as preparation method and application of 4-functionality polyurethane acrylic ester |
| CN108395522A (en) * | 2018-03-29 | 2018-08-14 | 广州市嵩达新材料科技有限公司 | A kind of epoxy acrylic resin of tetra functional and its preparation method and application |
| CN112175489A (en) * | 2020-09-04 | 2021-01-05 | 江苏利田科技股份有限公司 | Hybrid epoxy acrylate UV coating with high surface hardness |
| TWI781508B (en) * | 2020-10-30 | 2022-10-21 | 財團法人工業技術研究院 | Resin and ink |
| CN112409574A (en) * | 2020-11-24 | 2021-02-26 | 广东立邦长润发科技材料有限公司 | Ultraviolet light curing bright white resin and preparation method thereof |
| CN113215825A (en) * | 2021-04-29 | 2021-08-06 | 江苏利田科技股份有限公司 | Fabric crease-resistant UV finishing agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104003874B (en) | 2016-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104003874B (en) | A kind of 4 functionality aliphatic epoxy acrylate newly and preparation method thereof and application | |
| CN103274967B (en) | Tri-functional polyurethane acrylate, and preparation method and application thereof | |
| CN103224603B (en) | Urethane acrylate with six functionalities as well as preparation method and application thereof | |
| CN103725245B (en) | A kind of optical clear adhesive tape solvent-free UV solidified glue and Synthesis and applications thereof | |
| CN103214649B (en) | 9-functionality-degree polyurethane acrylate as well as preparation method and application thereof | |
| CN105859584B (en) | One kind being based on the 3 degree of functionality urethane acrylates and its preparation method and application of trihydroxy methyl second (third) alkane | |
| CN106700920B (en) | A kind of response type polysiloxanes flame retardant coating and preparation method thereof | |
| CN103242508B (en) | A kind of 4 functionality urethane acrylates and its preparation method and application | |
| CN105801829B (en) | 2 degree of functionality polycaprolactone polyurethane acrylate of one kind and its preparation method and application | |
| CN104003877B (en) | A kind of 8 functionality aliphatic epoxy acrylate and preparation method thereof and application | |
| CN104003880A (en) | Aliphatic epoxy acrylate with functionality of 3, and preparation method and application thereof | |
| CN103193953B (en) | Urethane acrylate with functionality of 12 as well as preparation method and application thereof | |
| CN102702479A (en) | Method for synthesizing modified epoxy acrylate | |
| CN104003872A (en) | New aliphatic epoxy acrylate with functionality of 2, and preparation method and application thereof | |
| CN105859997A (en) | 3-functionality-degree polycaprolactone urethane acrylate and preparation method and application thereof | |
| CN105859587B (en) | A kind of 4 degree of functionality urethane acrylates based on pentaerythrite and its preparation method and application | |
| CN105859585B (en) | A kind of 3 degree of functionality urethane acrylates based on glycerine and its preparation method and application | |
| CN104003879A (en) | Aliphatic epoxy acrylate with functionality of 2, and preparation method and application thereof | |
| CN103193960A (en) | Modified UV (Ultraviolet) photocuring pure-acrylic resin and preparation method thereof | |
| CN102838486A (en) | Ultraviolet light curing polyester acrylate and preparation method thereof | |
| CN104003875A (en) | Aliphatic epoxy acrylate with functionality of 6, and preparation method and application thereof | |
| CN103242507B (en) | Eight-functionality urethane acrylate as well as preparation method and application thereof | |
| CN105820063B (en) | A kind of 4 degree of functionality urethane acrylates based on anhydrous citric acid and its preparation method and application | |
| CN104003873B (en) | A kind of 4 functionality aliphatic epoxy acrylate and preparation method thereof and application | |
| CN104003876B (en) | A kind of 6 functionality aliphatic epoxy acrylate newly and preparation method thereof and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 226408 Jiangsu city of Nantong province Rudong county new Feng Li Zhen Road No. 120 Patentee after: Jiangsu Litian Technology Co.,Ltd. Address before: 226408 Jiangsu city of Nantong province Rudong county new Feng Li Zhen Road No. 120 Patentee before: JIANGSU LITIAN TECHNOLOGY Co.,Ltd. |