CN104961857A - Modified (methyl) acrylate resin and preparation method - Google Patents
Modified (methyl) acrylate resin and preparation method Download PDFInfo
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- CN104961857A CN104961857A CN201510381331.9A CN201510381331A CN104961857A CN 104961857 A CN104961857 A CN 104961857A CN 201510381331 A CN201510381331 A CN 201510381331A CN 104961857 A CN104961857 A CN 104961857A
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Abstract
The invention discloses modified (methyl) acrylate resin. The resin contains a (methyl) acrylate chain link, an unsaturated double bond and carboxylic group, an unsaturated double bond and epoxy group and an organic silicon group containing double bonds. The modified (methyl) acrylate resin can be solidified through various methods, has the characteristics of high hardness, high toughness, no adhesion, strong adhering force, good wear resistance and the like, and can be applied to fields such as coating, ink and adhesive. The invention further relates to a preparation method of the material.
Description
Technical field
The invention belongs to organic polymer synthesis technical field, particularly relating to one can multi-curing organic-silicon-modified (methyl) acrylate resin and preparation method thereof, and described resin can be applied to the field such as coating, sizing agent, ink of heat, UV-light, moisture, air curing.
Background technology
In prior art, propose the resin relating to various (methyl) esters of acrylic acid thermal curable, ultraviolet light polymerization, the resin after solidification has the advantages such as photocuring is fast, hardness of film is high, sticking power is good, good luster, resistance to chemical attack.
(methyl) acrylic resin solidified in two or more modes generally can reach more satisfactory effect, but the problem of easy adhesion after there is one-step solidification, raising molecular weight can make again viscosity increase is made troubles to construction, and degree of crosslinking increase can make toughness reduce.Add release layer can solve the problem, but can cost be increased.In addition, can not keep high rigidity and high tenacity, namely sticking power was not well not only but also adhesion simultaneously.
A kind of silicone-modified urethane acrylate hyperbranched oligomer and preparation method thereof is disclosed in Chinese patent CN101665561B, wherein said multi-curing coating is first by polyvalent alcohol vaccum dewatering, add vulcabond, synthesis of polyurethane performed polymer, then hyper-branched polyester is added, add hydroxy acrylate and stopper again, add catalyzer initiated polymerization, finally add two aminosiloxane and reactive thinner, reaction for some time, obtain siloxane modified polyurethane acrylate hyperbranched oligomer.This siloxane modified polyurethane acrylate hyperbranched oligomer and light trigger, reactive thinner, solvent, auxiliary agent are mixed, obtains ultraviolet-heat-moisture multi-curing material.This multi-curing material viscosity 200 mPas-800mPas, number-average molecular weight 2000-8000.Unsaturated double-bond is contained in oligopolymer in this coating and reactive thinner, can ultraviolet light polymerization.Ultraviolet light polymerization is the primary curing mode of this coating; Thermofixation is the heat energy formation additional polymerization by UV-light, and the unit of polymerization is urethane and acrylate; The siloxanes contained can moisture solidification, finally formation polymer interpenetration network structure.Here ultraviolet-heat-moisture multi-curing material, although by multiple curing mechanism, but mainly pass through ultraviolet light polymerization when using, and thermofixation and ultraviolet light polymerization will carry out simultaneously, if be only cured by the mode of heating, then can not film-forming, moisture solidification is also Curing mode.The pencil hardness of this ultraviolet-heat-moisture multi-curing material is 2H.It is coating material solidified for single multi-curing that the method obtains, and can not carry out regelate, make the finishing in type-approval process limited after solidification rolling in stamping forming process.
Summary of the invention
Problem to be solved by this invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides a kind of containing organosilyl can (methyl) acrylate resin and preparation method thereof of multi-curing, wherein multi-curing group comprises hydroxyl, epoxy group(ing) and double bond.This resin can keep the performance such as hardness, gloss, resistance to chemical attack of (methyl) acrylate resin, overcomes again the poor toughness of film, the shortcoming such as not wear-resisting simultaneously.
The technical solution adopted in the present invention is:
A kind of modification (methyl) acrylate resin, described resin has following structural formula:
Wherein M is (methyl) esters of acrylic acid chain link, comprise one or more in methyl acrylate, ethyl propenoate, butyl acrylate, isobutyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, M Cr, butenoic acid ethyl, octadecenic acid butyl ester, ethyl cinnamate, dimethyl maleate, dibutyl maleinate, dioctyl maleate, dimethyl fumarate, DEF
A is the group containing unsaturated double-bond and carboxylic acid, comprise one or more groups formed in vinylformic acid, methacrylic acid, oleic acid, 2-phenylacrylic acid, 3-phenylacrylic acid, 2-perfluoroalkyl acrylate, 3-(2-furyl) vinylformic acid, the acid of 3-iodopropylene, benzyl acrylic
G is the group containing unsaturated double-bond and epoxy group(ing), comprises oligopolymer or the multipolymer of Racemic glycidol (methyl) acrylate monomer or Racemic glycidol (methyl) acrylate,
S is the organosilicon radical containing double bond,
N
1, n
2for being greater than the integer of 1.
Chemical bond between G and A is formed by epoxy and carboxylic acid reaction.
One of shown in the following structure of described organosilicon radical:
Wherein R
1represent monovalent hydrocarbon or the hydrogen atom with 1-20 carbon atom, and n is the integer of more than 1, two R
1it is same or different group;
Wherein R
2represent that replace or unsubstituted, have straight chain or the branched-chain alkenyl of 2-20 carbon atom, and X represents halogen atom, alkoxyl group, phenoxy group or acetoxyl group, three X are same or different groups;
Wherein R
3represent that replace or unsubstituted, that there is 2-20 carbon atom side chain or branched-chain alkenyl, and R
4represent monovalent hydrocarbon, three R
4it is identical or not identical group;
Wherein R
5represent containing the alkyl of 1-20 carbon atom or hydrogen atom, and n be greater than 1 integer, two R
5same or different alkyl or hydrogen atom, R
6represent that replace or unsubstituted, there is straight chain or the branched-chain alkenyl of 2-20 carbon atom, R
7represent hydrogen or monovalent hydrocarbon.
A kind of preparation method of modification (methyl) acrylate resin, comprises the following steps:
(1) preparation of (methyl) acrylate, (methyl) glycidyl acrylate and Organosiliconcopolymere intermediate
Under the condition passing into rare gas element, solvent 1 is heated to 60 DEG C-90 DEG C, slowly adds monomer 1, monomer 2, initiator, molecular weight regulator, organosilyl mixed solution containing double bond, within 1 hour-6 hours, add; Architecture heat preservation 2 hours-10 hours, is warming up to 100 DEG C-130 DEG C, and is incubated 0.5 hour-4 hours, obtains multipolymer intermediate,
(2) preparation of modification (methyl) acrylate resin
The multipolymer intermediate that step (1) obtains is cooled to less than 60 DEG C, pass into air or other gases containing oxygen, add monomer 3, stopper, catalyzer, then 70 DEG C-100 DEG C are warmed up to, be incubated 2 hours-10 hours, system cools to less than 60 DEG C, adds stopper and solvent 2 stirs again, obtains modification (methyl) acrylate resin.
Organosilicon containing double bond used is organosilane monomer containing unsaturated double-bond or contains organosilyl macromole.
Described monomer 1 is (methyl) acrylic ester monomer, comprises methyl acrylate, ethyl propenoate, butyl acrylate, isobutyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, M Cr, butenoic acid ethyl, octadecenic acid butyl ester, ethyl cinnamate, dimethyl maleate, dibutyl maleinate, dioctyl maleate, dimethyl fumarate, one or more in DEF, described monomer 2 is the compound containing unsaturated double-bond and epoxy group(ing), comprise oligopolymer or the multipolymer of Racemic glycidol (methyl) acrylate monomer or Racemic glycidol (methyl) acrylate, described monomer 3 is the compound containing unsaturated double-bond and hydroxy-acid group, comprises vinylformic acid, methacrylic acid, oleic acid, 2-phenylacrylic acid, 3-phenylacrylic acid, 2-perfluoroalkyl acrylate, 3-(2-furyl) vinylformic acid, the acid of 3-iodopropylene, one or more in benzyl acrylic, described initiator is azo-initiator, organic peroxy class initiator or oxidation-reduction class initiator.
Described initiator is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyl, dibenzoyl peroxide, peroxy dicarbonate ethylhexyl, t-butyl hydrogen peroxide, Potassium Persulphate, hydrogen peroxide, potassium permanganate-oxalic acid, naphthoic acid be cuprous-dibenzoyl peroxide, hydrogen peroxide-Sulfothiorine.
Described molecular weight regulator is aliphatics mercaptan, tetracol phenixin, dithioesters, iodoform, 1-chloro-1-iodine alkane, sodium bisulfite, mercaptoethanol, mercaprol, Thiovanic acid, thiohydracrylic acid, sodium hypophosphite, in sodium formiate one or more, described catalyzer is triethylamine, trolamine, N, N-diethyl benzylamine, tetraethylammonium bromide, etamon chloride, triethylbenzyl ammonia chloride, triphenylphosphine, one or more in benzyltriphenylphosphonium bromide phosphine, stopper used is benzoquinones, first quinone, nitro-compound, arylamine, phenols, sulfocompound, oxygen, one or more in sulphur etc.
Described solvent 1 and solvent 2 are one or more in ethanol, Virahol, butanols, benzylalcohol, ether, tetrahydrofuran (THF), dioxane, acetone, butanone, pimelinketone, ethyl acetate, propyl acetate, butylacetate, benzene,toluene,xylene, Diethylene Glycol contracting methyl ether, propylene glycol monomethyl ether, ethoxyethylether, wherein, solvent 1 and solvent 2 can be identical solvents, also can be different solvents.
Compared with prior art, the invention has the beneficial effects as follows:
1. the present invention introduces organosilicon radical in the molecular chain of (methyl) acrylate resin, changes the distributing pattern that molecular chain is original, reduces fragility, increases snappiness, overcomes the shortcoming that methacrylate-based monomer copolymeric material fragility is large.
2. introduce three kinds of curing groups hydroxyls, epoxy group(ing) and unsaturated double-bonds, hydroxyl thermofixation, epoxy group(ing) thermofixation, UV-light can cause cationic curing, and double bond UV-light can cause radically curing, simultaneously on polymkeric substance containing organosilicon.Resin of the present invention has three kinds of curing groups, can solidify in many ways, heat, UV-light, moisture, air curing can be realized step by step, one or both groups are selected first to solidify, obtain pliable and tough material, adhesion, can be longer with the timed interval of secondary processing, just to deposit, in the process of secondary processing, then solidification obtains the good material of high rigidity, toughness completely., increase the scope of finishing in secondary processing process.Solidification process easily controls, and effectively can reduce the large and oxygen of the cure shrinkage that occurs in single ultraviolet light polymerization and hinder phenomenon.And then keep the performance such as hardness, gloss, resistance to chemical attack, overcome again the poor toughness of film, the shortcoming such as not wear-resisting simultaneously.
3. modification of the present invention (methyl) acrylate resin may be used for the fields such as coating, sizing agent, ink.
4. during synthetic resins intermediate, adopt the mode added continuously to feed in raw material, batch charging can be avoided or first add a part of mode adding surplus stock more continuously feeding in raw material, in the copolymerization of (methyl) acrylate monomer, due to the difference of reactivity ratio, skewness in each monomer polymerization to polymer, the problem causing performance to decline to some extent occurs, and is conducive to reducing molecular weight distributing index.
Embodiment
Modification provided by the invention (methyl) acrylate resin, be the copolymer resin that a kind of (methyl) acrylic equivalent weight is 100 g/eq-300g/eq, hydroxyl value is 20 mgKOH/g-500mgKOH/g, oxirane value is 0.1 mol/100g-6mol/100g, organosilicon weight content is 0.1%-50%, molecular weight is 5000-100000, described multi-curing group comprises hydroxyl, epoxy group(ing) and double bond.Below in detail the present invention will be described.
< monomer >
The present invention's monomer 1 used is (methyl) acrylic ester monomer, including but not limited to one or more in methyl acrylate, ethyl propenoate, butyl acrylate, isobutyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, M Cr, butenoic acid ethyl, octadecenic acid butyl ester, ethyl cinnamate, dimethyl maleate, dibutyl maleinate, dioctyl maleate, dimethyl fumarate, DEF.
The present invention's monomer 2 used is the compound containing epoxy group(ing) and unsaturated double-bond, including but not limited to oligopolymer or the multipolymer of Racemic glycidol (methyl) acrylate monomer or Racemic glycidol (methyl) acrylate.
The present invention's monomer 3 used is the monomer containing carboxyl and double bond, including but not limited to one or more in vinylformic acid, methacrylic acid, oleic acid, 2-phenylacrylic acid, 3-phenylacrylic acid, 2-perfluoroalkyl acrylate, 3-(2-furyl) vinylformic acid, the acid of 3-iodopropylene, benzyl acrylic.
< organosilicon >
Organosilicon used can be organosilane monomer containing unsaturated double-bond or containing organosilyl macromole, shown in the following structure of organosilicon radical:
Wherein R
1represent monovalent hydrocarbon or the hydrogen atom with 1-20 carbon atom, and n is the integer of more than 1, two R
1it can be same or different group;
Wherein R
2represent that replace or unsubstituted, have straight chain or the branched-chain alkenyl of 2-20 carbon atom, and X represents halogen atom, alkoxyl group, phenoxy group or acetoxyl group, three X can be same or different groups;
Wherein R
3represent that replace or unsubstituted, that there is 2-20 carbon atom side chain or branched-chain alkenyl, and R
4represent monovalent hydrocarbon, three R
4it can be identical or not identical group;
Wherein R
5represent containing the alkyl of 1-20 carbon atom or hydrogen atom, and n be greater than 1 integer, two R
5can be same or different alkyl or hydrogen atom, R
6represent that replace or unsubstituted, there is straight chain or the branched-chain alkenyl of 2-20 carbon atom, R
7represent hydrogen or monovalent hydrocarbon.
< initiator >
As the initiator of building-up reactions, including but not limited to initiator as azo-initiators such as Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyls; The organic peroxy class initiators such as dibenzoyl peroxide, peroxy dicarbonate ethylhexyl, t-butyl hydrogen peroxide; The inorganic peroxy such as Potassium Persulphate, hydrogen peroxide class initiator; Potassium permanganate-oxalic acid, naphthoic acid be cuprous-the oxidation-reduction class initiator such as dibenzoyl peroxide, hydrogen peroxide-Sulfothiorine.
< solvent >
Solvent 1 and solvent 2 can be enumerated as alcohols such as ethanol, Virahol, butanols, benzylalcohols; The ethers such as ether, tetrahydrofuran (THF), dioxane; The ketones such as acetone, butanone, pimelinketone; The lipids such as ethyl acetate, propyl acetate, butylacetate; Also can be the aromatics such as benzene,toluene,xylene; One or more in the ether alcohols such as Diethylene Glycol contracting methyl ether, propylene glycol monomethyl ether, ethoxyethylether, solvent 1 and solvent 2 can be identical solvents, also can be different solvents.
< molecular weight regulator >
As the molecular weight regulator of building-up reactions, including but not limited to aliphatics mercaptan, tetracol phenixin, dithioesters, iodoform, 1-chloro-1-iodine alkane, sodium bisulfite, mercaptoethanol, mercaprol, Thiovanic acid, thiohydracrylic acid, sodium hypophosphite, sodium formiate etc. wherein one or more.
< stopper >
As stopper, can select as one or more in benzoquinones, first quinone, nitro-compound, arylamine, phenols, sulfocompound, oxygen, sulphur etc.
< catalyzer >
As the catalyzer of building-up reactions, including but not limited to tertiary amines such as triethylamine, trolamine, N, N-diethyl benzylamines; The quaternary ammonium salts such as tetraethylammonium bromide, etamon chloride, triethylbenzyl ammonia chloride; One or more in the phosphine classes such as triphenylphosphine, benzyltriphenylphosphonium bromide phosphine.
< sheet base >
Basement membrane of the present invention is for supporting resin protective layer, and therefore basement membrane should have suitable mechanical property.Basement membrane example materials used comprise comprise polyethylene terephthalate, Polyethylene Naphthalate etc. polyester, polyethylene, polypropylene, polymeric amide, pi, poly-(methyl) acrylate of alkyl, (methyl) acrylate copolymer, cellulose triacetate, cellulose diacetate, polyvinyl chloride and vinyl acetate copolymer, tetrafluoroethylene and poly-trifluoro-ethylene.Prior applicability be polyethylene terephthalate, Polyethylene Naphthalate.Basement membrane thickness can be 10 μm ~ 300 μm, basement membrane material used be can be passed through modification or without the resin of modification.Membrane surface through corona, plasma treatment or can not process.
The preparation method of resin of the present invention, comprises the following steps:
(1) preparation of (methyl) acrylate, (methyl) glycidyl acrylate and Organosiliconcopolymere intermediate
Under the condition passing into rare gas element, solvent 1 is heated to 60 DEG C-90 DEG C, slowly adds monomer 1, monomer 2, initiator, molecular weight regulator, organosilyl mixed solution containing double bond, within 1 hour-6 hours, add; Architecture heat preservation 2 hours-10 hours, is warming up to 100 DEG C-130 DEG C, and is incubated 0.5-4 hour, obtains multipolymer intermediate,
(2) preparation of modification (methyl) acrylate resin
The multipolymer intermediate that step (1) obtains is cooled to less than 60 DEG C, pass into air or other gases containing oxygen, add monomer 3, stopper, catalyzer, then 70 DEG C-100 DEG C are warmed up to, be incubated 2 hours-10 hours, system cools to less than 60 DEG C, adds stopper and solvent 2 stirs 30 minutes again, obtains modification (methyl) acrylate resin.
Modification of the present invention (methyl) acrylate resin is coated on base material makes film, through 100 DEG C, 30s semicure, and 1200mJ/cm
2energy ultraviolet solidifies, and obtains solidified coating.
Evaluation method
The mensuration > of < pencil hardness
Pencil hardness is measured, heavy burden 750g, Mitsubishi pencil according to the method that GB/T 6739-2006 paint and varnish pencil method mensuration hardness of paint film provides.
The mensuration > of < wear resistance
Wear resistance measures according to HG/T 4302-2012 surface hardening polyester film wear resistance measuring method, and adopt 0000# Steel Wool, heavy burden is 100 grams.
The mensuration > of < sticking power
Whether with the little lattice drawing lattice device and to draw at surface resin film 100 1mm × 1mm, be seamless the pasting little lattice of scotch tape of 600, then open adhesive tape rapidly with 60 ° of angles by the model that Minnesota Mining and Manufacturing Company produces, observing little lattice edge has and comes off.
If little lattice are without any coming off, result is designated as 5B; If little lattice come off, 0-5 is individual, and result is designated as 4B; If little lattice come off, 5-15 is individual, and result is designated as 3B; If little lattice come off, 15-35 is individual, and result is designated as 2B; If little lattice come off, 35-65 is individual, and result is designated as 1B; If little lattice come off, number is greater than 65, and result is designated as 0B.
< flexible mensuration >
Snappiness measures according to GB/T1731-1993 paint film flexibility assay method.
< adhesive measures >
Adhesive is according to the mensuration of HG/T 2914-1997 film, sheet base anti-adhesive properties.
Below in conjunction with specific embodiment, the present invention is described in detail, but embodiments of the present invention not limit by these embodiments.
Embodiment 1
The synthesis of modification (methyl) acrylate resin intermediate
Agitator is being housed, prolong, nitrogen ingress pipe, in the reaction unit of thermometer, logical nitrogen, add 300 parts of butylacetates, be warming up to 80 DEG C, air in abundant removing reaction unit, start slowly to drip 300 parts of pre-configured glycidyl methacrylate (hereinafter referred to as GMA), 75 parts of methyl methacrylates (hereinafter referred to as MMA), 37 parts of γ-methacryloxypropyl trimethoxy silane, 12 parts of Diisopropyl azodicarboxylates (hereinafter referred to as AIBN), the mixing solutions that 1.5 parts of lauryl mercaptans (hereinafter referred to as DDM) form, slow dropping 3 hours, be incubated 5 hours, then, mixture in reaction unit is warming up to 120 DEG C under the condition passing into nitrogen, be incubated 2 hours, cool, obtain modification (methyl) acrylate resin intermediate.
The preparation of modification (methyl) acrylate resin
Above-mentioned resin intermediate is cooled to 60 DEG C, pass into air, add 122 parts of pre-configured vinylformic acid (hereinafter referred to as AA), 0.8 part of methylbenzoquinone (hereinafter referred to as MEHQ), 0.9 part of triphenylphosphine (hereinafter referred to as TPP) mixing solutions, slowly be warming up to 90 DEG C, continue to pass into air, be incubated 8 hours, be cooled to less than 60 DEG C, add 0.4 part of MEHQ, 250 parts of butanone, fully stir 30 minutes, obtain modification (methyl) acrylate resin.
Embodiment 2
The synthesis of modification (methyl) acrylate resin intermediate
Agitator is being housed, prolong, nitrogen ingress pipe, in the reaction unit of thermometer, logical nitrogen, add 300 parts of butylacetates, be warming up to 60 DEG C, air in abundant removing reaction unit, start slowly to drip 85.7 parts of pre-configured GMA, 226 parts of MMA, 37 parts of γ-methacryloxypropyl trimethoxy silane, 12 parts of AIBN, the mixing solutions of 1.5 parts of DDM compositions, slow dropping 6 hours, be incubated 2 hours, then, mixture in reaction unit is warming up to 130 DEG C under the condition passing into nitrogen, be incubated 0.5 hour, cool, obtain modification (methyl) acrylate resin intermediate.
The synthesis of modification (methyl) acrylate resin
Above-mentioned resin intermediate is cooled to 60 DEG C, pass into air, add 10.9 parts of pre-configured AA, 0.4 part of MEHQ, 0.5 part of TPP mixing solutions, slowly be warming up to 70 DEG C, continue to pass into air, be incubated 10 hours, be cooled to less than 60 DEG C, add 0.2 part of MEHQ, 74 parts of butanone, fully stir 30 minutes, obtain modification (methyl) acrylate resin.
Embodiment 3
The synthesis of modification (methyl) acrylate resin intermediate
Agitator is being housed, prolong, nitrogen ingress pipe, in the reaction unit of thermometer, logical nitrogen, add 300 parts of butylacetates, be warming up to 90 DEG C, air in abundant removing reaction unit, start slowly to drip 214.3 parts of pre-configured GMA, 192.6 parts of butyl methacrylate esters (referred to as BMA), 37 parts of γ-methacryloxypropyl trimethoxy silane, 12 parts of AIBN, the mixing solutions of 1.5 parts of DDM compositions, slow dropping 1 hour, be incubated 2 hours, then, mixture in reaction unit is warming up to 100 DEG C under the condition passing into nitrogen, be incubated 0.5 hour, cool, modification (methyl) acrylate resin intermediate.
The synthesis of modification (methyl) acrylate resin
Above-mentioned resin intermediate is cooled to 60 DEG C, pass into air, add 17.4 parts of pre-configured AA, 0.4 part of MEHQ, 0.5 part of TPP mixing solutions, slowly be warming up to 110 DEG C, continue to pass into air, be incubated 2 hours, be cooled to less than 60 DEG C, add 0.2 part of MEHQ, 176 parts of butanone, fully stir 30 minutes, obtain modification (methyl) acrylate resin.
Embodiment 4
The synthesis of modification (methyl) acrylate resin intermediate
Agitator is being housed, prolong, nitrogen ingress pipe, in the reaction unit of thermometer, logical nitrogen, add 300 parts of butylacetates, be warming up to 75 DEG C, air in abundant removing reaction unit, start slowly to drip 300 parts of pre-configured GMA, 15 parts of MMA, 222 parts of γ-methacryloxypropyl trimethoxy silane, 12 parts of AIBN, the mixing solutions of 1.5 parts of DDM compositions, slow dropping 4 hours, be incubated 7 hours, then, mixture in reaction unit is warming up to 120 DEG C under the condition passing into nitrogen, be incubated 1 hour, cool, obtain modification (methyl) acrylate resin intermediate.
The synthesis of modification (methyl) acrylate resin
Above-mentioned resin intermediate is cooled to 60 DEG C, pass into air, add 122 parts of pre-configured AA, 0.4 part of MEHQ, 0.5 part of TPP mixing solutions, slowly be warming up to 80 DEG C, continue to pass into air, be incubated 6 hours, be cooled to less than 60 DEG C, add 0.2 part of MEHQ, 359 parts of butanone, fully stir 30 minutes, obtain modification (methyl) acrylate resin.
Embodiment 5
Carry out according to mode in the same manner as in Example 1, difference is by 37 parts of γ-methacryloxypropyl trimethoxy silane in 37 parts of propenyl Trimethoxy silanes (A-151, U.S.'s carbon connection) alternate embodiment 1.
Comparative example 1
In the reaction unit that agitator, prolong, air leading-in conduit, thermometer are housed, blowing air, adds 520 parts of bisphenol A epoxide resins, be heated to 100 DEG C, add the 95 parts of AA prepared in advance, 1.23 parts of TPP and 1.85 part of MEHQ mixing solutionss, react 5 hours, obtain epoxy monoacrylate;
In the reaction unit that agitator, prolong, air leading-in conduit, thermometer are housed, logical nitrogen, add 87 parts of tolylene diisocyanates, be heated to 60 DEG C, add the 142 parts of hydroxy silicon oils (hydroxy radical content 6%) and 0.3 part of dibutyl tin laurate mixing solutions that prepare in advance, dropwise rear continuation reaction 2.5 hours, add the 29 parts of Hydroxyethyl acrylates and 0.05 part of MEHQ prepared in advance, reaction is warming up to 100 DEG C, react 2 hours, obtain one end and also have-the urethane acrylate of NCO group.
By above-mentioned epoxy monoacrylate and urethane acrylate mixing, 90 DEG C are reacted 4 hours, obtain modified epoxy acrylate resin.
The making of coating
Obtained can be added 2 parts of N3300,93 parts of butanone, 2.5 part 184 in multi-curing organic-silicon-modified (methyl) acrylate resin 100 parts, and 1.3 parts of UV6992, fully mix, coating film forming, 100 DEG C, 30s semicure, 1200mJ/cm
2energy ultraviolet solidifies, and obtains solidified coating.Test performance is in table 1.
Comparative example 2
The synthesis of modification (methyl) acrylate resin intermediate
Agitator is being housed, prolong, nitrogen ingress pipe, in the reaction unit of thermometer, logical nitrogen, add 75 parts of butylacetates, 75 parts of GMA, 18.7 part MMA, 9.3 parts of propenyl Trimethoxy silanes, the mixture of 3 parts of AIBN and 0.4 part DDM, air in abundant removing reaction unit, be warming up to 75 DEG C, be incubated 1 hour, start slowly to drip 225 parts of pre-configured GMA, 56.5 part MMA, 28 parts of propenyl Trimethoxy silanes, 9 parts of AIBN, the mixing solutions that 1.1 parts of lauryl mercaptan DDM form, slow dropping 4 hours, be incubated 7 hours, then, mixture in reaction unit is warming up to 120 DEG C under the condition passing into nitrogen, be incubated 1 hour, cool, obtain modification (methyl) acrylate resin intermediate.
The synthesis of modification (methyl) acrylate resin
Above-mentioned resin intermediate is cooled to 60 DEG C, pass into air, add 122 parts of pre-configured AA, 0.4 part of MEHQ, 0.5 part of TPP mixing solutions, slowly be warming up to 80 DEG C, continue to pass into air, be incubated 6 hours, be cooled to less than 60 DEG C, add 0.2 part of MEHQ, 359 parts of butanone, fully stir 30 minutes, obtain modification (methyl) acrylate resin.
Table 1 performance index
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 |
| Pencil hardness after thermofixation | 4B | 4B | 3B | 4B | 3B | B | 2B |
| Pencil hardness after ultraviolet light polymerization | 3H | 2H | 2H | 2H | 3H | 2H | 2H |
| Sticking power | 5B | 4B | 4B | 5B | 5B | 2B | 4B |
| Snappiness after thermofixation | Φ2mm | Φ2mm | Φ2mm | Φ2mm | Φ2mm | Φ5mm | Φ2mm |
| Wear resistance | >100 | >100 | >100 | >100 | >100 | 20 | 80 |
| Adhesive (after thermofixation) | √ | √ | √ | √ | √ | × | × |
| Adhesive (after ultraviolet light polymerization) | √ | √ | √ | √ | √ | √ | √ |
Evaluate and judge: adhesive: "×" represents adhesion, " √ " represents adhesion, and " △ " represents that only a few has adhesion.
Adopt modification (methyl) acrylate resin that obtains of the present invention can step curing, after the first step solidification, there is plasticity, adhesion, do not need to add release layer rolling, can reprocess shaping after rolling, make goods, it is good that film has higher pencil hardness wear resistance after ultraviolet light polymerization.As can be seen from table 1 data, adopt the resin that the present invention obtains, after thermofixation, pencil hardness is low, and all at below 2B, after thermofixation, snappiness is good, and meet Φ 2mm silk rod, after ultraviolet light polymerization, pencil hardness is all higher; Material antiblocking, abrasion resistant effect are good.The compound of epoxide group is provided to adopt bisphenol A type epoxy resin in comparative example 1, after synthesized resin thermosets, pencil hardness is high, be unfavorable for rolling and processing, adopt in comparative example 2 and first add the mode that a batch of material adds surplus stock more continuously and prepare, gained resin over-all properties declines.
Claims (9)
1. modification (methyl) acrylate resin, is characterized in that, described resin has following structural formula:
Wherein M is (methyl) esters of acrylic acid chain link, comprise one or more in methyl acrylate, ethyl propenoate, butyl acrylate, isobutyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, M Cr, butenoic acid ethyl, octadecenic acid butyl ester, ethyl cinnamate, dimethyl maleate, dibutyl maleinate, dioctyl maleate, dimethyl fumarate or DEF
A is the group containing unsaturated double-bond and carboxylic acid, comprise one or more groups formed in vinylformic acid, methacrylic acid, oleic acid, 2-phenylacrylic acid, 3-phenylacrylic acid, 2-perfluoroalkyl acrylate, 3-(2-furyl) vinylformic acid, the acid of 3-iodopropylene or benzyl acrylic
G is the group containing unsaturated double-bond and epoxy group(ing), comprises oligopolymer or the multipolymer of Racemic glycidol (methyl) acrylate monomer or Racemic glycidol (methyl) acrylate,
S is the organosilicon radical containing double bond,
N
1, n
2for being greater than the integer of 1.
2. modification according to claim 1 (methyl) acrylate resin, is characterized in that, the chemical bond between G and A is formed by epoxy and carboxylic acid reaction.
3. modification according to claim 1 (methyl) acrylate resin, is characterized in that, described organosilicon radical is one of shown in following structure:
Wherein R
1represent monovalent hydrocarbon or the hydrogen atom with 1-20 carbon atom, and n is the integer of more than 1, two R
1it is same or different group;
，
Wherein R
2represent that replace or unsubstituted, that have 2-20 carbon atom straight chain or branched-chain alkenyl, and X represents halogen atom, alkoxyl group, phenoxy group or acetoxyl group, three X are same or different groups;
Wherein R
3represent that replace or unsubstituted, that there is 2-20 carbon atom side chain or branched-chain alkenyl, and R
4represent monovalent hydrocarbon, three R
4it is identical or not identical group;
Wherein R
5represent containing the alkyl of 1-20 carbon atom or hydrogen atom, and n be greater than 1 integer, two R
5same or different alkyl or hydrogen atom, R
6represent that replace or unsubstituted, there is straight chain or the branched-chain alkenyl of 2-20 carbon atom, R
7represent hydrogen or monovalent hydrocarbon.
4. a preparation method for modification (methyl) acrylate resin, is characterized in that, comprise the following steps:
(1) preparation of (methyl) acrylate, (methyl) glycidyl acrylate and Organosiliconcopolymere intermediate
Under the condition passing into rare gas element, solvent 1 is heated to 60 DEG C-90 DEG C, slowly adds monomer 1, monomer 2, initiator, molecular weight regulator, organosilyl mixed solution containing double bond, within 1 hour-6 hours, add; Architecture heat preservation 2 hours-10 hours, is warming up to 100 DEG C-130 DEG C, and is incubated 0.5 hour-4 hours, obtains multipolymer intermediate,
(2) preparation of modification (methyl) acrylate resin
The multipolymer intermediate that step (1) obtains is cooled to less than 60 DEG C, pass into air or other gases containing oxygen, add monomer 3, stopper, catalyzer, then 70 DEG C-100 DEG C are warmed up to, be incubated 2 hours-10 hours, system cools to less than 60 DEG C, adds stopper and solvent 2 stirs again, obtains modification (methyl) acrylate resin.
5. the preparation method of modification according to claim 4 (methyl) acrylate resin, is characterized in that, the organosilicon containing double bond used is organosilane monomer containing unsaturated double-bond or according to claim 3ly contains organosilyl macromole.
6. the preparation method of modification according to claim 5 (methyl) acrylate resin, is characterized in that, described monomer 1 is (methyl) acrylic ester monomer, comprises methyl acrylate, ethyl propenoate, butyl acrylate, isobutyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, M Cr, butenoic acid ethyl, octadecenic acid butyl ester, ethyl cinnamate, dimethyl maleate, dibutyl maleinate, dioctyl maleate, dimethyl fumarate, one or more in DEF, described monomer 2 is the compound containing unsaturated double-bond and epoxy group(ing), comprise oligopolymer or the multipolymer of Racemic glycidol (methyl) acrylate monomer or Racemic glycidol (methyl) acrylate, described monomer 3 is the compound containing unsaturated double-bond and hydroxy-acid group, comprises vinylformic acid, methacrylic acid, oleic acid, 2-phenylacrylic acid, 3-phenylacrylic acid, 2-perfluoroalkyl acrylate, 3-(2-furyl) vinylformic acid, the acid of 3-iodopropylene, one or more in benzyl acrylic, described initiator is azo-initiator, organic peroxy class initiator or oxidation-reduction class initiator.
7. the preparation method of modification according to claim 6 (methyl) acrylate resin, it is characterized in that, described initiator is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyl, dibenzoyl peroxide, peroxy dicarbonate ethylhexyl, t-butyl hydrogen peroxide, Potassium Persulphate, hydrogen peroxide, potassium permanganate-oxalic acid, naphthoic acid be cuprous-dibenzoyl peroxide, hydrogen peroxide-Sulfothiorine.
8. the preparation method of modification according to claim 7 (methyl) acrylate resin, it is characterized in that, described molecular weight regulator is aliphatics mercaptan, tetracol phenixin, dithioesters, iodoform, 1-chloro-1-iodine alkane, sodium bisulfite, mercaptoethanol, mercaprol, Thiovanic acid, thiohydracrylic acid, sodium hypophosphite, in sodium formiate one or more, described catalyzer is triethylamine, trolamine, N, N-diethyl benzylamine, tetraethylammonium bromide, etamon chloride, triethylbenzyl ammonia chloride, triphenylphosphine, one or more in benzyltriphenylphosphonium bromide phosphine, stopper used is benzoquinones, first quinone, nitro-compound, arylamine, phenols, sulfocompound, oxygen, one or more in sulphur etc.
9. the preparation method of modification according to claim 8 (methyl) acrylate resin, it is characterized in that, described solvent 1 and solvent 2 are one or more in ethanol, Virahol, butanols, benzylalcohol, ether, tetrahydrofuran (THF), dioxane, acetone, butanone, pimelinketone, ethyl acetate, propyl acetate, butylacetate, benzene,toluene,xylene, Diethylene Glycol contracting methyl ether, propylene glycol monomethyl ether, ethoxyethylether, wherein, solvent 1 and solvent 2 are identical solvents, are also different solvents.
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