CN101613434B - Alcohol soluble polyacrylate resin and preparation method and application thereof - Google Patents
Alcohol soluble polyacrylate resin and preparation method and application thereof Download PDFInfo
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- CN101613434B CN101613434B CN 200910041128 CN200910041128A CN101613434B CN 101613434 B CN101613434 B CN 101613434B CN 200910041128 CN200910041128 CN 200910041128 CN 200910041128 A CN200910041128 A CN 200910041128A CN 101613434 B CN101613434 B CN 101613434B
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Abstract
The invention discloses an alcohol soluble polyacrylate resin and a preparation method and an application thereof; the preparation method comprises the following steps: taking 260-800 parts of alcohols solvent, adding the solvent in a reaction kettle with a mixer, a reflux condenser, a heating jacket and a nitrogen covering layer, then heating the system to 70-150 DEG C, mixing the mixture for 10-30min; adding acrylic ester used as hard monomers, acrylic ester used as soft monomers, polar functional group monomers, organosilane monomers and initiator to react for 4-7h and obtain alcohol soluble polyacrylate resin. The alcohol soluble polyacrylate resin prepared by the method of the invention has no excitant odour, the number-average molar mass is 10,000-200,000, the molecular weight distribution is 1.1-4 and the Brookfield viscosity of the resin system is 100-5000cp. The coating which is prepared by mixing the resin with other pigments, fillers and assistants can be applied in glass, aluminium coil and polypropylene plastic for surface decoration and protective function.
Description
Technical field
The present invention relates to a kind of alcohol soluble polyacrylate resin and preparation method thereof and application, this resin can be used as the main composition resin of environmentally friendly coating or environment-friendly ink.
Background technology
The discharging of the volatile organic compounds (VOC) of conventional solvent type coating has very havoc effect to the ecotope of the earth, and HUMAN HEALTH also is subjected to great threat simultaneously.Therefore, development greenization environmental friendliness coating becomes an important directions of current coatings industry development.Have the friendly type coating products of novel environmentals such as water-borne coatings, powder coating, ultraviolet-curing paint, high solid coating at present on the market.Water soluble paint is to be film forming matter with the water soluble resin, is representative with polyvinyl alcohol and various modifier thereof, in addition also has water-soluble Synolac, water-soluble Resins, epoxy and inorganic polymer water-base resin etc.
Some tradition use the field of solvent reducible coatings can't big area to be replaced by water-borne coatings at present, as woodwork coating.Enterprise's turnout of water-borne coatings is little, and the market share is smaller, a lot of enterprises only with it as technical reserve.Water-borne coatings is applied the major obstacle of being obstructed by wide scope, says from technical elements to mainly contain: (1) evaporation of water latent heat height, and film forming is longer time of drying, especially under the low temperature and high relative humidity environment; (2) contain the easy hydrolysis of resin of ester bond, so that the package stability of coating is relatively poor; (3) film in residual hydrophilic radical can reduce the water tolerance and the Corrosion Protection of filming; (4) surface tension of water is bigger, and is relatively poor to the sticking power of base material, and causes that easily the defective of filming is as foaming, pin hole etc.; (5) wetting and dispersed relatively poor to color stuffing easily produces phenomenons such as loose colour and layering.
The alcohol soluble paint is the environment-friendly type coating that receives much attention in recent years, and kinds such as alcohol soluble polyacrylate coating, alcohol soluble polyurethane coating, pure dissolubility epoxy coating are arranged.Can prepare that with alcoholic solvent the polyacrylate resin of good linkage force to be arranged be the key of preparation alcohol soluble polyacrylate coating.Spirit-soluble resin is the main film-forming components of pure soluble paint, and it is to obtain pure dissolubility energy by introduce enough polar groups or pure dissolubility segment in fluoropolymer resin.Alcohol soluble polyacrylate resin adopts " green solvent " in preparation and application process, as methyl alcohol, ethanol, propyl alcohol, propyl carbinol, isopropylcarbinol, ethylene glycol, propylene glycol, 1, alcohols materials such as 4-butyleneglycol, Virahol, hexanol are as the main volatile solvent, and part is added the environmental protection solubility promoter.Alcohol soluble polyacrylate coating has significantly reduced the pollution to environment in film process, and coating application and curing process are simple, levelling property and water tolerance are better, and sticking power is good on various grounds, have overcome the shortcoming of water-borne coatings constructional difficulties and water resistance difference.
Publication number be CN 101230125 the Chinese invention patent Shen Qing Publication a kind of alcohol-soluble polyurethane soluble in water and preparation method thereof.Add 1～20% wetting ability chainextender in preparation in this resin process, made that this resin can be water-soluble, can be used on timber, soft packaging and field such as laminated.But this resin possess hydrophilic property causes its poor water resistance, has limited it in the decoration on surfaces such as glass, plastics, aluminium coiled material and the application of function protection.
Publication number is the preparation method that the Chinese invention patent of CN 1353128 has been announced a kind of polyamide resin used for alcohol-soluble ink.The preparation method of this resin prepares in the pure soluble polyamide reaction system at dimeracid and quadrol, adds properties-correcting agent m-phthalic acid sulfonate.But pure soluble polyamide bad mechanical property has limited the occasion of its application, and is general only as resin for printing ink.
Summary of the invention
The object of the present invention is to provide the friendly type alcohol soluble polyacrylate resin of a kind of novel environmental, this alcohol soluble polyacrylate resin has good pure dissolubility, mechanical property, substrate adhesion and water resistance.
The principle of the invention: ethanol is important organic solvent, because it does nontoxic and mature preparation process, cheap soon, is called as " green solvent " of coating, becomes the main ingredient of alcoholic solvent in the coating in recent years gradually.The ethanol boiling point is 78.32 ℃, and specific refractory power is 1.3614, and surface tension (20 ℃) is 22.27 * 10
-3N/m, specific heat capacity (20 ℃) is 2.42kJ/ (kg*K), solubility parameter δ is 12.7.Because the ethanol rate of volatilization is fast, it is wrinkling that single employing ethanol can cause resin coating film to take place at film process as the alcohol soluble polyacrylate resin solvent, turns white paint film defect phenomenons such as shrinkage cavity.Therefore, adopt ethanol and other slow-evaporating solvents, as propyl alcohol, propyl carbinol, isopropylcarbinol, ethylene glycol, propylene glycol or 1, the 4-butyleneglycol mixes by a certain percentage, and it is moderate to be made into rate of volatilization, thereby avoids the generation of paint film defect phenomenon.And in the alcohols mixed solvent, add the certain proportion solubility promoter, help to strengthen the linkage force of alcohols mixed solvent and polyacrylate resin Semi-polarity functional group, improve the storage-stable performance of alcohol soluble polyacrylate resin.
Acrylate resin be meant acrylate or methacrylic ester homopolymer and with the multipolymer of other vinyl monomer.Developing rapidly of acrylate resin is because it has excellent comprehensive performances, as its weather resistance, the transparency, stability, is that also it can obtain the character of different hardness, suppleness and other requirement through the adjusting of prescription.In the synthol soluble polyacrylate resin process,, reduced the polymerization degree of polymkeric substance, caused alcohol soluble polyacrylate resin to can not get the ideal molecular weight because alcoholic solvent has higher chain transfer constant.Therefore, in synthol soluble polyacrylate resin process, can suitably reduce polymerization temperature, suitably reduce initiator amount, suitably increase the drop rate of mix monomer, suitably adopt semicontinuous dripping method, to obtain alcohol soluble polyacrylate resin polymkeric substance with desired molecular weight.
The linkage force of polyacrylate resin and alcoholic solvent and the solubility parameter of solvent have certain relation.According to the thermodynamic principles of solution theory, close or when equating when the solubility parameter of polymkeric substance and solvent, mixture heat Δ Hm=0, polymkeric substance and solvent mix fully, promptly are " similar mixing " principles.And alcoholic solvent contains high-load relatively hydrogen bond, belongs to the hydrogen bond high polar solvent of type of giving and accepting.The solubility parameter scope of alcoholic solvent is 11～16.Acrylate hard monomer homopolymer, as polymethylmethacrylate, polyethyl methacrylate, polyisopropyl methacrylate, polyacrylamide, PMAm, polystyrene etc., its solubility parameter is 5～8.Acrylate soft monomer homopolymer, as polyethyl acrylate, polyacrylic acid n-propyl, polyacrylic acid isopropyl ester, the positive butyl ester of polyacrylic acid, polyisobutyl acrylate, polyacrylic acid n-pentyl ester, the just own ester of polyacrylic acid, polyacrylic acid n-octyl, poly-n-propyl methacrylate, Vinalac 5920, polyisobutyl methacrylate, polymethyl acrylic acid n-pentyl ester, polymethyl acrylic acid own ester etc. just, its solubility parameter is 7～13.
The acrylate monomer that contains carboxyl, hydroxyl, amide group, amino, the contour polar functional group of ether, as poly-hydroxyl acrylic, polyacrylic acid hydroxyl methyl esters, Poly(Hydroxyethyl Methacrylate), polyacrylic acid hydroxypropyl acrylate, poly hydroxy ethyl acrylate, polyacrylic acid, polymethyl acrylic acid, polymethyl acrylic acid hydroxypropyl acrylate, polyacrylic acid dimethylamine ethyl ester, polyacrylic acid diethylamine ethyl ester, polymethyl acrylic acid dimethylamine ethyl ester, polymethyl diethylammonium salt ethyl ester, poly-maleic anhydride or polyacrylic acid-β-ethoxy ethyl ester, its solubility parameter is 9～14.In order to obtain good resinol dissolubility, preferably contain the acrylate monomer of carboxyl, amide group.
Polymkeric substance is " similar mixing " to the judgment basis that can solvent mix, and is after deliberation, for the high polar system that has hydrogen bond, but not necessarily suitable.Although the solubility parameter that is polymkeric substance and solvent is identical, its solvency power might not be best, has the difference meeting better on the contrary between the two slightly.So during design alcohol soluble polyacrylate resin prescription, should consider the situation of Theoretical Calculation result and experimental result deviation.
The silicone-modified polyacrylate resin has good thermotolerance, temperature-change resistance, water-fast protection against the tide, ageing-resistant performance.In alcohol soluble polyacrylate resin, introduce the Application Areas that the organosilane monomer can effectively enlarge alcohol soluble polyacrylate resin.It is free-radical polymerized to utilize double bond containing organosilane monomer and acrylic ester monomer to carry out, thereby introduces the silicon segment on main polymer chain, makes the organosilicon acrylic resin of stable performance.This method is one of at present the most frequently used method.Can carry out free-radical polymerized organosilane monomer with acrylate monomer is vinyl trichloro silane, vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three (beta-methoxy-oxyethyl group) silane, γ-An Bingjisanyiyangjiguiwan, γ-glycidoxypropyltrime,hoxysilane, γ-(methacryloxy) propyl trimethoxy silicane, N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan, γ-urea groups propyl-triethoxysilicane, γ-r-chloropropyl trimethoxyl silane or γ-chloropropyl triethoxysilane.
Preparation organic-silane-modified acrylic ester resin mainly contains two kinds of approach, and first kind is the physically modified method, and this method is simple to operate, but organosilane and acrylate structural, polarity differ bigger, cause the consistency of the two poor, have reduced the effect of modification.Second kind is chemic modified method, is to contain the organosilane of vinyl double bond by in the free-radical polymerized introducing acrylate molecule.To be organosilanes join on the acrylate molecule with the form of chemical bond the chemic modified method characteristics, overcomes the defective of physically modified method consistency difference.The preferred chemic modified method of preparation technology of the present invention
Organosilicon chemical modification acrylate resin is divided into polycondensation method, silicon hydrogen additive process, radical polymerization, interact network method etc. by reaction mechanism.Can be divided into organosilicon performed polymer/acrylate prepolymer method, organosilicon performed polymer/acrylate monomer method, organosilane monomer/acrylate monomer method, organosilane monomer/acrylate prepolymer method by the reaction raw materials form.The preferred organosilane monomer of preparation technology of the present invention/acrylate monomer method.Organosilicon chemical modification acrylate resin can be divided into mass polymerization, solution polymerization process, emulsion (microemulsion) polymerization by reactive mode.Preparation technology's preferred solution polymerization of the present invention.Can be divided into interpolation in early stage and later stage interpolation by the organosilane addition manner.The excellent preparation technology of the present invention selects the later stage to add.
Purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of alcohol soluble polyacrylate resin comprises the steps and processing condition:
The first step is got 260～800 parts of alcoholic solvents in mass fraction, is added in the reactor that agitator, reflux condensate device, heating jacket and blanket of nitrogen are housed, and system is warming up to 70～150 ℃ then, and the 500rpm rotating speed stirs 10～30min down; Described alcoholic solvent is methyl alcohol, ethanol, propyl alcohol, propyl carbinol, isopropylcarbinol, ethylene glycol, propylene glycol, 1, one or more in 4-butyleneglycol, Virahol and the hexanol;
Second step is in mass fraction, get 73～220 parts of esters of acrylic acid hard monomers, 53～160 parts of esters of acrylic acid soft monomers, 6～20 parts of polar functional group monomers and 2～10 parts of initiators mix, and drip then in the reactor, drip off in 1～2.5 hour, reacted again 3～5 hours, drip 2～40 parts of organosilane monomers then, reacted 1～2 hour, make alcohol soluble polyacrylate resin;
Described acrylate hard monomer is methyl methacrylate, Jia Jibingxisuanyizhi, isopropyl methacrylate, acrylamide, Methacrylamide, vinylbenzene or vinyl cyanide;
Described acrylate soft monomer is ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, vinylformic acid n-pentyl ester, the just own ester of vinylformic acid, vinylformic acid n-octyl, n propyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic acid n-pentyl ester, the just own ester of methacrylic acid or n octyl methacrylate;
Described polar functional group acrylate monomer is hydroxyl acrylic, vinylformic acid hydroxyl methyl esters, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, vinylformic acid, methacrylic acid, Rocryl 410, vinylformic acid dimethylamine ethyl ester, vinylformic acid diethylamine ethyl ester, dimethylaminoethyl methacrylate, methacrylic diethylammonium salt ethyl ester or senecioate-ethoxy ethyl ester;
Described functional silane compound is a vinyl trichloro silane, vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three (beta-methoxy-oxyethyl group) silane, γ-An Bingjisanyiyangjiguiwan, γ-glycidoxypropyltrime,hoxysilane, γ-(methacryloxy) propyl trimethoxy silicane, N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan, γ-urea groups propyl-triethoxysilicane, γ-r-chloropropyl trimethoxyl silane or γ-chloropropyl triethoxysilane;
Described initiator is benzoyl peroxide, Diisopropyl azodicarboxylate, di-t-butyl peroxide, peroxidation two tert-pentyls or t-butyl peroxy-acetate.
Described alcoholic solvent is preferably ethanol, propyl carbinol, isopropylcarbinol, propylene glycol or Virahol.
Described acrylate hard monomer is preferably methyl methacrylate, Jia Jibingxisuanyizhi or vinylbenzene.
Described acrylate soft monomer is preferably ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate or n propyl methacrylate.
The described stirring of step (1) is meant that at rotating speed be stirring under the 400-600rpm condition; The rate of addition that the described dropping of step (2) is advanced in the reactor is 40～95g/h.
The present invention also provides the alcohol soluble polyacrylate resin of method for preparing, and its number-average molecular weight is 10000～200000, and molecular weight distribution is 1.1～4, and the resin system brookfield viscosity is 100～5000cp.
Pencil hardness is 2H behind the described alcohol soluble polyacrylate resin dried coating film, and tensile strength is 45.3MPa, and elongation at break is 135%.
The present invention also provides the application of above-mentioned alcohol soluble polyacrylate resin.
The application of described alcohol soluble polyacrylate resin in surface decoration or transparent heat insulating dope: according to the mass fraction, 1000～1500 parts of alcohol soluble polyacrylate resins, 100～200 parts of metal complex pigments or functional obstruct ir radiation filler, 1～3 part of defoamer, 1～4 part of flow agent are carried out ground and mixed, make the alcohol soluble polyacrylate glass paint.
The application of described alcohol soluble polyacrylate resin in antifouling aluminium coil coating: according to the mass fraction, 800～1600 parts of alcohol soluble polyacrylate resins, 100～300 parts of titanium dioxide, 5～30 parts of cellulose thickeners, 1～3 part of defoamer, 1～3 part of flow agent, 0.5～5 part of BASF Tamol dispersion agent are carried out ground and mixed, make alcohol soluble polyacrylate aluminium coil coating.
The application of described alcohol soluble polyacrylate resin in code-spraying printing ink: according to the mass fraction, 900～2000 parts of alcohol soluble polyacrylate resins, 180～250 parts of metallized dyes, 8～16 parts of conducting salts, 1～3 part of defoamer, 1～5 part of adhesion promoter are carried out ground and mixed, make the alcohol soluble polyacrylate code-spraying printing ink.
The present invention compared with prior art has following advantage and beneficial effect:
(1) the obtained alcohol soluble polyacrylate resin of the present invention has adopted alcoholic solvent in preparation and preparation coating process, therefore can not produce the deleterious irritating smell of humans and animals, is the friendly type resin of a kind of novel environmental.
(2) contain carboxyl, hydroxyl, amide group, amino contour polar functional group on the obtained alcohol soluble polyacrylate resin molecular chain of the present invention, and molecular weight and moderate molecular weight distribution, make itself and alcoholic solvent have good linkage force, can dissolve each other with arbitrary proportion.
(3) the obtained alcohol soluble polyacrylate resin satisfactory mechanical property of the present invention, pencil hardness is 2H behind its dried coating film, and tensile strength is 45.3MPa, and elongation at break is 135%.
(4) the obtained alcohol soluble polyacrylate resin of the present invention is monomer modified through functional organosilane, has good various substrate adhesions.This alcohol soluble polyacrylate resin is filmed, and sticking power reaches 0.15N/mm on the polypropylene board ground
2, sticking power reaches 1 grade on the aluminium coiled material, and sticking power reaches 0 grade on glass substrate.
(5) the obtained alcohol soluble polyacrylate resin of the present invention is monomer modified through functional organosilane, has good water tolerance.The immersion of filming of this alcohol soluble polyacrylate resin is non-foaming, wrinkle resistant behind the 24h, does not come off non-whitening.
(6) production technique of the present invention is simple, resin price is cheap, easy construction, and can regulate resin Semi-polarity functional group, organosilane functional group kind and ratio easily according to actual needs, making the product that adapts to different environments for use and ground, thereby has the using value of adaptability and Geng Gao widely.
Embodiment
For better understanding the present invention, below in conjunction with embodiment the present invention is described further, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1
The first step is got 45 gram ethanol, is added in the reactor that agitator, reflux condensate device, heating jacket and blanket of nitrogen are housed, and system is warming up to 120 ℃ then, and the 500rpm rotating speed stirs 30min down.
Second step was got 19.5 gram methyl methacrylates, 12 gram vinylformic acid n-propyls, and 7.5 gram Rocryl 410s and 0.3 gram benzoyl peroxide mix, and drip in the reactor then, drip off in 1 hour.Reacted 4 hours, and mended and drip 1.5 gram γ-(methacryloxy) propyl trimethoxy silicanes, reacted discharging again 1.5 hours.
Prepared alcohol soluble polyacrylate resin environmental protection has no irritating odor storage-stable.After testing, this alcohol soluble polyacrylate resin number-average molecular weight is 52000, and molecular weight distribution is 2.2, and the resin system brookfield viscosity is 1200cp.
Embodiment 2
The first step is got 300 gram isopropylcarbinols, is added in the reactor that agitator, reflux condensate device, heating jacket and blanket of nitrogen are housed, and system is warming up to 85 ℃ then, and the 500rpm rotating speed stirs 25min down.
Second step was got 66 gram vinylbenzene, 58 gram ethyl propenoates, and 24 gram vinylformic acid and 1.2 gram Diisopropyl azodicarboxylates mix, and drip in the reactor then, drip off in 1.5 hours.React after 4 hours, mend and drip 18 gram vinyl three (beta-methoxy-oxyethyl group) silane.Reacted discharging again 2 hours.
Prepared alcohol soluble polyacrylate resin environmental protection has no irritating odor storage-stable.After testing, this resin number-average molecular weight is 83100, and molecular weight distribution is 2.5, and the resin system brookfield viscosity is 2200cp.
Embodiment 3
The first step is got 240 gram Virahols, is added in the reactor that agitator, reflux condensate device, heating jacket and blanket of nitrogen are housed, and system is warming up to 90 ℃ then, and the 500rpm rotating speed stirs 30min down.
Second step was got 60 gram Jia Jibingxisuanyizhis, 32 gram n propyl methacrylates, and 23 gram hydroxyl acrylics and 0.8 gram peroxidation, two tert-pentyls mix, and drip in the reactor then, drip off in 2 hours.React after 4 hours, mend and drip 10.4 gram vinyltriethoxysilanes.Reacted discharging again 1.5 hours.
Prepared alcohol soluble polyacrylate resin environmental protection has no irritating odor storage-stable.After testing, this resin number-average molecular weight is 42500, and molecular weight distribution is 4.1, and the resin system brookfield viscosity is 2500cp.
Embodiment 4
The first step is got 1000 gram ethanol and 225 gram propyl carbinols, is added in the reactor that agitator, reflux condensate device, heating jacket and blanket of nitrogen are housed, and system is warming up to 85 ℃ then, and the 500rpm rotating speed stirs 30min down.
Second step was got 280 gram Jia Jibingxisuanyizhis, 150 gram isopropyl acrylates, and 52 gram vinylformic acid and 3.5 gram Diisopropyl azodicarboxylates mix, and drip in the reactor then, drip off in 1 hour.React after 4 hours, mend and drip 10.4 gram γ-chloropropyl triethoxysilanes, reacted discharging again 2 hours.
Prepared alcohol soluble polyacrylate resin environmental protection has no irritating odor storage-stable.After testing, this resin number-average molecular weight is 113000, and molecular weight distribution is 2.1, and the resin system brookfield viscosity is 3000cp.
Embodiment 5
The first step is got 500 gram ethanol and 100 gram propylene glycol, is added in the reactor that agitator, reflux condensate device, heating jacket and blanket of nitrogen are housed, and system is warming up to 85 ℃ then, and the 600rpm rotating speed stirs 25min down.
Second step was got 158 gram vinylbenzene, 132 gram ethyl propenoates, and 36 gram vinylformic acid and 2.4 gram peroxidation, two tert-pentyls mix, and drip in the reactor then, drip off in 1 hour.React after 4 hours, mend and drip 36 gram vinyl three (beta-methoxy-oxyethyl group) silane.Reacted discharging again 2 hours.
Prepared alcohol soluble polyacrylate resin environmental protection has no irritating odor storage-stable.After testing, this resin number-average molecular weight is 105000, and molecular weight distribution is 2.9, and the resin system brookfield viscosity is 3500cp.
Embodiment 6
The first step is got 427 gram propylene glycol, is added in the reactor that agitator, reflux condensate device, heating jacket and blanket of nitrogen are housed, and system is warming up to 85 ℃ then, and the 400rpm rotating speed stirs 30min down.
Second step was got 140 gram methyl methacrylates, 32 gram isopropyl acrylates, and 40 gram hydroxyl acrylics and 1.6 gram Diisopropyl azodicarboxylates mix, and drip in the reactor then, drip off in 2 hours.React after 4 hours, mend and drip 36 gram γ-chloropropyl triethoxysilanes, reacted discharging again 1.5 hours.
Prepared alcohol soluble polyacrylate resin environmental protection has no irritating odor storage-stable.After testing, this resin number-average molecular weight is 95000, and molecular weight distribution is 2.3, and the resin system brookfield viscosity is 2500cp.
Embodiment 7
The first step is got 617 gram ethanol, is added in the reactor that agitator, reflux condensate device, heating jacket and blanket of nitrogen are housed, and system is warming up to 85 ℃ then, and the 500rpm rotating speed stirs 30min down.
Second step was got 87 gram isopropyl methacrylates, 95 gram n-butyl acrylates, and 47.5 gram methacrylic acids and 1.9 gram Diisopropyl azodicarboxylates mix, and drip in the reactor then, drip off in 1 hour.React after 4 hours, mend and drip 28.5 gram vinyltriethoxysilanes.Reacted discharging again 1.5 hours.
Prepared alcohol soluble polyacrylate resin environmental protection has no irritating odor storage-stable.After testing, this resin number-average molecular weight is 135000, and molecular weight distribution is 1.6, and the resin system brookfield viscosity is 3500cp.
Embodiment 8
The first step is got 1120 gram ethanol, is added in the reactor that agitator, reflux condensate device, heating jacket and blanket of nitrogen are housed, and system is warming up to 110 ℃ then, and the 500rpm rotating speed stirs 25min down.
Second step was got 176 gram methyl methacrylates, 132 gram n-butyl acrylates, and 18 gram vinylformic acid diethylamine ethyl esters and 3.2 gram benzoyl peroxides mix, and drip in the reactor then, drip off in 1 hour.React after 4 hours, mend and drip 32 gram vinyl trichloro silanes.Reacted discharging again 2 hours.
Prepared alcohol soluble polyacrylate resin environmental protection has no irritating odor storage-stable.After testing, this resin number-average molecular weight is 68000, and molecular weight distribution is 2.9, and the resin system brookfield viscosity is 2900cp.
Embodiment 9
The first step is got 1100 gram ethanol, is added in the reactor that agitator, reflux condensate device, heating jacket and blanket of nitrogen are housed, and system is warming up to 90 ℃ then, and the 500rpm rotating speed stirs 20min down.
Second step was got 467.5 gram vinyl cyanide, 110 gram Propenoic acid, 2-methyl, isobutyl esters, and 27.5 gram vinylformic acid dimethylamine ethyl esters and 5.5 gram Diisopropyl azodicarboxylates mix, and drip in the reactor then, drip off in 1.5 hours.Reacted 4 hours, and mended and drip 71.5 gram vinyltrimethoxy silanes.Reacted discharging again 1.5 hours.
Prepared alcohol soluble polyacrylate resin environmental protection has no irritating odor storage-stable.After testing, this alcohol soluble polyacrylate resin number-average molecular weight is 62000, and molecular weight distribution is 2.5, and the resin system brookfield viscosity is 2200cp.
Embodiment 10
The first step is got 600 gram ethanol and 450 gram propyl carbinols, is added in the reactor that agitator, reflux condensate device, heating jacket and blanket of nitrogen are housed, and system is warming up to 85 ℃ then, and the 500rpm rotating speed stirs 30min down.
Second step was got 273 gram Methacrylamides, 92.4 gram n propyl methacrylates, and 21 gram senecioate-ethoxy ethyl esters and 4.2 gram Diisopropyl azodicarboxylates mix, and drip in the reactor then, drip off in 2.5 hours.Reacted 4 hours, and mended Dropwise 5 0.4 gram γ-(methacryloxy) propyl trimethoxy silicane.Reacted discharging again 1.5 hours.
Prepared alcohol soluble polyacrylate resin environmental protection has no irritating odor storage-stable.After testing, this alcohol soluble polyacrylate resin number-average molecular weight is 55000, and molecular weight distribution is 3, and the resin system brookfield viscosity is 2800cp.
Embodiment 11
The first step is got 700 gram ethanol, is added in the reactor that agitator, reflux condensate device, heating jacket and blanket of nitrogen are housed, and system is warming up to 120 ℃ then, and the 500rpm rotating speed stirs 20min down.
Second step was got 280 gram vinylbenzene, 140 gram vinylformic acid n-pentyl esters, and 14 gram vinylformic acid hydroxyl methyl esters and 3.5 gram benzoyl peroxides mix, and drip in the reactor then, drip off in 1 hour.Reacted 4 hours, and mended Dropwise 5 2.5 gram γ-glycidoxypropyltrime,hoxysilane.Reacted discharging again 1.5 hours.
Prepared alcohol soluble polyacrylate resin environmental protection has no irritating odor storage-stable.After testing, this alcohol soluble polyacrylate resin number-average molecular weight is 45000, and molecular weight distribution is 3.4, and the resin system brookfield viscosity is 3200cp.
Embodiment 12
The first step is got 960 gram ethanol and 200 gram isopropylcarbinols, is added in the reactor that agitator, reflux condensate device, heating jacket and blanket of nitrogen are housed, and system is warming up to 140 ℃ then, and the 500rpm rotating speed stirs 30min down.
Second step was got 360 gram methyl methacrylates, 96 gram Propenoic acid, 2-methyl, isobutyl esters, and 26.4 gram senecioate-ethoxy ethyl esters and 4.8 gram di-t-butyl peroxides mix, and drip in the reactor then, drip off in 1 hour.Reacted 4 hours, and mended and drip 72 gram γ-urea groups propyl-triethoxysilicanes.Reacted discharging again 1.5 hours.
Prepared alcohol soluble polyacrylate resin environmental protection has no irritating odor storage-stable.After testing, this alcohol soluble polyacrylate resin number-average molecular weight is 85000, and molecular weight distribution is 3.2, and the resin system brookfield viscosity is 3500cp.
Embodiment 13
1600 gram embodiment, 1 obtained alcohol soluble polyacrylate resin is knocked down stirring tank, start dispersion machine, slowly add 200 gram metal complex pigments then, the 2000rpm rotating speed stirs 5min down.Add the BYK020 type defoamer of 3 gram BYK companies and the BYK301 type flow agent of 4 gram BYK companies then, can obtain alcohol soluble polyacrylate stained glass decorative paint behind the stirring 10min.
When construction, this glass decoration coating is sprayed on glass surface by spray gun.Then 30 ℃ dry 72 hours or down 80 ℃ of dry 1 hour of bakings down, can get pot-metal glass and film.
The specific performance of filming is as shown in table 1:
Table 1 coating coating performance index
| Test event | The result | Testing method |
| Sticking power | 0 grade | GB?1720-79 |
| Hardness | ?2H | GB/T?6739-1996 |
| Water tolerance | There is not difference behind the 24h | GB/T?1733-93 |
Because this alcohol soluble polyacrylate resin is monomer modified through functional organosilane, makes its shortcoming that has overcome traditional pure soluble paint poor water resistance, it is filmed can not produce behind the immersion 24h in water and turns white, and is wrinkling, the loss of gloss phenomenon; Its coating film gloss degree height, bright in luster, free from extraneous odour has good sticking power, hardness characteristics simultaneously.
Embodiment 14
800 gram embodiment, 3 obtained alcohol soluble polyacrylate resins are knocked down stirring tank, start dispersion machine, slowly add 100 gram metal complex pigments then, the 2000rpm rotating speed stirs 5min down.Add the BYK020 type defoamer of 2 gram BYK companies and the BYK301 type flow agent of 1 gram BYK company then, can obtain alcohol soluble polyacrylate stained glass decorative paint behind the stirring 10min.
When construction, this glass decoration coating is sprayed on glass surface by spray gun.Then 30 ℃ dry 72 hours or down 80 ℃ of dry 1 hour of bakings down, can get pot-metal glass and film.
The specific performance of filming is as shown in table 2:
Table 2 coating coating performance index
| Test event | The result | Testing method |
| Sticking power | 0 grade | GB?1720-79 |
| Hardness | ?2H | GB/T?6739-1996 |
| Water tolerance | There is not difference behind the 24h | GB/T?1733-93 |
Because this alcohol soluble polyacrylate resin is monomer modified through functional organosilane, makes its shortcoming that has overcome traditional pure soluble paint poor water resistance, it is filmed can not produce behind the immersion 24h in water and turns white, and is wrinkling, the loss of gloss phenomenon; Its coating film gloss degree height, bright in luster, free from extraneous odour has good sticking power, hardness characteristics simultaneously.
Embodiment 15
1000 gram embodiment, 3 obtained alcohol soluble polyacrylate resins are knocked down stirring tank, start dispersion machine, slowly add the functional obstruct ir radiation filler of 150 grams then, the 2000rpm rotating speed stirs 5min down.Add the BYK020 type defoamer of 1 gram BYK company and the BYK303 type flow agent of 2 gram BYK companies then, can obtain alcohol soluble polyacrylate transparent heat insulating glass coating behind the stirring 10min.
When construction, this glass decoration coating is sprayed on glass surface by spray gun.Then 30 ℃ dry 72 hours or down 80 ℃ of dry 1 hour of bakings down, can get transparent heat insulating glass and film.
The specific performance of filming is as shown in table 3:
Table 3 coating coating performance index
| Test event | The result | Testing method |
| Sticking power | 0 grade | GB?1720-79 |
| Hardness | ?2H | GB/T?6739-1996 |
| Water tolerance | There is not difference behind the 24h | GB/T?1733-93 |
| Visible light transmissivity (380～780nm) | ?90％ | Ultra-violet and visible spectrophotometer |
| Infrared light transmitance (780～2500nm) | 30％ | UV, visible light near infrared scanner |
This alcohol dissolubility transparent heat insulating glass coating system consistency is good, and obstruct ir radiation fillers dispersed is even, makes it keep the good infrared light barrier property while, and visible light transmissivity reaches 90%.And this coating energy stable storage is more than 1 year.
Embodiment 16
1600 gram embodiment, 8 obtained alcohol soluble polyacrylate resins are knocked down stirring tank, start dispersion machine, slowly add 300 gram rutile titanium dioxides then, 30 gram carboxymethyl cellulose thickeners stir 5min under the 4000rpm rotating speed.Add the BYK020 defoamer of 3 gram BYK companies, the BYK303 flow agent and the 5 gram Tamol850 of the BASF AG dispersion agents of 3 gram BYK companies then, can obtain alcohol soluble polyacrylate aluminium coil coating behind the stirring 10min.
When construction, this aluminium coil coating is sprayed on aluminium coiled material surface by spray gun.Then 30 ℃ dry 72 hours or down 80 ℃ of dry 2 hours of bakings down, can get the aluminium coil coating and film.
The specific performance of filming is as shown in table 4:
Table 4 coating coating performance index
| Test event | The result | Testing method |
| Sticking power | 0 grade | GB?1720-79 |
| Hardness | ?2H | GB/T?6739-1996 |
| Water tolerance | There is not difference behind the 24h | GB/T?1733-93 |
| With water contact angle | 96 degree | The JY-82 contact angle instrument |
| With the glycerine contact angle | 99 degree | The JY-82 contact angle instrument |
This aluminium coil coating is filmed and is had the characteristics of good flexibility, sticking power, hardness, water tolerance, weathering resistance.This aluminium coil coating is filmed and water and oily contact angle reach 96 degree and 99 respectively and spend simultaneously, can play certain resistant easy cleaning effect.
Embodiment 17
800 gram embodiment, 4 obtained alcohol soluble polyacrylate resins are knocked down stirring tank, start dispersion machine, slowly add 100 gram rutile titanium dioxides then, 5 gram carboxymethyl cellulose thickeners stir 5min under the 4000rpm rotating speed.Add the BYK020 defoamer of 1 gram BYK company, the BYK303 flow agent and the 0.5 gram Tamol850 of the BASF AG dispersion agent of 1 gram BYK company then, can obtain alcohol soluble polyacrylate aluminium coil coating behind the stirring 10min.
When construction, this aluminium coil coating is sprayed on aluminium coiled material surface by spray gun.Then 30 ℃ dry 72 hours or down 80 ℃ of dry 2 hours of bakings down, can get the aluminium coil coating and film.
The specific performance of filming is as shown in table 5:
Table 5 coating coating performance index
| Test event | The result | Testing method |
| Sticking power | 0 grade | GB?1720-79 |
| Hardness | ?2H | GB/T?6739-1996 |
| Water tolerance | There is not difference behind the 24h | GB/T?1733-93 |
| With water contact angle | 95 degree | The JY-82 contact angle instrument |
| With the glycerine contact angle | 102 degree | The JY-82 contact angle instrument |
This aluminium coil coating is filmed and is had the characteristics of good flexibility, sticking power, hardness, water tolerance, weathering resistance.This aluminium coil coating is filmed and water and oily contact angle reach 95 degree and 102 respectively and spend simultaneously, can play certain resistant easy cleaning effect.
Embodiment 18
1000 gram embodiment, 10 obtained alcohol soluble polyacrylate resins are knocked down stirring tank, start dispersion machine, slowly add 200 gram rutile titanium dioxides then, 10 gram carboxymethyl cellulose thickeners stir 5min under the 4000rpm rotating speed.Add the BYK020 defoamer of 1 gram BYK company, the BYK303 flow agent and the 2 gram Tamol850 of the BASF AG dispersion agents of 2 gram BYK companies then, can obtain alcohol soluble polyacrylate aluminium coil coating behind the stirring 10min.
When construction, this aluminium coil coating is sprayed on aluminium coiled material surface by spray gun.Then 30 ℃ dry 72 hours or down 80 ℃ of dry 2 hours of bakings down, can get the aluminium coil coating and film.
The specific performance of filming is as shown in table 6:
Table 6 coating coating performance index
| Test event | The result | Testing method |
| Sticking power | 0 grade | GB?1720-79 |
| Hardness | ?2H | GB/T?6739-1996 |
| Water tolerance | There is not difference behind the 24h | GB/T?1733-93 |
| With water contact angle | 95 degree | The JY-82 contact angle instrument |
| With the glycerine contact angle | 99 degree | The JY-82 contact angle instrument |
This aluminium coil coating is filmed and is had the characteristics of good flexibility, sticking power, hardness, water tolerance, weathering resistance.This aluminium coil coating is filmed and water and oily contact angle reach 95 degree and 99 respectively and spend simultaneously, can play certain resistant easy cleaning effect.
Embodiment 19
2000 gram embodiment, 11 obtained alcohol soluble polyacrylate resins are knocked down stirring tank, start dispersion machine, slowly add 250 gram metallized dye B-27 then, 16 gram conducting salt potassiumphosphates stir 10min under the 1500rpm rotating speed.Add the BYK020 defoamer of 3 gram BYK companies, the EP2325 type adhesion promoter of 5 gram goldschmidt chemical corporation then, can obtain the alcohol soluble polyacrylate code-spraying printing ink behind the stirring 10min.
The printing ink specific performance is as shown in table 7:
Table 7 coating coating performance index
| Test event | The result | Testing method |
| Sticking power | 0.15N/mm 2 | GB/T?5210-198 |
| Hardness | 2H | GB/T?6739-1996 |
| Surface drying time | 6s | GB/T?6753·2-8 |
This alcohol soluble polyacrylate code-spraying printing ink has overcome the shortcoming of conventional polypropylene acid esters code-spraying printing ink substrate adhesion difference, and its film adhesive reaches 0.15N/mm
2And environment-protecting asepsis, rate of volatilization is fast, and it is convenient to use.
Embodiment 20
900 gram embodiment, 11 obtained alcohol soluble polyacrylate resins are knocked down stirring tank, start dispersion machine, slowly add 180 gram metallized dye B-27 then, 8 gram conducting salt potassiumphosphates stir 10min under the 1500rpm rotating speed.Add the BYK020 defoamer of 1 gram BYK company, the EP2325 type adhesion promoter of 1 gram goldschmidt chemical corporation then, can obtain the alcohol soluble polyacrylate code-spraying printing ink behind the stirring 10min.
The printing ink specific performance is as shown in table 8:
Table 8 coating coating performance index
| Test event | The result | Testing method |
| Sticking power | 0.15N/mm 2 | GB/T?5210-198 |
| Hardness | 2H | GB/T?6739-1996 |
| Surface drying time | 5s | GB/T?6753·2-8 |
This alcohol soluble polyacrylate code-spraying printing ink has overcome the shortcoming of conventional polypropylene acid esters code-spraying printing ink substrate adhesion difference, and its film adhesive reaches 0.15N/mm
2And environment-protecting asepsis, rate of volatilization is fast, and it is convenient to use.
Embodiment 21
1000 gram embodiment, 12 obtained alcohol soluble polyacrylate resins are knocked down stirring tank, start dispersion machine, slowly add 230 gram metallized dye B-27 then, 10 gram conducting salt potassiumphosphates stir 10min under the 1500rpm rotating speed.Add the BYK020 defoamer of 1 gram BYK company, the EP2325 type adhesion promoter of 3 gram goldschmidt chemical corporation then, can obtain the alcohol soluble polyacrylate code-spraying printing ink behind the stirring 10min.
The printing ink specific performance is as shown in table 9.This alcohol soluble polyacrylate code-spraying printing ink has overcome the shortcoming of conventional polypropylene acid esters code-spraying printing ink substrate adhesion difference, and its film adhesive reaches 0.15N/mm
2And environment-protecting asepsis, rate of volatilization is fast, and it is convenient to use.
Table 9 coating coating performance index
| Test event | The result | Testing method |
| Sticking power | 0.15N/mm 2 | GB/T?5210-198 |
| Hardness | 2H | GB/T?6739-1996 |
| Surface drying time | 6s | GB/T?6753·2-8 |
Claims (10)
1. the preparation method of an alcohol soluble polyacrylate resin is characterized in that: comprise the steps and processing condition:
The first step is got 260～800 parts of alcoholic solvents in mass fraction, is added in the reactor that agitator, reflux condensate device, heating jacket and blanket of nitrogen are housed, and system is warming up to 70～150 ℃ then, stirs 10～30min; Described alcoholic solvent is methyl alcohol, ethanol, propyl carbinol, isopropylcarbinol, ethylene glycol, propylene glycol, 1, one or more in 4-butyleneglycol, Virahol and the hexanol;
Second step is in mass fraction, get 73～220 parts of hard monomers, 53～160 parts of esters of acrylic acid soft monomers, 6～20 parts of polar functional group monomers and 2～10 parts of initiators mix, drip in the reactor then, reacted again 3～5 hours, drip 2～40 parts of organosilane monomers then, reacted 1～2 hour, and made alcohol soluble polyacrylate resin;
Described hard monomer is methyl methacrylate, Jia Jibingxisuanyizhi, isopropyl methacrylate, acrylamide, Methacrylamide, vinylbenzene or vinyl cyanide;
Described acrylate soft monomer is ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, vinylformic acid n-pentyl ester, the just own ester of vinylformic acid, vinylformic acid n-octyl, n propyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic acid n-pentyl ester, the just own ester of methacrylic acid or n octyl methacrylate;
Described polar functional group monomer is hydroxyl acrylic, vinylformic acid hydroxyl methyl esters, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, vinylformic acid, methacrylic acid, Rocryl 410, vinylformic acid dimethylamine ethyl ester, vinylformic acid diethylamine ethyl ester, dimethylaminoethyl methacrylate, methacrylic diethylammonium salt ethyl ester or senecioate-ethoxy ethyl ester;
Described organosilane monomer is a vinyl trichloro silane, vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three (beta-methoxy-oxyethyl group) silane, γ-An Bingjisanyiyangjiguiwan, γ-glycidoxypropyltrime,hoxysilane, γ-(methacryloxy) propyl trimethoxy silicane, N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan, γ-urea groups propyl-triethoxysilicane, γ-r-chloropropyl trimethoxyl silane or γ-chloropropyl triethoxysilane;
Described initiator is benzoyl peroxide, Diisopropyl azodicarboxylate, di-t-butyl peroxide, peroxidation two tert-pentyls or t-butyl peroxy-acetate.
2. the preparation method of alcohol soluble polyacrylate resin according to claim 1, it is characterized in that: described alcoholic solvent is ethanol, propyl carbinol, isopropylcarbinol, propylene glycol or Virahol.
3. the preparation method of alcohol soluble polyacrylate resin according to claim 1, it is characterized in that: described hard monomer is methyl methacrylate, Jia Jibingxisuanyizhi or vinylbenzene.
4. the preparation method of alcohol soluble polyacrylate resin according to claim 1, it is characterized in that: described acrylate soft monomer is ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate or n propyl methacrylate.
5. the preparation method of alcohol soluble polyacrylate resin according to claim 1 is characterized in that: the described stirring of step (1) is meant that at rotating speed be stirring under the 400-600rpm condition; The rate of addition that the described dropping of step (2) is advanced in the reactor is 40～95g/h.
6. the alcohol soluble polyacrylate resin of the described method preparation of a claim 1, it is characterized in that: described alcohol soluble polyacrylate resin number-average molecular weight is 10000～200000, molecular weight distribution is 1.1～4, and the resin system brookfield viscosity is 100～5000cp.
7. alcohol soluble polyacrylate resin according to claim 6 is characterized in that: pencil hardness is 2H behind the described alcohol soluble polyacrylate resin dried coating film, and tensile strength is 45.3MPa, and elongation at break is 135%.
8. the application of the described alcohol soluble polyacrylate resin of claim 6 in surface decoration or transparent heat insulating dope, it is characterized in that: according to the mass fraction, 1000～1500 parts of alcohol soluble polyacrylate resins, 100～200 parts of metal complex pigments or functional obstruct ir radiation filler, 1～3 part of defoamer, 1～4 part of flow agent are carried out ground and mixed, make the alcohol soluble polyacrylate glass paint.
9. the application of the described alcohol soluble polyacrylate resin of claim 6 in antifouling aluminium coil coating, it is characterized in that: according to the mass fraction, 800～1600 parts of alcohol soluble polyacrylate resins, 100～300 parts of titanium dioxide, 5～30 parts of cellulose thickeners, 1～3 part of defoamer, 1～3 part of flow agent, 0.5～5 part of BASF Tamol dispersion agent are carried out ground and mixed, make alcohol soluble polyacrylate aluminium coil coating.
10. the application of the described alcohol soluble polyacrylate resin of claim 6 in code-spraying printing ink, it is characterized in that: according to the mass fraction, 900～2000 parts of alcohol soluble polyacrylate resins, 180～250 parts of metallized dyes, 8～16 parts of conducting salts, 1～3 part of defoamer, 1～5 part of adhesion promoter are carried out ground and mixed, make the alcohol soluble polyacrylate code-spraying printing ink.
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