CN103694409A - Method for preparing high-adhesive force solid acrylic resin modified by organosilane - Google Patents
Method for preparing high-adhesive force solid acrylic resin modified by organosilane Download PDFInfo
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Abstract
The invention discloses a method for preparing high-adhesive force solid acrylic resin modified by organosilane. The method disclosed by the invention can be used for preparing the high-adhesive force solid acrylic resin by introducing an organosilane monomer into acrylic resin through a chemically bonding mode; the prepared modified solid acrylic resin as an additive is added to a powder coating system, can outstandingly enhance the adhesive force of a powder coating layer on a substrate and specific substrates, such as a galvanized plate and stainless steel, especially, cannot influence the storage stability of the powder coating due to excellent self characteristics of the solid acrylic resin and achieves certain improvement on the solvent resistance and boiling resistance of the powder coating layer.
Description
Technical field
The present invention relates to paint additive technical field, be specifically related to a kind of preparation method of organosilane-modified high adhesive force solid propenoic acid resin.
Background technology
Relative liquid coating, powder coating is not used solvent so the solvent-free volatilization of application process, and there is the advantages such as recovery utilization rate is high, easy to operate, productivity is high, dried coating film is fast, therefore in fields such as automobile, household electrical appliance, machinery, building, boats and ships, be widely adopted, to substitute liquid coating.Yet for some special substrate such as glass, stainless steel, galvanized sheet, pottery, the sticking power of common powder coating is poor, thereby affect the application performances such as the weathering resistance of filming, water boiling resistance, limited the range of application of powder coating.At present, can organosilane be incorporated in powder coating by physical method, normally adopt common liquid silane coupling agent, method by fillers dispersed joins in powder coating, the method can to a certain degree be improved the tack of coating, but inconvenient operation, and tend to make the storage characteristics of coating to decline, even can produce certain disadvantageous effect to the solvent resistance of filming, water boiling resistance.
Summary of the invention
For addressing the above problem, the invention discloses a kind of preparation method of organosilane-modified high adhesive force solid propenoic acid resin, the present invention is incorporated into organosilane monomer in acrylic resin, to make a kind of organosilane-modified high adhesive force solid propenoic acid resin by chemically combined mode, the high adhesive force solid propenoic acid resin that gained is silane-modified, Tg is controlled at 50-80 ℃, number-average molecular weight is approximately controlled at 5000-20000, comprises the following steps:
(1) raw material mixes: silane compound is mixed by a certain percentage with (methyl) alkyl acrylate, styrene-based monomers, initiator and molecular weight adjusting agent, make monomer mixture;
(2) polyreaction: add a certain amount of polymer solvent in reaction vessel, be heated to reflux state, keep reflux state, and at the uniform velocity drip monomer mixture in reaction vessel, within the regular hour, dropwise, then regulate reaction mass to certain temperature, after insulated and stirred reaction certain hour, add again a certain amount of initiator, secondary insulation reaction certain hour;
(3) aftertreatment: use the method steaming of normal pressure and underpressure distillation to desolventize, material is poured in aluminium dish while hot, and cooling, pulverizing, obtains silane-modified high adhesive force solid propenoic acid resin of the present invention.
The silane compound using in step (1) is the silane compound containing thiazolinyl or methacryloxy, containing the silane compound of thiazolinyl, can be a kind of in vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane.The silane compound that contains methacryloxy can be a kind of in 3-methacryloxypropyl methyl dimethoxysilane, 3-methyl allyl acyloxypropyl trimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxyl silane, gross weight based on monomer mixture, the consumption of silane compound is 10wt%-40wt%;
(methyl) alkyl acrylate using in step (1) comprises alkyl acrylate, for example methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, ethyl acrylate, dodecyl acrylate, octadecyl acrylate, cyclohexyl acrylate, isobornyl acrylate, benzyl acrylate etc.; Alkyl methacrylate is as methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, Tert-butyl Methacrylate, Propenoic acid, 2-methyl, isobutyl ester, methacrylic acid-2-ethylhexyl, methacrylic dodecyl gallate, stearyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate etc.They can use separately, also can two or more mix use.Gross weight based on monomer mixture, the consumption of (methyl) alkyl acrylate is 20wt%-50wt%;
The concrete example of styrene-based monomers using in step (1) comprises a kind of as in vinyl toluene, dimethyl styrene, Three methyl Benzene ethene, ethyl styrene, diethylbenzene ethene, triethylbenzene ethene, propylstyrene, butylstyrene, hexyl benzene ethene, heptyl benzene ethene, octyl group vinylbenzene etc. of vinylbenzene and ring-alkylated styrenes.Gross weight based on monomer mixture, the usage quantity of styrene-based monomers is 10wt%-40wt%.
In step (1), molecular weight adjusting agent used can be tert-dodecyl mercaptan, n-dodecyl mercaptan etc.Gross weight based on monomer mixture, molecular weight adjusting agent consumption is 0.1wt%-3wt%;
In step (1), the example of the initiator that uses comprises that azo compound is as 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2-methylbutyronitrile), 2,2 '-azo two (2,4-methyl pentane nitrile) etc.; Organo-peroxide is as lauryl peroxide, tert-butyl peroxide, benzoyl peroxide, isopropyl benzene hydroperoxide, diisopropyl peroxydicarbonate, t-butylperoxy pivarate etc.Whole total monomer weights based on used, polymerization starter consumption is about 0.1wt%-5wt%.
The polymer solvent using in step (2) is aromatic hydrocarbons, a kind of as in benzene,toluene,xylene, ethylbenzene, o-Xylol; Be preferably toluene;
Saidly in step (2) within the scope of certain hour, drip off, certain hour can be 3-5 hour.Said adjusting reaction is that certain temperature can be 70 ℃-90 ℃ to certain temperature.Said insulated and stirred reaction certain hour, certain hour is controlled at 3-5 hour.Said secondary insulation reaction certain hour, certain hour is controlled at 1-2 hour.
A kind of organosilane-modified high adhesive force solid propenoic acid resin of the present invention, can be used as adhesion promoter for polyester/HAA, polyester/TGIC, polyester/epoxy powder coating formula, consumption is about 1%-3%, can significantly improve above-mentioned coating to performances such as the sticking power of some special substrates and water boiling resistance, resistance to solvents, and not affect the stability in storage of powder coating.
Specific embodiment
In order to illustrate that better the present invention, spy enumerate following embodiment, but the present invention is not limited in following embodiment.
comparative example 1
At the upper 250g of the adding toluene of four-hole boiling flask that is equipped with the 1000ml of whipping appts, prolong, dropping funnel, thermometer and nitrogen inlet, be filled with nitrogen, stir and be heated to and reflux, drip monomer mixture (formula is in Table 1), it is 3.5 hours that time for adding is controlled, after dropwising, be cooled to 70 ℃, this temperature insulation reaction 3 hours, with 20g toluene, dissolve 3g 2,2 '-Diisopropyl azodicarboxylate, once joins in reaction system, then is incubated back flow reaction 1.5 hours.Use the method for air distillation to remove most of solvent, when a small amount of solvent of residue, can use underpressure distillation instead except desolventizing, blowing, cooling, pulverizing, finally obtain acrylic resin 1 while hot.Raw material add-on, experimental result are in Table 1.
embodiment 1
At the upper 250g of the adding toluene of four-hole boiling flask that is equipped with the 1000ml of whipping appts, prolong, dropping funnel, thermometer and nitrogen inlet, be filled with nitrogen, be heated to reflux, drip monomer mixture (formula is in Table 1), it is 3.5 hours that time for adding is controlled, after dropwising, be cooled to 70 ℃, this temperature insulation reaction 3 hours, with 20g toluene, dissolve 3g 2,2 '-Diisopropyl azodicarboxylate, once joins in reaction system, then is incubated back flow reaction 1.5 hours.Use the method for air distillation to remove most of solvent, when a small amount of solvent of residue, can use underpressure distillation instead except desolventizing, while hot blowing, cooling, pulverizing.Finally obtain the silane-modified acrylic resin 1 of product.
embodiment 2-3preparation method is identical with embodiment 1, and monomer mixture proportioning, in Table 1, makes respectively silane-modified acrylic resin 2 and 3, and experimental result is in Table 1.
table 1
*: vinyl trichloro silane
embodiment 4:
At the upper 250g of the adding toluene of four-hole boiling flask that is equipped with the 1000ml of whipping appts, prolong, dropping funnel, thermometer and nitrogen inlet, be filled with nitrogen, be heated to reflux, drip monomer mixture (formula is in Table 2), it is 3.5 hours that time for adding is controlled, after dropwising, be cooled to 90 ℃, this temperature insulation reaction 3 hours, with 20g toluene, dissolve 2g tert-butyl peroxide and once join in reaction system, then be incubated back flow reaction 1 hour.Use the method for air distillation to remove most of solvent, when a small amount of solvent of residue, can use underpressure distillation instead except desolventizing, while hot blowing, cooling, pulverizing.Finally obtain silane-modified acrylic resin 4.Experimental result is in Table 2.
embodiment 5-6:
preparation method is identical with embodiment 4.Monomer mixture formula, in Table 2, makes silane-modified acrylic resin 5-6.Experimental result is in Table 2.
table 2
*: 3-methacryloxypropyl triethoxyl silane
embodiment 7:
At the upper 130g of the adding toluene of four-hole boiling flask that is equipped with the 1000ml of whipping appts, prolong, dropping funnel, thermometer and nitrogen inlet, be filled with nitrogen, be heated to reflux, drip monomer mixture (formula is in Table 3), it is 3.5 hours that time for adding is controlled, after dropwising, be cooled to 80 ℃, this temperature insulation reaction 3 hours, with 20g toluene, dissolve 3g 2,2 '-azo two (2-methylbutyronitrile) once joins in reaction system, then is incubated back flow reaction 2 hours.Use the method for air distillation to remove most of solvent, when a small amount of solvent of residue, can use underpressure distillation instead except desolventizing, while hot blowing, cooling, pulverizing.Finally obtain silane-modified acrylic resin 7.Experimental result is in Table 3.
embodiment 8:
At the upper 220g of the adding toluene of four-hole boiling flask that is equipped with the 1000ml of whipping appts, prolong, dropping funnel, thermometer and nitrogen inlet, be filled with nitrogen, be heated to reflux, drip monomer mixture (formula is in Table 3), remaining step is with embodiment 7, make silane-modified acrylic resin 8, experimental result is in Table 3.
embodiment 9:
The upper 190g of the adding toluene of four-hole boiling flask being equipped with the 1000ml of whipping appts, prolong, dropping funnel, thermometer and nitrogen inlet, is filled with nitrogen, is heated to reflux, and drips monomer mixture (formula is in Table 3), and remaining step is with real
Execute example 7, make silane-modified acrylic resin 9, experimental result is in Table 3.
table 3
*: vinyl silane tri-butyl peroxy (toluene solution that contains 40% silane)
application examples 1,4,7
Respectively the silane-modified acrylic resin of preparation example 1,4,7 preparations is applied in polyester/hydroxyalkyl amide type powder coating by table 4 formula.Powder coating preparation process is: in filling a prescription, dry blending is even in proportion for each component, then through melting mixing machine, extrude, melting temperature is 100 ℃, extrudate compressing tablet, cooling, pulverizing, cross 180 mesh sieves and obtain respectively powder coating 1,4,7, use the method for electrostatic spraying respectively gained powder coating to be coated on galvanized iron sheet, 200 ° of C toast 15 minutes, make powder and film.Method is measured film performance according to the rules, the results are shown in Table 4.
application examples 2,5,8
Respectively the silane-modified acrylic resin of preparation example 2,5,8 preparations is applied in polyester/TGIC type powder coating by table 5 formula.Powder coating preparation process is: in filling a prescription, dry blending is even in proportion for each component, then through melting mixing machine, extrude, melting temperature is 100 ℃, extrudate compressing tablet, cooling, pulverizing, cross 180 mesh sieves and obtain respectively powder coating 2,5,8, use the method for electrostatic spraying respectively gained powder coating to be coated on stainless steel plate, 200 ° of C toast 15 minutes, make powder and film.Method is measured film performance according to the rules, the results are shown in Table 5.
application examples 3,6,9
Respectively the silane-modified acrylic resin of preparation example 2,5,8 preparations is applied in polyester/epoxy powder coating by table 6 formula.Powder coating preparation process is: in filling a prescription, dry blending is even in proportion for each component, then through melting mixing machine, extrude, melting temperature is 100 ℃, extrudate compressing tablet, cooling, pulverizing, cross 180 mesh sieves and obtain respectively powder coating 3,6,9, use the method for electrostatic spraying respectively gained powder coating to be coated on galvanized iron sheet, 200 ° of C toast 15 minutes, make powder and film.Method is measured film performance according to the rules, the results are shown in Table 6.
compare application examples 1-5
According to formula in table 4, with application examples 1 method, prepare powder coating, then with application examples 1 method, make powder and film, and method is measured film performance in accordance with regulations, the results are shown in Table 4.
compare application examples 6-10
According to formula in table 5, with application examples 2 methods, prepare powder coating, then with application examples 2 methods, make powder and film, and method is measured film performance in accordance with regulations, the results are shown in Table 5.
compare application examples 11-15
According to formula in table 6, with application examples 3 methods, prepare powder coating, then with application examples 3 methods, make powder and film, and method is measured film performance in accordance with regulations, the results are shown in Table 6.
Coating and performance test methods and the judgement criteria of filming are as follows:
coating storage characteristics:according to method described in GB/T 21782.8-2008, measure, respectively the coating powder of 100g different ingredients is packed in the test tube of same size, put in 40 ℃ of baking ovens and continue baking 28 days, then take out, according to following standard determination.Zero: unchanged or occur slight clustering phenomena, easily fragmentation of hand for coating powder ball; Δ: occur obvious compacting phenomenon, coating powder ball is more and need apply pressure by hand ability fragmentation; *: occur clearly compacting phenomenon, coating powder ball is a lot of and be difficult to pinch fragmentation with hand, must could be broken with machinery.
appearance of film:range estimation appearance of film situation, uses standard determination below, ◎: film coated surface is smooth, even, free of pinholes; Zero: film and present slight unfairness, even, free of pinholes; *: film and there is very poor planarization, inhomogeneous, have a pin hole.
sticking power:the GB/T 9286-1998 of take measures as standard, and result decision method is divided into 5 grades, and 0: cut edge is completely level and smooth, none lattice comes off; 1: at otch infall, have a little coating shedding, but cross cut area is influenced, can not obviously be greater than 5%; 2: otch infall/or notching edge have coating shedding, affected cross cut area is obviously greater than 5%, is less than 15%; 3: coating partly or entirely comes off with large fragment along cut edge, and/or in grid different piece, partly or entirely peel off, affected cross cut area is obviously large 15%, is less than 35%; 4: along cut edge, large fragment peels off coating, and/or coming off partly or entirely appears in some grids.Affected cross cut area is obviously large 35%, is less than 65%; 5: affected cross cut area obvious large 65%.
water boiling resistance sticking power:with GB/T 1733-93, soak boiling test method and carry out, soak after boiling water 30min, take out coolingly, by sticking power method, test and evaluate.
the sticking power of resistance to solvent:with first method (infusion method) in GB9274 1, carry out, then by sticking power method, test and evaluate.
table 4
1: vibrin, acid number 20-24mgKOH/g, Dutch DSM N. V. product
2: hydroxyalkyl amide, Lu'an City Jie Tongda chemical industry limited liability company product
3: polyacrylate flow agent, German Worlee company product
4: barium sulfate, Guizhou China adds meticulous mining industry company limited product
table 5
1: vibrin, acid number 29-34mgKOH/g, Anhui Shenjian New Material Co., Ltd.'s product
2:TGIC, Switzerland HUNTSMAN company product
3: polyacrylate flow agent, German Worlee company product
table 6
1: bisphenol A type epoxy resin, epoxy equivalent (weight) 0.12, Dow Chemical's product
2: vibrin, acid number 68-75mgKOH/g, DSM N. V.'s product
3: polyacrylate flow agent, German Worlee company product
Finally it should be noted that: above embodiment only, in order to technical scheme of the present invention to be described, is not intended to limit; Although the present invention is had been described in detail with reference to previous embodiment, those of ordinary skill in the art is to be understood that: its technical scheme that still can record aforementioned each embodiment is modified, or part technical characterictic is wherein equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution depart from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (3)
1. the preparation method of an organosilane-modified high adhesive force solid propenoic acid resin, it is characterized in that: a kind of silane monomer is incorporated in acrylic resin and is made by chemically combined mode, the high adhesive force solid propenoic acid resin that gained is organosilane-modified, Tg is controlled at 50-80 ℃, number-average molecular weight is approximately controlled at 5000-20000, and its preparation process is:
(1) raw material mixes: a kind of silane compound is mixed by a certain percentage with (methyl) alkyl acrylate, styrene-based monomers, initiator and molecular weight adjusting agent, make monomer mixture;
(2) polyreaction: add a certain amount of polymer solvent in reaction vessel, be heated to reflux state, keep reflux state, and at the uniform velocity drip monomer mixture in reaction vessel, within the regular hour, dropwise, then regulate reaction mass to certain temperature, and after insulated and stirred reaction certain hour, add again a certain amount of initiator, secondary insulation reaction certain hour;
(3) aftertreatment: use the method steaming of normal pressure and underpressure distillation to desolventize, material is poured in aluminium dish while hot, and cooling, pulverizing, obtains organosilane-modified high adhesive force solid propenoic acid resin of the present invention.
2. according to claim 1
onethe preparation method who plants organosilane-modified high adhesive force solid propenoic acid resin, is characterized in that:
The silane compound using in step (1) is the silane compound containing thiazolinyl or methacryloxy, silane compound containing thiazolinyl can be vinyl trichloro silane, vinyltrimethoxy silane, a kind of in vinyltriethoxysilane, the silane compound that contains methacryloxy can be 3-methacryloxypropyl methyl dimethoxysilane, 3-methyl allyl acyloxypropyl trimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, a kind of in 3-methacryloxypropyl triethoxyl silane, gross weight based on monomer mixture, the consumption of silane compound is 10wt%-40wt%,
(methyl) alkyl acrylate using in step (1) comprises alkyl acrylate, for example methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, ethyl acrylate, dodecyl acrylate, octadecyl acrylate, cyclohexyl acrylate, isobornyl acrylate, benzyl acrylate etc.; Alkyl methacrylate is as methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, Tert-butyl Methacrylate, Propenoic acid, 2-methyl, isobutyl ester, methacrylic acid-2-ethylhexyl, methacrylic dodecyl gallate, stearyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate etc., they can use separately, also can two or more mix use, gross weight based on monomer mixture, the consumption of (methyl) alkyl acrylate is 20wt%-50wt%;
The concrete example of styrene-based monomers using in step (1) comprises a kind of as in vinyl toluene, dimethyl styrene, Three methyl Benzene ethene, ethyl styrene, diethylbenzene ethene, triethylbenzene ethene, propylstyrene, butylstyrene, hexyl benzene ethene, heptyl benzene ethene, octyl group vinylbenzene etc. of vinylbenzene and ring-alkylated styrenes, gross weight based on monomer mixture, the usage quantity of styrene-based monomers is 10wt%-40wt%;
In step (1), molecular weight adjusting agent used can be tert-dodecyl mercaptan, n-dodecyl mercaptan etc., the gross weight based on monomer mixture, and molecular weight adjusting agent consumption is 0.1wt%-3wt%;
In step (1), the example of the initiator that uses comprises that azo compound is as 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2-methylbutyronitrile), 2,2 '-azo two (2,4-methyl pentane nitrile) etc., organo-peroxide is as lauryl peroxide, tert-butyl peroxide, benzoyl peroxide, isopropyl benzene hydroperoxide, diisopropyl peroxydicarbonate, t-butylperoxy pivarate etc., whole total monomer weights based on used, polymerization starter consumption is about 0.1wt%-5wt%.
3. according to claim 1
onethe preparation method who plants organosilane-modified high adhesive force solid propenoic acid resin, is characterized in that:
The polymer solvent using in step (2) is aromatic hydrocarbons, and a kind of as in benzene,toluene,xylene, ethylbenzene, o-Xylol is preferably toluene;
Saidly in step (2) within the scope of certain hour, drip off, certain hour can be 3-5 hour, said adjusting reaction is to certain temperature, certain temperature can be 70 ℃-90 ℃, said insulated and stirred reaction certain hour, certain hour is controlled at 3-5 hour, said secondary insulation reaction certain hour, and certain hour is controlled at 1-2 hour.
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