CN100487007C - Process for preparing acrylate resin for powder paint - Google Patents
Process for preparing acrylate resin for powder paint Download PDFInfo
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- CN100487007C CN100487007C CNB2006100162637A CN200610016263A CN100487007C CN 100487007 C CN100487007 C CN 100487007C CN B2006100162637 A CNB2006100162637 A CN B2006100162637A CN 200610016263 A CN200610016263 A CN 200610016263A CN 100487007 C CN100487007 C CN 100487007C
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Abstract
The preparation process of acrylate resin for powder paint is one high molecular compound polymerizing process with only C-C unsaturated bond reaction. The materials includes dispersing medium in 250.0-2000.0 weight portions, monomer mixture in 100.0 weight portions, free radical initiator in 0.5-8.0 weight portions and chain transferring agent in 0-1.0 weight portions. The dispersing medium is mixture of alcohol or ether and deionized water; and the monomer mixture consists of soft monomer 9-25 wt%, hard monomer 54-70 wt% and functional monomer 8-37 wt%. The polymerizing process includes compounding mixed reactant liquid, preparing dispersing medium and reaction condition and reaction and stilling to separate out product. The present invention is superior to available technology, and the obtained acrylate resin has high storage stability and can prepare powder paint with high mechanical performance and high outdoor endurance.
Description
Technical field
Technical scheme of the present invention relates to the polymerization technique process of only reacting the macromolecular compound that obtains with carbon-to-carbon unsaturated bond, the specifically preparation method of acrylate resin for powder paint.
Background technology
Powder coating is a kind of environmental type coating that does not contain volatile organic solvent, has the characteristics of solvent-free, low pollution, high-level efficiency, an application moulding, and Application Areas is extensive, has bright development prospect.In the manufacturing of powder coating, can broadly be divided into thermoset and thermoplastic coating according to employed raw material.Thermosetting coating is compared with the thermoplastic coating that is derived from thermoplastic compounds, and it is often more tough and tensile, and more anti-solvent and washing composition have better cohesive strength with metal material, and can not soften when being exposed to comparatively high temps.The acrylic resin powder coating belongs to thermosetting coating, because characteristics such as its good decorative property, weathering resistance be strong, protect light rate height, sticking power is superior are widely used in medium-to-high grade fields such as household electrical appliance, outdoor pipe, freeway guardrail, lamp decoration, bike, motorcycle, automobile finish, automobile finishing paint, its excellent weather resistance and hard is in epoxide powder coating, use properties even be better than polyester powder coating.
Solution polymerization process is to produce acrylate resin for powder paint method the most commonly used, and its technology is simple, system stable, reaction conversion ratio is high, relative molecular weight and distribution thereof are controlled easily, and the acrylic resin that synthesizes is effective.CN 1123302A discloses the method that a kind of solution polymerization process preparation contains the acrylic resin of epoxide group, and the optimum weight of this resin is that 3000～5500 (number-average molecular weights), softening temperature are 100～110 ℃.But the solvent of using in the solution polymerization mostly is the bigger toluene of toxicity, dimethylbenzene greatly, and is very big to operator's Health hazard, and energy consumption is bigger in the solvent removal process of resin solution.CN 1215732A discloses the preparation method of a kind of hydroxyl acrylic emulsion synthetic method and powdered resin thereof, ACRYLIC EMULSION is synthetic by emulsion polymerisation process under emulsifying agent, initiator, molecular weight regulator participate in by monomer mixture, emulsion is through overregulating the pH value, add dispersion agent (barium metaborate or barium sulfate), filtration drying and obtain powdered resin.US 6,762, and 248 disclose the method that a kind of suspension polymerization contains the acrylic resin of epoxy group(ing), and polyreaction is at 80 ℃, 2kg/cm
2(1.96 * 10
5Pa) carry out under the pressure condition, the resin weight-average molecular weight that synthesizes is 3000～20000, and epoxy equivalent (weight) is at 350～1200g/eq.CN 1456613A discloses a kind of micro-suspension one-step method powder coating manufacture method, and its technology is with compositions such as water, suspension dispersive agent elder generation ultra-sonic dispersion, makes dispersion liquid, afterwards all the other compositions is added polymeric kettle and carries out suspension polymerization.But the acrylic resin molecular weight that letex polymerization and suspension polymerization are produced is general bigger, in resin, water-soluble substances can residually be arranged simultaneously, as dispersion agent, emulsifying agent, stablizer etc., the introducing of these impurity will influence water tolerance, levelling property, apparent property and the mechanical property of coating.Related to the method for preparing acrylic resin with mass polymerization among the CN 1283205A, but its process more complicated, and also resin viscosity is big during mass polymerization, there is a large amount of reaction heat to emit, very easily take place, make reaction process be difficult to control, realize that suitability for industrialized production has difficulties sudden and violent gathering.The preparation method of aforesaid propylene acid resin exists or exists respectively complex process, serious, the uppity shortcoming of quality product of environmental pollution.
Summary of the invention
Technical problem to be solved by this invention is: a kind of preparation method of acrylate resin for powder paint is provided, i.e. and dispersion polymerization processes, it has overcome complex process, serious, the uppity shortcoming of quality product of environmental pollution.
The present invention solves this technical problem the technical scheme that is adopted: the preparation method of acrylate resin for powder paint of the present invention is a dispersion polymerization processes, may further comprise the steps:
(1) reactant batching
Reactant is formed and proportioning is
| Composition | The quality proportioning of forming |
| Dispersion medium | 250.0～2000.0 |
| Mix monomer | 100.0 |
| Radical initiator | 0.5～8.0 |
| Chain- |
0 or 0.1～1.0 |
Above-mentioned dispersion medium is a kind of alcohol or ether and the formulated mixture of deionized water, the mass ratio 1.0～7.0:1.0 of alcohol and water, and wherein alcohol is alkyl monocarbon alcohol, alkyl diol, ether is the alkyl diol monoether,
Above-mentioned mix monomer is a soft monomer 9%～25% by mass percent, hard monomer 54%～70% and function monomer 8%～37% 3 kind of monomer is formed, wherein soft monomer is an acrylic ester compound, hard monomer is a methyl acrylic ester compound, vinylbenzene and derivative thereof, vinyl-acetic ester, or a kind of in the acrylonitrile compound or two kinds, function monomer is a glycidyl acrylate, glycidyl methacrylate, glycidyl allyl ether, methylene-succinic acid, vinylformic acid, methacrylic acid, propenoic acid beta-hydroxy ethyl ester, Jia Jibingxisuanβ-Qiang Yizhi, the propenoic acid beta-hydroxy propyl ester, methacrylic acid β-hydroxypropyl acrylate, or N hydroxymethyl acrylamide
Above-mentioned radical initiator is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dilauroyl peroxide or dicumyl peroxide,
Above-mentioned chain-transfer agent is the alkyl sulfhydryl compounds;
(2) dispersion polymerization
1. the preparation of reactant mixed solution
The mix monomer by (1) step defined composition and proportioning of aequum is placed a container, add radical initiator by (1) step defined composition and proportioning, be stirred to and be dissolved into as clear as crystal liquid fully, form and proportioning adding chain-transfer agent by (1) step defined again, be stirred well to dissolving fully, be mixed with the reactant mixed solution;
2. the preparation of dispersion medium and reaction conditions
To form and the dispersion medium of proportioning join one and agitator, spherical condensation tube, constant pressure funnel, thermometer are housed, are connected with in the four-hole bottle of nitrogen protection by (1) step defined, and be heated to 65 ℃～140 ℃ of the polymeric reaction temperatures of setting with water bath with thermostatic control or oil bath;
3. react and leave standstill and separate out product
2. go on foot in the four-hole bottle of set reaction conditions to (2), the dropping time be in 0.5～1 hour semicontinuous dropping or disposable adding by (1) the 1. reactant mixed solution for preparing of step, the insulation reaction time is 6 hours～12 hours, the liquid that contains polymkeric substance after reaction finishes is the little mixture that turns blue of homogeneous, it is cooled to room temperature, after 5 minutes～3 hours, little homogeneous liquid that turns blue becomes the white casse thing of homogeneous, polymkeric substance is separated out from dispersion medium, after leaving standstill 24 hours, upper strata water white transparency clear liquid is a dispersion medium, and lower floor's white precipitate material is an acrylic resin, and the dispersion medium on upper strata is poured out, the resin isolation of lower floor is come out, be positioned in the wealthy mouthful of container, at 80 ℃, vacuum-drying made acrylate resin for powder paint through grinding after 6 hours under the condition of vacuum tightness 0.098MPa.
Above-mentioned soft monomer is ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, vinylformic acid n-octyl or Isooctyl acrylate monomer, and hard monomer is a kind of in methyl methacrylate, Jia Jibingxisuanyizhi, isopropyl methacrylate, methacrylic tert-butyl acrylate, vinylbenzene, vinyl toluene, ethyl styrene, vinyl-acetic ester, vinyl cyanide or the methacrylonitrile or two kinds.
Used alcohol is methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, ethylene glycol, propylene glycol, butyleneglycol, a condensed ethandiol or tirethylene glycol in the above-mentioned dispersion medium, and ether is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, butyleneglycol monomethyl ether or butyleneglycol list ether.
Described alkyl sulfhydryl compounds chain-transfer agent is n-dodecyl mercaptan, uncle's lauryl mercaptan, octane base mercaptan or octane-iso base mercaptan.
Prepare the acrylic resin that contains different functional groups that the dispersion polymerization processes of acrylate resin for powder paint is prepared by the present invention, the number-average molecular weight of its resin is 3000～20000, and molecular weight distribution is less than 2.0; Record the non-volatile content of rosin products greater than 98.0% by GB6554-86; The second-order transition temperature that records resin with dsc is 40～80 ℃; The epoxy equivalent (weight) of the epoxy acrylic resin that wherein prepares is at 400～1200g/eq.
The invention has the beneficial effects as follows:
(1) environmental protection, the dispersion medium that the inventive method is used is the mixture of alcohols material and water, is the clean and environment-friendly solvent, can the health of human body not worked the mischief, and can recycle.
(2) technology is simple, and in the technology of the inventive method, after polyreaction was finished, polymkeric substance can be precipitated out from medium, thereby had saved the subtractive process of a large amount of solvents, and the settling process of polymkeric substance can be regulated and control by temperature.
(3) quality product is controlled easily, except monomer, initiator and dispersion medium, does not introduce the stable impurity that carries out of other assisted reaction systems in the reaction process of the inventive method.With this understanding, polymerization process still can be carried out more stably, and there is not the problem as emulsion or suspension polymerization introducing emulsifying agent or dispersion agent impurity in the acrylic resin excellent performance that synthesizes.Moreover, according to the different requirements of using, utilize dispersion polymerization processes of the present invention, prepare the acrylic resin of different used for powder coating, comprise Hydroxylated acrylic resin, carboxyl acrylic resin and epoxy group(ing) acrylic resin by the monomeric introducing of difference in functionality.
Stability in storage by the acrylic resin of the used for powder coating of the inventive method preparation is good.
By the good mechanical property of the prepared powder coating of acrylic resin of the inventive method preparation, exterior durability is strong.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
The 1HNMR spectrogram of Fig. 1 epoxy acrylic resin with and the structural formula of random copolymers.
The Fourier transform infrared spectroscopy figure of Fig. 2 epoxy acrylic resin.
The stereoscan photograph of particle in synthetic among Fig. 3 embodiment 5 (methyl) acrylate polymer solution.
The stereoscan photograph of particle in synthetic among Fig. 4 embodiment 6 (methyl) acrylate polymer solution.
The DSC graphic representation of Fig. 5 synthetic resins: (a) synthetic resins among the embodiment 9; (b) synthetic resins among the embodiment 10.
The structural formula of epoxy acrylic resin and 1HNMR spectrum among Fig. 6 embodiment 14.
The Fourier transform infrared spectroscopy figure of epoxy acrylic resin among Fig. 7 embodiment 14.
The DSC graphic representation of Fig. 8 synthetic resins: (a) synthetic acrylic resin among the embodiment 16; (b) synthetic acrylic resin among the embodiment 17; (c) synthetic acrylic resin among the embodiment 18.
Above-mentioned 1HNMR is the english abbreviation (down together) of proton nmr spectra, and DSC is the english abbreviation (down together) of dsc.
Embodiment
Embodiment 1
Synthesizing of epoxy acrylic resin
(1) reactant batching
Reactant is formed and proportioning is: dispersion medium is 60.0g dehydrated alcohol and 20.0g deionized water; Mix monomer comprises soft monomer n-butyl acrylate (following represent with BA) 2.4g, hard monomer methyl methacrylate (following represent with MMA) 14.4g and function monomer glycidyl methacrylate (following represent with GMA) 7.2g; Radical initiator is Diisopropyl azodicarboxylate (following represent with AIBN) 0.72g; Chain-transfer agent is 0, does not promptly add chain-transfer agent.
(2) dispersion polymerization
1. the preparation of reactant mixed solution
Accurately weighing is all passed through underpressure distillation and is removed the glycidyl methacrylate 7.2g of stopper, methyl methacrylate 14.4g and n-butyl acrylate 2.4g, place the 50ml beaker to mix these three kinds of monomers, the Diisopropyl azodicarboxylate 0.72g of weighing after with ethyl alcohol recrystallization, join in the mix monomer, be stirred to and be dissolved into as clear as crystal liquid fully;
2. the preparation of dispersion medium and reaction conditions
Get 60.0g dehydrated alcohol, 20.0g deionized water in the 100ml beaker, mix, pour in the 250ml four-hole bottle of a thermometer that 0～150 ℃ in agitator, spherical condensation tube, range be housed, nitrogen conduit, with the water bath with thermostatic control heating, with polymerization temperature (below use T
pExpression) is set in 65 ℃, feeds nitrogen air is discharged, open water of condensation;
3. react and leave standstill and separate out product
By the time after the temperature of dispersion medium 2. reaches design temperature, disposable adding reactant mixed solution 1., insulation reaction 12 hours, the liquid that contains polymkeric substance after reaction finishes is the little mixture that turns blue of homogeneous, it is cooled to room temperature, after 20 minutes, little homogeneous liquid that turns blue becomes the white casse thing of homogeneous, and polymkeric substance is separated out from dispersion medium.After leaving standstill 24 hours, upper strata water white transparency clear liquid is a dispersion medium, lower floor's white precipitate material is an acrylic resin, the upper strata reaction medium is poured out, lower-layer resin is separated, be placed in the watch-glass, vacuum-drying can obtain the used for powder coating epoxy acrylic resin after 6 hours under 80 ℃, vacuum tightness 0.098MPa condition.
With gel permeation chromatography record above-mentioned resin number-average molecular weight (below use M
nExpression) be 1.95 ten thousand; This resin properties viscosity (following usefulness [η] expression) that records with acetone under 25 ℃ of conditions is 1.65dL/g; With hydrochloric acid-acetone method titration epoxy group content, the epoxy equivalent (weight) (following represent with EEW) that records this resin is 559g/eq; With dsc (following represent) with DSC record this resin second-order transition temperature (below use T
gExpression) it is 78.49 ℃; The non-volatile content that records this resin according to GB6554-86 is 99.02%.Know that by test result epoxy equivalent (weight) and non-volatile content all meet the requirement of powder coating resin.The structural characterization of synthetic epoxy acrylic resin is seen Fig. 1 and Fig. 2, and the ownership of the structural formula of resin and characteristic group thereof marks with alphabetical a, b, c, d, e, f, g respectively in the 1HNMR spectral line among Fig. 1.In the infrared spectrogram of Fig. 2 synthetic resins, find out 909cm significantly
-1With 846cm
-1The charateristic avsorption band at place is the characteristic absorbance of epoxy group(ing) among the GMA, 1732cm
-1The place is the charateristic avsorption band of carbonyl in the ester bond.Can prove that by 1HNMR and infrared spectra synthetic resins is GMA, MMA and three kinds of monomeric random copolymerss of BA.
Embodiment 2
Remove reactant formed and proportioning use instead for: dispersion medium is 40.0g dehydrated alcohol and 40.0g deionized water, mix monomer comprises soft monomer BA 1.6g, hard monomer MMA 9.6g and function monomer GMA 4.8g, outside the radical initiator AIBN0.48g, other are all with embodiment 1, [η] that record obtained resin is 1.59dL/g, EEW is 536g/eq, and the second-order transition temperature that records this resin with DSC is 72.30 ℃, and non-volatile content is 99.15%.
Embodiment 3～4
Except that data listed in the table 1 and outside the following explanation, other are all with embodiment 1.
The implementation data of table 1 embodiment 3～4
| The reaction conditions when of preparing burden | Embodiment 3 | |
| Dehydrated alcohol (g) | 60.0 | 60.0 |
| Deionized water (g) | 20.0 | 20.0 |
| Function monomer GMA (g) | 4.8 | 7.2 |
| Hard monomer MMA (g) | 9.6 | 14.4 |
| Soft monomer BA (g) | 1.6 | 2.4 |
| Radical initiator AIBN (g) | 0.64 | 0.72 |
| T p(℃) | 75 | 80 |
| The insulation reaction time (hour) | 8 | 8 |
The liquid mixture all-in-one-piece white casse thing after 31 minutes that contains polymkeric substance after reaction finishes among the embodiment 3; The liquid mixture that contains polymkeric substance after reaction finishes among the embodiment 4 was integral the white casse thing after 54 minutes.The acrylic resin performance that is synthesized thus sees Table 2.
Table 2 embodiment 3,4 makes the performance of acrylic resin
| Embodiment number | EEW(g/eq) | Non-volatile content (%) | T g(℃) | [η](dL/g) |
| Embodiment 3 | 603 | 98.25 | Do not survey | 1.42 |
| |
610 | 98.80 | 77.51 | 1.21 |
Embodiment 5～6
Except that data listed in the table 3 and following explanation, other are all with embodiment 1.
The implementation data of table 3 embodiment 5～6
| The reaction conditions when of preparing burden | Embodiment 5 | Embodiment 6 |
| Dehydrated alcohol (g) | 60.0 | 60.0 |
| Deionized water (g) | 20.0 | 20.0 |
| Function monomer GMA (g) | 7.2 | 7.2 |
| Hard monomer MMA (g) | 14.4 | 14.4 |
| Soft monomer BA (g) | 2.4 | 2.4 |
| Radical initiator AIBN (g) | 0.72 | 1.92 |
| T p(℃) | 80 | 80 |
| The dropping time (hour) | 1 | 1 |
The dropping time in the table 3 is to point to (2) of embodiment 1 2. to go on foot in the four-hole bottle of set reaction conditions, in the dropping time is semicontinuous being added dropwise to by (1) the 1. reactant mixed solution of the present embodiment for preparing of step in 1 hour, and the insulation reaction time is 8 hours.The acrylic resin performance that is synthesized thus sees Table 4.Fig. 3 and Fig. 4 are respectively the stereoscan photographs of particle shape in the liquid of implementing among example 5 and the embodiment 6 to be generated after the insulation reaction end of dispersion polymerization step that contains (methyl) acrylic ester polymer, polymer particle is a kind of micron-sized globe as can be seen from Figure, and dispersive is more even.
Table 4 embodiment 5,6 makes the performance of acrylic resin
| Embodiment number | EEW(g/eq) | Non-volatile content (%) | T g(℃) | [η](dL/g) | M n | Molecular weight distributing index |
| Embodiment 5 | 612 | 98.73 | 74.86 | 1.26 | 15536 | 1.61 |
| Embodiment 6 | 636 | 98.61 | 72.27 | 0.87 | Do not survey | Do not survey |
Embodiment 7～8
Listed as table 5, except that add chain-transfer agent octane base mercaptan in the reactant batching, other are all with embodiment 5.The acrylic resin performance that is synthesized thus sees Table 6.
The implementation data of table 5 embodiment 7～8
| The reaction conditions when of preparing burden | Embodiment 7 | Embodiment 8 |
| Dehydrated alcohol (g) | 60.0 | 60.0 |
| Deionized water (g) | 20.0 | 20.0 |
| Function monomer GMA (g) | 7.2 | 7.2 |
| Hard monomer MMA (g) | 14.4 | 14.4 |
| Soft monomer BA (g) | 2.4 | 2.4 |
| Radical initiator AIBN (g) | 0.72 | 0.72 |
| Octane base mercaptan (g) | 0.024 | 0.24 |
| T p(℃) | 80 | 80 |
| The dropping time (hour) | 1 | 1 |
Table 6 embodiment 7,8 makes the performance of acrylic resin
| Embodiment number | EEW(g/eq) | Little volatile content (%) | T g(℃) | [η](dL/g) | M n |
| Embodiment 7 | 600 | 99.04 | 68.20 | 1.19 | Do not survey |
| Embodiment 8 | 620 | 98.75 | 65.40 | 0.78 | 9398 |
Except that data listed in the table 7, other are all with embodiment 5.
The implementation data of table 7 embodiment 9～10
| The reaction conditions when of preparing | Embodiment | 9 | Embodiment 10 |
| Dehydrated alcohol (g) | 60.0 | 60.0 | |
| Deionized water (g) | 20.0 | 20.0 | |
| Function monomer GMA (g) | 7.2 | 8.73 | |
| Hard monomer MMA (g) | 13.2 | 13.09 | |
| Soft monomer BA (g) | 3.6 | 2.18 | |
| Radical initiator AIBN (g) | 0.72 | 0.72 | |
| T p(℃) | 80 | 80 | |
| The dropping time (time) | 1 | 1 |
The acrylic resin performance that is synthesized thus sees Table 8.(a) among Fig. 5 is the DSC graphic representation of synthesizing propylene acid resin among the embodiment 9, (b) is the DSC graphic representation of synthesizing propylene acid resin among the embodiment 10.Utilize this DSC curve to measure the second-order transition temperature T of resin
g, T
gIt is the sign of resin stability in storage.The glass transition of being found out these two embodiment synthetic acrylic resins by Fig. 5 is apparent in view, and the stability in storage of resin is good.
Table 8 embodiment 9,10 makes the performance of acrylic resin
| Embodiment number | EEW(g/eq) | Non-volatile content (%) | T g(℃) | [η](dL/g) | M n | Molecular weight distributing |
| Embodiment | ||||||
| 9 | 600 | 98.65 | 69.07 | 1.21 | 13329 | 1.73 |
| Embodiment 10 | 457 | 99.02 | 72.69 | 1.31 | Do not survey | Do not survey |
Embodiment 11
(1) reactant batching
Reactant is formed and proportioning is: dispersion medium is 68.57g ethylene glycol monomethyl ether and 11.43g deionized water; Mix monomer comprises BA 1.6g, MMA 9.6g and GMA 4.8g; Radical initiator AIBN 0.48g.
(2) dispersion polymerization
1. the preparation of reactant mixed solution
Accurately weighing is all passed through underpressure distillation and is removed the GMA 4.8g of stopper, MMA 9.6g and BA 1.6g, place the 50ml beaker to mix above three kinds of monomers, the AIBN 0.48g of weighing after with ethyl alcohol recrystallization, join in the mix monomer, be stirred to glass stick and be dissolved into as clear as crystal liquid fully;
2. the preparation of dispersion medium and reaction conditions
The deionized water that takes by weighing the ethylene glycol monomethyl ether of 68.57g and 11.43g is in the 100ml beaker, mix with glass stick, pour in the 250ml four-hole bottle of a thermometer that 0～150 ℃ in agitator, spherical condensation tube, range be housed, nitrogen conduit, with the water bath with thermostatic control heating, with T
pBe set in 80 ℃, feed nitrogen air is discharged, open water of condensation;
3. react and leave standstill and separate out product
By the time after the temperature of dispersion medium 2. reaches design temperature, disposable adding reactant mixed solution 1., insulation reaction 6 hours, the liquid that contains polymkeric substance after reaction finishes is the little mixture that turns blue of homogeneous, it is cooled to room temperature, after 20 minutes, little homogeneous liquid that turns blue becomes the white casse thing of homogeneous, and polymkeric substance is separated out from dispersion medium.After leaving standstill 24 hours, upper strata water white transparency clear liquid is a dispersion medium, lower floor's white precipitate material is an acrylic resin, the upper strata reaction medium is poured out, lower-layer resin is separated, be placed in the watch-glass, vacuum-drying can obtain the used for powder coating epoxy acrylic resin after 6 hours under 80 ℃, vacuum tightness 0.098MPa condition.
The EEW of the epoxy acrylic resin that makes of method is 546g/eq thus, and non-volatile content is 98.48%, and Mn is 17717, and molecular weight distributing index is 1.69, T
gIt is 70.5 ℃.
Embodiment 12～13
Except that data listed in the table 9 and following explanation, other are all with embodiment 5.
The implementation data of table 9 embodiment 12～13
| The reaction conditions when of preparing burden | Embodiment 12 | Embodiment 13 |
| Ethylene glycol monomethyl ether (g) | 68.57 | 68.57 |
| Deionized water (g) | 11.43 | 11.43 |
| Function monomer GMA (g) | 4.8 | 4.8 |
| Hard monomer MMA (g) | 9.6 | 9.6 |
| Soft monomer BA (g) | 1.6 | 1.6 |
| Radical initiator AIBN (g) | 0.48 | 0.48 |
| T p(℃) | 90 | 100 |
| The dropping time (hour) | 0.5 | 0.5 |
After dropwising in 0.5 hour, the insulation reaction time is 6 hours, and the acrylic resin performance that is synthesized thus sees Table 10.
The performance of table 10 embodiment 12,13 preparation acrylic resins
| Embodiment number | EEW(g/eq) | Non-volatile content (%) | T g(℃) | M n |
| Embodiment 12 | 601 | 98.64 | 65.24 | 9930 |
| Embodiment 13 | 524 | 98.71 | 63.30 | Do not survey |
Head is executed example 14～15
Except that data listed in the table 11 and following explanation, other are all with embodiment 12.
The implementation data of table 11 embodiment 14～15
| The reaction conditions when of preparing burden | Embodiment 14 | Embodiment 15 |
| Ethylene glycol monomethyl ether (g) | 68.57 | 68.57 |
| Deionized water (g) | 11.43 | 11.43 |
| Function monomer GMA (g) | 4.8 | 4.8 |
| Hard monomer MMA (g) | 9.6 | 9.6 |
| Soft monomer BA (g) | 1.6 | 1.6 |
| Radical initiator AIBN (g) | 0.08 | 0.80 |
| T p(℃) | 100 | 100 |
| The dropping time (hour) | 0.5 | 0.5 |
The acrylic resin performance that is synthesized thus sees Table 12.The 1HNMR and the resin structure formula of embodiment 14 synthetic resins are seen Fig. 6, and the characteristic group ownership about resin among the figure marks with alphabetical a, b, c, d, e, f, g respectively in the 1HNMR spectral line.Fig. 7 is the Fourier transform infrared spectroscopy figure of the epoxy acrylic resin that synthesizes of embodiment 14, as can be seen from the figure 909cm
-1With 846cm
-1The charateristic avsorption band at place is the characteristic absorbance of epoxy group(ing) among the GMA, 1732cm
-1The place is the charateristic avsorption band of carbonyl in the ester bond.Can prove that by 1HNMR and infrared spectra synthetic resins is GMA, MMA and three kinds of monomeric random copolymerss of BA.
The performance of table 12 embodiment 14,15 preparation acrylic resins
| Embodiment number | EEW(g/eq) | Non-volatile content (%) | T g(℃) | M n | Molecular weight distributing index |
| Embodiment 14 | 550 | 98.49 | 68.20 | Do not survey | Do not survey |
| Embodiment 15 | 586 | 98.17 | 64.32 | 5100 | 1.58 |
Embodiment 16～18
Except that data listed in the table 13 and following explanation, other are all with embodiment 12
The implementation data of table 13 embodiment 16～18
| The reaction conditions when of preparing burden | Embodiment 16 | Embodiment 17 | Embodiment 18 |
| Ethylene glycol monomethyl ether (g) | 68.57 | 68.57 | 68.57 |
| Deionized water (g) | 11.43 | 11.43 | 11.43 |
| Function monomer GMA (g) | 4.8 | 4.8 | 5.83 |
| Hard monomer MMA (g) | 9.6 | 8.8 | 8.73 |
| Soft monomer BA (g) | 1.6 | 2.4 | 1.45 |
| Radical initiator AIBN (g) | 0.48 | 0.48 | 0.48 |
| T p(℃) | 100 | 100 | 100 |
| The dropping time (hour) | 0.5 | 0.5 | 0.5 |
The acrylic resin performance that is synthesized thus sees Table 14.(a) among Fig. 8 is the DSC graphic representation of synthetic acrylic resin among the embodiment 16; (b) be the DSC graphic representation of synthetic acrylic resin among the embodiment 17; (c) be the DSC graphic representation of synthetic acrylic resin among the embodiment 18, by the glass transition of these resins is apparent in view as can be seen on the figure, the stability in storage of resin is good.
The performance of table 14 embodiment 16,17,18 preparation acrylic resins
| Embodiment number | EEW(g/eq) | Non-volatile content (%) | T g(℃) | M n | Molecular weight distributing index |
| Embodiment 16 | 551 | 99.14 | 67.41 | 5895 | 1.61 |
| Embodiment 17 | 598 | 99.57 | 57.22 | 7232 | 1.64 |
| Embodiment 18 | 499 | 98.65 | 67.38 | Do not survey | Do not survey |
Embodiment 19～20
Except that data listed in the table 15 and following explanation, other are all with embodiment 11.
The implementation data of table 15 embodiment 19～20
| The reaction conditions when of preparing burden | Embodiment 19 | |
| Ethylene glycol monomethyl ether (g) | 100.0 | 17.5 |
| Deionized water (g) | 60.0 | 2.5 |
| Function monomer GMA (g) | 2.4 | 2.4 |
| Hard monomer MMA (g) | 4.8 | 4.8 |
| Soft monomer BA (g) | 0.8 | 0.8 |
| Radical initiator AIBN (g) | 0.24 | 0.24 |
| T p(℃) | 80 | 80 |
The EEW of 19,20 synthetic epoxy acrylic resins of embodiment is respectively 570,558g/eq, and non-volatile content is respectively 98.76%, 99.12%, T
gBe respectively 65.37,63.42 ℃.
Embodiment 21～22
Change the soft monomer n-butyl acrylate among the embodiment 16 the vinylformic acid n-propyl of equimolar amount into, other data and operation constitute embodiment 21 by embodiment 16; Change the soft monomer n-butyl acrylate among the embodiment 16 Isooctyl acrylate monomer of equimolar amount into, other data and operation constitute embodiment 22 by embodiment 16.More than two embodiment institute synthetic epoxy acrylic resin meet the used for powder coating requirement.
Embodiment 23～31
Change the hard monomer methyl methacrylate among the embodiment 16 vinyl-acetic ester of equimolar amount into, other data and operation constitute embodiment 23 by embodiment 16; Change the hard monomer methyl methacrylate among the embodiment 16 vinylbenzene of equimolar amount into, other data and operation constitute embodiment 24 by embodiment 16; Change the hard monomer methyl methacrylate among the embodiment 16 Jia Jibingxisuanyizhi of equimolar amount into, other data and operation constitute embodiment 25 by embodiment 16; Change the hard monomer methyl methacrylate among the embodiment 16 isopropyl methacrylate of equimolar amount into, other data and operation constitute embodiment 26 by embodiment 16; Change the hard monomer methyl methacrylate among the embodiment 16 the methacrylic tert-butyl acrylate of equimolar amount into, other data and operation constitute embodiment 27 by embodiment 16; Change the hard monomer methyl methacrylate among the embodiment 16 vinyl toluene of equimolar amount into, other data and operation constitute embodiment 28 by embodiment 16; Change the hard monomer methyl methacrylate among the embodiment 16 ethyl styrene of equimolar amount into, other data and operation constitute embodiment 29 by embodiment 16; Change the hard monomer methyl methacrylate among the embodiment 16 vinyl cyanide of equimolar amount into, other data and operation constitute embodiment 30 by embodiment 16; That change the hard monomer methyl methacrylate among the embodiment 16 into equimolar amount or methacrylonitrile, other data and operation constitute embodiment 31 by embodiment 16.More than nine embodiment institute synthetic acrylic resins meet the used for powder coating requirement.
Embodiment 32～33
Change the function monomer glycidyl methacrylate among the embodiment 17 glycidyl acrylate of equimolar amount into, other data and operation constitute embodiment 32 by embodiment 17; Change the function monomer glycidyl methacrylate among the embodiment 17 glycidyl allyl ether of equimolar amount into, other data and operation constitute embodiment 33 by embodiment 17.More than two embodiment institute synthetic epoxy acrylic resin meet the used for powder coating requirement.
Embodiment 34～35
Synthesizing of carboxyl type acrylic resin
Except that data listed in the table 16 and outside the following explanation, other are all with embodiment 1.
The implementation data of table 16 embodiment 34～35
| Ratio of components | Embodiment 34 | Embodiment 35 |
| Dehydrated alcohol (g) | 60.0 | 60.0 |
| Deionized water (g) | 20.0 | 20.0 |
| Function monomer MAA (g) | 2.35 | 1.92 |
| Hard monomer MMA (g) | 7.06 | 6.0 |
| Soft monomer BA (g) | 5.88 | 5.28 |
| Hard monomer St (g) | 8.71 | 10.8 |
| Radical initiator AIBN (g) | 0.72 | 0.72 |
| T p(℃) | 80 | 80 |
| The insulation reaction time (hour) | 8 | 8 |
MAA in the table 16 is a methacrylic acid, is used as function monomer; St is a vinylbenzene, is used as hard monomer.Make carboxyl type acrylic resin thus.
Embodiment 36～37
Change the function monomer methacrylic acid among the embodiment 34 vinylformic acid of equimolar amount into, other data and operation constitute embodiment 36 by embodiment 34; Change the function monomer methacrylic acid among the embodiment 35 methylene-succinic acid of equimolar amount into, other data and operation constitute embodiment 37 by embodiment 35.More than two embodiment institute synthetic carboxyl type acrylic resin meet the used for powder coating requirement.
Embodiment 38～39
Synthesizing of oh type acrylic resin
Except that data listed in the table 17 and outside the following explanation, other are all with embodiment 1.
The implementation data of table 17 embodiment 38～39
| Ratio of components | Embodiment 38 | Embodiment 39 |
| Ethylene glycol monomethyl ether (g) | 60.0 | 60.0 |
| Deionized water (g) | 10.0 | 10.0 |
| Function monomer HEMA (g) | 4.0 | 3.56 |
| Hard monomer MMA (g) | 6.4 | 6.22 |
| Soft monomer BA (g) | 2.4 | 2.67 |
| Hard monomer St (g) | 3.2 | 3.56 |
| Radical initiator AIBN (g) | 0.48 | 0.48 |
| T p(℃) | 100 | 100 |
| The insulation reaction time (hour) | 6 | 6 |
HEMA in the table 17 is a Jia Jibingxisuanβ-Qiang Yizhi, is used as function monomer.Make the oh type acrylic resin thus.
Change the function monomer Jia Jibingxisuanβ-Qiang Yizhi among the embodiment 38 propenoic acid beta-hydroxy ethyl ester of equimolar amount into, other data and operation constitute embodiment 40 by embodiment 38; Change the function monomer Jia Jibingxisuanβ-Qiang Yizhi among the embodiment 39 the methacrylic acid β-hydroxypropyl acrylate of equimolar amount into, other data and operation constitute embodiment 41 by embodiment 39.More than two embodiment institute synthetic oh type acrylic resin meet the used for powder coating requirement.
Embodiment 42～43
Change the function monomer Jia Jibingxisuanβ-Qiang Yizhi among the embodiment 38 the propenoic acid beta-hydroxy propyl ester of equimolar amount into, other data and operation constitute embodiment 42 by embodiment 38; Change the function monomer Jia Jibingxisuanβ-Qiang Yizhi among the embodiment 38 N hydroxymethyl acrylamide of equimolar amount into, other data and operation constitute embodiment 43 by embodiment 38.More than two embodiment institute synthetic acrylic resin meet the used for powder coating requirement.
Embodiment 44
With 50 parts of institute's synthetic epoxy acrylic resins among the embodiment 14,10.45 parts of dodecanedioic acids (DDDA), TiO
237 parts, 1.5 parts of flow agents, 0.6 part of st-yrax, catalyzer 0.45 part (parts by weight) mixes, and melt extrudes, pulverizes, sieves, and makes 200 purposes white epoxy group(ing) acrylic powder coating.
Embodiment 45
With 60 parts of institute's synthetic epoxy acrylic resins among the embodiment 14, acid number is 152.7 parts of the carboxy(l)polyesters of 40mgKOH/g, TiO
235 parts, 2.0 parts of flow agents, 0.5 part of st-yrax, catalyzer 0.40 part (parts by weight) mixes, and melt extrudes, pulverizes, sieves, and makes 200 purpose mat acrylic powder coating.
Embodiment 46
The powder coating electrostatic spraying of embodiment 44,45 gained in surface-treated steel plate test piece, is put into 190 ℃ of constant temperature ovens, solidify 20min.Can obtain all better the filming of hardness, sticking power, smoothness, mechanical property.
Embodiment 47～51
Change the soft monomer n-butyl acrylate among the embodiment 4 ethyl propenoate of equimolar amount into, other data and operation constitute embodiment 47 by embodiment 4; Change the soft monomer n-butyl acrylate among the embodiment 4 isopropyl acrylate of equimolar amount into, other data and operation constitute embodiment 48 by embodiment 4; Change the soft monomer n-butyl acrylate among the embodiment 4 isobutyl acrylate of equimolar amount into, other data and operation constitute embodiment 49 by embodiment 4; Change the soft monomer n-butyl acrylate among the embodiment 4 the vinylformic acid n-octyl of equimolar amount into, other data and operation constitute embodiment 50 by embodiment 4; Change the soft monomer n-butyl acrylate among the embodiment 4 Isooctyl acrylate monomer of equimolar amount into, other data and operation constitute embodiment 51 by embodiment 4.More than five embodiment institute synthetic acrylic resins meet the used for powder coating requirement.
Embodiment 52～55
Change the radical initiator Diisopropyl azodicarboxylate among the embodiment 4 2,2'-Azobis(2,4-dimethylvaleronitrile) of equimolar amount into, other data and operation constitute embodiment 52 by embodiment 4; Change the radical initiator Diisopropyl azodicarboxylate among the embodiment 4 dibenzoyl peroxide of equimolar amount into, other data and operation constitute embodiment 53 by embodiment 4; Change the radical initiator Diisopropyl azodicarboxylate among the embodiment 4 dilauroyl peroxide of equimolar amount into, other data and operation constitute embodiment 54 by embodiment 4; Change the radical initiator Diisopropyl azodicarboxylate among the embodiment 4 dicumyl peroxide of equimolar amount into, other data and operation constitute embodiment 55 by embodiment 4.More than four embodiment institute synthetic acrylic resins meet the used for powder coating requirement.
Embodiment 56～65
Change the dispersion medium ethanol among the embodiment 4 methyl alcohol of equimolar amount into, other data and operation constitute embodiment 56 by embodiment 4; Change the dispersion medium ethanol among the embodiment 4 propyl alcohol of equimolar amount into, other data and operation constitute embodiment 57 by embodiment 4; Change the dispersion medium ethanol among the embodiment 4 Virahol of equimolar amount into, other data and operation constitute embodiment 58 by embodiment 4; Change the dispersion medium ethanol among the embodiment 4 butanols of equimolar amount into, other data and operation constitute embodiment 59 by embodiment 4; Change the dispersion medium ethanol among the embodiment 4 isopropylcarbinol of equimolar amount into, other data and operation constitute embodiment 60 by embodiment 4; Change the dispersion medium ethanol among the embodiment 4 ethylene glycol of equimolar amount into, polymeric reaction temperature is adjusted to 110 ℃, and other data and operation constitute embodiment 61 by embodiment 4; Change the dispersion medium ethanol among the embodiment 4 propylene glycol of equimolar amount into, polymeric reaction temperature is adjusted to 120 ℃, and other data and operation constitute embodiment 62 by embodiment 4; Change the dispersion medium ethanol among the embodiment 4 butyleneglycol of equimolar amount into, polymeric reaction temperature is adjusted to 130 ℃, and other data and operation constitute embodiment 63 by embodiment 4; Change the dispersion medium ethanol among the embodiment 4 one condensed ethandiol of equimolar amount into, polymeric reaction temperature is adjusted to 140 ℃, and other data and operation constitute embodiment 64 by embodiment 4; Change the dispersion medium ethanol among the embodiment 4 tirethylene glycol of equimolar amount into, other data and operation constitute embodiment 65 by embodiment 4.More than ten embodiment institute synthetic acrylic resins meet the used for powder coating requirement.
Embodiment 66～70
Change the dispersion medium ethylene glycol monomethyl ether among the embodiment 13 ethylene glycol monoethyl ether of equimolar amount into, other data and operation constitute embodiment 66 by embodiment 13; Change the dispersion medium ethylene glycol monomethyl ether among the embodiment 13 propylene glycol monomethyl ether of equimolar amount into, other data and operation constitute embodiment 67 by embodiment 13; Change the dispersion medium ethylene glycol monomethyl ether among the embodiment 13 dihydroxypropane single-ether of equimolar amount into, other data and operation constitute embodiment 68 by embodiment 13; Change the dispersion medium ethylene glycol monomethyl ether among the embodiment 13 the butyleneglycol monomethyl ether of equimolar amount into, other data and operation constitute embodiment 69 by embodiment 13; Change the dispersion medium ethylene glycol monomethyl ether among the embodiment 13 the butyleneglycol list ether of equimolar amount into, other data and operation constitute embodiment 70 by embodiment 13.More than five embodiment institute synthetic acrylic resins meet the used for powder coating requirement.
Embodiment 71～73
Change the chain-transfer agent octane base mercaptan among the embodiment 7 n-dodecyl mercaptan of equimolar amount into, other data and operation constitute embodiment 71 by embodiment 7; Change the chain-transfer agent octane base mercaptan among the embodiment 7 uncle's lauryl mercaptan of equimolar amount into, other data and operation constitute embodiment 72 by embodiment 7; Change the chain-transfer agent octane base mercaptan among the embodiment 7 the octane-iso base mercaptan of equimolar amount into, other data and operation constitute embodiment 73 by embodiment 7.More than three embodiment institute synthetic acrylic resins meet the used for powder coating requirement.
Claims (4)
1. the preparation method of acrylate resin for powder paint is characterized in that: adopt dispersion polymerization processes, may further comprise the steps:
(1) reactant batching
Reactant is formed and proportioning is
The quality proportioning that becomes to be grouped into
Dispersion medium 250.0～2000.0
Mix monomer 100.0
Radical initiator 0.5～8.0
Chain-transfer agent 0 or 0.1～1.0
Above-mentioned dispersion medium is a kind of alcohol or ether and the formulated mixture of deionized water, the mass ratio 1.0～7.0:1.0 of alcohol and water, and wherein alcohol is alkyl monocarbon alcohol, alkyl diol, ether is the alkyl diol monoether,
Above-mentioned mix monomer is a soft monomer 9%～25% by mass percent, hard monomer 54%～70% and function monomer 8%～37% 3 kind of monomer is formed, wherein soft monomer is an acrylic ester compound, hard monomer is a methyl methacrylate, Jia Jibingxisuanyizhi, isopropyl methacrylate, the methacrylic tert-butyl acrylate, vinylbenzene, vinyl toluene, ethyl styrene, vinyl-acetic ester, vinyl cyanide, or a kind of in the methacrylonitrile or two kinds, function monomer is a glycidyl acrylate, glycidyl methacrylate, glycidyl allyl ether, methylene-succinic acid, vinylformic acid, methacrylic acid, propenoic acid beta-hydroxy ethyl ester, Jia Jibingxisuanβ-Qiang Yizhi, the propenoic acid beta-hydroxy propyl ester, methacrylic acid β-hydroxypropyl acrylate, or N hydroxymethyl acrylamide
Above-mentioned radical initiator is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dilauroyl peroxide or dicumyl peroxide,
Above-mentioned chain-transfer agent is the alkyl sulfhydryl compounds;
(2) dispersion polymerization
1. the preparation of reactant mixed solution
The mix monomer by (1) step defined composition and proportioning of aequum is placed a container, add radical initiator by (1) step defined composition and proportioning, be stirred to and be dissolved into as clear as crystal liquid fully, form and proportioning adding chain-transfer agent by (1) step defined again, be stirred well to dissolving fully, be mixed with the reactant mixed solution;
2. the preparation of dispersion medium and reaction conditions
To form and the dispersion medium of proportioning join one and agitator, spherical condensation tube, constant pressure funnel, thermometer are housed, are connected with in the four-hole bottle of nitrogen protection by (1) step defined, and be heated to 65 ℃～140 ℃ of the polymeric reaction temperatures of setting with water bath with thermostatic control or oil bath;
3. react and leave standstill and separate out product
2. go on foot in the four-hole bottle of set reaction conditions to (2), the dropping time be in 0.5～1 hour semicontinuous dropping or disposable adding by (1) the 1. reactant mixed solution for preparing of step, the insulation reaction time is 6 hours～12 hours, the liquid that contains polymkeric substance after reaction finishes is the little mixture that turns blue of homogeneous, it is cooled to room temperature, after 5 minutes～3 hours, little homogeneous liquid that turns blue becomes the white casse thing of homogeneous, polymkeric substance is separated out from dispersion medium, after leaving standstill 24 hours, upper strata water white transparency clear liquid is a dispersion medium, and lower floor's white precipitate material is an acrylic resin, and the dispersion medium on upper strata is poured out, the resin isolation of lower floor is come out, be positioned in the wealthy mouthful of container, at 80 ℃, vacuum-drying made acrylate resin for powder paint through grinding after 6 hours under the condition of vacuum tightness 0.098MPa.
2. according to the preparation method of the described acrylate resin for powder paint of claim 1, it is characterized in that: described soft monomer is ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, vinylformic acid n-octyl or Isooctyl acrylate monomer.
3. according to the preparation method of the described acrylate resin for powder paint of claim 1, it is characterized in that: used alcohol is methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, ethylene glycol, propylene glycol, butyleneglycol, a condensed ethandiol or tirethylene glycol in the described dispersion medium, and ether is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, butyleneglycol monomethyl ether or butyleneglycol list ether.
4. according to the preparation method of the described acrylate resin for powder paint of claim 1, it is characterized in that: described alkyl sulfhydryl compounds chain-transfer agent is n-dodecyl mercaptan, uncle's lauryl mercaptan, octane base mercaptan or octane-iso base mercaptan.
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| CN101831025B (en) * | 2010-05-19 | 2013-04-03 | 肖磊 | Water-base resin and paint with high corrosion resistance and cohesiveness, environmental protection and low consumption and preparation method thereof |
| CN102372816B (en) * | 2010-08-09 | 2013-12-18 | 德清县明泉安邦化工有限公司 | Aqueous acrylic resin emulsion, preparation method, and coating composition thereof |
| CN102332346B (en) * | 2011-06-20 | 2013-04-10 | 珠海长先化学科技有限公司 | Method for producing environmental-friendly insulating oil |
| CN103980787A (en) * | 2014-04-30 | 2014-08-13 | 张家港江南粉末涂料有限公司 | Acrylic acid transparent powdery paint for glazing and preparation method thereof |
| CN104693937A (en) * | 2015-03-12 | 2015-06-10 | 湖州中辰建设有限公司 | Novel corrosion-resistant acrylic resin powder coating for ceramics |
| CN110343208B (en) * | 2019-06-11 | 2020-07-28 | 中山华明泰科技股份有限公司 | Preparation method and application of powdery acrylic resin |
| CN111978461B (en) * | 2020-08-31 | 2022-07-05 | 滁州金桥德克新材料有限公司无锡分公司 | Water-based functional acrylic resin and preparation method thereof |
| CN112011244B (en) * | 2020-09-02 | 2021-09-14 | 合肥工业大学 | Continuous production method of GMA acrylic resin powder coating |
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