CN100430424C - Process for preparing acrylate resin for powder paint - Google Patents
Process for preparing acrylate resin for powder paint Download PDFInfo
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- CN100430424C CN100430424C CNB2006100162641A CN200610016264A CN100430424C CN 100430424 C CN100430424 C CN 100430424C CN B2006100162641 A CNB2006100162641 A CN B2006100162641A CN 200610016264 A CN200610016264 A CN 200610016264A CN 100430424 C CN100430424 C CN 100430424C
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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 333.3-1000.0 weight portions, monomer mixture in 100.0 weight portions, free radical initiator in 0.5-8.0 weight portions, chain transferring agent in 0-1.0 weight portions and dispersant in 5.0-30.0 weight portions. The dispersing medium is mixture of alcohol or ethylene glycol monomethyl ether and deionized water; and the monomer mixture consists of soft monomer, hard monomer and functional monomer. 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, specifically prepares the method for 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 the control easily that distributes, 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, adopts 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 | 333.3～1000.0 |
| Mix monomer | 100.0 |
| Radical initiator | 0.5～8.0 |
| Chain-transfer agent | 0 or 0.1～1.0 |
| Dispersion agent | 5.0～30.0 |
Described dispersion medium is ethanol or ethylene glycol monomethyl ether and the formulated mixture of deionized water, the mass ratio 1.67～6: 1 of ethanol or ethylene glycol monomethyl ether and water,
Described mix monomer is that soft monomer 9%～25%, hard monomer 54%～70% and function monomer 8%～37% 3 kind of a monomer are formed by mass percent, wherein soft monomer is a n-butyl acrylate, hard monomer is methyl methacrylate or methyl methacrylate and vinylbenzene, function monomer is glycidyl methacrylate, methacrylic acid or Jia Jibingxisuanβ-Qiang Yizhi
Described radical initiator is a Diisopropyl azodicarboxylate,
Described chain-transfer agent is an octane base mercaptan,
Described dispersion agent is the big monomer of urethane type, and its structure is two keys-isocyanic ester segment-polyether segment-isocyanic ester segment-two keys (I)+two keys-isocyanic ester segment-polyether segment (II);
(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 dispersion agent and 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 ℃～110 ℃ 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.
Described dispersion agent is the big monomer of urethane type, and its structure is two keys-isocyanic ester segment-polyether segment-isocyanic ester segment-two keys (I)+two keys-isocyanic ester segment-polyether segment (II).When synthetic step during wherein based on the big monomer of (I) as follows: the vulcabond of 0.2mol is placed four-hole bottle, add 1 catalyzer dibutyl tin laurate, feed nitrogen and remove oxygen, the hydroxy polyethers that slowly adds 0.1mol afterwards, use when viscosity is too big with vulcabond and polyethers quality summation almost quite quality methyl methacrylate dilute, dripped 1 hour in 25～30 ℃, insulation reaction 2～3 hours, to theory-NCO (english abbreviation of isocyanate groups, down together) behind the content, the acrylic ester compound that the material of the two keys of introducing of adding 0.2mol promptly contains a hydroxyl carries out two key end-blockings; When synthetic step when wherein accounting for the big monomer of main body with (II) as follows: the vulcabond that takes by weighing 0.1mol is in four-hole bottle, adding and vulcabond and polyethers quality summation almost quite the methyl methacrylate of quality as reaction diluent, add 1 catalyzer dibutyl tin laurate, feed the nitrogen deoxygenation, the material that slowly drips the two keys of introducing of 0.1mol in 25～30 ℃ of beginnings promptly contains the acrylic ester compound of a hydroxyl, dripped 1 hour, insulation reaction after 2～3 hours to theoretical-NCO content, property adding hydroxy polyethers again can obtain the big monomer of urethane based on (II) in 25～30 ℃ of reactions after 2～3 hours.
The material of the two keys of above-mentioned introducing is a Jia Jibingxisuanβ-Qiang Yizhi, hydroxy polyethers is that molecular weight is 200 to contain the polyoxyethylene enediol of hydroxyl or for molecular weight is 1000 polyoxypropyleneglycol, described isocyanic ester is aromatic tolylene diisocyanate.
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 and kind are controlled easily, do not exist letex polymerization or suspension polymerization to introduce the problem of emulsifying agent, dispersion agent and stablizer impurity in the reaction process of the inventive method.Moreover, according to the different requirements of using, utilize dispersion polymerization processes of the present invention, prepare the acrylic resin that different powder art coating are used, comprise Hydroxylated acrylic resin, carboxyl acrylic resin and epoxy group(ing) acrylic resin by the monomeric introducing of difference in functionality.
(4) used the big monomer dispersant of a kind of novel urethane, owing to contain carbon-to-carbon double bond in the big monomer, can participate in the copolymerization process, thereby played the effect of dispersion agent, make polyreaction more steadily carry out, and when polymkeric substance is not separated out from medium, make polymer particle become micron-sized microballoon and exist.
Stability in storage by the acrylic resin of the inventive method preparation is good.
By the prepared powder coating good mechanical property 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.
Fig. 1 (a) HEMA and TDI reaction after product TH; (b) infrared spectra of the big monomer THP200 of urethane.
The 1HNMR of the big monomer THP200 of Fig. 2 urethane.
Fig. 3 (a) HEMA and TDI reaction after product TH; (b) infrared spectra of the big monomer THP1000 of urethane.
Synthetic acrylic resin infrared spectrogram among Fig. 4 embodiment 3.
The stereoscan photograph of particle in synthetic among Fig. 5 embodiment 3 (methyl) acrylic acid polymer solution.
The stereoscan photograph of particle in synthetic among Fig. 6 embodiment 4 (methyl) acrylic acid polymer solution.
The stereoscan photograph of particle in synthetic among Fig. 7 embodiment 9 (methyl) acrylic acid polymer solution.
The stereoscan photograph of particle in synthetic among Fig. 8 embodiment 10 (methyl) acrylic acid polymer solution.
Above-mentioned 1HNMR is the english abbreviation (together lower) of proton nmr spectra, HEMA is the english abbreviation (together lower) of β-hydroxyethyl methacry-late, TDI is 2, the english abbreviation of 4-toluene di-isocyanate(TDI) (together lower), TH is the english abbreviation (together lower) of HEMA and TDI product, THP is the english abbreviation (together lower) of the large monomer of polyurethane, THP200 is for the large monomer of polyurethane that Polyoxyethylene glycol 200 synthesize (lower with), and THP1000 is for the large monomer of polyurethane that polyoxypropyleneglycol 1000 synthesize (under together).
Embodiment
The preparation of the big monomer dispersant of urethane type
The 250ml four-hole bottle is placed water bath with thermostatic control, assemble spherical condensation tube, anchor formula stirring rod, thermometer, nitrogen conduit equipment series on the four-hole bottle.17.42g TDI is joined in the four-hole bottle, add simultaneously 50.0g MMA (english abbreviation of methyl methacrylate, down with) in four-hole bottle as reaction diluent, add a dibutyl tin laurate as catalyzer.Bath temperature is controlled at 30 ℃, feeds nitrogen and water of condensation, start agitator.On condenser, connect a constant pressure funnel, 13.01g HEMA is joined in the dropping funnel, beginning slowly is added drop-wise in the four-hole bottle, dropwises after 30 minutes, in 30 ℃ of isothermal reactions 3 hours, reach theoretical-NCO content, obtaining an end contains two key the other ends and contains-the first step product TH of NCO, and afterwards, disposable adding 20.0g polyoxyethylene enediol 200 was in 30 ℃ of isothermal reactions 3 hours, can obtain the big monomer THP200 of urethane, this material is the water white transparency thin liquid.Fig. 1 and Fig. 2 are respectively the structural characterization that utilizes infrared spectra and 1HNMR that reaction product is carried out.Fig. 1 (a) is the infrared spectra of HEMA and TDI reaction product, 2275cm among the figure
-1The place is the charateristic avsorption band of-NCO, 815cm
-1The place is the characteristic absorbance of carbon-carbon double bond, 1537cm
-1The place is the characteristic absorbance of carbamate, 1719cm
-1The place is the absorption peak of ester bond.Fig. 1 (b) is the infrared spectra of the big monomer THP200 of urethane, as can be seen from the figure 2275cm
-1The place-the absorption peak completely dissolve of NCO, and 815cm
-1The characteristic peak of carbon-carbon double bond is kept.The reaction of this proof polyether Glycols and TH is more abundant.Fig. 2 is the 1HNMR of the big monomer THP200 of urethane, and the main component of product such as molecular formula are depicted as the material that contains a terminal double bond.In the product ownership of proton such as letter mark, a place is in the polyoxyethylene enediol 200-OCH
2CH
2Proton signal peak in the-segment, c, d are respectively the proton signal peak in the carbon-to-carbon double bond, and one group of peak at b place is phenyl ring proton signal peak.
Embodiment 2
As embodiment 1 assembling instrument, 8.71g TDI is added in the four-hole bottle, add 50.0g MMA simultaneously in the 250ml four-hole bottle, add a dibutyl tin laurate as catalyzer, bath temperature is controlled at 30 ℃, feed nitrogen and water of condensation, start agitator, connect a constant pressure funnel on condenser, 6.51g HEMA is joined in the dropping funnel, beginning slowly is added drop-wise in the four-hole bottle, dropwise after 30 minutes, in 30 ℃ of isothermal reactions 3 hours, reach theory-NCO content, obtaining an end contains two key the other ends and contains-the first step product TH of NCO.Afterwards, disposable adding 50.0g polyoxypropyleneglycol 1000 can obtain the big monomer THP1000 of water white urethane in 30 ℃ of isothermal reactions 3 hours.Fig. 3 (a) is the infrared spectra of HEMA and TDI reaction product, and embodiment 1 is seen in its analysis.Fig. 3 (b) is the infrared spectra of the big monomer THP1000 of urethane, as can be seen from the figure 2275cm
-1The place-the absorption peak completely dissolve of NCO, and 815cm
-1The characteristic peak of carbon-carbon double bond is kept.
Embodiment 3
Synthesizing of epoxy acrylic resin
(1) reactant batching
Reactant is formed and proportioning is: dispersion medium is 50.0g dehydrated alcohol and 30.0g deionized water; Mix monomer comprises soft monomer n-butyl acrylate (following represent with BA) 1.0g, hard monomer MMA 6.0g and function monomer glycidyl methacrylate (following represent with GMA) 3.0g; Radical initiator is Diisopropyl azodicarboxylate (following represent with AIBN) 0.30g; Dispersion agent is the big monomer THP2001.5g of institute's synthetic urethane among the embodiment 1; Chain-transfer agent is 0.
(2) dispersion polymerization
1. the preparation of reactant mixed solution
Accurately weighing is all passed through underpressure distillation and is removed the GMA3.0g of stopper, MMA6.0g and BA1.0g, place the 50ml beaker to mix above three kinds of monomers, violent stirring mixed among synthetic dispersion agent THP2001.5g joined above three kinds of mix monomers, the Diisopropyl azodicarboxylate 0.30g 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 50.0g dehydrated alcohol, 30.0g 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 10 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.
Among the embodiment 3 infrared spectra of synthetic acrylic resin as shown in Figure 4,1537cm
-1The place is the characteristic absorbance of carbamate, proves that the big monomer of urethane has been incorporated in the resin 1733cm
-1The place is the absorption peak of ester bond, 909cm
-1, 846cm
-1The place is the charateristic avsorption band of epoxy group(ing).Fig. 5 is the stereoscan photograph of the ecosystem particle when polymkeric substance was not separated out in " liquid that contains polymkeric substance after the reaction end " during embodiment 3 (2) 3. went on foot.As can be seen from the figure, the polymkeric substance that generates in the ecosystem dispersion medium is micron-sized near-spherical particle.
Embodiment 4
Remove and reactant to be formed and proportioning is used instead and is dehydrated alcohol 62.5g, deionized water 37.5g, dispersion agent THP2002.0g, other are all with embodiment 3.The stereoscan photograph of the ecosystem particle when polymkeric substance was not separated out in " liquid that contains polymkeric substance after the reaction end " during (2) of this embodiment of Fig. 6 3. went on foot.As can be seen from the figure, the polymkeric substance that generates in the ecosystem dispersion medium is micron-sized near-spherical particle.
Except that data listed in the table 1, other are all with embodiment 3.
The implementation data of table 1 embodiment 5～6
| The reaction conditions when of preparing | 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 | |
| Dispersion agent THP200 | 2.4 | 2.4 | |
| Radical initiator AIBN (g) | 0.12 | 1.92 | |
| T p(℃) | 80 | 80 | |
| The dropping time (hour) | 1 | 1 |
Embodiment 7～8
Except that data listed in the table 2, other are all with embodiment 3.
The implementation data of table 2 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 | 8.73 |
| Hard monomer MMA (g) | 13.2 | 13.09 |
| Soft monomer BA (g) | 3.6 | 2.18 |
| Dispersion agent THP200 | 2.4 | 2.4 |
| Radical initiator AIBN (g) | 0.72 | 0.72 |
| T p(℃) | 80 | 80 |
| The dropping time (time) | 1 | 1 |
Embodiment 9～10
Except that data listed in the table 3 and outside the following explanation, other make the acrylic resin that contains epoxy-functional thus all with embodiment 3.The urethane big monomer dispersant of THP1000 in the table for making by embodiment 2.
Fig. 7 and Fig. 8 are respectively the stereoscan photographs of the ecosystem particle when polymkeric substance was not separated out in " liquid that contains polymkeric substance after the reaction end " during (2) of embodiment 9 and embodiment 10 3. went on foot.As can be seen from the figure, the polymkeric substance that generates in the ecosystem dispersion medium is micron-sized near-spherical material, since the effect that big monomer has served as dispersion agent, the micro polymer ball shape comparison rule of preparation, and relatively evenly.Stereoscan photograph among the comparative example 3,4, the stabilization of THP1000 is better than the effect of THP200 as can be known.
The implementation data of table 3 embodiment 9～10
| Ratio of components | Embodiment 9 | Embodiment 10 |
| Ethanol (g) | 50.0 | 55.0 |
| Deionized water (g) | 30.0 | 25.0 |
| Function monomer GMA (g) | 3.0 | 3.0 |
| Hard monomer MMA (g) | 6.0 | 6.0 |
| Soft monomer BA (g) | 1.0 | 1.0 |
| Dispersion agent THP1000 | 0.5 | 1.5 |
| Radical initiator AIBN (g) | 0.30 | 0.30 |
| T p(℃) | 65 | 65 |
Embodiment 11～12
Listed as table 4, except that adding chain-transfer agent and the THP1000 in the reactant batching, other are all with embodiment 3.
The implementation data of table 4 embodiment 11～12
| Ratio of components | Embodiment 11 | Embodiment 12 |
| 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 |
| Dispersion agent THP1000 | 2.40 | 3.60 |
| Radical initiator AIBN (g) | 0.72 | 0.72 |
| Chain-transfer agent octane base mercaptan (g) | 0.024 | 0.24 |
| T p(℃) | 80 | 80 |
| The dropping time (hour) | 1 | 1 |
Embodiment 13～14
Except that material and data listed in the table 5, other are all with embodiment 3.
The implementation data of table 5 embodiment 13～14
| The reaction conditions when of preparing burden | Embodiment 13 | Embodiment 14 |
| Ethylene glycol monomethyl ether (g) | 60.0 | 60.0 |
| Deionized water (g) | 10.0 | 10.0 |
| Function monomer GMA (g) | 4.8 | 4.8 |
| Hard monomer MMA (g) | 9.6 | 9.6 |
| Soft monomer BA (g) | 1.6 | 1.6 |
| THP1000 | 1.6 | 1.6 |
| Radical initiator AIBN (g) | 0.48 | 0.48 |
| T p(℃) | 90 | 100 |
| The dropping time (hour) | 0.5 | 0.5 |
Embodiment 15～16
Synthesizing of carboxyl type acrylate resin
Except that data listed in the table 6 and outside the following explanation, other are all with embodiment 3.MAA in the table 6 is a methacrylic acid, is used as function monomer; St is a vinylbenzene, is used as hard monomer.Make carboxyl type acrylic resin thus.
The implementation data of table 6 embodiment 15～16
| Ratio of components | Embodiment 15 | Embodiment 16 |
| 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 |
| Dispersion agent THP200 | 2.40 | 3.60 |
| Radical initiator AIBN (g) | 0.72 | 0.72 |
| The dropping time (hour) | 1 | 1 |
| T p(℃) | 80 | 80 |
Embodiment 17～18
Synthesizing of oh type acrylate resin
Except that data listed in the table 7 and outside the following explanation, other are all with embodiment 3.
The implementation data of table 7 embodiment 17～18
| Ratio of components | Embodiment 17 | Embodiment 18 |
| 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 |
| Dispersion agent THP1000 | 1.6 | 2.40 |
| The dropping time (hour) | 1 | 1 |
| Radical initiator AIBN (g) | 0.48 | 0.48 |
| The dropping time (hour) | 0.5 | 0.5 |
| T p(℃) | 100 | 100 |
| The insulation reaction time (hour) | 6 | 6 |
HEMA in the table 7 is a Jia Jibingxisuanβ-Qiang Yizhi, is used as function monomer.Make the oh type acrylic resin thus.
Claims (2)
1. prepare the method for acrylate resin for powder paint, it 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 333.3～1000.0
Mix monomer 100.0
Radical initiator 0.5～8.0
Chain-transfer agent 0 or 0.1～1.0
Dispersion agent 5.0～30.0
Described dispersion medium is ethanol or ethylene glycol monomethyl ether and the formulated mixture of deionized water, the mass ratio 1.67～6: 1 of ethanol or ethylene glycol monomethyl ether and water,
Described mix monomer is that soft monomer 9%～25%, hard monomer 54%～70% and function monomer 8%～37% 3 kind of a monomer are formed by mass percent, wherein soft monomer is a n-butyl acrylate, hard monomer is methyl methacrylate or methyl methacrylate and vinylbenzene, function monomer is glycidyl methacrylate, methacrylic acid or Jia Jibingxisuanβ-Qiang Yizhi
Described radical initiator is a Diisopropyl azodicarboxylate,
Described chain-transfer agent is an octane base mercaptan,
Described dispersion agent is the big monomer of urethane type, and its structure is two keys-isocyanic ester segment-polyether segment-isocyanic ester segment-two keys (I)+two keys-isocyanic ester segment-polyether segment (II);
(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 dispersion agent and 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 ℃～110 ℃ 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 described method for preparing acrylate resin for powder paint of claim 1, it is characterized in that: used dispersion agent is with the big monomer THP200 of 200 synthetic urethane of polyoxyethylene enediol type or for using the big monomer THP1000 of 1000 synthetic urethane of polyoxypropyleneglycol.
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| CN101220122B (en) * | 2008-01-30 | 2010-06-02 | 上海华明高技术（集团）有限公司 | Plastics toughening agent containing nano-calcium carbonate and polyalcohol, and method for producing the same |
| CN102060949B (en) * | 2010-12-09 | 2012-07-04 | 河北工业大学 | Method for preparing polyvinyl chloride modifier through dispersion polymerization |
| CN103172797B (en) * | 2013-03-13 | 2015-05-20 | 华南师范大学 | Polyacrylate/polyester resin prepolymer in interpenetration network structure, method for preparing same and powdery coating with same |
| CN104725543A (en) * | 2015-03-18 | 2015-06-24 | 阜阳市诗雅涤新材料科技有限公司 | Ultrahigh-acid value acrylate resin as well as synthesis method and application of resin |
| CN106154390B (en) * | 2016-09-21 | 2019-06-07 | 深圳市华星光电技术有限公司 | It is coated with the preparation method and liquid crystal display panel of type dye polarization elements |
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Assignee: CSE (Guangzhou) Co., Ltd. Assignor: Hebei University of Technology Contract record no.: 2010440001037 Denomination of invention: Process for preparing acrylate resin for powder paint Granted publication date: 20081105 License type: Exclusive License Open date: 20070411 Record date: 20100727 |
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