CN102070767B - Preparation method of anti-aging ultraviolet cured acrylic-polyurethane resin containing fluorine - Google Patents
Preparation method of anti-aging ultraviolet cured acrylic-polyurethane resin containing fluorine Download PDFInfo
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- CN102070767B CN102070767B CN 201010594310 CN201010594310A CN102070767B CN 102070767 B CN102070767 B CN 102070767B CN 201010594310 CN201010594310 CN 201010594310 CN 201010594310 A CN201010594310 A CN 201010594310A CN 102070767 B CN102070767 B CN 102070767B
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Abstract
The invention provides a preparation method of anti-aging ultraviolet cured acrylic-polyurethane resin containing fluorine. The preparation method comprises the following steps: (1) adding polyisocyanate in a three-necked bottle; (2) after dropwise adding in the step (1), regulating the temperature of an oil bath pot, reacting for 4.5-8 hours, then stopping the reaction; (3) reacting for 8-12 hours at 50-70 DEG C; and (4) testing the product after the reaction in the step (3), determining the solid content of the product, and adding 5-15 parts of reactive monomer diluent by weight according to the solid content to obtain the product. The invention has the advantages that the preparation method is beneficial to spraying and construction; the curing time is shorter than that of the traditional UV-cured polyurethane, all the properties of the paint film are better, and the anti-aging property is improved.
Description
Technical field
The present invention relates to a kind of preparation method of fluorine-containing urethane resin, relate in particular to a kind of preparation method of anti-aging ultraviolet cured acrylic-polyurethane resin containing fluorine.
Background technology
Along with the fast development of modern industry, more and more higher for the service requirements of coating, except basic water-fast, anti-solvent, oil resistant etc. require, in the severe environment such as ultraviolet ray, ozone, acid rain, high low temperature alternation, also require to have certain erosion resistance.For the conduction of coating, grease proofing, waterproof, the function such as heat insulation the part particular requirement is arranged also in addition.
Ultraviolet-curing paint has utilized ultraviolet radiation to make this curing new technology of paint solidification film forming, compares with thermofixation, and it has VOC free (volatile organic matter) release, saves the energy, production efficiency advantages of higher, is a kind of environmentally friendly technology.At present, UV-cured resin is widely used for the fields such as chemical industry, electronics, light industry, machinery, transportation, communication with its unique technical superiority.But conventional UV-cured resin physical strength is relatively poor, and not ageing-resistant.
Urethane (PU) material can freely regulated Soft hard segment structure because of its uniqueness, the existing general application in elastomerics, fiber, coating and bonding agent field.Fluoro-containing group is introduced in the PU structure, the mechanical property and the two-phase microstructure features that had both kept the PU excellence, surface property and the overall performance of PU have been improved to a great extent again, give the material excellence low surface energy, refuse water, oil repellent, oilness, heat-resisting chemical-resistant and anti-staining property and good biocompatibility, become the emerging developing direction of PU at present.Because fluoroacrylate raw material monomer kind is many, synthetic relatively easy, so this fluorine introducing mode has larger handiness and Applied economy is worth.For example, CN1882618A provides a kind of (methyl) acrylate that comprises the fluorinated alkyl and Photoepolymerizationinitiater initiater and can be as the fluorine containing photocurable composition of luminescent material etc., along with fluorine content increases, the hydrolytic resistance of filming, humidity resistance, surface property, optical characteristics, mechanical characteristic, stability in storage have more excellent improvement.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of anti-aging ultraviolet cured acrylic-polyurethane resin containing fluorine, ultraviolet-curing paint exists wet-heat resisting, low temperature resistant, anti-mould, salt spray resistance, the relatively poor problem of oil resistance at present, the present invention is mainly for above problem, adopt polyisocyanates, contain two key monohydroxy acrylate and poly-hydroxy fluorinated acrylate resin is raw material, synthesized a kind of ageing-resistant UV by more manageable reaction conditions and method and solidified the fluorine-containing urethane resin.
The present invention is achieved like this, and it is characterized in that method steps is:
(1) there-necked flask, agitator, prolong, thermometer are installed, adjusting the oil bath pan temperature is 20 ~ 50 ℃, in there-necked flask, add 30 ~ 50 mass parts multicomponent isocyanates, at the uniform velocity drip 20 ~ 30 mass parts monohydroxy acrylate monomers and 0.1 ~ 1 mass parts of catalyst mixing solutions with constant pressure funnel in there-necked flask, rate of addition is controlled within 0.5 ~ 2 hour and drips off;
(2) after step (1) dropwises, adjusting the oil bath pan temperature is 50 ~ 70 ℃, heated and stirred reaction 4.5 ~ 8h under this temperature; With the Di-n-Butyl Amine that configures-acetone titration residual isocyanate group content, determine residual content, stopped reaction after it reaches theoretical reacting value;
(3) in step (2) reaction product, add the fluorine-containing acrylic polyol resin of 15 ~ 30 mass parts, 0.1 ~ 1 mass parts of catalyst and 0.5 ~ 1.5 mass parts stopper, keep temperature of reaction at 50 ~ 70 ℃, reacted 8 ~ 12 hours, measure isocyanate group mass contg, stopped reaction after content is less than 2% with acetone-Di-n-Butyl Amine method;
(4) the reacted product of test procedure (3) is determined the solid content of product, adds the reactive monomer thinner of 5 ~ 15 weight parts according to solid content, namely gets product.
Described fluorine-containing acrylic polyol resin is the fluorine-containing aliphatic acrylate of trifunctional, perfluoro alkyl phosphoester acrylic ester or fluorine-containing hyperbranched polyester acrylic ester.
Described multicomponent isocyanate is tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, triphenylmethane triisocyanate, vulcabond low-grade polymer (trimerization/pentamer) and biuret, poly methylene poly phenyl poly isocyanate or hexamethylene diisocyanate trimer.
It is described that to contain two key monohydroxy acrylate be Hydroxyethyl acrylate, Propylene glycol monoacrylate, pentaerythritol diacrylate, tetramethylol methane tetraacrylate or TriMethylolPropane(TMP) mono alkenyl ether.
A kind of in the organo-metallic salt catalyzer such as the tertiary amine catalysts such as described catalyzer is triethylamine, diethylene diamine, the N-methylmorpholine and two lauric acid butyl tin, stannous octoate and organo-bismuth.
Described stopper is minute subtype stopper such as MEHQ, Resorcinol, para benzoquinone, phenothiazine, beta-phenyl naphthylamines, p-ten.-butylcatechol, perhaps a kind of in the inorganics such as cuprous chloride, iron trichloride.
Described polyhydroxy polycarboxylic acrylate resin is that the following material of solution polymerization makes: one or more (methyl) vinylformic acid and C1-C6 contain the esterification monomer of fluoroalkyl alcohol, and one or more (methyl) vinylformic acid and C1-C6 contain at least a kind of (methyl) acrylic ester monomer that contains hydroxyl of esterification monomer of fluoroalkyl alcohol.
Described reactive monomer thinner is Viscoat 295 (TMPTA), ethoxylated trimethylolpropane triacrylate (EO
3-TMPTA), propylene glycol diacrylate (DPGDA), tri (propylene glycol) diacrylate (TPGDA) or 1,6 hexanediol diacrylate (HDDA).
Advantage of the present invention is: selected multicomponent isocyanate and poly-hydroxy fluorinated acrylate itself are macromole and polyfunctional group, toxicity is little, degree of crosslinking is high, the product properties of preparation is excellent and stable, the introducing of fluoropolymer can form thin film at substrate surface, substrate surface tension force is significantly reduced, less than general liquid, thereby show hydrophobic and oil repellent and antifouling function.In addition, can regulate dope viscosity after the interpolation reactive thinner, be conducive to spraying application, set time while is faster than traditional UV curing urethane speed, and the paint film properties is more excellent, and has improved ageing resistance.
Embodiment
Embodiment 1:
The present embodiment illustrates the preparation method of ageing-resistant fluorine-containing urethane resin provided by the invention.
(1) adjusts oil bath pan temperature to 40 ℃, the diphenylmethanediisocyanate that in there-necked flask, adds 40 weight parts, utilize constant pressure funnel that the mixing solutions of the dibutyl tin laurate of the Hydroxyethyl acrylate of 25 weight parts and 0.3 weight part is slowly splashed in the there-necked flask, dropwised in 2 hours;
(2) after step (1) dropwises, adjusting the oil bath pan temperature is 60 ℃, after 6 hours, measures isocyanate content every 1 hour with acetone-Di-n-Butyl Amine method in reaction under this temperature, after question response reaches preset value, i.e. and stopped reaction; The mixing solutions that reaction is obtained is poured into and is cooled to 30 ℃ in the constant pressure funnel
(3) the 4-oxygen sylvan of 30 weight part four-functional group fluorinated hydroxy acrylate, 0.3 part of catalyzer dibutyl tin laurate and 0.5 weight part is poured in the there-necked flask, mix the reacted product of rear dropping step (2), dropwise in 1 hour, 65 ℃ of lower reactions 10 hours, measure isocyanate group mass contg, stopped reaction after content is less than 2% with acetone-Di-n-Butyl Amine method;
(4) the reacted product of test procedure (3) is determined the solid content of product, adds the reactive monomer thinner of 15 weight parts according to solid content, namely gets product.
Embodiment 2:
The present embodiment illustrates the preparation method of ageing-resistant fluorine-containing urethane resin provided by the invention.
(1) adjusts oil bath pan temperature to 40 ℃, the poly methylene poly phenyl poly isocyanate that in there-necked flask, adds 35 weight parts, utilize constant pressure funnel that the mixing solutions of the dibutyl tin laurate of the pentaerythritol diacrylate of 30 weight parts and 0.5 weight part is slowly splashed in the there-necked flask, dropwised in 1.5 hours;
(2) after step (1) dropwises, adjusting the oil bath pan temperature is 55 ℃, after 6 hours, measures isocyanate content every 1 hour with acetone-Di-n-Butyl Amine method in reaction under this temperature, after question response reaches preset value, i.e. and stopped reaction; The mixing solutions that reaction is obtained is poured into and is cooled to 30 ℃ in the constant pressure funnel
(3) dihydroxy-benzene of 25 weight part perfluoro alkyl phosphoester acrylic esters, 0.4 part of catalyzer dibutyl tin laurate and 0.5 weight part is poured in the there-necked flask, mix the reacted product of rear dropping step (2), dropwise in 1 hour, 60 ℃ of lower reactions 12 hours, measure isocyanate group mass contg, stopped reaction after content is less than 2% with acetone-Di-n-Butyl Amine method;
(4) the reacted product of test procedure (3) is determined the solid content of product, adds the reactive monomer thinner of 12 weight parts according to solid content, namely gets product.
Embodiment 3:
The present embodiment illustrates the preparation method of ageing-resistant fluorine-containing urethane resin provided by the invention.
(1) adjusts oil bath pan temperature to 40 ℃, the poly methylene poly phenyl poly isocyanate that in there-necked flask, adds 35 weight parts, utilize constant pressure funnel that the mixing solutions of the dibutyl tin laurate of the pentaerythritol diacrylate of 30 weight parts and 0.5 weight part is slowly splashed in the there-necked flask, dropwised in 1.5 hours;
(2) after step (1) dropwises, adjusting the oil bath pan temperature is 55 ℃, after 6 hours, measures isocyanate content every 1 hour with acetone-Di-n-Butyl Amine method in reaction under this temperature, after question response reaches preset value, i.e. and stopped reaction; The mixing solutions that reaction is obtained is poured into and is cooled to 30 ℃ in the constant pressure funnel
(3) dihydroxy-benzene of 20 weight part fluorine-containing hyperbranched polyester acrylic esters, 0.5 part of catalyzer dibutyl tin laurate and 0.6 weight part is poured in the there-necked flask, mix the reacted product of rear dropping step (2), dropwise in 1 hour, 60 ℃ of lower reactions 12 hours, measure isocyanate group mass contg, stopped reaction after content is less than 0.2% with acetone-Di-n-Butyl Amine method;
(4) the reacted product of test procedure (3) is determined the solid content of product, adds the reactive monomer thinner of 14 weight parts according to solid content, namely gets product.
Embodiment 4:
The present embodiment explanation take ageing-resistant fluorine-containing urethane resin provided by the invention as matrix resin prepares ageing-resistant fluorine-containing polyurethane resin coating.
Product among the embodiment 1 is taken out 100 weight parts, add 16.6 weight part titanium dioxides, 5.8 weight part talcum powder, 3.8 weight part light calcium carbonates, 3.2 weight part process whites, 5.4 weight part silicone oil, use the high speed shear dispersion machine, rotating speed is 3000 rev/mins, obtains ageing-resistant fluorine-containing urethane colored paint after 10 minutes.
Add 0.21 weight part light trigger TPO, 0.58 weight part light trigger 184, stir, leave standstill.
The tinplate that will apply with 400 purpose sand paperings is wiped clean with being stained with the base material that spirituous wet cotton will apply, and according to GB 1727-1992 spraying paint film, film thickness is between 23-35 μ m.The complete panel of spraying is placed on the ventilation, uses 600W ultraviolet light polymerization light irradiation after half an hour until solvent evaporates, irradiation distance is 30cm, and irradiation time is no more than 50s.
Embodiment 5:
The present embodiment explanation take ageing-resistant fluorine-containing urethane resin provided by the invention as matrix resin prepares ageing-resistant fluorine-containing polyurethane resin coating.
Product among the embodiment 2 is taken out 120 weight parts, add 23.5 weight part titanium dioxides, 1.6 weight part carbon blacks, 15 weight part talcum powder, 6.9 weight part light calcium carbonates, 9.8 weight part wilkinites, 4.5 weight part methyl-silicone oils, use the high speed shear dispersion machine, rotating speed is 3000 rev/mins, obtains ageing-resistant fluorine-containing urethane colored paint after 15 minutes.
Add 0.72 weight part light trigger, 819,0.31 weight part light triggers 1173, stir, leave standstill.
Adopt the base material that the same procedure processing will apply in the example 4, same method spraying paint film, curing.
Application Example 6:
The present embodiment explanation take ageing-resistant fluorine-containing urethane resin provided by the invention as matrix resin prepares ageing-resistant fluorine-containing polyurethane resin coating.
Product among the embodiment 3 is taken out 150 weight parts, and the filler of equal in quality in adding and the Application Example 2 uses the high speed shear dispersion machine, and rotating speed is 3000 rev/mins, obtains ageing-resistant fluorine-containing urethane colored paint after 3 hours.
Add identical light trigger among the embodiment 5, stir, leave standstill.
Adopt the base material that the same procedure processing will apply among the embodiment 4, same method spraying paint film, curing.
Embodiment 7
The present embodiment illustrates the performance of ageing-resistant fluorine-containing polyurethane resin coating provided by the invention.
The resin that above-described embodiment 4-6 is obtained carries out performance test, and it the results are shown in Table 1.
(1) solids coatings
Measure according to GB/T1725-1979 (1989);
(2) the drying varniss time
Test according to GB/T1728-1979 (1989);
(3) paint film thermotolerance
Test according to GB/T1733-1979 (1989).Heat-resisting rear placement 30min treats that it is cooled under the standard conditions naturally, detects impact property and sticking power in 1h;
(4) lower temperature resistance
Test plate (panel) with having prepared places-55 ± 2 ℃ refrigerator 4h, takes out test plate (panel), and 23 ± 2 ℃ of temperature, relative humidity is placed 30min 55 ± 5% times, then checks paint film;
(5) water tolerance
Carry out according to GB/T1733-1993, water-fastly dry the water mark with absorbent cotton or soft paper afterwards, place 30min and treat that it is cooled under the standard conditions naturally, in 1h, detect pencil hardness and sticking power;
(6) humidity resistance
Carry out according to GB/T1740-1979 (1989), place 30min behind the humidity resistance and treat that it is cooled under the standard conditions naturally, detects sticking power in 1h;
(7) fungus resistance
Test according to GB/T1741-1979 (1989);
(8) salt fog resistance
Test according to GB/T1771-1991;
(9) anti-4109 lubricating oil
According among the GB/T9274-1988 5.4 carry out, dry oil stain with absorbent cotton or soft paper behind the oil resistant, place 30min and treat that it is cooled under the standard conditions naturally, detects pencil hardness, sticking power in 1h.
(10) anti-No. 3 rocket engine fuels
According among the GB/T9274-1988 5.4 carry out, dry oil stain with absorbent cotton or soft paper behind the oil resistant, place 30min and treat that it is cooled under the standard conditions naturally, detects pencil hardness, sticking power in 1h;
(11) anti-No. 10 hydraulic efficiency oil
According among the GB/T9274-1988 5.4 carry out, dry oil stain with absorbent cotton or soft paper behind the oil resistant, place 30min and treat that it is cooled under the standard conditions naturally, detects pencil hardness, sticking power in 1h;
(12) anti-No. 120 aviation spirit
According among the GB/T9274-1988 5.4 carry out, dry oil stain with absorbent cotton or soft paper behind the oil resistant, place 30min and treat that it is cooled under the standard conditions naturally, detects pencil hardness, sticking power in 1h.
Behind every anti-aging test, concrete data see the following form one to table three:
Table one
Table two
Table three
Claims (4)
1. the preparation method of an anti-aging ultraviolet cured acrylic-polyurethane resin containing fluorine is characterized in that method steps is:
(1) there-necked flask, agitator, prolong, thermometer are installed, adjusting the oil bath pan temperature is 20 ~ 50 ℃, in there-necked flask, add 30 ~ 50 mass parts multicomponent isocyanates, at the uniform velocity drip 20 ~ 30 mass parts monohydroxy acrylate monomers and 0.1 ~ 1 mass parts of catalyst mixing solutions with constant pressure funnel in there-necked flask, rate of addition is controlled within 0.5 ~ 2 hour and drips off; Described catalyzer is triethylamine, diethylene diamine, a kind of in N-methylmorpholine, two lauric acid butyl tin, stannous octoate and the organo-bismuth;
(2) after step (1) dropwises, adjusting the oil bath pan temperature is 50 ~ 70 ℃, heated and stirred reaction 4.5 ~ 8h under this temperature; With the Di-n-Butyl Amine that configures-acetone titration residual isocyanate group content, determine residual content, stopped reaction after it reaches theoretical reacting value;
(3) in step (2) reaction product, add the fluorine-containing acrylic polyol resin of 15 ~ 30 mass parts, 0.1 ~ 1 mass parts of catalyst and 0.5 ~ 1.5 mass parts stopper, keep temperature of reaction at 50 ~ 70 ℃, reacted 8 ~ 12 hours, measure isocyanate group mass contg, stopped reaction after content is less than 2% with acetone-Di-n-Butyl Amine method; Described stopper is a kind of in MEHQ, Resorcinol, para benzoquinone, phenothiazine, beta-phenyl naphthylamines, p-ten.-butylcatechol or cuprous chloride, the iron trichloride inorganics; Described polyhydroxy polycarboxylic acrylate resin is that the following material of solution polymerization makes: one or more (methyl) vinylformic acid and C1-C6 contain the esterification monomer of fluoroalkyl alcohol, at least a kind of (methyl) acrylic ester monomer that contains hydroxyl;
(4) the reacted product of test procedure (3) is determined the solid content of product, adds the reactive monomer thinner of 5 ~ 15 weight parts according to solid content, namely gets product; Described reactive monomer thinner is Viscoat 295 (TMPTA), ethoxylated trimethylolpropane triacrylate (EO
3-TMPTA), propylene glycol diacrylate (DPGDA), tri (propylene glycol) diacrylate (TPGDA) or 1,6 hexanediol diacrylate (HDDA).
2. the preparation method of anti-aging ultraviolet cured acrylic-polyurethane resin containing fluorine according to claim 1 is characterized in that described fluorine-containing acrylic polyol resin is the fluorine-containing aliphatic acrylate of trifunctional, perfluoro alkyl phosphoester acrylic ester or fluorine-containing hyperbranched polyester acrylic ester.
3. the preparation method of anti-aging ultraviolet cured acrylic-polyurethane resin containing fluorine according to claim 1 is characterized in that described multicomponent isocyanate is tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, triphenylmethane triisocyanate, diisocyanate trimer and biuret, poly methylene poly phenyl poly isocyanate or hexamethylene diisocyanate trimer.
4. the preparation method of anti-aging ultraviolet cured acrylic-polyurethane resin containing fluorine according to claim 1 is characterized in that described monohydroxy acrylate is Hydroxyethyl acrylate, Propylene glycol monoacrylate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102659995A (en) * | 2012-04-24 | 2012-09-12 | 南昌航空大学 | Preparation method of ultraviolet-curable water-borne fluorinated paint with low surface energy |
| CN105837723A (en) * | 2016-04-12 | 2016-08-10 | 湖南省金海科技有限公司 | Ultraviolet light curing fluorocarbon resin and manufacturing method thereof |
| CN112608448B (en) * | 2020-12-30 | 2021-10-29 | 江南大学 | Preparation method of high-elasticity hand-feeling wear-resistant multi-arm photocuring resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006071567A1 (en) * | 2004-12-28 | 2006-07-06 | 3M Innovative Properties Company | Fluoroacrylate-multifunctional acrylate copolymer compositions |
| CN1882618A (en) * | 2003-11-21 | 2006-12-20 | 大日本油墨化学工业株式会社 | Fluorine containing photocurable composition |
| CN101020731A (en) * | 2007-03-12 | 2007-08-22 | 安徽大学 | Process of preparing solvent type fluoric acrylate copolymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1882618A (en) * | 2003-11-21 | 2006-12-20 | 大日本油墨化学工业株式会社 | Fluorine containing photocurable composition |
| WO2006071567A1 (en) * | 2004-12-28 | 2006-07-06 | 3M Innovative Properties Company | Fluoroacrylate-multifunctional acrylate copolymer compositions |
| CN101020731A (en) * | 2007-03-12 | 2007-08-22 | 安徽大学 | Process of preparing solvent type fluoric acrylate copolymer |
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