CN103665310A - Preparation method of temperature-resistant UV (ultraviolet) curing resin - Google Patents
Preparation method of temperature-resistant UV (ultraviolet) curing resin Download PDFInfo
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- CN103665310A CN103665310A CN201310678049.8A CN201310678049A CN103665310A CN 103665310 A CN103665310 A CN 103665310A CN 201310678049 A CN201310678049 A CN 201310678049A CN 103665310 A CN103665310 A CN 103665310A
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- 229920005989 resin Polymers 0.000 title claims abstract description 32
- 239000011347 resin Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229920000728 polyester Polymers 0.000 claims abstract description 15
- 150000002009 diols Chemical class 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims abstract description 11
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 7
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical group COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 5
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical group COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 238000012952 Resampling Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 5
- 229920002635 polyurethane Polymers 0.000 abstract description 5
- 239000004814 polyurethane Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000001723 curing Methods 0.000 abstract description 3
- 229920005749 polyurethane resin Polymers 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract 2
- 239000003112 inhibitor Substances 0.000 abstract 2
- 239000012948 isocyanate Substances 0.000 abstract 2
- 150000002513 isocyanates Chemical class 0.000 abstract 2
- 238000006116 polymerization reaction Methods 0.000 abstract 2
- 238000003848 UV Light-Curing Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OELQSSWXRGADDE-UHFFFAOYSA-N 2-methylprop-2-eneperoxoic acid Chemical compound CC(=C)C(=O)OO OELQSSWXRGADDE-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006221 furniture coating Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- -1 wherein Polymers 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a preparation method of a temperature-resistant UV (ultraviolet) curing resin. The temperature-resistant UV curing resin is characterized in that linear polyurethane is synthesized by taking double-component mixed diol, isocyanate and hydroxyacrylate as main raw materials through a long chain method, so that the resin material is modified, thus effectively combining the heat resistance and elasticity of phthalic anhydride type polyester diol and other diol materials. The preparation method comprises the following specific preparation steps: selecting appropriate and proper amounts of mixed diol, isocyanate, hydroxyacrylate, catalyst and polymerization inhibitor; and performing the steps of feeding the main raw materials into a kettle, primary thermostatic reaction, adding the polymerization inhibitor and hydroxyacrylate, secondary thermostatic reaction, adding the catalyst, heating reaction and the like, thus obtaining the UV polyurethane elastic resin. The novel UV polyurethane resin produced by the method has the advantages of high/low temperature resistance and good elasticity.
Description
Technical field
The present invention relates to the resin synthesis technical field in Chemicals, be specially a kind of preparation method of heat-resistance type UV cured resin.
Background technology
UV coating mainly refers under UV-irradiation, by the light trigger comprising in the material system of coating, in absorbing wavelength, be that 40nm can produce free radical after the UV-light of 400nm, make oligopolymer in system and a class new coating of the rapid crosslinking curing film forming of reactive thinner, the principal feature of this class coating is solid containing high, curing speed is fast, ready coating solidifies, sticking power is good, fullness ratio is good, hardness is high, weather resistance is superior, transparency is good, minimum irritating smell, to person toxicological harmless effect, it is environmental friendly product, simultaneously, comprehensive cost is low, thereby be widely used in all trades and professions.And elastic polyurethane resin has high-clarity, high tenacity and good resistance to solvent and chemical resistant properties, and also have gloss retention good, the advantage such as easy to clean and be widely used in the fields such as coating, furniture coating, tackiness agent.
At present, elastic polyurethane resin, as a study hotspot, because it can not only keep self elastic basis, can also have other characteristics and function.In the prior art, apply comparatively widely elastic resin have polyether polyurethane-acrylate, polycarbonate polyurethane acrylate, polycaprolactone-type urethane acrylate and polyester polyurethane acrylate, wherein, polyether polyurethane-acrylate has good extensibility, but tensile strength is very poor, easy fracture; Polycarbonate has good over-all properties, but due to its very expensive use that has limited it of price; Polycaprolactone-type urethane acrylate intensity and stretching force are all more moderate, but price is also somewhat expensive; And polyester polyurethane acrylate is generally that strength ratio is better, but stretching force is inadequate, and meanwhile, it is exactly that temperature difference resistance can be all not ideal enough that these above-mentioned urethane acrylates all also exist this common defect.So, under above-mentioned technical background, synthetic a kind of can high-and low-temperature resistance environment, possess better elastic urethane acrylate material again, possess better development prospect and marketable value.
Summary of the invention
Technical problem solved by the invention is to provide a kind of preparation method of heat-resistance type UV cured resin, to solve the shortcoming in above-mentioned background technology.
Technical problem solved by the invention realizes by the following technical solutions:
A preparation method for heat-resistance type UV cured resin, wherein, each main raw material carries out proportioning by molar fraction and is:
Two component mixing dibasic alcohol 0.28;
Isocyanic ester 0.42;
Hydroxy acrylate 0.28;
In the present invention, the described pair of component mixing dibasic alcohol be in phthalic anhydride type polyester diol and adipic acid type polyester diol, polycaprolactone dibasic alcohol, these three kinds of dibasic alcohol of polytetrahydrofuran dibasic alcohol any one in molar ratio the ratio of 1:1 be mixed.
In the present invention, described isocyanic ester is a kind of in diphenylmethanediisocyanate, tolylene diisocyanate, isophorone diisocyanate.
In the present invention, described hydroxy acrylate is hydroxyethyl methylacrylate or Rocryl 410.
Except above-mentioned three groups of major ingredient, in reaction process of the present invention, be also added with catalyzer and stopper, wherein, catalyzer is dibutyl tin laurate, its consumption is 0.01% ~ 0.2% of above-mentioned three groups of main raw material composition total masses, and stopper is MEHQ, its consumption be above-mentioned three groups of main raw material compositions total mass 0.1% ~ 0.3%.
Its concrete preparation process is:
1), raw material mixes: first two-pack is mixed to dibasic alcohol and isocyanic ester according to the proportioning of carrying out of the molar fraction in component, and be evenly mixed and made into mixture;
2) a, isothermal reaction: the mixture obtaining in step 1) is joined in reactor, in 20min, be evenly warmed up to 50 ℃ ~ 70 ℃, then in reactor, the speed with 80r/min stirs, and keeping under the agitation condition of reactor, keeping the isothermal reaction of 60 ℃, reaction times is 2h ~ 5h, the sample that takes a morsel after having reacted is surveyed nco value, if nco value not in 4% ~ 5% interval range in time, keeps reaction conditions to continue to react 1h in reactor;
3) when the nco value, secondary isothermal reaction: if step 2) recording is controlled at 4% ~ 5%, can in the stirring velocity downhill reaction still of 80r/min, add stopper and hydroxy acrylate, make reactor temperature remain on 60 ℃ or 70 ℃, and carry out constant temperature synthesis under normal pressure, the reaction times is 1 ~ 2h;
4), temperature reaction: add catalyzer in reactor, and the temperature of reaction in reactor is progressively elevated to 70 ℃ or 80 ℃ in 10min, keep temperature isothermal reaction 2 ~ 3 h in reactor, then its nco value of sample measurement that takes a morsel;
5), resin forming: if NCO≤0.2% recording in step 4), stopped reaction still, prepares heat-resistance type UV cured resin finished product of the present invention; If during the NCO > 0.2% recording in step 4), again detect again after just continuing to react 1h under 70 ℃ or 80 ℃ of conditions, until measured NCO≤0.2%.
The present invention chooses two-pack diol mixture will and adopts the formula of the methacrylic acid hydroxyl ester of high glass transition temperature heat resistant structure to coordinate the synthetic method of employing backbone to carry out modification to resin material, the mixing dibasic alcohol structure that the described pair of component mixing dibasic alcohol forms can effectively comprehensive phthalic anhydride type polyester diol and thermotolerance performance and the elastic performance of other dibasic alcohol materials, in the preparation that the auxiliary isocyanic ester adding and hydroxy acrylate are used in resin material, introduces heat-resisting rigid chain segment to improve the heat resistance of its finished-product material.Simultaneously raw material choose and technique control on consider hard section high with the microphase separation degree of soft section, be conducive to improve the over-all properties of polyurethane elastomer.
In addition, adopt the synthetic linear polyester relative molecular mass of long-chain method higher, the tensile strength of linear polyester material, elongation all can improve like this, can effectively improve the physical strength of this resin material and relevant tension, pressure performance; Meanwhile, because the atomic radical in its finished product mostly is compound with regular structure, containing polarity and the many linear polyesters of rigid radical, intermolecular hydrogen bonding is many, causes the crystallization degree of material high, can improve intensity and the solvent resistance of material.
Beneficial effect: the present invention has adopted two component mixing dibasic alcohol to coordinate isocyanic ester and hydroxy acrylate to carry out manufacture as raw material, select suitable stopper and catalyzer to coordinate twice isothermal reaction in technique to carry out resin material preparation simultaneously, can make whole smooth production process easily control, finished product consistence significantly improves, batch good stability; Its resin finished product of preparing can significantly promote the temperature classification of paint film, in the work-ing life of having improved final finished, also can coordinate other auxiliary agents effectively to improve moisture-resistant sex change, oil-proofness and tension, pressure and the scraping performance of finished product.
Embodiment
Give an actual example and describe the present invention below.
Embodiment 1
First by 1mol phthalic anhydride type polyester diol (A
1), 1mol adipic acid type polyester diol (A
2) and 3mol tolylene diisocyanate (B
2) be mixed to form mixture; The mixture obtaining is joined in reactor, in 20min, be evenly warmed up to 60 ℃, and keep still interior reaction temperature isothermal reaction 4 h of 60 ℃ under the agitation condition of the speed of 80r/min, the sample that takes a morsel is surveyed nco value, measures nco values for three times to be respectively 4.2%, 4.2%, 4.1% kept stable constant continuously.
In reactor, add 2mol Rocryl 410 (C
2), and add and account for A
1, A
2, B
2, C
21 ‰ MEHQ of composition total mass, as stopper, under the condition stirring, is controlled temperature at 70 ℃ of constant temperature synthesis under normal pressure 1 h at 80r/min; Add again and account for A
1, A
2, B
2, C
22 ‰ dibutyl tin laurate of composition total mass, as catalyzer, increases the temperature to 80 ℃ by reactor temperature in 10min, then isothermal reaction 2 h; Its nco value of sample measurement that takes a morsel again, the NCO recording is 0.19%≤0.2%, completes reaction, opens reactor and obtains finished product.
In the present embodiment, the cured resin finished product preparing in reactor is that structure is to be C
2-B
2-A
1-B
2-A
1-B
2-C
2, C
2-B
2-A
1-B
2-A
2-B
2-C
2, C
2-B
2-A
2-B
2-A
2-B
2-C
2the mixture of three compounds, this mixture is heat-resistance type UV cured resin.
Embodiment 2
First by 1mol phthalic anhydride type polyester diol (A
1), 1mol polycaprolactone dibasic alcohol (A
3) and 3mol isophorone diisocyanate (B
3) be mixed to form mixture; The mixture obtaining is joined in reactor, in 20min, be evenly warmed up to 50 ℃, under the agitation condition of the speed of 80r/min, keep 60 ℃ of isothermal reaction 2h.The continuous nco value of measuring for three times of the sample that takes a morsel is respectively 4.5%, 4.5%, 4.6%, is stationary value.
In reactor, add 2mol hydroxyethyl methylacrylate (C
1), and add and account for A
1, A
3, B
3, C
11 ‰ MEHQ of composition total mass, as stopper, under the condition stirring, is controlled temperature at 70 ℃ of constant temperature synthesis under normal pressure 1 h at 80r/min; Add again and account for A
1, A
3, B
3, C
12 ‰ dibutyl tin laurates of composition total mass, as catalyzer, progressively increase the temperature to 80 ℃, then isothermal reaction 2 h; Its nco value of sample measurement that takes a morsel again, the NCO recording is 0.18%≤0.2%, completes reaction, opens reactor and obtains finished product.
In the present embodiment, the cured resin finished product preparing in reactor is that structure is to be C
1-B
3-A
1-B
3-A
1-B
3-C
1, C
1-B
3-A
1-B
3-A
3-B
3-C
1, C
1-B
3-A
3-B
3-A
3-B
3-C
1mixture, this mixture is heat-resistance type UV cured resin.
Embodiment 3
First by 1mol phthalic anhydride type polyester diol (A
1), 1mol polytetrahydrofuran dibasic alcohol (A
4) and 3mol diphenylmethanediisocyanate (B
1) be mixed to form mixture; The mixture obtaining is joined in reactor, in 20min, be evenly warmed up to 60 ℃, and under the agitation condition of the speed of 80r/min, keep 60 ℃ of isothermal reaction 4 h.The sample that takes a morsel is surveyed nco value, and the continuous nco value of measuring for three times is respectively 4.6%, 4.6%, 4.6%, keeps stablizing constant.
In reactor, add 2mol hydroxyethyl methylacrylate (C
1), and add and account for A
1, A
4, B
1, C
11 ‰ MEHQ of composition total mass, as stopper, under the condition stirring, is controlled temperature at 60 ℃ of constant temperature synthesis under normal pressure 2 h at 80r/min; Add again and account for A
1, A
4, B
1, C
12 ‰ dibutyl tin laurate of composition total mass, as catalyzer, progressively increases the temperature to 70 ℃, then isothermal reaction 2 h; Its nco value of sample measurement that takes a morsel again, the NCO recording is 0.22%, is greater than 0.2%, be chosen in reactor and continue to keep the reaction conditions reaction 1h of 70 ℃, after 1h, again detect, the NCO recording is 0.18%≤0.2%, complete reaction, open reactor and obtain finished product.
In the present embodiment, the cured resin finished product preparing in reactor is that structure is to be C
1-B
1-A
1-B
1-A
1-B
1-C
1, C
1-B
1-A
1-B
1-A
4-B
1-C
1, C
1-B
1-A
4-B
1-A
4-B
1-C
1mixture, this mixture is heat-resistance type UV cured resin.
More than show and described ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and specification sheets, describes just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (5)
1. a preparation method for heat-resistance type UV cured resin, is characterized in that, each main raw material carries out proportioning by molar fraction and is:
Two component mixing dibasic alcohol 0.28;
Isocyanic ester 0.42;
Hydroxy acrylate 0.28;
In said components, the described pair of component mixing dibasic alcohol be in phthalic anhydride type polyester diol and adipic acid type polyester diol, polycaprolactone dibasic alcohol, these three kinds of dibasic alcohol of polytetrahydrofuran dibasic alcohol any one in molar ratio the ratio of 1:1 be mixed,
The concrete preparation process of heat-resistance type UV cured resin is:
1), raw material mixes: first two-pack is mixed to dibasic alcohol and isocyanic ester according to the proportioning of carrying out of the molar fraction in component, and be evenly mixed and made into mixture;
2) a, isothermal reaction: the mixture obtaining in step 1) is joined in reactor, in 20min, be evenly warmed up to 50 ℃ ~ 70 ℃, then in reactor, the speed with 80r/min stirs, and keeping under the agitation condition of reactor, keeping the isothermal reaction of 60 ℃, reaction times is 2h ~ 5h, reacted rear sample thief and surveyed nco value, if nco value not in 4% ~ 5% interval range in time, keeps reaction conditions to continue to react 1h in reactor;
3) when the nco value, secondary isothermal reaction: if step 2) recording is controlled at 4% ~ 5%, in the stirring velocity downhill reaction still of 80r/min, add stopper and hydroxy acrylate, make reactor temperature remain on 60 ℃ or 70 ℃, and carry out constant temperature synthesis under normal pressure, the reaction times is 1 ~ 2h;
4), temperature reaction: add catalyzer in reactor, and the temperature of reaction in reactor is progressively elevated to 70 ℃ or 80 ℃ in 10min, keep temperature isothermal reaction 2 ~ 3 h in reactor, resampling product are measured its nco value;
5), resin forming: if NCO≤0.2% recording in step 4), stopped reaction still, prepares heat-resistance type UV cured resin finished product; If during the NCO > 0.2% recording in step 4), again detect again after just continuing to react 1h under 70 ℃ or 80 ℃ of conditions, until measured NCO≤0.2%.
2. the preparation method of a kind of heat-resistance type UV cured resin according to claim 1, is characterized in that, described isocyanic ester is a kind of in diphenylmethanediisocyanate, tolylene diisocyanate, isophorone diisocyanate.
3. the preparation method of a kind of heat-resistance type UV cured resin according to claim 1, is characterized in that, described hydroxy acrylate is hydroxyethyl methylacrylate or Rocryl 410.
4. the preparation method of a kind of heat-resistance type UV cured resin according to claim 1, is characterized in that, described stopper is MEHQ, its consumption be above-mentioned three groups of main raw material compositions total mass 0.1% ~ 0.3%.
5. the preparation method of a kind of heat-resistance type UV cured resin according to claim 1, is characterized in that, described catalyzer is dibutyl tin laurate, and its consumption is 0.01% ~ 0.2% of above-mentioned three groups of main raw material composition total masses.
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| CN109071754A (en) * | 2016-03-04 | 2018-12-21 | 陶氏环球技术有限责任公司 | The method for being used to prepare urethane acrylate |
| CN112094164A (en) * | 2020-09-16 | 2020-12-18 | 湖北三江航天江河化工科技有限公司 | Photocuring propellant and preparation method thereof |
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| CN102153721A (en) * | 2010-12-27 | 2011-08-17 | 广东嘉宝莉化工集团有限公司 | Modified polyurethane elastic curing agent and preparation method thereof |
| CN102153914A (en) * | 2011-04-14 | 2011-08-17 | 兰州理工大学 | Preparation method of water-based UV ink (ultraviolet) of unsaturated polyester polyurethane segmented copolymer |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104031229A (en) * | 2014-06-16 | 2014-09-10 | 常州华科聚合物股份有限公司 | Polyurethane modified resin for air vane and preparation methods of polyurethane modified resin |
| CN109071754A (en) * | 2016-03-04 | 2018-12-21 | 陶氏环球技术有限责任公司 | The method for being used to prepare urethane acrylate |
| CN109071754B (en) * | 2016-03-04 | 2021-09-10 | 陶氏环球技术有限责任公司 | Process for preparing urethane acrylates |
| CN112094164A (en) * | 2020-09-16 | 2020-12-18 | 湖北三江航天江河化工科技有限公司 | Photocuring propellant and preparation method thereof |
| CN112094164B (en) * | 2020-09-16 | 2022-05-17 | 湖北三江航天江河化工科技有限公司 | Photocuring propellant and preparation method thereof |
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