CN103665310B - A kind of preparation method of heat-resistance type UV cured resin - Google Patents
A kind of preparation method of heat-resistance type UV cured resin Download PDFInfo
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- CN103665310B CN103665310B CN201310678049.8A CN201310678049A CN103665310B CN 103665310 B CN103665310 B CN 103665310B CN 201310678049 A CN201310678049 A CN 201310678049A CN 103665310 B CN103665310 B CN 103665310B
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- 229920005989 resin Polymers 0.000 title claims abstract description 31
- 239000011347 resin Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920000728 polyester Polymers 0.000 claims abstract description 15
- 150000002009 diols Chemical class 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 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
- 150000002148 esters Chemical class 0.000 claims abstract description 10
- 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 28
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000003786 synthesis reaction 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
- 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
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 229920005749 polyurethane resin Polymers 0.000 abstract description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 229920002803 thermoplastic polyurethane Polymers 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
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000004519 manufacturing process 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
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 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
- 238000011161 development Methods 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
A kind of preparation method of heat-resistance type UV cured resin, this heat-resistance type UV cured resin utilizes two component mixing dibasic alcohol, isocyanic ester, hydroxy acrylate as main raw material, adopt long-chain method synthesizing linear urethane, modification is carried out to resin material, can the thermotolerance performance of effectively comprehensive phthalic anhydride type polyester diol and other dibasic alcohol materials and elastic performance, its concrete preparation process comprises: choose suitable and appropriate mixing dibasic alcohol, isocyanic ester, hydroxy acrylate, catalyzer and stopper; Enter still, an isothermal reaction through main raw material, add stopper and hydroxy acrylate, secondary isothermal reaction, add the step such as catalyzer, temperature reaction, prepare UV elastic polyurethane resin.The novel UV urethane resin produced by method of the present invention has the advantage of high-low temperature resistant, good springiness.
Description
Technical field
The present invention relates to the resins 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 comprised in the material system of coating be can produce free radical after the UV-light of 40nm to 400nm in absorbing wavelength, make a class new coating of the oligopolymer in system and 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, thus be widely used in all trades and professions.And elastic polyurethane resin has high-clarity, high tenacity and good solvent resistant 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 is as a study hotspot, because it can not only keep the basis of natural resiliency, 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 price very expensive and limit its use; Polycaprolactone-type urethane acrylate intensity and stretching force are all more moderate, but price is also somewhat expensive; And polyester polyurethane acrylate to be generally strength ratio 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, synthesize 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 the preparation method providing a kind 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 is phthalic anhydride type polyester diol and adipic acid type polyester diol, the ratio of any one 1:1 in molar ratio in polycaprolactone diols, these three kinds of dibasic alcohol of polytetrahydrofuran dibasic alcohol is mixed.
In the present invention, described isocyanic ester is the one 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, catalyzer and stopper is also added with in reaction process of the present invention, 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 is 0.1% ~ 0.3% of the total mass of above-mentioned three groups of main raw material compositions.
Its concrete preparation process is:
1), raw material mixing: first two-pack is mixed dibasic alcohol and isocyanic ester and carry out proportioning according to the molar fraction in component, and Homogeneous phase mixing makes mixture;
2) a, isothermal reaction: the mixture obtained in step 1) is joined in reactor, 50 DEG C ~ 70 DEG C are evenly warmed up in 20min, then stir with the speed of 80r/min in a kettle., and under the agitation condition keeping reactor, keep the isothermal reaction of 60 DEG C, reaction times is 2h ~ 5h, nco value surveyed by the sample that takes a morsel after having reacted, if when nco value is not in the interval range of 4% ~ 5%, keeps reaction conditions to continue reaction 1h in reactor;
3), secondary isothermal reaction: if step 2) nco value that records controls 4% ~ 5% time, then can add stopper and hydroxy acrylate in the stirring velocity downhill reaction still of 80r/min, make reactor temperature remain on 60 DEG C or 70 DEG C, 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 DEG C or 80 DEG C in 10min, keep temperature and 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% recorded in step 4), stopped reaction still, namely prepares heat-resistance type UV cured resin finished product of the present invention; If during the NCO > 0.2% recorded in step 4), again detect again, until measured NCO≤0.2% after just continuing to react 1h under 70 DEG C or 80 DEG C of conditions.
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 and adopts the synthetic method of backbone to carry out modification to resin material, the mixing dibasic alcohol structure of described pair of component mixing dibasic alcohol composition can the thermotolerance performance of effectively comprehensive phthalic anhydride type polyester diol and other dibasic alcohol materials and elastic performance, and the auxiliary isocyanic ester that adds and hydroxy acrylate are then used in the preparation of resin material introduces heat-resisting rigid chain segment to improve the heat resistance of its finished-product material.Simultaneously choose and technique control is considered that hard section is high with the microphase separation degree of soft section at raw material, be conducive to the over-all properties of raising polyurethane elastomer.
In addition, adopt the linear polyester relative molecular mass of long-chain method synthesis higher, tensile strength, the elongation of such linear polyester material all can improve, and effectively can improve physical strength and relevant tension, the pressure performance of this resin material; Meanwhile, because the atomic radical in its finished product mostly is compound with regular structure, containing polarity and the many linear polyester 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: present invention employs two component mixing dibasic alcohol and coordinate isocyanic ester and hydroxy acrylate to carry out manufacture as raw material, select twice isothermal reaction in suitable stopper and catalyst complex technique to carry out resin material preparation simultaneously, whole smooth production process can be made easily to control, finished product consistence significantly improves, and lot stability is good; Its resin finished product prepared significantly can improve the temperature classification of paint film, improves the work-ing life of final finished, and other auxiliary agents also can be coordinated effectively to improve the moisture-resistant sex change of finished product, oil-proofness and tension, pressure and scraping performance.
Embodiment
Give an actual example below and describe the present invention.
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 obtained is joined in reactor, 60 DEG C are evenly warmed up in 20min, and under the agitation condition of the speed of 80r/min, keep still interior reaction temperature isothermal reaction 4 h of 60 DEG C, nco value surveyed by the sample that takes a morsel, and measures nco values for three times to be respectively 4.2%, 4.2%, 4.1% kept stable constant continuously.
2mol Rocryl 410 (C is added in reactor
2), and add and account for A
1, A
2, B
2, C
2composition total mass 1 ‰ MEHQ as stopper, 80r/min stir condition under, control temperature is at 70 DEG C of constant temperature synthesis under normal pressure 1 h; Add again and account for A
1, A
2, B
2, C
2composition total mass 2 ‰ dibutyl tin laurate as catalyzer, reactor temperature is increased the temperature to 80 DEG C in 10min, then isothermal reaction 2 h; Take a morsel sample measurement its nco value again, and the NCO recorded is 0.19%≤0.2%, namely completes reaction, opens reactor and obtains finished product.
In the present embodiment, the cured resin finished product prepared in a kettle. is structure is 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 diols (A
3) and 3mol isophorone diisocyanate (B
3) be mixed to form mixture; The mixture obtained is joined in reactor, in 20min, is evenly warmed up to 50 DEG C, under the agitation condition of the speed of 80r/min, keep 60 DEG C of isothermal reaction 2h.The continuous nco value that measures for three times of the sample that takes a morsel is respectively 4.5%, 4.5%, 4.6%, is stationary value.
2mol hydroxyethyl methylacrylate (C is added in reactor
1), and add and account for A
1, A
3, B
3, C
1composition total mass 1 ‰ MEHQ as stopper, 80r/min stir condition under, control temperature is at 70 DEG C of constant temperature synthesis under normal pressure 1 h; 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 DEG C, then isothermal reaction 2 h; Take a morsel sample measurement its nco value again, and the NCO recorded is 0.18%≤0.2%, namely completes reaction, opens reactor and obtains finished product.
In the present embodiment, the cured resin finished product prepared in a kettle. is structure is 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 obtained is joined in reactor, in 20min, is evenly warmed up to 60 DEG C, and under the agitation condition of the speed of 80r/min, keep 60 DEG C of isothermal reaction 4 h.Nco value surveyed by the sample that takes a morsel, and the continuous nco value that measures for three times is respectively 4.6%, 4.6%, 4.6%, and maintenance is stablized constant.
2mol hydroxyethyl methylacrylate (C is added in reactor
1), and add and account for A
1, A
4, B
1, C
1composition total mass 1 ‰ MEHQ as stopper, 80r/min stir condition under, control temperature is at 60 DEG C of constant temperature synthesis under normal pressure 2 h; Add again and account for A
1, A
4, B
1, C
1composition total mass 2 ‰ dibutyl tin laurate as catalyzer, progressively increase the temperature to 70 DEG C, then isothermal reaction 2 h; Take a morsel sample measurement its nco value again, and the NCO recorded is 0.22%, is greater than 0.2%, again detect after selecting the reaction conditions continuing maintenance 70 DEG C in reactor to react 1h, 1h, the NCO recorded is 0.18%≤0.2%, namely complete reaction, open reactor and obtain finished product.
In the present embodiment, the cured resin finished product prepared in a kettle. is structure is 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 describe 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; what describe in above-described embodiment and specification sheets 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.Application claims protection domain 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 is phthalic anhydride type polyester diol and adipic acid type polyester diol, the ratio of any one 1:1 in molar ratio in polycaprolactone diols, these three kinds of dibasic alcohol of polytetrahydrofuran dibasic alcohol is mixed,
The concrete preparation process of heat-resistance type UV cured resin is:
1), raw material mixing: first two-pack is mixed dibasic alcohol and isocyanic ester and carry out proportioning according to the molar fraction in component, and Homogeneous phase mixing makes mixture;
2) a, isothermal reaction: the mixture obtained in step 1) is joined in reactor, 50 DEG C ~ 70 DEG C are evenly warmed up in 20min, then stir with the speed of 80r/min in a kettle., and under the agitation condition keeping reactor, keep the isothermal reaction of 60 DEG C, reaction times is 2h ~ 5h, react rear sample thief and surveyed nco value, if when nco value is not in the interval range of 4% ~ 5%, in reactor, keep reaction conditions to continue reaction 1h;
3), secondary isothermal reaction: if step 2) nco value that records controls 4% ~ 5% time, then in the stirring velocity downhill reaction still of 80r/min, add stopper and hydroxy acrylate, make reactor temperature remain on 60 DEG C or 70 DEG C, 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 DEG C or 80 DEG C in 10min, keep temperature and isothermal reaction 2 ~ 3 h in reactor, resampling product measure its nco value;
5), resin forming: if NCO≤0.2% recorded in step 4), stopped reaction still, namely prepares heat-resistance type UV cured resin finished product; If during the NCO > 0.2% recorded in step 4), again detect again, until measured NCO≤0.2% after just continuing to react 1h under 70 DEG C or 80 DEG C of conditions.
2. the preparation method of a kind of heat-resistance type UV cured resin according to claim 1, it is characterized in that, described isocyanic ester is the one in diphenylmethanediisocyanate, tolylene diisocyanate, isophorone diisocyanate.
3. the preparation method of a kind of heat-resistance type UV cured resin according to claim 1, it 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, it is characterized in that, described stopper is MEHQ, and its consumption is 0.1% ~ 0.3% of the total mass of above-mentioned three groups of main raw material compositions.
5. the preparation method of a kind of heat-resistance type UV cured resin according to claim 1, it 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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| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101372530A (en) * | 2008-08-08 | 2009-02-25 | 中国工程物理研究院化工材料研究所 | Water-based light-cured polyurethane resin 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 |
| 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 |
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| CN101372530A (en) * | 2008-08-08 | 2009-02-25 | 中国工程物理研究院化工材料研究所 | Water-based light-cured polyurethane resin and preparation method thereof |
| 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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