CN103387656A - Preparation method of UV (ultraviolet) curing metal coating prepolymer - Google Patents
Preparation method of UV (ultraviolet) curing metal coating prepolymer Download PDFInfo
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- CN103387656A CN103387656A CN2013103556749A CN201310355674A CN103387656A CN 103387656 A CN103387656 A CN 103387656A CN 2013103556749 A CN2013103556749 A CN 2013103556749A CN 201310355674 A CN201310355674 A CN 201310355674A CN 103387656 A CN103387656 A CN 103387656A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 71
- 239000002184 metal Substances 0.000 title claims abstract description 71
- 239000011248 coating agent Substances 0.000 title claims abstract description 70
- 238000000576 coating method Methods 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 16
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 16
- 229920000570 polyether Polymers 0.000 claims abstract description 16
- 238000007599 discharging Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 13
- -1 hydroxyl acrylic ester Chemical class 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000004448 titration Methods 0.000 claims abstract description 7
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 4
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000003848 UV Light-Curing Methods 0.000 claims description 52
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 15
- 239000003112 inhibitor Substances 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 10
- 239000004925 Acrylic resin Substances 0.000 claims description 8
- 229920000178 Acrylic resin Polymers 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- 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 7
- 238000000034 method Methods 0.000 claims description 7
- 238000003556 assay Methods 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000207 volumetry Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- QXIQCNFSNJEMOD-UHFFFAOYSA-N 3-hydroxybutan-2-yl prop-2-enoate Chemical compound CC(O)C(C)OC(=O)C=C QXIQCNFSNJEMOD-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- HGXVKAPCSIXGAK-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine;4,6-diethyl-2-methylbenzene-1,3-diamine Chemical compound CCC1=CC(CC)=C(N)C(C)=C1N.CCC1=CC(C)=C(N)C(CC)=C1N HGXVKAPCSIXGAK-UHFFFAOYSA-N 0.000 claims description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 2
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 2
- 241001112258 Moca Species 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims 1
- 239000007805 chemical reaction reactant Substances 0.000 claims 1
- 150000004985 diamines Chemical class 0.000 claims 1
- 150000003384 small molecules Chemical class 0.000 claims 1
- 238000004383 yellowing Methods 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000003431 cross linking reagent Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229920005862 polyol Polymers 0.000 abstract 2
- 150000003077 polyols Chemical class 0.000 abstract 2
- 239000000758 substrate Substances 0.000 abstract 2
- 208000005156 Dehydration Diseases 0.000 abstract 1
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- 239000011521 glass Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000002530 phenolic antioxidant Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 238000000016 photochemical curing Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000002334 glycols Chemical class 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000007039 two-step reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000012970 tertiary amine catalyst Substances 0.000 description 1
Abstract
The invention relates to a preparation method of a UV (ultraviolet) curing metal coating prepolymer. The preparation method comprises the following steps of: performing dehydration treatment on a mixture of polyester polyol and polyether polyol, wherein the number average molecular weight of the polyester polyol or the polyether polyol is 800-5000, and the viscosity is 600-1500mPa. S (25 DEG C); adding a tertiary amine type or metal organic compound catalyst, stirring and uniformly mixing at room temperature, further adding diisocyanate, stirring at room temperature for 30min, further heating to 50-70 DEG C for reaction, reacting for 1-1.5h, then adding an appropriate quantity of cross-linking agent into a system, and continuously reacting; reacting for 3-5h, and then adding a certain quantity of hydroxyl acrylic ester and a certain quantity of phenolic antioxidant into the system after the end of chain extension reaction; and determining the content of NCO through a titration method, stopping reaction when a required theoretical value is achieved, and discharging. By adopting the preparation method disclosed by the invention, the technical problems that the adhesion of a cured film on a metal substrate is poor, the substrate is damaged or the metal glass is affected, the curing rate is not high, the production efficiency is further low, the yellowing resistance and flexibility of the film are poor and the like can be solved.
Description
Technical field
The invention belongs to the environmental protection coating material field, be specifically related to a kind of preparation method of UV curing metal coating prepolymer.
Background technology
All the time, in paint field, especially in the coating material solidified field of UV, the sticking power of UV cured film and metal base and to the corrosive nature of metal base, be to need the key problem that solves, the photo-curing rate of UV coating and the mechanical property of cured film are also the major issues that need to solve, and the fundamental way that addresses these problems the key problems such as sticking power especially is the structure design of prepolymer.The present invention has just synthesized a kind of to metal base sticking power is good, anticorrosion, solidification rate is fast, mechanical property is excellent UV curing metal coating prepolymer for the problems referred to above designs.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of UV curing metal coating prepolymer, it is concentrated and has solved the existing deficiency of existing UV curing metal coating: as the poor adhesive force of cured film to metal base, on metal base certain corrosive nature is arranged and damage base material or affect that metalluster sense, solidification rate not highly cause that production efficiency is low, the yellowing resistance of film and snappiness poor etc., the present invention provides a kind of feasible solution by the structure design to prepolymer for the solution of the problems referred to above.
Technical solution of the present invention is:
A kind of preparation method of UV curing metal coating prepolymer, its special character is: comprise the following steps:
1] mixture of the pure and mild polyether glycol of polyester polyols is carried out processed, all molecular mass is between 800-5000 relatively for the number of described polyester polyol or polyether glycol, and viscosity is between 600-1500mPa.S (25 ℃);
2] add tertiary amines or Catalyzed by Organometallic Compounds agent, stirring at room mixes,
3] add again the vulcabond stirring at room 30 minutes, then be warming up to reaction under 50-70 ℃, react after 1-1.5 hour, add linking agent to continue reaction in system;
4] reaction is after 3-5 hour, and chain extending reaction adds hydroxy acrylate and oxidation inhibitor to system after finishing again.
5] determine the content of NCO by volumetry, when reaching required theoretical value, stopped reaction, discharging, namely obtain required UV curing metal coating prepolymer.
Above-mentioned steps 3] while adding linking agent, add the reactive thinner of adjusting viscosity.
Each above-mentioned step is reacted starting material consumption by weight: vulcabond 14-32 part; Polyether glycol 20-40 part; Polyester polyol: 20-40; Acrylic resin 5-20 part; Linking agent 1-5 part; 0.5 part-1 part of catalyzer; Oxidation inhibitor: 0.5-1 part; Reactive thinner: 100-500 part.
Above-mentioned processed, that polyester polyol or polyether glycol or mixture are both added in reactor, start stirring, and the heating that heats up, make liquid temperature reach 50-70 ℃ of left and right, start vacuum pump, make vacuum tightness in reactor rise to slowly 0.098-0.1MPa, the control temperature in the kettle is 100-120 ℃, and discharging after 3 hours is placed in airtight storage tank standby.
above-mentioned content by titration measuring NCO is determined level of response, its method is described as: take the 5g prepolymer, put into the dry flask of crossing, add 20mL Di-n-Butyl Amine solution standardized solution with transfer pipet, the THF that adds again the 50mL drying, shake up, add the 100mL anhydrous isopropyl alcohol, with the agent of giving instruction of 0.5mL tetrabromo-mcresolsulfonphthalein, be titrated to yellow with the hydrochloric acid soln of 1N and be terminal, do again finally blank assay, then calculate the content of NCO group by NCO%=mLHCl blank-mLHCl sample/example weight x4.2, when reaching theoretical value, NCO content represents that reaction finishes, discharging, obtain required UV curing metal coating prepolymer.
Above-mentioned vulcabond comprises any of TDI, MDI, HDI, TMHDI, IPDI and HXDI combination, especially use wherein IPDI and HDI as preferably, or two kinds of compound use effects is better.
The pure and mild polyether glycol of above-mentioned polyester polyols comprises any of PDA, PEA, PBA, PCL, PCDL, PTMEG, PEG and PPG combination, especially with PCL or PCL, mixes result of use the best with two kinds of PTMEG.
Above-mentioned acrylic resin comprises (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, pentaerythritol triacrylate, Dipentaerythritol five acrylate and epoxy acrylate; The present invention selects epoxy acrylate or (methyl) crylic acid hydroxy ester to participate in reaction or regulation system viscosity as function monomer.
Above-mentioned linking agent comprises BDO, ethylene glycol, 1,2-PD, 1,3-PD, glycol ether, 1,6-hexylene glycol, MOCA, DMTDA, DETDA, thanomin, diethanolamine or trolamine.The linking agent that mainly uses in the present invention is aminated compounds;
Described reactive thinner comprises alkyl acrylate, glycols diacrylate, propandiols diacrylate and epoxy acrylate etc.
Described catalyzer comprises triethylenediamine, two (dimethylaminoethyl) ether, 2-(2-dimethylamino-oxyethyl group) ethanol, stannous octoate, dibutyl tin laurate, carboxylic acid potassium, organic mercury or organic lead.Especially use a kind of as optimal selection in stannous octoate, dibutyl tin laurate.
Described oxidation inhibitor is mainly used in preventing that prepolymer thermal-oxidative degradation or functional grafted monomer from occurring crosslinked, comprise 2, any of 6-ditertbutylparacresol, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, butyl or octyl group aniline and phosphorous acid ester combination.Select wherein a kind of or with the phosphorous acid ester compound use, have better effect.
The UV curing metal coating prepolymer that a kind of above-mentioned preparation method prepares, its special character is: this UV curing metal coating prepolymer is equipped with appropriate metallic pigment, multifunctional reactive thinner, light trigger and other auxiliary agents is applied to prepare UV curing metal coating.
The preparation method of a kind of UV curing metal of the present invention coating prepolymer, wherein polyvalent alcohol is after processed, added organic tin catalyzer and vulcabond stirring at room 30 minutes, heat up again and react the regular hour between 50-70 ℃, then add the functional chainextender that is conducive to improve sticking power to carry out chain extending reaction, total reaction time is at 3-5 hour.
The preparation method of a kind of UV curing metal coating prepolymer of the present invention, wherein, add epoxy acrylate or (methyl) Propylene glycol monoacrylate to carry out end capping, 50-70 ℃ of reaction times at 3-7 hour.
The invention has the advantages that:
Its product of the present invention is the water white transparency thick liquid, is equipped with a certain amount of reactive thinner, and namely obtaining can be for the prepolymer that is mixed with UV curing metal coating.
Its UV that is mixed with of the present invention is coating material solidified, and is good to the sticking power of metal base, to metal base certain corrosion-resisting function is arranged and cut have good metalluster sense, photo-curing rate is fast, cured film has excellent yellowing resistance and snappiness.
Embodiment
For further illustrating the technology of the present invention, be described in detail below in conjunction with specific embodiment, the present invention includes but be not limited to following examples.
Embodiment 1
A kind of preparation method of UV curing metal coating prepolymer, wherein, each component concentration is by mass parts: 32 parts of vulcabond; 30 parts of polyether glycols; Polyester polyol: 30; 5 parts of acrylic resins; 3 parts of linking agents.Other auxiliary agents include but not limited to 0.5 part of catalyzer; Oxidation inhibitor: 1 part; 200 parts of reactive thinners.
A kind of preparation method of UV curing metal coating prepolymer, its preparation process is as follows: PTMEG and PEG are carried out processed under certain condition, add organotin catalysts, stirring at room mixes, then adds respectively TDI and HDI, is warming up between 50-70 ℃, after the reaction certain hour, to the linking agent that adds aforementioned proportion in system, above two-step reaction total time is no more than 5 hours, then adds the oxidation inhibitor insulation reaction of epoxy acrylate and specified amount.Determine the content of NCO by volumetry, when reaching required theoretical value, stopped reaction, discharging, namely obtain required UV curing metal coating prepolymer.
Wherein, the number of PTMEG and PEG when all relative molecular mass is 1000,25 ℃ viscosity in the 600mPa.S left and right.
Wherein, PTMEG and PEG needed through processed before adding TDI and HDI, be after PTMEG and PEG drop into reactor, heat up, when the temperature of mixture reaches 50 ℃, start vacuum pump, make vacuum tightness in reactor rise to slowly 0.098-0.1MPa, control temperature in the kettle and be 3 hours, 110 ℃ of left and right, standby.
wherein said content by titration measuring NCO is determined level of response, its method is described as: take the 5g prepolymer, put into the dry flask of crossing, the 20mL Di-n-Butyl Amine standardized solution that adds new preparation with transfer pipet, the THF that adds again the 50mL drying, shake up, add the 100mL anhydrous isopropyl alcohol, with the agent of giving instruction of 0.5mL tetrabromo-mcresolsulfonphthalein, be titrated to yellow with the hydrochloric acid soln of 1N and be terminal, do again finally blank assay, then calculate the content of NCO group by NCO%=mLHCl blank-mLHCl sample/example weight x4.2, when reaching theoretical value, NCO content represents that reaction finishes, discharging, obtain required UV curing metal coating prepolymer.
A kind of preparation method of UV curing metal coating prepolymer, wherein, only need to add a certain amount of reactive thinner, and namely obtaining can be for being mixed with UV curing metal coating prepolymer.
The UV that the UV curing metal coating prepolymer that a kind of preparation method of UV curing metal coating prepolymer obtains is mixed with is coating material solidified, sticking power to metal base is good, the film of testing the coating material solidified formation of this UV by cross-hatching does not come off, to metal base certain corrosion-resisting function is arranged and cut have good metalluster sense, photo-curing rate is fast, photocuring speed rate＜=(more than 15 seconds), cured film had excellent yellowing resistance and snappiness in 5 seconds, and excellent yellowing resistance is embodied under natural light to place and still was the water white transparency shape in 1-6 month; The film that excellent snappiness is embodied in the coating material solidified formation of this UV repeatedly folding 90 degree-180 degree without escutcheon, do not ftracture.
Embodiment 2
A kind of preparation method of UV curing metal coating prepolymer, wherein, each component concentration is by mass parts: 32 parts of vulcabond; 20 parts of polyether glycols; Polyester polyol: 30; 15 parts of acrylic resins; 3 parts of linking agents.Other auxiliary agents include but not limited to 0.5 part of catalyzer; Oxidation inhibitor: 1 part; 150 parts of reactive thinners.
A kind of preparation method of UV curing metal coating prepolymer, its preparation process is as follows: PTMEG and PCL are carried out processed under certain condition, add tertiary amine catalyst, stirring at room mixes, add again IPDI, be warming up between 50-70 ℃, after the reaction certain hour, to the linking agent (can add as required the reactive thinner adjusting viscosity with function group) that adds hydroxyl or other functional groups of aforementioned proportion in system, above two-step reaction total time is no more than 5 hours, then adds the oxidation inhibitor insulation reaction of epoxy acrylate and specified amount.Determine the content of NCO by volumetry, when reaching required theoretical value, stopped reaction, discharging, namely obtain required prepolymer.
Wherein, the number of PTMEG and PCL when all relative molecular mass is 1000,25 ℃ viscosity in the 600mPa.S left and right.
Wherein, PTMEG and PCL needed through processed before adding IPDI, be after PTMEG and PCL drop into reactor, heat up, when the temperature of mixture reaches 50 ℃, start vacuum pump, make vacuum tightness in reactor rise to slowly 0.098-0.1MPa, control temperature in the kettle and be 3 hours, 110 ℃ of left and right, standby.
wherein said content by titration measuring NCO is determined level of response, its method is described as: take the 5g prepolymer, put into the dry flask of crossing, the 20mL Di-n-Butyl Amine standardized solution that adds new preparation with transfer pipet, the THF that adds again the 50mL drying, shake up, add the 100mL anhydrous isopropyl alcohol, with the agent of giving instruction of 0.5mL tetrabromo-mcresolsulfonphthalein, be titrated to yellow with the hydrochloric acid soln of 1N and be terminal, do again finally blank assay, then calculate the content of NCO group by NCO%=mLHCl blank-mLHCl sample/example weight x4.2, when reaching theoretical value, NCO content represents that reaction finishes, discharging, obtain required UV curing metal coating prepolymer.
The UV that the UV curing metal coating prepolymer that a kind of preparation method of UV curing metal coating prepolymer obtains is mixed with is coating material solidified, sticking power to metal base is good, the film of testing the coating material solidified formation of this UV by cross-hatching does not come off, to metal base certain corrosion-resisting function is arranged and cut have good metalluster sense, photo-curing rate is fast, photocuring speed rate＜=(more than 15 seconds), cured film had excellent yellowing resistance and snappiness in 5 seconds, and excellent yellowing resistance is embodied under natural light to place and still was the water white transparency shape in 1-6 month; The film that excellent snappiness is embodied in the coating material solidified formation of this UV repeatedly folding 90 degree-180 degree without escutcheon, do not ftracture.
Embodiment 3
A kind of preparation method of UV curing metal coating prepolymer, wherein, each component concentration is by mass parts: 32 parts of vulcabond; 10 parts of polyether glycols; Polyester polyol: 35; 20 parts of acrylic resins; 3 parts of linking agents.Other auxiliary agents include but not limited to 0.5 part of catalyzer; Oxidation inhibitor: 1 part; 250 parts of reactive thinners.
A kind of preparation method of UV curing metal coating prepolymer, its preparation process is as follows: PTMEG, PCL and PPG are carried out processed under certain condition, add organotin catalysts, stirring at room mixes, add respectively again IPDI and HDI, be warming up between 50-70 ℃, after the reaction certain hour, to the linking agent with carboxyl (can add as required appropriate reactive thinner adjusting viscosity) that adds aforementioned proportion in system, above two-step reaction total time is no more than 5 hours, then adds the oxidation inhibitor insulation reaction of epoxy acrylate and specified amount.Determine the content of NCO by volumetry, when reaching required theoretical value, stopped reaction, discharging, namely obtain required UV curing metal coating prepolymer.
Wherein, the number of PTMEG, PPG and PEG when all relative molecular mass is 1000,25 ℃ viscosity in the 600mPa.S left and right.
Wherein, before adding vulcabond, oligopolymer dibasic alcohol system need be passed through processed, be after the oligopolymer dibasic alcohol drops into reactor, to heat up, when the temperature of mixture reaches 50 ℃, start vacuum pump, make vacuum tightness in reactor rise to slowly 0.098-0.1MPa, control temperature in the kettle and be 3 hours, 110 ℃ of left and right, standby.
wherein said content by titration measuring NCO is determined level of response, its method is described as: take the 5g prepolymer, put into the dry flask of crossing, the 20mL Di-n-Butyl Amine solution that adds new preparation with transfer pipet, the THF that adds again the 50mL drying, shake up, add the 100mL anhydrous isopropyl alcohol, with the agent of giving instruction of 0.5mL tetrabromo-mcresolsulfonphthalein, be titrated to yellow with the hydrochloric acid soln of 1N and be terminal, do again finally blank assay, then calculate the content of NCO group by NCO%=mLHCl blank-mLHCl sample/example weight x4.2, when reaching theoretical value, NCO content represents that reaction finishes, discharging, obtain required UV curing metal coating prepolymer.
The UV that the UV curing metal coating prepolymer that a kind of preparation method of UV curing metal coating prepolymer obtains is mixed with is coating material solidified, sticking power to metal base is good, the film of testing the coating material solidified formation of this UV by cross-hatching does not come off, to metal base certain corrosion-resisting function is arranged and cut have good metalluster sense, photo-curing rate is fast, photocuring speed rate＜=(more than 15 seconds), cured film had excellent yellowing resistance and snappiness in 5 seconds, and excellent yellowing resistance is embodied under natural light to place and still was the water white transparency shape in 1-6 month; The film that excellent snappiness is embodied in the coating material solidified formation of this UV repeatedly folding 90 degree-180 degree without escutcheon, do not ftracture.
Embodiment 4
The preparation method of a kind of UV curing metal coating prepolymer of the present invention, wherein, each component concentration is by mass parts: 32 parts of vulcabond; 15 parts of polyether glycols; Polyester polyol: 30; 20 parts of epoxy acrylic resins; 3 parts of linking agents.Other auxiliary agents include but not limited to 0.5 part of catalyzer; Oxidation inhibitor: 1 part; 500 parts of reactive thinners.
A kind of preparation method of UV curing metal coating prepolymer, its preparation process is as follows: PTMEG and PCL are carried out processed under certain condition, add organotin catalysts, stirring at room mixes, then adds respectively IPDI and HXDI, is warming up between 50-70 ℃, after the reaction certain hour, to the organosilicon cross-linking agent that adds aforementioned proportion in system, above two-step reaction total time is no more than 5 hours, then adds the oxidation inhibitor insulation reaction of epoxy acrylate and specified amount.Determine the content of NCO by volumetry, when reaching required theoretical value, stopped reaction, discharging, namely obtain required UV curing metal coating prepolymer.
Wherein, the number of PTMEG and PCL when all relative molecular mass is 1000,25 ℃ viscosity in the 600mPa.S left and right.
Wherein, oligopolymer dibasic alcohol system need be passed through processed, after namely the oligopolymer dibasic alcohol drops into reactor, heat up, when the temperature of mixture reaches 50 ℃, start vacuum pump, make vacuum tightness in reactor rise to slowly 0.098-0.1MPa, control temperature in the kettle and be 3 hours, 110 ℃ of left and right, standby.
wherein said content by titration measuring NCO is determined level of response, its method is described as: take the 5g prepolymer, put into the dry flask of crossing, the 20mL Di-n-Butyl Amine solution that adds new preparation with transfer pipet, the THF that adds again the 50mL drying, shake up, add the 100mL anhydrous isopropyl alcohol, with the agent of giving instruction of 0.5mL tetrabromo-mcresolsulfonphthalein, be titrated to yellow with the hydrochloric acid soln of 1N and be terminal, do again finally blank assay, then calculate the content of NCO group by NCO%=mLHCl blank-mLHCl sample/example weight x4.2, when reaching theoretical value, NCO content represents that reaction finishes, discharging, obtain required UV curing metal coating prepolymer.
The UV that the UV curing metal coating prepolymer that a kind of preparation method of UV curing metal coating prepolymer obtains is mixed with is coating material solidified, sticking power to metal base is good, the film of testing the coating material solidified formation of this UV by cross-hatching does not come off, to metal base certain corrosion-resisting function is arranged and cut have good metalluster sense, photo-curing rate is fast, photocuring speed rate＜=(more than 15 seconds), cured film had excellent yellowing resistance and snappiness in 5 seconds, and excellent yellowing resistance is embodied under natural light to place and still was the water white transparency shape in 1-6 month; The film that excellent snappiness is embodied in the coating material solidified formation of this UV repeatedly folding 90 degree-180 degree without escutcheon, do not ftracture.
Claims (10)
1. the preparation method of a UV curing metal coating prepolymer is characterized in that: comprise the following steps:
1] mixture of the pure and mild polyether glycol of polyester polyols is carried out processed, the number-average molecular weight of described polyester polyol or polyether glycol is between 800-5000, and viscosity is between 600-1500mPa.S (25 ℃);
2] add tertiary amines or Catalyzed by Organometallic Compounds agent, stirring at room mixes,
3] add again the vulcabond stirring at room 30 minutes, then be warming up to reaction under 50-70 ℃, react after 1-1.5 hour, add appropriate linking agent to continue reaction in system;
4] reaction is after 3-5 hour, and chain extending reaction adds a certain amount of hydroxy acrylate and a certain amount of oxidation inhibitor to system after finishing again;
5] determine the content of NCO by volumetry, when reaching required theoretical value, stopped reaction, discharging, namely obtain required UV curing metal coating prepolymer.
2. the preparation method of UV curing metal coating prepolymer according to claim 1, is characterized in that: described step 3] while adding appropriate linking agent, add the reactive thinner of appropriate adjusting viscosity.
3. the preparation method of described UV curing metal coating prepolymer according to claim 1 and 2 is characterized in that: described each step reaction starting material consumption by weight: vulcabond 14-32 part; Polyether glycol 20-40 part; Polyester polyol: 20-40; Acrylic resin 5-20 part; Linking agent 1-5 part; 0.5 part-1 part of catalyzer; Oxidation inhibitor: 0.5-1 part; Reactive thinner: 0-500 part.
4. the preparation method of UV curing metal coating prepolymer according to claim 3, it is characterized in that: described processed, be that polyester polyol or polyether glycol or mixture are both added in reactor, start stirring, and the heating that heats up, make liquid temperature reach 50-70 ℃ of left and right, start vacuum pump, make vacuum tightness in reactor rise to slowly 0.098-0.1MPa, the control temperature in the kettle is 100-120 ℃, discharging after 3 hours, be placed in airtight storage tank standby.
5. the preparation method of UV curing metal coating prepolymer according to claim 4, it is characterized in that, described content by titration measuring NCO is determined level of response, its method is described as: take the 5g prepolymer, put into the dry flask of crossing, add 20mL Di-n-Butyl Amine solution standardized solution with transfer pipet, the THF that adds again the 50mL drying, shake up, add the 100mL anhydrous isopropyl alcohol, with the agent of giving instruction of 0.5mL tetrabromo-mcresolsulfonphthalein, be titrated to yellow with the hydrochloric acid soln of 1N and be terminal, do again finally blank assay, then calculate the content of NCO group by NCO%=mLHCl blank-mLHCl sample/example weight x4.2, when reaching theoretical value, NCO content represents that reaction finishes, discharging, obtain required UV curing metal coating prepolymer.
6. the preparation method of UV curing metal coating prepolymer according to claim 5, it is characterized in that: described vulcabond comprises any of TDI, MDI, HDI, TMHDI, IPDI and HXDI combination.
7. the preparation method of UV curing metal coating prepolymer according to claim 6, is characterized in that: any of the pure and mild polyether glycol of described polyester polyols such as PDA, PEA, PBA, PCL, PCDL, PTMEG, PEG and PPG combination.
8. method according to claim 7, it is characterized in that: described acrylic resin comprises (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, pentaerythritol triacrylate, Dipentaerythritol five acrylate and epoxy acrylate.
9. the preparation method of UV curing metal coating prepolymer according to claim 8 is characterized in that:
Described linking agent mainly comprises small molecules dibasic alcohol, diamine and alcohol amine compound; Be specially BDO, ethylene glycol, 1,2-PD, 1,3-PD, glycol ether, 1,6-hexylene glycol, MOCA, DMTDA, DETDA, thanomin, diethanolamine or trolamine;
Described reactive thinner comprises alkyl acrylate, glycols diacrylate, propandiols diacrylate and epoxy acrylate;
Described catalyzer comprises tertiary amines and organo-metallic compounds; Be specially triethylenediamine, two (dimethylaminoethyl) ether, 2-(2-dimethylamino-oxyethyl group) ethanol, stannous octoate, dibutyl tin laurate, carboxylic acid potassium, organic mercury or organic lead;
Described oxidation inhibitor comprises any of 2,6 ditertiary butyl p cresol, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, butyl or octyl group aniline and phosphorous acid ester combination.
10. a UV curing metal coating prepolymer that utilizes claim 1 preparation method to prepare, is characterized in that: this UV curing metal coating prepolymer is equipped with appropriate metallic pigment, multifunctional reactive thinner, light trigger and other auxiliary agents is applied to prepare UV curing metal coating.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622857A (en) * | 2016-04-01 | 2016-06-01 | 武汉大学 | Preparation method of interpenetrating-network-structure water-based polyurethane nano composite material |
| CN108484870A (en) * | 2018-03-05 | 2018-09-04 | 华南理工大学 | It is a kind of to prepare UV cured polyurethane acrylates and preparation method thereof with waste PET bottle |
| CN110092885A (en) * | 2019-05-27 | 2019-08-06 | 江苏睿浦树脂科技有限公司 | A kind of UV curable urethane acrylate resin and preparation method thereof |
| CN111019076A (en) * | 2019-12-24 | 2020-04-17 | 郑州大学 | Rapid UV-cured hyperbranched polyurethane acrylate and preparation method thereof |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438257A (en) * | 2003-03-06 | 2003-08-27 | 华南理工大学 | Acrylic polyurethane copolymer emulsion, its preparation method and use |
| CN101358048A (en) * | 2008-09-19 | 2009-02-04 | 华南理工大学 | Ultraviolet cured paint for electric product surface coating |
| CN101481448A (en) * | 2009-02-03 | 2009-07-15 | 广州慧谷化学有限公司 | Active oligomer, preparation thereof and white board erasable ultraviolet cured paint containing the same |
| CN102604035A (en) * | 2012-03-13 | 2012-07-25 | 广东深展实业有限公司 | Ultraviolet cured two-degree-of-functionality polyurethane acrylic ester base coating resin for vacuum coating |
-
2013
- 2013-08-15 CN CN201310355674.9A patent/CN103387656B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438257A (en) * | 2003-03-06 | 2003-08-27 | 华南理工大学 | Acrylic polyurethane copolymer emulsion, its preparation method and use |
| CN101358048A (en) * | 2008-09-19 | 2009-02-04 | 华南理工大学 | Ultraviolet cured paint for electric product surface coating |
| CN101481448A (en) * | 2009-02-03 | 2009-07-15 | 广州慧谷化学有限公司 | Active oligomer, preparation thereof and white board erasable ultraviolet cured paint containing the same |
| CN102604035A (en) * | 2012-03-13 | 2012-07-25 | 广东深展实业有限公司 | Ultraviolet cured two-degree-of-functionality polyurethane acrylic ester base coating resin for vacuum coating |
Non-Patent Citations (1)
| Title |
|---|
| 江峰等: "交联剂型水性聚氨酯-丙烯酸酯木器涂料性能研究", 《涂料工业》, vol. 38, no. 9, 30 September 2008 (2008-09-30), pages 25 - 29 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622857A (en) * | 2016-04-01 | 2016-06-01 | 武汉大学 | Preparation method of interpenetrating-network-structure water-based polyurethane nano composite material |
| CN108484870A (en) * | 2018-03-05 | 2018-09-04 | 华南理工大学 | It is a kind of to prepare UV cured polyurethane acrylates and preparation method thereof with waste PET bottle |
| CN108484870B (en) * | 2018-03-05 | 2021-02-12 | 华南理工大学 | UV-cured polyurethane acrylate prepared from waste PET (polyethylene terephthalate) bottles and preparation method thereof |
| CN110092885A (en) * | 2019-05-27 | 2019-08-06 | 江苏睿浦树脂科技有限公司 | A kind of UV curable urethane acrylate resin and preparation method thereof |
| CN111019076A (en) * | 2019-12-24 | 2020-04-17 | 郑州大学 | Rapid UV-cured hyperbranched polyurethane acrylate and preparation method thereof |
| 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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