CN102604531B - Hyperbranched ultraviolet cured coating and preparation method thereof - Google Patents
Hyperbranched ultraviolet cured coating and preparation method thereof Download PDFInfo
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- CN102604531B CN102604531B CN201210033065.7A CN201210033065A CN102604531B CN 102604531 B CN102604531 B CN 102604531B CN 201210033065 A CN201210033065 A CN 201210033065A CN 102604531 B CN102604531 B CN 102604531B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000576 coating method Methods 0.000 title claims abstract description 11
- 239000011248 coating agent Substances 0.000 title claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000003973 paint Substances 0.000 claims description 36
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 22
- 150000002148 esters Chemical class 0.000 claims description 21
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229920000728 polyester Polymers 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 9
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 9
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 6
- 230000006837 decompression Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 239000002904 solvent Substances 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- 239000007983 Tris buffer Substances 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 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 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical group CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- 230000035939 shock Effects 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 abstract description 6
- 229920002635 polyurethane Polymers 0.000 abstract description 6
- 238000010276 construction Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- -1 acrylic ester Chemical class 0.000 abstract 1
- 239000003085 diluting agent Substances 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 229940117969 neopentyl glycol Drugs 0.000 description 6
- 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 description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 3
- 102100026735 Coagulation factor VIII Human genes 0.000 description 3
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 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 description 2
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
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- 229920003023 plastic Polymers 0.000 description 2
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- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- IQQVCMQJDJSRFU-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO IQQVCMQJDJSRFU-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004258 Ethoxyquin Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- SORGEQQSQGNZFI-UHFFFAOYSA-N [azido(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(N=[N+]=[N-])OC1=CC=CC=C1 SORGEQQSQGNZFI-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical class C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
- 229940093500 ethoxyquin Drugs 0.000 description 1
- 235000019285 ethoxyquin Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention discloses a hyperbranched ultraviolet cured coating, which comprises the following raw materials by weight: 65-80 percent of acrylic ester terminal hyperbranched polyurethane, 15-33.5 percent of an active monomer diluent, 0.5-2 percent of a photoinitiator, and 1-3 percent of a flatting agent. Moreover, the invention also discloses a preparation method of the hyperbranched ultraviolet cured coating. The hyperbranched ultraviolet cured coating has the characteristics of being low in viscosity, high in reactivity, high in solubility, good in intermiscibility and the like, can improve the construction environment, can be rapidly cured and is good in physical and chemical properties of a coating film, and is suitable for indoor and outdoor utilization.
Description
Technical field
The present invention relates to technical field of coatings, relate in particular to a kind of hyperbranched ultraviolet-curing paint and preparation method thereof.
Background technology
Ultraviolet-curing paint is to using UV-light as hardening with radiation light source, and light trigger in coating absorbs ultraviolet luminous energy and forms free radical, thereby initiation resin and reactive monomer generation polymerization, crosslinking reaction are filmed liquid state and reached curing.This ultraviolet-curing paint, do not need heating, can be on the inflammable grounds such as paper, plastics, leather and timber film-forming rapidly, thereby compare with the coating of other types, there is pollution-free, the feature such as curing speed is fast, solidification value is low, production efficiency is high, volatile matter is low, environmental protection and energy saving, coating performance excellence, rub resistance, solvent resistance and contamination resistance are good, in the application of the production fields such as woodenware, paper, metal, plastics and electronic information, have obtained development fast.Along with the pay attention to day by day to environment protection, ultraviolet-curing paint is expected to replace or part replaces tradition coating material solidified.
Ultraviolet-curing paint system is generally comprised of light-cured polyurethane, reactive monomer thinner, light trigger and each analog assistant.In light-cured polyurethane, contain C=C unsaturated double-bond, it forms three-dimensional net structure after solidifying, and the physicochemical property of cured film is played a decisive role.Prior art ultraviolet-curing paint system is basis mainly with the urethane with acrylate-functional groups greatly, and general types has unsaturated polyester, acrylic acid epoxy ester, acrylated polyurethane resin, acrylic acid polyester resin, acroleic acid esterification silicone resin, polyenoid/mercaptan system, polyether acrylate resin etc.
Yet light-cured polyurethane is linear polymer mostly in prior art, with its viscosity of increase of molecular weight, constantly increase, need to add a large amount of reactive monomer thinners to carry out adjusting viscosity.Because reactive monomer thinner has special irritating smell and higher toxicity, therefore, on the one hand construction environment has been brought to pollution and detrimentally affect to a certain degree, can cause that on the other hand solidification rate reduces, cured film is shunk, thereby cause the decline of the physical and chemical indexs such as paint film adhesion.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of can fast setting and excellent performance, can improve construction environment, be suitable for the hyperbranched ultraviolet-curing paint that indoor and outdoor is used.Another object of the present invention is to provide the preparation method of above-mentioned hyperbranched ultraviolet-curing paint.
Object of the present invention is achieved by the following technical programs:
A kind of hyperbranched ultraviolet-curing paint provided by the invention, its raw material consists of by weight percentage: hold acrylate hyperbranched urethane 65～80%, reactive monomer thinner 15～33.5%, light trigger 0.5～2%, flow agent 1～3%.
Further, reactive monomer thinner of the present invention is with one, two, three, four, five or six acrylate-based Rocryl 410s (HEMA), 1, 6-hexylene glycol double methacrylate (HDDA), neopentylglycol diacrylate (NPGDA), two contracting propylene glycol double methacrylates (DPGDA), tripropylene glycol double methacrylate (TPGDA), tirethylene glycol double methacrylate (DEGDA), triethylene Glycol double methacrylate (TEGDA), triethylene Glycol double methyl methacrylate (TEGDMA), two (methyl) acrylate of ethoxyquin dihydroxyphenyl propane, trimethylolpropane tris (methyl) acrylate (TMPTA), pentaerythritol triacrylate (PETA), the Viscoat 295 of ethoxylation [TMP (EO) TA], tetramethylol methane tetraacrylate (PETTA), two contracting trimethylolpropane tetra-acrylate (DTMPTTA), Dipentaerythritol five acrylate (DPPA), one or more combination in dipentaerythritol acrylate (DPHA).Described light trigger is alpha-hydroxyalkyl benzophenone class (as Darocure 1173,2959,184); benzil class (as Irgacure 651), the one or more combination in α-amine alkylbenzene ketone (as Irgacure 907,369), acylphosphine oxide (as Irgacure 819).
Another object of the present invention is achieved by the following technical programs:
The preparation method of above-mentioned hyperbranched ultraviolet-curing paint provided by the invention, comprises the following steps:
(1) hold the synthetic of acrylate hyperbranched urethane
(1-1) preparation of hyper-branched polyester (HBPE)
Neopentyl glycol, dimethylol propionic acid and tosic acid are added in reaction flask, according to mol ratio neopentyl glycol: dimethylol propionic acid=1: 6～20, the consumption of tosic acid is 0.05～0.1% of neopentyl glycol and dimethylol propionic acid total amount by weight percentage; Under nitrogen protection, after 130～150 ℃ of thermotonus 3～5h, stop logical nitrogen, change decompression vacuum pumping and continue reaction 3～5h, cool to 50 ℃ and add acetone solution after following, then after hexanaphthene precipitation, vacuum-drying hyper-branched polyester;
(1-2) preparation of the isocyanic ester TDIHPA monomer of half end-blocking
By isocyanic ester and be 0.08～0.15% with respect to isocyanic ester massfraction Resorcinol or MEHQ add in reaction flask, and using dibutyl tin laurate (DBTDL) as catalyzer, the mixing solutions that stirs dropping Propylene glycol monoacrylate to be dissolved in acetone and form, wherein the molar weight of Propylene glycol monoacrylate equates with isocyanic ester, reacts the isocyanic ester TDIHPA monomer that 2.5～3.5h obtains half end-blocking at 30～60 ℃ of temperature;
(1-3) the acrylate hyperbranched urethane of synthetic end
The acetone soln of the hyper-branched polyester HBPE that step (1-1) is prepared is added in the isocyanic ester TDIHPA monomer of half end-blocking that step (1-2) makes, wherein the mol ratio of the isocyanic ester TDIHPA monomer of hyper-branched polyester HBPE and half end-blocking is 1: 8～20, at 50～70 ℃ of temperature, react 1～4h, solvent acetone is extracted in decompression out, obtains the acrylate hyperbranched urethane of end of uV curable;
(2) preparation of ultraviolet-curing paint
According to proportioning consumption, step (1) is synthesized to the acrylate hyperbranched urethane of end obtaining, join in reaction flask with reactive monomer thinner, make system temperature maintain 25～35 ℃, stir until after mixing completely, add while stirring flow agent, light trigger, it is mixed, make hyperbranched ultraviolet-curing paint.
In such scheme, the hyper-branched polyester that preparation method's step of the present invention (1-1) obtains, its molecular weight is Mw=1600～2800g/mol, Mn=800～2000g/mol, degree of branching DB=0.45～0.5.
The present invention adopts melt-polycondensation to synthesize and makes the hyper-branched polyester prepolymer with multiterminal hydroxyl, and this hyper-branched polyester prepolymer further reacts with the isocyanic ester of Propylene glycol monoacrylate half end-blocking the acrylate hyperbranched urethane of end that makes uV curable; Then mix and obtain hyperbranched ultraviolet-curing paint according to proportioning consumption with reactive monomer thinner, flow agent, light trigger.
The present invention has following beneficial effect:
(1) the acrylate hyperbranched urethane of end that the present invention prepares, reactive behavior is high, narrow molecular weight distribution, and each side chain length is consistent, has ball symmetrical structure.After this urethane and reactive monomer thinner, light trigger and other auxiliary agent are mixed evenly by a certain percentage of the weight, the ultraviolet-curing paint obtaining has low viscosity, high reaction activity, higher solubleness and the good features such as intermiscibility, workability is good, can fast setting and paint film physicochemical property excellent, be suitable for indoor and outdoor and use.
(2) the acrylate hyperbranched urethane of the end in the present invention, owing to can providing a lot of terminal functionality in molecule, and functional group can be various and special molecular conformation, is therefore not easy to occur molecular entanglement.Compare with the simple linear polymer of close molecular weight, the viscosity under same concentration is much lower, can effectively improve the mobility of curable resin.Meanwhile, because it has larger solubleness in solvent, therefore can reduce the consumption of reactive monomer thinner, reduce cost, reduce the pollution of environment and impact.In addition, its numerous terminal functionality can be used for the modification of different target, also makes resin have good sticking power.
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment
Embodiment mono-:
1, the hyperbranched ultraviolet-curing paint of the present embodiment, its raw material forms as shown in table 1 by weight percentage:
The formula of table 1 embodiment mono-hyperbranched ultraviolet-curing paint forms
2, the preparation method of the hyperbranched ultraviolet-curing paint of the present embodiment is as follows:
(1) hold the synthetic of acrylate hyperbranched urethane
(1-1) preparation of hyper-branched polyester (HBPE)
Neopentyl glycol, dimethylol propionic acid and tosic acid are added in reaction flask, according to mol ratio neopentyl glycol: dimethylol propionic acid=1: 14, the consumption of tosic acid is 0.05% of neopentyl glycol and dimethylol propionic acid total amount by weight percentage; Under nitrogen protection after 140 ℃ of thermotonus 4h, stop logical nitrogen, change decompression vacuum pumping and continue reaction 4h, after below cooling to 50 ℃, add acetone solution, after hexanaphthene precipitation, vacuum-drying, obtain hyper-branched polyester again, its molecular weight is Mw=2165g/mol, Mn=1536g/mol, degree of branching DB=0.49; Its molecular structure is as follows:
(1-2) preparation of the isocyanic ester TDIHPA monomer of half end-blocking
By tolylene diisocyanate 2,4-TDI, Resorcinol (its consumption be TDI quality 0.15%) join in reaction flask, using DBTDL as catalyzer, the mixing solutions that stirs dropping Propylene glycol monoacrylate to be dissolved in acetone and form, the wherein molar weight of Propylene glycol monoacrylate and tolylene diisocyanate 2,4-TDI equates, at 45 ℃ of temperature, reacts 3h, obtains the isocyanic ester TDIHPA monomer of half end-blocking;
(1-3) the acrylate hyperbranched urethane of synthetic end
The acetone soln of the hyper-branched polyester HBPE that step (1-1) is prepared is added in the isocyanic ester TDIHPA monomer of half end-blocking that step (1-2) makes, the mol ratio of HBPE and TDIHPA is 1: 14, at 60 ℃ of temperature, react 3.5h, solvent acetone is extracted in decompression out, obtains the acrylate hyperbranched urethane of end of uV curable;
(2) preparation of hyperbranched ultraviolet-curing paint
By 72 grams of the synthetic acrylate hyperbranched urethane of end obtaining of step (1), and by 4 grams of Rocryl 410s (HEMA), 1, the reactive monomer thinner of 15 grams of 6-hexylene glycol double methacrylates (HDDA), 6 grams of compositions of trimethylolpropane tris (methyl) acrylate (TMPTA) joins in reaction flask, make system temperature maintain 30 ℃, stir until after mixing completely, add while stirring 1 gram of flow agent (BYK-355), 2 grams of light triggers (Darocure 1173), it is mixed, make hyperbranched ultraviolet-curing paint.
Embodiment bis-:
The present embodiment and embodiment mono-difference are: in the preparation method of hyperbranched ultraviolet-curing paint, and being prepared as of the isocyanic ester MDIHPA monomer of its step (1-2) half end-blocking:
Diphenylmethanediisocyanate MDI, MEHQ (its consumption be MDI quality 0.08%) are added in reaction flask, using DBTDL as catalyzer, the mixing solutions that stirs dropping Propylene glycol monoacrylate to be dissolved in acetone and form, wherein the molar weight of Propylene glycol monoacrylate equates with diphenylmethanediisocyanate MDI, at 55 ℃ of temperature, react 3h, obtain the isocyanic ester MDIHPA monomer of half end-blocking.
Embodiment tri-:
The present embodiment and embodiment mono-difference are: hyperbranched ultraviolet-curing paint formula form, reactive monomer thinner is only the HEMA (Rocryl 410) of single functionality.
Embodiment tetra-:
The present embodiment and embodiment mono-difference are: hyperbranched ultraviolet-curing paint formula form, reactive monomer thinner is only the HDDA (1,6-hexylene glycol double methacrylate) of difunctionality.
Embodiment five:
The present embodiment and embodiment tetra-differences are: hyperbranched ultraviolet-curing paint formula form, its raw material consists of by weight percentage: acrylate-based client super branched polyurethane 67%, reactive monomer thinner 30%, light trigger 2%, flow agent 1%.
Embodiment six:
The present embodiment and embodiment tetra-differences are: hyperbranched ultraviolet-curing paint formula form, its raw material consists of by weight percentage: acrylate-based client super branched polyurethane 80%, reactive monomer thinner 17%, light trigger 2%, flow agent 1%.
Embodiment seven:
The present embodiment and embodiment mono-difference are: hyperbranched ultraviolet-curing paint formula form, reactive monomer thinner is only trimethylolpropane tris (methyl) acrylate (TMPTA) of three-functionality-degree.
Embodiment eight:
The present embodiment and embodiment mono-difference are: hyperbranched ultraviolet-curing paint formula form as shown in table 2.
The formula of table 2 embodiment eight hyperbranched ultraviolet-curing paints forms
Hyperbranched ultraviolet-curing paint prepared by above-described embodiment is coated on tinplate, the ultraviolet lamp that is placed in 5 revs/min of rotating speeds, power 16W, wavelength 253.7nm carries out irradiation, its set to touch time is 5 seconds, after irradiation solidifies completely, obtains water white cured film.According to national standard, detect, the performance of gained cured film is as shown in table 3.
The performance of table 3 embodiment mono-～eight ultraviolet light polymerization acrylate-based client super branched polyurethane coating
Claims (3)
1. a hyperbranched ultraviolet-curing paint, is characterized in that its raw material consists of by weight percentage: hold acrylate hyperbranched urethane 72%, reactive monomer thinner 25%, light trigger 2%, flow agent 1%; With respect to raw material, described reactive monomer thinner is by weight percentage by Rocryl 410 4%, 1, and 6-hexylene glycol double methacrylate 15%, trimethylolpropane tris (methyl) acrylate 6% form; Described light trigger is Darocure 1173, and flow agent is BYK-355; The viscosity of described coating is 6732mPas, and be 18s set time completely, and snappiness is 2mm, and shrinking percentage is 3%, and resistance to impact shock is 40kg.cm, and sticking power is 2 grades, and gel fraction is 2%.
2. the preparation method of hyperbranched ultraviolet-curing paint described in claim 1, is characterized in that comprising the following steps:
(1) hold the synthetic of acrylate hyperbranched urethane
(1-1) preparation of hyper-branched polyester
Neopentyl glycol, dimethylol propionic acid and tosic acid are added in reaction flask, according to mol ratio neopentyl glycol: dimethylol propionic acid=1: 6～20, the consumption of tosic acid is 0.05～0.1% of neopentyl glycol and dimethylol propionic acid total amount by weight percentage; Under nitrogen protection, after 130～150 ℃ of thermotonus 3～5h, stop logical nitrogen, change decompression vacuum pumping and continue reaction 3～5h, cool to 50 ℃ and add acetone solution after following, then after hexanaphthene precipitation, vacuum-drying hyper-branched polyester;
(1-2) preparation of the isocyanic ester TDIHPA monomer of half end-blocking
By isocyanic ester and be 0.08～0.15% with respect to isocyanic ester massfraction Resorcinol or MEHQ add in reaction flask, and using dibutyl tin laurate as catalyzer, the mixing solutions that stirs dropping Propylene glycol monoacrylate to be dissolved in acetone and form, wherein the molar weight of Propylene glycol monoacrylate equates with isocyanic ester, reacts the isocyanic ester TDIHPA monomer that 2.5～3.5h obtains half end-blocking at 30～60 ℃ of temperature;
(1-3) the acrylate hyperbranched urethane of synthetic end
The acetone soln of the hyper-branched polyester that step (1-1) is prepared is added in the isocyanic ester TDIHPA monomer of half end-blocking that step (1-2) makes, wherein the mol ratio of the isocyanic ester TDIHPA monomer of hyper-branched polyester and half end-blocking is 1: 8～20, at 50～70 ℃ of temperature, react 1～4h, solvent acetone is extracted in decompression out, obtains the acrylate hyperbranched urethane of end of uV curable;
(2) preparation of ultraviolet-curing paint
According to proportioning consumption, step (1) is synthesized to the acrylate hyperbranched urethane of end obtaining, join in reaction flask with reactive monomer thinner, make system temperature maintain 25～35 ℃, stir until after mixing completely, add while stirring flow agent, light trigger, it is mixed, make hyperbranched ultraviolet-curing paint.
3. the preparation method of hyperbranched ultraviolet-curing paint according to claim 2, it is characterized in that: the hyper-branched polyester that described step (1-1) obtains, its molecular weight is Mw=1600～2800g/mol, Mn=800～2000g/mol, degree of branching DB=0.45～0.5.
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