CN111410906A - Non-isocyanate polyurethane photocureable coating - Google Patents
Non-isocyanate polyurethane photocureable coating Download PDFInfo
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- CN111410906A CN111410906A CN202010409513.3A CN202010409513A CN111410906A CN 111410906 A CN111410906 A CN 111410906A CN 202010409513 A CN202010409513 A CN 202010409513A CN 111410906 A CN111410906 A CN 111410906A
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- isocyanate polyurethane
- isocyanate
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- photocureable
- photocureable coating
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- 239000012948 isocyanate Substances 0.000 title claims abstract description 53
- 238000000576 coating method Methods 0.000 title claims abstract description 31
- 239000011248 coating agent Substances 0.000 title claims abstract description 28
- 239000004814 polyurethane Substances 0.000 title claims abstract description 25
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 24
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000002562 thickening agent Substances 0.000 claims description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 claims 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims 1
- 108010010803 Gelatin Proteins 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims 1
- 229920000159 gelatin Polymers 0.000 claims 1
- 239000008273 gelatin Substances 0.000 claims 1
- 235000019322 gelatine Nutrition 0.000 claims 1
- 235000011852 gelatine desserts Nutrition 0.000 claims 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 abstract description 24
- -1 acrylic ester Chemical class 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 2
- RQGNEYFWHWFECS-UHFFFAOYSA-N amino formate Chemical group NOC=O RQGNEYFWHWFECS-UHFFFAOYSA-N 0.000 abstract 1
- 238000004804 winding Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 239000011527 polyurethane coating Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 5
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- SIDXFGMQLJSRTB-UHFFFAOYSA-N (2-butylphenyl)-diphenylphosphanium bromide Chemical compound [Br-].CCCCC1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 SIDXFGMQLJSRTB-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- UIYHUUARNKRKGV-UHFFFAOYSA-N 2-prop-2-enoxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OCC=C UIYHUUARNKRKGV-UHFFFAOYSA-N 0.000 description 2
- JFMGYULNQJPJCY-UHFFFAOYSA-N 4-(hydroxymethyl)-1,3-dioxolan-2-one Chemical compound OCC1COC(=O)O1 JFMGYULNQJPJCY-UHFFFAOYSA-N 0.000 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 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012994 photoredox catalyst Substances 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 241000219322 Dianthus Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- MYTMXVHNEWBFAL-UHFFFAOYSA-L dipotassium;carbonate;hydrate Chemical compound O.[K+].[K+].[O-]C([O-])=O MYTMXVHNEWBFAL-UHFFFAOYSA-L 0.000 description 1
- 230000005662 electromechanics Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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- 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
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- 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
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of photocureable coatings, in particular to a non-isocyanate polyurethane photocureable coating. In order to respond to the national requirement of green sustainable development and reduce the use of isocyanate polyurethane in the water-based photocureable coating from the source, the invention provides the non-isocyanate polyurethane photocureable coating, wherein the non-isocyanate polyurethane prepolymer is used as a component of the photocureable coating and is photocured with acrylic ester, photoinitiator and the like under a certain condition to form a coating film on the surface of a material, two branched chains on each repeating unit of the molecular structure of the non-isocyanate polyurethane prepolymer and the non-isocyanate polyurethane prepolymer or the acrylic ester form a spatial three-dimensional structure with high interweaving, winding and crosslinking density, and the structure can protect an amino formate group which is easy to hydrolyze in the molecular structure of the non-isocyanate polyurethane from contacting with moisture in the air to a certain extent, so that the performances of the photocureable coating film, such as water resistance, hardness, glossiness and the like, are greatly improved.
Description
Technical Field
The invention relates to the technical field of photocureable coatings, in particular to a non-isocyanate polyurethane photocureable coating.
Background
The polyurethane coating has excellent performances of wear resistance, flexibility, adhesive force, chemical resistance and the like, is widely applied to various fields of national economy such as buildings, automobile industry, electromechanics, ships, aviation, light industry, textile and the like, and plays an important role in the polymer material industry.
Polyurethanes are generally obtained by reacting polyisocyanates with substances having active hydrogen groups. The process for producing polyurethanes from polyisocyanates, in particular, has the following disadvantages: (1) the isocyanate has strong irritation and toxicity, is susceptible to dermatitis, respiratory diseases and asthma after being contacted for a long time, and has small relative molecular weight, high vapor pressure, high toxicity and easy leakage to cause danger; (2) isocyanate is very sensitive to moisture, and under the normal condition, the water content of raw materials is required to be lower than 0.3 percent, otherwise, the raw materials are easy to foam, so that the storage and the transportation of the raw materials are inconvenient; (3) the carbamate group is a group easy to hydrolyze, and can be hydrolyzed under certain conditions, so that the water resistance, acid and alkali resistance and weather resistance of the product are reduced; (4) the isocyanate is mainly produced by a phosgene method, a large amount of inflammable, explosive, extremely toxic and highly toxic substances exist in the production process, the production process is complex, the number of control points is large, the industrial production of the isocyanate has high entrance threshold due to the limitations of safety, environmental protection, technology, scale and the like, and the isocyanate is monopolized by a few enterprises and has high price. The traditional polyurethane coating uses a large amount of acetone as a solvent, and causes pollution to the environment in the use process. With the environmental protection issue being emphasized, regulations for limiting the emission of organic compounds are generally established in various countries in order to reduce environmental pollution, and the application of solvent type polyurethane coatings is limited.
The waterborne polyurethane coating is a waterborne coating taking water as a solvent, so that the VOC content in the coating is greatly reduced. However, the single-component waterborne polyurethane coating prepared by the traditional method has a low crosslinking degree, and compared with a solvent-based polyurethane coating, the single-component waterborne polyurethane coating has poor chemical resistance and water resistance, and poor hardness and surface gloss (Yangsheng, Dianthus pink, Chenkino. the technical progress of the waterborne polyurethane coating is reviewed in [ J ]. chemical engineering and technology markets, 2004(10):18-23.), in order to improve the chemical resistance, solvent resistance and other properties of the single-component waterborne polyurethane, the common method is to blend, copolymerize and graft-modify the polyurethane and other resins, although the method can greatly improve the properties of the single-component waterborne polyurethane, the method cannot reduce the use of isocyanate from the source.
In recent years, along with the improvement of environmental protection concept, occupational health and safety consciousness of people, the harmfulness of isocyanate draws great attention of all social circles, and relevant laws and regulations are provided. The mass fraction of free monomers in isocyanate polymer is strictly regulated by the world health organization to be less than 0.5%, and the mass fraction of free isocyanate in indoor space is strictly regulated by the national standard GB 18581-2009 hazardous substance limit in solvent-based wood coatings for interior decoration and finishing materials to be less than 0.2%. Therefore, the development of the non-isocyanate polyurethane waterborne photocureable coating which has excellent chemical resistance and water resistance and higher hardness and surface gloss is imperative.
Disclosure of Invention
Aiming at the prior art, the invention aims to solve the technical problems that: how to prepare a non-isocyanate polyurethane photocuring coating film with excellent chemical resistance and water resistance and higher hardness and surface gloss.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a preparation method of a non-isocyanate polyurethane prepolymer, which comprises the following steps:
(1) adding 50.00g of pyromellitic dianhydride, 35m L g of glycerol carbonate and 2g of 4-dimethylpyridine into 150m L of anhydrous tetrahydrofuran, heating the mixed reactants to reflux until the pyromellitic dianhydride in the reaction mixture is completely dissolved, continuing heating the reaction mixture to reflux for 2h, then cooling to room temperature, carrying out reduced pressure stripping on the solvent, and purifying the crude product to obtain a product I, wherein the reaction formula is as follows:
(2) adding 50kg of monoallyl phthalate and 40L N, N-dimethylformamide into a reflux heating reactor, adding 1.5kg of butyl triphenyl phosphine bromide into the reactor, preheating the reactor to 100 ℃, adding 340L epoxy chloropropane into the reactor, reacting for 5 hours at 100 ℃, after the reaction is finished, distilling under reduced pressure to remove unreacted epoxy chloropropane, cooling the reaction system to 40 ℃, adding 120L dichloromethane and 70kg of sodium hydroxide solution with the mass fraction of 50%, vacuumizing the reactor to be less than or equal to-0.1 MPa, keeping the reactor for 1 hour, fully removing water in the reactor, continuously preserving the temperature for 4 hours at 40 ℃, filtering and washing a reaction product to obtain filtrate, separating the filtrate, and distilling under reduced pressure to obtain a product II, wherein the reaction formula is as follows:
(3) adding 18g of the product I, 24g of the product II, 0.02g of benzyltriethylammonium chloride and 0.02g of 2, 6-di-tert-butyl-4-methylphenol into 20g of Dimethylformamide (DMF) solution, and reacting at 100 ℃ until 1672cm in an infrared detection reaction system-1Near vC＝OAnd 1250cm-1Near vC-OThe characteristic peak of carboxyl disappears, the reaction is finished, then 40ml ethyl acetate is added into the liquid obtained by the reaction and mixed evenly, the solution is transferred into a separating funnel and washed 3 times by 40ml 10 wt% potassium carbonate aqueous solution, z is washed 3 times by distilled water, the ethyl acetate layer is collected, and a product III is obtained by rotary evaporation, and the reaction formula is as follows:
(3) the product III reacts with diamine derivatives to obtain non-isocyanate polyurethane prepolymer
Mixing the product II with diamine derivatives according to a molar ratio of 1:1, and reacting in an oven at 50-70 ℃ for 5-20h to obtain the non-isocyanate polyurethane prepolymer, wherein the molecular structure of the prepolymer is as follows:
specifically, the diamine derivative is one of ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 1, 5-pentylenediamine, 1, 6-hexylenediamine, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, piperazine, azodiamine and conjugated unsaturated alkyl diamine.
Specifically, the non-isocyanate polyurethane prepolymer and components such as acrylate, a photoinitiator, water and the like form a photocuring coating, and a protective coating film is formed on the surface of an aluminum foil, glass and a PC plate through curing.
The invention has the beneficial effects that:
(1) the non-isocyanate polyurethane photocureable coating prepared by the method has better hardness, water resistance and chemical corrosion resistance.
(2) The non-isocyanate polyurethane prepolymer used in the invention adopts a product of ring-opening polymerization of epoxy ester and diamine derivatives, radically reduces the use of polyisocyanate in the production process of polyurethane, meets the requirement of green sustainable development of the current society, and has good application prospect.
Drawings
FIG. 1: is product III1HNMR spectrogram.
Detailed Description
The present invention will now be described in further detail with reference to examples.
Example 1
The preparation of the non-isocyanate polyurethane prepolymer is specifically carried out according to the following steps:
(1) adding 50.00g of pyromellitic dianhydride, 35m of L glycerol carbonate and 2g of 4-dimethylpyridine into 150m of L of anhydrous tetrahydrofuran, heating the mixed reactants to reflux until the pyromellitic dianhydride in the reaction mixture is completely dissolved, continuously heating the reaction mixture to reflux for 2 hours, cooling to room temperature, carrying out reduced pressure stripping on the solvent, and purifying the crude product to obtain a product I;
(2) adding 50kg of monoallyl phthalate and 40L N, N-dimethylformamide into a reflux heating reactor, adding 1.5kg of butyl triphenyl phosphine bromide into the reactor, preheating the reactor to 100 ℃, adding 340L epoxy chloropropane into the reactor, reacting for 5 hours at 100 ℃, after the reaction is finished, carrying out reduced pressure distillation to remove unreacted epoxy chloropropane, cooling the reaction system to 40 ℃, adding 120L dichloromethane and 70kg of sodium hydroxide solution with the mass fraction of 50%, vacuumizing the reactor to be less than or equal to-0.1 MPa, keeping the reactor for 1 hour, fully removing water in the reactor, continuously preserving the temperature for 4 hours at 40 ℃, filtering and washing a reaction product to obtain filtrate, and carrying out liquid separation and reduced pressure distillation on the filtrate to obtain a product II;
(3) 18g of product I, 24g of product II, 0.02g of benzylTriethylammonium chloride (TEDA), 0.02g 2, 6-di-tert-butyl-4-methylphenol were added to 20g Dimethylformamide (DMF) solution and reacted at 100 ℃ until 1672cm in the infrared detection reaction system-1Near vC＝OAnd 1250cm-1Near vC-OThe characteristic peak of carboxyl disappears, the reaction is finished, then 40ml ethyl acetate is added into the liquid obtained by the reaction and mixed evenly, the solution is transferred into a separating funnel and washed 3 times by 40ml 10 wt% potassium carbonate water solution, z is washed 3 times by distilled water, an ethyl acetate layer is collected, a product III is obtained by a rotary evaporation mode, and the product III is prepared1H-NMR(ppm)：4.01-4.59(m，8H，-CH2-O-)；4.79(m，2H，-CH-O-C＝O)；4.78(m，2H，-C(-OH)-C-)；4.86(m，4H，＝C-CH2-) according to the formula (I); 5.31-6.05(m, 6H, ═ C-H); 7.72-8.03(m, 8H, -Ph-H); 8.23(s, 2H, -Ph-H), it follows that the present invention has succeeded in preparing product III;
(3) the product III reacts with diamine derivatives to obtain non-isocyanate polyurethane prepolymer
Mixing 10kg of the product III with ethylenediamine according to the molar ratio of 1:1, and reacting in a 50 ℃ oven for 5 hours to obtain a non-isocyanate polyurethane prepolymer, which is recorded as NIPU 1.
Example 2 differs from example 1 in that: the step (3) in the preparation method of the non-isocyanate polyurethane prepolymer is carried out according to the following method:
mixing 10kg of the product III with 1, 5-pentanediamine according to a molar ratio of 1:1, and reacting in an oven at 60 ℃ for 8h to obtain a non-isocyanate polyurethane prepolymer, which is recorded as NIPU 2.
Example 3 differs from example 1 in that: the step (3) in the preparation method of the non-isocyanate polyurethane prepolymer is carried out according to the following method:
mixing 10kg of the product III with 1, 5-pentanediamine according to a molar ratio of 1:1, and reacting in an oven at 70 ℃ for 10h to obtain a non-isocyanate polyurethane prepolymer, which is recorded as NIPU 3.
Example 4 differs from example 1 in that: the step (3) in the preparation method of the non-isocyanate polyurethane prepolymer is carried out according to the following method:
mixing 10kg of the product III with o-phenylenediamine according to the molar ratio of 1:1, and reacting in an oven at 70 ℃ for 20 hours to obtain a non-isocyanate polyurethane prepolymer, which is recorded as NIPU 4.
Example 5 differs from example 1 in that: the step (3) in the preparation method of the non-isocyanate polyurethane prepolymer is carried out according to the following method:
5kg of the product III is mixed with ethylenediamine according to the molar ratio of 1:1, and then the mixture reacts in a 60 ℃ oven for 5 hours to obtain a non-isocyanate polyurethane prepolymer which is marked as NIPU 5.
Example 6 differs from example 1 in that: the step (3) in the preparation method of the non-isocyanate polyurethane prepolymer is carried out according to the following method:
mixing 15kg of the product III with ethylenediamine according to the molar ratio of 1:1, and reacting in an oven at 60 ℃ for 5 hours to obtain a non-isocyanate polyurethane prepolymer, which is recorded as NIPU 6.
Example 7 differs from example 1 in that: the step (3) in the preparation method of the non-isocyanate polyurethane prepolymer is carried out according to the following method:
and (3) mixing 20kg of the product III with ethylenediamine according to the molar ratio of 1:1, and reacting in an oven at 60 ℃ for 5 hours to obtain a non-isocyanate polyurethane prepolymer, which is recorded as NIPU 7.
The preparation examples 1-7 of the photocureable coating are carried out according to the following formula in parts by weight, and the specific formula is shown in table 1:
uniformly mixing the non-isocyanate polyurethane prepolymer, the acrylate, the flatting agent, the defoaming agent, the thickening agent, the photoinitiator and water, and stirring for 1-3h at the speed of 1000rpm of 800-.
TABLE 1
Comparative example 1 was the same formulation as paint 1 except that: the amount of the acrylic ester added is 10 parts.
Comparative example 2 is the same as paint 1 except that: the amount of the acrylic ester added is 30 parts.
The photocuring coating prepared in examples 1 to 7 and comparative examples 1 to 2 was roll-coated on the surface of aluminum foil, PC and glass plate, irradiated for 5 seconds with a 4KW uv lamp as a radiation source, and cured, and the sample was subjected to various property tests and evaluations, the test results of which are shown in table 2 below:
TABLE 2
Note: performance testing of the materials in Table 2 the following test standards were tested
Boiling resistance: boiling in 100 deg.C boiling water for a certain time, and recording the time when the coating begins swelling and falling off.
Adhesion force: refer to the national standard GB/T9286 test for marking paint films of colored paint and varnish.
Pencil hardness: refer to the national standard GB/T6739 Pencil determination method for hardness of paint film.
Wear resistance: after the sample is rubbed back and forth 20 times by using 0000# steel wool (loaded with 1 kg), the number of scratches of more than or equal to 1cm on the surface of the sample is observed to judge the wear resistance of the coating film.
Alkali resistance: soaking in 10% NaOH solution (20 deg.C) for 5 min to determine whether the coating has blushing, bubbling and peeling phenomena.
Salt spray resistance: refer to the national standard GB/T1771-2007 determination of neutral salt spray resistance of colored paint and varnish.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (8)
1. The non-isocyanate polyurethane photocureable coating is characterized by comprising the following components in parts by weight:
2. the non-isocyanate polyurethane photocurable coating according to claim 1, wherein the molecular structure of the non-isocyanate prepolymer is:
wherein n is 10-20.
3. The non-isocyanate polyurethane photocurable coating of claim 1, wherein: the acrylate is methyl acrylate, ethyl acrylate or hydroxyethyl acrylate.
4. The non-isocyanate polyurethane photocurable coating of claim 1, wherein: the leveling agent is prepared by the following chemical formula: BYK-333, BYK-310, BYK-306 and BYK-300.
5. The non-isocyanate polyurethane photocurable coating of claim 1, wherein: the defoaming agent is a water-based organic silicon defoaming agent.
6. The non-isocyanate polyurethane photocurable coating of claim 1, wherein: the thickener is German gelatin: PUR40, PUR42, PUR60, PUR64 or PUR 69.
7. The non-isocyanate polyurethane photocurable coating of claim 1, wherein: the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxycyclohexyl phenyl ketone or 2-isopropyl thioxanthone.
8. The non-isocyanate polyurethane photocurable coating of claim 1, wherein: the mass ratio of the non-iso-isocyanate prepolymer to the acrylate is 4-5: 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113912839A (en) * | 2021-11-08 | 2022-01-11 | 淄博锐捷新技术开发有限公司 | Water-based non-isocyanate polyurethane prepolymer, coating and preparation method thereof |
| JP7033636B1 (en) | 2020-10-02 | 2022-03-10 | 大日精化工業株式会社 | A method for producing an aqueous dispersion of a polyhydroxyurethane resin, a gas barrier film, and an aqueous dispersion of a polyhydroxyurethane resin. |
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