CN114560993A - Preparation method of chalcone-terminated photosensitive waterborne polyurethane/epoxy acrylate - Google Patents
Preparation method of chalcone-terminated photosensitive waterborne polyurethane/epoxy acrylate Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- 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
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Abstract
The invention provides chalcone-terminated photosensitive waterborne polyurethane and a preparation method thereof, and a waterborne polyurethane/epoxy acrylate curing film prepared from the chalcone-terminated photosensitive waterborne polyurethane, wherein the photosensitive waterborne polyurethane is prepared from raw materials comprising polyisocyanate, oligomer polyol and chalcone, the polyurethane is subjected to end-capping treatment by the chalcone, a photosensitive group is added into the polyurethane through a covalent bond, so that the polyurethane is endowed with excellent photocuring performance, the photosensitive waterborne polyurethane/epoxy acrylate curing film has photosensitivity under the irradiation of ultraviolet light and visible light, the curing can be completed without adding a photoinitiator, and meanwhile, the waterborne polyurethane/epoxy acrylate curing film prepared from the photosensitive waterborne polyurethane serving as the raw material has good thermal stability, strong adhesive force and impact strength, and good application prospect.
Description
Technical Field
The invention relates to the technical field of photocuring materials, in particular to chalcone-terminated photosensitive waterborne polyurethane/epoxy acrylate, a preparation method thereof and a method for preparing a cured film of waterborne polyurethane acrylate.
Background
Polyurethane (PU) is a high molecular polymer containing repeated carbamate (-NHCOO-) units, and the PU performance mainly comprises a structure of a soft segment and a hard segment. The hard segment is generally made of isocyanate, and influences the physical properties of the material; the soft segment is generally composed of oligomeric polyols and affects the flexibility and low temperature properties of the material. PU is widely applied to the fields of wood floor paint, paper paint, building paint, leather paint and the like. PU is classified into solvent-borne polyurethane and waterborne polyurethane. The solvent type polyurethane is added with an organic solvent in the preparation process, so that certain potential safety hazards exist in the storage and transportation processes, and organic pollutants are discharged more. The waterborne polyurethane takes water as dispersed phase polyurethane, compared with solvent type polyurethane, the waterborne polyurethane has the advantages of small smell, low VOC (volatile organic compound) emission, energy conservation, environmental protection, good mechanical property, easy modification and the like, and is widely applied to the adhesive and coating industries. People's environmental awareness is continuously strengthened and the country limits the solvent-based polyurethane, so that people's research on the waterborne polyurethane becomes a hotspot.
Research shows that chalcone is a flavane compound of alpha, beta-unsaturated aromatic ketone and is the core of various important biological compounds. Chalcone and derivatives thereof have wide pharmacological activity, wherein the activities of tumor resistance, inflammation resistance, ulcer resistance, bacteria resistance, oxidation resistance and the like are reported. Chalcones contain α, β -unsaturated carbonyl groups as optically active functional groups and crosslink by [2+2] cycloaddition of carbon-carbon double bonds under ultraviolet radiation.
The UV-cured polyurethane has better effects on reducing atmospheric pollution and saving energy due to the adoption of UV curing, meets the development requirements of the current environment-friendly energy-saving safe material, and thus becomes the development direction of the current polyurethane coating. Chalcone has a photosensitive group, and no article reports that chalcone is introduced into polyurethane at present.
Disclosure of Invention
Based on the above technical background, the present inventors have made a keen search and, as a result, have found that: the polyurethane is subjected to end-capping treatment by chalcone, a photosensitive group is introduced into a polyurethane chain through a covalent bond, and the chalcone end-capped photosensitive waterborne polyurethane is prepared, has excellent photocuring performance, has photosensitivity under the irradiation of ultraviolet light and visible light, can be cured without adding a photoinitiator, and is good in thermal stability and strong in adhesive force and impact strength of a waterborne polyurethane/epoxy acrylate cured film prepared from the photosensitive waterborne polyurethane.
The first aspect of the present invention is to provide a chalcone terminated photosensitive aqueous polyurethane prepared from raw materials including a polyisocyanate, an oligomeric polyol and chalcone.
The second aspect of the present invention provides a preparation method of the chalcone terminated photosensitive aqueous polyurethane according to the first aspect of the present invention, the preparation method comprising the following steps:
step 1, mixing polyisocyanate, oligomer polyol and a water-based chain extender, heating, and reacting in the presence of a catalyst to obtain isocyanate-terminated polyurethane;
step 2, adding chalcone into the polyurethane obtained in the step 1 to obtain chalcone-terminated polyurethane;
and 3, cooling, adding a neutralizing agent for reaction, cooling again, adding water for mixing to obtain the chalcone terminated waterborne polyurethane.
The third aspect of the present invention provides a chalcone-terminated photosensitive aqueous polyurethane/epoxy acrylate cured film, wherein the aqueous polyurethane/epoxy acrylate cured film is prepared from photosensitive aqueous polyurethane and an epoxy acrylate emulsion as raw materials, and the photosensitive aqueous polyurethane is the chalcone-terminated photosensitive aqueous polyurethane described in the first aspect of the present invention or the chalcone-terminated photosensitive aqueous polyurethane prepared by the preparation method described in the second aspect of the present invention.
Drawings
FIG. 1 shows the absorbance curves of example 1 under different light sources;
FIG. 2 shows the absorbance curves of the products obtained in examples 1 and 2 under Led365nm UV lamp;
FIG. 3 is a graph showing the degree of crosslinking of the products obtained in example 1 and example 2 at different light intensities;
FIG. 4 shows a schematic representation of the degree of crosslinking in different solvents for example 1 and example 2;
figure 5 shows the TGA and DTG curves for the products made in example 1 and example 2.
Detailed Description
The present invention will be described in detail below, and features and advantages of the present invention will become more apparent and apparent with reference to the following description.
The main chain of the polyurethane contains repeated-HNCOO-structural units, generally consists of soft segment monomers and hard segment monomers, and the proportion of the hard segment monomers and the soft segment monomers is adjusted to obtain the thermosetting and thermoplastic polyurethane. The aqueous polyurethane is mainly prepared by a prepolymer method, groups with hydrophilicity are introduced into polyurethane prepolymers capped by-NCO, and polyurethane molecular chains are emulsified and dispersed in water after chain extension.
The first aspect of the present invention is to provide a chalcone terminated photosensitive aqueous polyurethane prepared from raw materials including a polyisocyanate, an oligomeric polyol and chalcone.
In the prior art, isocyanate can react with some weak reactive hydrides, the obtained product is stable at normal temperature, and reverse reaction occurs under certain conditions, namely 'blocking' and 'unblocking'. Polyisocyanates are a special class of chemicals with-N ═ C ═ O functional groups, which mainly affect the mechanical properties of polyurethane materials.
In the present invention, the polyisocyanate is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated benzyl diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate, preferably selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate and isophorone diisocyanate, and more preferably isophorone diisocyanate.
The oligomer polyol mainly affects the elasticity and low-temperature performance of the material, and is selected from one or more of polyester polyol, polyether polyol and polycarbonate polyol.
Preferably, the oligomer polyol is selected from one or more of ethylene oxide glycol, polypropylene oxide glycol, polytetramethylene ether glycol and polytetrahydrofuran ether glycol. More preferably, the oligomeric polyol is polytetrahydrofuran ether glycol. It has good low temperature resistance, hydrolysis resistance and mould resistance.
The chalcone is selected from one or more of 4-beta-hydroxyethyl oxycodone, 4-hydroxyethyl oxy-4 ' -dimethylamino chalcone, 4-dimethylamino chalcone and 3-hydroxy-4 ' -methoxy chalcone, and preferably selected from one or two of 4-beta-hydroxyethyl oxycodone and 4-hydroxyethyl oxy-4 ' -dimethylamino chalcone.
Chalcone is a flavane compound of alpha, beta-unsaturated aromatic ketone, and double bonds on the chalcone can generate dimerization reaction under the irradiation of 300nm ultraviolet light or visible light. Experiments show that the polyurethane has alpha, beta-unsaturated carbonyl optical active functional groups of the chalcone by using the chalcone for end capping, and the polyurethane is crosslinked through cycloaddition of carbon-carbon double bonds under the irradiation of ultraviolet rays. The polyurethane has higher photoreaction activity and complete photocrosslinking characteristic in the absence of a photosensitizer.
The raw materials comprise the following components in parts by weight: based on 30 parts by weight of the polyisocyanate,
40-75 parts by weight of oligomer polyol;
20-35 parts by weight of chalcone.
Preferably, the polyisocyanate is used in an amount of 30 parts by weight,
50-70 parts by weight of oligomer polyol;
22-30 parts of chalcone;
more preferably, the polyisocyanate is added to the reaction mixture in an amount of 30 parts by weight based on the polyisocyanate,
55-60 parts by weight of oligomer polyol;
24-26 parts by weight of chalcone.
According to a preferred embodiment of the present invention, the raw material further includes an aqueous chain extender, which is a substance that contains an ionic group or a group capable of being ionized and is introduced while the prepolymer is subjected to chain extension.
The aqueous chain extender is selected from one or more than one of sulfonate chain extenders, preferably selected from one or more than one of dimethylolpropionic acid, dimethylolbutyric acid, dimethylolpentanoic acid and dimethylolhexanoic acid, and more preferably is dimethylolpropionic acid with hydrophilic carboxyl.
The aqueous chain extender is 4 to 8 parts by weight, preferably 4.5 to 7 parts by weight, and more preferably 5 to 6 parts by weight, based on 30 parts by weight of the polyisocyanate.
The raw material also comprises a neutralizing agent, wherein the neutralizing agent is selected from one or more of organic bases, preferably selected from one or more of diethanolamine, triethanolamine, triethylamine, N-dimethyl isopropanolamine, triethylene diamine and dimethyl cyclohexylamine, and more preferably selected from one or two of triethanolamine and triethylamine. The addition of a certain amount of neutralizing agent can make the obtained waterborne polyurethane more stable.
The neutralizing agent is 3 to 7 parts by weight, preferably 4 to 6 parts by weight, more preferably 5 to 5.5 parts by weight, based on 30 parts by weight of the polyisocyanate. The addition of the neutralizing agent in parts by weight can ensure that the polyurethane has better thermal stability under the condition of keeping other properties basically unchanged.
During the preparation process, a catalyst is also added, wherein the catalyst is one or more selected from stannous octoate, tetramethyl butanediamine, triethylene diamine and dibutyltin dilaurate, preferably one or two selected from tetramethyl butanediamine and dibutyltin dilaurate, and more preferably dibutyltin dilaurate. The addition of the catalyst allows the reaction to proceed rapidly.
The catalyst is 0.1 to 0.3 parts by weight, preferably 0.12 to 0.25 parts by weight, more preferably 0.15 to 0.2 parts by weight, based on 30 parts by weight of the polyisocyanate.
Compared with the traditional solvent type polyurethane, the chalcone terminated waterborne polyurethane disclosed by the invention has the advantages of environmental protection, safety and difficult combustion by replacing an organic solvent with water, retains the excellent performance of the solvent type polyurethane, and has the advantages of small smell, good mechanical property, good compatibility, no pollution, low VOC (volatile organic compound) emission, easiness in operation and processing and the like. Meanwhile, the invention adopts chalcone to carry out end-capping treatment on polyurethane molecules, and introduces optical active groups into a polyurethane chain through covalent bonds, so as to prepare the photosensitive waterborne polyurethane with high solid content and good photocuring performance. The waterborne polyurethane can realize photocuring under the irradiation of ultraviolet light and visible light without adding a photoinitiator, and has good thermal stability.
Meanwhile, the chalcone-terminated photosensitive waterborne polyurethane is used as a raw material for preparing a cured film, so that the adhesive force and the impact resistance of the cured film can be improved. The adhesive force of a curing film prepared by using the water-based polyurethane as a raw material can be improved to 0 grade, and the impact resistance can be improved by 10-25 times.
The second aspect of the present invention provides a preparation method of the chalcone terminated photosensitive aqueous polyurethane according to the first aspect of the present invention, the preparation method comprising the following steps:
step 1, mixing polyisocyanate, oligomer polyol and a water-based chain extender, heating, and reacting in the presence of a catalyst to obtain isocyanate-terminated polyurethane;
step 2, adding chalcone into the polyurethane obtained in the step 1 to obtain chalcone-terminated polyurethane;
and 3, cooling, adding a neutralizing agent for reaction, cooling again, adding water for mixing to obtain the chalcone terminated waterborne polyurethane.
This step is specifically described and illustrated below.
Step 1, mixing polyisocyanate, oligomer polyol and a water-based chain extender, heating, and reacting in the presence of a catalyst to obtain isocyanate-terminated polyurethane.
The polyisocyanate is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated benzyl diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate, preferably selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate and isophorone diisocyanate, and more preferably isophorone diisocyanate.
The oligomer polyol is one or more selected from polyester polyol, polyether polyol and polycarbonate polyol. Preferably one or more selected from the group consisting of ethylene oxide glycol, polypropylene oxide glycol, polytetramethylene ether glycol and polytetrahydrofuran ether glycol, more preferably polytetrahydrofuran ether glycol.
The aqueous chain extender is selected from one or more of sulfonate chain extenders, preferably selected from one or more of dimethylolpropionic acid, dimethylolbutyric acid, dimethylolvaleric acid and dimethylolcaproic acid, and more preferably is dimethylolpropionic acid with hydrophilic carboxyl.
Preferably, the aqueous chain extender is dissolved in the solvent and then reacts with the polyisocyanate and the oligomer diol, and after the substances are fully dissolved in the solvent, the substances are dispersed more uniformly, so that the reaction can be carried out more completely.
The solvent is selected from one or more of acetone, butanone and N-methyl pyrrolidone. After the aqueous chain extender is dissolved in the solvent, the aqueous chain extender can be better mixed with other raw materials.
The catalyst is selected from one or more of stannous octoate, tetramethyl butanediamine, triethylene diamine and dibutyltin dilaurate, preferably selected from one or two of tetramethyl butanediamine and dibutyltin dilaurate, and more preferably dibutyltin dilaurate. The addition of the above catalyst allows the reaction to proceed rapidly.
In the present invention, based on 30 parts by weight of the polyisocyanate,
40-75 parts by weight of oligomer polyol;
4-8 parts of a water-based chain extender;
0.1 to 0.3 part by weight of a catalyst.
Preferably, the polyisocyanate is added to the polyisocyanate in an amount of 30 parts by weight,
50-70 parts by weight of oligomer polyol;
4.5-7 parts by weight of a water-based chain extender;
0.12 to 0.25 part by weight of a catalyst.
More preferably, the polyisocyanate is used in an amount of 30 parts by weight,
55-60 parts by weight of oligomer polyol;
4.5-7 parts by weight of a water-based chain extender;
0.15 to 0.2 part by weight of a catalyst.
The amount of each substance affects the mechanical properties of the finally obtained polyurethane, and the inventors have found that when the amount of the polyisocyanate and the oligomer polyol is in the above range, the obtained polyurethane has excellent adhesion and good impact resistance while maintaining other properties substantially unchanged.
In the invention, the reaction is carried out under the protection of nitrogen, so that side reaction is prevented, and the reaction temperature is 70-100 ℃, preferably 75-90 ℃, and more preferably 80 ℃.
The reaction time is 2-5 h, preferably 3-4 h, and more preferably 3.5 h.
Tests show that the photosensitive waterborne polyurethane prepared at the reaction temperature is relatively complete in polymerization and relatively high in crosslinking degree.
And 2, adding chalcone into the polyurethane obtained in the step 1 to obtain chalcone-terminated polyurethane.
The chalcone is selected from one or more of 4-beta-hydroxyethyl oxycodone, 4-hydroxyethyl oxy-4 ' -dimethylamino chalcone, 4-dimethylamino chalcone and 3-hydroxy-4 ' -methoxy chalcone, and preferably selected from one or two of 4-beta-hydroxyethyl oxycodone and 4-hydroxyethyl oxy-4 ' -dimethylamino chalcone.
The amount of the chalcone is 20 to 35 parts by weight, preferably 22 to 30 parts by weight, and more preferably 24 to 26 parts by weight, based on 30 parts by weight of the polyisocyanate.
The reaction temperature is 70-100 ℃, preferably 75-90 ℃, and more preferably 80 ℃.
The reaction time is 3-7 h, preferably 4-6 h, and more preferably 5 h.
According to the invention, chalcone is introduced into polyurethane, so that the polyurethane has an optically active functional group, and the photocuring performance is endowed, so that the prepared polyurethane has higher photoreaction activity or photocrosslinking characteristic to ultraviolet light in the absence of a photosensitizer. Compared with the curing of common polyurethane, the curing agent is more energy-saving, environment-friendly, green and efficient. Meanwhile, the introduction of chalcone is found to improve the impact resistance and the adhesive force of the prepared cured film.
And 3, cooling, adding a neutralizing agent for reaction, cooling again, adding water for mixing to obtain the chalcone terminated waterborne polyurethane.
And cooling to 40-50 ℃ for reaction, preferably cooling to 40 ℃ for reaction.
The reaction time is 20-50 min, preferably 20-30 min.
The neutralizing agent is selected from one or more of organic alkali, preferably selected from one or more of diethanolamine, triethanolamine, triethylamine, N-dimethyl isopropanolamine, triethylene diamine and dimethyl cyclohexylamine, and more preferably selected from one or two of triethanolamine and triethylamine.
The neutralizing agent is 3 to 7 parts by weight, preferably 4 to 6 parts by weight, more preferably 5 to 5.5 parts by weight, based on 30 parts by weight of the polyisocyanate.
And cooling to 25-35 ℃, preferably adding water at 25-30 ℃ for mixing for 1-2 hours, preferably for 1 hour.
The mixing is carried out under high-speed stirring, so that water and the waterborne polyurethane are uniformly mixed, and the water is added to control the solid content of the polyurethane to be 30-50 wt%, preferably 35-45 wt%.
The rotating speed is 700-1000 r/min, preferably 800 r/min.
The third aspect of the invention provides a chalcone-terminated photosensitive aqueous polyurethane/epoxy acrylate cured film, which is prepared from photosensitive aqueous polyurethane and an epoxy acrylate emulsion serving as raw materials.
The photosensitive waterborne polyurethane is chalcone terminated photosensitive waterborne polyurethane described in the first aspect of the invention or chalcone terminated photosensitive waterborne polyurethane prepared by the preparation method described in the second aspect of the invention.
The curing film is further added with water in the preparation process, and the mass ratio of the photosensitive waterborne polyurethane to the epoxy acrylate emulsion to the water is (5-15): (1-30): (5-30), preferably the mass ratio is (5-10): (1-3): (5-10).
According to a preferred embodiment of the present invention, the epoxy acrylate emulsion is obtained by photocuring trimethylolpropane trimethacrylate, methyl methacrylate, epoxy acrylate, acrylic acid and triethanolamine in the presence of a siloxane coupling agent and a photoinitiator. The light curing mode is preferably ultraviolet light curing.
The adhesive comprises 1 to 5 parts by weight of trimethylolpropane trimethacrylate, 1 to 5 parts by weight of methyl methacrylate, 2 to 8 parts by weight of epoxy acrylate, 0.5 to 2 parts by weight of acrylic acid, 0.2 to 1.5 parts by weight of triethanolamine, 0.2 to 3 parts by weight of a siloxane coupling agent, and 0.2 to 2 parts by weight of a photoinitiator.
The initiator is an ultraviolet initiator, and is selected from one or more of 2-hydroxymethyl phenyl propane-1-ketone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-p-ethyl ether phenyl acetone and isopropyl thioxanthone, preferably 2-hydroxymethyl phenyl propane-1-ketone. In addition, tests show that the ultraviolet initiator is added in the preparation process of the curing film, so that the curing time can be effectively shortened, and the energy conservation and the environmental protection are realized.
The siloxane coupling agent is preferably KH570
In the invention, trimethylolpropane trimethacrylate plays a role of a diluent and is used as a solvent for reducing the viscosity of a reactant blend, and in the experimental process, the product obtained by using trimethylolpropane trimethacrylate as the diluent has moderate crosslinking density and high activity, and the product obtained after photocuring has good toughness, improved impact resistance and reduced cost.
The chalcone-terminated photosensitive waterborne polyurethane/epoxy acrylate is cured by adopting an ultraviolet curing mode, and compared with the traditional thermosetting mode, the ultraviolet curing mode has the characteristics of energy conservation, environmental protection, greenness and high efficiency.
The waterborne polyurethane/epoxy acrylate curing film is prepared in an ultraviolet curing mode, and the photocuring time is 5-60 min, preferably 10-30 min.
Preferably, the drying is carried out before photocuring, preferably, the drying is carried out for 20-30 h at 40-60 ℃, and then the drying is carried out for 20-30 h in a vacuum environment at 50-70 ℃. Drying removes water, which is not only beneficial to improving the photocuring speed, but also beneficial to forming a uniform and continuous cured film.
The cured film prepared from the waterborne polyurethane acrylate has strong adhesive force and impact strength, the hardness of the cured film is small, the cured film is HB-1B, the glossiness is 135-191, the adhesive force is strong, the degree is 0-2, and the contact angle is 65-90 degrees.
The invention has the following beneficial effects:
(1) according to the invention, the polyurethane molecules are subjected to end-capping treatment by using chalcone, and optically active groups are introduced into a polyurethane chain through covalent bonds, so that the photosensitive waterborne polyurethane is prepared, and has excellent photocuring performance;
(2) in the process of preparing the chalcone-terminated waterborne polyurethane, water is used for replacing an organic solvent, so that the excellent performance of the traditional solvent type polyurethane is kept, and the chalcone-terminated waterborne polyurethane has the advantages of safety, combustion resistance, small smell, excellent mechanical performance, good compatibility, no public nuisance, low VOC (volatile organic compound) emission, easiness in operation and processing and the like;
(3) the waterborne polyurethane disclosed by the invention has good photocuring performance, has photosensitivity under the radiation of ultraviolet light and visible light under the condition that a photoinitiator is not required to be added, and has the characteristics of energy conservation, environmental friendliness, greenness and high efficiency compared with the traditional thermosetting method;
(4) the cured film prepared from the waterborne polyurethane has good thermal stability, strong adhesive force and impact strength, small hardness and strong adhesive force;
(5) the preparation method provided by the invention is simple, mild in condition, and good in performance of the prepared product, and has a good application prospect.
Examples
The invention is further illustrated by the following specific examples, which are intended to be illustrative only and not limiting to the scope of the invention.
Example 1
Under the protection of nitrogen, 30g of isophorone diisocyanate (IPDI), 56g of polytetrahydrofuran ether glycol (PTMG-1000) and 5.6g of dimethylolpropionic acid (DMPA) are added into a container, the temperature is raised to 80 ℃, 0.17g of dibutyltin dilaurate (DBTDL) is added, and the reaction is carried out for 3.5 hours, so as to obtain isocyanate-terminated polyurethane;
adding 25g of 4-beta-hydroxyethyl oxygen chalcone (HEOC), reacting for 5 hours at the temperature of 80 ℃ to obtain chalcone end-capped waterborne polyurethane;
cooling to 40 ℃, adding 5g of TEA, and reacting for 20-30 min; and cooling to 25-30 ℃, adding deionized water to control the solid content to be 40 wt.%, and stirring at a high speed of 800r/min for 1h to obtain the chalcone terminated waterborne polyurethane emulsion PTMG-CWPU.
Example 2
Preparation was carried out in a similar manner to example 1 except that the soft block was 56g of polyethylene glycol (PEG-1000), and the other steps were the same, to obtain a chalcone-terminated aqueous polyurethane emulsion PEG-CWPU.
Example 3
1.2g of trimethylolpropane trimethacrylate, 2.8g of methyl methacrylate, 2.7g of epoxy acrylate, 0.58g of acrylic acid, 0.27g of KH5700.28g of photoinitiator and 0.28g of triethanolamine are sequentially added into a beaker and stirred uniformly for later use. Coating the epoxy acrylate emulsion on a substrate, then irradiating the substrate by using an ultraviolet lamp in the air to obtain a cured film, and cooling the cured film to room temperature for later use. The cured film is labeled a 1.
5g of the chalcone-terminated aqueous polyurethane emulsion prepared in example 1, 2g of epoxy acrylate and 6.3g of deionized water are added into a container and stirred until the emulsion is completely dispersed, so that the aqueous polyurethane epoxy acrylate emulsion is obtained.
Coating the aqueous polyurethane acrylate emulsion on a substrate, drying for 24h in a constant-temperature oven at 50 ℃, taking out, drying for 24h in a vacuum oven at 60 ℃, then illuminating for 10-30 min in the air by using an ultraviolet lamp to obtain an aqueous polyurethane/epoxy acrylate cured film, and cooling to room temperature for later use. The waterborne polyurethane/epoxy acrylate cured film is labeled B1.
Example 4
The preparation was carried out in a similar manner to example 2, with the only difference that: 1.2g of trimethylolpropane trimethacrylate, 2.8g of methyl methacrylate, 4g of epoxy acrylate, 0.7g of acrylic acid, 0.32g of KH5700.34g of photoinitiator and 0.34g of triethanolamine are sequentially added into a beaker, and the mixture is uniformly stirred for later use. The emulsion is labeled 2. Coating the epoxy acrylate emulsion on a substrate, then illuminating the substrate by an ultraviolet lamp in the air to obtain a cured film, and cooling the cured film to room temperature for later use. The cured film is labeled a 2.
5g of the chalcone terminated aqueous polyurethane emulsion prepared in example 1, 2g of epoxy acrylate and 6.3g of deionized water were added to a vessel and stirred until the emulsion was completely dispersed. The obtained waterborne polyurethane/epoxy acrylate cured film is marked as B2.
Example 5
The preparation was carried out in a similar manner to example 2, with the only difference that: 1.2g of trimethylolpropane trimethacrylate, 2.8g of methyl methacrylate, 6g of epoxy acrylate, 0.87g of acrylic acid, 0.4g of KH5700.42g of photoinitiator and 0.43g of triethanolamine are sequentially added into a beaker, and are uniformly stirred for later use. The emulsion is labeled 3. Coating the epoxy acrylate emulsion on a substrate, then irradiating the substrate by using an ultraviolet lamp in the air to obtain a cured film, and cooling the cured film to room temperature for later use. The cured film is labeled a 3.
5g of the chalcone terminated aqueous polyurethane emulsion from example 1, 2g of epoxy acrylate and 6.3g of deionization were added to a vessel until the emulsion was completely dispersed. The obtained waterborne polyurethane/epoxy acrylate cured film is marked as B3.
Example 6
The preparation was carried out in a similar manner to example 2, with the only difference that: 1.6g of trimethylolpropane trimethacrylate, 2.4g of methyl methacrylate, 2.7g of epoxy acrylate, 0.58g of acrylic acid, 0.27g of KH5700.28g of photoinitiator and 0.28g of triethanolamine are sequentially added into a beaker and stirred uniformly for later use. The cured film is labeled a 4.
5g of the chalcone terminated aqueous polyurethane emulsion from example 1, 2g of epoxy acrylate and 6.3g of deionized water were added to a vessel and stirred until the emulsion was completely dispersed. The obtained waterborne polyurethane/epoxy acrylate cured film is marked as B4.
Example 7
The preparation was carried out in a similar manner to example 2, with the only difference that: 1.6g of trimethylolpropane trimethacrylate, 2.4g of methyl methacrylate, 4g of epoxy acrylate, 0.7g of acrylic acid, 0.32g of KH5700.34g of photoinitiator and 0.34g of triethanolamine are sequentially added into a beaker, and the mixture is uniformly stirred for later use. The cured film is labeled a 5.
5g of the chalcone terminated aqueous polyurethane emulsion from example 1, 2g of epoxy acrylate and 6.3g of deionized water were added to a vessel and stirred until the emulsion was completely dispersed. The obtained waterborne polyurethane/epoxy acrylate cured film is marked as B5.
Example 8
The preparation was carried out in a similar manner to example 2, with the only difference that: 1.6g of trimethylolpropane trimethacrylate, 2.4g of methyl methacrylate, 6g of epoxy acrylate, 0.87g of acrylic acid, 0.4g of KH5700.42g of photoinitiator and 0.43g of triethanolamine are sequentially added into a beaker, and are uniformly stirred for later use. The cured film is labeled a 6.
5g of the chalcone terminated aqueous polyurethane emulsion from example 1, 2g of epoxy acrylate and 6.3g of deionized water were added to a vessel and stirred until the emulsion was completely dispersed. The obtained waterborne polyurethane/epoxy acrylate cured film is marked as B6.
Example 9
The preparation was carried out in a similar manner to example 2, with the only difference that: 2.8g of trimethylolpropane trimethacrylate, 1.2g of methyl methacrylate, 2.7g of epoxy acrylate, 0.58g of acrylic acid, 0.27g of KH5700.28g of photoinitiator and 0.28g of triethanolamine are sequentially added into a beaker, and the mixture is uniformly stirred for later use. The cured film is labeled a 7.
5g of the chalcone terminated aqueous polyurethane emulsion from example 1, 2g of epoxy acrylate and 6.3g of deionized water were added to a vessel and stirred until the emulsion was completely dispersed. The obtained waterborne polyurethane/epoxy acrylate cured film is marked as B7.
Example 10
The preparation was carried out in a similar manner to example 2, with the only difference that: 2.8g of trimethylolpropane trimethacrylate, 1.2g of methyl methacrylate, 4g of epoxy acrylate, 0.7g of acrylic acid, 0.32g of KH5700.34g of photoinitiator and 0.34g of triethanolamine are sequentially added into a beaker, and the mixture is uniformly stirred for later use. The cured film is labeled A8.
5g of the chalcone terminated aqueous polyurethane emulsion from example 1, 2g of epoxy acrylate and 6.3g of deionized water were added to a vessel and stirred until the emulsion was completely dispersed. The obtained waterborne polyurethane/epoxy acrylate cured film is marked as B8.
Example 11
The preparation was carried out in a similar manner to example 2, with the only difference that: 2.8g of trimethylolpropane trimethacrylate, 1.2g of methyl methacrylate, 6g of epoxy acrylate, 0.87g of acrylic acid, 0.42g of KH5700, 0.4g of photoinitiator and 0.43g of triethanolamine are sequentially added into a beaker, and the mixture is uniformly stirred for later use. The cured film is labeled a 9.
5g of the chalcone terminated aqueous polyurethane emulsion from example 1, 2g of epoxy acrylate and 6.3g of deionized water were added to a vessel and stirred until the emulsion was completely dispersed. The obtained waterborne polyurethane/epoxy acrylate cured film is marked as B9.
Examples of the experiments
Experimental example 1
The chalcone terminated photosensitive waterborne polyurethane prepared in examples 1-2 was subjected to a photosensitivity test. The specific test process is as follows:
(1) the sample of example 1 was dissolved in ethanol, 365nm ultraviolet light was intercepted by a GY-500 type high-pressure mercury lamp, a ZWB2 filter, 254nm ultraviolet light was intercepted by a GY-500 type high-pressure mercury lamp, a JB420 filter, 420nm visible light, Led365nm ultraviolet light, Led395nm ultraviolet light, and 254nm ultraviolet germicidal lamp were used as radiation light sources in this order, and the change in absorbance was recorded by an ultraviolet-visible spectrophotometer, as shown in fig. 1.
(2) Samples from examples 1 and 2 were dissolved in ethanol solutions, respectively, and applied to cuvettes, the solvent was evaporated to form a film at room temperature, and the absorbance change was recorded on an ultraviolet-visible spectrophotometer using Led365nm uv lamp as the radiation source, as shown in fig. 2.
(3) Examples 1 and 2 were dissolved in an ethanol solution and the degree of photocrosslinking was measured at different light intensities using an Led365nm uv lamp as a light source, as shown in fig. 3. Light (cross-linking degree calculation method:
)。
(4) examples 1 and 2 were dissolved in different solvents (1, 4-dioxane, tetrahydrofuran, dichloromethane, chloroform) and photocrosslinked using Led365nm uv lamp as the radiation source, the degree of change is shown in figure 4.
As can be seen from FIG. 1, the photosensitive waterborne polyurethane prepared by the invention can realize photocuring under both ultraviolet light and visible light, and has good photocuring performance.
As can be seen from FIG. 2, the photosensitive waterborne polyurethane prepared in the examples 1 and 2 of the present invention has good photo-curing performance under the irradiation of ultraviolet light.
FIGS. 3(a) and 3(b) show the degree of crosslinking of the photosensitive aqueous polyurethane obtained in example 1 and example 2 at different light intensities, respectively, and it can be seen that the degree of crosslinking of the photosensitive aqueous polyurethane obtained in the present invention gradually increases with the increase in light intensity.
FIGS. 4(a) and 4(b) show the degree of crosslinking of the photosensitive waterborne polyurethanes prepared in examples 1 and 2 in different solvents, respectively, and it can be seen from the figures that the waterborne polyurethanes prepared in examples 1 and 2 have good degree of crosslinking in different solvents, which can substantially reach 100%.
Experimental example 2 Heat stability test
The thermal stability of the products obtained in example 1 and example 2 was tested as follows: under the nitrogen atmosphere, the heating rate is 10 ℃/min, and the temperature of the test sample is 0-600 ℃. TGA and DTG profiles for example 1 and example 2 were recorded using a Q600 thermogravimetric analyzer as shown in figure 5.
Fig. 5(a) shows the TGA and DTG curves for the product made in example 1, and fig. 5(b) shows the TGA and DTG curves for the product made in example 2.
As can be seen from FIG. 5, the chalcone terminated photosensitive waterborne polyurethane has good thermal stability, and still has good thermal stability after photocuring.
Experimental example 3
The method for measuring the impact strength of the epoxy acrylate curing film and the waterborne polyurethane acrylate curing film prepared in the embodiments 3-11 comprises the following specific steps:
(1) before the use, whether the center of the impact rod is consistent with the center of the concave hole on the base of the impactor or not is checked, and if deviation exists, the internal hexagonal screw on the base of the impactor can be adjusted.
(2) And checking whether the alignment mark is aligned to the zero line, slightly putting down the impact hammer, observing whether the positioning line is superposed with the zero line, and adjusting screws on two sides of the alignment mark if the positioning line is deviated from the zero line.
(3) And lifting the impact hammer by the right hand, and flatly placing the solidified film tinplate sample on the pillow block by the left hand, wherein the distance between an impact point and the edge of the detection plate is not less than 15 mm.
(4) According to the specification of the product standard, the height of the impact hammer is fixed, and the impact hammer falls down and is hit on the curing film sample plate by hands.
(5) And repeatedly moving the cured film sample plate to enable the impact hammer to fall on different positions of the sample plate, and reporting the maximum height of the coating film without cracking or disengaging. The test results are shown in tables 1 and 2.
TABLE 1
TABLE 2
From tables 1 and 2, it can be seen that the hardness of the waterborne polyurethane/epoxy acrylate cured film is reduced, and the impact strength (the range of the instrument is 0-50 cm) is greatly improved.
Further, the impact strength of the waterborne polyurethane/epoxy acrylate cured film obtained by adding the photosensitive waterborne polyurethane is remarkably improved compared with that of a cured film without adding waterborne polyurethane.
Experimental example 4
The properties of the epoxy acrylate cured films and the waterborne urethane acrylate cured films prepared in examples 3 to 11 were analyzed. The specific test performance and test procedure were as follows:
(1) determination of gel content of cured film
Weighing a solidified film sample, soaking the sample in acetone for 12h, replacing an acetone solution, continuously soaking for 12h, filtering the solution, drying to constant weight, and recording the weight.
Gel content (%) × 100% (mass after acetone immersion/mass before acetone immersion).
(2) Measurement of hardness of cured film: this experiment was performed according to GB/T1730-1993.
(3) Measurement of gloss of cured film: ETB-0686 type gloss meter.
(4) Hardness of the cured film: GB/T1730-1993 standard.
(5) Adhesive force of a cured film: GB/T9286-1998 standard.
(6) Contact angle of cured film: model JC2000D1 contact angle measuring instrument.
Tables 1 and 2 show the performance analysis of the epoxy acrylate cured film and the aqueous urethane acrylate cured film prepared in examples 3 to 11 of the present invention.
From tables 1 and 2, it can be seen that the hardness of the aqueous polyurethane/epoxy acrylate cured film is reduced, and the adhesion is greatly improved.
Further, the adhesive force of the waterborne polyurethane/epoxy acrylate cured film obtained by adding the photosensitive waterborne polyurethane is remarkably improved compared with that of a cured film without adding waterborne polyurethane. The adhesive force of the waterborne polyurethane/epoxy acrylate curing film prepared by the invention can reach 0 grade at most, and basically no peeling occurs after grid marking.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A chalcone terminated photosensitive aqueous polyurethane, wherein the photosensitive aqueous polyurethane is prepared from raw materials comprising a polyisocyanate, an oligomeric polyol, and chalcone.
2. The photosensitive aqueous polyurethane according to claim 1, wherein the polyisocyanate is added to the polyurethane in an amount of 30 parts by weight,
40-75 parts by weight of oligomer polyol;
20-35 parts of chalcone.
3. The photosensitive aqueous polyurethane according to claim 1,
the oligomer polyol is one or more selected from polyester polyol, polyether polyol and polycarbonate polyol;
the chalcone is one or more selected from 4-beta-hydroxyethyl oxygen chalcone, 4-hydroxyethyl oxygen-4 '-dimethylamino chalcone, 4-dimethylamino chalcone and 3-hydroxy-4' -methoxy chalcone.
4. The photosensitive waterborne polyurethane of claim 1, wherein the raw material further comprises an aqueous chain extender, and the aqueous chain extender is one or more selected from sulfonate chain extenders;
the aqueous chain extender is 4 to 8 parts by weight based on 30 parts by weight of polyisocyanate.
5. The photosensitive aqueous polyurethane of claim 1, wherein the raw material further comprises a neutralizing agent, and the neutralizing agent is one or more selected from organic bases;
the neutralizing agent is 3 to 7 parts by weight based on 30 parts by weight of the polyisocyanate.
6. The photosensitive aqueous polyurethane according to claim 1,
the waterborne polyurethane can realize photocuring under the irradiation of ultraviolet light and visible light without adding a photoinitiator;
the adhesive force of a cured film prepared by using the water-based polyurethane as a raw material can be improved to 0 grade, and the impact resistance can be improved by 10-25 times.
7. A method for producing the photosensitive aqueous polyurethane according to any one of claims 1 to 6, characterized in that the production method comprises the steps of:
step 1, mixing polyisocyanate, oligomer polyol and a water-based chain extender, heating, and reacting in the presence of a catalyst to obtain isocyanate-terminated polyurethane;
step 2, adding chalcone into the polyurethane obtained in the step 1 to obtain chalcone-terminated polyurethane;
and 3, cooling, adding a neutralizing agent for reaction, cooling again, adding water for mixing to obtain the chalcone terminated waterborne polyurethane.
8. The method according to claim 7, wherein, in step 1,
the reaction temperature is 70-100 ℃, and the reaction time is 2-5 h;
in the step 2, the reaction temperature is 70-100 ℃, and the reaction time is 3-7 h.
9. The production method according to claim 7, wherein, in step 3,
cooling to 40-50 ℃ for reaction, wherein the reaction time is 20-50 min;
then cooling to 25-35 ℃, and mixing for 1-2 h.
10. A chalcone-terminated photosensitive waterborne polyurethane/epoxy acrylate cured film is characterized in that the waterborne polyurethane/epoxy acrylate cured film is prepared by taking photosensitive waterborne polyurethane and epoxy acrylate emulsion as raw materials;
the photosensitive waterborne polyurethane is the photosensitive waterborne polyurethane of one of claims 1 to 6 or the photosensitive waterborne polyurethane prepared by the preparation method of one of claims 7 to 9.
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