CN114149565B - Preparation method of photo-curable hyperbranched polyurethane-epoxy acrylate - Google Patents
Preparation method of photo-curable hyperbranched polyurethane-epoxy acrylate Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a preparation method of photo-curable hyperbranched polyurethane-epoxy acrylate, which comprises the steps of firstly synthesizing hyperbranched polyisocyanate, then reacting with glycidol to obtain hyperbranched polyurethane-epoxy resin, and finally performing ring-opening reaction with acrylic acid or methacrylic acid to obtain the photo-curable hyperbranched polyurethane-epoxy acrylate. The method is simple and feasible, and has high feasibility, and the prepared photo-curable hyperbranched polyurethane-epoxy acrylate has high curing speed, high hardness of a cured film, good flexibility and good wear resistance.
Description
Technical Field
The invention belongs to the technical field of photo-curing resin, and particularly relates to a preparation method of photo-curing hyperbranched polyurethane-epoxy acrylate.
Background
The Ultraviolet (UV) curing technology is a novel energy-saving and environment-friendly technology, and is increasingly widely applied to industries such as paint, ink, adhesive and the like by virtue of the characteristics of high efficiency, energy saving and environment friendliness. The ultraviolet curing material contains a very small amount of solvent, and is known as a new generation of green technology. Since the first generation of ultraviolet curing woodenware paint was developed by Bayer company in 1968, ultraviolet curing technology has been rapidly developed worldwide. Hyperbranched polymers are highly branched macromolecules having a three-dimensional dendritic structure. Compared with dendritic macromolecules, the hyperbranched polymer has the advantages of small branching degree, wide molecular weight distribution, more isomers, no rule of the dendritic macromolecules in the geometric shape and defects in the molecular structure. But has the advantages of low viscosity, high solubility, good film forming property and the like, and the synthesis process is simple, low in cost and beneficial to large-scale production, so that the hyperbranched polymer has important theoretical research significance and has wide application prospect.
Compared with the conventional photo-curing resin, the hyperbranched UV resin has lower viscosity and more terminal active groups, and has great advantages in photo-curing formula products.
Chinese patent application No. 201310667832.4 proposes a hyperbranched polyurethane acrylate UV light-cured resin and a preparation method thereof, wherein diisocyanate monomers are reacted with dihydric alcohol first, and then reacted with monoamino polyhydroxy monomers to prepare an ABn reaction intermediate with one isocyanate group and a plurality of hydroxyl groups as end groups; the ABn reaction intermediate undergoes self-polycondensation reaction to prepare hyperbranched polyurethane (HPU-Xm) containing terminal hydroxyl groups; reacting diisocyanate monomer with hydroxyalkyl acrylate to prepare a reaction intermediate C containing isocyanate and acrylic double bond end groups; and (3) reacting the reaction intermediate C with HPU-Xm to prepare the UV light-curable hyperbranched polyurethane acrylate resin product containing a plurality of double bonds. The intermediate and the final product synthesized by the method are in a solid state, and a solvent is needed to reduce the viscosity in the use process.
Chinese patent application No. 202010778052.7 discloses a method for preparing hyperbranched urethane acrylate resin for UV light curing, which uses diisocyanate and hydroxyalkyl acrylate to react in aprotic solvent to prepare intermediate, and then reacts with hydroxyl-terminated hyperbranched polyester with 5-64 functional groups in aprotic solvent to obtain hyperbranched urethane acrylate resin for UV light curing containing 5-64 terminal acrylic double bonds. In the synthesis process, the solid resin is dissolved by an organic solvent, and finally, the solid resin is separated and dried, so that a white powdery product is obtained.
The two routes all use more solvents to reduce the viscosity of the system, then the solvents are removed to obtain solid powder samples, and the large-scale use of the solvents increases the VOC emission and the production cost and does not accord with the current environment-friendly concept.
Disclosure of Invention
The invention aims to: the invention aims to overcome the defects in the prior art and provide a simple preparation method for preparing the photo-curable hyperbranched polyurethane-epoxy acrylate with low viscosity and high drying speed.
The technical scheme is as follows: in order to achieve the above object, the present invention adopts the following technical scheme:
a method for preparing photo-curable hyperbranched polyurethane-epoxy acrylate, which comprises the following steps:
(1) Using polyisocyanate to react with polyol to synthesize hyperbranched polyisocyanate;
(2) Hyperbranched polyisocyanate is used to react with glycidol to obtain hyperbranched polyurethane-epoxy resin,
(3) And (3) performing ring-opening reaction on hyperbranched polyurethane-epoxy resin and acrylic acid or methacrylic acid to obtain the photocurable hyperbranched polyurethane-epoxy acrylate.
As a preferred scheme, the preparation method of the photo-curable hyperbranched polyurethane-epoxy acrylate comprises the following steps of: the polyisocyanate and the organotin catalyst with certain mass are placed in a reaction flask, polyol is slowly added into the reaction flask by a dropping funnel in a dropwise manner, and the reaction is carried out at 50-100 ℃ until the isocyanate content of the system reaches a theoretical value.
As a preferred scheme, the preparation method of the photo-curable hyperbranched polyurethane-epoxy acrylate comprises the following steps of: and (3) placing hyperbranched polyisocyanate with a certain mass into a reaction flask, slowly dropwise adding glycidol by using a dropping funnel, and reacting at 70-110 ℃ until the isocyanate content of the system reaches a theoretical value.
As a preferred scheme, the preparation method of the photo-curable hyperbranched polyurethane-epoxy acrylate comprises the following steps of: placing hyperbranched polyurethane-epoxy resin and a quaternary ammonium salt catalyst with certain mass into a reaction flask, slowly dripping acrylic acid or methacrylic acid into the reaction flask by using a dropping funnel, and reacting at 90-120 ℃ until the acid value of the system is below 5 mgKOH/g.
As a preferred scheme, the preparation method of the photo-curable hyperbranched polyurethane-epoxy acrylate comprises the following steps that (1) the molar ratio of isocyanate groups in polyisocyanate to hydroxyl groups in polyol is controlled to be 2-10;
controlling the ratio of the molar quantity of glycidol to the molar quantity of isocyanate groups in the hyperbranched polyisocyanate to be 1.01-1.06;
and (3) controlling the ratio of the molar quantity of the acrylic acid or the methacrylic acid to the molar quantity of the epoxy groups in the hyperbranched polyurethane-epoxy resin to be between 0.95 and 1.03.
As a preferred embodiment, the above-mentioned preparation method of a photocurable hyperbranched polyurethane-epoxy acrylate, wherein the polyisocyanate is selected from one or more of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), toluene diisocyanate trimer, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer, xylylene Diisocyanate (XDI), 4 '-diphenylmethane diisocyanate (MDI), and 4,4' -dicyclohexylmethane diisocyanate (HMDI). Particular preference is given to the isophorone diisocyanate IPDI, toluene diisocyanate TDI and hexamethylene diisocyanate HDI trimer or mixtures thereof.
Preferably, the preparation method of the photo-curable hyperbranched polyurethane-epoxy acrylate comprises the step of preparing a polyurethane-epoxy acrylate, wherein the polyol is selected from one or more of trimethylolpropane, glycerol, pentaerythritol, ethoxylated trimethylolpropane, propoxylated trimethylolpropane, ethoxylated pentaerythritol, propoxylated pentaerythritol, polyethylene glycol and polypropylene glycol. Particularly preferred are polypropylene glycol, ethoxylated trimethylol propane and ethoxylated trimethylol propane.
As a preferred scheme, the preparation method of the photo-curable hyperbranched polyurethane-epoxy acrylate is characterized in that the organic tin catalyst is selected from one or more of dibutyl tin dilaurate, stannous octoate, stannous chloride and monobutyl tin oxide.
As a preferable scheme, the preparation method of the photo-curable hyperbranched polyurethane-epoxy acrylate is characterized in that the quaternary ammonium salt catalyst is one or more of tetrabutylammonium bromide, tetrabutylammonium chloride, tetramethylammonium bromide and tetramethylammonium chloride.
The beneficial effects of the invention are as follows:
the invention synthesizes hyperbranched polyisocyanate by using polyisocyanate and polyol, then reacts with glycidol to obtain hyperbranched polyurethane-epoxy resin, and finally carries out ring opening reaction with acrylic acid or methacrylic acid to obtain photo-curable hyperbranched polyurethane-epoxy acrylate. The method uses continuous feeding and a one-pot method to synthesize the photo-curable hyperbranched polyurethane-epoxy acrylate, is simple and easy to implement, and does not generate three wastes.
Compared with the prior art, the synthetic route is novel, the prepared hyperbranched polyurethane-epoxy resin has higher functional groups and good curing activity, and the cured film has higher hardness and flexibility at the same time, so that good technical effect is achieved.
Detailed Description
Example 1
A method for preparing photo-curable hyperbranched polyurethane-epoxy acrylate, comprising the following steps:
(1) After 500 g of polypropylene glycol (PPG 1000) and 0.2 g of dibutyl tin dilaurate were mixed, the mixture was slowly dropped into 505 g of HDI trimer (Korschun N3300) to react at 70℃until the NCO content reached 7.8%, and the temperature of the reaction system was lowered to room temperature to obtain hyperbranched polyisocyanate.
(2) 149.7 g of glycidol is dripped into the system, 0.05 g of dibutyl tin dilaurate is added, and the reaction is continued at 80 ℃ until the NCO content reaches below 0.2%, thus obtaining the hyperbranched polyurethane-epoxy resin.
(3) A mixture of 147 g of acrylic acid and 3.9 g of tetrabutylammonium chloride is dripped into the system, and the mixture reacts at 100 ℃ until the acid value of the system is reduced to below 5mgKOH/g, thus obtaining the photo-curable hyperbranched polyurethane-epoxy acrylate.
Example 2
A method for preparing photo-curable hyperbranched polyurethane-epoxy acrylate, comprising the following steps:
(1) After 176.7 g of ethoxylated trimethylol propane (EO 9 TMP) and 0.15 g of dibutyl tin dilaurate were mixed, slowly added dropwise to 388.5 g of isophorone diisocyanate IPDI, the temperature was kept at 70℃until the NCO content reached 18.6%, and the temperature of the reaction system was lowered to room temperature to obtain hyperbranched polyisocyanate.
(2) 187.1 g of glycidol is added into the reaction system in a dropwise manner, 0.03 g of monobutyl tin oxide is added, and the reaction is continued at 80 ℃ until the NCO content reaches below 0.2%, so that the hyperbranched polyurethane-epoxy resin is obtained.
(3) A mixture of 72 g of acrylic acid, 129 g of methacrylic acid and 3 g of tetramethyl ammonium bromide is dripped into the system, and the mixture reacts at 100 ℃ until the acid value of the system is reduced to below 5mg KOH/g, so as to obtain the photo-curable hyperbranched polyurethane-epoxy acrylate.
Example 3
A method for preparing photo-curable hyperbranched polyurethane-epoxy acrylate, comprising the following steps:
(1) 88.7 g of ethoxylated trimethylol propane (EO 3 TMP) are mixed with 0.1 g of dibutyltin dilaurate, slowly added dropwise to a mixture of 220 g of isophorone diisocyanate IPDI and 130.6 g of toluene diisocyanate TDI, kept at 65℃until the NCO content reaches 23.8%, and the temperature of the reaction system is lowered to room temperature to obtain hyperbranched polyisocyanate.
(2) 185.3 g of glycidol is dripped into the reaction system, 0.02 g of stannous octoate is added, and the reaction is continued at 80 ℃ until the NCO content reaches below 0.2%, thus obtaining the hyperbranched polyurethane-epoxy resin.
(3) A mixture of 215 g of methacrylic acid and 1 g of tetrabutylammonium chloride is dripped into the system, and the mixture reacts at 100 ℃ until the acid value of the system is reduced to below 5mgKOH/g, thus obtaining the photo-curable hyperbranched polyurethane-epoxy acrylate.
Comparative example 1
(1) 300 g of polycaprolactone butanediol ester 600 (number average molecular weight 600) are added dropwise into a mixture of 0.05 g of dibutyl tin dilaurate and 222 g of isophorone diisocyanate IPDI, stirred uniformly, heated slowly to 75 ℃ for reaction until NCO content reaches 8.0%, and cooled to room temperature.
(2) And (3) dropwise adding a mixture of 118 g of hydroxyethyl acrylate and 0.5 g of para-hydroxyanisole into the reaction system, and slowly heating to 85 ℃ for reaction until the NCO content reaches below 0.2%, thus obtaining the photo-curable polyurethane acrylic resin.
Comparative example 2
(1) 500 g of polypropylene glycol (PPG 1000) are added dropwise to a mixture of 0.06 g of tin dibutyldilaurate and 174 g of toluene diisocyanate TDI, the temperature is slowly raised to 65℃until the NCO content reaches 6.2% and the reaction is allowed to cool to room temperature.
(2) 118 g of hydroxyethyl acrylate is dripped into the reaction system, and the temperature is slowly increased to 85 ℃ for reaction until the NCO content reaches below 0.2%, thus obtaining the photo-curable polyurethane acrylic resin.
Performance test examples
The resins of examples 1 to 3, comparative examples 1 to 2, and leveling agent BYK-333 (available from Pick chemical Co., ltd.) were prepared as described in the following Table 1, and photo-curing varnishes were prepared as photo-initiator 1173 (Jiangsu Sanmu group Co., ltd.) and the combination properties of the respective groups were measured, and the results are shown in Table 2 below.
TABLE 1 photo-curable varnish formulations
| 1# | 2# | 3# | 4# | 5# | |
| Example 1 | 97.5 | ||||
| Example 2 | 97.5 | ||||
| Example 3 | 97.5 | ||||
| Comparative example 1 | 97.5 | ||||
| Comparative example 2 | 97.5 | ||||
| Leveling agent BYK-333 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Photoinitiator 1173 | 2 | 2 | 2 | 2 | 2 |
TABLE 2 comparative results of photo-curable varnish test experiments
Pencil hardness was tested as described in national standard GB/T6739-2006.
Flexibility was tested according to the method described in national standard GB/T1731-1993.
RCA abrasion resistance was tested as described in U.S. standard ASTM F2357-04.
The experimental results show that the photo-curable hyperbranched polyurethane-epoxy acrylate prepared by synthesizing the photo-curable hyperbranched polyurethane-epoxy acrylate has high curing activity, high hardness, high flexibility and high wear resistance, and particularly the photo-curable hyperbranched polyurethane-epoxy acrylate prepared in the embodiment 3 has the best performance. The synthetic route of the invention has good technical effect.
Claims (5)
1. The preparation method of the photo-curable hyperbranched polyurethane-epoxy acrylate is characterized by comprising the following steps of:
(1) Using polyisocyanate to react with polyol to synthesize hyperbranched polyisocyanate; the specific method comprises the following steps: placing polyisocyanate and an organotin catalyst with certain mass into a reaction flask, slowly dropwise adding polyol into the reaction flask by using a dropping funnel, controlling the molar ratio of isocyanate groups in the polyisocyanate to hydroxyl groups in the polyol to be 2-10, and reacting at 50-100 ℃ until the isocyanate content of the system reaches a theoretical value;
(2) The hyperbranched polyisocyanate reacts with glycidol to obtain hyperbranched polyurethane-epoxy resin; the specific method comprises the following steps: placing hyperbranched polyisocyanate with certain mass into a reaction flask, slowly dropwise adding glycidol by using a dropping funnel, controlling the ratio of the molar quantity of the glycidol to the molar quantity of isocyanic acid radical in the hyperbranched polyisocyanate to be 1.01-1.06, and reacting at 70-110 ℃ until the isocyanate content of the system reaches a theoretical value;
(3) Ring-opening reaction is carried out on hyperbranched polyurethane-epoxy resin and acrylic acid or methacrylic acid to obtain photocurable hyperbranched polyurethane-epoxy acrylate; the specific method comprises the following steps: placing hyperbranched polyurethane-epoxy resin and a quaternary ammonium salt catalyst with certain mass into a reaction flask, slowly dropwise adding acrylic acid or methacrylic acid by using a dropping funnel, controlling the ratio of the molar quantity of the acrylic acid or the methacrylic acid to the molar quantity of epoxy groups in the hyperbranched polyurethane-epoxy resin to be between 0.95 and 1.03, and reacting at 100-120 ℃ until the acid value of the system reaches a theoretical value.
2. The method for preparing the photo-curable hyperbranched polyurethane-epoxy acrylate according to claim 1, wherein the polyisocyanate is selected from one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate trimer, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer, xylylene diisocyanate, 4 '-diphenylmethane diisocyanate and 4,4' -dicyclohexylmethane diisocyanate.
3. The method for preparing the photo-curable hyperbranched polyurethane-epoxy acrylate according to claim 1, wherein the polyol is one or more selected from trimethylolpropane, glycerol, pentaerythritol, ethoxylated trimethylolpropane, propoxylated trimethylolpropane, ethoxylated pentaerythritol, propoxylated pentaerythritol, polyethylene glycol and polypropylene glycol.
4. The method for preparing the photo-curable hyperbranched polyurethane-epoxy acrylate according to claim 1, wherein the organotin catalyst is one or more selected from the group consisting of dibutyl tin dilaurate, stannous octoate, stannous chloride and monobutyl tin oxide.
5. The method for preparing the photo-curable hyperbranched polyurethane-epoxy acrylate according to claim 1, wherein the quaternary ammonium salt catalyst is one or more of tetrabutylammonium bromide, tetrabutylammonium chloride, tetramethylammonium bromide and tetramethylammonium chloride.
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| KR101738356B1 (en) * | 2016-04-27 | 2017-05-22 | 충북대학교 산학협력단 | Composition comprising hyperbranched polyglycerol containing epoxy or acrylate end functional group and preparation method of the same |
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