CN114716647A - Photocuring acrylate and preparation method thereof - Google Patents
Photocuring acrylate and preparation method thereof Download PDFInfo
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- CN114716647A CN114716647A CN202210360084.4A CN202210360084A CN114716647A CN 114716647 A CN114716647 A CN 114716647A CN 202210360084 A CN202210360084 A CN 202210360084A CN 114716647 A CN114716647 A CN 114716647A
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
- C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention belongs to the technical field of light-cured materials. The invention provides a photocuring acrylate and a preparation method thereof, wherein the photocuring acrylate is prepared from 27.2-50.8 parts of polyol, 9.6-10.0 parts of maleic anhydride, 10-30 parts of toluene, 0.5-5 parts of catalyst a, 28.2-112.8 parts of isocyanate, 0.5-0.7 part of polymerization inhibitor and 0.1-0.5 part of catalyst b. The method takes polyhydric alcohol as a core, and firstly carries out esterification reaction with maleic anhydride to obtain an intermediate A; then the residual hydroxyl is reacted with-NCO group in isocyanate to introduce photosensitive group, and the photo-curing acrylic ester is synthesized. The acrylate provided by the invention has low viscosity, light color, high curing speed and good adhesive force; the acrylate provided by the invention retains a certain amount of hydroxyl on molecules, thereby providing the possibility for introducing functional groups or forming high polymers in the next step.
Description
Technical Field
The invention relates to the technical field of photocuring materials, in particular to photocuring acrylate and a preparation method thereof.
Background
The UV curing technology is a new energy-saving and environment-friendly technology, pentaerythritol or dipentaerythritol polyacrylate is one of basic raw materials of a radiation curing system, is an important multifunctional monomer and diluent in an ultraviolet curing system, has the advantages of high double bond content, high curing speed, excellent curing film performance, low volatility and the like, is widely used in the fields of photocuring ink, coating, adhesive, printing plate materials, electronic industry and the like, and is widely applied in developed countries such as the United states and the like. The prior synthesis process is a traditional alkyd direct esterification method and has the defects of low reaction yield, complex post-treatment and high viscosity.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a photocuring acrylate and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a photocuring acrylate which is prepared from the following raw materials in parts by mass:
27.2-50.8 parts of polyol, 9.6-10.0 parts of maleic anhydride, 10-30 parts of toluene, 0.5-5 parts of catalyst a, 28.2-112.8 parts of isocyanate, 0.5-0.7 part of polymerization inhibitor and 0.1-0.5 part of catalyst b.
Preferably, the polyol comprises pentaerythritol, dipentaerythritol, trimethylolpropane or ditrimethylolpropane;
the catalyst a is tetrabutyl titanate, the isocyanate is isocyanate ethyl acrylate, the polymerization inhibitor is 2, 5-di-tert-butyl hydroquinone, and the catalyst b is bismuth laurate.
The invention also provides a preparation method of the photocuring acrylate, which comprises the following steps:
(1) under the vacuum condition, adding maleic anhydride into a mixed system of toluene, polyol and a catalyst a in several times to perform esterification reaction to obtain an intermediate A;
(2) and mixing the intermediate A, isocyanate, a polymerization inhibitor and a catalyst b, and reacting to obtain the photocuring acrylate.
Preferably, in the step (1), the addition times of the maleic anhydride are more than or equal to 5 times, and the interval time between two adjacent times is more than or equal to 1 h.
Preferably, the esterification reaction in the step (1) is carried out at 105-110 ℃, and the vacuum degree under the vacuum condition is-0.02-0.05 MPa.
Preferably, the mixing mode in the step (2) is to add the isocyanate dropwise into the intermediate A and then add the polymerization inhibitor and the catalyst b;
the dripping time is 1-1.5 h.
Preferably, the reaction in step (2) is carried out in a stirring state, and the rotation speed of the stirring is 250-350 rpm.
Preferably, the temperature of the reaction in the step (2) is 65-85 ℃.
Preferably, the reaction time in the step (2) is 4-5 h.
Preferably, after the reaction in the step (2) is finished, vacuum treatment is carried out, wherein the vacuum degree of the vacuum treatment is-0.05 to-0.08 MPa, the temperature is 80 to 90 ℃, and the time is 0.5 to 1.5 hours.
The invention provides a photocuring acrylate which is prepared from raw materials of polyol, maleic anhydride, toluene, a catalyst a, isocyanate, a polymerization inhibitor and a catalyst b. The method takes polyhydric alcohol as a core, and firstly carries out esterification reaction with maleic anhydride to obtain an intermediate A; then the residual hydroxyl is reacted with-NCO group in isocyanate to introduce photosensitive group, and the photo-curing acrylic ester is synthesized. The acrylate provided by the invention has low viscosity, light color, high curing speed and good adhesive force; according to the invention, tetrabutyl titanate is used as a catalyst when the intermediate A is synthesized, so that the subsequent reaction is slightly influenced, washing is not required, and the discharge of waste liquid is reduced; the acrylate provided by the invention retains a certain amount of hydroxyl on the molecule, and provides possibility for introducing functional groups or forming high polymers in the next step.
Drawings
FIG. 1 is a reaction scheme of step (1) of the present invention;
FIG. 2 is a reaction scheme of step (2) of the present invention.
Detailed Description
The invention provides a photocuring acrylate which is prepared from the following raw materials in parts by mass:
27.2-50.8 parts of polyol, 9.6-10.0 parts of maleic anhydride, 10-30 parts of toluene, 0.5-5 parts of catalyst a, 28.2-112.8 parts of isocyanate, 0.5-0.7 part of polymerization inhibitor and 0.1-0.5 part of catalyst b.
In the present invention, the amount of the polyol is 27.2 to 50.8 parts, preferably 30 to 47 parts, more preferably 33 to 44 parts, and still more preferably 37 to 40 parts.
In the present invention, the polyol preferably comprises pentaerythritol, dipentaerythritol, trimethylolpropane or ditrimethylolpropane.
In the invention, the content of the maleic anhydride is 9.6-10.0 parts, preferably 9.7-9.9 parts, and more preferably 9.75-9.85 parts.
In the present invention, the toluene is 10 to 30 parts, preferably 12 to 28 parts, more preferably 14 to 26 parts, and still more preferably 18 to 22 parts.
In the present invention, the amount of the catalyst a is 0.5 to 5 parts, preferably 1 to 4.5 parts, more preferably 1.5 to 4 parts, and still more preferably 2.5 to 3 parts.
In the present invention, the catalyst a is preferably tetrabutyl titanate.
In the present invention, the isocyanate is 28.2 to 112.8 parts, preferably 30 to 111 parts, more preferably 40 to 101 parts, and still more preferably 60 to 81 parts.
In the present invention, the isocyanate is preferably isocyanate ethyl acrylate.
In the present invention, the polymerization inhibitor is 0.5 to 0.7 part, preferably 0.52 to 0.68 part, more preferably 0.54 to 0.66 part, and still more preferably 0.58 to 0.62 part.
In the present invention, the polymerization inhibitor is preferably 2, 5-di-tert-butylhydroquinone.
In the present invention, the amount of the catalyst b is 0.1 to 0.5 part, preferably 0.2 to 0.4 part, more preferably 0.25 to 0.35 part, and still more preferably 0.3 part.
In the present invention, the catalyst b is preferably bismuth laurate.
The invention also provides a preparation method of the photocuring acrylate, which comprises the following steps:
(1) under the vacuum condition, adding maleic anhydride into a mixed system of toluene, polyhydric alcohol and a catalyst a in batches to perform esterification reaction to obtain an intermediate A;
(2) and mixing the intermediate A, isocyanate, a polymerization inhibitor and a catalyst b, and reacting to obtain the photocuring acrylate.
In the present invention, the atmosphere under vacuum in step (1) is preferably nitrogen, helium or argon.
In the invention, toluene, polyalcohol and catalyst a are mixed uniformly, then the temperature is controlled to be esterification temperature, and then maleic anhydride is added in several times.
In the present invention, the number of times of adding the maleic anhydride in portions in step (1) is preferably not less than 5 times, more preferably not less than 6 times, and still more preferably not less than 7 times; the time interval between two adjacent times is preferably not less than 1 hour, more preferably not less than 1.2 hours, and still more preferably not less than 1.5 hours.
In the invention, the temperature of the esterification reaction in the step (1) is preferably 105-110 ℃, more preferably 106-109 ℃, and more preferably 107-108 ℃; the vacuum degree under the vacuum condition is preferably-0.02-0.05 MPa, more preferably-0.01-0.04 MPa, and even more preferably 0.01-0.02 MPa.
In the present invention, the change in the acid value is monitored in real time during the esterification reaction in the step (1), and the target value of the acid value is preferably 0.2mgKOH/g or less, more preferably 0.18mgKOH/g or less, and still more preferably 0.15mgKOH/g or less; cooling the solution after the acid value reaches a target value, wherein the target temperature of cooling is preferably not more than 60 ℃, more preferably not more than 55 ℃, and still more preferably not more than 50 ℃; the time for cooling is preferably not more than 30min, more preferably not more than 25min, and still more preferably not more than 20 min; and obtaining an intermediate A containing toluene after the temperature reduction is finished.
In the present invention, the reaction principle of step (1) is shown in FIG. 1.
In the present invention, intermediate A containing toluene is obtained and then mixed with isocyanate.
In the present invention, the mixing in step (2) is preferably carried out by adding dropwise isocyanate to the intermediate A followed by adding the polymerization inhibitor and the catalyst b.
In the invention, the dripping time is preferably 1 to 1.5 hours, more preferably 1.1 to 1.4 hours, and even more preferably 1.2 to 1.3 hours.
In the invention, stirring is started after the dropwise adding is finished, and the stirring speed is preferably 250-350 rpm, more preferably 260-340 rpm, and even more preferably 280-320 rpm; the time is preferably 5 to 15min, more preferably 6 to 14min, and still more preferably 8 to 12 min.
In the present invention, after the stirring timing was ended, the polymerization inhibitor and the catalyst b were added, and the temperature rise was started.
In the present invention, the reaction in step (2) is preferably carried out under stirring, and the rotation speed of the stirring is preferably 250 to 350rpm, more preferably 260 to 340rpm, and even more preferably 280 to 320 rpm.
In the invention, the reaction temperature in the step (2) is preferably 65-85 ℃, more preferably 70-80 ℃, and more preferably 74-76 ℃; the time for raising the temperature to the reaction temperature is preferably 60min or less, more preferably 55min or less, and still more preferably 50min or less.
In the invention, reaction timing is started after the reaction temperature is reached; the reaction time in the step (2) is preferably 4-5 h, more preferably 4.2-4.8 h, and even more preferably 4.4-4.6 h.
In the invention, after the reaction in the step (2) is finished, vacuum treatment is carried out, wherein the vacuum degree of the vacuum treatment is preferably-0.05 to-0.08 MPa, more preferably-0.06 to-0.07 MPa, and more preferably-0.065 MPa; the temperature is preferably 80-90 ℃, more preferably 82-88 ℃, and more preferably 84-86 ℃; the time is preferably 0.5 to 1.5 hours, more preferably 0.6 to 1.4 hours, and more preferably 0.8 to 1.2 hours; the purpose of the vacuum treatment is to remove toluene.
In the invention, after the vacuum treatment is finished, the product is naturally cooled to room temperature, and the photocuring acrylate is obtained.
In the present invention, the reaction principle of step (2) is shown in FIG. 2.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Mixing 10g of toluene, 27.2g of pentaerythritol and 2.5g of tetrabutyl titanate, heating to 110 ℃ under the conditions of nitrogen protection and 0.01MPa, adding maleic anhydride by 5 times, wherein the mass of the maleic anhydride is 9.8g, the interval time of each addition is 1h, the addition amount of each addition is equal, monitoring the change of an acid value in real time after all additions are finished, and cooling to 60 ℃ within 30min when the acid value is 0.2mgKOH/g to obtain an intermediate A;
dropwise adding 56.4g of isocyanate ethyl acrylate into the intermediate A for 1h, and after dropwise adding, controlling the stirring speed to be 300rpm and stirring for 10 min; after stirring, adding 2.6 g of 5-di-tert-butylhydroquinone and 0.5g of bismuth laurate, keeping the stirring speed unchanged, controlling the heating time to be 60min, heating to 80 ℃, and reacting for 5h at 80 ℃; after the reaction is finished, keeping the mixed system at 85 ℃ and under the pressure of-0.08 MPa for 1h to remove toluene, and then naturally cooling to room temperature to obtain the photocuring acrylate.
The photocurable acrylate prepared in this example was subjected to performance testing and the results are reported in table 1.
Example 2
Mixing 30g of toluene, 50g of ditrimethylolpropane and 1.3g of tetrabutyl titanate, heating to 105 ℃ under the conditions of nitrogen protection and 0.04MPa, adding maleic anhydride for 6 times, wherein the mass of the maleic anhydride is 9.6g, the interval time of each addition is 1h, the addition amount of each time is equal, monitoring the change of an acid value in real time after all the maleic anhydride is added, and cooling to 55 ℃ within 25min when the acid value is 0.18mgKOH/g to obtain an intermediate A;
dropwise adding 84.6g of isocyanate ethyl acrylate into the intermediate A for 1h, and after dropwise adding, controlling the stirring speed to be 350rpm and stirring for 15 min; after stirring, adding 2.5g, 5-di-tert-butylhydroquinone and 0.4g bismuth laurate, keeping the stirring speed unchanged, controlling the heating time to be 50min, heating to 85 ℃, and reacting for 4h at 85 ℃; after the reaction is finished, keeping the mixed system at 80 ℃ and under-0.06 MPa for 0.5h to remove toluene, and then naturally cooling to room temperature to obtain the photocuring acrylate.
The photocurable acrylate prepared in this example was subjected to performance testing and the results are reported in table 1.
Example 3
Mixing 10g of toluene, 26.8g of trimethylolpropane and 2.3g of tetrabutyl titanate, heating to 110 ℃ under the condition of nitrogen protection and-0.01 MPa, adding maleic anhydride for 5 times, wherein the mass of the maleic anhydride is 9.8g, the interval time of each addition is 1.1h, the addition amount of each time is equal, monitoring the change of an acid value in real time after all the maleic anhydride is added, and cooling to 50 ℃ within 30min when the acid value is 0.15mgKOH/g to obtain an intermediate A;
dropwise adding 35.2g of isocyanate ethyl acrylate into the intermediate A for 1.3h, and after dropwise adding, controlling the stirring speed to be 280rpm and stirring for 10 min; after stirring, adding 2.7 g of 5-di-tert-butylhydroquinone and 0.1g of bismuth laurate, keeping the stirring speed unchanged, controlling the heating time to be 55min, heating to 65 ℃, and reacting for 4.5h at 65 ℃; after the reaction is finished, keeping the mixed system at 80 ℃ and-0.07 MPa for 1.3h to remove toluene, and then naturally cooling to room temperature to obtain the photocuring acrylate.
The photocurable acrylate prepared in this example was subjected to performance testing and the results are reported in table 1.
Example 4
Mixing 30g of toluene, 50.8g of dipentaerythritol and 3.8g of tetrabutyl titanate, heating to 105 ℃ under the condition of nitrogen protection and-0.015 MPa, adding maleic anhydride for 6 times, wherein the mass of the maleic anhydride is 9.8g, the interval time of each addition is 1h, the addition amount of each addition is equal, after all the maleic anhydride is added, monitoring the change of an acid value in real time, and when the acid value is 0.2mgKOH/g, cooling to 55 ℃ in 35min to obtain an intermediate A;
dropwise adding 84.6g of isocyanate ethyl acrylate into the intermediate A for 1.4h, and after dropwise adding, controlling the stirring speed to be 260rpm and stirring for 12 min; after stirring, adding 2.5g of 5-di-tert-butylhydroquinone and 0.4g of bismuth laurate, keeping the stirring rate unchanged, controlling the heating time to be 50min, heating to 80 ℃, and reacting for 5h at 80 ℃; after the reaction is finished, the mixed system is kept for 0.8h in the environment of 90 ℃ and minus 0.05MPa to remove toluene, and then the mixed system is naturally cooled to the room temperature, so that the photocuring acrylic ester is obtained.
The photocurable acrylate prepared in this example was subjected to performance testing and the results are reported in table 1.
TABLE 1 photocuring acrylate Performance index
| Initial viscosity (mpa.s) | |
| Example 1 | 1995 |
| Example 2 | 2865 |
| Example 3 | 1765 |
| Example 4 | 3660 |
From the above examples, the present invention provides a photocurable acrylate prepared from polyol, maleic anhydride, toluene, catalyst a, isocyanate, polymerization inhibitor and catalyst b. The method takes polyhydric alcohol as a core, and firstly carries out esterification reaction with maleic anhydride to obtain an intermediate A; then the residual hydroxyl is reacted with-NCO group in isocyanate to introduce photosensitive group, and the photo-curing acrylic ester is synthesized. The viscosity of the acrylate provided by the invention can be as low as 1765mpa & s, and the acrylate has excellent performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The photocuring acrylate is characterized by being prepared from the following raw materials in parts by mass:
27.2-50.8 parts of polyol, 9.6-10.0 parts of maleic anhydride, 10-30 parts of toluene, 0.5-5 parts of catalyst a, 28.2-112.8 parts of isocyanate, 0.5-0.7 part of polymerization inhibitor and 0.1-0.5 part of catalyst b.
2. The photocurable acrylate of claim 1 wherein said polyol comprises pentaerythritol, dipentaerythritol, trimethylolpropane, or ditrimethylolpropane;
the catalyst a is tetrabutyl titanate, the isocyanate is isocyanate ethyl acrylate, the polymerization inhibitor is 2, 5-di-tert-butyl hydroquinone, and the catalyst b is bismuth laurate.
3. The method for preparing a photocurable acrylate according to claim 1 or 2, comprising the steps of:
(1) under the vacuum condition, adding maleic anhydride into a mixed system of toluene, polyhydric alcohol and a catalyst a in batches to perform esterification reaction to obtain an intermediate A;
(2) and mixing the intermediate A, isocyanate, a polymerization inhibitor and a catalyst b, and reacting to obtain the photocuring acrylate.
4. The method according to claim 3, wherein in the step (1), the number of times of adding the maleic anhydride in portions is 5 or more, and the interval between two adjacent times is 1h or more.
5. The method according to claim 3 or 4, wherein the esterification reaction in the step (1) is carried out at a temperature of 105 to 110 ℃ and a vacuum degree under a vacuum condition of-0.02 to 0.05 MPa.
6. The production method according to claim 5, wherein the mixing in the step (2) is carried out by adding dropwise isocyanate into the intermediate A and then adding a polymerization inhibitor and a catalyst b;
the dripping time is 1-1.5 h.
7. The method according to claim 3 or 6, wherein the reaction in the step (2) is carried out under stirring at a rotation speed of 250 to 350 rpm.
8. The method according to claim 7, wherein the temperature of the reaction in the step (2) is 65 to 85 ℃.
9. The preparation method according to claim 8, wherein the reaction time in the step (2) is 4 to 5 hours.
10. The preparation method according to claim 3 or 9, wherein the vacuum treatment is performed after the reaction in the step (2), wherein the vacuum degree of the vacuum treatment is-0.05 to-0.08 MPa, the temperature is 80 to 90 ℃, and the time is 0.5 to 1.5 hours.
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| CN105859588A (en) * | 2016-04-15 | 2016-08-17 | 江苏利田科技股份有限公司 | 4-functionality-degree polycaprolactone urethane acrylate and preparation method and application thereof |
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