CN115677493A - Preparation method of photosensitive hexa-functional polyester acrylate - Google Patents
Preparation method of photosensitive hexa-functional polyester acrylate Download PDFInfo
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- CN115677493A CN115677493A CN202211319588.8A CN202211319588A CN115677493A CN 115677493 A CN115677493 A CN 115677493A CN 202211319588 A CN202211319588 A CN 202211319588A CN 115677493 A CN115677493 A CN 115677493A
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Abstract
The invention discloses a preparation method of photosensitive six-functional polyester acrylate. According to the invention, through a large number of experimental screening, the optimal raw material composition, proportion and process synthesis steps are obtained, and the prepared hexafunctional polyester acrylate has high cost performance, good stability, excellent comprehensive performances such as hardness, flexibility and luster.
Description
Technical Field
The invention relates to an oligomer for photosensitive coating, in particular to a preparation method of novel photosensitive six-functional polyester acrylate, belonging to the technical field of high polymer materials.
Background
Ultraviolet curing is a material surface treatment technology appearing in the 60's of the 20 th century, and refers to a technology of adding a photoinitiator (or referred to as a photosensitizer) into a system with a special formula (generally referred to as a photocuring system), and absorbing high-intensity ultraviolet light generated in ultraviolet photocuring equipment through the photoinitiator to generate active free radicals or cations so as to initiate polymerization, crosslinking, grafting and the like, so that the reaction is converted from liquid to solid within a certain time. The existing photocuring system is mainly divided into a free radical type and a cationic type, wherein the former mainly comprises that a photoinitiator is excited by ultraviolet irradiation to generate active free radicals, the formed active free radicals continuously initiate active double bonds in the system to generate a polymerization crosslinking reaction, and the latter mainly comprises that a cationic photoinitiator absorbs ultraviolet light to generate strong protonic acid to catalyze oxygen heterocycles and the like to generate an addition polymerization reaction. At present, the field of application of free-radical photocuring systems is still far greater than that of cationic systems in terms of economic suitability. Therefore, the prepolymer has attracted much attention as a free radical type photocurable prepolymer which is most easily designed in molecular structure.
The invention synthesizes the polyester acrylate containing six effective ends through a creative design scheme to obtain a novel six-functional photosensitive prepolymer with excellent comprehensive performance.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a novel polyester acrylate synthesis method, which comprises the steps of selecting acryloyl chloride, oxalyl chloride and tartaric acid through a large number of experimental screens, obtaining an intermediate I with four terminal carboxyl groups and two active terminal double bonds through certain reaction conditions, and then reacting the intermediate I with hydroxyethyl acrylate and butanediol diglycidyl ether to finally obtain the novel photosensitive six-functional polyester acrylate. The photosensitive six-functional polyester acrylate provided by the invention can be widely applied to various photocureable coating systems which need high reactivity and low viscosity.
Technical solution to achieve the above objects, the present invention adopts the following technical solutions:
a preparation method of novel photosensitive six-functional polyester acrylate comprises the following steps:
(1) Firstly, preparing an intermediate I with four terminal carboxyl groups and two active terminal double bonds by selecting acryloyl chloride, tartaric acid and oxalyl chloride through certain reaction conditions;
(2) Then the intermediate I reacts with hydroxyethyl acrylate and butanediol diglycidyl ether under certain conditions to prepare the photosensitive hexafunctional polyester acrylate.
The preparation method of the novel photosensitive six-functional polyester acrylate comprises the following steps:
(1) Firstly, selecting 5-20 parts by mass of acryloyl chloride, 15-30 parts by mass of tartaric acid and 5-20 parts by mass of oxalyl chloride, and preparing an intermediate I with four terminal carboxyl groups and two active terminal double bonds under certain reaction conditions;
(2) Then the intermediate I reacts with 20-45 parts by mass of hydroxyethyl acrylate and 0-3 parts by mass of butanediol diglycidyl ether under certain conditions to prepare the photosensitive six-functional polyester acrylate.
Preferably, in the preparation method of the novel photosensitive hexafunctional polyester acrylate, the specific steps of the step (1) are as follows: dissolving acryloyl chloride and oxalyl chloride in 7 parts by mass of toluene, slowly dropwise adding the solution into 14 parts by mass of toluene in which tartaric acid is dissolved, removing acid mist generated by reaction by using micro-vacuum of-0.001 to-0.01 MPa while dropwise adding the solution, wherein the dropwise adding time is 1 to 8 hours, continuously reacting under a vacuum degree after the dropwise adding is finished, controlling the reaction temperature to be between-10 and 40 ℃, the reaction time is 5 to 12 hours, and cooling after the reaction is finished to obtain an intermediate I with four terminal carboxyl groups and two active terminal double bonds;
as a preferable scheme, the preparation method of the novel photosensitive six-functional polyester acrylate comprises the following specific steps of the step (2): adding hydroxyethyl acrylate into the intermediate I, adding 0-0.5 mass part of antioxidant hypophosphorous acid, 0-0.5 mass part of polymerization inhibitor hydroquinone and 0-1 mass part of catalyst p-toluenesulfonic acid, controlling the reaction time to be 5-10 hours, controlling the reaction temperature to be 90-150 ℃, cooling to below 80 ℃ when the acid value is lower than 10mgKOH/g, adding butanediol diglycidyl ether and 0-0.5 mass part of catalyst triphenylphosphine, controlling the reaction time to be 1-3 hours, controlling the reaction temperature to be 90-120 ℃, starting vacuum-0.1 MPa after the reaction is finished, and desolventizing for 1.5-4 hours to obtain the finished product of the photosensitive hexafunctional polyester acrylate.
The key point of the invention is that the synthesis of the intermediate I needs to strictly control the vacuum environment, the material proportion, the dropping time, the reaction temperature and the reaction time, as tartaric acid and oxalyl chloride are both two functional group raw materials, once proper reaction conditions are not strictly controlled, unpredictable chain-shaped multifunctional structures can appear, the viscosity of the resin can be rapidly increased at the moment, and a final product with excellent comprehensive performance can not be obtained, and the used butanediol diglycidyl ether can effectively reduce the acid value of the final product, and can ensure good storage and use stability of the target product.
The key point of the invention is that the vacuum environment is strictly controlled when the intermediate I is synthesized, and because the reaction has a certain reversible tendency, when the vacuum environment is controlled, the acid mist of hydrochloric acid generated by the positive reaction can be removed in time while the solvent in the system is prevented from being removed, so that the intermediate I with four terminal carboxyl groups and two active terminal double bonds can be synthesized.
Has the advantages that: according to the invention, a large number of experimental screens are carried out, acryloyl chloride, oxalyl chloride and tartaric acid are selected to obtain an intermediate I with four terminal carboxyl groups and two active terminal double bonds, and the intermediate I reacts with hydroxyethyl acrylate and butanediol diglycidyl ether to finally prepare the novel photosensitive hexafunctional polyester acrylate. The photosensitive six-functional polyester acrylate provided by the invention can be widely applied to various photocureable coating systems which need high reactivity and low viscosity. And the experimental result shows that the hexafunctional polyester acrylate provided by the invention has the comprehensive properties of good stability, low viscosity, high curing speed, high hardness, good flexibility and the like, and can solve the defects of the prior art.
Drawings
FIG. 1 is a reaction scheme of the present invention.
Detailed Description
Example 1
A preparation method of novel photosensitive six-functional polyester acrylate comprises the following steps:
(1) 13 parts by mass of acryloyl chloride and 9.1 parts by mass of oxalyl chloride are dissolved in 7 parts by mass of toluene and slowly dripped into 14 parts by mass of toluene in which 21.6 parts by mass of tartaric acid is dissolved, acid mist generated by the reaction is removed by using-0.008 MPa micro vacuum while dripping, the dripping time is 4 hours, the reaction is continued under the vacuum degree after the dripping is finished, the reaction temperature is controlled at-5 ℃, the reaction time is 10 hours, and an intermediate I is obtained after the reaction is finished. The reaction yield is about 94%, of the intermediate I 1 H-NMR tests showed that the chemical shift around 2.0, representing the shift of the hydrogen atom on the hydroxyl group on tartaric acid disappeared, while the peak area ratio representing the chemical shift around 11.0 for the hydrogen atom of the carboxylic acid on intermediate I and around 6.05 for the hydrogen atom on the tertiary carbon of the C = C double bond was about 2:1, indicating that intermediate I had been successfully synthesized.
(2) Uniformly mixing the intermediate I product obtained in the step (1) with 33.5 parts by mass of hydroxyethyl acrylate, adding 0.1 part by mass of antioxidant hypophosphorous acid, 0.1 part by mass of polymerization inhibitor hydroquinone and 0.5 part by mass of catalyst p-toluenesulfonic acid, controlling the reaction time to be 9 hours, controlling the reaction temperature to be 118 ℃, cooling to be below 80 ℃ when the acid value is lower than 10mgKOH/g, adding 1 part by mass of butanediol diglycidyl ether and 0.1 part by mass of catalyst triphenylphosphine, controlling the reaction time to be 2.5 hours, controlling the reaction temperature to be 115 ℃, starting vacuum-0.1 MPa after the reaction is finished, and desolventizing for 2 hours to obtain the finished product of the novel photosensitive hexafunctional polyester acrylate. The reaction yield is about 92 percent, and the final product is 1 H-NMR measurement, the ratio of the peak areas representing about 6.05 chemical shifts of the hydrogen atom on the tertiary carbon of the C = C double bond in the final product and about 6.02 chemical shifts of the hydrogen atom on the tertiary carbon carrying the hydrogen atom in the structural orthotartaric acid position was about 3:2,this result indicates that the final product has been successfully synthesized.
Example 2
A preparation method of novel photosensitive six-functional polyester acrylate comprises the following steps:
(1) 13 parts by mass of acryloyl chloride and 7 parts by mass of oxalyl chloride are dissolved in 7 parts by mass of toluene, the mixture is slowly dripped into 14 parts by mass of toluene in which 21.6 parts by mass of tartaric acid is dissolved, acid mist generated by the reaction is removed by using-0.008 MPa micro vacuum while the dripping is carried out, the dripping time is 4 hours, the reaction is continued under the vacuum degree after the dripping is finished, the reaction temperature is controlled at 0 ℃, the reaction time is 10 hours, and an intermediate I is obtained after the reaction is finished. The reaction yield was about 49%. Of intermediate I 1 H-NMR tests show that the peak area ratio of chemical shift representing about 11.0 of the hydrogen atom of the carboxylic acid on the intermediate I and chemical shift representing about 6.05 of the hydrogen atom on the tertiary carbon in the C = C double bond is far larger than 2:1, which indicates that a relatively obvious chain structure is formed, and indicates that the reaction quantity and the reaction temperature experimental conditions for synthesizing the intermediate I in the step are unreasonable and have great influence on the reaction.
(2) Uniformly mixing the reaction product of the intermediate I in the step (1) with 35.3 parts by mass of hydroxyethyl acrylate, adding 0.1 part by mass of antioxidant hypophosphorous acid, 0.1 part by mass of polymerization inhibitor hydroquinone and 0.8 part by mass of catalyst p-toluenesulfonic acid, controlling the reaction time to be 9 hours, controlling the reaction temperature to be 125 ℃, cooling to be below 80 ℃ when the acid value is lower than 10mgKOH/g, adding 1 part by mass of butanediol diglycidyl ether and 0.1 part by mass of catalyst triphenylphosphine, controlling the reaction time to be 2.5 hours, controlling the reaction temperature to be 120 ℃, starting vacuum to be 0.1MPa after the reaction is finished, and desolventizing for 2 hours to obtain the finished novel photosensitive six-functional polyester acrylate. The reaction yield was about 48%.
Example 3
A preparation method of novel photosensitive six-functional polyester acrylate comprises the following steps:
(1) Will 13 mass portionsDissolving acryloyl chloride and 9.1 parts by mass of oxalyl chloride in 7 parts by mass of toluene, slowly dropwise adding the mixture into 14 parts by mass of toluene in which 21.6 parts by mass of tartaric acid is dissolved, removing acid mist generated by the reaction by using-0.004 MPa micro-vacuum while dropwise adding, wherein the dropwise adding time is 4 hours, continuously reacting under the vacuum degree after the dropwise adding is finished, controlling the reaction temperature to be-5 ℃, and the reaction time to be 10 hours, and obtaining an intermediate I after the reaction is finished. The reaction yield is about 67%, of the intermediate I 1 The chemical shift around 2.0, which represents the shift of the hydrogen atom on the hydroxyl group on tartaric acid, did not completely disappear by H-NMR measurement, indicating that the degree of vacuum in this step greatly affects the reaction. The intermediate I synthesized under the vacuum condition does not completely reach the design standard. The key point of the step is that the vacuum environment needs to be strictly controlled when the intermediate I is synthesized, and because the reaction has a certain reversible tendency, when the optimal vacuum environment is controlled, the hydrochloric acid mist generated by the positive reaction can be timely removed while the solvent in the system is prevented from being removed, so that the synthesis efficiency is improved.
(2) Uniformly mixing the reaction product of the intermediate I in the step (1) with 33.5 parts by mass of hydroxyethyl acrylate, adding 0.1 part by mass of antioxidant hypophosphorous acid, 0.1 part by mass of polymerization inhibitor hydroquinone and 0.5 part by mass of catalyst p-toluenesulfonic acid, controlling the reaction time to be 7 hours, controlling the reaction temperature to be 125 ℃, cooling to be below 80 ℃ when the acid value is lower than 10mgKOH/g, adding 1 part by mass of butanediol diglycidyl ether and 0.1 part by mass of catalyst triphenylphosphine, controlling the reaction time to be 2 hours, controlling the reaction temperature to be 120 ℃, starting vacuum-0.1 MPa after the reaction is finished, and desolventizing for 2 hours to obtain the finished product of the novel photosensitive hexafunctional polyester acrylate. The reaction yield was about 66%.
Example 4 Performance testing
The photosensitive hexa-functional photocurable resin obtained in example 1 was subjected to property measurement, and the specific experimental results are shown in table 1 below.
TABLE 1 Performance test results
Note: the curing speed in the table is 80mW/cm directly on a UV curing machine 2 The hardness and the gloss of the light intensity curing test are measured according to the GB/T13448-2006 standard, and the flexibility test is measured according to the GB/T1731 standard.
The experiment results show that the novel photosensitive hexa-functional polyester acrylate prepared in the embodiment 1 has the characteristics of good stability and excellent comprehensive 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 amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (6)
1. A preparation method of novel photosensitive six-functional polyester acrylate is characterized by comprising the following steps:
(1) Firstly, preparing an intermediate I with four terminal carboxyl groups and two active terminal double bonds by selecting acryloyl chloride, tartaric acid and oxalyl chloride through certain reaction conditions;
(2) Then the intermediate I reacts with hydroxyethyl acrylate and butanediol diglycidyl ether under certain conditions to prepare the photosensitive hexafunctional polyester acrylate.
2. The method for preparing the novel photosensitive hexafunctional polyester acrylate according to claim 1, comprising the following steps:
(1) Firstly, selecting 5-20 parts by mass of acryloyl chloride, 15-30 parts by mass of tartaric acid and 5-20 parts by mass of oxalyl chloride, and preparing an intermediate I with four terminal carboxyl groups and two active terminal double bonds under certain reaction conditions;
(2) Then the intermediate I reacts with 20-45 parts by mass of hydroxyethyl acrylate and 0-3 parts by mass of butanediol diglycidyl ether under certain conditions to prepare the photosensitive hexafunctional polyester acrylate.
3. The method for preparing a novel photosensitive hexafunctional polyester acrylate according to claim 1 or 2, wherein the step (1) comprises the following specific steps: dissolving acryloyl chloride and oxalyl chloride in 7 parts by mass of toluene, slowly dropwise adding the mixture into 14 parts by mass of toluene in which tartaric acid is dissolved, removing acid mist generated by reaction by using micro-vacuum of-0.001 to-0.01 MPa while dropwise adding, wherein the dropwise adding time is 1 to 8 hours, continuously reacting under a vacuum degree after the dropwise adding is finished, controlling the reaction temperature to be between-10 ℃ and 40 ℃, the reaction time is 5 to 12 hours, and cooling after the reaction is finished to obtain an intermediate I with four terminal carboxyl groups and two active terminal double bonds;
4. the method for preparing a novel photosensitive hexafunctional polyester acrylate according to claim 1 or 2, wherein the step (2) comprises the following steps: adding hydroxyethyl acrylate into the intermediate I, adding 0-0.5 mass part of antioxidant hypophosphorous acid, 0-0.5 mass part of polymerization inhibitor hydroquinone and 0-1 mass part of catalyst p-toluenesulfonic acid, controlling the reaction time to be 5-10 hours, controlling the reaction temperature to be 90-150 ℃, cooling to below 80 ℃ when the acid value is lower than 10mgKOH/g, adding butanediol diglycidyl ether and 0-0.5 mass part of catalyst triphenylphosphine, controlling the reaction time to be 1-3 hours, controlling the reaction temperature to be 90-120 ℃, starting vacuum-0.1 MPa after the reaction is finished, and desolventizing for 1.5-4 hours to obtain the finished product of photosensitive six-functional polyester acrylate;
5. the method for preparing the novel photosensitive hexafunctional polyester acrylate according to claim 1, comprising the steps of
(1) Dissolving 13 parts by mass of acryloyl chloride and 9.1 parts by mass of oxalyl chloride in 7 parts by mass of toluene, slowly dropwise adding the mixture into 14 parts by mass of toluene in which 21.6 parts by mass of tartaric acid is dissolved, removing acid mist generated by the reaction by using-0.01 MPa micro-vacuum while dropwise adding, wherein the dropwise adding time is 4 hours, continuously reacting under the vacuum degree after the dropwise adding is finished, controlling the reaction temperature to be-5 ℃ and the reaction time to be 10 hours, and obtaining an intermediate I after the reaction is finished;
(2) Uniformly mixing the intermediate I with 33.5 parts by mass of hydroxyethyl acrylate, adding 0.1 part by mass of antioxidant hypophosphorous acid, 0.1 part by mass of polymerization inhibitor hydroquinone and 0.5 part by mass of catalyst p-toluenesulfonic acid, controlling the reaction time to be 9 hours, the reaction temperature to be 118 ℃, cooling to be below 80 ℃ when the acid value is lower than 10mgKOH/g, adding 1 part by mass of butanediol diglycidyl ether and 0.1 part by mass of catalyst triphenylphosphine, controlling the reaction time to be 2.5 hours, the reaction temperature to be 115 ℃, starting vacuum to be 0.1MPa after the reaction is finished, and desolventizing for 2 hours to obtain the finished product of the photosensitive hexafunctional polyester acrylate.
6. Use of the photosensitive hexafunctional polyester acrylate of any one of claims 1 to 5 for the preparation of oligomers for photosensitive coatings.
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