Acrylic liquid crystal photosensitive resin and preparation method thereof

文档序号:388710 发布日期:2021-12-14 浏览:7次 中文

阅读说明:本技术 一种丙烯酸液晶光敏树脂及其制备方法 (Acrylic liquid crystal photosensitive resin and preparation method thereof ) 是由 陈少云 卓东贤 华文强 陈明雪 孙晓露 瞿波 王睿 郑燕玉 刘小英 李文杰 于 2021-09-28 设计创作,主要内容包括:本发明公开了一种丙烯酸液晶光敏树脂及其制备方法。将含介晶基元且端部带有-OH的化合物、EHC和催化剂1混合,反应得到溶液A;滴加NaOH到溶液A中,去除反应生成的水,继续反应后将产物过滤除去NaCl,所得滤液除去多余的EHC,得到溶液B;溶液B与甲醇/丙酮溶液混合,降温结晶,得到的结晶物用甲醇洗涤并抽滤、烘干,得到液晶环氧树脂C;将液晶环氧树脂C和阻聚剂混合反应,待环氧树脂C完全融化后,滴加丙烯酸和催化剂2,反应得到丙烯酸液晶光敏树脂。所述丙烯酸液晶光敏树脂具有液晶有序和网络交联两者的优势,其力学性能、耐热性、尺寸稳定性、成型工艺性优异,通过紫外光照射来实现其固化,具有固化速度快、污染小、节省能源等优点。(The invention discloses an acrylic liquid crystal photosensitive resin and a preparation method thereof. Mixing a compound containing mesomorphic elements and having-OH at the end, EHC and a catalyst 1, and reacting to obtain a solution A; dropwise adding NaOH into the solution A, removing water generated in the reaction, continuously reacting, filtering a product to remove NaCl, and removing redundant EHC from the obtained filtrate to obtain a solution B; mixing the solution B with a methanol/acetone solution, cooling and crystallizing, washing the obtained crystal with methanol, filtering, and drying to obtain liquid crystal epoxy resin C; and mixing the liquid crystal epoxy resin C and a polymerization inhibitor for reaction, dropwise adding acrylic acid and a catalyst 2 after the epoxy resin C is completely melted, and reacting to obtain the acrylic acid liquid crystal photosensitive resin. The acrylic liquid crystal photosensitive resin has the advantages of both liquid crystal order and network crosslinking, is excellent in mechanical property, heat resistance, dimensional stability and forming manufacturability, is cured by ultraviolet irradiation, and has the advantages of high curing speed, small pollution, energy conservation and the like.)

1. A preparation method of acrylic liquid crystal photosensitive resin is characterized by comprising the following steps: the method comprises the following steps:

(1) mixing a compound containing mesomorphic elements and having-OH at the end, epichlorohydrin and 0.1 catalyst 1 as raw materials, and introducing N2Protecting, and then reacting for 5-24 hours at 40-100 ℃ to obtain a solution A;

(2) slowly dropwise adding a NaOH solution, removing water generated in the reaction by using a vacuum pump under reduced pressure, continuously reacting for 0.1-4 hours, then pouring the product into a separating funnel, filtering to remove NaCl, and removing redundant epoxy chloropropane from the obtained filtrate to obtain a solution B;

(3) mixing the solution B with a methanol/acetone solution, cooling and crystallizing, washing and filtering the obtained crystal with methanol, and drying the product to obtain liquid crystal epoxy resin C;

(4) adding liquid crystal epoxy resin C and a polymerization inhibitor into a flask according to the molar ratio, setting the reaction temperature to be 90-150 ℃, slowly dropwise adding acrylic acid after the epoxy resin C is completely melted, dropwise adding a catalyst 2, reacting for 0.5-5.0 hours, and cooling to obtain the acrylic liquid crystal photosensitive resin.

2. The method for preparing an acrylic liquid crystal photosensitive resin according to claim 1, wherein: the mesogen-containing compound with-OH at the end is one or a combination of 4-hydroxyphenyl 4-hydroxybenzoate, 4 '-biphenol, 3',5,5 '-tetramethylbiphenol, 4- ((4-hydroxyphenoxy) carbonyl) phenyl 4-hydroxybenzoate, 2, 3-bis (4-hydroxyphenyl) acrylonitrile and 4,4' -propylidenebisphenol in step (1).

3. The method for preparing an acrylic liquid crystal photosensitive resin according to claim 1, wherein: the catalyst 1 in the step (1) is one or a combination of tetramethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetraethylammonium bromide, tetrabutylammonium hydrogen sulfate, benzyltriethylammonium chloride, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride or tetradecyltrimethylammonium chloride.

4. The method for preparing an acrylic liquid crystal photosensitive resin according to claim 1, wherein: the concentration of the NaOH solution in the step (2) is 30-60%.

5. The method for preparing an acrylic liquid crystal photosensitive resin according to claim 1, wherein: the ratio of the solution B to the methanol/acetone solution in the step (3) is 1.0: 0.1-1.0: 10, and the drying temperature of the product is 60-100 ℃.

6. The method for preparing an acrylic liquid crystal photosensitive resin according to claim 1, wherein: the polymerization inhibitor in the step (4) is one or a combination of hydroquinone, benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butyl hydroquinone and 2, 5-di-tert-butyl hydroquinone.

7. The method for preparing an acrylic liquid crystal photosensitive resin according to claim 1, wherein: the method is characterized in that: the catalyst 2 in the step (4) is one or a combination of N, N-diethylaniline, N-dimethyl-p-toluidine, N-dimethylbenzylamine, N-dimethylcyclohexylamine, N '-dimethylpyridine and N, N' -diethylpiperazine.

8. An acrylic liquid crystal photosensitive resin, which is characterized in that: which is obtained by the production method according to any one of claims 1 to 7.

Technical Field

The invention relates to the technical field of ultraviolet curing materials, in particular to an acrylic liquid crystal photosensitive resin and a preparation method thereof.

Background

Compared with other forming technologies, the photocuring forming technology has the advantages of high speed, short curing forming time, energy conservation and no pollution, and the formed material has excellent performances in the aspects of hardness, chemical resistance, wear resistance and the like. The development of any molding technique is based on materials with excellent properties. Therefore, the development of novel photosensitive resin materials is gradually becoming the key of innovative breakthrough of photochemical polymerization technology and is a necessary way to expand the application field of photochemical polymerization technology.

Thermosetting liquid crystal resins are an extremely important branch of liquid crystal polymers. Functional liquid crystal micromolecules are obtained by terminating liquid crystal elements with reactive functions, and then the functional liquid crystal micromolecules are cured to form a locally ordered cross-linked reticular polymer, so that the characteristics of liquid crystal ordering and thermosetting are combined, and the novel thermosetting polymer is prepared. The structural composition of the thermosetting liquid crystal resin is mesomorphic element, spacer chain and reaction functional group, which is simply expressed as: F-S-M-S-F (M is mesogen, S is spacer chain, F is reactive functional group). Mesogens are the primary reason why the resin achieves orientational order. The reactive functional groups at two ends of the resin mainly comprise acrylate groups, epoxy groups, vinyl groups and the like; among them, acrylic group-terminated resins are widely used because of their versatility, excellent durability and low cost. The thermosetting liquid crystal resin has better performance than the traditional thermosetting resin in many aspects, so the thermosetting liquid crystal resin has better application prospect in the fields of high-performance composite materials for structures, coatings, adhesives, functional materials and the like.

The acrylic liquid crystal resin is one of thermosetting liquid crystal resins, has good forming manufacturability of unsaturated polyester resin and has the characteristic of ordered liquid crystal orientation. The acrylic liquid crystal resin has low phase transition temperature and good solubility, so the acrylic liquid crystal resin has better molding manufacturability than imide, cyanate and ethynyl liquid crystal resins. However, the reported acrylate liquid crystal resin often contains flexible main chains and spacing chains, so that the heat resistance is poor, and the reports of the mechanical properties at home and abroad are relatively less. The acrylic liquid crystal resin can be cured by heat under the conditions of initiator initiation or thermal initiation to obtain a cured resin. However, the acrylic liquid crystal resin is generally photopolymerized due to the limitations of the initiation system and temperature. When the photopolymerization is adopted, the polymerization temperature can be randomly selected within the liquid phase temperature range, and the two processes of orientation and polymerization can be completely independent, namely, the polymerization is carried out after the liquid crystal resin can be fully oriented. However, this method is suitable for preparing thin films and is not suitable for parts with larger thickness.

Therefore, the research on the acrylic liquid crystal photosensitive resin which is low in processing cost, can be cured by ultraviolet light and has good comprehensive performance is actively carried out, and the acrylic liquid crystal photosensitive resin has important theoretical significance and application value.

Disclosure of Invention

Aiming at the conditions and defects of the prior art, the invention aims to provide an acrylic liquid crystal photosensitive resin with excellent performance and simple synthesis process and a preparation method thereof. The acrylic liquid crystal photosensitive resin provided by the invention has excellent thermo-mechanical properties.

In order to achieve the purpose, the invention adopts the technical scheme that:

a preparation method of acrylic liquid crystal photosensitive resin comprises the following steps:

(1) mixing 10 parts of mesomorphic-containing compound with-OH at the end, 50-500 parts of epoxy chloropropane (EHC) and 0.1-1.0 part of catalyst 1 serving as raw materials in terms of mole, and introducing N2Protecting, and then reacting for 5-24 hours at 40-100 ℃ to obtain a solution A;

(2) according to the molar ratio, slowly dripping 20-50 parts of NaOH solution (with the concentration of 30% -60%) into the solution A, and removing water generated by the reaction by using a vacuum pump under reduced pressure; after continuously reacting for 0.1-4 hours, pouring the product into a separating funnel, filtering to remove NaCl, and removing redundant EHC from the obtained filtrate by using a rotary evaporator to obtain a solution B;

(3) and mixing the solution B with a methanol/acetone solution (the ratio is 1.0: 0.1-1.0: 10), placing the mixture into a refrigerator for cooling and crystallizing, washing the obtained crystal with methanol, performing suction filtration, and drying the product in an oven at the temperature of 60-100 ℃ to obtain a milky solid, namely the liquid crystal epoxy resin C.

(4) Taking 10 parts of liquid crystal epoxy resin C and 0.1-1.0 part of polymerization inhibitor by mol, adding the components into a flask, and setting the reaction temperature to be 90-150 ℃; after the epoxy resin C is completely melted, slowly dripping 20-25 parts of acrylic acid and 0.01-0.1 part of catalyst 2; and reacting for 0.5-5.0 hours, and cooling to obtain light yellow viscous resin, namely the acrylic liquid crystal photosensitive resin.

Preferably, the mesogen-containing compound having-OH at the end is one or a combination of 4-hydroxyphenyl 4-hydroxybenzoate, 4 '-biphenyldiol, 3',5,5 '-tetramethylbiphenyldiol, 4- ((4-hydroxyphenoxy) carbonyl) phenyl 4-hydroxybenzoate, 2, 3-bis (4-hydroxyphenyl) acrylonitrile, and 4,4' -propylidenebisphenol.

Preferably, the catalyst 1 described in step (1) is one or a combination of tetramethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetraethylammonium bromide, tetrabutylammonium hydrogen sulfate, benzyltriethylammonium chloride, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, and the like.

Preferably, the polymerization inhibitor in the step (4) is one or a combination of hydroquinone, benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butyl hydroquinone and 2, 5-di-tert-butyl hydroquinone.

Preferably, the catalyst 2 in the step (4) is one or a combination of N, N-diethylaniline, N-dimethyl-p-toluidine, N-dimethylbenzylamine, N-dimethylcyclohexylamine, N '-dimethylpyridine, N' -diethylpiperazine, etc.

The preparation process of the acrylic liquid crystal photosensitive resin comprises the following steps:

compared with the prior art, the invention has the beneficial effects that: the acrylic liquid crystal photosensitive resin provided by the invention has the advantages of wide raw material source and simple synthesis process, and is suitable for large-scale production and application. The liquid acrylic liquid crystal photosensitive resin has a molecular structure with a large number of rigid mesogens, and can generate an anisotropic mesomorphic domain in situ in a forming process, so that the liquid acrylic liquid crystal photosensitive resin has excellent performances of self-reinforcement, high strength, high modulus and the like. Meanwhile, the grafted acrylic acid group can be cured by irradiation of ultraviolet light, and in addition, the molecular structure of the grafted acrylic acid group does not contain a special molecular component of a flexible chain segment, so that the grafted acrylic acid group has excellent heat resistance and low size shrinkage, the defect of poor heat resistance is effectively overcome, and the grafted acrylic acid group can be widely applied to the fields of adhesives, special coatings, nonlinear optical materials and the like and has wide development potential.

Drawings

FIG. 1 is a reaction involved in the method for preparing an acrylic liquid crystal photosensitive resin according to the present invention.

FIG. 2 shows nuclear magnetic hydrogen spectrum of acrylic liquid crystal photosensitive resin prepared in example 1 of the present invention: (1H-NMR)。

FIG. 3 is a thermogravimetric analysis (TGA) curve of acrylic liquid crystal photosensitive resin prepared in example 1 of the present invention under nitrogen atmosphere with a temperature rise rate of 10 ℃/min.

FIG. 4 is a DSC curve of the acrylic liquid crystal photosensitive resin prepared in example 1 of the present invention in a nitrogen atmosphere at a temperature increase rate of 10 deg.C/min.

FIG. 5 is an XRD curve of the acrylic liquid crystal photosensitive resin prepared in example 1 of the present invention.

Detailed Description

Example 1

(1) 23.0g of 4-hydroxyphenyl 4-hydroxybenzoate,230ml of Epichlorohydrin (EHC) and 0.5g of tetramethylammonium chloride are mixed as raw materials, and N is introduced2Protecting, and then reacting for 12 hours at 60 ℃ to obtain a solution A;

(2) then slowly dropwise adding NaOH solution (0.25mol, concentration of 45%) into the solution A, removing water generated in the reaction by using a vacuum pump under reduced pressure, continuously reacting for 0.5 hour, pouring the product into a separating funnel, filtering to remove NaCl, and removing redundant EHC from the obtained filtrate by using a rotary evaporator to obtain solution B;

(3) mixing the solution B with a methanol/acetone solution (the ratio is 1.0:1.0), placing the mixture into a refrigerator for cooling and crystallizing, washing an obtained crystal with methanol, performing suction filtration, and drying a product in an oven at 60 ℃ to obtain a milky white solid, namely liquid crystal epoxy resin C;

(4) adding 19.3g (0.05mol) of liquid crystal epoxy resin C and 0.15g of hydroquinone into a flask, and setting the reaction temperature to be 110 ℃; and after the liquid crystal epoxy resin C is completely melted, slowly dropwise adding 7.9g (0.11mol) of acrylic acid, dropwise adding 0.06g of N, N-diethylaniline, reacting for 2.5 hours, discharging, and cooling to obtain light yellow viscous resin, namely the acrylic acid liquid crystal photosensitive resin.

Referring to FIG. 2, it is a nuclear magnetic hydrogen spectrum of the acrylic liquid crystal photosensitive resin prepared in example 1 of the present invention: (1H-NMR). 4 hydrogen proton peaks of mesogen benzene ring correspond to 4 characteristic peaks on 8.3-6.7 ppm, which indicates that the structure of mesogen is not destroyed. The characteristic peaks of hydrogen protons on the side chain are located at 3.7-4.4 ppm, and the characteristic peaks of hydrogen protons of carbon-carbon double bonds are located at 6.5 ppm and 5.7 ppm.

Referring to FIG. 3, it is a thermogravimetric analysis (TGA) curve of the acrylic liquid crystal photosensitive resin prepared in example 1 of the present invention under nitrogen atmosphere with a temperature rise rate of 10 ℃/min. The initial decomposition temperature was 309.2 ℃, the 50% decomposition temperature was 411.5 ℃ and the maximum decomposition temperature reached 389.1 ℃. Therefore, the acrylic liquid crystal photosensitive resin has better thermal stability.

Referring to FIG. 4, it is a DSC curve of the acrylic liquid crystal photosensitive resin prepared in example 1 of the present invention in a nitrogen atmosphere at a temperature increase rate of 10 deg.C/min. The DSC result shows that the phase transition temperature range of the acrylic liquid crystal photosensitive resinThe enclosure is 16-43 ℃. The acrylic liquid crystal photosensitive resin has 44 obvious endothermic peaks. The endothermic peak at-30 ℃ represents the glass transition temperature (T) of the acrylic liquid crystal photosensitive resing). The endothermic peak appearing at 16 ℃ is the melting point (T) of the acrylic liquid crystal photosensitive resinm). The endothermic peak appearing at 30 ℃ indicates that the acrylic liquid crystal photosensitive resin is transformed from a smectic phase to a nematic phase. The endothermic peak appearing at 43 ℃ is the clearing point temperature (T) of the acrylic liquid crystal photosensitive resini) When this temperature is exceeded, the liquid crystal phase of the acrylic liquid crystal photosensitive resin disappears. Thus, it was demonstrated that the acrylic liquid crystal photosensitive resin can retain liquid crystallinity at room temperature.

Referring to FIG. 5, it is an XRD pattern of the acrylic liquid crystal photosensitive resin prepared in example 1 of the present invention. And (3) carrying out ultraviolet curing on the acrylic liquid crystal photosensitive resin, and carrying out XRD test. In the figure, a broad dispersion peak appears only in the vicinity of 20 °, and it is presumed that the resin has a nematic phase structure. The acrylic liquid crystal photosensitive resin still retains the liquid crystal property after being cured.

The prepared acrylic liquid crystal photosensitive resin is uniformly coated on a glass sheet and then is subjected to 365nm ultraviolet light (100 mW/cm)2) And (5) irradiating in an ultraviolet curing box under irradiation. And pouring the prepared resin into a grinding tool, and after the ultraviolet curing is completed, the surface of the product is smooth, and the Shore hardness is 78 HD.

Example 2

(1) 0.1mol of 4,4' -biphenol, 360ml of epoxy chloropropane (EHC) and 0.003mol of tetrabutylammonium bromide are taken as raw materials to be mixed, and N is introduced2Protecting, and then reacting for 18 hours at 50 ℃ to obtain a solution A;

(2) then slowly dripping NaOH solution (0.30mol, concentration 40%) into the solution A, and removing water generated by the reaction by using a vacuum pump under reduced pressure; after continuously reacting for 2.5 hours, pouring the product into a separating funnel, filtering to remove NaCl, and removing redundant EHC from the obtained filtrate by using a rotary evaporator to obtain a solution B;

(3) mixing the solution B with a methanol/acetone solution (the ratio is 1.0:3.0), placing the mixture into a refrigerator for cooling and crystallizing, washing an obtained crystal with methanol, performing suction filtration, and drying a product in an oven at 80 ℃ to obtain a milky white solid, namely liquid crystal epoxy resin C;

(4) adding 14.9g (0.05mol) of liquid crystal epoxy resin C and 0.25g of benzoquinone into a flask, and setting the reaction temperature to be 140 ℃; after the liquid crystal epoxy resin C was completely melted, 7.9g (0.11mol) of acrylic acid and 0.08g of N, N-dimethyl-p-toluidine were slowly added dropwise. And discharging after reacting for 4.0 hours, and cooling to obtain light yellow viscous resin, namely the acrylic liquid crystal photosensitive resin.

The prepared acrylic liquid crystal photosensitive resin is uniformly coated on a glass sheet and then is subjected to 365nm ultraviolet light (100 mW/cm)2) And (5) irradiating in an ultraviolet curing box under irradiation. And pouring the prepared resin into a grinding tool, and after the ultraviolet curing is completed, the surface of the product is smooth, and the Shore hardness is 65 HD.

Example 3

(1) 0.1mol of 3,3',5,5' -tetramethyl diphenol, 120ml of Epichlorohydrin (EHC) and 0.006mol of tetrabutylammonium chloride are taken as raw materials to be mixed, and N is introduced2Protecting, and then reacting for 6 hours at 80 ℃ to obtain a solution A;

(2) then slowly dropwise adding NaOH solution (0.20mol, the concentration of 60%) into the solution A, removing water generated in the reaction by using a vacuum pump under reduced pressure, continuously reacting for 4.0 hours, pouring the product into a separating funnel, filtering to remove NaCl, and removing redundant EHC from the obtained filtrate by using a rotary evaporator to obtain solution B;

(3) mixing the solution B with a methanol/acetone solution (the ratio is 1.0:0.5), placing the mixture into a refrigerator for cooling and crystallizing, washing an obtained crystal with methanol, performing suction filtration, and drying a product in an oven at 100 ℃ to obtain a milky white solid, namely liquid crystal epoxy resin C;

(4) adding 17.5g (0.05mol) of liquid crystal epoxy resin C and 0.30g of methyl hydroquinone into a flask, and setting the reaction temperature to be 120 ℃; after the liquid crystal epoxy resin C is completely melted, slowly dropwise adding 8.6g (0.12mol) of acrylic acid, dropwise adding 0.04g of N, N-dimethyl cyclohexylamine, reacting for 5.0 hours, discharging, and cooling to obtain light yellow viscous resin, namely the acrylic acid liquid crystal photosensitive resin.

The prepared acrylic liquid crystal photosensitive resin is uniformly coated on a glass sheet and then is subjected to 365nm ultraviolet light (100 mW/cm)2) And (5) irradiating in an ultraviolet curing box under irradiation. And pouring the prepared resin into a grinding tool, and after the ultraviolet curing is completed, the surface of the product is smooth, and the Shore hardness is 75 HD.

Example 4

(1) 0.1mol of 4- ((4-hydroxyphenoxy) carbonyl) phenyl 4-hydroxybenzoate, 1050ml of Epichlorohydrin (EHC) and 0.01mol of tetraethylammonium bromide are used as raw materials to be mixed, and N is introduced2Protecting, and then reacting for 24 hours at 100 ℃ to obtain a solution A;

(2) then slowly dropwise adding NaOH solution (0.40mol, concentration of 50%) into the solution A, removing water generated in the reaction by using a vacuum pump under reduced pressure, continuously reacting for 0.5 hour, pouring the product into a separating funnel, filtering to remove NaCl, and removing redundant EHC from the obtained filtrate by using a rotary evaporator to obtain solution B;

(3) mixing the solution B with a methanol/acetone solution (the ratio is 1.0:5.0), placing the mixture into a refrigerator for cooling and crystallizing, washing an obtained crystal with methanol, performing suction filtration, and drying a product in an oven at 80 ℃ to obtain a milky white solid, namely liquid crystal epoxy resin C;

(4) adding 23.1g (0.05mol) of liquid crystal epoxy resin C and 0.25g of 2-tert-butylhydroquinone into a flask, and setting the reaction temperature to be 150 ℃; after the liquid crystal epoxy resin C is completely melted, slowly dropwise adding 7.2g (0.10mol) of acrylic acid, dropwise adding 0.10g of N, N-diethylaniline, reacting for 1.0 hour, discharging, and cooling to obtain light yellow viscous resin, namely the acrylic acid liquid crystal photosensitive resin.

The prepared acrylic liquid crystal photosensitive resin is uniformly coated on a glass sheet and then is subjected to 365nm ultraviolet light (100 mW/cm)2) And (5) irradiating in an ultraviolet curing box under irradiation. And pouring the prepared resin into a grinding tool, and after the ultraviolet curing is completed, the surface of the product is smooth, and the Shore hardness is 72 HD.

Example 5

(1) 0.1mol of 2, 3-bis (4-hydroxyphenyl) acrylonitrile, 950ml of Epichlorohydrin (EHC) and 0.001mol of tetrabutylammonium hydrogen sulfate are used as raw materials to be mixed, and N is introduced2Protecting, and then reacting for 10 hours at 40 ℃ to obtain a solution A;

(2) then slowly dropwise adding NaOH solution (0.30mol, the concentration of 60%) into the solution A, removing water generated in the reaction by using a vacuum pump under reduced pressure, continuously reacting for 3.0 hours, pouring the product into a separating funnel, filtering to remove NaCl, and removing redundant EHC from the obtained filtrate by using a rotary evaporator to obtain solution B;

(3) mixing the solution B with a methanol/acetone solution (the ratio is 1.0:10), placing the mixture into a refrigerator for cooling and crystallizing, washing an obtained crystal with methanol, performing suction filtration, and drying a product in an oven at 90 ℃ to obtain a milky solid, namely the liquid crystal epoxy resin;

(4) 17.5g (0.05mol) of liquid crystal epoxy resin C and 0.10g of 2, 5-di-tert-butyl hydroquinone were charged into a flask, and the reaction temperature was set to 100 ℃; after the liquid crystal epoxy resin C is completely melted, slowly dropwise adding 7.9g (0.11mol) of acrylic acid, dropwise adding 0.02g of N, N-dimethylbenzylamine, reacting for 3.5 hours, discharging, and cooling to obtain light yellow viscous resin, namely the acrylic acid liquid crystal photosensitive resin.

The prepared acrylic liquid crystal photosensitive resin is uniformly coated on a glass sheet and then is subjected to 365nm ultraviolet light (100 mW/cm)2) And (5) irradiating in an ultraviolet curing box under irradiation. And pouring the prepared resin into a grinding tool, and after the ultraviolet curing is completed, the surface of the product is smooth, and the Shore hardness is 75 HD.

Example 6

(1) 0.1mol of 4,4' -propylene biphenol, 120ml of epoxy chloropropane (EHC) and 0.002mol of benzyltriethylammonium chloride are mixed as raw materials, and N is introduced2Then reacting for 12 hours at 60 ℃ to obtain a solution A;

(2) then slowly dropwise adding NaOH solution (0.20mol, concentration of 45%) into the solution A, removing water generated in the reaction by using a vacuum pump under reduced pressure, continuously reacting for 1.0 hour, pouring the product into a separating funnel, filtering to remove NaCl, and removing redundant EHC from the obtained filtrate by using a rotary evaporator to obtain solution B;

(3) mixing the solution B with a methanol/acetone solution (the ratio is 1.0:3.5), placing the mixture into a refrigerator for cooling and crystallizing, washing an obtained crystal with methanol, performing suction filtration, and drying a product in an oven at 80 ℃ to obtain a milky white solid, namely the liquid crystal epoxy resin;

(4) adding 16.9g (0.05mol) of liquid crystal epoxy resin C and 0.15g of hydroquinone into a flask, and setting the reaction temperature to be 110 ℃; after the liquid crystal epoxy resin C is completely melted, slowly dropwise adding 7.9g (0.11mol) of acrylic acid, dropwise adding 0.06g of N, N' -diethylpiperazine, reacting for 0.5 hour, discharging, and cooling to obtain light yellow viscous resin, namely the acrylic acid liquid crystal photosensitive resin.

The prepared acrylic liquid crystal photosensitive resin is uniformly coated on a glass sheet and then is subjected to 365nm ultraviolet light (100 mW/cm)2) And (5) irradiating in an ultraviolet curing box under irradiation. And pouring the prepared resin into a grinding tool, and after the ultraviolet curing is completed, the surface of the product is smooth, and the Shore hardness is 65 HD.

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