CN103030745A - Water-based photo-cured unsaturated polyester and preparation method thereof - Google Patents

Abstract

该方法制备的聚酯具有稳定性好、耐水好、固化速度快、光泽度高的特点。The invention relates to a class of water-based unsaturated polyester with ultraviolet curing properties and a synthesis method thereof. Water-based photocurable unsaturated polyester is characterized in that its chemical structural formula is:

The polyester prepared by the method has the characteristics of good stability, good water resistance, fast curing speed and high gloss.

Description

Water-based photocurable unsaturated polyester and preparation method thereof

technical field

The invention relates to a class of water-based unsaturated polyester with ultraviolet curing properties and a synthesis method thereof.

Background technique

Since the German Bayer company developed the first generation of UV-curable coatings (UVCC) in the 1960s, because this technology fully complies with the 3E principle, it has fast curing speed, no volatile solvents, energy saving, low cost, and automatic production. characteristics, has maintained a rapid development. Since oligomers, the main components used in photocurable coating systems, generally have high viscosity, more reactive diluents must be added to adjust viscosity and improve rheology before use, and most of these reactive diluents are toxic and irritating. On the other hand, with the gradual improvement of people's awareness of environmental protection and the stricter environmental protection regulations of various countries, water-based coatings have become one of the main directions of coating development, and their easily adjustable low viscosity makes them suitable for spraying. In this case, UV-curable water-based coatings emerged as the times require, which combines the advantages of both and has become a very active research and development field. Unsaturated polyester resin (UPR) has excellent mechanical properties, electrical properties, chemical corrosion resistance, and simple processing technology, so it has developed rapidly abroad in recent years, and is one of the fastest-growing varieties of thermosetting resins. Widely used in industry, agriculture, traffic and transportation and other fields. Therefore, the research on the synthesis of photocurable waterborne unsaturated polyester is required by the development of society and market economy, and has high application value.

The O ₂ in the ground state is essentially a diradical, so it has a strong addition activity to the active radicals generated during the photoinitiation process, forming a relatively stable peroxide radical. This process is fast and can compete with the addition reaction of active radicals to monomers, and has the most significant hindrance to the polymerization process. Oxygen inhibition is very harmful to the UV curing process, especially when the coating film thickness is thin. Not only the dissolved oxygen molecules in the formula system hinder the polymerization, but also during the photoinitiation process, with the consumption of oxygen molecules in the curing system, the oxygen in the air on the coating surface can also rapidly diffuse into the cured coating to continue to hinder the polymerization. Oxygen that continuously diffuses into the coating from the outside is the main reason for hindering polymerization. Oxygen inhibition is also most likely to occur in the superficial layers of the coating or throughout thinner coatings, because oxygen molecules from the environment diffuse more easily in these areas.

When photocuring in air, the oxygen inhibition effect often leads to the situation that the bottom layer of the coating is cured, and the surface is not cured and sticky. Oxygen inhibition can eventually lead to a large number of oxidative structures such as hydroxyl groups, carbonyl groups, and peroxyl groups on the surface of the coating, thereby affecting the long-term stability of the coating, and may even affect the hardness, gloss, and scratch resistance of the cured paint film. performance.

Contents of the invention

The purpose of the present invention is to provide a water-based photocurable unsaturated polyester and its preparation method, the polyester prepared by the method has the characteristics of good stability.

In order to achieve the above object, the technical solution adopted by the present invention is: water-based photocurable unsaturated polyester, which is characterized in that its chemical structural formula is:

R₄为

或其中p₁=2、3、4、5、6、7、8、9或10，p₂=1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19或20，p₃=1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24或25；In formula (1): R ₁ is H or CH ₃ ; R ₂ is H or CH ₃ ; R ₃ is

_R4 is

or where p ₁ =2, 3, 4, 5, 6, 7, 8, 9 or 10, p ₂ =1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 , 14, 15, 16, 17, 18, 19 or 20, p ₃ =1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25;

q ₁ is 1 or 2; q ₂ is 1 or 2; m=2, 3, 4, 5 or 6, n=0, 1, 2, 3, 4, 5, 6, 7 or 8.

According to the above scheme, q1+q2=p, p=2 or 3.

The above-mentioned preparation method of water-based photocurable unsaturated polyester (one of the methods adopting the bulk polymerization method) is characterized in that it includes the following steps: 1) under the protection of nitrogen, the mass parts of 40-60 polyol The mixture, 40-60 parts by mass of the polybasic acid mixture, and 0.1-0.3 parts by mass of antioxidant are added to a four-port reactor with stirring, and the bulk polymerization method is adopted;

The polyol mixture is composed of ① trimethylolpropane monoallyl ether, ② polyol and ③ dimethylol propionic acid three raw materials, wherein trimethylolpropane monoallyl ether accounts for 1% of the mass of the polyol mixture 33%-82.5% (20-33 parts by mass), dimethylolpropionic acid accounts for 16.6-45% of the mass of the polyol mixture (10-18 parts by mass);

The polybasic acid mixture is composed of the following two raw materials: ① a mixture of one or two of saturated dibasic acids or saturated (including those containing benzene rings) acid anhydrides in any proportion, ② and unsaturated dibasic acids or Unsaturated acid anhydrides containing carbon-carbon double bonds (excluding benzene rings); among them, unsaturated dibasic acids or unsaturated acid anhydrides containing carbon-carbon double bonds (excluding benzene rings) account for 16.6-52.5% of the mass of the polybasic acid mixture (10-21 parts by mass);

2) Raise the temperature to 140°C, keep it warm for 1h, then raise the temperature to 150°C, and keep it warm for 1h (keep reflux in this state, without draining); then take 1h to raise the temperature to 180°C, and keep it warm for 2h (and keep the reaction at this temperature) , and then keep dehydration for 0.5-1h under the vacuum degree of 0.040MPa; the amount of nitrogen can be appropriately increased to facilitate drainage, and the reaction is until the acid value reaches the theoretical value of the formula design (this theoretical value has different theoretical values according to the formula design);

3) Cool down to 150°C, add 0.2-0.5 mass parts of polymerization inhibitor, continue to cool down to 95°C; drop 7-15 mass parts of glycidyl methacrylate into the reactor, and add 0.1-0.3 mass parts Tetramethylammonium iodide; react at this temperature until the acid value reaches the theoretical value of the formula design (this theoretical value has different theoretical values according to the formula design); cool down to 65 ° C, add a neutralizer to neutralize the pH of the product The value is 7-8, and the product (ie unsaturated polyester) is obtained; the product is stirred and diluted with water (high-speed stirring for 15min-30min, the speed of the high-speed stirring is 800-1200 rpm), and the amount of water added is the product (Equivalent to the entire unsaturated polyester) 50%-200% of the mass, that is, water-based light-curable unsaturated polyester.

The above-mentioned preparation method of water-based photocurable unsaturated polyester (method 2 using the bulk polymerization method) is characterized in that it includes the following steps: ①Under the protection of nitrogen, the mass parts of the polyol mixture of 40-60 , 35-55 parts by mass of polybasic acid mixture, 0.1-0.3 parts by mass of antioxidant are added in a four-port reactor with stirring, and the bulk polymerization method is adopted;

The polyol mixture is composed of ① trimethylolpropane monoallyl ether, ② polyol and ③ dimethylol propionic acid three raw materials, wherein trimethylolpropane monoallyl ether accounts for 1% of the mass of the polyol mixture 33%-82.5% (20-33 parts by mass), dimethylolpropionic acid accounts for 16.6-45% of the mass of the polyol mixture (10-18 parts by mass);

The polybasic acid mixture is composed of the following two raw materials: ① a mixture of one or two of saturated dibasic acids or saturated (including those containing benzene rings) acid anhydrides in any proportion, ② and unsaturated dibasic acids or Unsaturated acid anhydrides containing carbon-carbon double bonds (excluding benzene rings); among them, unsaturated dibasic acids or unsaturated acid anhydrides containing carbon-carbon double bonds (excluding benzene rings) account for 8.5%-27.5% of the mass of the polybasic acid mixture % (5-11 parts by mass);

②Raise the temperature to 140°C, keep it warm for 1 hour, then raise the temperature to 150°C, and keep it warm for 1 hour (keep reflux in this state, without draining); then take 1 hour to raise the temperature to 180°C, and then add 5-10 parts by mass of unsaturated acid or carbon-containing Unsaturated acid anhydrides with carbon double bonds (excluding benzene rings), keep warm for 2 hours (and keep the reaction at this temperature), and then keep dehydration for 0.5-1 hours under a vacuum of 0.040MPa; the amount of nitrogen can be appropriately increased to facilitate drainage , until the acid value reaches the theoretical value of formula design (this theoretical value has different theoretical values according to formula design);

③ Cool down to 150°C, add 0.2-0.5 parts by mass of polymerization inhibitor, continue to cool down to 95°C; drop 7-15 parts by mass of glycidyl methacrylate into the reactor, and add 0.1-0.3 parts by mass Tetramethylammonium iodide, react at this temperature until the acid value reaches the theoretical value of the formula design (this theoretical value has different theoretical values according to the formula design); cool down to 65°C, add a neutralizer to neutralize the pH value of the product 7-8, the product (ie unsaturated polyester) is obtained; the product is stirred and diluted with water (high-speed stirring for 15min-30min, the speed of the high-speed stirring is 800-1200 rpm), and the amount of water added is the product ( Equivalent to 50%-200% of the mass of the whole unsaturated polyester), that is, water-based light-curable unsaturated polyester can be obtained.

According to the above scheme, the polyhydric alcohol is propylene glycol, ethylene glycol, hexanediol, diethylene glycol, dipropylene glycol or neopentyl glycol and the like.

According to the above scheme, the saturated dibasic acid is any one of adipic acid, suberic acid, succinic acid, malonic acid, glutaric acid, etc., or any two or more of them are mixed in any proportion; Saturated acid anhydrides (including those containing benzene rings) are phthalic anhydride, succinic anhydride, trimellitic anhydride, etc.; unsaturated dibasic acids are maleic acid or fumaric acid, etc.; those containing carbon-carbon double bonds (excluding benzene rings) The unsaturated anhydride is maleic anhydride.

According to the above scheme, the antioxidant is triphenyl phosphite.

According to the above scheme, the polymerization inhibitor is selected from hydroquinone, methyl hydroquinone, p-benzoquinone, tert-butyl catechol, 2,6-di-tert-butyl-4-cresol, etc. Any one or any two or more are mixed in any proportion.

According to the above scheme, the neutralizing agent is an organic amine neutralizing agent (N,N--dimethylethanolamine).

Product use: The water-based light-curable unsaturated polyester of the present invention can be used in wood coatings, and has high application value in the fields of wood and wood finishing. Since the water-based photocurable unsaturated polyester (resin) of the present invention is diluted with water, it avoids the harm of solvents and reactive diluents to the human body, realizes low VOC, and is easy to recycle and reprocess paper, and can be applied to paper varnish . The present invention can also be used in other fields where high temperature film formation is not possible, such as electronic packaging, adhesives, printing plates, electronics industry and the like.

The beneficial effects of the invention are: the polyester prepared by the method has the characteristics of good stability, good water resistance, fast curing speed and high gloss.

Detailed ways

The content of the present invention is further illustrated below through the examples, but the content of the present invention is not limited only to the following examples. Embodiment 1 (one of the method that adopts bulk polymerization method):

The preparation method (one of bulk polymerization method) of aqueous photocurable unsaturated polyester, it comprises the following steps:

① Under the protection of nitrogen, 33.00g trimethylolpropane monoallyl ether, 9.23g neopentyl glycol (polyol), 17.53g dimethylol propionic acid, 14.77g phthalic anhydride ( saturated (including benzene ring) anhydride), 10.15g maleic anhydride [unsaturated anhydride containing carbon-carbon double bond (excluding benzene ring)], 15.84g adipic acid (saturated dibasic acid), and 0.26g of antioxidant (triphenyl phosphite) was added to a four-port reactor equipped with a stirrer, condenser, thermometer and dripping device, and the bulk polymerization method was adopted.

②Raise the temperature to 140°C, keep it warm for 1h, then raise the temperature to 150°C, and keep it warm for 1h (keep reflux in this state, without draining). Then it takes 1 hour to raise the temperature to 180°C, keep it warm for 2 hours, and keep the reaction at this temperature, and then keep it under a vacuum of 0.040MPa for 0.5-1 hour to dehydrate. It is possible to appropriately increase the amount of nitrogen to facilitate drainage, and react until the acid value reaches 80.

③ Cool down to 150°C, add 0.30g of polymerization inhibitor, and continue to cool down to 95°C. Add 14.5g of glycidyl methacrylate (GMA) dropwise into the reactor, and add 0.30g of tetramethylammonium iodide, and drop it in half an hour. React at this temperature until the acid value reaches 20. Cool down to 65°C, and add 3g of neutralizing agent for neutralization (until the pH value of the product is 7-8) to obtain the product (unsaturated polyester), the mass of which is 110g, and stir at a speed of 800r/min for 15min , and then slowly add 140g of water to dilute (stirring at high speed for half an hour) to obtain water-based photocurable unsaturated polyester (water-based photocurable unsaturated polyester with hydroxyl terminals).

The antioxidant used in this experiment was triphenyl phosphite.

The polymerization inhibitor used in this experiment was hydroquinone.

The neutralizing agent used in this experiment was N,N-dimethylethanolamine.

The hardness test in this experiment is tested by the method of pencil hardness tester, and the test results are shown in the table below.

The water resistance test of this experiment is carried out in water at 25°C. The qualified standard is that the film does not bubble, discolor, or fall off. The test results are shown in the table below.

The storage stability is placed in a glass bottle at room temperature, and the qualified standard is that the resin solution does not delaminate and does not change color. The test results are shown in the table below.

The product specification of embodiment 1 is as shown in table 1 below:

Table 1

Exterior Yellowish, transparent (high gloss)

Solid content 43.1wt% (high solid content) pH value (after dilution) 8 Acid value (solid content) 20 Number average molecular weight 900 hardness 1h Water resistance (25°C) 72h no change Storage stability (room temperature) No change for 180 days (good stability)

Table 1 shows that the polyester prepared by this method has the characteristics of good stability, high solid content, fast curing speed (2500w high-pressure mercury lamp 20s rapid film formation), and high gloss.

Embodiment 2 (the method two that adopts bulk polymerization method):

A preparation method for water-based photocurable unsaturated polyester (method two using bulk polymerization), which comprises the following steps:

①Under the protection of nitrogen, 20.00g trimethylolpropane monoallyl ether, 16.50g neopentyl glycol, 12.00g dimethylolpropionic acid, 11.00g phthalic anhydride, 9.00g maleic anhydride , 10.00g of adipic acid, and 0.21g of antioxidant were added to a four-port reactor with a stirrer, condenser, thermometer and dripping device, and the bulk polymerization method was adopted.

②Raise the temperature to 140°C, keep it warm for 1h, then raise the temperature to 150°C, and keep it warm for 1h (keep reflux in this state, without draining). Then it takes 1 hour to raise the temperature to 180°C, then add 9.00g of maleic anhydride, keep it warm for 2 hours, and keep the reaction at this temperature, and then keep 0.5 dehydration under the vacuum degree of 0.040MPa. The amount of nitrogen can be appropriately increased to facilitate drainage, and the acid value can reach 62.

③ Cool down to 150°C, add 0.32g of polymerization inhibitor, and continue to cool down to 95°C. 8.00 g of glycidyl methacrylate (GMA) was added dropwise into the reactor, and 0.22 g of tetramethylammonium iodide (catalyst) was added. React at this temperature until the acid value reaches 22. Cool down to 65°C, and add 2.40g of neutralizing agent for neutralization (until the pH value of the product is 7-8) to obtain the product (unsaturated polyester), the quality of the product is 90g, stirring at a speed of 800r/min 15min, then slowly add 180g of water to dilute (stirring at high speed for half an hour) to obtain water-based photocurable unsaturated polyester (water-based photocurable unsaturated polyester with hydroxyl terminals).

The antioxidant used in this experiment was triphenyl phosphite.

The polymerization inhibitor used in this experiment was hydroquinone.

The neutralizing agent used in this experiment was N,N-dimethylethanolamine.

The hardness test in this experiment is tested by the method of pencil hardness tester, and the test results are shown in the table below.

The water resistance test of this experiment is carried out in water at 25°C. The qualified standard is that the film does not bubble, discolor, or fall off. The test results are shown in the table below.

The storage stability is placed in a glass bottle at room temperature, and the qualified standard is that the resin solution does not delaminate and does not change color. The test results are shown in the table below.

The product specification of embodiment 2 is as shown in table 2 below:

Table 2

Exterior light yellow, transparent Solid content 33.3%

pH value (after dilution) 8 Acid value (solid content) twenty two Number average molecular weight 2300 hardness 3h (high hardness) Water resistance (25°C) No change for 120h (good water resistance) Storage stability (room temperature) No change for 180 days (good stability)

Table 2 shows: the polyester prepared by this method has the characteristics of high hardness, good stability, good water resistance, fast curing speed (2500w high-pressure mercury lamp 20s rapid film formation), and high gloss.

Embodiment 3 (one of the method that adopts bulk polymerization method):

A preparation method for water-based photocurable unsaturated polyester (one of the methods using bulk polymerization), which comprises the following steps:

①Under the protection of nitrogen, 15.00g trimethylolpropane monoallyl ether, 18.75g neopentyl glycol, 10.00g dimethylol propionic acid, 25.00g phthalic anhydride, 11.88g maleic anhydride , 18.75g of adipic acid, and 0.26g of antioxidants were added to a four-port reactor with a stirrer, condenser, thermometer and dripping device, and the bulk polymerization method was adopted.

②Raise the temperature to 140°C, keep it warm for 1h, then raise the temperature to 150°C, and keep it warm for 1h (keep reflux in this state, without draining). Then take 1 hour to raise the temperature to 180°C, keep it warm for 2 hours, and keep the reaction at this temperature, then keep it under vacuum 0.040MPa for 0.5-1 hour to dehydrate. It is possible to appropriately increase the amount of nitrogen to facilitate drainage, and react until the acid value reaches 150.

③ Cool down to 150°C, add 0.30g of polymerization inhibitor, and continue to cool down to 95°C. Add 14g of glycidyl methacrylate (GMA) dropwise into the reactor, and add 0.30g of tetramethylammonium iodide, and drop it in half an hour. React at this temperature until the acid value reaches 80. Cool down to 65°C, and add 10g of N,N-dimethylethanolamine neutralizing agent for neutralization (to a pH value of 7-8 of the product) to obtain the product (unsaturated polyester), the quality of which is 101g, 800r Stir at a speed of 15 min, then slowly add 135g of water to dilute (stir at high speed for half an hour), and then obtain water-based photocurable unsaturated polyester.

The antioxidant used in this experiment was triphenyl phosphite.

The polymerization inhibitor used in this experiment was hydroquinone.

The neutralizing agent used in this experiment was N,N-dimethylethanolamine.

The hardness test in this experiment is tested by the method of pencil hardness tester, and the test results are shown in the table below.

The water resistance test of this experiment is carried out in water at 25°C. The qualified standard is that the film does not bubble, discolor, or fall off. The test results are shown in the table below.

The storage stability is placed in a glass bottle at room temperature, and the qualified standard is that the resin solution does not delaminate and does not change color. The test results are shown in the table below.

The product specification of embodiment 3 is as shown in table 3 below:

table 3

Exterior light yellow, transparent Solid content 40% pH value (after dilution) 8 Acid value (solid content) 80

Number average molecular weight 1300 hardness 2 hours water resistant 96h (good water resistance) Storage stability (room temperature) No change for 180 days (good stability)

Table 3 shows: the polyester prepared by this method has the characteristics of good stability, high solid content, good water resistance, fast curing speed (2500w high-pressure mercury lamp 20s rapid film formation), and high gloss.

Example 4

It is basically the same as Example 1, except that: "neopentyl glycol" is replaced by "propylene glycol"; "adipic acid" is replaced by "suberic acid"; "hydroquinone" is replaced by "methylterephthalic acid" Phenol" instead. Product technical index is identical with embodiment 1.

Example 5

It is basically the same as Example 1, except that: "neopentyl glycol" is replaced by "ethylene glycol"; "adipic acid" is replaced by "succinic acid"; "hydroquinone" is replaced by "p-benzoquinone "replace. Product technical index is identical with embodiment 1.

Example 6

It is basically the same as Example 1, except that: "neopentyl glycol" is replaced by "hexanediol"; "adipic acid" is replaced by "malonic acid"; "hydroquinone" is replaced by "tert-butyl Catechol” instead. Product technical index is identical with embodiment 1.

Example 7

It is basically the same as Example 1, except that: "neopentyl glycol" is replaced by "diethylene glycol"; "adipic acid" is replaced by "glutaric acid"; "hydroquinone" is replaced by " 2,6-di-tert-butyl-4-methylphenol" instead. Product technical index is identical with embodiment 1.

Example 8

It is basically the same as Example 1, except that "neopentyl glycol" is replaced by "dipropylene glycol"; "hydroquinone" is replaced by "methylhydroquinone and p-benzoquinone", and methyl Hydroquinone 0.22g, p-benzoquinone 0.12g. Product technical index is identical with embodiment 1.

Example 9

The preparation method of water-based photocurable unsaturated polyester (one of the methods using bulk polymerization method), it comprises the following steps: 1) under the protection of nitrogen, mix 60g of polyol mixture, 60g of polybasic acid mixture, 0.3g of The antioxidant is added into the four-port reactor with stirring, and the bulk polymerization method is adopted;

The polyol mixture is composed of ① trimethylolpropane monoallyl ether, ② polyol and ③ dimethylol propionic acid three raw materials, wherein trimethylolpropane monoallyl ether accounts for 1% of the mass of the polyol mixture 82.5%, dimethylolpropionic acid accounts for 16.6% of the mass of the polyol mixture;

Described polybasic acid mixture is made up of following two kinds of raw materials: 1. saturated (comprising that contains benzene ring) acid anhydride, 2. and the unsaturated acid anhydride that contains carbon-carbon double bond (excluding benzene ring); Wherein, containing carbon-carbon double bond ( 52.5% of the polybasic acid mixture mass that the unsaturated acid anhydride that does not comprise benzene ring) accounts for;

The polyhydric alcohol is propylene glycol. Saturated (including those containing benzene rings) acid anhydrides are phthalic anhydrides. The unsaturated acid anhydride containing carbon-carbon double bond (excluding benzene ring) is maleic anhydride. The antioxidant is triphenyl phosphite.

2) Raise the temperature to 140°C, keep it warm for 1h, then raise the temperature to 150°C, and keep it warm for 1h (keep reflux in this state, without draining); then take 1h to raise the temperature to 180°C, and keep it warm for 2h (and keep the reaction at this temperature) , and then keep dehydration for 0.5-1h under the vacuum degree of 0.040MPa; the amount of nitrogen can be appropriately increased to facilitate drainage, and the acid value can reach the theoretical value of 168 in formula design;

3) Cool down to 150°C, add 0.5g of polymerization inhibitor, continue to cool down to 95°C; drop 15g of glycidyl methacrylate into the reactor, and add 0.3g of tetramethylammonium iodide; this temperature React under low temperature until the acid value reaches the theoretical value of 100 in formula design; cool down to 65°C, add 12g neutralizer to neutralize the product to a pH value of 7-8, and obtain the product (ie unsaturated polyester); stir the product and add water Dilution (high-speed stirring for 15min-30min, the speed of the high-speed stirring is 800-1200 rpm), the amount of water added is 100% of the mass of the product (equivalent to the entire unsaturated polyester), that is, to obtain water-based photocurable unsaturated polyester polyester.

Described polymerization inhibitor selects hydroquinone for use. The neutralizer is an organic amine neutralizer (N,N-dimethylethanolamine).

The hardness test in this experiment is tested by the method of pencil hardness tester, and the test results are shown in the table below.

The water resistance test of this experiment is carried out in water at 25°C. The qualified standard is that the film does not bubble, discolor, or fall off. The test results are shown in the table below.

The storage stability is placed in a glass bottle at room temperature, and the qualified standard is that the resin solution does not delaminate and does not change color. The test results are shown in the table below.

The product specification of embodiment 9 is as shown in table 4 below:

Table 4

Exterior Yellowish, transparent (high gloss) Solid content 50wt% pH value (after dilution) 8 Acid value (solid content) 100 Number average molecular weight 900 hardness 1h Water resistance (25°C) 48h no change Storage stability (room temperature) No change for 180 days (good stability)

Table 4 shows: the polyester prepared by this method has the characteristics of good stability, high solid content, fast curing speed (2500w high-pressure mercury lamp 20s rapid film formation), and high gloss.

Example 10

The preparation method of water-based photocurable unsaturated polyester (one of the methods using bulk polymerization method), it comprises the following steps: 1) under the protection of nitrogen, mix 40g of polyol mixture, 40g of polybasic acid mixture, 0.1g of The antioxidant is added into the four-port reactor with stirring, and the bulk polymerization method is adopted;

The polyol mixture is composed of ① trimethylolpropane monoallyl ether, ② polyol and ③ dimethylol propionic acid three raw materials, wherein trimethylolpropane monoallyl ether accounts for 1% of the mass of the polyol mixture 33%, dimethylolpropionic acid accounts for 45% of the mass of the polyol mixture;

The polybasic acid mixture is composed of the following two raw materials: ① saturated dibasic acid, ② and unsaturated dibasic acid; wherein, unsaturated dibasic acid accounts for 52.5% of the mass of the polybasic acid mixture;

The polyhydric alcohol is propylene glycol. The saturated dibasic acid is adipic acid; the unsaturated dibasic acid is fumaric acid. The antioxidant is triphenyl phosphite.

2) Raise the temperature to 140°C, keep it warm for 1h, then raise the temperature to 150°C, and keep it warm for 1h (keep reflux in this state, without draining); then take 1h to raise the temperature to 180°C, and keep it warm for 2h (and keep the reaction at this temperature) , and then keep dehydration for 0.5-1h under the vacuum degree of 0.040MPa; the amount of nitrogen can be appropriately increased to facilitate drainage, and the acid value can reach the theoretical value of 105 in formula design;

3) Cool down to 150°C, add 0.2g of polymerization inhibitor, continue to cool down to 95°C; drop 7g of glycidyl methacrylate into the reactor, and add 0.1g of tetramethylammonium iodide; this temperature React at low temperature until the acid value reaches the theoretical value of 70 in formula design; cool down to 65°C, add a neutralizer to neutralize the product to a pH value of 7-8, and obtain the product (that is, unsaturated polyester); stir the product and add water to dilute (high-speed stirring for 15min-30min, the speed of the high-speed stirring is 800-1200 rpm), the amount of water added is 200% of the mass of the product (equivalent to the entire unsaturated polyester), that is, the water-based photocurable unsaturated polyester is obtained. ester.

Described polymerization inhibitor selects hydroquinone for use. The neutralizer is an organic amine neutralizer (N,N-dimethylethanolamine).

The hardness test in this experiment is tested by the method of pencil hardness tester, and the test results are shown in the table below.

The water resistance test of this experiment is carried out in water at 25°C. The qualified standard is that the film does not bubble, discolor, or fall off. The test results are shown in the table below.

The storage stability is placed in a glass bottle at room temperature, and the qualified standard is that the resin solution does not delaminate and does not change color. The test results are shown in the table below.

The product specification of embodiment 10 is as shown in table 5 below:

table 5

Exterior Yellowish, transparent (high gloss) Solid content 33wt% pH value (after dilution) 8 Acid value (solid content) 70 Number average molecular weight 2800 hardness 3h (high hardness) Water resistance (25°C) No change for 120h (good water resistance) Storage stability (room temperature) No change for 180 days (good stability)

Table 5 shows: the polyester prepared by this method has the characteristics of good stability, high hardness, fast curing speed (2500w high-pressure mercury lamp 20s rapid film formation), and high gloss.

Example 12

It is basically the same as Example 1, except that "phthalic anhydride" is replaced by "succinic anhydride". Product technical index is identical with embodiment 1.

Example 13

It is basically the same as Example 1, except that "phthalic anhydride" is replaced by "trimellitic anhydride". Product technical index is identical with embodiment 1.

Each raw material listed in the present invention, as well as the upper and lower limits and interval values of each raw material in the present invention, and the upper and lower limits and interval values of process parameters (such as temperature, time, etc.) can all realize the present invention, and are not listed one by one here. Example.

Claims (9)

1. Water-based photocurable unsaturated polyester, characterized in that its chemical structural formula is: In formula (1): R ₁ is H or CH ₃ ; R ₂ is H or CH ₃ ; R ₃ is _R4 is

or

where p ₁ =2, 3, 4, 5, 6, 7, 8, 9 or 10, p ₂ =1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 , 14, 15, 16, 17, 18, 19 or 20, p ₃ =1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25; q ₁ is 1 or 2; q ₂ is 1 or 2; m=2, 3, 4, 5 or 6, n=0, 1, 2, 3, 4, 5, 6, 7 or 8. 2. The water-based photocurable unsaturated polyester according to claim 1, characterized in that: q1+q2=p, p=2 or 3. 3. The preparation method of water-based photocurable unsaturated polyester as claimed in claim 1, characterized in that: it comprises the following steps: 1) under the protection of nitrogen, the mass parts are 40-60 polyol mixture, 40 -60 parts by mass of polybasic acid mixture, 0.1-0.3 parts by mass of antioxidant are added to a four-port reactor with stirring; The polyol mixture is composed of ① trimethylolpropane monoallyl ether, ② polyol and ③ dimethylol propionic acid three raw materials, wherein trimethylolpropane monoallyl ether accounts for 1% of the mass of the polyol mixture 33%-82.5%, dimethylolpropionic acid accounts for 16.6-45% of the mass of the polyol mixture; The polybasic acid mixture is composed of the following two raw materials: ① a mixture of one or two of saturated dibasic acids or saturated acid anhydrides in any proportion, ② and unsaturated dibasic acids or unsaturated acid anhydrides; The saturated dibasic acid or unsaturated acid anhydride accounts for 16.6-52.5% of the mass of the polybasic acid mixture; 2) Heat up to 140°C, hold for 1 hour, then heat up to 150°C, hold for 1 hour; then heat up to 180°C for 1 hour, hold for 2 hours, and then keep for 0.5-1 hour under vacuum of 0.040MPa for dehydration; 3) Cool down to 150°C, add 0.2-0.5 mass parts of polymerization inhibitor, continue to cool down to 95°C; drop 7-15 mass parts of glycidyl methacrylate into the reactor, and add 0.1-0.3 mass parts part of tetramethylammonium iodide; cool down to 65°C, add a neutralizing agent to neutralize the product to a pH value of 7-8, and obtain the product; stir the product and add water to dilute, and the amount of water added is 50% of the product quality- 200%, that is, water-based photocurable unsaturated polyester can be obtained. 4. the preparation method of water-based photocurable unsaturated polyester as claimed in claim 1, is characterized in that: it comprises the following steps: 1. under the protection of nitrogen, the polyol mixture that mass parts are 40-60, 35- 55 parts by mass of polybasic acid mixture and 0.1-0.3 parts by mass of antioxidant are added to a four-port reactor with stirring; The polyol mixture is composed of ① trimethylolpropane monoallyl ether, ② polyol and ③ dimethylol propionic acid three raw materials, wherein trimethylolpropane monoallyl ether accounts for 1% of the mass of the polyol mixture 33%-82.5%, dimethylolpropionic acid accounts for 16.6-45% of the mass of the polyol mixture; The polybasic acid mixture is composed of the following two raw materials: ① a mixture of one or two of saturated dibasic acids or saturated acid anhydrides in any proportion, ② and unsaturated dibasic acids or unsaturated acid anhydrides; The saturated dibasic acid or unsaturated acid anhydride accounts for 8.5%-27.5% of the mass of the polybasic acid mixture; ②Raise the temperature to 140°C, keep it warm for 1h, then raise the temperature to 150°C, and keep it warm for 1h; Keep dehydration for 0.5-1h under the temperature of 0.040MPa; ③ Cool down to 150°C, add 0.2-0.5 parts by mass of polymerization inhibitor, continue to cool down to 95°C; drop 7-15 parts by mass of glycidyl methacrylate into the reactor, and add 0.1-0.3 parts by mass Tetramethylammonium iodide; lower the temperature to 65°C, add a neutralizing agent to neutralize the product to a pH value of 7-8, and obtain the product; stir the product and add water to dilute, and the amount of water added is 50%-200% of the product quality %, to obtain water-based photocurable unsaturated polyester. 5. According to the preparation method of water-based photocurable unsaturated polyester according to claim 3-4, it is characterized in that: the polyhydric alcohol is propylene glycol, ethylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol or neopentyl glycol. 6. According to the preparation method of water-based photocurable unsaturated polyester according to claim 3-4, it is characterized in that: the saturated dibasic acid is adipic acid, suberic acid, succinic acid, malonic acid, pentanedioic acid, Any one or any two or more of the diacids are mixed in any proportion; the saturated anhydride is phthalic anhydride, succinic anhydride or trimellitic anhydride; the unsaturated dibasic acid is maleic acid or fumaric acid; The unsaturated anhydride is maleic anhydride. 7. The method for preparing water-based photocurable unsaturated polyester according to claim 3-4, characterized in that: the antioxidant is triphenyl phosphite. 8. According to the preparation method of water-based photocurable unsaturated polyester according to claim 3-4, it is characterized in that: said polymerization inhibitor is selected from hydroquinone, methyl hydroquinone, p-benzoquinone, tertiary butyl Any one of catechol and 2,6-di-tert-butyl-4-methylphenol or any two or more of them are mixed in any proportion. 9. The method for preparing water-based photocurable unsaturated polyester according to claims 3-4, characterized in that: the neutralizing agent is an organic amine neutralizing agent.