CN116496450A - A kind of unsaturated polyester resin and its preparation method and application - Google Patents

Abstract

The invention discloses an unsaturated polyester resin, which comprises the following raw materials in parts by weight: 80-90 parts of phthalic anhydride, 90-95 parts of maleic anhydride, 75-90 parts of ethylene glycol, polymerization inhibitor 0.03-0.07 parts of styrene derivatives, 60-85 parts of styrene derivatives, and 0.08-0.14 parts of paraffin. The styrene derivatives have the characteristics of safety and environmental protection, good thermal stability, and good flame retardancy; the invention also discloses the Preparation method of saturated polyester resin. The unsaturated polyester resin provided by the invention has excellent thermal stability, flame retardancy and bonding strength; the unsaturated polyester resin, inorganic filler and auxiliary agent are prepared into an anchoring agent, and the anchoring agent shows excellent bonding Strength, fatigue resistance and elongation at break.

Description

A kind of unsaturated polyester resin and its preparation method and application

technical field

The invention belongs to the field of polymer materials, and in particular relates to an unsaturated polyester resin, a preparation method thereof, and an application in an anchoring agent.

Background technique

Unsaturated polyester resin is a kind of synthetic resin, which is generally formed by polycondensation of unsaturated dibasic acid and diol or saturated dibasic acid and unsaturated diol, and has ester bond and unsaturated double bond. Molecular compound, with the advantages of heat resistance, chemical corrosion resistance, good mechanical properties, electrical separation and excellent manufacturing process, is widely used in the preparation of synthetic fibers, adhesives, coatings, plastics and insulating materials.

The patent with application number CN201610736140.4 provides a corrosion-resistant unsaturated polyester resin for anchoring agent, including the following raw materials: maleic anhydride, diethylene glycol, dicyclopentadiene, isophthalic anhydride , terephthalic acid, ethylene glycol, propylene glycol, rosin, phloroglucinol, hydroquinone, styrene, dibutyl ethyl tin oxide, zinc acetate, antimony acetate, tetrabutyl titanate, cobalt isooctanoate, Cobalt cyclopentanoate, methyl ethyl ketone peroxide and hexafluorobutyl methacrylate, the raw material components of this invention are synergistic, endowing unsaturated polyester resin with excellent corrosion resistance; the patent application number CN201610743503.7 provides A high tensile strength unsaturated polyester resin for an anchoring agent, comprising the following raw materials: acid reactants, alcohol reactants, thermoplastic elastomers, initiators, accelerators, crosslinking agents, silane-modified inorganic fillers, each The synergistic effect between the components endows the unsaturated polyester resin with excellent tensile strength; in the above inventions, styrene is used as the crosslinking agent. Styrene is cheap, has a wide source of materials, low viscosity, and has good blendability with the resin , can dissolve initiators and accelerators well, and the double bond of styrene is active, and it is easy to carry out copolymerization reaction, but styrene is a carcinogen, with a low boiling point, strong volatility, flammable and explosive, and styrene is used as the exchange The bonding strength of the unsaturated polyester resin prepared by the combination agent is low.

In order to meet the market demand, it is urgent to develop an unsaturated polyester resin that is safe and environmentally friendly, has good thermal stability, good flame retardancy, and high bonding strength.

Contents of the invention

In view of the deficiencies in the prior art, the object of the present invention is to provide an unsaturated polyester resin, which is safe and environmentally friendly, has good thermal stability, good flame retardancy and high bonding strength. The present invention also provides The preparation method of the unsaturated polyester resin and its application in anchoring agent.

The technical scheme that the present invention takes for realizing the above object is:

An unsaturated polyester resin, comprising the following raw materials in parts by weight: 80-90 parts of phthalic anhydride, 90-95 parts of maleic anhydride, 75-90 parts of ethylene glycol, and 0.03-0.07 parts of polymerization inhibitor 60-85 parts of styrene derivatives, 0.08-0.14 parts of paraffin; the preparation method of said styrene derivatives is as follows:

S1. Disperse acrylic acid and epichlorohydrin in toluene, then add chromium acetate, heat up to 95-105°C, stir for 4-7h, concentrate, extract, and distill under reduced pressure to obtain intermediate 1;

S2. Disperse (4-vinylphenyl)methanol and potassium hydroxide in deionized water, then sequentially add benzyltriethylammonium chloride, intermediate 1 obtained in step S1, heat up to 55-60°C, and stir for 3 -6h, after concentration, extraction and distillation under reduced pressure, intermediate 2 was obtained;

S3. Disperse the intermediate 2 obtained in step S2 in acetone, then add phosphoric acid, heat up to 65-75°C, stir for 6-10 hours, concentrate, extract, and distill under reduced pressure to obtain a styrene derivative;

The synthetic route of styrene derivative is as follows:

The present invention uses acrylic acid and epichlorohydrin as raw materials, and under the catalysis of chromium acetate, the ring-opening reaction of epoxy compounds occurs to obtain intermediate 1; the structure of intermediate 1 contains halogen, and potassium hydroxide and benzyl triethyl Under the action of ammonium chloride, O-alkylation reaction with (4-vinylphenyl)methanol to obtain intermediate 2; intermediate 2 and phosphoric acid undergo esterification reaction under heating conditions to obtain styrene derivatives .

In order to obtain styrene derivatives and ensure product consistency, the molar ratio of acrylic acid, epichlorohydrin and chromium acetate described in step S1 is 0.9-1.2:1:0.01-0.02, and the addition of acrylic acid in toluene is 0.12- 0.15g/mL; the molar ratio of (4-vinylphenyl)methanol, potassium hydroxide, benzyltriethylammonium chloride and intermediate 1 described in step S2 is 1.0-1.4:0.7-1.1:0.04- 0.08:1, the addition of (4-vinylphenyl)methanol in deionized water is 0.11-0.16g/mL; the molar ratio of intermediate 2 and phosphoric acid described in step S3 is 1:0.8-1.3, the intermediate in acetone The addition amount of body 2 is 0.13-0.17g/mL.

Preferably, the polymerization inhibitor is one or more of 2-methylhydroquinone, hydroquinone and p-tert-butylcatechol.

The preparation method of above-mentioned unsaturated polyester resin, comprises the following steps:

(1) Under a nitrogen atmosphere, mix phthalic anhydride, maleic anhydride, ethylene glycol, and some polymerization inhibitors, and reflux at a temperature of 140-230°C until the acid value reaches 20-30mgKOH/g;

(2) Cool down to 140-160°C, add part of polymerization inhibitor, and stir evenly;

(3) Lower the temperature to 100-120°C, add styrene derivatives, the remaining polymerization inhibitor and paraffin, stir evenly, and cool to room temperature to obtain unsaturated polyester resin.

In order to prevent the risk of gelation in the production process, the addition of the polymerization inhibitor described in the step (1) is 20-25% of the total mass of the polymerization inhibitor, and the addition of the polymerization inhibitor described in the step (2) is 50-60% of the total mass of the polymerizing agent.

The present invention also provides a kind of application of unsaturated polyester resin in anchoring agent, comprises the following steps:

A1. Prepare materials according to the following components by weight: 85-115 parts of unsaturated polyester resin, 0.1-0.2 parts of N,N-dimethylaniline, 100-135 parts of silica powder filler, and 4-8 parts of curing agent , 0.3-0.7 parts of coupling agent, 2-5 parts of aluminum powder;

A2. Stir unsaturated polyester resin, N,N-dimethylaniline, aluminum powder, and coupling agent at 35-45°C for 20-30 minutes, cool to room temperature, then add silicon micropowder filler and continue stirring for 15-20 minutes;

A3. When using, mix the product obtained in step A2 with the curing agent and apply it to the part to be anchored;

Wherein, the curing agent is one or more of benzoyl peroxide, dibenzoyl peroxide and lauroyl peroxide, and the coupling agent is silane coupling agent KH-570 or silane coupling agent KH -560.

The present invention has the following beneficial effects: the present invention chemically modifies styrene, introduces acrylate and phosphate structures into styrene, and obtains styrene derivatives, which are safe and environmentally friendly, have good thermal stability, and The phosphate group and the carboxylate group in the acrylate can further improve the flame retardant performance of styrene. At the same time, the double bond in the acrylate structure makes the styrene derivative have a higher copolymerization reaction. Activity; unsaturated polyester resin prepared with styrene derivatives as cross-linking agent has excellent thermal stability, flame retardancy and bonding strength; unsaturated polyester resin, inorganic filler and auxiliary agent are prepared as anchoring agent, The anchoring agent exhibits excellent bonding strength, fatigue resistance and elongation at break.

Detailed ways

The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application. Apparently, the described embodiments are only some of the embodiments of the present application, not all of them. Based on the embodiments in this application, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the scope of protection of this application. The raw materials used in the following examples are common commercially available products.

Example 1

A preparation method of styrene derivatives, comprising the following steps:

S1. Disperse acrylic acid and epichlorohydrin in toluene, then add chromium acetate, heat up to 100°C, stir for 7 hours, remove part of the toluene by concentration, then add deionized water and ethyl acetate for extraction, take the organic phase and decompress Distill to obtain intermediate 1, wherein the mol ratio of acrylic acid, epichlorohydrin and chromium acetate is 1.1:1:0.015, the addition of acrylic acid in toluene is 0.13g/mL, and the volume ratio of deionized water and ethyl acetate is 1:1;

S2. Disperse (4-vinylphenyl)methanol and potassium hydroxide in deionized water, then sequentially add benzyltriethylammonium chloride, intermediate 1 obtained in step S1, heat up to 60°C, stir for 4h, and concentrate After extraction with ethyl acetate, the organic phase is distilled under reduced pressure to obtain intermediate 2, wherein the mol ratio of (4-vinylphenyl)methanol, potassium hydroxide, benzyltriethylammonium chloride to intermediate 1 is 1.2:0.9:0.05:1, the amount of (4-vinylphenyl)methanol added in deionized water is 0.14g/mL;

S3. Disperse the intermediate 2 obtained in step S2 in acetone, then add phosphoric acid, raise the temperature to 70°C, stir for 8 hours, remove part of the acetone through concentration, extract with ethyl acetate, take the organic phase and distill under reduced pressure to obtain the styrene derivative Thing, wherein the mol ratio of intermediate 2 and phosphoric acid is 1:1.2, and the add-on of intermediate 2 in acetone is 0.16g/mL;

The synthetic route of styrene derivative is as follows:

The NMR results of styrene derivatives are: ¹ HNMR (300MHz, acetone-d6) δ7.67(d, 2H), 7.23(d, 2H), 6.70-6.72(m, 1H), 6.41(d, 1H), 6.10-6.14(m, 1H), 5.85(d, 1H), 5.74(d, 1H), 5.25(d, 1H), 4.94-4.97(m, 1H), 4.63(s, 2H), 4.58(d, 1H), 4.34(d, 1H), 4.21(s, 2H), 3.80(d, 1H), 3.54(d, 1H).

A preparation method of unsaturated polyester resin, comprising the following steps:

(1) Prepare materials according to the following components in parts by weight: 80 parts of phthalic anhydride, 90 parts of maleic anhydride, 90 parts of ethylene glycol, 0.05 parts of polymerization inhibitor, 70 parts of styrene derivatives, paraffin wax 0.1 copies;

(2) Under a nitrogen atmosphere, mix phthalic anhydride, maleic anhydride, ethylene glycol, and some polymerization inhibitors, and reflux at 220°C until the acid value reaches 20-30mgKOH/g;

(3) Cool down to 150°C, add part of polymerization inhibitor, and stir evenly;

(4) Cool down to 100°C, add styrene derivatives, remaining polymerization inhibitor and paraffin, stir evenly, and cool to room temperature to obtain unsaturated polyester resin;

Wherein, the polymerization inhibitor is p-tert-butylcatechol, and the addition amount of the polymerization inhibitor described in the step (2) is 25% of the total mass of the polymerization inhibitor, and the addition of the polymerization inhibitor described in the step (3) The amount is 50% of the total mass of the polymerization inhibitor.

Example 2

A kind of application of unsaturated polyester resin in anchoring agent, comprises the following steps:

A1. Prepare materials according to the following components in parts by weight: 105 parts of unsaturated polyester resin prepared in Example 1, 0.1 part of N,N-dimethylaniline, 120 parts of silicon micropowder filler (1250 mesh, purchased From Henan Lierte New Material Co., Ltd.), 5 parts of curing agent, 0.4 part of coupling agent, 3 parts of aluminum powder (the number of mesh is 200 mesh, purchased from Changyuan City Mingyu Aluminum Industry Co., Ltd.);

A2. Stir unsaturated polyester resin, N,N-dimethylaniline, aluminum powder, and coupling agent at 40°C for 30 minutes, cool to room temperature, then add silicon micropowder filler and continue stirring for 15 minutes;

A3. When using, mix the product obtained in step A2 with the curing agent and apply it to the part to be anchored;

Wherein, the curing agent is benzoyl peroxide, and the coupling agent is silane coupling agent KH-570.

Example 3

A method for preparing an unsaturated polyester resin is prepared according to the method of Example 1, with the difference that: the number of parts of styrene derivatives is changed to 60 parts, and the parts by weight of other raw materials remain unchanged.

Example 4

A method for preparing an unsaturated polyester resin, prepared according to the method of Example 1, with the difference that: the number of parts of styrene derivatives is changed to 75 parts, and the parts by weight of other raw materials remain unchanged.

Example 5

A method for preparing an unsaturated polyester resin, prepared according to the method of Example 1, with the difference that: the number of parts of styrene derivatives is changed to 85 parts, and the parts by weight of other raw materials remain unchanged.

Comparative example 1

A method for preparing an unsaturated polyester resin is prepared according to the method of Example 1, with the difference that: the parts by weight of styrene derivatives are changed to 40 parts, and the parts by weight of other raw materials remain unchanged.

Comparative example 2

A preparation method of unsaturated polyester resin, prepared according to the method of Example 1, the difference is that: styrene derivatives are replaced by styrene.

The application of the unsaturated polyester resin described in Examples 3-5 and Comparative Examples 1-2 in the anchoring agent was prepared according to the process described in Example 2.

The flame retardant performance test of the unsaturated polyester resin prepared in Example 1 and Comparative Example 2 is carried out below. Experimental procedure: Immerse glass fiber cloth (12cm×12cm) in unsaturated polyester resin, ultrasonically treat it for 5 minutes, take it out and dry it, and use the same flame to ignite the center of the bottom edge of the sample in the vertical direction. The experimental results show that the glass fiber cloth treated with the unsaturated polyester resin obtained in Comparative Example 2 shows burning spread and sufficient in the test, and then causes the fire to burn in a large area, while the glass fiber cloth treated with the unsaturated polyester resin obtained in Example 1 When the glass fiber cloth is tested, the fire only exists on the combustion path and does not extend to other directions, and it is quickly extinguished at the end of the fire; the unsaturated polyester resin prepared in Example 1 shows good flame retardancy.

The unsaturated polyester resins prepared in Example 1, Examples 3-5, and Comparative Examples 1-2 are prepared into resin glue respectively, and related performance tests are carried out. The resin glue preparation method is: 100 kilograms of unsaturated polyester resin , 0.8 kg of 1% cobalt isooctanoate, 0.3 kg of BYK-W9010 additive, 100 kg of heavy calcium carbonate powder and mix evenly, and add 1.5 kg of methyl ethyl ketone peroxide to disperse evenly when used. The gel time and 80°C thermal stability test are carried out in accordance with GB/T7193-2008 "Unsaturated Polyester Resin Test Method"; the storage period test conditions are (25±1)°C, humidity 55±1%; the bond strength test will be The resin glue is coated on the PMMA acrylic plate, and the test sample is obtained after pressing, drying and curing. The bonding area is 25mm×5mm, and the thickness of the adhesive layer is 0.1mm. Use a universal testing machine to pull the two plates apart in opposite directions , tested at an ambient temperature of 25°C; the results are shown in Table 1. As can be seen from the data in the table, compared with Comparative Example 1-2, the gel time of the resin glue prepared by the unsaturated polyester resin obtained in Example 1 and Example 3-5 is short, and the thermal stability is good at 80 ° C. The bonding strength is high, and the overall performance of the unsaturated polyester resin prepared in Example 1 is the best; Compared with Comparative Example 2, the addition of styrene derivatives in Comparative Example 1 makes the gel time of the unsaturated polyester resin , thermal stability at 80°C, and bonding strength have been improved to a certain extent; compared with Comparative Example 2, the styrene derivatives added in Example 1, Example 3, and Comparative Example 1 have a certain effect on the effect of unsaturated polyester resin Storage stability has little effect.

Table 1 Unsaturated polyester resin performance test results

Test items Gel time/min 80℃ thermal stability/h Storage period/day Adhesive strength/MPa Example 1 11.7 114 90 4.15 Example 3 12.6 109 90 4.02 Example 4 12.5 111 88 4.09 Example 5 13.8 106 87 4.04 Comparative example 1 17.2 85 90 3.11 Comparative example 2 20.9 60 90 1.87

The anchoring agents prepared in Example 2 and Comparative Examples 1-2 were tested for related performances below. Adhesive strength and fatigue resistance are tested in accordance with GB50728-2011 "Technical Specifications for Safety Appraisal of Engineering Structure Reinforcement Materials" in dry (C30, 25°C, 7d) and wet (C30, 25°C, 7d) state constrained pull-out bonding Strength and fatigue resistance (3 million times, the specimen is not damaged); the elongation at break test is carried out in accordance with GB/T2567-2021 "Resin Casting Body Performance Test Method"; the results are shown in Table 2. As can be seen from the table, compared with Comparative Example 1-2, the anchoring agent prepared in Example 2 shows excellent bonding strength, fatigue resistance and elongation at break; compared with Comparative Example 2, Comparative Example The styrene derivatives added in 1 can greatly improve the performance of the anchoring agent.

Table 2 Anchoring agent performance test results

The invention chemically modifies styrene, introduces acrylate and phosphate structures into styrene, and obtains styrene derivatives. The styrene derivatives have the characteristics of safety and environmental protection, good thermal stability, and good flame retardancy. The unsaturated polyester resin prepared with styrene derivatives as cross-linking agent has excellent thermal stability, flame retardancy and bonding strength; the unsaturated polyester resin, inorganic filler and auxiliary agent are prepared as anchoring agent, and the anchoring agent Exhibits excellent bonding strength, fatigue resistance and elongation at break.

Although the embodiments of the present application have been shown and described, those skilled in the art can understand that various changes, modifications and substitutions can be made to these embodiments without departing from the principle and spirit of the present application. and modifications, the scope of the application is defined by the appended claims and their equivalents.

Claims (9)

1. an unsaturated polyester resin, is characterized in that, comprises the raw material of following parts by weight: phthalic anhydride 80-90 parts, maleic anhydride 90-95 parts, ethylene glycol 75-90 parts, 0.03-0.07 part of polymerization inhibitor, 60-85 part of styrene derivative, 0.08-0.14 part of paraffin; the preparation method of said styrene derivative is as follows: S1. Disperse acrylic acid and epichlorohydrin in toluene, then add chromium acetate, heat up to 95-105°C, stir for 4-7h, concentrate, extract, and distill under reduced pressure to obtain intermediate 1, the structural formula of intermediate 1 for: S2. Disperse (4-vinylphenyl)methanol and potassium hydroxide in deionized water, then sequentially add benzyltriethylammonium chloride, intermediate 1 obtained in step S1, heat up to 55-60°C, and stir for 3 -6h, through concentration, extraction, and distillation under reduced pressure, intermediate 2 is obtained, and the structural formula of intermediate 2 is: S3. Disperse the intermediate 2 obtained in step S2 in acetone, then add phosphoric acid, heat up to 65-75°C, stir for 6-10h, concentrate, extract, and distill under reduced pressure to obtain styrene derivatives, styrene derivatives The structural formula is: 2. a kind of unsaturated polyester resin according to claim 1, is characterized in that, the mol ratio of acrylic acid, epichlorohydrin and chromium acetate described in step S1 is 0.9-1.2:1:0.01-0.02, toluene The amount of acrylic acid added is 0.12-0.15g/mL. 3. a kind of unsaturated polyester resin according to claim 1, is characterized in that, (4-vinylphenyl) methyl alcohol, potassium hydroxide, benzyltriethylammonium chloride and intermediate described in step S2 The molar ratio of body 1 is 1.0-1.4:0.7-1.1:0.04-0.08:1, and the amount of (4-vinylphenyl)methanol added in deionized water is 0.11-0.16g/mL. 4. a kind of unsaturated polyester resin according to claim 1 is characterized in that, the mol ratio of intermediate 2 and phosphoric acid described in step S3 is 1:0.8-1.3, and the add-on of intermediate 2 in acetone is 0.13-0.17g/mL. 5. a kind of unsaturated polyester resin according to claim 1, is characterized in that, described inhibitor is one in 2-methylhydroquinone, hydroquinone, p-tert-butylcatechol species or two or more. 6. according to the preparation method of a kind of unsaturated polyester resin described in any one of claim 1-5, it is characterized in that, comprising the following steps: (1) Under a nitrogen atmosphere, mix phthalic anhydride, maleic anhydride, ethylene glycol, and some polymerization inhibitors, and reflux at a temperature of 140-230°C until the acid value reaches 20-30mgKOH/g; (2) Cool down to 140-160°C, add part of polymerization inhibitor, and stir evenly; (3) Lower the temperature to 100-120°C, add styrene derivatives, the remaining polymerization inhibitor and paraffin, stir evenly, and cool to room temperature to obtain unsaturated polyester resin. 7. the preparation method of a kind of unsaturated polyester resin according to claim 6 is characterized in that, the add-on of stopper described in step (1) is 20-25% of stopper gross mass, step The adding amount of the polymerization inhibitor described in (2) is 50-60% of the total mass of the polymerization inhibitor. 8. according to the application of a kind of unsaturated polyester resin described in any one of claim 1-5 in anchoring agent, it is characterized in that, comprises the following steps: A1. Prepare materials according to the following components by weight: 85-115 parts of unsaturated polyester resin, 0.1-0.2 parts of N,N-dimethylaniline, 100-135 parts of silica powder filler, and 4-8 parts of curing agent , 0.3-0.7 parts of coupling agent, 2-5 parts of aluminum powder; A2. Stir unsaturated polyester resin, N,N-dimethylaniline, aluminum powder, and coupling agent at 35-45°C for 20-30 minutes, cool to room temperature, then add silicon micropowder filler and continue stirring for 15-20 minutes; A3. When using, mix the product obtained in step A2 with the curing agent, and apply it to the site to be anchored. 9. the application of a kind of unsaturated polyester resin in anchoring agent according to claim 8, is characterized in that, described curing agent is benzoyl peroxide, dibenzoyl peroxide, lauroyl peroxide One or more than two, the coupling agent is silane coupling agent KH-570 or silane coupling agent KH-560.