Unsaturated polyester resin for repairing ultraviolet curing pipeline

Abstract

The invention discloses unsaturated polyester resin for repairing an ultraviolet curing pipeline, and belongs to the technical field of preparation of unsaturated polyester resin. The unsaturated polyester resin for repairing the ultraviolet curing pipeline is prepared from the following components in parts by weight: 20 to 30 parts of maleic anhydride, 15 to 25 parts of phthalic anhydride, 19.8 to 34.1 parts of ethylene glycol, 24.3 to 41.8 parts of propylene glycol, 4 to 10 parts of a composite ultraviolet curing agent, 1 to 3 parts of a modified temperature-sensitive agent, 2 to 5 parts of carbon nanotubes, 0.1 to 0.5 part of hydroquinone and 0.5 to 1.2 parts of an antioxidant 1010. The unsaturated polyester resin prepared by the method has excellent temperature-responsive phase change, mechanical property, catalytic photocuring property and chemical corrosion resistance.

Description

Technical Field

[0001] The present invention belongs to the technical field of unsaturated polyester resin preparation, and particularly relates to an unsaturated polyester resin for ultraviolet-curable pipeline repair. Background Art

[0002] Unsaturated polyester resin is formed by the polycondensation of saturated diols and saturated and unsaturated dibasic acids. After this polymer is dissolved in active monomers, a resin solution with good fluidity can be formed. By adding additives such as initiators and promoters, the unsaturated polyester resin can be rapidly cured at room temperature or slightly higher temperatures to form a cured product with high strength and corrosion resistance. In the field of pipeline repair, traditional repair methods such as replacing new pipelines and excavation repair not only have high costs and long construction periods, but also have a greater impact on the environment. With the progress of technology and the improvement of environmental awareness, people have started to demand more efficient and environmentally friendly pipeline repair methods. The ultraviolet-curable pipeline repair technology has emerged as the times require. It uses ultraviolet light to initiate the curing reaction of unsaturated polyester resin, tightly bonding the repair material to the inner wall of the pipeline to form a smooth and solid repair layer.

[0003] Patent CN113667106B discloses an ultraviolet-curable itaconic acid-based polyester resin, which includes the following components in weight percentages: small molecule polyols 48.86 - 52%; itaconic acid 19.3 - 22.16%; dibasic acid 28 - 28.16%; catalyst 0.22 - 0.4%; first inhibitor 0.02%; second inhibitor 0.06%; antioxidant 0.34 - 0.4%. This method synthesizes the itaconic acid-based polyester resin by the melt polycondensation method, solving the defects in the performance of unsaturated polyester resin in photocuring applications, especially in the application of photocuring wood primers, such as poor surface drying property and difficulty in sanding. It can completely replace some ordinary photocuring resins such as polyester acrylate and be applied to photocuring wood primers, and can also be applied to many fields such as stone coatings, wood primer topcoats, and plastic paints. However, there is still room for improvement in the ultraviolet curing performance, mechanical properties, and corrosion resistance of the resin prepared by this method. Summary of the Invention

[0004] The purpose of the present invention is to provide an unsaturated polyester resin for ultraviolet-curable pipeline repair, aiming to solve the technical problems of poor ultraviolet curing performance, mechanical properties, and mechanical properties of unsaturated polyester resin in the prior art.

[0005] To achieve the above purpose, the present invention adopts the following technical solutions:

[0006] The present invention provides an unsaturated polyester resin for ultraviolet-curable pipeline repair, which is composed of the following components in parts by weight: 20-30 parts of maleic anhydride, 15-25 parts of phthalic anhydride, 19.8-34.1 parts of ethylene glycol, 24.3-41.8 parts of propylene glycol, 4-10 parts of a composite ultraviolet curing agent, 1-3 parts of a modified thermosensitive agent, 2-5 parts of carbon nanotubes, 0.1-0.5 part of hydroquinone, and 0.5-1.2 part of antioxidant 1010. Among them, the composite ultraviolet curing agent is prepared from rosin acid, 1,9-nonanediol, epichlorohydrin, and 2-methylacrylic acid as the main raw materials, and the modified thermosensitive agent is prepared from bis(2-ethoxyethyl)amine, triethylamine, isobutenoyl chloride, dimethylethylsilane, and tris(pentafluorophenyl)borane as the main raw materials.

[0007] Preferably, the preparation method of the composite ultraviolet curing agent includes the following steps:

[0008] Q1: Add rosin acid, zinc chloride, and oxalic acid into a container, heat and stir in an oil bath, then cool down and add ethanol, stir to dissolve, filter, then dropwise add to distilled water, filter, dry, dissolve, and purify to obtain Compound 1;

[0009] Q2: Add 1,9-nonanediol, tetrabutylammonium bromide, and epichlorohydrin into a container, stir and react in a water bath, then add sodium hydroxide, add it in three equal batches, and continue to react after adding. After the reaction is completed, filter by suction, rotary evaporate, filter by suction, and collect the filtrate to obtain Compound 2;

[0010] Q3: Add Compound 1 into a container, then add Compound 2 and concentrated sulfuric acid, heat and stir to react. After the reaction is completed, filter by suction to obtain Compound 3; Add Compound 3, triphenylphosphine, and sodium nitrite into a container, heat and stir, then slowly dropwise add 2-methylacrylic acid, heat and stir in an oil bath, and after stirring, obtain the composite ultraviolet curing agent.

[0011] In the above process, the synthesis reaction formula of the composite ultraviolet curing agent is as follows:

[0012]

[0013] The results of mass spectrometry analysis of Compound 1 are as follows: m / z: 300.21 (100.0%), 301.21 (21.7%), 302.22 (2.3%); the results of mass spectrometry analysis of Compound 2 are as follows: m / z: 216.17 (100.0%), 217.18 (13.4%), 218.18 (1.4%); the results of mass spectrometry analysis of Compound 3 are as follows: m / z: 498.37 (100.0%), 499.37 (34.6%), 500.38 (6.9%), 501.38 (1.0%); the results of mass spectrometry analysis of the composite UV curing agent are as follows: m / z: 584.41 (100.0%), 585.41 (39.8%), 586.41 (8.6%), 587.42 (1.5%).

[0014] Preferably, in Q1, the dosage ratio of rosin acid, zinc chloride, oxalic acid and ethanol is (11.8 - 12.5) g : (0.32 - 0.41) g : (0.43 - 0.58) g : (18 - 23) mL. The temperature for heating and stirring in an oil bath is 180 - 200 °C, the stirring time is 8 - 10 h, the temperature is lowered to 100 - 110 °C, the drying temperature is 34 - 38 °C, and the drying time is 20 - 24 h.

[0015] Preferably, in Q2, the dosage ratio of 1,9 - nonanediol, tetrabutylammonium bromide, epichlorohydrin and sodium hydroxide is (30.12 - 31.48) g : (3.08 - 3.36) g : (2.33 - 2.48) g : (14.8 - 16.7) g. The temperature for stirring and reacting in a water bath is 60 - 65 °C, the reaction time is 30 - 45 min, with an interval of 30 - 45 min, and the continued reaction time is 1 - 2 h.

[0016] Preferably, in Q3, the dosage ratio of Compound 1 and Compound 2 is (9.94 - 10.15) g : (25.8 - 29.3) g. The temperature for heating and stirring the reaction is 60 - 80 °C, and the reaction time is 6 - 8 h; the dosage ratio of Compound 3, triphenylphosphine, sodium nitrite and methacrylic acid is (10.21 - 11.03) g : (0.12 - 0.16) g : (0.011 - 0.018) g : (4.87 - 5.12) g. The temperature for heating and stirring is increased to 80 - 85 °C, the temperature for heating in an oil bath is 80 - 85 °C, and the stirring time is 10 - 12 h.

[0017] Preferably, the preparation method of the modified thermosensitive agent includes the following steps:

[0018] S1: Add bis(2-ethoxyethyl)amine and triethylamine into a reaction vessel filled with dichloromethane, stir at low temperature, dissolve methacryloyl chloride in dichloromethane and then slowly add it dropwise into the reaction vessel, let it stand at room temperature, filter, wash, extract, dry, rotary evaporate, and distill under reduced pressure to obtain monomer A;

[0019] S2: Add monomer A into a container containing dichloromethane, then successively add N,N-dimethylacrylamide, dimethylethylsilane and tris(pentafluorophenyl)borane, stir at room temperature, continue to add N,N-dimethylacrylamide, monomer A and dichloromethane, stir and react at room temperature. After the reaction is completed, add methanol and purify to obtain the modified thermosensitive agent.

[0020] In the above process, first, bis(2-ethoxyethyl)amine and methacryloyl chloride undergo a nucleophilic substitution reaction to obtain monomer A. Tris(pentafluorophenyl)borane activates the Si-H bond in dimethylethylsilane, enabling it to undergo an addition reaction with monomer A and N,N-dimethylacrylamide. Subsequently, an addition reaction continues to obtain the modified thermosensitive agent.

[0021] Preferably, in S1, the dosage ratio of bis(2-ethoxyethyl)amine, triethylamine and methacryloyl chloride is (40.2 - 41.8) g : (38.1 - 39.4) g : (24.8 - 25.6) g, the low-temperature stirring temperature is 0 - 2 °C, the stirring time is 15 - 25 min, the standing time is 10 - 12 h, wash with dichloromethane, extract successively with 1 mol / L hydrochloric acid, distilled water and saturated sodium chloride solution, and dry with anhydrous magnesium sulfate.

[0022] Preferably, in S2, the dosage ratio of monomer A, N,N-dimethylacrylamide, dimethylethylsilane, tris(pentafluorophenyl)borane, the continuously added monomer A and the continuously added N,N-dimethylacrylamide is (0.18 - 0.25) g : (0.091 - 0.112) g : (5.12 - 5.38) mL : (0.01 - 0.011) g : (0.18 - 0.25) g : (0.092 - 0.108) g, the room-temperature stirring time is 8 - 10 h, and the room-temperature continuous stirring time is 16 - 20 h.

[0023] Preferably, the preparation method of the unsaturated polyester resin for ultraviolet-curable pipeline repair includes the following steps:

[0024] Step 1: Add maleic anhydride, phthalic anhydride, ethylene glycol and propylene glycol into a reaction kettle, heat and stir to react to obtain a composite resin;

[0025] Step 2: Sequentially add a composite ultraviolet curing agent, a modified thermosensitive agent, carbon nanotubes, hydroquinone, and antioxidant 1010 to the composite resin, stir and mix to obtain an unsaturated polyester resin for ultraviolet light-curing pipeline repair.

[0026] In summary, due to the adoption of the above technical solutions, the beneficial effects of the present invention are as follows:

[0027] 1. The present invention first uses rosin acid, 1,9-nonanediol, epichlorohydrin, and 2-methylacrylic acid as the main raw materials to prepare a composite ultraviolet curing agent. Subsequently, using bis(2-ethoxyethyl)amine, triethylamine, isobutenoyl chloride, dimethylethylsilane, and tris(pentafluorophenyl)borane as the main raw materials, a modified thermosensitive agent is prepared. Adding the composite ultraviolet curing agent and the modified thermosensitive agent to the preparation process of the unsaturated polyester resin can effectively improve the temperature-responsive phase change, mechanical properties, catalytic photocuring property, and chemical corrosion resistance of the unsaturated polyester resin.

[0028] 2. Adding the prepared composite ultraviolet curing agent to the unsaturated polyester resin can effectively shorten the ultraviolet light-curing time, improve the construction efficiency, and at the same time can also improve the mechanical properties and chemical corrosion resistance of the unsaturated polyester resin.

[0029] 3. Adding the prepared modified thermosensitive agent to the unsaturated polyester resin can effectively improve its temperature-responsive phase change, and can also improve the crosslinking density and mechanical properties. Specific Embodiments

[0030] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

[0031] Example 1: This example discloses a preparation method of a composite ultraviolet curing agent, including the following steps:

[0032] Q1: Add 12.1 g of rosin acid, 0.36 g of zinc chloride, and 0.51 g of oxalic acid to a container, heat and stir in an oil bath at 190 °C for 8 h, then cool to 100 °C, add 20 mL of ethanol, stir to dissolve, filter, and then dropwise add to 100 mL of distilled water, filter, dry at 38 °C for 24 h, dissolve, and purify to obtain Compound 1;

[0033] Q2: Add 30.8 g of 1,9-nonanediol, 3.22 g of tetrabutylammonium bromide, and 2.41 g of epichlorohydrin into a container, stir and react in a 65 °C water bath for 45 min, then add 15.7 g of sodium hydroxide, add it evenly in three batches at intervals of 30 min. After the addition, continue to react for 2 h. After the reaction is completed, filter by suction, rotary evaporate, filter by suction again, and collect the filtrate to obtain Compound 2;

[0034] Q3: Add 10.04 g of Compound 1 into a container, then add 27.5 g of Compound 2 and 0.04 mL of concentrated sulfuric acid with a volume fraction of 98 vt%, heat and stir at 70 °C for 8 h. After the reaction is completed, filter by suction to obtain Compound 3; Add 10.62 g of Compound 3, 0.14 g of triphenylphosphine, and 0.014 g of sodium nitrite into a container, heat and stir at 85 °C, then slowly dropwise add 5.01 g of 2-methylacrylic acid, heat and stir in an 85 °C oil bath for 12 h. After stirring is completed, a composite ultraviolet curing agent is obtained.

[0035] This example discloses a preparation method of a modified thermosensitive agent, including the following steps:

[0036] S1: Add 41 g of bis(2-ethoxyethyl)amine and 38.7 g of triethylamine into a reaction container containing 700 mL of dichloromethane, stir at low temperature of 0 °C for 15 min, dissolve 25.2 g of isobutyryl chloride in 80 mL of dichloromethane and then slowly drop it into the reaction container, let it stand at room temperature for 12 h, filter, wash with dichloromethane, extract successively with 1 mol / L hydrochloric acid, distilled water, and saturated sodium chloride solution, dry with anhydrous magnesium sulfate, rotary evaporate, and distill under reduced pressure to obtain monomer A;

[0037] S2: Add 0.21 g of monomer A into a container containing 1.98 mL of dichloromethane, then successively add 0.101 g of N,N-dimethylacrylamide, 5.25 mL of dimethylethylsilane, and 0.0105 g of tris(pentafluorophenyl)borane, stir at room temperature for 8 h, continue to add 0.1 g of N,N-dimethylacrylamide, 0.21 g of monomer A, and 1.98 mL of dichloromethane, and continue to stir and react at room temperature for 18 h. After the reaction is completed, add methanol and purify to obtain the modified thermosensitive agent.

[0038] This example discloses an unsaturated polyester resin for ultraviolet curing pipeline repair, which is composed of the following components in parts by weight: 25 parts of maleic anhydride, 20 parts of phthalic anhydride, 26.9 parts of ethylene glycol, 33.1 parts of propylene glycol, 7 parts of composite ultraviolet curing agent, 2 parts of modified thermosensitive agent, 3.5 parts of carbon nanotubes, 0.3 part of hydroquinone, and 0.8 part of antioxidant 1010.

[0039] This example discloses a preparation method of an unsaturated polyester resin for ultraviolet curing pipeline repair, including the following steps:

[0040] Step 1: Add maleic anhydride, phthalic anhydride, ethylene glycol and propylene glycol into a reaction kettle, heat and stir to react to obtain a composite resin.

[0041] Step 2: Sequentially add a composite ultraviolet curing agent, a modified thermosensitive agent, carbon nanotubes, hydroquinone and antioxidant 1010 into the composite resin, stir and mix to obtain an unsaturated polyester resin for ultraviolet light curing pipeline repair.

[0042] Example 2: This example discloses a preparation method of a composite ultraviolet curing agent, including the following steps:

[0043] Q1: Add 11.8 g of rosin acid, 0.32 g of zinc chloride and 0.43 g of oxalic acid into a container, heat and stir in an oil bath at 190 °C for 8 h, then cool down to 100 °C, add 18 mL of ethanol, stir to dissolve, filter, then dropwise add it into 100 mL of distilled water, filter, dry at 38 °C for 24 h, dissolve and purify to obtain Compound 1.

[0044] Q2: Add 30.12 g of 1,9-nonanediol, 3.08 g of tetrabutylammonium bromide and 2.33 g of epichlorohydrin into a container, stir and react in a water bath at 65 °C for 45 min, then add 14.8 g of sodium hydroxide, add it in three equal batches at intervals of 30 min. After adding, continue to react for 2 h. After the reaction ends, filter by suction, rotary evaporate, filter by suction, and collect the filtrate to obtain Compound 2.

[0045] Q3: Add 9.94 g of Compound 1 into a container, then add 25.8 g of Compound 2 and 0.04 mL of concentrated sulfuric acid with a volume fraction of 98 vt%, heat and stir to react at 70 °C for 8 h. After the reaction ends, filter by suction to obtain Compound 3. Add 10.21 g of Compound 3, 0.12 g of triphenylphosphine and 0.011 g of sodium nitrite into a container, heat and stir at 85 °C, then slowly dropwise add 4.87 g of 2-methylacrylic acid, heat and stir in an oil bath at 85 °C for 12 h. After stirring ends, obtain the composite ultraviolet curing agent.

[0046] This example discloses a preparation method of a modified thermosensitive agent, including the following steps:

[0047] S1: Add 40.2 g of bis(2-ethoxyethyl)amine and 38.1 g of triethylamine into a reaction container filled with 700 mL of dichloromethane, stir at low temperature of 0 °C for 15 min, dissolve 24.8 g of isobutenoyl chloride in 80 mL of dichloromethane and slowly dropwise add it into the reaction container, let it stand at room temperature for 12 h, filter, wash with dichloromethane, extract with 1 mol / L hydrochloric acid, distilled water and saturated sodium chloride solution in sequence, dry with anhydrous magnesium sulfate, rotary evaporate and distill under reduced pressure to obtain Monomer A.

[0048] S2: Add 0.18 g of monomer A into a container containing 1.98 mL of dichloromethane. Subsequently, add 0.091 g of N,N-dimethylacrylamide, 5.12 mL of dimethylethylsilane, and 0.01 g of tris(pentafluorophenyl)borane in sequence. Stir at room temperature for 8 h. Then continue to add 0.092 g of N,N-dimethylacrylamide, 0.18 g of monomer A, and 1.98 mL of dichloromethane, and continue to stir and react at room temperature for 18 h. After the reaction is completed, add methanol and purify to obtain the modified thermosensitive agent.

[0049] This example discloses an unsaturated polyester resin for ultraviolet curing pipeline repair, which is composed of the following components in parts by weight: 20 parts of maleic anhydride, 25 parts of phthalic anhydride, 19.8 parts of ethylene glycol, 24.3 parts of propylene glycol, 10 parts of a composite ultraviolet curing agent, 1 part of a modified thermosensitive agent, 2 parts of carbon nanotubes, 0.5 part of hydroquinone, and 0.5 part of antioxidant 1010.

[0050] This example discloses a preparation method of an unsaturated polyester resin for ultraviolet curing pipeline repair, including the following steps:

[0051] Step 1: Add maleic anhydride, phthalic anhydride, ethylene glycol, and propylene glycol into a reaction kettle, heat and stir to react to obtain a composite resin;

[0052] Step 2: Sequentially add a composite ultraviolet curing agent, a modified thermosensitive agent, carbon nanotubes, hydroquinone, and antioxidant 1010 to the composite resin, stir and mix to obtain an unsaturated polyester resin for ultraviolet curing pipeline repair.

[0053] Example 3: This example discloses a preparation method of a composite ultraviolet curing agent, including the following steps:

[0054] Q1: Add 12.5 g of rosin acid, 0.41 g of zinc chloride, and 0.58 g of oxalic acid into a container. After heating and stirring in an oil bath at 190 °C for 8 h, cool down to 100 °C, add 23 mL of ethanol, stir to dissolve, filter, then dropwise add to 100 mL of distilled water, filter, dry at 38 °C for 24 h, dissolve, and purify to obtain Compound 1;

[0055] Q2: Add 31.48 g of 1,9-nonanediol, 3.36 g of tetrabutylammonium bromide, and 2.48 g of epichlorohydrin into a container. Stir and react in a water bath at 65 °C for 45 min. Then add 16.7 g of sodium hydroxide, add it in three equal batches at intervals of 30 min. After adding, continue to react for 2 h. After the reaction is completed, carry out suction filtration, rotary evaporation, suction filtration, and collect the filtrate to obtain Compound 2;

[0056] Q3: Add 10.15 g of Compound 1 into a container, then add 29.13 g of Compound 2 and 0.04 mL of concentrated sulfuric acid with a volume fraction of 98 vt%, heat and stir the reaction at 70 °C for 8 h. After the reaction is completed, perform suction filtration to obtain Compound 3; add 11.03 g of Compound 3, 0.16 g of triphenylphosphine, and 0.018 g of sodium nitrite into a container, heat and stir at 85 °C, then slowly dropwise add 5.12 g of 2-methylacrylic acid, and heat and stir in an oil bath at 85 °C for 12 h. After stirring is completed, obtain the composite ultraviolet curing agent.

[0057] This example discloses a preparation method of a modified thermosensitive agent, including the following steps:

[0058] S1: Add 41.8 g of bis(2-ethoxyethyl)amine and 39.4 g of triethylamine into a reaction container filled with 700 mL of dichloromethane, stir at low temperature of 0 °C for 15 min, dissolve 25.6 g of isobutyryl chloride in 80 mL of dichloromethane and then slowly dropwise add it into the reaction container, let it stand at room temperature for 12 h, filter, wash with dichloromethane, extract successively with 1 mol / L hydrochloric acid, distilled water, and saturated sodium chloride solution, dry with anhydrous magnesium sulfate, perform rotary evaporation, and perform vacuum distillation to obtain monomer A;

[0059] S2: Add 0.25 g of monomer A into a container containing 1.98 mL of dichloromethane, then successively add 0.112 g of N,N-dimethylacrylamide, 5.38 mL of dimethylethylsilane, and 0.011 g of tris(pentafluorophenyl)borane, stir at room temperature for 8 h, continue to add 0.108 g of N,N-dimethylacrylamide, 0.25 g of monomer A, and 1.98 mL of dichloromethane, and continue to stir and react at room temperature for 18 h. After the reaction is completed, add methanol for purification to obtain the modified thermosensitive agent.

[0060] This example discloses an unsaturated polyester resin for ultraviolet curing pipeline repair, which is composed of the following components in parts by weight: 30 parts of maleic anhydride, 15 parts of phthalic anhydride, 34.1 parts of ethylene glycol, 41.8 parts of propylene glycol, 4 parts of composite ultraviolet curing agent, 3 parts of modified thermosensitive agent, 5 parts of carbon nanotubes, 0.1 part of hydroquinone, and 1.2 parts of antioxidant 1010.

[0061] This example discloses a preparation method of an unsaturated polyester resin for ultraviolet curing pipeline repair, including the following steps:

[0062] Step 1: Add maleic anhydride, phthalic anhydride, ethylene glycol, and propylene glycol into a reaction kettle, heat and stir the reaction to obtain a composite resin;

[0063] Step 2: Sequentially add a composite ultraviolet curing agent, a modified thermosensitive agent, carbon nanotubes, hydroquinone, and antioxidant 1010 to the composite resin, stir and mix to obtain an unsaturated polyester resin for ultraviolet light-curing pipeline repair.

[0064] Example 4: This example discloses a preparation method of a composite ultraviolet curing agent, including the following steps:

[0065] Q1: Add 11.9 g of rosin acid, 0.34 g of zinc chloride, and 0.48 g of oxalic acid to a container, heat and stir in an oil bath at 190 °C for 8 h, then cool to 100 °C, add 19 mL of ethanol, stir to dissolve, filter, then dropwise add to 100 mL of distilled water, filter, dry at 38 °C for 24 h, dissolve, and purify to obtain Compound 1;

[0066] Q2: Add 30.43 g of 1,9-nonanediol, 3.15 g of tetrabutylammonium bromide, and 2.38 g of epichlorohydrin to a container, stir and react in a water bath at 65 °C for 45 min, then add 15.2 g of sodium hydroxide, add it in three equal batches at intervals of 30 min. After adding, continue to react for 2 h. After the reaction is completed, filter by suction, rotary evaporate, filter by suction, and collect the filtrate to obtain Compound 2;

[0067] Q3: Add 10.01 g of Compound 1 to a container, then add 26.4 g of Compound 2 and 0.04 mL of concentrated sulfuric acid with a volume fraction of 98 vt%, heat and stir at 70 °C for 8 h. After the reaction is completed, filter by suction to obtain Compound 3; Add 10.41 g of Compound 3, 0.13 g of triphenylphosphine, and 0.013 g of sodium nitrite to a container, heat and stir at 85 °C, then slowly dropwise add 4.93 g of 2-methylacrylic acid, heat and stir in an oil bath at 85 °C for 12 h. After stirring, obtain the composite ultraviolet curing agent.

[0068] This example discloses a preparation method of a modified thermosensitive agent, including the following steps:

[0069] S1: Add 40.6 g of bis(2-ethoxyethyl)amine and 38.3 g of triethylamine to a reaction container containing 700 mL of dichloromethane, stir at low temperature of 0 °C for 15 min, dissolve 25.1 g of isobutenoyl chloride in 80 mL of dichloromethane and slowly dropwise add it to the reaction container, let it stand at room temperature for 12 h, filter, wash with dichloromethane, extract successively with 1 mol / L hydrochloric acid, distilled water, and saturated sodium chloride solution, dry with anhydrous magnesium sulfate, rotary evaporate, and perform vacuum distillation to obtain Monomer A;

[0070] S2: Add 0.19 g of monomer A into a container containing 1.98 mL of dichloromethane. Subsequently, add 0.095 g of N,N-dimethylacrylamide, 5.21 mL of dimethylethylsilane, and 0.0103 g of tris(pentafluorophenyl)borane in sequence. Stir at room temperature for 8 h. Then continue to add 0.096 g of N,N-dimethylacrylamide, 0.19 g of monomer A, and 1.98 mL of dichloromethane, and continue to stir and react at room temperature for 18 h. After the reaction is completed, add methanol and purify to obtain the modified thermosensitive agent.

[0071] This example discloses an unsaturated polyester resin for ultraviolet-curable pipeline repair, which is composed of the following components in parts by weight: 22 parts of maleic anhydride, 18 parts of phthalic anhydride, 22.8 parts of ethylene glycol, 28.7 parts of propylene glycol, 5 parts of a composite ultraviolet curing agent, 1.5 parts of a modified thermosensitive agent, 3 parts of carbon nanotubes, 0.2 part of hydroquinone, and 0.6 part of antioxidant 1010.

[0072] This example discloses a preparation method of an unsaturated polyester resin for ultraviolet-curable pipeline repair, which includes the following steps:

[0073] Step 1: Add maleic anhydride, phthalic anhydride, ethylene glycol, and propylene glycol into a reaction kettle, heat and stir to react to obtain a composite resin;

[0074] Step 2: Sequentially add a composite ultraviolet curing agent, a modified thermosensitive agent, carbon nanotubes, hydroquinone, and antioxidant 1010 to the composite resin, stir and mix to obtain an unsaturated polyester resin for ultraviolet-curable pipeline repair.

[0075] Example 5: This example discloses a preparation method of a composite ultraviolet curing agent, which includes the following steps:

[0076] Q1: Add 12.3 g of rosin acid, 0.38 g of zinc chloride, and 0.57 g of oxalic acid into a container. After heating and stirring in an oil bath at 190 °C for 8 h, cool down to 100 °C, add 21 mL of ethanol, stir to dissolve, filter, then dropwise add it into 100 mL of distilled water, filter, dry at 38 °C for 24 h, dissolve, and purify to obtain Compound 1;

[0077] Q2: Add 31.21 g of 1,9-nonanediol, 3.28 g of tetrabutylammonium bromide, and 2.44 g of epichlorohydrin into a container. Stir and react in a water bath at 65 °C for 45 min, then add 16.1 g of sodium hydroxide, add it in three equal batches at intervals of 30 min. After adding, continue to react for 2 h. After the reaction is completed, carry out suction filtration, rotary evaporation, suction filtration, and collect the filtrate to obtain Compound 2;

[0078] Q3: Add 10.12 g of Compound 1 into a container, then add 28.3 g of Compound 2 and 0.04 mL of concentrated sulfuric acid with a volume fraction of 98 vt%, heat and stir the reaction at 70 °C for 8 h. After the reaction is completed, perform suction filtration to obtain Compound 3; add 10.87 g of Compound 3, 0.15 g of triphenylphosphine and 0.016 g of sodium nitrite into a container, heat and stir at 85 °C, then slowly dropwise add 5.08 g of 2-methylacrylic acid, and heat and stir in an oil bath at 85 °C for 12 h. After stirring is completed, obtain the composite ultraviolet curing agent.

[0079] This example discloses a preparation method of a modified thermosensitive agent, including the following steps:

[0080] S1: Add 41.3 g of bis(2-ethoxyethyl)amine and 39.1 g of triethylamine into a reaction container filled with 700 mL of dichloromethane, stir at low temperature of 0 °C for 15 min, dissolve 25.4 g of isobutyryl chloride in 80 mL of dichloromethane and then slowly dropwise add it into the reaction container, let it stand at room temperature for 12 h, filter, wash with dichloromethane, extract successively with 1 mol / L hydrochloric acid, distilled water and saturated sodium chloride solution, dry with anhydrous magnesium sulfate, perform rotary evaporation, and perform vacuum distillation to obtain monomer A;

[0081] S2: Add 0.24 g of monomer A into a container containing 1.98 mL of dichloromethane, then successively add 0.106 g of N,N-dimethylacrylamide, 5.32 mL of dimethylethylsilane and 0.0107 g of tris(pentafluorophenyl)borane, stir at room temperature for 8 h, continue to add 0.104 g of N,N-dimethylacrylamide, 0.24 g of monomer A and 1.98 mL of dichloromethane, and continue to stir and react at room temperature for 18 h. After the reaction is completed, add methanol and purify to obtain the modified thermosensitive agent.

[0082] This example discloses an unsaturated polyester resin for ultraviolet curing pipeline repair, which is composed of the following components in parts by weight: 28 parts of maleic anhydride, 22 parts of phthalic anhydride, 30.7 parts of ethylene glycol, 38.5 parts of propylene glycol, 9 parts of composite ultraviolet curing agent, 2.5 parts of modified thermosensitive agent, 4 parts of carbon nanotubes, 0.4 part of hydroquinone, 1.1 parts of antioxidant 1010.

[0083] This example discloses a preparation method of an unsaturated polyester resin for ultraviolet curing pipeline repair, including the following steps:

[0084] Step 1: Add maleic anhydride, phthalic anhydride, ethylene glycol and propylene glycol into a reaction kettle, heat and stir the reaction to obtain a composite resin;

[0085] Step 2: Sequentially add a composite ultraviolet curing agent, a modified thermosensitive agent, carbon nanotubes, hydroquinone, and antioxidant 1010 to the composite resin, and stir and mix to obtain an unsaturated polyester resin for ultraviolet light-curing pipeline repair.

[0086] Comparative Example 1: Compared with Example 1, in the process of preparing the unsaturated polyester resin for ultraviolet light-curing pipeline repair in Comparative Example 1, the composite ultraviolet curing agent is not added, and other conditions remain unchanged.

[0087] Comparative Example 2: Compared with Example 1, in the process of preparing the unsaturated polyester resin for ultraviolet light-curing pipeline repair in Comparative Example 2, the modified thermosensitive agent is not added, and other conditions remain unchanged.

[0088] Experimental Example: Perform performance tests on the unsaturated polyester resins prepared in Examples 1-5 and Comparative Examples 1-2. Test the temperature-responsive phase change performance and catalytic photocuring performance of the samples according to GB / T 7193-2008, test the mechanical properties of the samples according to GB / T 2567-2008, and test the corrosion resistance of the samples according to GB / T 3857-2017. The test results are shown in Table 1:

[0089] Table 1

[0090]

[0091] It can be seen from the test results in Table 1 that the unsaturated polyester resins prepared in Examples 1-5 of the present invention have excellent... From the comparison between Comparative Example 1 and Examples 1-5, it can be seen that adding a composite ultraviolet curing agent can effectively shorten the ultraviolet curing time, improve the mechanical properties and chemical corrosion resistance of the unsaturated polyester resin; from the comparison between Comparative Example 2 and Examples 1-5, it can be seen that adding a modified thermosensitive agent can effectively improve the temperature-responsive phase change and mechanical properties of the unsaturated polyester resin.

[0092] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution of the present invention and its inventive concept, makes equivalent substitutions or changes, and should be covered within the protection scope of the present invention.

[0093] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the present invention to only the specific embodiments. Obviously, according to the content of this specification, many modifications and changes can be made. This specification selects and specifically describes these embodiments to better explain the principle and practical application of the present invention, so that those skilled in the art can well understand and utilize the present invention. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. An unsaturated polyester resin for UV-curing pipeline repair, characterized in that: The invention is composed of the following components in parts by weight: 20-30 parts of maleic anhydride, 15-25 parts of phthalic anhydride, 19.8-34.1 parts of ethylene glycol, 24.3-41.8 parts of propylene glycol, 4-10 parts of a composite ultraviolet curing agent, 1-3 parts of a modified temperature-sensitive agent, 2-5 parts of carbon nanotubes, 0.1-0.5 parts of hydroquinone, and 0.5-1.2 parts of an antioxidant 1010. The composite ultraviolet curing agent is prepared from rosin acid, 1,9-nonanediol, epichlorohydrin and 2-methylacrylic acid as main raw materials, and the modified temperature-sensitive agent is prepared from bis(2-ethoxyethyl)amine, triethylamine, isobutylene chloride, dimethylethylsilane and tris(pentafluorophenyl)borane as main raw materials.

2. The unsaturated polyester resin for UV-curable pipeline repair according to claim 1, characterized in that: The preparation method of the composite ultraviolet curing agent comprises the following steps: Q1: Add rosin acid, zinc chloride and oxalic acid to a container, heat and stir in an oil bath, cool and add ethanol, stir to dissolve, filter, then add dropwise to distilled water, filter, dry, dissolve, and purify to obtain compound 1; Q2: Add 1,9-nonanediol, tetrabutylammonium bromide and epichlorohydrin to a container, stir in a water bath to react, then add sodium hydroxide in three equal batches, continue to react after the addition is complete, filter, rotary evaporate, filter, collect the filtrate, and obtain compound 2; Q3: Add compound 1 to a container, then add compound 2 and concentrated sulfuric acid, heat and stir to react, and after the reaction is completed, filter to obtain compound 3; add compound 3, triphenylphosphine and sodium nitrite to a container, heat and stir, then slowly add 2-methylacrylic acid dropwise, heat and stir in an oil bath, and after the stirring is completed, a composite UV curing agent is obtained.

3. The unsaturated polyester resin for UV-curable pipeline repair according to claim 2, characterized in that: In the Q1, the usage ratio of rosin acid, zinc chloride, oxalic acid and ethanol is (11.8-12.5) g: (0.32-0.41) g: (0.43-0.58) g: (18-23) mL.

4. The unsaturated polyester resin for UV-curable pipeline repair according to claim 2, characterized in that: In Q2, the dosage ratio of 1,9-nonanediol, tetrabutylammonium bromide, epichlorohydrin and sodium hydroxide is (30.12-31.48) g: (3.08-3.36) g: (2.33-2.48) g: (14.8-16.7) g, the reaction temperature is 60-65°C with stirring in a water bath, the reaction time is 30-45 min, the interval is 30-45 min, and the continued reaction time is 1-2 h.

5. The unsaturated polyester resin for UV-curable pipeline repair according to claim 2, characterized in that: In Q3, the usage ratio of compound 1 and compound 2 is (9.94-10.15) g:(25.8-29.3) g; the usage ratio of compound 3, triphenylphosphine, sodium nitrite and 2-methylacrylic acid is (10.21-11.03) g:(0.12-0.16) g:(0.011-0.018) g:(4.87-5.12) g.

6. The unsaturated polyester resin for UV-curable pipeline repair according to claim 1, characterized in that: The preparation method of the modified temperature sensitive agent comprises the following steps: S1: adding bis(2-ethoxyethyl)amine and triethylamine to a reaction vessel filled with dichloromethane, stirring at low temperature, dissolving methacryloyl chloride in dichloromethane and slowly adding dropwise to the reaction vessel, standing at room temperature, filtering, washing, extracting, drying, rotary evaporation, and distilling under reduced pressure to obtain monomer A; S2: Add monomer A to a container containing dichloromethane, and then add N,N-dimethylacrylamide, dimethylethylsilane and tri(pentafluorophenyl)borane in sequence, stir at room temperature, continue to add N,N-dimethylacrylamide, monomer A and dichloromethane, stir at room temperature to react, after the reaction is completed, add methanol, purify, and obtain a modified thermosensitive agent.

7. The unsaturated polyester resin for UV-curable pipeline repair according to claim 6, characterized in that: In the S1, the usage ratio of bis(2-ethoxyethyl)amine, triethylamine and methacryloyl chloride is (40.2-41.8) g: (38.1-39.4) g: (24.8-25.6) g, the low-temperature stirring temperature is 0-2°C, the stirring time is 15-25 min, and the standing time is 10-12 h.

8. The UV-curable unsaturated polyester resin for pipeline repair according to claim 6, characterized in that: In the S2, the usage ratio of monomer A, N,N-dimethylacrylamide, dimethylethylsilane, tri(pentafluorophenyl)borane, the monomer A added continuously and the N,N-dimethylacrylamide added continuously is (0.18-0.25) g: (0.091-0.112) g: (5.12-5.38) mL: (0.01-0.011) g: (0.18-0.25) g: (0.092-0.108) g.

9. The method for preparing the UV-curable unsaturated polyester resin for pipeline repair according to any one of claims 1 to 8, characterized in that: The following steps are involved: Step 1: adding maleic anhydride, phthalic anhydride, ethylene glycol and propylene glycol into a reaction kettle, heating and stirring to react, and obtaining a composite resin; Step 2: Add the composite UV curing agent, modified temperature sensitive agent, carbon nanotubes, hydroquinone and antioxidant 1010 to the composite resin in sequence, stir and mix, and obtain UV-curable unsaturated polyester resin for pipeline repair.

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