Photocuring lining hose and preparation method thereof

Abstract

The invention provides a photocuring lining hose and a preparation method thereof, the hose is obtained by sequentially combining a polyethylene film layer, a photocuring fiber resin layer and a polytetrafluoroethylene film layer from inside to outside, the light-curing fiber resin layer is prepared by brushing light-curing resin on two sides of glass fiber cloth; the photocuring resin comprises the following components in parts by weight: 110 parts of epoxy photosensitive modified polyester resin, 2-5 parts of a thickening agent, 32-42 parts of a diluent and 1-2 parts of a defoaming agent; the preparation method of the epoxy photosensitive modified polyester resin comprises the following steps: adding 50-60 parts by weight of epoxy resin and 2-5 parts by weight of a catalyst hexadecyl trimethyl ammonium bromide into 100 parts by weight of unsaturated polyester, and adding 1-3 parts by weight of a polymerization inhibitor hydroquinone when the reaction temperature is 110-120 DEG C, the reaction time is 2 hours and the acid value is lower than 7 mg KOH / g, so as to obtain the epoxy photosensitive modified polyester resin. Then adding 60-65 parts of an active monomer and 5-8 parts of modified hyperbranched polyurethane, keeping the temperature at 80-90 DEG C and stirring for 1 hour, cooling to 70 DEG C or below, adding 4-7 parts of an ultraviolet light initiator, and uniformly mixing to obtain the water-based paint. The tensile strength and the moisture resistance of the product are comprehensively improved.

Description

Technical Field

[0001] The invention belongs to the technical field of liner hoses, and in particular relates to a light-cured liner hose and a preparation method thereof. Background Art

[0002] Urban underground pipelines are extremely important public infrastructure and the lifeline for maintaining the normal operation of modern cities. However, due to the limitations of construction conditions, poor quality of pipeline materials and backward construction technology in the past, accidents involving urban underground pipelines were frequently reported in the media, causing not only significant economic and property losses, but also casualties. Compared with excavation repair and other trenchless repair methods, the use of UV light curing trenchless repair technology has little impact on traffic, fast construction speed and short cycle; no wastewater or exhaust gas is discharged during the construction and repair process, which saves energy and is environmentally friendly; the construction equipment occupies a small area, has low noise and little impact on the surrounding environment; the inner lining pipe after construction has high strength and good comprehensive performance, and is suitable for various underground pipelines.

[0003] The existing Chinese invention patent with publication number CN117146070A discloses a one-time molded UV-curable hose material for repairing the inner lining of a water supply pipe, including an outer layer, a structural layer and a barrier layer; the outer layer is the outermost layer of the hose, which is impermeable to UV radiation and also plays a role in preventing puncture; the structural layer is formed by glass fiber impregnated with resin; an anchoring layer is provided between the barrier layer and the structural layer; the anchoring layer is located inside the structural layer and in contact with the structural layer, and the anchoring layer is combined with the barrier layer through a hot melt. The barrier layer is provided on the inner side of the structural layer to effectively prevent the UV-curable hose material from being used with a reactive diluent without harmful substances (such as styrene), and the risk of components of the UV-curable hose being minimized after curing from the repaired pipe is minimized, thereby ensuring the safety of the water supply pipe after repair.

[0004] However, the difference in ultraviolet absorption, compatibility issues and curing shrinkage between unsaturated polyester resin and epoxy resin result in differences in physical properties after curing, such as strength and ductility. This mismatch in performance can cause inconsistent behavior of the composite material when subjected to stress, which directly affects the overall performance and reliability of the material, such as tensile strength and moisture resistance (tensile strength retention in high humidity environments). Summary of the invention

[0005] In order to solve the problems existing in the background technology, the present invention provides a light-cured lined hose and a preparation method thereof, which comprehensively improves the tensile strength and moisture resistance (tensile strength retention rate in a high humidity environment) of the product.

[0006] In order to achieve the above-mentioned purpose, the present invention provides a method for preparing a light-curing lining hose, which comprises combining a polyethylene film layer, a light-curing fiber resin layer and a polytetrafluoroethylene film layer in sequence from the inside to the outside, wherein the light-curing fiber resin layer is prepared by brushing light-curing resin on both sides of a glass fiber cloth, and the brushing amount on both sides is the same, and both are 20%-22% of the weight of the glass fiber cloth; the light-curing resin comprises the following raw material components by weight: 110 parts of epoxy photosensitive modified polyester resin, 2-5 parts of thickener, 32-42 parts of diluent and 1-2 parts of defoaming agent;

[0007] The preparation method of the epoxy photosensitive modified polyester resin is as follows: by weight, 50-60 parts of epoxy resin and 2-5 parts of catalyst hexadecyltrimethylammonium bromide are added to 100 parts of unsaturated polyester, the reaction temperature is 110-120° C., the reaction time is 2 hours, and when the acid value is lower than 7 mg KOH / g, 1-3 parts of inhibitor hydroquinone is added, and then 60-65 parts of active monomers and 5-8 parts of modified hyperbranched polyurethane are added, the mixture is kept warm and stirred at 80-90° C. for 1 hour, the temperature is lowered to below 70° C., 4-7 parts of ultraviolet initiator are added, and the mixture is mixed evenly to obtain the epoxy photosensitive modified polyester resin.

[0008] Furthermore, the preparation method of the unsaturated polyester is as follows: phthalic anhydride, maleic anhydride, propylene glycol and diethylene glycol are added into a three-necked flask with a stirrer and a straight tube condenser in a mass ratio of 1:1:1.8:0.4, and then an antioxidant is added, and stirring is started after heating and melting, and the temperature is gradually increased, and the reaction temperature does not exceed 210°C, and the distillation head temperature does not exceed 105°C, until the acid value drops to 10% of the initial acid value, and vacuum dehydration is performed to reduce the acid value to less than 5% of the initial acid value, thereby obtaining the unsaturated polyester.

[0009] Furthermore, the antioxidant includes a phenolic antioxidant and a phosphorus antioxidant, and the mass ratio of the two is (1-3):1.

[0010] Furthermore, the added amount of the antioxidant is 0.5-0.8% of the total mass of phthalic anhydride, maleic anhydride, propylene glycol and diethylene glycol.

[0011] Furthermore, the preparation method of the modified hyperbranched polyurethane is as follows:

[0012] A1. Weigh 15-25 g of diethanolamine and weigh succinic anhydride in a molar ratio of 1, place in a three-necked flask, add 150 mL of dimethylacetamide, and stir at room temperature for 1 h to obtain an intermediate;

[0013] A2, weigh 25-32g of trimethylolpropane and 0.4-0.7g of p-toluenesulfonic acid, place in a four-necked bottle, add 100mL of toluene, heat to 120°C and start to dropwise add the intermediate obtained in A1, after the dropwise addition is complete, continue to react until no water is generated to obtain a hyperbranched polyurethane;

[0014] A3. Cool the hyperbranched polyurethane obtained in A2 to 60°C, add 15 g of pyridine and raise the temperature to reflux, then dropwise add 10 g of palmitoyl chloride, control the total reaction time to 6 h, stop the reaction, dropwise add the cooled solution into ether, precipitate the polymer, separate and dry to obtain the modified hyperbranched polyurethane.

[0015] Furthermore, the active monomers include styrene and methyl methacrylate, and the mass ratio of the two is 1:(1-2).

[0016] Furthermore, the ultraviolet light initiator includes benzoin methyl ether and / or benzoin ethyl ether.

[0017] Furthermore, the diluent includes isobornyl acrylate and / or neopentyl glycol diacrylate; the thickener includes active magnesium oxide and / or fumed silica.

[0018] Furthermore, the defoaming agent includes polydimethylsiloxane and / or polyether.

[0019] In a second aspect, the present invention provides a light-cured lined hose, which is produced by the above-mentioned preparation method.

[0020] This application has the following beneficial effects:

[0021] 1. The present invention chemically reacts epoxy resin and unsaturated polyester through the action of catalyst hexadecyltrimethylammonium bromide to form a denser cross-linked network. This structural optimization enables the material to have a higher cross-linking density after light curing, thereby improving the tensile strength;

[0022] The participation of modified hyperbranched polyurethane and active monomers synergistically promotes the interaction between molecules and synergistically enhances the cohesion of the material, thereby further improving the tensile strength; at the same time, the increase in the number of chemical bonds, the introduction of polar groups, the increase in cross-linking density, and the improvement in the compatibility of the resin system can all enhance the moisture resistance of the material, that is, synergistically improve the strength retention rate of the material in a high-humidity environment.

[0023] 2. In the preparation of modified hyperbranched polyurethane, the three-dimensional quasi-spherical structure of the hyperbranched polyurethane can effectively absorb and disperse the energy applied from the outside in the resin. This "internal toughening" effect significantly enhances the material's ability to resist crack propagation, thereby improving the tensile strength of the resin after curing; the hyperbranched polyurethane has good compatibility with other components of the resin and helps to form a homogeneous structure. This homogeneous structure can reduce microphase separation and help improve the mechanical and thermal properties of the material, thereby enhancing the tensile strength and moisture resistance of the material; the introduction of hyperbranched polyurethane can also enhance the storage modulus and glass transition temperature of epoxy resin cured products. The improvement of these thermal properties enables the material to maintain excellent mechanical properties and dimensional stability when exposed to a high humidity environment for a long time.

[0024] 3. In the preparation of modified hyperbranched polyurethane, pyridine as a catalyst and solvent can provide a stable reaction environment, which is conducive to the full reaction of palmitoyl chloride with the active groups in the hyperbranched polyurethane. Through sufficient chemical modification, more polar groups and long-chain alkyl groups are introduced. The polar groups can form stronger hydrogen bonds with the hydroxyl groups in the epoxy resin. This enhanced intermolecular force increases the cohesive energy of the material, thereby increasing the tensile strength of the cured resin; the introduction of long-chain alkyl groups increases the entanglement and interconnection of the molecular chains, forming a denser cross-linked network, which not only improves the mechanical properties of the material, but also limits the penetration and diffusion of water molecules in the resin, thereby improving the moisture resistance of the material. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 , a comparative trend diagram of the tensile strength of the light-cured lined hoses obtained in Examples 1-7 of the present invention and Comparative Examples 1-5;

[0026] Figure 2 , a comparative trend chart of the moisture resistance (tensile strength retention after water immersion) of the light-cured lined hoses prepared in Examples 1-7 of the present invention and Comparative Examples 1-5. DETAILED DESCRIPTION

[0027] The present application is further described in detail below with reference to the embodiments.

[0028] Unless otherwise specified, the raw materials used in the examples and comparative examples of the present application are all commercially available.

[0029] Example 1: A method for preparing a light-cured lined hose, comprising combining a polyethylene film layer, a light-cured fiber resin layer and a polytetrafluoroethylene film layer in sequence from the inside to the outside.

[0030] The polyethylene film layer adopts a high-transmittance PE film purchased from Linyi Sirius Plastic Products Co., Ltd. The polytetrafluoroethylene film layer adopts a polytetrafluoroethylene film purchased from Shenzhen Deli New Materials Co., Ltd. The light-curable fiber resin layer is self-made.

[0031] This process is an existing technology. Specifically, the film materials, namely the polyethylene film layer and the polytetrafluoroethylene film layer, are first prepared. These film materials need to be precisely cut to fit the shape and size of the final product. Then the homemade light-curable fiber resin layer is arranged between the polyethylene film layer and the polytetrafluoroethylene film layer to ensure that the three are tightly fitted. Here, a press or manual pressure can be used to help the materials fit tightly. The laminated multilayer material is then curled into a tube, and the edges are sealed using adhesives or heat welding to ensure the stability and sealing of the tubular structure.

[0032] The light-curable fiber resin layer is made by brushing light-curable resin on both sides of glass fiber cloth, and the brushing amount on both sides is the same, and both are 21% of the weight of the glass fiber cloth. The glass fiber cloth was purchased from Hejian Shilei Glass Fiber Cloth Factory (Article No. 008).

[0033] The photocurable resin includes the following raw material components by weight: 110 parts of epoxy photosensitive modified polyester resin, 3 parts of thickener, 37 parts of diluent and 1.5 parts of defoamer. The thickener is fumed silica (Cabot CAB-O-SIL TG-828F), the diluent is isobornyl acrylate (IBOA), and the defoamer is polydimethylsiloxane (Jiangsu Jianyu JY-810). When preparing, all the raw material components are put into a stirrer and stirred at room temperature to obtain the product.

[0034] The preparation method of epoxy photosensitive modified polyester resin is as follows: by weight, 55 parts of epoxy resin and 4 parts of catalyst hexadecyltrimethylammonium bromide are added to 100 parts of unsaturated polyester, the reaction temperature is about 115°C, the reaction time is 2h, and when the acid value is lower than 7mg KOH / g, 2 parts of inhibitor hydroquinone are added, and then 63 parts of active monomers and 6 parts of modified hyperbranched polyurethane are added, and the mixture is kept warm and stirred at about 85°C for 1h, cooled to below 70°C, 6 parts of ultraviolet initiator are added, and mixed evenly to obtain epoxy photosensitive modified polyester resin.

[0035] Epoxy resin (E44) was purchased from Shaanxi Lanxin Chemical Co., Ltd. Hexadecyltrimethylammonium bromide (1631) was purchased from Henan Lichi Fine Chemical Co., Ltd. Active monomers include styrene and methyl methacrylate, and the mass ratio of the two is 1:1.5. Benzoin ethyl ether was used as the ultraviolet light initiator.

[0036] The preparation method of unsaturated polyester is as follows: phthalic anhydride, maleic anhydride, propylene glycol and diethylene glycol are added to a three-necked flask with a stirrer and a straight tube condenser in a mass ratio of 1:1:1.8:0.4, and then an antioxidant is added. The antioxidant is specifically a mixture of a phenolic antioxidant (butylated hydroxyanisole) and a phosphorus antioxidant (antioxidant 3010), and the mass ratio of the two is 2:1. The amount of antioxidant added is 0.6% of the total mass of phthalic anhydride, maleic anhydride, propylene glycol and diethylene glycol. After heating and melting, stirring is started, and the temperature is gradually increased. The reaction temperature is controlled between 200-210°C. Small fluctuations within this range do not affect the reaction process and do not exceed 210°C. The temperature of the distillation head does not exceed 105°C until the acid value drops to 10% of the initial acid value, and vacuum dehydration is performed to reduce the acid value to less than 5% of the initial acid value, ensuring that the reaction is nearly completed and most of the water produced has been removed, thereby obtaining an unsaturated polyester.

[0037] Phthalic anhydride was purchased from Tesco Chemical (Hubei) Co., Ltd. Maleic anhydride was purchased from Hubei Xinrunde Chemical Co., Ltd. Propylene glycol (premium grade) was purchased from Zhengzhou Ruichang Chemical Products Co., Ltd. Diethylene glycol was purchased from Tianjin Zhonghe Shengtai Chemical Co., Ltd.

[0038] The preparation method of modified hyperbranched polyurethane is as follows:

[0039] A1. Weigh 20 g of diethanolamine and 19.03 g of succinic anhydride at a molar ratio of 1, place in a three-necked flask, add 150 mL of dimethylacetamide, and stir at room temperature for 1 h to obtain an intermediate.

[0040] A2. Weigh 28 g of trimethylolpropane and 0.5 g of p-toluenesulfonic acid, place in a four-necked bottle, add 100 mL of toluene, raise the temperature to 120° C. and begin to dropwise add the intermediate obtained in A1. After the dropwise addition is complete, continue the reaction until no water is generated to obtain a hyperbranched polyurethane.

[0041] A3. Cool the hyperbranched polyurethane obtained in A2 to 60°C, add 15 g of pyridine and raise the temperature to reflux, then dropwise add 10 g of palmitoyl chloride, control the total reaction time to 6 h, stop the reaction, dropwise add the cooled solution into ether, precipitate the polymer, separate and dry to obtain the modified hyperbranched polyurethane.

[0042] Embodiment 2: The difference between this embodiment and embodiment 1 is that the light-curable fiber resin layer is made by brushing light-curable resin on both sides of glass fiber cloth, and the brushing amount on both sides is the same, and both are 20% of the weight of glass fiber cloth. The light-curable resin includes the following raw material components by weight: 110 parts of epoxy photosensitive modified polyester resin, 2 parts of thickener, 32 parts of diluent and 1 part of defoaming agent.

[0043] Embodiment 3: The difference between this embodiment and embodiment 1 is that the light-curable fiber resin layer is made by brushing light-curable resin on both sides of glass fiber cloth, and the brushing amount on both sides is the same, and both are 22% of the weight of glass fiber cloth. The light-curable resin includes the following raw material components by weight: 110 parts of epoxy photosensitive modified polyester resin, 5 parts of thickener, 42 parts of diluent and 2 parts of defoaming agent.

[0044] Example 4: The difference between this example and Example 1 is that the preparation method of epoxy photosensitive modified polyester resin is as follows: by weight, 50 parts of epoxy resin and 2 parts of catalyst hexadecyl trimethyl ammonium bromide are added to 100 parts of unsaturated polyester, the reaction temperature is about 110°C, the reaction time is 2h, and when the acid value is lower than 7mg KOH / g, 1 part of inhibitor hydroquinone is added, and then 60 parts of active monomers and 5 parts of modified hyperbranched polyurethane are added, and the mixture is stirred at about 80°C for 1h, cooled to below 70°C, 4 parts of ultraviolet initiator are added, and mixed well to obtain epoxy photosensitive modified polyester resin. Among them, the active monomers include styrene and methyl methacrylate, and the mass ratio of the two is 1:1.

[0045] Example 5: The difference between this example and Example 1 is that the preparation method of epoxy photosensitive modified polyester resin is as follows: by weight, 60 parts of epoxy resin and 5 parts of catalyst hexadecyl trimethyl ammonium bromide are added to 100 parts of unsaturated polyester, the reaction temperature is about 120°C, the reaction time is 2h, and when the acid value is lower than 7mg KOH / g, 3 parts of inhibitor hydroquinone are added, and then 65 parts of active monomers and 8 parts of modified hyperbranched polyurethane are added, and the mixture is stirred at about 90°C for 1h, cooled to below 70°C, and 7 parts of ultraviolet initiator are added, mixed evenly, and epoxy photosensitive modified polyester resin is obtained. Among them, the active monomers include styrene and methyl methacrylate, and the mass ratio of the two is 1:2.

[0046] Example 6: The difference between this example and Example 1 is that the preparation method of the modified hyperbranched polyurethane is as follows:

[0047] A1. Weigh 15 g of diethanolamine and succinic anhydride at a molar ratio of 1, place in a three-necked flask, add 150 mL of dimethylacetamide, and stir at room temperature for 1 h to obtain an intermediate.

[0048] A2. Weigh 25 g of trimethylolpropane and 0.4 g of p-toluenesulfonic acid, place in a four-necked bottle, add 100 mL of toluene, raise the temperature to 120° C. and begin to dropwise add the intermediate obtained in A1. After the dropwise addition is complete, continue the reaction until no water is generated to obtain a hyperbranched polyurethane.

[0049] A3. Cool the hyperbranched polyurethane obtained in A2 to 60°C, add 15 g of pyridine and raise the temperature to reflux, then dropwise add 10 g of palmitoyl chloride, control the total reaction time to 6 h, stop the reaction, dropwise add the cooled solution into ether, precipitate the polymer, separate and dry to obtain the modified hyperbranched polyurethane.

[0050] Example 7: The difference between this example and Example 1 is that the preparation method of the modified hyperbranched polyurethane is as follows:

[0051] A1. Weigh 25 g of diethanolamine and succinic anhydride at a molar ratio of 1, place in a three-necked flask, add 150 mL of dimethylacetamide, and stir at room temperature for 1 h to obtain an intermediate.

[0052] A2. Weigh 32 g of trimethylolpropane and 0.7 g of p-toluenesulfonic acid, place in a four-necked bottle, add 100 mL of toluene, raise the temperature to 120° C. and begin to dropwise add the intermediate obtained in A1. After the dropwise addition is complete, continue the reaction until no water is generated to obtain a hyperbranched polyurethane.

[0053] A3. Cool the hyperbranched polyurethane obtained in A2 to 60°C, add 15 g of pyridine and raise the temperature to reflux, then dropwise add 10 g of palmitoyl chloride, control the total reaction time to 6 h, stop the reaction, dropwise add the cooled solution into ether, precipitate the polymer, separate and dry to obtain the modified hyperbranched polyurethane.

[0054] Comparative Example 1: The difference between this comparative example and Example 1 is that the modified hyperbranched polyurethane is replaced by a hyperbranched polyurethane.

[0055] Specifically, the preparation method of the epoxy photosensitive modified polyester resin is as follows: by weight, 55 parts of epoxy resin and 4 parts of catalyst hexadecyltrimethylammonium bromide are added to 100 parts of unsaturated polyester, the reaction temperature is about 115° C., the reaction time is 2 hours, and when the acid value is lower than 7 mg KOH / g, 2 parts of inhibitor hydroquinone are added, and then 63 parts of active monomers and 6 parts of hyperbranched polyurethane are added, and the mixture is kept warm and stirred at about 85° C. for 1 hour, cooled to below 70° C., 6 parts of ultraviolet initiator are added, and mixed evenly to obtain the epoxy photosensitive modified polyester resin.

[0056] The preparation method of hyperbranched polyurethane is as follows:

[0057] A1. Weigh 20 g of diethanolamine and 19.03 g of succinic anhydride at a molar ratio of 1, place in a three-necked flask, add 150 mL of dimethylacetamide, and stir at room temperature for 1 h to obtain an intermediate.

[0058] A2. Weigh 28 g of trimethylolpropane and 0.5 g of p-toluenesulfonic acid, place in a four-necked bottle, add 100 mL of toluene, raise the temperature to 120° C. and begin to dropwise add the intermediate obtained in A1. After the dropwise addition is complete, continue the reaction until no water is generated to obtain a hyperbranched polyurethane.

[0059] Comparative Example 2: The difference between this comparative example and Example 1 is that the modified hyperbranched polyurethane is deleted.

[0060] Specifically, the preparation method of the epoxy photosensitive modified polyester resin is as follows: by weight, 55 parts of epoxy resin and 4 parts of catalyst hexadecyltrimethylammonium bromide are added to 100 parts of unsaturated polyester, the reaction temperature is about 115° C., the reaction time is 2 hours, and when the acid value is lower than 7 mg KOH / g, 2 parts of inhibitor hydroquinone are added, and then 63 parts of active monomers are added, and the mixture is kept warm and stirred at about 85° C. for 1 hour, cooled to below 70° C., 6 parts of ultraviolet light initiator are added, and mixed well to obtain the epoxy photosensitive modified polyester resin.

[0061] Comparative Example 3: The difference between this comparative example and Example 1 is that the active monomer is deleted.

[0062] Specifically, the preparation method of the epoxy photosensitive modified polyester resin is as follows: by weight, 55 parts of epoxy resin and 4 parts of catalyst hexadecyltrimethylammonium bromide are added to 100 parts of unsaturated polyester, the reaction temperature is about 115° C., the reaction time is 2 hours, and when the acid value is lower than 7 mg KOH / g, 2 parts of inhibitor hydroquinone are added, and then 6 parts of modified hyperbranched polyurethane are added, and the mixture is kept warm and stirred at about 85° C. for 1 hour, cooled to below 70° C., 6 parts of ultraviolet initiator are added, and mixed evenly to obtain the epoxy photosensitive modified polyester resin.

[0063] Comparative Example 4: The difference between this comparative example and Example 1 is that the modified hyperbranched polyurethane and the active monomer are deleted.

[0064] Specifically, the preparation method of the epoxy photosensitive modified polyester resin is as follows: by weight, 55 parts of epoxy resin and 4 parts of catalyst hexadecyltrimethylammonium bromide are added to 100 parts of unsaturated polyester, the reaction temperature is about 115° C., the reaction time is 2 hours, and when the acid value is lower than 7 mg KOH / g, 2 parts of inhibitor hydroquinone are added, the mixture is kept warm and stirred at about 85° C. for 1 hour, the temperature is lowered to below 70° C., 6 parts of ultraviolet light initiator are added, and the mixture is mixed evenly to obtain the epoxy photosensitive modified polyester resin.

[0065] Comparative Example 5: The difference between this comparative example and Example 1 is that the epoxy photosensitive modified polyester resin is replaced by an epoxy resin-unsaturated polyester photosensitive mixture.

[0066] Specifically, the photocurable resin includes the following raw material components by weight: 110 parts of epoxy resin-unsaturated polyester photosensitive mixture, 3 parts of thickener, 37 parts of diluent and 1.5 parts of defoaming agent.

[0067] The preparation method of the epoxy resin-unsaturated polyester photosensitive mixture is as follows: 55 parts of epoxy resin, 100 parts of unsaturated polyester and 6 parts of ultraviolet light initiator are mixed evenly by weight to obtain the epoxy resin-unsaturated polyester photosensitive mixture.

[0068] Test example 1: Test item: tensile strength.

[0069] Test subjects: Examples 1-7 and Comparative Examples 1-5 were used to prepare light-cured lined hoses (after the same existing standard light-curing treatment).

[0070] Test basis: GB / T1447-2005.

[0071] Test results: See Table 1.

[0072] Test Example 2: Test item: moisture resistance (tensile strength retention rate in a high humidity environment).

[0073] Test subjects: Examples 1-7 and Comparative Examples 1-5 were used to prepare light-cured lined hoses (after the same existing standard light-curing treatment).

[0074] Test method: Soak in water at 50±2℃ for 7 days, 14 days, and 21 days, test the tensile strength after soaking, and calculate the strength retention rate. Strength retention rate = tensile strength after soaking / tensile strength before soaking*100%.

[0075] Test results: See Table 1.

[0076] Table 1. Test data of test example 1 and test example 2

[0077]

[0078] Result analysis: Analyze Examples 1-7 and combine the data in Table 1 and Figure 1-2 It can be seen that the light-cured liner hose produced by the present invention has stable performance, a tensile strength of over 271 MPa, excellent moisture resistance, and a tensile strength retention rate of over 95.9% after immersion in water for 7 days, a tensile strength retention rate of over 93.0% after immersion in water for 14 days, and a tensile strength retention rate of over 89.1% after immersion in water for 21 days.

[0079] Analyze Example 1 and Comparative Examples 1-2 and combine the data in Table 1 and Figure 1-2 It can be seen that in the preparation of epoxy photosensitive modified polyester resin, the addition of hyperbranched polyurethane can improve the tensile strength and moisture resistance of the photocurable lining hose; the modified hyperbranched polyurethane is obtained by modifying the hyperbranched polyurethane with pyridine and palmitoyl chloride, and then used to prepare epoxy photosensitive modified polyester resin, which can further improve the tensile strength and moisture resistance of the photocurable lining hose.

[0080] From the analysis of Example 1 and Comparative Examples 2-4 and in combination with the data in Table 1 and 1-2, it can be seen that in the preparation of epoxy photosensitive modified polyester resin, the participation of active monomers and modified hyperbranched polyurethane can correspondingly improve the tensile strength and moisture resistance of the photocurable lining hose, and there is a synergistic effect between the two in terms of performance improvement.

[0081] Analyze Example 1 and Comparative Examples 4-5 and combine the data in Table 1 and Figure 1-2 It can be seen that the epoxy resin and unsaturated polyester are pre-prepared in advance to obtain epoxy photosensitive modified polyester resin by the technical means of the present invention. Compared with preparing the epoxy resin-unsaturated polyester photosensitive mixture by physical mixing, the tensile strength and moisture resistance of the photocurable lining hose can be significantly improved.

[0082] In addition, through Figure 2 (Compare the longitudinal distances between the three curves) It can also be seen that, as the immersion time in water increases, the decrease in the tensile strength retention rate of the light-cured lined hoses prepared in Examples 1-7 of the present invention is smaller; while as the immersion time in water increases, the decrease in the tensile strength retention rate of the light-cured lined hoses prepared in Comparative Examples 1-5 is significantly greater.

[0083] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0084] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A method for preparing a light-curing lined hose, comprising combining a polyethylene film layer, a light-curing fiber resin layer and a polytetrafluoroethylene film layer in sequence from the inside to the outside; the light-curing fiber resin layer is prepared by brushing light-curing resin on both sides of a glass fiber cloth, and the amount of light-curing resin on both sides is the same, and both are 20%-22% of the weight of the glass fiber cloth; characterized in that: The photocurable resin comprises the following raw material components by weight: 110 parts of epoxy photosensitive modified polyester resin, 2-5 parts of thickener, 32-42 parts of diluent and 1-2 parts of defoamer; The preparation method of the epoxy photosensitive modified polyester resin is as follows: by weight, 50-60 parts of epoxy resin and 2-5 parts of catalyst are added to 100 parts of unsaturated polyester, the reaction temperature is 110-120° C., the reaction time is 2 hours, when the acid value is lower than 7 mg KOH / g, 1-3 parts of inhibitor are added, and then 60-65 parts of active monomer and 5-8 parts of modified hyperbranched polyurethane are added, after stirring at 80-90° C. for 1 hour, the temperature is lowered to below 70° C., 4-7 parts of ultraviolet initiator are added, and the mixture is mixed evenly to obtain the epoxy photosensitive modified polyester resin.

2. The method for preparing a light-cured lined hose according to claim 1, characterized in that: The preparation method of the unsaturated polyester is as follows: phthalic anhydride, maleic anhydride, propylene glycol and diethylene glycol are added into a three-necked flask in a mass ratio of 1:1:1.8:0.4, and then an antioxidant is added, and stirring is started after heating and melting, and the temperature is continued to be raised, the reaction temperature does not exceed 210°C, and the temperature of the distillation head does not exceed 105°C, until the acid value drops to 10% of the initial acid value, and vacuum dehydration is performed to reduce the acid value to less than 5% of the initial acid value, so as to obtain the unsaturated polyester.

3. The method for preparing a light-cured lined hose according to claim 2, characterized in that: The antioxidants include phenolic antioxidants and phosphorus antioxidants, and the mass ratio of the two is (1-3):

1.

4. The method for preparing a light-cured lined hose according to claim 2 or 3, characterized in that: The added amount of the antioxidant is 0.5-0.8% of the total mass of phthalic anhydride, maleic anhydride, propylene glycol and diethylene glycol.

5. The method for preparing a light-cured lined hose according to claim 1, characterized in that: The preparation method of the modified hyperbranched polyurethane is as follows: A1. Weigh 15-25 g of diethanolamine and weigh succinic anhydride in a molar ratio of 1, place in a three-necked flask, add 150 mL of dimethylacetamide, and stir at room temperature for 1 h to obtain an intermediate; A2, weigh 25-32g of trimethylolpropane and 0.4-0.7g of p-toluenesulfonic acid, place in a four-necked bottle, add 100mL of toluene, heat to 120°C and start to dropwise add the intermediate obtained in A1, after the dropwise addition is complete, continue to react until no water is generated to obtain a hyperbranched polyurethane; A3. Cool the hyperbranched polyurethane obtained in A2 to 60°C, add 15 g of pyridine and raise the temperature to reflux, then dropwise add 10 g of palmitoyl chloride, control the total reaction time to 6 h, stop the reaction, dropwise add the cooled solution into ether, precipitate the polymer, separate and dry to obtain the modified hyperbranched polyurethane.

6. The method for preparing a light-cured lined hose according to claim 1, characterized in that: The active monomers include styrene and methyl methacrylate, and the mass ratio of the two is 1:(1-2).

7. The method for preparing a light-cured lined hose according to claim 1, characterized in that: The ultraviolet light initiator includes benzoin methyl ether and / or benzoin ethyl ether.

8. The method for preparing a light-cured lined hose according to claim 1, characterized in that: The diluent includes isobornyl acrylate and / or neopentyl glycol diacrylate; the thickener includes active magnesium oxide and / or fumed silica.

9. The method for preparing a light-cured lined hose according to claim 1, characterized in that: The defoaming agent includes polydimethylsiloxane and / or polyether.

10. A light-cured lined hose, characterized in that: The method is prepared according to any one of claims 1 to 9.

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