Underground pipeline repairing material based on UV resin and preparation process thereof

Abstract

The invention relates to the technical field of research and development of pipeline repair materials, and discloses an underground pipeline repair material based on UV resin and a preparation process thereof. The underground pipeline repairing material based on the UV resin is prepared from the following raw materials in parts by weight: 40 to 60 parts of unsaturated polyester resin, 1 to 5 parts of crosslinking diluent, 5 to 8 parts of thickening agent, 5 to 8 parts of preservative, 5 to 15 parts of dibutyl phthalate and 10 to 30 parts of photoinitiator. The novel underground pipeline repairing material based on the UV resin is researched, developed and prepared, and the material has excellent mechanical performance and corrosion resistance and can be used as a raw material used in a trenchless pipeline repairing and reinforcing method.

Description

Technical Field

[0001] The invention relates to the technical field of pipeline repair material research and development, and specifically to an underground pipeline repair material based on UV resin and a preparation process thereof. Background Art

[0002] As a municipal public infrastructure, urban underground pipelines are responsible for urban sewage and waterlogging prevention. As underground pipelines age, they are affected by pedestrian and vehicle loads on the road, and their structural damage and aging continue to increase. The pipeline structure and strength gradually fail to meet the operation requirements. In addition, during the long-term operation of old underground pipelines, scale will gradually form on the inner wall of the pipeline and continue to thicken, which is prone to defects such as chemical corrosion perforation and strength reduction.

[0003] The traditional mechanical excavation repair and reinforcement technology of pipelines is subject to many constraints, which will have a great impact on the travel and traffic of surrounding residents. However, the trenchless repair technology has a smaller impact and can effectively solve the problem of underground pipelines. At present, the most widely used trenchless repair method is the in-situ curing method (CIPP), which is to place the resin-impregnated hose into the damaged pipeline close to the inner wall by pulling or flipping, and then cure the hose to form an inner lining through heat curing, UV curing, etc., to achieve the purpose of repairing the pipeline.

[0004] The quality of trenchless repair technology depends on pipeline repair materials. As a key component of trenchless pipeline repair materials, the structure, properties, preparation and modification methods of unsaturated polyester resin have important research value.

[0005] A cross-linking diluent is a component that provides unsaturated double bonds to participate in the cross-linking curing reaction. It also plays a role in dissolving the resin and adjusting the viscosity of the system. Currently, the most commonly used cross-linking diluent is styrene. However, the mechanical strength of polyester using styrene as a cross-linking diluent decreases after curing, which is more difficult for underground pipeline repair materials that bear loads for a long time. In addition, styrene also has obvious destructive effects on human health and environmental ecology, which no longer conforms to the general trend of pursuing green environmental protection. Therefore, it is necessary to develop new cross-linking diluents to replace styrene.

[0006] The search found that cage-type silsesquioxane (POSS) is an organic-inorganic hybrid core-shell structure material. Due to its special structure, good chemical stability and excellent insulation, it has the potential to enhance the corrosion effect when incorporated into polymers.

[0007] The present invention cites the following references:

[0008] The doctoral dissertation of Shanghai Jiao Tong University, "Synthesis of organic-inorganic hybrid polymers containing cage-type and macrocyclic oligomeric silsesquioxanes and research on their structures and properties", disclosed the chemical structure and synthesis method of sodium octaphenyltetrasilanol;

[0009] Harbin Institute of Technology Master's thesis "Q x M y "Synthesis of type POSS and preparation and performance study of its PMMA composite materials" discloses the chemical structure and synthesis method of octamethylammonium POSS ammonium salt (TMN-POSS). Summary of the invention

[0010] The invention develops and prepares a UV resin-based underground pipeline repair material with excellent mechanical properties and corrosion resistance, which can be used as a raw material for a trenchless pipeline repair and reinforcement method.

[0011] A UV resin-based underground pipeline repair material comprises the following raw materials in parts by weight: 40 to 60 parts by weight of unsaturated polyester resin, 1 to 5 parts by weight of a cross-linking diluent, 5 to 8 parts by weight of a thickener, 5 to 8 parts by weight of a preservative, 5 to 15 parts by weight of dibutyl phthalate, and 10 to 30 parts by weight of a photoinitiator;

[0012] Wherein, the cross-linking diluent is cross-linking diluent I or cross-linking diluent II.

[0013] Preferably, the preparation method of the cross-linking diluent I is: using octaphenyltetrasilanol sodium salt as a raw material, using 3-acryloxypropylmethyldimethoxysilane as a capping agent, and preparing the cross-linking diluent I by a top corner capping method under the catalysis of triethylamine.

[0014] Preferably, the preparation method of the cross-linking diluent II is: the cross-linking diluent II is prepared by subjecting 1,3-dibromopropane to an allyl etherification reaction with the oxygen anion group of octamethylammonium POSS ammonium salt under the action of NaH.

[0015] Preferably, the thickener is magnesium oxide or silicon dioxide.

[0016] Preferably, the preservative is graphene oxide or organic montmorillonite.

[0017] Preferably, the photoinitiator is composed of benzophenone and benzoin isopropyl ether in a mass ratio of 1:(3-4).

[0018] Preferably, the impact resistance of the repair material is >10000 g·cm, the hardness grade reaches 2H, and there is no loss of gloss, bubbling, or shedding after being immersed in a strong acid or alkali solution for 480 hours.

[0019] A preparation process of an underground pipeline repair material based on UV resin comprises the following steps:

[0020] Step 1: Add unsaturated polyester resin, cross-linking diluent, thickener and preservative into dibutyl phthalate and disperse at a speed of 1000-1400 r / min for 1-3 hours to fully mix;

[0021] Step 2: Add a photoinitiator, maintain a rotation speed of 1000-1400 r / min for 20-40 minutes, and stir evenly to obtain an underground pipeline repair material based on UV resin.

[0022] The application method of the UV resin-based underground pipeline repair material in the field of trenchless underground pipeline repair is as follows: immersing the glass fiber cloth into the UV resin-based underground pipeline repair material, heating it to 30-50°C for full immersion, and placing it in a flat vulcanizer for rolling to prepare a glass fiber hose impregnated with the resin; by pulling and compacting with compressed air, the glass fiber hose impregnated with the resin is tightly fitted to the inner wall of the pipeline to be repaired, an ultraviolet lamp with a wavelength of 350-370nm and a power of 250-350W is placed in the hose and the ultraviolet lamp is controlled to move at a speed of 0.3-0.5m / min in the hose, so that the hose is gradually solidified from one end to the other end, tightly attached to the inner wall of the pipeline to be repaired, and a hard pipe-in-pipe structure is formed, so that the underground pipeline that has been damaged or has lost its transportation function can be repaired in situ.

[0023] Beneficial effects:

[0024] The present invention uses an unsaturated polyester resin matrix component, adds a crosslinking diluent, a thickener, a preservative, dibutyl phthalate, a photoinitiator and other auxiliary components, and conducts a research and development experiment on the crosslinking diluent, and develops and synthesizes a diene-type crosslinking diluent and an octene-type crosslinking diluent based on a cage-type polysilsesquioxane;

[0025] Based on this, a new type of underground pipeline repair material based on UV resin was prepared, which has excellent mechanical properties and corrosion resistance. Experimental results show that the underground pipeline repair material based on UV resin developed by the present invention has an impact resistance of >10000g·cm, a hardness grade of 2H, and no gloss loss, bubbling, or shedding after immersion in a strong acid and alkali solution for 480 hours. When used in pipeline repair, it has a technical effect of significantly improving the corrosion resistance of the inside of the pipeline. DETAILED DESCRIPTION

[0026] Embodiment 1:

[0027] Preparation of UV resin-based underground pipeline repair material I: According to the formula in Table 1, the formula amount of TC-191DC unsaturated polyester resin, cross-linking diluent I, magnesium oxide, and graphene oxide are added to the formula amount of dibutyl phthalate and dispersed at a speed of 1200 r / min for 2 hours, and then the formula amount of benzophenone and benzoin isopropyl ether are added, and the speed is maintained at 1200 r / min for 30 minutes. Stir evenly to obtain UV resin-based underground pipeline repair material I;

[0028] Table 1 Formula of UV resin-based underground pipeline repair material I (mass percentage)

[0029]

[0030]

[0031] Wherein, the chemical structure and a preparation process of the cross-linking diluent I are as shown in Experimental Example 1;

[0032] Application experiment of UV resin-based underground pipeline repair material I: The glass fiber cloth is immersed in the UV resin-based underground pipeline repair material I at room temperature, heated to 40°C to allow the UV resin-based underground pipeline repair material I to be fully impregnated into the glass fiber cloth, and then placed in a flat vulcanizer for rolling to prepare a glass fiber hose impregnated with resin; then the glass fiber hose impregnated with resin is compressed by pulling compressed air to make the hose fit tightly to the inner wall of the pipeline to be repaired, an ultraviolet lamp with a wavelength of 365nm and a power of 300W is placed in the hose and the ultraviolet lamp is controlled to move at a speed of 0.4m / min in the hose, so that the hose is gradually solidified from one end to the other end, close to the inner wall of the pipeline to be repaired, forming a hard "tube in tube" structure, so that the underground pipeline that has been damaged or has lost its transportation function can be repaired in situ.

[0033] Embodiment 2:

[0034] Preparation of UV resin-based underground pipeline repair material II: Compared with UV resin-based underground pipeline repair material I, the only difference is that: cross-linking diluent II is used to replace cross-linking diluent I, so as to prepare UV resin-based underground pipeline repair material II;

[0035] Among them, the chemical structure and a preparation process of the cross-linking diluent II are as shown in Experimental Example 2.

[0036] Comparative Example:

[0037] Preparation of basic underground pipeline repair material: Compared with the underground pipeline repair material I based on UV resin, the only difference is that no cross-linking diluent I is used.

[0038] Performance Testing:

[0039] The tinplate sheet was used as the substrate, and was sequentially cleaned with a cleaning agent at room temperature and ultrasonically for 20 minutes, rinsed with deionized water for 4 times, and ultrasonically cleaned with ethanol at room temperature for 5 minutes, and rinsed with deionized water for 2 times, and then dried at 80°C; the underground pipeline repair material based on UV resin was applied to the surface of the tinplate sheet with a brush, and the coating was irradiated with a UV curing lamp (wavelength 365nm, power 300W), with the irradiation light source 10cm away from the coating, and the irradiation time was 3min. After the coating was fully cured, it was placed in a cool and dry place to air dry for 24h, and the performance test was carried out;

[0040] (1) Impact resistance is tested according to GB / T 1732-1993 “Determination of impact resistance of paint films”;

[0041] (2) Hardness is tested according to GB / T 6739-2006 Paints and varnishes - Pencil method;

[0042] (3) Acid and alkali resistance test was conducted according to GB / T 1763-1979 “Determination of chemical resistance of paint film”. The specific test steps are as follows: immerse two-thirds of the length of the sample in 5% sodium hydroxide (sulfuric acid) solution for 480 hours, and observe whether there is obvious loss of gloss, blistering, shedding, etc. on the surface of the plate;

[0043] The above experimental results are shown in Table 2 below.

[0044] Table 2 Performance test results of underground pipeline repair materials based on UV resin

[0045]

[0046] Through comprehensive analysis of the above experimental results, the following conclusions can be drawn:

[0047] Compared with the repair material without adding the cross-linking diluent, the two UV resin-based underground pipeline repair materials prepared by the present invention can significantly improve the impact resistance and hardness, and also achieve the beneficial effect of significantly improving the corrosion resistance of the pipeline interior.

[0048] Experimental Example 1:

[0049] Preparation of cross-linking diluent I: Using sodium octaphenyltetrasilanol as a raw material and 3-acryloxypropylmethyldimethoxysilane as a capping agent, the cross-linking diluent I was synthesized by the top angle capping method under the catalysis of triethylamine, and its chemical structure is:

[0050]

[0051] The specific experimental steps for preparing the cross-linking diluent I are as follows: under the protection of nitrogen, 5.8 g of sodium octaphenyltetrasilane, 1.5 mL of triethylamine and 50 mL of tetrahydrofuran are added to a three-necked flask, and stirred and dissolved for 2 h under ice bath conditions, and then 20 mL of tetrahydrofuran solution containing 2.2 g of methyldichlorosilane is slowly added dropwise to the three-necked flask, the ice bath is removed, and the reaction is stirred at room temperature for 24 h, the solvent is removed by rotary evaporation, and the solution is repeatedly washed with methanol and vacuum dried to obtain the cross-linking diluent I;

[0052] The cross-linking diluent I is characterized by hydrogen nuclear magnetic resonance spectrum: 1 H NMR (CDCl3, 400MHz) δ: 0.09 (s, 6H), 0.95-0.98 (t, 4H), 1.72-1.79 (m, 4H), 4. 04-4.08 (t, 4H), 5.84-5.87 (dd, 4H), 6.06-6.13 (dd, 2H), 7.32-7.55 (m, 40H).

[0053] Experimental Example 2:

[0054] Preparation of cross-linking diluent II: 1,3-dibromopropane and the oxygen anion group of octamethylammonium POSS ammonium salt (TMN-POSS) undergo allyl etherification reaction under the action of NaH to generate cross-linking diluent II, whose chemical structure is:

[0055]

[0056] The specific experimental steps for preparing the cross-linking diluent II are as follows: 4.1 g 1,3-dibromopropane and 3.6 g octamethylammonium POSS ammonium salt are dissolved in 50 mL N,N-dimethylformamide, 1.0 g NaH is added at an ice bath temperature of 0°C, the reaction is stirred at an ice bath of 0°C for 1 h, and at a water bath of 20°C for 18 h. After the reaction is completed, the cross-linking diluent II is obtained by extraction with ethyl acetate, washing with distilled water, rotary evaporation and vacuum drying.

[0057] The nuclear magnetic resonance hydrogen spectrum of the cross-linking diluent II is characterized as follows: 1 H NMR (CDCl3, 400MHz) δ: 4.26-4.38 (m, 16H), 5.19-5.23 (dt, 16H), 5.75-5.86 (dt, 8H).

Claims

1. An underground pipeline repair material based on UV resin, characterized in that: The invention comprises the following raw materials in parts by weight: 40 to 60 parts by weight of unsaturated polyester resin, 1 to 5 parts by weight of cross-linking diluent, 5 to 8 parts by weight of thickener, 5 to 8 parts by weight of preservative, 5 to 15 parts by weight of dibutyl phthalate, and 10 to 30 parts by weight of photoinitiator; Wherein, the cross-linking diluent is cross-linking diluent I or cross-linking diluent II: The chemical structure of the cross-linking diluent I is: The chemical structure of the cross-linking diluent II is:

2. The underground pipeline repair material based on UV resin according to claim 1, characterized in that: The preparation method of the cross-linking diluent I is as follows: using octaphenyltetrasilane sodium salt as a raw material, using 3-acryloxypropylmethyldimethoxysilane as a capping agent, and preparing the cross-linking diluent I by a top angle capping method under the catalysis of triethylamine.

3. The underground pipeline repair material based on UV resin according to claim 1, characterized in that: The preparation method of the cross-linking diluent II is as follows: 1,3-dibromopropane and the oxygen anion group of octamethylammonium POSS ammonium salt undergo allyl etherification reaction under the action of NaH to prepare the cross-linking diluent II.

4. The underground pipeline repair material based on UV resin according to claim 1, characterized in that: The thickener is magnesium oxide or silicon dioxide.

5. The underground pipeline repair material based on UV resin according to claim 1, characterized in that: The preservative is graphene oxide or organic montmorillonite.

6. The underground pipeline repair material based on UV resin according to claim 1, characterized in that: The photoinitiator consists of benzophenone and benzoin isopropyl ether, and the mass ratio thereof is 1:(3-4).

7. The underground pipeline repair material based on UV resin according to claim 1, characterized in that: The repair material has an impact resistance of >10000 g·cm, a hardness grade of 2H, and no gloss loss, bubbling, or shedding after being immersed in a strong acid or alkali solution for 480 hours.

8. A process for preparing an underground pipeline repair material based on UV resin according to any one of claims 1 to 7, characterized in that: The following steps are involved: Step 1: Add unsaturated polyester resin, cross-linking diluent, thickener and preservative into dibutyl phthalate and disperse at a speed of 1000-1400 r / min for 1-3 hours to fully mix; Step 2: Add a photoinitiator, maintain a rotation speed of 1000-1400 r / min for 20-40 minutes, and stir evenly to obtain an underground pipeline repair material based on UV resin.

9. Application of an underground pipeline repair material based on UV resin according to any one of claims 1 to 7 in the field of trenchless underground pipeline repair, characterized in that: The application method comprises the following steps: immersing the glass fiber cloth into the underground pipeline repair material based on UV resin, heating the cloth to 30-50° C. for full immersion, and placing the cloth in a flat vulcanizer for rolling to prepare a glass fiber hose impregnated with the resin; making the glass fiber hose impregnated with the resin fit tightly with the inner wall of the pipeline to be repaired by pulling and pressing with compressed air, placing an ultraviolet lamp with a wavelength of 350-370 nm and a power of 250-350 W in the hose, and controlling the ultraviolet lamp to move at a speed of 0.3-0.5 m / min in the hose, so that the hose is gradually solidified from one end to the other end, and is closely attached to the inner wall of the pipeline to be repaired, so as to form a hard pipe-in-pipe structure, so that the underground pipeline that has been damaged or has lost its transportation function can be repaired in situ.

Images