Glass fiber reinforced plastic threaded elastic sealant, preparation method and application thereof

Abstract

This invention provides a fiberglass thread elastic sealant, its preparation method, and its application. By weight percentage, the fiberglass thread elastic sealant comprises component A and component B. Component A includes liquid polysulfide adhesive, 5-bromo-3-fluoro-2-(vinyloxy)-benzaldehyde, epoxy resin E-51, thermoplastic elastomer TPV, rubber-plastic alloy, dibutyl phthalate, fumed silica, defoamer, and reinforcing carbon black, with the sum of the weight percentages of all components being 100%. Component B includes manganese dioxide, 910 toughening epoxy curing agent, sulfur powder, microcrystalline wax, calcium carbonate powder, dibutyl phthalate, and 2,4,6-tris(dimethylaminomethyl)phenol, with the sum of the weight percentages of all components being 100%.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of glass fiber reinforced plastic pipe threaded connection, and particularly relates to a glass fiber reinforced plastic threaded elastic sealant, a preparation method and application thereof. BACKGROUND

[0002] Glass fiber reinforced plastic is a composite material formed by using glass fiber to reinforce specific resin, and has the advantages of light material, strong corrosion resistance, smooth inner surface, low friction coefficient and small heat transfer coefficient. With the continuous development of the oil and gas industry, a large number of metal gathering and transportation pipelines are laid in the oilfield operation area. Although multiple corrosion prevention measures such as internal and external corrosion prevention coating and injection of corrosion inhibitor are taken, corrosion leakage or fouling will still occur over time, which will cause leakage, environmental pollution and other problems, and seriously affect normal production operation. In view of the many advantages of glass fiber reinforced plastic gathering and transportation pipelines, they have been used in the field of oilfield gathering and transportation pipelines. The glass fiber reinforced plastic gathering and transportation pipelines are connected into long pipelines through threaded connection. Before the threaded connection, a solidifiable glass fiber reinforced plastic threaded sealant is uniformly applied to ensure the overall sealing of the pipeline. However, during the actual operation of the glass fiber reinforced plastic gathering and transportation pipeline, due to the influence of pressure fluctuation of the gathering and transportation system, vibration caused by fluid flow and ground temperature, threaded decoupling or leakage may occur during field use. According to relevant data, the most common position of glass fiber reinforced plastic gathering and transportation pipeline accidents is the threaded connection part.

[0003] After the glass fiber reinforced plastic gathering and transportation pipeline is laid, it needs to be used for a long time, so the sealant at the connection between the pipes also needs to have long-term use performance. However, the existing glass fiber reinforced plastic threaded sealant product has the problems of large change in curing time with temperature, small adhesive strength and insufficient toughness. SUMMARY

[0004] In order to overcome the above-mentioned shortcomings of the prior art, the purpose of the present application is to provide a glass fiber reinforced plastic threaded elastic sealant, a preparation method and application thereof. The sealant has the characteristics of high elasticity, large adhesive strength, strong medium resistance and the like, can maintain high adhesive strength and appropriate curing time and excellent toughness in high and low temperature environments, can effectively block the leakage gap of the glass fiber reinforced plastic threaded connection, and has strong sealing effect.

[0005] In order to achieve the above-mentioned purpose, the following technical solutions are adopted in the present application:

[0006] The application provides a glass steel threaded elastic sealant, which comprises an A component and a B component, and the mass ratio of the A component to the B component is 20:(4-5); the A component comprises the following components in percentage by weight: 15-25% of liquid polysulfide glue, 10-16% of 5-bromo-3-fluoro-2-(vinyl oxy)-benzaldehyde, 10-15% of epoxy resin E-51, 7-13% of thermoplastic elastomer TPV, 8-14% of rubber plastic alloy, 7-13% of dibutyl phthalate, 1-5% of fumed silica, 0.5-2% of defoaming agent, and 15-25% of reinforcing carbon black, and the sum of the percentages by weight of all the components of the A component is 100%;

[0007] The B component comprises the following components: 7-13% of manganese dioxide, 8-12% of epoxy curing agent, 1-2% of sulfur powder, 15-18% of microcrystalline wax, 25-35% of calcium carbonate powder, 25-32% of dibutyl phthalate, and 1-5% of 2,4,6-tris(dimethyl aminomethyl) phenol, and the sum of the percentages by weight of all the components of the B component is 100%.

[0008] The application further provides a preparation method of the glass steel threaded elastic sealant, which comprises the following steps:

[0009] 5-bromo-3-fluoro-2-(vinyl oxy)-benzaldehyde is prepared, and the liquid polysulfide glue, 5-bromo-3-fluoro-2-(vinyl oxy)-benzaldehyde, epoxy resin E-51, thermoplastic elastomer TPV, rubber plastic alloy, dibutyl phthalate, fumed silica, defoaming agent and reinforcing carbon black are mixed in proportion to obtain the A component;

[0010] Manganese dioxide, epoxy curing agent, sulfur powder, microcrystalline wax, calcium carbonate powder, dibutyl phthalate and 2,4,6-tris(dimethyl aminomethyl) phenol are mixed in proportion to obtain the B component;

[0011] The A component and the B component are mixed in a mass ratio of 20:(4-5) to obtain the glass steel threaded elastic sealant.

[0012] In the specific implementation process, the preparation of 5-bromo-3-fluoro-2-(vinyl oxy)-benzaldehyde comprises the following steps:

[0013] S1: 5-bromo-3-fluoro-2-hydroxybenzaldehyde is mixed with dibromoethane and dissolved in N,N-dimethylformamide, anhydrous potassium carbonate is added, the temperature is raised to a first set temperature and reacted for a first set time, the temperature is lowered to room temperature after the reaction is completed, then the organic phase is extracted, combined and washed, and the organic phase is post-treated to obtain 5-bromo-3-fluoro-2-(2-bromoethoxy)-benzaldehyde;

[0014] S2: dissolve 5-bromo-3-fluoro-2-(2-bromoethoxy)-benzaldehyde in anhydrous tetrahydrofuran, lower the temperature to a second set temperature under a protective gas, add potassium tert-butoxide, stir the reaction at a third set temperature for a second set time, after the reaction is completed, purify the reaction liquid to obtain 5-bromo-3-fluoro-2-(ethenyloxy)-benzaldehyde.

[0015] In the implementation process, in the S1, the mass ratio of the 5-bromo-3-fluoro-2-hydroxybenzaldehyde to the dibromoethane is (18-23):(20-26).

[0016] In the implementation process, in the S1, the mass ratio of the dibromoethane to the anhydrous potassium carbonate is (20-26):(13-20).

[0017] In the implementation process, in the S1, the first set temperature is 75-85℃, and the first set time is 15-17h.

[0018] In the implementation process, in the S2, the mass ratio of the 5-bromo-3-fluoro-2-(2-bromoethoxy)-benzaldehyde to the potassium tert-butoxide is (17-23):(5-10).

[0019] In the implementation process, in the S2, the second set temperature is -18--22℃, the third set temperature is -17--22℃, and the second set time is 1-2h.

[0020] The application further provides an application of the glass steel threaded elastic sealant in a glass steel pipeline.

[0021] Compared with the prior art, the application has the following beneficial effects:

[0022] The application provides a glass steel threaded elastic sealant, which comprises A component and B component, wherein the introduction of 5-bromo-3-fluoro-2-(vinyl oxy)-benzaldehyde monomer in the A component is mainly to introduce fluorine atoms into the whole system, so that the system has excellent heat resistance, oxidation resistance, oil resistance, corrosion resistance and atmospheric aging resistance, so that the sealant can not only adapt to normal working conditions, but also adapt to harsh environments such as high temperature, large temperature difference in four seasons and the like. The liquid polysulfide rubber is a raw material, and the polysulfide rubber has excellent properties such as oil resistance, solvent resistance, oxygen and ozone resistance, water resistance, high and low temperature resistance and the like after polymerization with manganese dioxide, has a long storage time, good flexibility, can long-term quality glass steel threaded sealing, and can also adapt to the vibration of the pipeline caused by the change of the internal medium pressure of the glass steel pipeline and the change of the environmental temperature. The epoxy resin can make up for the insufficient bonding strength of the polysulfide rubber. The thermoplastic elastomer TPV has excellent dynamic fatigue resistance, high tear resistance, compression deformation resistance, excellent weather resistance, good wear resistance and excellent flame retardation and ultraviolet resistance, and has excellent erosion resistance to water-based acid and alkali liquid and polar oil. The introduction of the filler is mainly to improve the dynamic fatigue resistance and tear resistance of the whole system, and also improves the toughness, and the addition to the glass agent can greatly improve the toughness, weather resistance and a series of comprehensive properties of the product. The rubber-plastic alloy is an excellent oil-resistant material, has large strength, oil resistance, solvent resistance, weather resistance and outstanding heat aging resistance, and is suitable for long-term service operation. Dibutyl phthalate is used as a plasticizer to increase the softness of the system. Fumed silica is used as a thickening agent to adjust the dilution of the system. The defoaming agent is used to prevent foam formation or reduce the original foam. Reinforcing carbon black is used as a filler to improve the strength of the system. The manganese dioxide powder in the B component of the system is a initiator of the polysulfide rubber; the sulfur powder is a promoter for the polymerization of the manganese dioxide initiated polysulfide rubber; the calcium carbonate is a filler; the 910 toughening epoxy curing agent is an epoxy curing agent, which also has the function of improving the toughness of the system; and the microcrystalline wax has good flexibility and large elongation, and is used to improve the gloss of the system.

[0023] The glass steel threaded sealant can long-term bear the erosion, impact of the conveying medium, vibration environment temperature change and other factors caused by the change of the conveying medium pressure, has good weather resistance and corrosion resistance, can be applied to the surrounding environment temperature and has good toughness, and can bear long-term and frequent vibration and pressure impact. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 A process diagram for preparing 5-bromo-3-fluoro-2-(vinyl oxy)-benzaldehyde of the application. DETAILED DESCRIPTION

[0025] To enable persons skilled in the art to understand the features and effects of the present application, the following is a general description and definition of the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific words used herein have the usual meaning understood by those skilled in the art of the present application, and in the event of a conflict, the definitions in the specification shall prevail.

[0026] Theories and mechanisms described and disclosed herein, whether correct or not, should not be considered limiting on the scope of the present application, which is defined only by the claims. The present application can be implemented in ways other than those specifically set forth herein without departing from the essential or underlying teachings thereof.

[0027] Herein, all features defined by numerical ranges or percentage ranges, such as numerical values, amounts, contents and concentrations, are for the sake of brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have encompassed and specifically disclosed all possible sub-ranges and individual numerical values within the range (including integers and fractions).

[0028] Herein, unless otherwise specified, "comprise", "include", "contain", "have" or similar words are intended to cover the meaning of "consist of" and "consist essentially of", for example, "A comprises a" covers the meaning of "A comprises a and other" and "A comprises only a".

[0029] Herein, for the sake of brevity, all possible combinations of the various technical features in the various embodiments or examples are not described. Therefore, the various technical features in the various embodiments or examples can be combined in any manner as long as there is no contradiction, and all possible combinations should be considered as falling within the scope of the present specification.

[0030] The present application provides a glass fiber reinforced plastic threaded elastic sealant, a preparation method and an application thereof.

[0031] The present application will be further described in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present application and not intended to limit the scope of the present application. Furthermore, it should be understood that those skilled in the art can make various modifications or changes to the present application after reading the content taught by the present application, and these equivalent forms also fall within the scope of the claims attached hereto.

[0032] The following examples use conventional apparatus in the art. The experimental methods in the following examples, unless otherwise specified, are usually carried out under conventional conditions, or under the conditions recommended by the manufacturer. In the following examples, various raw materials are used, unless otherwise specified, and conventional commercially available products are used, which are conventional specifications in the art. In the specification of the present application and in the following examples, unless otherwise specified, "%" means weight percent, "parts" means weight parts, and the ratio means weight ratio.

[0033] The present application provides a glass steel threaded elastic sealant, the glass steel threaded elastic sealant comprises A component and B component by weight percentage, the mass ratio of A component to B component is 20:(4-5). A component comprises: 15%-25% of liquid polysulfide glue, 10%-16% of 5-bromo-3-fluoro-2-(vinyl oxy)-benzaldehyde, 10%-15% of epoxy resin E-51, 7%-13% of thermoplastic elastomer TPV, 8%-14% of rubber plastic alloy, 7%-13% of dibutyl phthalate, 1%-5% of fumed silica, 0.5%-2% of defoaming agent, 15%-25% of reinforcing carbon black, the sum of the weight percentages of all components is 100%; the liquid polysulfide rubber is JLY-124 type of Jinxi Chemical Research Institute Co., Ltd., the material is a raw material for preparing polysulfide glue, the polysulfide glue has excellent properties such as oil resistance, solvent resistance, oxygen and ozone resistance, water resistance, high and low temperature resistance after polymerization with manganese dioxide, has long storage time, good flexibility, can long-term quality glass steel threaded seal, can also adapt to the vibration of the pipeline caused by the change of the internal medium pressure of the glass steel pipeline and the environmental temperature.

[0034] The introduction of 5-bromo-3-fluoro-2-(vinyl oxy)-benzaldehyde monomer mainly introduces fluorine atoms into the whole system, and endows the system with excellent heat resistance, oxidation resistance, oil resistance, corrosion resistance and atmospheric aging resistance, so that the application can not only adapt to conventional working conditions, but also adapt to harsh environments such as deserts, gobi, large temperature difference between seasons and the like.

[0035] E-51 epoxy resin is used to make up for the insufficient bonding strength of polysulfide glue, and the above raw material is easily available in the market.

[0036] The thermoplastic elastomer TPV has excellent dynamic fatigue resistance, high tear resistance, compression deformation resistance, excellent weather resistance, good wear resistance and excellent flame retardant and ultraviolet resistance, and has excellent corrosion resistance to water-based acid and alkali liquids and polar oil products. The introduction of the filler mainly improves the dynamic fatigue resistance and tear resistance of the whole system, and also improves the toughness. The addition to the system greatly improves the toughness, weather resistance and a series of comprehensive properties of the product. The selected SEBS thermoplastic elastomer TPV is sold by Shanghai Foreign Power International Trade Co., Ltd.

[0037] The rubber plastic alloy is an excellent oil-resistant material with high strength, oil resistance, solvent resistance, weather resistance and outstanding heat aging resistance, and is suitable for long-term service operation. The material used in the application is NV3460-3H produced by Hengshui Ruian Rubber Plastic Technology Co., Ltd.

[0038] Dibutyl phthalate is a common plasticizer, increasing the softness of the system, the above raw materials are easy to buy in the market.

[0039] Fumed silica is a thickening agent for adjusting the dilution of the system, and A380 produced by Degussa is selected in the application.

[0040] The surface tension of the defoaming agent system prevents the formation of foam or reduces the existing foam, and the X-278 type defoaming agent of Yantai Hengxin Chemical Technology Co., Ltd. X-278 type defoaming agent.

[0041] Reinforcing carbon black is mainly used as a filler and to improve the strength of the system, and the N550 of Cabot, USA, is used in the application.

[0042] The B component comprises 7-13% of manganese dioxide, 8-12% of an epoxy curing agent, preferably 910 toughened epoxy curing agent, 1-2% of sulfur powder, 15-18% of microcrystalline wax, 25-35% of calcium carbonate powder, 25-32% of dibutyl phthalate, and 1-5% of 2,4,6-tris(dimethylaminomethyl) phenol, and the sum of the weight percentages of all components is 100%.

[0043] Manganese dioxide powder is a polymerization initiator of polysulfide glue; sulfur powder is a promoter for the polymerization of manganese dioxide-initiated polysulfide glue; calcium carbonate is a filler, and DMP-30 is a promoter for the curing of epoxy resin in the system, and the above components are easy to buy in the market. The particle size of the above powder components is selected to be in the range of 30-60 microns. 910 toughened epoxy curing agent is an epoxy curing agent, and the curing agent also has the function of improving the toughness of the system, and the product can be purchased at Changsha Chemical Research Institute. Microcrystalline wax has good flexibility, large elongation, and improves the gloss of the system, and the 70# microcrystalline wax product produced by Sinopec is selected in the system.

[0044] The application also provides a preparation method of the glass steel threaded elastic sealant, comprising the following steps:

[0045] Preparation of the A component:

[0046] Step 1: Preparation of 5-bromo-3-fluoro-2-(vinyl oxy)-benzaldehyde:

[0047] As Figure 1The compound 5-bromo-3-fluoro-2-hydroxybenzaldehyde and dibromoethane with a mass ratio of (18-23):(20-26) were dissolved in DMF, anhydrous potassium carbonate (13-20 g) was added, the mass ratio of dibromoethane to anhydrous potassium carbonate was (20-26):(13-20), and the temperature was raised to 75-85°C for 15-17 h. After being cooled to room temperature, the reaction solution was poured into water (480-510 mL), then extracted with ethyl acetate (190-210 mL), and the organic phase was combined and washed with saturated brine (190-210 mL). The organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure, and then purified by silica gel column chromatography to obtain a yellow oil.

[0048] The obtained product No. 1, 5-bromo-3-fluoro-2-(2-bromoethoxy)-benzaldehyde (17-23 g), was dissolved in anhydrous THF (140-160 mL), and the temperature was lowered to -18 to -22°C under nitrogen protection, and potassium tert-butoxide (5-10 g) was added, the mass ratio of 5-bromo-3-fluoro-2-(2-bromoethoxy)-benzaldehyde to potassium tert-butoxide was (17-23):(5-10), and the reaction was stirred at -17 to -22°C for 1-2 h. After the reaction was completed, the reaction solution was directly quickly purified by silica gel column to obtain a yellow oil, which was product No. 2, 5-bromo-3-fluoro-2-(vinyloxy)-benzaldehyde.

[0049] Step two: liquid polysulfide glue, 5-bromo-3-fluoro-2-(vinyloxy)-benzaldehyde, epoxy resin E-51, thermoplastic elastomer TPV, rubber-plastic alloy, dibutyl phthalate, fumed silica, defoaming agent, and reinforcing carbon black were mixed in a certain proportion for 1-1.5 h to prepare component A;

[0050] Step three: manganese dioxide, 910 toughened epoxy curing agent, sulfur powder, microcrystalline wax, calcium carbonate, calcium carbonate powder, dibutyl phthalate, and 2,4,6-tris(dimethylaminomethyl)phenol were mixed and stirred in a certain proportion for 2-2.5 h to prepare component B;

[0051] Step four: components A and B were mixed in a mass ratio of 100:(20-25) to prepare a glass steel threaded elastic sealant.

[0052] The glass steel threaded elastic sealant was evenly applied to the surface of the glass steel threaded surface with a brush equipped with a brush, and used as a sealant for glass steel gathering pipelines.

[0053] Example 1:

[0054] The weight ratio of each component of the A component is: liquid polysulfide glue 20%, 5-bromo-3-fluoro-2-(vinyl-oxy)-benzaldehyde 13%, epoxy resin E-51 12%, thermoplastic elastomer TPV 10%, rubber-plastic alloy 11%, dibutyl phthalate 10%, fumed silica 3%, defoaming agent 1%, reinforcing carbon black 20%.

[0055] The 5-bromo-3-fluoro-2-(vinyl-oxy)-benzaldehyde in the A component is prepared according to the following method:

[0056] First step: Compound 5-bromo-3-fluoro-2-hydroxybenzaldehyde (21.9 g, 0.10 mol) and dibromoethane (22.5 g, 0.12 mol) are dissolved in DMF (250 mL), anhydrous potassium carbonate (16.6 g, 0.12 mol) is added, and the temperature is raised to 80°C for 16 hours. After cooling to room temperature, the reaction solution is poured into water (500 mL), and then extracted with ethyl acetate (200 mL) three times, and the organic phase is combined and washed with saturated brine (200 mL). The organic phase is dried over anhydrous sodium sulfate, filtered, and the filtrate is concentrated under reduced pressure, and then purified by silica gel column chromatography to obtain 22.2 g of yellow oil, with a yield of about 68%.

[0057] Second step: The product 5-bromo-3-fluoro-2-(2-bromoethoxy)-benzaldehyde obtained in step 1 (20.0 g, 61.3 mmol) is dissolved in anhydrous THF (150 mL), and the temperature is lowered to -20°C under nitrogen protection, and potassium tert-butoxide (7.2 g, 64.4 mmol) is added, and the reaction is stirred at -17°C for 1 hour. After the reaction is completed, the reaction solution is quickly purified by silica gel column to obtain 5-bromo-3-fluoro-2-(vinyl-oxy)-benzaldehyde in the form of yellow oil, with a yield of about 55%.

[0058] The product No. 2 is 5-bromo-3-fluoro-2-(vinyl-oxy)-benzaldehyde.

[0059] The weight ratio of each component of the B component is: manganese dioxide 10%, 910 toughened epoxy curing agent 10.5%, sulfur powder 1.5%, microcrystalline wax 17%, calcium carbonate powder 30%, dibutyl phthalate 28%, DMP-30 3%.

[0060] The preparation method is: first, 5-bromo-3-fluoro-2-(vinyl-oxy)-benzaldehyde is prepared according to the above process, and then the A component is prepared by mixing and stirring the above-mentioned A component in the proportion of 1 hour; the B component is mixed and stirred for 2.5 hours according to the above-mentioned proportion. After the preparation of the A component and the B component is completed, the A component:B component is 100:22 before use, and then it is used after being stirred uniformly. It is uniformly applied to the surface of the glass steel thread by using the equipped brush.

[0061] Example 2:

[0062] The individual components of the A component are in the following weight ratio: liquid polysulfide glue 23%, 5-bromo-3-fluoro-2-(ethenyloxy)-benzaldehyde 11%, epoxy resin E-51 13%, thermoplastic elastomer TPV 12%, rubber-plastic alloy 9%, dibutyl phthalate 11%, fumed silica 4%, defoaming agent 1%, reinforcing carbon black 16%.

[0063] The 5-bromo-3-fluoro-2-(ethenyloxy)-benzaldehyde in the A component is prepared according to the following method:

[0064] First step: Compound 5-bromo-3-fluoro-2-hydroxybenzaldehyde (21.9 g, 0.10 mol) and dibromoethane (22.5 g, 0.12 mol) are dissolved in DMF (250 mL), anhydrous potassium carbonate (16.6 g, 0.12 mol) is added, and the temperature is raised to 80°C for 16 hours. After cooling to room temperature, the reaction solution is poured into water (500 mL), and then extracted with ethyl acetate (200 mL x 3), and the organic phase is combined and washed with saturated brine (200 mL). The organic phase is dried over anhydrous sodium sulfate, filtered, and the filtrate is concentrated under reduced pressure, and then purified by silica gel column chromatography to obtain 22.2 g of yellow oil, with a yield of about 68%.

[0065] Second step: The product 5-bromo-3-fluoro-2-(2-bromoethoxy)-benzaldehyde obtained in step 1 (20.0 g, 61.3 mmol) is dissolved in anhydrous THF (150 mL), and the temperature is lowered to -20°C under nitrogen protection, and potassium tert-butoxide (7.2 g, 64.4 mmol) is added, and stirred at -19°C for 1 hour. After the reaction is completed, the reaction solution is directly quickly purified by silica gel column to obtain 5-bromo-3-fluoro-2-(ethenyloxy)-benzaldehyde in the form of yellow oil, with a yield of about 55%.

[0066] The product No. 2 is 5-bromo-3-fluoro-2-(ethenyloxy)-benzaldehyde.

[0067] The individual components of the B component are in the following weight ratio: manganese dioxide 12%, 910 toughened epoxy curing agent 11.5%, sulfur powder 1.5%, microcrystalline wax 15%, calcium carbonate powder 30%, dibutyl phthalate 27%, DMP-30 3%.

[0068] The preparation method is as follows: first, 5-bromo-3-fluoro-2-(ethenyloxy)-benzaldehyde is prepared according to the above process, and then the A component is prepared by mixing and stirring the above-mentioned A component in the above-mentioned proportions for 1 hour; the B component is prepared by mixing and stirring the above-mentioned proportions for 2 hours. After the preparation of the A component and the B component is completed, the A component and the B component are used according to the ratio of A component:B component = 100:22, and are stirred uniformly before use, and are evenly applied to the surface of the glass steel thread using the provided brush.

[0069] Example 3:

[0070] The individual components of the A component are in a weight ratio of: liquid polysulfide 20%, 5-bromo-3-fluoro-2-(vinyloxy)-benzaldehyde 14%, epoxy resin E-51 11%, thermoplastic elastomer TPV 10%, rubber-plastic alloy 11%, dibutyl phthalate 12%, fumed silica 3%, defoaming agent 1%, reinforcing carbon black 18%.

[0071] The 5-bromo-3-fluoro-2-(vinyloxy)-benzaldehyde in the A component is prepared according to the following method:

[0072] First step: Compound 5-bromo-3-fluoro-2-hydroxybenzaldehyde (21.9 g, 0.10 mol) and dibromoethane (22.5 g, 0.12 mol) are dissolved in DMF (250 mL), anhydrous potassium carbonate (16.6 g, 0.12 mol) is added, and the temperature is raised to 80°C for 16 hours. After cooling to room temperature, the reaction solution is poured into water (500 mL), and then extracted with ethyl acetate (200 mL x 3), and the organic phase is washed with saturated brine (200 mL). The organic phase is dried with anhydrous sodium sulfate, filtered, and the filtrate is concentrated under reduced pressure, and then purified by silica gel column chromatography to obtain 22.2 g of yellow oil, with a yield of about 68%.

[0073] Second step: The product 5-bromo-3-fluoro-2-(2-bromoethoxy)-benzaldehyde obtained in step 1 (20.0 g, 61.3 mmol) is dissolved in anhydrous THF (150 mL), and the temperature is lowered to -20°C under nitrogen protection, and potassium tert-butoxide (7.2 g, 64.4 mmol) is added, and stirred at -20°C for 1 hour. After the reaction is completed, the reaction solution is directly quickly purified by silica gel column to obtain 5-bromo-3-fluoro-2-(vinyloxy)-benzaldehyde in the form of yellow oil, with a yield of about 55%.

[0074] The product No. 2 is 5-bromo-3-fluoro-2-(vinyloxy)-benzaldehyde.

[0075] The individual components of the B component are in a weight ratio of: manganese dioxide 11%, 910 toughening epoxy curing agent 10.5%, sulfur powder 1.5%, microcrystalline wax 16%, calcium carbonate powder 29%, dibutyl phthalate 29%, DMP-30 3%.

[0076] The preparation method is: first, 5-bromo-3-fluoro-2-(ethenyloxy)-benzaldehyde is prepared according to the above process, then the A component is prepared by mixing and stirring the A component according to the above proportion for 1.2 hours; the B component can be prepared by mixing and stirring the B component according to the above proportion for 2.2 hours. After the preparation of the A component and the B component is completed, the A component: B component = 100:23 is used before use, and the mixture is stirred uniformly before use. The prepared mixture is uniformly applied to the surface of the glass steel thread by using the provided brush.

[0077] Example 4:

[0078] The weight ratio of each component of the A component is: liquid polysulfide 15%, 5-bromo-3-fluoro-2-(ethenyloxy)-benzaldehyde 16%, epoxy resin E-51 15%, thermoplastic elastomer TPV 13%, rubber-plastic alloy 14%, dibutyl phthalate 7%, fumed silica 1%, defoaming agent 0.5%, reinforcing carbon black 18.5%.

[0079] The 5-bromo-3-fluoro-2-(ethenyloxy)-benzaldehyde in the A component is prepared according to the following method:

[0080] First step: Compound 5-bromo-3-fluoro-2-hydroxybenzaldehyde (18.0 g) and dibromoethane (20.0 g) are dissolved in DMF (250 mL), anhydrous potassium carbonate (13.0 g) is added, and the temperature is raised to 75°C for 15 hours. After the temperature is lowered to room temperature, the reaction solution is poured into water (500 mL), then extracted with ethyl acetate (200 mL x 3), and the combined organic phase is washed with saturated brine (200 mL). The organic phase is dried over anhydrous sodium sulfate, filtered, and the filtrate is concentrated under reduced pressure, then purified by silica gel column chromatography to obtain a yellow oil.

[0081] Second step: The product 5-bromo-3-fluoro-2-(2-bromoethoxy)-benzaldehyde (17.0 g) obtained in step 1 is dissolved in anhydrous THF (150 mL), and the temperature is lowered to -20°C under nitrogen protection. Potassium tert-butoxide (5.0 g) is added, and the reaction is stirred at -18°C for 1 hour. After the reaction is completed, the reaction solution is directly quickly purified by silica gel column to obtain yellow oil 5-bromo-3-fluoro-2-(ethenyloxy)-benzaldehyde.

[0082] The product No. 2 is 5-bromo-3-fluoro-2-(ethenyloxy)-benzaldehyde.

[0083] The weight ratio of each component of the B component is: manganese dioxide 13%, 910 toughened epoxy curing agent 12%, sulfur powder 1%, microcrystalline wax 18%, calcium carbonate powder 30%, dibutyl phthalate 25%, DMP-30 1%.

[0084] The preparation method is: first, 5-bromo-3-fluoro-2-(ethenyloxy)-benzaldehyde is prepared according to the above process, then A component is prepared by mixing and stirring A component according to the above proportion for 1h; B component is prepared by mixing and stirring B component according to the above proportion for 2h. After the preparation of A component and B component is completed, A component: B component = 100:20 is used before use, and then it can be used after being stirred uniformly. It is uniformly applied to the glass steel thread surface by using the equipped brush.

[0085] Example 5:

[0086] The weight ratio of each component of A component is: liquid polysulfide 25%, 5-bromo-3-fluoro-2-(ethenyloxy)-benzaldehyde 10%, epoxy resin E-51 10%, thermoplastic elastomer TPV 7%, rubber-plastic alloy 8%, dibutyl phthalate 13%, fumed silica 5%, defoaming agent 2%, reinforcing carbon black 20%.

[0087] The 5-bromo-3-fluoro-2-(ethenyloxy)-benzaldehyde in A component is prepared according to the following method:

[0088] First step: Compound 5-bromo-3-fluoro-2-hydroxybenzaldehyde (23.0 g) and dibromoethane (26.0 g) are dissolved in DMF (250 mL), anhydrous potassium carbonate (20.0 g) is added, and the temperature is raised to 85°C for 17 hours. After the temperature is lowered to room temperature, the reaction solution is poured into water (500 mL), and then extracted with ethyl acetate (200 mL x 3), and the combined organic phase is washed with saturated brine (200 mL). The organic phase is dried with anhydrous sodium sulfate, filtered, and the filtrate is concentrated under reduced pressure, and then purified by silica gel column chromatography to obtain a yellow oil.

[0089] Second step: The product 5-bromo-3-fluoro-2-(2-bromoethoxy)-benzaldehyde (23.0 g) obtained in step 1 is dissolved in anhydrous THF (150 mL), and the temperature is lowered to -20°C under nitrogen protection, and then potassium tert-butoxide (10.0 g) is added, and the reaction is stirred at -17 to -22°C for 1 hour. After the reaction is completed, the reaction solution is directly quickly purified by silica gel column to obtain yellow oil 5-bromo-3-fluoro-2-(ethenyloxy)-benzaldehyde.

[0090] The product No. 2 is 5-bromo-3-fluoro-2-(ethenyloxy)-benzaldehyde.

[0091] The weight ratio of each component of B component is: manganese dioxide 7%, 910 toughened epoxy curing agent 8%, sulfur powder 2%, microcrystalline wax 15%, calcium carbonate powder 35%, dibutyl phthalate 32%, DMP-30 1%.

[0092] The preparation method is: first, according to the above process, 5-bromo-3-fluoro-2- (vinyl oxy) -benzaldehyde is prepared, then the A component is prepared by mixing and stirring the A component according to the above proportion for 1.5h; the B component is prepared by mixing and stirring the B component according to the above proportion for 2.5h. After the preparation of the A component and the B component is completed, before use, according to the proportion of A component: B component = 100:25, after stirring uniformly, it can be used, and it is uniformly coated on the glass steel thread surface with the equipped brush.

[0093] Example 6:

[0094] The weight ratio of each component of the A component is: liquid polysulfide 15%, 5-bromo-3-fluoro-2- (vinyl oxy) -benzaldehyde 13%, epoxy resin E-51 15%, thermoplastic elastomer TPV 13%, rubber plastic alloy 14%, dibutyl phthalate 13%, fumed silica 1%, defoaming agent 1%, reinforcing carbon black 15%.

[0095] The 5-bromo-3-fluoro-2- (vinyl oxy) -benzaldehyde in the A component is prepared according to the following method:

[0096] First step: dissolve compound 5-bromo-3-fluoro-2-hydroxybenzaldehyde (20.0g) and dibromoethane (23.0g) in DMF (250mL), add anhydrous potassium carbonate (15.0g), and heat to 80℃ for 16 hours. After cooling to room temperature, pour the reaction liquid into water (500mL), then extract with ethyl acetate (200mL x 3), and combine the organic phases, then wash with saturated brine (200mL). Dry the organic phase with anhydrous sodium sulfate, filter, and concentrate the filtrate under reduced pressure, then purify by silica gel column chromatography to obtain a yellow oil.

[0097] Second step: dissolve the product 5-bromo-3-fluoro-2- (2-bromoethoxy) -benzaldehyde (22.0g) obtained in step 1 in anhydrous THF (150mL), and cool to -20℃ under nitrogen protection, then add potassium tert-butoxide (8.0g), and stir at -17℃ for 1 hour. After the reaction is completed, the reaction liquid is directly quickly purified by silica gel column to obtain yellow oil 5-bromo-3-fluoro-2- (vinyl oxy) -benzaldehyde.

[0098] The product No. 2 is 5-bromo-3-fluoro-2- (vinyl oxy) -benzaldehyde.

[0099] The weight ratio of each component of the B component is: manganese dioxide 13%, 910 toughened epoxy curing agent 8%, sulfur powder 2%, microcrystalline wax 18%, calcium carbonate powder 25%, dibutyl phthalate 29%, DMP-30 5%.

[0100] The preparation method is: first, according to the above process, 5-bromo-3-fluoro-2-(ethenyloxy)-benzaldehyde is prepared, then the A component is prepared by mixing and stirring the A component according to the above proportion for 1h; the B component is prepared by mixing and stirring the B component according to the above proportion for 2h. After the preparation of the A component and the B component is completed, before use, the A component and the B component are mixed according to the proportion of A component: B component = 100: 24, and then used after stirring uniformly. The prepared brush is used to evenly coat the glass steel thread surface.

[0101] Example 7:

[0102] The weight ratio of each component of the A component is: liquid polysulfide 20%, 5-bromo-3-fluoro-2-(ethenyloxy)-benzaldehyde 10%, epoxy resin E-51 12%, thermoplastic elastomer TPV 12%, rubber-plastic alloy 9%, dibutyl phthalate 7%, fumed silica 4%, defoaming agent 1%, reinforcing carbon black 25%.

[0103] The 5-bromo-3-fluoro-2-(ethenyloxy)-benzaldehyde in the A component is prepared according to the following method:

[0104] First step: dissolve compound 5-bromo-3-fluoro-2-hydroxybenzaldehyde (21.9g, 0.10mol) and dibromoethane (22.5g, 0.12mol) in DMF (250mL), add anhydrous potassium carbonate (16.6g, 0.12mol), and heat to 80℃ for 16 hours. Reduce to room temperature, pour the reaction liquid into water (500mL), then extract with ethyl acetate (200mL x 3), and combine the organic phase, then wash with saturated brine (200mL). Dry the organic phase with anhydrous sodium sulfate, filter, and concentrate the filtrate under reduced pressure, then purify by silica gel column chromatography to obtain a yellow oil.

[0105] Second step: dissolve the product 5-bromo-3-fluoro-2-(2-bromoethoxy)-benzaldehyde (20.0g, 61.3mmol) obtained in step 1 in anhydrous THF (150mL), and cool to -20℃ under nitrogen protection. Add potassium tert-butoxide (7.2g, 64.4mmol), and stir at -22℃ for 1 hour. After the reaction is completed, the reaction liquid is directly quickly purified by silica gel column to obtain yellow oil 5-bromo-3-fluoro-2-(ethenyloxy)-benzaldehyde.

[0106] The product No. 2 is 5-bromo-3-fluoro-2-(ethenyloxy)-benzaldehyde.

[0107] The weight ratio of each component of the B component is: manganese dioxide 12%, 910 toughened epoxy curing agent 12%, sulfur powder 2%, microcrystalline wax 15%, calcium carbonate powder 25%, dibutyl phthalate 32%, DMP-30%.

[0108] The preparation method is: first, 5-bromo-3-fluoro-2-(vinyl-oxy)-benzaldehyde is prepared according to the above process, then A component is prepared by mixing and stirring A component of the above-mentioned proportions for 1.5 hours; B component is prepared by mixing and stirring B component of the above-mentioned proportions for 2.5 hours. After A component and B component are prepared, A component:B component=100:21 is used before use, and the mixture is stirred uniformly before use, and then the mixture is uniformly applied to the glass steel thread surface using the provided brush.

[0109] The two-component glass steel thread sealant prepared according to the above formula and process can be prepared into a sealant product with high toughness, vibration resistance, corrosion resistance and high medium sealing, etc.

[0110] Performance test:

[0111]

[0112]

[0113] The present application relates to a sealant used in the threaded connection of glass steel pipe, which has high elasticity, large bonding strength, strong medium resistance and other characteristics, can effectively block the leakage gap of glass steel thread, and has strong sealing effect.

[0114] The above content only illustrates the technical idea of the present application, and cannot limit the protection scope of the present application. Any modification made according to the technical idea of the present application on the basis of the technical scheme falls within the protection scope of the claims of the present application.

Claims

1. A glass reinforced thread elastic sealant, characterized in that, The glass steel threaded elastic sealant comprises an A component and a B component, and the mass ratio of the A component to the B component is 20:(4-5). The A component comprises, in percentage by weight, 15-25% of liquid polysulfide glue, 10-16% of 5-bromo-3-fluoro-2-(vinyl-oxy)-benzaldehyde, 10-15% of epoxy resin E-51, 7-13% of thermoplastic elastomer TPV, 8-14% of rubber-plastic alloy, 7-13% of dibutyl phthalate, 1-5% of fumed silica, 0.5-2% of defoaming agent, and 15-25% of reinforcing carbon black, and the sum of the percentages by weight of all the component raw materials of the A component is 100%. The B component comprises, in percentage by weight, 7-13% of manganese dioxide, 8-12% of epoxy curing agent, 1-2% of sulfur powder, 15-18% of microcrystalline wax, 25-35% of calcium carbonate powder, 25-32% of dibutyl phthalate, and 1-5% of 2,4,6-tris(dimethylaminomethyl)phenol, and the sum of the percentages by weight of all the component raw materials of the B component is 100%.

2. A method of preparing a glass steel threaded elastomeric seal according to claim 1, characterized in that, The method comprises the following steps: 5-bromo-3-fluoro-2-(vinyl-oxy)-benzaldehyde is prepared, and liquid polysulfide glue, 5-bromo-3-fluoro-2-(vinyl-oxy)-benzaldehyde, epoxy resin E-51, thermoplastic elastomer TPV, rubber-plastic alloy, dibutyl phthalate, fumed silica, defoaming agent, and reinforcing carbon black are mixed in proportion to prepare the A component; manganese dioxide, epoxy curing agent, sulfur powder, microcrystalline wax, calcium carbonate powder, dibutyl phthalate, and 2,4,6-tris(dimethylaminomethyl)phenol are mixed in proportion to prepare the B component; The A component and the B component are mixed in a mass ratio of 20:(4-5) to prepare the glass steel threaded elastic sealant.

3. The method of claim 2, wherein the glass steel threaded elastomeric seal is prepared by the steps of: The preparation of 5-bromo-3-fluoro-2-(vinyl-oxy)-benzaldehyde comprises the following steps: S1: 5-bromo-3-fluoro-2-hydroxybenzaldehyde is mixed with dibromoethane and dissolved in N,N-dimethylformamide, anhydrous potassium carbonate is added, the temperature is raised to a first set temperature and reacted for a first set time, the temperature is then lowered to room temperature, and then the organic phase is extracted, combined, washed, and treated to obtain 5-bromo-3-fluoro-2-(2-bromoethoxy)-benzaldehyde; S2: 5-bromo-3-fluoro-2-(2-bromoethoxy)-benzaldehyde is dissolved in anhydrous tetrahydrofuran, the temperature is lowered to a second set temperature under a protective gas, potassium tert-butoxide is added, and the reaction is stirred at a third set temperature for a second set time, and then the reaction liquid is purified to prepare 5-bromo-3-fluoro-2-(vinyl-oxy)-benzaldehyde.

4. The method for preparing the fiberglass thread elastic sealant according to claim 3, characterized in that, In S1, the mass ratio of 5-bromo-3-fluoro-2-hydroxybenzaldehyde to dibromoethane is (18-23):(20-26).

5. The method for preparing the fiberglass thread elastic sealant according to claim 3, characterized in that, In S1, the mass ratio of dibromoethane to anhydrous potassium carbonate is (20-26):(13-20).

6. The method of claim 3, wherein the glass steel threaded elastomeric seal is prepared by the steps of: In S1, the first set temperature is 75-85℃, and the first set time is 15-17h.

7. The method for preparing the fiberglass thread elastic sealant according to claim 3, characterized in that, In the S2, the mass ratio of the 5-bromo-3-fluoro-2-(2-bromoethoxy)-benzaldehyde to potassium tert-butoxide is (17-23):(5-10).

8. The method for preparing the fiberglass thread elastic sealant according to claim 3, characterized in that, In the S2, the second set temperature is -18 to -22 DEG C, the third set temperature is -17 to -22 DEG C, and the second set time is 1 to 2 hours.

9. The use of the glass steel threaded elastic sealant according to claim 1 in a glass steel pipeline.

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