Hydrolysis-resistant hydrophobic polyurea with water resistance and corrosion resistance as well as preparation method and application of hydrolysis-resistant hydrophobic polyurea

Abstract

The invention provides hydrolysis-resistant hydrophobic polyurea with water resistance and corrosion resistance as well as a preparation method and application thereof.The hydrolysis-resistant hydrophobic polyurea is based on fluorine-containing alkyl hydroxyl silane modified dimer acid polyester, and the structural formula of fluorine-containing alkyl hydroxyl silane is shown as the following formula I: # imgabs0 #. The hydrolysis-resistant hydrophobic polyurea which is low in cost and has water resistance and corrosion resistance can effectively improve the water resistance, corrosion resistance and the like due to the fact that the coating is compact, has hydrophobic performance and isolates permeation of moisture and oxygen. Particularly, when the hydrolysis-resistant hydrophobic polyurea is subjected to process implementation, the hydrolysis-resistant hydrophobic polyurea has excellent waterproof and anti-corrosion processes.

Description

Technical Field

[0001] The present invention belongs to the field of functional polymers and waterproof coatings, and in particular relates to a hydrolysis-resistant hydrophobic polyurea having both waterproof and anti-corrosion properties, a preparation method and applications thereof, and specifically relates to a preparation method of a hydrolysis-resistant hydrophobic polyurea based on a fluorinated alkylhydroxysilane-modified dimer acid polyester and its application in waterproofing and anti-corrosion. Background Art

[0002] As a new type of waterproof material, polyurea has the advantages of 100% solid content, no volatile organic compounds, fast curing, spraying on any curved surface, good mechanical properties, dense coating, and long service life. It has been widely used in civil waterproofing, anti-corrosion and other fields. At the same time, how to further improve the hydrophobicity, hydrolysis resistance, and anti-corrosion ability of polyurea, thereby increasing the service life of polyurea in sewage treatment systems and expanding the scope of application of polyurea is of positive significance.

[0003] The Chinese patent document with the publication number CN112794987A and the publication date of May 14, 2021, entitled "A Flame Retardant Polyurea-Polyurethane" discloses a flame retardant polyurea based on DOPO flame retardant modified by end-hydroxyl-terminated polysiloxane. It has certain hydrophobic properties while being flame retardant, but its preparation process is relatively complicated, and the reaction of silanol and diisocyanate is used. The formed silicone ester group is easily hydrolyzed, and its use is greatly restricted. This process uses a large amount of organic solvents and needs to be removed after each reaction process. The final product still has a large amount of organic solvents, a low solid content, a long process route, and high costs, making it difficult to promote.

[0004] The Chinese patent document with the publication number CN114702886A and the publication date July 5, 2022, entitled "A plant oil-based polyurea hydrophobic coating and its preparation method" discloses a plant oil-based polyurea hydrophobic coating and its preparation method, which mainly uses castor oil and perfluorinated compound-modified nanofillers to achieve the purpose of hydrophobicity. Its preparation process is also relatively complicated, with a long reaction time, and requires filtering, washing and other processes, which produces a large amount of wastewater. In addition, the use of relatively expensive perfluorinated compounds has a high overall cost.

[0005] The Chinese patent document with publication number CN112126329A and publication date December 25, 2020, entitled "A spray-type water conservancy dam anti-ice pull wear-resistant polyurea coating and its processing technology" discloses a spray-type water conservancy dam anti-ice pull wear-resistant polyurea coating and its processing technology. In the technical solution disclosed in the patent document, it introduces a two-component spray-type polyurea, which uses polydimethylsiloxane as a hydrophobic agent and directly reacts with components such as polyether and isocyanate. The compatibility of polydimethylsiloxane and other components is poor, and there is also the problem of easy hydrolysis of silicone ester groups, which affects the service life.

[0006] In summary, there is currently no solution for the preparation of hydrolysis-resistant hydrophobic polyurea with simple process and low cost. Summary of the invention

[0007] In order to overcome the shortcomings of the prior art, the purpose of the present invention is to provide a hydrolysis-resistant hydrophobic polyurea that is both waterproof and anti-corrosion, a preparation method and its application. The technical solution described in the present invention provides a hydrolysis-resistant, hydrophobic and anti-corrosion polyurea coating with a simple process route and low cost. Because its coating is dense and has hydrophobic properties, it isolates the penetration of water and oxygen, and can effectively improve its waterproof and anti-corrosion properties.

[0008] In order to achieve the above object, the present invention proposes a fluorine-containing alkylhydroxysilane, the structural formula of which is shown below:

[0009]

[0010] Wherein, n is an integer from 4 to 100, and m is an integer from 1 to 10;

[0011] R1 is hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy, aromatic, heterocyclic or alicyclic;

[0012] R2 is hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy, aromatic, heterocyclic or alicyclic.

[0013] In the technical solution described in the present invention, the inventors obtain fluorinated alkylhydroxysilane-modified dimer acid polyester based on dimer acid and partially fluorinated alkylsiloxane, and further obtain hydrolysis-resistant hydrophobic polyurea. Among them, dimer acid is a bio-based dicarboxylic acid, which is mainly prepared from unsaturated fatty acids of vegetable oils such as soybean oil fatty acids, cottonseed oil fatty acids, and linseed oil fatty acids as raw materials. The main chain is a C18 hydrocarbon structure and has two C9 flexible side chains. Therefore, the polyester polyol synthesized using dimer acid as a raw material has advantages over traditional polyester polyols, such as high hydrolysis resistance, thermal stability, chemical resistance, and antioxidant properties.

[0014] Alkylhydroxysilane is a kind of silicone with silanol chain as the main body and alkoxy chain hydroxyl end-capped at both ends. It has the hydrophobicity and flexibility of ordinary silanes, and is terminated by alkoxy hydroxyl groups, which avoids the disadvantage of poor hydrolysis stability of silicone ester groups generated by the reaction of silanol end-capping with active groups such as acids and isocyanates.

[0015] The present invention adopts partially fluorinated alkylhydroxy siloxane, which not only further increases the hydrophobicity, but also avoids the high cost caused by perfluorosiloxane.

[0016] It should be noted that the fluorine-containing alkylhydroxysiloxane of the present invention is obtained by uniformly mixing hydrogenated silicone oil and allyl fluorinated polyether under stirring, raising the temperature to 80-90° C., adding a platinum catalyst for reaction, and reacting for 3-5 hours.

[0017] The hydrogen-containing silicone oil is shown in the following formula II:

[0018]

[0019] The allyl fluorinated polyether is shown in the following formula III:

[0020]

[0021] Preferably, n is an integer of 4 to 50, preferably, n is an integer of 4 to 20;

[0022] Or, m is an integer from 1 to 5;

[0023] or, R1 is hydrogen, methyl, ethyl, isopropyl, propyl, butyl, isobutyl, sec-butyl, tert-butyl, aromatic, heterocyclic or alicyclic;

[0024] Or, R2 is hydrogen, methyl, ethyl, isopropyl, propyl, butyl, isobutyl, sec-butyl, tert-butyl, aromatic, heterocyclic or alicyclic.

[0025] Preferably, the number average molecular weight of the fluorine-containing alkylhydroxysilane is 500-2000, preferably, the number average molecular weight is 500-1000.

[0026] In a second aspect, the present invention provides a hydrolysis-resistant hydrophobic polyurea that is both waterproof and anti-corrosive. The hydrolysis-resistant hydrophobic polyurea is prepared from the above-mentioned fluorine-containing alkylhydroxy silane.

[0027] It should be noted that in the technical solution described in the present invention, polyurea is an elastic substance generated by the reaction of an isocyanate component (i.e., component A) and an amino compound component (i.e., component B). Polyurea is divided into single-component polyurea and two-component polyurea, wherein the two-component polyurea is a dense coating formed by rapid mixing of isocyanic acid and amino compounds through special spraying equipment and instantaneous reaction solidification.

[0028] In a third aspect, the present invention provides a method for preparing the above-mentioned hydrolysis-resistant hydrophobic polyurea, the preparation method comprising the following steps:

[0029] Step S1: subjecting 10 to 20 parts of the above-mentioned fluorinated alkylhydroxysilane, 60 to 100 parts of dimer acid, and 0.1 to 1 part of toluenesulfonic acid to a first esterification reaction, and then adding 5 to 30 parts of a small molecular diol to react, and performing reduced pressure distillation to obtain a dimer acid polyester diol modified with a fluorinated alkylhydroxysilane;

[0030] Step S2: mixing the dimer acid polyester diol and the polyether diol obtained in step S1 in a ratio of 10-50:30-60 parts, adding 30-120 parts of diisocyanate for reaction, and then adding 0-10 parts of reactive diluent to obtain component A of hydrolysis-resistant hydrophobic polyurea;

[0031] Step S3: Component A obtained in step S2 is mixed with component B of hydrolysis-resistant hydrophobic polyurea to obtain hydrolysis-resistant hydrophobic polyurea, wherein the component B comprises one or more of the following components: hydroxyl-terminated polyether, amine-terminated polyether, primary amine chain extender, secondary amine chain extender, color paste, powder, defoamer, light stabilizer or catalyst. Preferably, the small molecule diol is one or more of the following:

[0032] Ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, methylpropylene glycol, neopentyl glycol or hexylene glycol.

[0033] Preferably, the reactive diluent is propylene carbonate or ethylene carbonate.

[0034] Preferably, the number average molecular weight of the polyether diol is 500-5000, and more preferably, the number average molecular weight of the polyether diol is 600-3000.

[0035] The polyether diol is selected from any one or more of terminal hydroxyl polybutadiene, polyoxypropylene polyol, polyoxypropylene ethylene oxide polyol, polyoxyethylene polyol, and polytetrahydrofuran diol.

[0036] It should be noted that, in the technical solution described in the present invention, the active diluent is used to adjust the viscosity.

[0037] Preferably, in step S1, the specific operation is as follows: 10 to 20 parts of fluorinated alkylhydroxysilane are added to a reaction kettle, the temperature is raised to 110 to 120° C. under stirring, the pressure is reduced to below -0.09 MPa by vacuum, dehydration is carried out, nitrogen is filled in to release the pressure after 1 to 4 hours, 60 to 100 parts of dimer acid and 0.1 to 1 part of p-toluenesulfonic acid are added, the temperature is raised to between 140 and 220° C., the first step of esterification reaction is carried out, after reacting for 2 to 6 hours, 5 to 30 parts of small molecule diols are added, the reaction is continued for 2 to 6 hours, and reduced pressure distillation is carried out to obtain dimer acid polyester diol modified with fluorinated alkylhydroxysilane.

[0038] Preferably, in the step S2, the specific operation is as follows: 10 to 50 parts of the above-obtained fluorinated alkylhydroxysilane-modified dimer acid polyester diol and 30 to 60 parts of polyether diol are added to a reaction kettle, heated to 110 to 120°C under stirring, vacuumed and decompressed to below -0.09 MPa, dehydrated, filled with nitrogen to release the pressure after 1 to 4 hours, cooled to 30 to 60°C, added 30 to 120 parts of diisocyanate, heated to 75 to 85°C, reacted for 1 to 4 hours, started to cool, cooled to 30 to 60°C, added 0 to 10 parts of active diluent, stirred evenly, and obtained component A of hydrolysis-resistant hydrophobic polyurea.

[0039] It should be noted that the hydrolysis-resistant hydrophobic polyurea can be stored in a sealed manner filled with nitrogen.

[0040] In a fourth aspect, the present invention provides a hydrolysis-resistant hydrophobic coating, wherein the hydrolysis-resistant hydrophobic coating comprises a component A and a component B, wherein the component A is an isocyanate prepolymer, and the isocyanate prepolymer comprises the above-mentioned fluorine-containing alkyl silane.

[0041] Preferably, the component B includes one or more of the following components: hydroxyl-terminated polyether, amine-terminated polyether, primary amine chain extender, secondary amine chain extender, color paste, powder, defoamer, light stabilizer or catalyst.

[0042] Preferably, the component B is prepared by the following method:

[0043] 0-50 parts of hydroxyl-terminated polyether, 0-80 parts of amine-terminated polyether, 10-30 parts of primary amine chain extender, 5-20 parts of secondary amine chain extender, 0-10 parts of color paste, 0-10 parts of powder, 0-1 part of defoamer, 0-1 part of light stabilizer and 0-1 part of catalyst are added into a reaction kettle, the temperature is raised to 110-120°C with stirring, the pressure is reduced to below -0.09MPa by vacuum, dehydration is carried out, nitrogen is filled in to release the pressure after 1-4 hours, and the temperature is lowered to 30-50°C to obtain component B.

[0044] It should be noted that component B can be stored in a sealed container filled with nitrogen.

[0045] Preferably, the amount of the amine-terminated polyether component added is 5 to 80 parts.

[0046] Preferably, the hydroxyl-terminated polyether is selected from one or more of the following: C280, C220, NJ405, NJ4100 and 330N, preferably C220 or 330N.

[0047] Preferably, the amine-terminated polyether is selected from One or more of the series D2000, T5000, T403, D400, D4000, T3000, more preferably one or more of the following group: T5000, D2000, D400 and T403.

[0048] Preferably, the primary amine chain extender is selected from one or more of the following groups: diethyltoluenediamine (such as E100), dimethylthiotoluenediamine (such as E300), diaminodicyclohexylmethane, isophoronediamine, trimethylhexamethylenediamine, 4,4'-methylenebis(2,6-diethyl)aniline and 4,4'-methylenebis(2,6-diisopropyl)aniline. Preferably, the primary amine chain extender is: E100 and E300.

[0049] Preferably, the secondary amine chain extender is selected from one or more of the following groups: 4,4'-bis-sec-butylaminodiphenylmethane (such as UNILINK4200, referred to as U4200, WANLINK6200), 1,4'-bis-sec-butylaminobenzene. Preferably, the secondary amine chain extender is U4200.

[0050] Preferably, the powder is selected from one or more of the following groups: aluminum oxide, talc or calcium carbonate powder.

[0051] Preferably, the catalyst is an organobismuth catalyst.

[0052] In a fifth aspect, the present invention proposes the use of the above-mentioned fluorine-containing alkylhydroxy silane, hydrolysis-resistant hydrophobic polyurea, or hydrolysis-resistant hydrophobic coating in waterproof and anti-corrosion materials.

[0053] Preferably, the following method is used:

[0054] Equal volume spraying is carried out at 55-75°C and 15-25MPa.

[0055] Compared with the prior art, the at least one technical solution adopted in the embodiments of this specification can achieve the following beneficial effects:

[0056] The technical solution described in the present invention provides a hydrolysis-resistant hydrophobic polyurea that is simple in process route, low in cost, and waterproof and anti-corrosion. Because its coating is dense and has hydrophobic properties, it isolates the penetration of moisture and oxygen, and can effectively improve its waterproof and anti-corrosion properties.

[0057] In addition, since the prior art requires additional anti-corrosion and waterproofing processes, the hydrolysis-resistant hydrophobic polyurea described in the present invention has both waterproof and anti-corrosion properties. Therefore, when the hydrolysis-resistant hydrophobic polyurea described in the present invention is used, no additional waterproofing and anti-corrosion process is required, which has the advantage of simple process. DETAILED DESCRIPTION

[0058] The embodiments of the present application are described in detail below.

[0059] The following describes the implementation methods of the present application through specific examples, and those skilled in the art can easily understand other advantages and effects of the present application from the contents disclosed in this specification. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. The present application can also be implemented or applied through other different specific implementation methods, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present application. It should be noted that, in the absence of conflict, the following embodiments and the features in the embodiments can be combined with each other. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in the field without making creative work belong to the scope of protection of the present application.

[0060] It should be noted that various aspects of the embodiments within the scope of the appended claims are described below. It should be apparent that the aspects described herein can be embodied in a wide variety of forms, and any specific structure and / or function described herein is merely illustrative. Based on the present application, it should be understood by those skilled in the art that an aspect described herein can be implemented independently of any other aspect, and two or more of these aspects can be combined in various ways. For example, any number and aspect described herein can be used to implement the device and / or practice the method. In addition, other structures and / or functionalities other than one or more of the aspects described herein can be used to implement this device and / or practice this method.

[0061] Embodiment 1:

[0062] 1. Add 10 parts of small molecular fluorinated alkylhydroxy silane into the reaction kettle, heat it to 110-120°C under stirring, evacuate and reduce the pressure to below -0.09MPa for dehydration, fill with nitrogen to release the pressure after 2 hours, add 60 parts of dimer acid and 0.5 parts of p-toluenesulfonic acid, heat it to between 170 and 220°C, and carry out the first step of esterification reaction. After 3 hours of reaction, add 6.5 parts of ethylene glycol and continue to react for 3 hours, and distill under reduced pressure to remove excess small molecular alcohol and water generated by the reaction, so as to obtain dimer acid polyester diol modified with fluorinated alkylhydroxy silane.

[0063] 2. Add 10 parts of the above-obtained fluorinated alkylhydroxy silane-modified dimer acid polyester diol and 30 parts of a polyether diol with a molecular weight of 2000 into a reaction kettle, heat to 110-120°C under stirring, evacuate and reduce pressure to below -0.09MPa, dehydrate, fill with nitrogen to release pressure after 2 hours, cool to 30-60°C, add 30.7 parts of diphenylmethane diisocyanate, heat to 75-85°C, react for 1-4 hours, detect the isocyanate content to the set value, stop the reaction, start cooling to 30-60°C, add 5 parts of active diluent, mix well and package, and store in a nitrogen-filled sealed container to obtain a hydrolysis-resistant, hydrophobic polyurea component A. The isocyanate content of this component is 11.7% and the viscosity is 600-900mPas.

[0064] 3. Heat 68 parts of amine-terminated polyether D2000, 10 parts of amine-terminated polyether T5000, 16 parts of primary amine chain extender E100, 6 parts of secondary amine chain extender U4200, 5 parts of color paste, 5 parts of aluminum oxide and 0.5 parts of defoamer to 110-120°C under stirring, evacuate and reduce the pressure to below -0.09MPa, dehydrate, fill with nitrogen to release the pressure after 1-4 hours, cool to 30-50°C, package, and store in a nitrogen-filled sealed state to obtain hydrolysis-resistant and hydrophobic polyurea component B.

[0065] Components A and B are sprayed onto PVC sheets or polytetrafluoroethylene sheets pre-coated with release agents at a volume ratio of 1:1 through polyurea spraying equipment at 60-75°C and 15-22MPa, and solid forming can be performed quickly to obtain a coating.

[0066] The obtained coating was cured for 7 days under standard test conditions and then tested. The contact angle was measured using a contact angle meter and the mechanical properties were measured in accordance with GB / T23446-2009.

[0067] The test results are as follows:

[0068] The coating has a contact angle of 103-105°, a tensile strength of 12.3MPa, and an elongation at break of 320%. After being soaked in 60°C hot water for 30 days, the tensile strength retention rate is 91%, and the elongation at break is 350%. After being soaked in 10% hydrochloric acid solution for 30 days, the tensile strength retention rate is 90%, and the elongation at break is 345%. After being soaked in 10% sodium hydroxide solution for 30 days, the tensile strength retention rate is 91%, and the elongation at break is 382%. After artificial weathering for 2000h, the tensile strength retention rate is 110%, and the elongation at break is 315%. After 2000h of neutral salt spray, there is no rust, no blistering, and no shedding.

[0069] Embodiment 2:

[0070] 1. Add 12 parts of small molecular fluorinated alkylhydroxy silane to the reactor, heat it to 110-120°C under stirring, evacuate and reduce the pressure to below -0.09MPa for dehydration, fill with nitrogen to release the pressure after 2 hours, add 70 parts of dimer acid and 0.3 parts of p-toluenesulfonic acid, heat it to between 170 and 220°C, and carry out the first step of esterification reaction. After 3 hours of reaction, add 12 parts of propylene glycol and continue to react for 3 hours, and distill under reduced pressure to remove excess small molecular alcohol and water generated by the reaction, so as to obtain dimer acid polyester diol modified with fluorinated alkylhydroxy silane.

[0071] 2. Add 20 parts of the above obtained fluorinated alkylhydroxy silane modified dimer acid polyester diol and 50 parts of polytetrahydrofuran ether diol with a molecular weight of 2000 into a reaction kettle, heat to 110-120°C under stirring, evacuate and reduce pressure to below -0.09MPa, dehydrate, fill with nitrogen to release pressure after 2 hours, cool to 30-60°C, add 60.3 parts of diphenylmethane diisocyanate, heat to 75-85°C, react for 1-4 hours, detect the isocyanate content to the set value, stop the reaction, start cooling to 30-60°C, add 5 parts of active diluent, mix well and package, fill with nitrogen and store in a sealed manner to obtain hydrolysis-resistant and hydrophobic polyurea component A. The isocyanate content of this component is 13% and the viscosity is 600-900mPas.

[0072] 3. Add 20 parts of hydroxyl-terminated polyether C220, 44 parts of amine-terminated polyether D2000, 10 parts of amine-terminated polyether T5000, 19 parts of primary amine chain extender E100, 7 parts of secondary amine chain extender U4200, 2.5 parts of color paste, 8 parts of talcum powder and 0.5 parts of organic bismuth catalyst into the reaction kettle, heat it to 110-120°C under stirring, evacuate the pressure to below -0.09MPa, dehydrate, fill with nitrogen to release the pressure after 1-4 hours, cool it to 30-50°C, package it, and store it in a sealed container filled with nitrogen to obtain hydrolysis-resistant and hydrophobic polyurea component B.

[0073] Components A and B are sprayed onto PVC sheets or polytetrafluoroethylene sheets pre-coated with release agents at a volume ratio of 1:1 through polyurea spraying equipment at 60-75°C and 15-22MPa, and solid forming can be performed quickly to obtain a coating.

[0074] The obtained coating was cured for 7 days under standard test conditions and then tested. The contact angle was measured using a contact angle meter and the mechanical properties were measured in accordance with GB / T23446-2009.

[0075] The test results are as follows:

[0076] The coating has a contact angle of 105-107°, a tensile strength of 13.8MPa, and an elongation at break of 350%. After being soaked in 60°C hot water for 30 days, the tensile strength retention rate is 92%, and the elongation at break is about 400%. After being soaked in 10% hydrochloric acid solution for 30 days, the tensile strength retention rate is 91%, and the elongation at break is 385%. After being soaked in 10% sodium hydroxide solution for 30 days, the tensile strength retention rate is 92%, and the elongation at break is 390%. After artificial weathering for 2000h, the tensile strength retention rate is 106%, and the elongation at break is 331%. After 2000h of neutral salt spray, there is no rust, no blistering, and no shedding.

[0077] Embodiment 3:

[0078] 1. Add 20 parts of small molecular fluorinated alkylhydroxy silane into the reaction kettle, heat it to 110-120°C under stirring, evacuate and reduce the pressure to below -0.09MPa for dehydration, fill with nitrogen to release the pressure after 2 hours, add 80 parts of dimer acid and 0.3 parts of p-toluenesulfonic acid, heat it to 170-220°C, and carry out the first step of esterification reaction. After 3 hours of reaction, add 16.6 parts of butanediol and continue to react for 3 hours, and distill under reduced pressure to remove excess small molecular alcohol and water generated by the reaction, so as to obtain dimer acid polyester diol modified with fluorinated alkylhydroxy silane.

[0079] 2. Add 15 parts of the above obtained fluorinated alkylhydroxy silane modified dimer acid polyester diol and 50 parts of polyether diol with a molecular weight of 4000 into a reaction kettle, heat to 110-120°C under stirring, evacuate and reduce pressure to below -0.09MPa, dehydrate, fill with nitrogen to release pressure after 2 hours, cool to 30-60°C, add 56.2 parts of diphenylmethane diisocyanate, heat to 75-85°C, react for 1-4 hours, detect the isocyanate content to the set value, stop the reaction, start cooling to 30-60°C, add 3 parts of active diluent, mix well and package, fill with nitrogen and store in a sealed container to obtain hydrolysis-resistant and hydrophobic polyurea component A. The isocyanate content of this component is 13.9% and the viscosity is 600-900mPas.

[0080] 3. Add 58.5 parts of amine-terminated polyether D2000, 8 parts of amine-terminated polyether T5000, 3 parts of amine-terminated polyether D400, 20.5 parts of primary amine chain extender E100, 10 parts of secondary amine chain extender U4200, 10 parts of calcium carbonate powder and 0.5 parts of defoamer into a reaction kettle, heat to 110-120°C under stirring, evacuate and reduce the pressure to below -0.09MPa for dehydration, fill with nitrogen to release the pressure after 1-4 hours, cool to 30-50°C, package, and store in a sealed container filled with nitrogen to obtain hydrolysis-resistant and hydrophobic polyurea component B.

[0081] Components A and B are sprayed onto PVC sheets or polytetrafluoroethylene sheets pre-coated with release agents at a volume ratio of 1:1 through polyurea spraying equipment at 60-75°C and 15-22MPa, and solid forming can be performed quickly to obtain a coating.

[0082] The obtained coating was cured for 7 days under standard test conditions and then tested. The contact angle was measured using a contact angle meter and the mechanical properties were measured in accordance with GB / T23446-2009.

[0083] The test results are as follows:

[0084] The coating has a contact angle of 100-103°, a tensile strength of 17.2MPa, and an elongation at break of 460%. After being soaked in 60°C hot water for 30 days, the tensile strength retention rate is 90%, and the elongation at break is about 500%. After being soaked in 10% hydrochloric acid solution for 30 days, the tensile strength retention rate is 90%, and the elongation at break is 483%. After being soaked in 10% sodium hydroxide solution for 30 days, the tensile strength retention rate is 91%, and the elongation at break is 510%. After artificial weathering for 2000h, the tensile strength retention rate is 116%, and the elongation at break is 476%. After 2000h of neutral salt spray, there is no rust, no blistering, and no shedding.

[0085] Example 4

[0086] 1. Add 15 parts of small molecular fluorinated alkylhydroxy silane into the reaction kettle, heat it to 110-120°C under stirring, evacuate and reduce the pressure to below -0.09MPa for dehydration, fill with nitrogen to release the pressure after 2 hours, add 90 parts of dimer acid and 0.5 parts of p-toluenesulfonic acid, heat it to between 170 and 220°C, and carry out the first step of esterification reaction. After 3 hours of reaction, add 22 parts of neopentyl glycol and continue to react for 3 hours, and distill under reduced pressure to remove excess small molecular alcohol and water generated by the reaction, so as to obtain dimer acid polyester diol modified with fluorinated alkylhydroxy silane.

[0087] 2. Add 30 parts of the above-obtained fluorinated alkylhydroxy silane-modified dimer acid polyester diol and 60 parts of a polyether diol with a molecular weight of 3000 into a reaction kettle, heat to 110-120°C under stirring, evacuate and reduce pressure to below -0.09MPa, dehydrate, fill with nitrogen to release pressure after 2 hours, cool to 30-60°C, add 91 parts of diphenylmethane diisocyanate, heat to 75-85°C, react for 1-4 hours, detect the isocyanate content to the set value, stop the reaction, start cooling to 30-60°C, add 7 parts of active diluent, mix well and package, and store in a sealed container filled with nitrogen to obtain a hydrolysis-resistant, hydrophobic polyurea component A. The isocyanate content of this component is 14.9% and the viscosity is 600-900mPas.

[0088] 3. Add 10 parts of hydroxyl-terminated polyether 330N, 56 parts of amine-terminated polyether D2000, 5 parts of amine-terminated polyether D400, 22 parts of primary amine chain extender E100, 7 parts of secondary amine chain extender U4200, 5 parts of color paste, 5 parts of talc, 0.5 parts of defoamer, 1 part of light stabilizer and 0.5 parts of organic bismuth catalyst into the reaction kettle, heat to 110-120°C under stirring, evacuate and reduce the pressure to below -0.09MPa, dehydrate, fill with nitrogen to release the pressure after 1-4 hours, cool to 30-50°C, package, and store in a sealed nitrogen-filled state to obtain hydrolysis-resistant and hydrophobic polyurea component B.

[0089] Components A and B are sprayed onto PVC sheets or polytetrafluoroethylene sheets pre-coated with release agents at a volume ratio of 1:1 through polyurea spraying equipment at 60-75°C and 15-22MPa, and solid forming can be performed quickly to obtain a coating.

[0090] The obtained coating was cured for 7 days under standard test conditions and then tested. The contact angle was measured using a contact angle meter and the mechanical properties were measured in accordance with GB / T23446-2009.

[0091] The test results are as follows:

[0092] The coating has a contact angle of 107-110°, a tensile strength of 18.9 MPa, and an elongation at break of 500%. After being soaked in 60°C hot water for 30 days, the tensile strength retention rate is 93% and the elongation at break is about 520%. After being soaked in 10% hydrochloric acid solution for 30 days, the tensile strength retention rate is 88% and the elongation at break is 480%. After being soaked in 10% sodium hydroxide solution for 30 days, the tensile strength retention rate is 92% and the elongation at break is 545%. After artificial weathering for 2000 hours, the tensile strength retention rate is 110% and the elongation at break is 490%. After 2000 hours of neutral salt spray, there is no rust, no blistering, and no shedding.

[0093] Embodiment 5:

[0094] 1. Add 15 parts of small molecular fluorinated alkylhydroxy silane into the reaction kettle, heat it to 110-120°C under stirring, evacuate and reduce the pressure to below -0.09MPa for dehydration, fill with nitrogen to release the pressure after 2 hours, add 100 parts of dimer acid and 0.3 parts of p-toluenesulfonic acid, heat it to between 170 and 220°C, and carry out the first step of esterification reaction. After 3 hours of reaction, add 21 parts of butanediol and continue to react for 3 hours, and distill under reduced pressure to remove excess small molecular alcohol and water generated by the reaction, so as to obtain dimer acid polyester diol modified with fluorinated alkylhydroxy silane.

[0095] 2. Add 45 parts of the above-obtained fluorinated alkylhydroxy silane-modified dimer acid polyester diol and 60 parts of 3000 molecular weight polyether diol to a reaction kettle, heat to 110-120°C under stirring, evacuate and reduce pressure to below -0.09MPa, dehydrate, fill with nitrogen to release pressure after 2 hours, cool to 30-60°C, add 118 parts of diphenylmethane diisocyanate, heat to 75-85°C, react for 1-4 hours, detect the isocyanate content to the set value, stop the reaction, start cooling to 30-60°C, add 9 parts of active diluent, mix well and package, fill with nitrogen and store in a sealed container to obtain hydrolysis-resistant and hydrophobic polyurea component A. The isocyanate content of this component is 15.7% and the viscosity is 600-900mPas.

[0096] 3. Add 58.5 parts of amine-terminated polyether D2000, 7 parts of amine-terminated polyether T5000, 4 parts of amine-terminated polyether T403, 22.5 parts of primary amine chain extender E100, 8 parts of secondary amine chain extender U4200, 5 parts of color paste, 5 parts of aluminum oxide and 1 part of light stabilizer into the reaction kettle, heat it to 110-120°C under stirring, evacuate the pressure to below -0.09MPa, dehydrate, fill with nitrogen to release the pressure after 1-4 hours, cool it to 30-50°C, package it, and store it in a sealed place filled with nitrogen to obtain hydrolysis-resistant and hydrophobic polyurea component B.

[0097] Components A and B are sprayed onto PVC sheets or polytetrafluoroethylene sheets pre-coated with release agents at a volume ratio of 1:1 through polyurea spraying equipment at 60-75°C and 15-22MPa, and solid forming can be performed quickly to obtain a coating.

[0098] The obtained coating was cured for 7 days under standard test conditions and then tested. The contact angle was measured using a contact angle meter and the mechanical properties were measured in accordance with GB / T23446-2009.

[0099] The test results are as follows:

[0100] The coating has a contact angle of 107-110°, a tensile strength of 20.1 MPa, and an elongation at break of 470%. After being soaked in 60°C hot water for 30 days, the tensile strength retention rate is 93%, and the elongation at break is about 490%. After being soaked in 10% hydrochloric acid solution for 30 days, the tensile strength retention rate is 92%, and the elongation at break is 485%. After being soaked in 10% sodium hydroxide solution for 30 days, the tensile strength retention rate is 91%, and the elongation at break is 534%. After artificial weathering for 2000 hours, the tensile strength retention rate is 106%, and the elongation at break is 489%. After 2000 hours of neutral salt spray, there is no rust, no blistering, and no shedding.

[0101] Application examples:

[0102] The hydrolysis-resistant hydrophobic polyurea and hydrolysis-resistant hydrophobic coating of Examples 1 to 5 of this case can be widely used in the waterproofing and anti-corrosion scenarios required for different buildings and structures. For example, they can also be applied to municipal infrastructure such as sewage treatment pools, drainage pipes, box culverts and integrated pipeline corridors.

[0103] Since the hydrolysis-resistant hydrophobic polyurea and hydrolysis-resistant hydrophobic coating in this case have extremely excellent waterproof and anti-corrosion properties, they are very suitable for some scenes with high waterproof requirements, such as building roofs, basements, pools, stands, etc.

[0104] Expansion joints, construction joints, wall pipes or embedded parts in construction projects also have certain requirements for waterproofing. Therefore, they are also very suitable for spraying the hydrolysis-resistant hydrophobic polyurea and hydrolysis-resistant hydrophobic coatings in this case.

[0105] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable ordinary technicians in the field to understand the content of the present invention and implement it accordingly, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made based on the essence of the content of the present invention should be included in the protection scope of the present invention.

Claims

1. A fluorine-containing alkylhydroxysilane, characterized in that: Its structural formula is shown in the following formula I: Wherein, n is an integer from 4 to 100, and m is an integer from 1 to 10; R1 is hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy, aromatic, heterocyclic or alicyclic; R2 is hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy, aromatic, heterocyclic or alicyclic.

2. The fluorine-containing alkylhydroxysilane according to claim 1, characterized in that The n is an integer of 4 to 50; Or, m is an integer from 1 to 5; or, R1 is hydrogen, methyl, ethyl, isopropyl, propyl, butyl, isobutyl, sec-butyl, tert-butyl, aromatic, heterocyclic or alicyclic; Or, R2 is hydrogen, methyl, ethyl, isopropyl, propyl, butyl, isobutyl, sec-butyl, tert-butyl, aromatic, heterocyclic or alicyclic.

3. The fluorine-containing alkylhydroxysilane according to claim 1 or 2, characterized in that The number average molecular weight of the fluorine-containing alkylhydroxysilane is 500-2000, preferably, the number average molecular weight is 500-1000.

4. A hydrolysis-resistant hydrophobic polyurea that is both waterproof and anticorrosive, characterized in that: The hydrolysis-resistant hydrophobic polyurea is prepared from the fluorine-containing alkylhydroxysilane according to any one of claims 1 to 3.

5. The method for preparing the hydrolysis-resistant hydrophobic polyurea according to claim 4, characterized in that: The preparation method comprises the following steps: Step S1: subjecting 10 to 20 parts of the fluorinated alkylhydroxysilane as claimed in any one of claims 1 to 3, 60 to 100 parts of dimer acid and 0.1 to 1 part of toluenesulfonic acid to a first esterification reaction, then adding 5 to 30 parts of a small molecule diol to react, and performing reduced pressure distillation to obtain a dimer acid polyester diol modified with a fluorinated alkylhydroxysilane; Step S2: mixing the dimer acid polyester diol and the polyether diol obtained in step S1 in a ratio of 10-50:30-60 parts, adding 30-120 parts of diisocyanate for reaction, and then adding 0-10 parts of reactive diluent to obtain component A of hydrolysis-resistant hydrophobic polyurea; Step S3: Component A obtained in step S2 is mixed with component B of hydrolysis-resistant hydrophobic polyurea to obtain hydrolysis-resistant hydrophobic polyurea, wherein component B includes one or more of the following components: terminal hydroxyl polyether, terminal amine polyether, primary amine chain extender, secondary amine chain extender, color paste, powder, defoamer, light stabilizer or catalyst.

6. The preparation method according to claim 5, characterized in that: The small molecule diols are one or more of the following: Ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, methylpropylene glycol, neopentyl glycol or hexylene glycol.

7. The preparation method according to claim 5, characterized in that: The active diluent is propylene carbonate or ethylene carbonate.

8. A hydrolysis-resistant hydrophobic coating, characterized in that: The hydrolysis-resistant hydrophobic coating comprises a component A and a component B, wherein the component A is an isocyanate prepolymer, and the isocyanate prepolymer comprises the fluorine-containing alkyl silane as claimed in any one of claims 1 to 3.

9. The hydrolysis-resistant hydrophobic coating according to claim 8, characterized in that: The component B includes one or more of the following components: hydroxyl-terminated polyether, amine-terminated polyether, primary amine chain extender, secondary amine chain extender, color paste, powder, defoamer, light stabilizer or catalyst.

10. Use of the fluorine-containing alkylhydroxysilane according to any one of claims 1 to 3, the hydrolysis-resistant hydrophobic polyurea according to claim 4, or the hydrolysis-resistant hydrophobic coating according to claim 8 or 9 in waterproof and anticorrosive materials.

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