Wear-resistant and aging-resistant polyurea marine oil pipe and preparation method thereof

Abstract

The invention relates to the technical field of coatings, and particularly discloses a wear-resistant and aging-resistant polyurea type marine oil pipe and a preparation method thereof.The preparation method specifically comprises the steps that primer paint and finish paint which are formed by separately mixing a material A and a material B are prepared, rapid curing is conducted through a high-functionality modified polyurethane prepolymer and a diluted curing agent, and the wear-resistant and aging-resistant polyurea type marine oil pipe is obtained. An auxiliary agent with an epoxy group is added to carry out a high-crosslinking-degree reaction, so that the obtained paint has high hardness; the prepared finish paint is composed of resin, a chain extender and a curing agent, and a wear-resistant auxiliary agent and a long-chain fatty alcohol auxiliary agent are added, so that the mechanical property of the paint can be improved; the primer and the finish paint are sequentially sprayed on the rubber hose and then subjected to vulcanization reaction, crosslinking of the primer and the finish paint is promoted, and the prepared polyurea type ocean oil pipe is high in wear resistance and aging resistance and suitable for ocean energy transportation.

Description

Technical Field

[0001] The invention belongs to the technical field of coatings, and in particular relates to a wear-resistant and aging-resistant polyurea type marine oil pipe and a preparation method thereof. Background Art

[0002] The development of marine resources is becoming more and more extensive. Marine floating oil pipelines are pipelines used to transport petroleum in the ocean. Their safety is of vital importance. When they are placed in the ocean for transportation, the action of seawater can easily accelerate the aging of the pipelines. The resulting wear loads can cause pipeline damage, resulting in pipeline rupture and leakage of transported energy, causing serious economic losses and environmental pollution. Therefore, it is necessary to enhance the corrosion and wear resistance of the oil pipelines to make them more suitable for marine transportation operations, which has great research significance.

[0003] Spraying polyurea elastomer technology is a new type of environmentally friendly technology. It is solvent-free, non-volatile and pollution-free, with a 100% high solid content, and thus does not produce harmful substances and irritating odors, which is extremely beneficial to environmental protection. Spraying polyurea elastomer technology combines new technologies, new elastomers and new processes. It is a new type of coating technology that integrates the advantages of plastics, rubber, coatings, and fiberglass. It breaks through the limitations of traditional environmentally friendly coating technologies and has a wide market demand. Spraying polyurea elastomer technology organically combines the excellent performance of polyurea with the construction technology of rapid spraying and on-site curing, making it show unparalleled superiority in engineering applications. Compared with other general environmentally friendly coatings such as high-solid coatings, water-based coatings, light-curing coatings, powder coatings, etc., the curing reaction is too slow, and continuous thickening is not allowed, and the construction efficiency is extremely low. Spray polyurea elastomer technology can quickly cure, and the interval between layers is only a few minutes. It does not require at least 12 hours of drying time before it can be put into use or the next layer of construction. There is no limit on the final construction thickness of the coating, and it can be continuously constructed on the vertical surface without sagging. In addition, spray polyurea elastomer technology has excellent physical properties and construction performance. It can completely or partially replace traditional polyurethane, epoxy resin, fiberglass and polyolefin compounds, and has broad application prospects in chemical corrosion protection, pipeline corrosion protection, mine wear resistance, sewage treatment, building waterproofing, water conservancy engineering and other industries;

[0004] However, the current polyurea coating is still prone to damage and fall off after long-term use in special environments such as the marine environment with high ion concentration, which is prone to corrosion and wear. In cold weather, the temperature of seawater is lower, and the coating is easy to harden and break. Therefore, it is of great research significance to develop an outer coating for rubber hoses with high mechanical strength and high stability. Summary of the invention

[0005] In view of the above problems, the object of the present invention is to provide a wear-resistant and aging-resistant polyurea type marine oil pipe and a preparation method thereof.

[0006] The technical contents of the present invention are as follows:

[0007] The present invention provides a method for preparing a wear-resistant and aging-resistant polyurea type marine oil pipe, comprising the following steps:

[0008] Step S1: preparing a primer: stirring a modified polyurethane prepolymer and butyl acetate to obtain component A0, and uniformly mixing a polyamine, butyl acetate and an auxiliary agent 1 to obtain component B0;

[0009] The modified polyurethane prepolymer is prepared by first mixing phthalic anhydride and polysulfide rubber in a mass ratio of 3-5:21-24 to obtain a mixture, then adding phthalic anhydride and polysulfide rubber in a volume ratio of 14-17:25-35 to the mixed solution and reacting for 100-140 minutes at a vacuum degree of 0.1-0.3 MPa and a temperature of 130-150° C. to obtain the obtained product.

[0010] The mixed solution is composed of ethylene oxide and propylene glycol in a volume ratio of 1:1-3;

[0011] The auxiliary agent 1 is alkylene oxide;

[0012] The modified prepolymer in the primer has high functionality and high reaction activity, which promotes the crosslinking reaction and curing reaction. The addition of the small molecular functional group epoxy compound as the auxiliary agent allows the reaction to proceed fully and the polymerization to be highly uniform, thereby improving the mechanical properties and stability of the coating.

[0013] Step S2: preparing topcoat: adding isocyanate into a reaction kettle, then dropping a wear-resistant additive and heating the reaction in a nitrogen atmosphere to obtain polyurea elastic A, then mixing polyether polyamine, diethyltoluenediamine and additive 2 to obtain polyurea elastic B;

[0014] The temperature-raising reaction is carried out by filling dry nitrogen for protection, heating to 70-100° C. and keeping the temperature for 90-180 minutes;

[0015] The wear-resistant additive is obtained by mixing the wear-resistant component with polyoxypropylene ether glycol at a solid-liquid ratio of 4-7:30-35 g / mL;

[0016] The wear-resistant component is silicon powder;

[0017] The auxiliary agent 2 is a long-chain fatty alcohol;

[0018] Step S3: Clean the rubber hose, remove oil and dust, and then evenly spray the primer obtained by mixing A0 and B0 on ​​the rubber hose, and then evenly spray the topcoat obtained by mixing polyurea A and polyurea B on the primer, the spraying thickness of the primer and topcoat is 6 kg / m2, and then put it into a vulcanization tank at a temperature of 60-70°C for vulcanization dry hot air drying time of 100-140min, and then naturally cure in the air for 6-8 days;

[0019] The vulcanization can promote the cross-linking reaction between the carbamate groups in the primer and the topcoat and the hydroxyl groups in the primer and the amino groups in the topcoat, thereby improving the mechanical strength and stability of the coating.

[0020] The present invention also provides a wear-resistant and aging-resistant polyurea marine oil pipe made by the above method, wherein the polyurea marine oil pipe comprises components A0, B0, A and B;

[0021] The component A0 comprises the following components in parts by weight: 60-75 parts of modified polyurethane prepolymer and 10-25 parts of butyl acetate;

[0022] The component B0 comprises the following components in parts by weight: 5-15 parts of polyamine, 50-80 parts of butyl acetate and 11-5 parts of auxiliary agent 1;

[0023] The component A comprises the following components by weight: 70-90 parts of isocyanate and 5-10 parts of wear-resistant additive;

[0024] The component B comprises the following components in parts by weight: 60-70 parts of polyether polyamine, 10-20 parts of diethyltoluenediamine and 1-10 parts of auxiliary agent 2.

[0025] The beneficial effects of the present invention are as follows:

[0026] The preparation method of the polyurea type marine oil pipe provided by the invention comprises the following steps: spraying polyurethane primer and polyurea topcoat on a rubber hose, wherein the primer and the topcoat are prepared by mixing material A and material B separately, and rapidly curing a high-functionality modified polyurethane prepolymer with a diluted curing agent, and adding an auxiliary agent with an epoxy group to react with a high degree of crosslinking, so that the obtained paint has high hardness; the prepared topcoat is composed of a resin, a chain extender, and a curing agent, and is added with a wear-resistant auxiliary agent and a long-chain fatty alcohol auxiliary agent, silicon micropowder increases the rigid structure, and the introduction of alkyl and fatty acid long-chain structures promotes the obtained paint to deform and move when subjected to force, thereby improving the adhesion of the paint and reducing loss; the primer and the topcoat are sprayed on the rubber hose in sequence and then subjected to a vulcanization reaction, so that the primer and the topcoat are crosslinked, and the obtained polyurea type marine oil pipe has strong wear resistance and aging resistance. DETAILED DESCRIPTION

[0027] The present invention is further described in detail below through specific implementation cases. It should be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of protection of the present invention. After reading the present invention, various equivalent forms of modifications to the present invention by those skilled in the art are all within the scope of the claims attached to this application.

[0028] Unless otherwise specified, all raw materials and reagents of the present invention are raw materials and reagents from the conventional market.

[0029] Example 1

[0030] A method for preparing a wear-resistant and aging-resistant polyurea marine oil pipe comprises the following steps:

[0031] Step S1: preparing a primer: stirring 70 parts of a modified polyurethane prepolymer and 18 parts of butyl acetate to obtain component A0, and uniformly mixing 10 parts of hexamethylenetetramine, 65 parts of butyl acetate and 3 parts of propylene oxide to obtain component B0;

[0032] The modified polyurethane prepolymer is prepared by mixing phthalic anhydride and polysulfide rubber in a mass ratio of 4:23 to obtain a mixture, and then adding a mixed solution of ethylene oxide and propylene glycol in a volume ratio of 1:2 in a volume ratio of 15:30, and reacting for 120 minutes at a vacuum degree of 0.2MPa and a temperature of 140°C; Step S2: preparing a topcoat: adding 80 parts of isocyanate to a reaction kettle, and then dropping 3 parts of a wear-resistant additive obtained by mixing silicon micropowder with polyoxypropylene ether glycol in a solid-liquid ratio of 5:32g / mL, and heating the mixture in a nitrogen atmosphere to obtain a polyurea elastic A, and the heating The reaction is filled with dry nitrogen for protection, the temperature is raised to 80°C, and the temperature is kept for 130 minutes, and then 65 parts of polyether polyamine, 15 parts of diethyltoluenediamine and 3 parts of octadecyl alcohol are mixed uniformly to obtain polyurea elastic B; step S3: the rubber hose is cleaned, degreased and dusted, and then the primer obtained by mixing A0 and B0 is evenly sprayed on the rubber hose, and then the topcoat obtained by mixing polyurea A and polyurea B is evenly sprayed on the primer, and the spraying thickness of the primer and the topcoat is 6 kg / m2, and then the vulcanization tank is put into the vulcanization dry hot air drying time at a temperature of 65°C for 120 minutes, and then naturally cured in the air for 7 days.

[0033] Example 2

[0034] A method for preparing a wear-resistant and aging-resistant polyurea marine oil pipe comprises the following steps:

[0035] Step S1: preparing a primer: stirring 60 parts of a modified polyurethane prepolymer and 10 parts of butyl acetate to obtain component A0, and uniformly mixing 5 parts of tetramethylenediamine, 50 parts of butyl acetate and 1 part of 1,2-butylene oxide to obtain component B0;

[0036] The modified polyurethane prepolymer is prepared by mixing phthalic anhydride and polysulfide rubber in a mass ratio of 3:21 to obtain a mixture, and then adding 14:25 in a volume ratio to a mixed solution of ethylene oxide and propylene glycol in a volume ratio of 1:1, and reacting at a vacuum degree of 0.1 MPa and a temperature of 130° C. for 100 minutes to obtain the mixture;

[0037] Step S2: preparing topcoat: adding 70 parts of isocyanate into a reaction kettle, and then dropping 1 part of a wear-resistant additive obtained by mixing silicon micropowder with polyoxypropylene ether glycol at a solid-liquid ratio of 4:30 g / mL, and heating the mixture in a nitrogen atmosphere to obtain polyurea elastic A. The temperature-raising reaction is performed by charging dry nitrogen for protection, heating the temperature to 70° C., and keeping the temperature for 90 minutes. Then, 60 parts of polyether polyamine, 10 parts of diethyltoluenediamine and 1 part of hexadecanol are uniformly mixed to obtain polyurea elastic B.

[0038] Step S3: Clean, degrease and deash the rubber hose, then evenly spray the primer obtained by mixing A0 and B0 on ​​the rubber hose, and then evenly spray the topcoat obtained by mixing polyurea A and polyurea B on the primer, the spraying thickness of the primer and topcoat is 6 kg / m2, and then put it into the vulcanization tank for vulcanization at a temperature of 60°C and dry hot air drying for 100 minutes, and then naturally cure in the air for 6 days.

[0039] Example 3

[0040] A method for preparing a wear-resistant and aging-resistant polyurea marine oil pipe comprises the following steps:

[0041] Step S1: preparing a primer: stirring 75 parts of a modified polyurethane prepolymer and 25 parts of butyl acetate to obtain component A0, and uniformly mixing 15 parts of ethylenediamine, 80 parts of butyl acetate and 5 parts of 1,4-dioxane to obtain component B0;

[0042] The modified polyurethane prepolymer is prepared by mixing phthalic anhydride and polysulfide rubber in a mass ratio of 5:24 to obtain a mixture, then adding 17:35 in a volume ratio to a mixed solution of ethylene oxide and propylene glycol in a volume ratio of 1:3, and reacting at a vacuum degree of 0.3 MPa and a temperature of 150° C. for 140 minutes to obtain a mixture;

[0043] Step S2: preparing topcoat: adding 90 parts of isocyanate into a reaction kettle, and then dropping 5 parts of a wear-resistant additive obtained by mixing silicon micropowder with polyoxypropylene ether glycol at a solid-liquid ratio of 7:35 g / mL, and heating the mixture in a nitrogen atmosphere to obtain polyurea elastic A. The temperature-raising reaction is performed by charging dry nitrogen for protection, heating the temperature to 100° C., and keeping the temperature for 180 minutes. Then, 70 parts of polyether polyamine, 20 parts of diethyltoluenediamine and 5 parts of n-octanol are uniformly mixed to obtain polyurea elastic B.

[0044] Step S3: Clean, degrease and deash the rubber hose, then evenly spray the primer obtained by mixing A0 and B0 on ​​the rubber hose, and then evenly spray the topcoat obtained by mixing polyurea A and polyurea B on the primer, the spraying thickness of the primer and topcoat is 6 kg / m2, and then put it into the vulcanization tank for vulcanization at a temperature of 70°C and dry hot air drying for 140 minutes, and then naturally cure in the air for 8 days.

[0045] Example 4

[0046] A method for preparing a wear-resistant and aging-resistant polyurea marine oil pipe comprises the following steps:

[0047] Step S1: preparing a primer: stirring 60 parts of a modified polyurethane prepolymer and 25 parts of butyl acetate to obtain component A0, and uniformly mixing 5 parts of diethylenetriamine, 80 parts of butyl acetate and 1 part of alkylene oxide to obtain component B0;

[0048] The modified polyurethane prepolymer is prepared by mixing phthalic anhydride and polysulfide rubber in a mass ratio of 3-5:21-24 to obtain a mixture, then adding 17:25 in a volume ratio to a mixed solution of ethylene oxide and propylene glycol in a volume ratio of 1:1, and reacting at a vacuum degree of 0.3 MPa and a temperature of 130° C. for 140 minutes to obtain the mixture;

[0049] Step S2: preparing topcoat: adding 70 parts of isocyanate into a reaction kettle, and then dropping 5 parts of a wear-resistant additive obtained by mixing silicon micropowder with polyoxypropylene ether glycol at a solid-liquid ratio of 7:30 g / mL, and heating the mixture in a nitrogen atmosphere to obtain polyurea elastic A. The temperature-raising reaction is performed by charging dry nitrogen for protection, heating the temperature to 70° C., and keeping the temperature for 180 minutes. Then, 60 parts of polyether polyamine, 20 parts of diethyltoluenediamine and 1 part of octadecanetriol are uniformly mixed to obtain polyurea elastic B.

[0050] Step S3: Clean, degrease and deash the rubber hose, then evenly spray the primer obtained by mixing A0 and B0 on ​​the rubber hose, and then evenly spray the topcoat obtained by mixing polyurea A and polyurea B on the primer, the spraying thickness of the primer and topcoat is 6 kg / m2, and then put it into the vulcanization tank for vulcanization at a temperature of 60°C and dry hot air drying for 140 minutes, and then naturally cure in the air for 6 days.

[0051] Example 5

[0052] A method for preparing a wear-resistant and aging-resistant polyurea marine oil pipe comprises the following steps:

[0053] Step S1: preparing a primer: stirring 70 parts of a modified polyurethane prepolymer and 10 parts of butyl acetate to obtain component A0, and uniformly mixing 10 parts of triethylenetetramine, 80 parts of butyl acetate and 3 parts of methyl propylene oxide to obtain component B0;

[0054] The modified polyurethane prepolymer is prepared by mixing phthalic anhydride and polysulfide rubber in a mass ratio of 3:23 to obtain a mixture, then adding 15:35 in a volume ratio to a mixed solution of ethylene oxide and propylene glycol in a volume ratio of 1:2, and reacting at a vacuum degree of 0.2 MPa and a temperature of 140° C. for 140 minutes to obtain a mixture;

[0055] Step S2: preparing topcoat: adding 80 parts of isocyanate into a reaction kettle, and then dropping 1 part of a wear-resistant additive obtained by mixing silicon micropowder with polyoxypropylene ether glycol at a solid-liquid ratio of 4:35 g / mL, and heating the mixture in a nitrogen atmosphere to obtain polyurea elastic A. The temperature-raising reaction is performed by charging dry nitrogen for protection, heating the temperature to 100° C., and keeping the temperature for 140 minutes. Then, 60 parts of polyether polyamine, 15 parts of diethyltoluenediamine and 3 parts of hexadecanediol are uniformly mixed to obtain polyurea elastic B.

[0056] Step S3: Clean, degrease and deash the rubber hose, then evenly spray the primer obtained by mixing A0 and B0 on ​​the rubber hose, and then evenly spray the topcoat obtained by mixing polyurea A and polyurea B on the primer, the spraying thickness of the primer and topcoat is 6 kg / m2, and then put it into the vulcanization tank for vulcanization dry hot air drying at a temperature of 65°C for 100 minutes, and then naturally cure in the air for 8 days.

[0057] Comparative Example 1

[0058] The difference between Comparative Example 1 and Example 1 is that the polyurethane prepolymer of Comparative Example 1 is not modified, and the other properties remain unchanged.

[0059] Comparative Example 2

[0060] The difference between Comparative Example 2 and Example 1 is that the wear-resistant additive in Comparative Example 2 is replaced by ethylene glycol, and the other parts remain unchanged.

[0061] Comparative Example 3

[0062] The difference between Comparative Example 3 and Example 1 is that the auxiliary agent 2 in Comparative Example 3 is replaced by propylene glycol, and the other components remain unchanged.

[0063] The performance tests of the polyurea marine oil pipes prepared in the examples and comparative examples are shown in Table 1.

[0064] Table 1 Performance data

[0065]

[0066] It can be seen from Table 1 that the polyurea type marine oil pipe prepared in the present invention has good mechanical properties, good wear resistance and aging resistance, and high tensile strength and impact strength.

[0067] The polyurea type marine oil pipe of the present invention adopts composite paint for coating protection, and both the primer and the topcoat adopt AB double mixture. High-functionality modified polyurethane prepolymer and additives containing epoxy groups are added to the primer, and the polymerization degree is higher than that of unmodified polyurethane prepolymer; wear-resistant additives and long-chain alcohol additives are added to the topcoat, and compared with general additives, the topcoat has better wear resistance, higher stability and strong aging resistance.

Claims

1. A method for preparing a wear-resistant and aging-resistant polyurea type marine oil pipe, characterized in that: The following steps are involved: Step S1: preparing a primer: stirring a modified polyurethane prepolymer and butyl acetate to obtain component A0, and uniformly mixing a polyamine, butyl acetate and an auxiliary agent 1 to obtain component B0; Step S2: preparing topcoat: adding isocyanate into a reaction kettle, then dropping a wear-resistant additive and heating the reaction in a nitrogen atmosphere to obtain polyurea elastic A, then mixing polyether polyamine, diethyltoluenediamine and additive 2 to obtain polyurea elastic B; Step S3: Clean, degrease and deash the rubber hose, then evenly spray the primer obtained by mixing A0 and B0 on ​​the rubber hose, and then evenly spray the topcoat obtained by mixing polyurea A and polyurea B on the primer, the spraying thickness of the primer and topcoat is 6 kg / m2, and then put it into a vulcanization tank for vulcanization at a temperature of 60-70°C and dry hot air drying for 100-140 minutes, and then naturally cure in the air for 6-8 days.

2. The method for preparing a wear-resistant and aging-resistant polyurea marine oil pipe according to claim 1, characterized in that: The preparation of the modified polyurethane prepolymer in step S1 is to first mix phthalic anhydride and polysulfide rubber in a mass ratio of 3-5:21-24 to obtain a mixture, and then add phthalic anhydride and polysulfide rubber in a volume ratio of 14-17:25-35 to the mixed solution and react at a vacuum degree of 0.1-0.3MPa and a temperature of 130-150°C for 100-140min to obtain the obtained mixture.

3. The method for preparing a wear-resistant and aging-resistant polyurea type marine oil pipe according to claim 2, characterized in that: The mixed solution is composed of ethylene oxide and propylene glycol in a volume ratio of 1:1-3.

4. The method for preparing a wear-resistant and aging-resistant polyurea marine oil pipe according to claim 1, characterized in that: The auxiliary agent 1 in step S1 is alkylene oxide.

5. The method for preparing a wear-resistant and aging-resistant polyurea type marine oil pipe according to claim 1, characterized in that: The temperature-raising reaction in step S2 is carried out by filling with dry nitrogen for protection, heating to 70-100° C., and keeping the temperature for 90-180 minutes.

6. The method for preparing a wear-resistant and aging-resistant polyurea marine oil pipe according to claim 1, characterized in that: The wear-resistant additive in step S2 is obtained by mixing the wear-resistant component with polyoxypropylene ether glycol at a solid-liquid ratio of 4-7:30-35 g / mL.

7. The method for preparing a wear-resistant and aging-resistant polyurea marine oil pipe according to claim 6, characterized in that: The wear-resistant component is silicon powder.

8. The method for preparing a wear-resistant and aging-resistant polyurea marine oil pipe according to claim 1, characterized in that: The auxiliary agent 2 in step S2 is a long-chain fatty alcohol.

9. A wear-resistant and aging-resistant polyurea marine oil pipe made according to the method according to any one of claims 1 to 8.

10. The wear-resistant and aging-resistant polyurea marine oil pipe according to claim 9, characterized in that: The polyurea type marine oil pipe comprises components A0, B0, A and B; The component A0 comprises the following components in parts by weight: 60-75 parts of modified polyurethane prepolymer and 10-25 parts of butyl acetate; The component B0 comprises the following components in parts by weight: 5-15 parts of polyamine, 50-80 parts of butyl acetate and 11-5 parts of auxiliary agent 1; The component A comprises the following components by weight: 70-90 parts of isocyanate and 5-10 parts of wear-resistant additive; The component B comprises the following components in parts by weight: 60-70 parts of polyether polyamine, 10-20 parts of diethyltoluenediamine and 1-10 parts of auxiliary agent 2.

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