Butadiene modified ethylene propylene rubber-acrylate polymer elastomer resin as well as preparation method and application thereof

Abstract

The invention relates to the technical field of coating preparation, and particularly discloses butadiene modified ethylene propylene rubber-acrylate polymer elastomer resin as well as a preparation method and application of the butadiene modified ethylene propylene rubber-acrylate polymer elastomer resin. Meanwhile, the acrylate monomers can be subjected to copolymerization reaction with the hydroxyl polybutadiene under the action of the initiator to form an interpenetrating structure with the hydroxyl polybutadiene, so that the hydroxyl polybutadiene-polyacrylate elastomer resin is formed; the polybutadiene-acrylate polymer elastomer and the hydroxyl polybutadiene-polyacrylate elastomer resin have good compatibility, so that the mixture has excellent performances of external sightseeing brightness, polymer cold resistance and after-tack resistance in a normal temperature state after being cured by the cross-linking agent; the coating can meet the surface coating protection requirements of aluminum alloy and stainless steel in a specific ultra-low temperature state, and also has good ultraviolet resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of coating preparation, and particularly relates to a butadiene-modified ethylene-propylene rubber-acrylate polymer elastomer resin, a preparation method thereof, and an application thereof. Background Art

[0002] Under ultra-low temperature (long-term service temperature ≤ -100 °C) conditions, the coating protection of metals is limited by the change in the shrinkage stress of the film after crystallization due to the regular arrangement of polymer segments in the coating polymer at ultra-low temperature, resulting in cracking. Therefore, the metal protection at ultra-low temperature has been a blank in materials chemistry at home and abroad so far. In order to reduce the crystallinity of the film material molecules at low temperature, the structural disorder degree (entropy increase) of the polymer is a reliable way to improve the toughness of the low-temperature film material in theory. However, in the actual application process, due to the rare occurrence of the application environment of metal protection at ultra-low temperature, people have always lacked attention to ultra-low temperature metal protection, and related research is still blank.

[0003] Chinese Patent Document CN112225845A discloses a fast-drying, solvent-free ethylene-propylene-diene monomer and acrylate hybrid resin, a preparation method thereof, and an application in waterproof coatings. The preparation method mainly includes the following steps: (1) catalytic epoxidation of ethylene-propylene-diene monomer rubber; (2) preparation of a solvent-free ethylene-propylene-diene monomer and acrylate hybrid resin, by using a solvent-free ethylene-propylene-diene monomer and acrylate hybrid resin as the resin, and using the active monomers (acrylate or methacrylate) in the resin as the solvent to reduce the coating viscosity and improve the construction performance of the coating. However, the cold resistance of the prepared waterproof coating still needs to be further improved. Summary of the Invention

[0004] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a butadiene-modified ethylene-propylene rubber-acrylate polymer elastomer resin, a preparation method thereof, and an application thereof.

[0005] In order to achieve the above purpose, the present invention adopts the following technical solutions:

[0006] In the first aspect, the present invention provides a preparation method of a butadiene-modified ethylene-propylene rubber-acrylate polymer elastomer resin, including the following steps: adding butadiene-modified ethylene-propylene rubber and part of the solvent into a reactor, stirring until the rubber powder is completely dissolved, heating to 100 - 135 °C, then dropping acrylate monomers and part of the initiator, after the dropping is completed, keeping the temperature for reaction for 50 - 70 min, then adding the remaining solvent and the remaining initiator, continuing to keep the temperature for reaction for 3.5 - 4 h, after the reaction is completed, cooling to 50 - 60 °C, and filtering to obtain the butadiene-modified ethylene-propylene rubber-acrylate polymer elastomer resin.

[0007] In the technical solution of the present invention, based on the mass fraction of the preparation raw materials, it includes: 5-15 parts of butadiene-modified ethylene-propylene rubber, 35-45 parts of acrylate monomer, 0.5-2 parts of initiator, and 40-50 parts of solvent.

[0008] In the technical solution of the present invention, the glass transition temperature of the butadiene-modified ethylene-propylene rubber is lower than -50 °C.

[0009] In the technical solution of the present invention, the acrylate monomer is selected from at least two of butyl methacrylate, acrylic acid, hydroxypropyl acrylate, hydroxybutyl acrylate, butyl acrylate, isooctyl acrylate, lauryl methacrylate, and isobornyl acrylate.

[0010] In the technical solution of the present invention, the initiator is selected from at least one of benzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide, and di-tert-amyl peroxide.

[0011] In the technical solution of the present invention, the solvent is selected from hydrocarbon solvents, ketone solvents, ester solvents, or ether solvents.

[0012] In the technical solution of the present invention, the amount of the solvent added for the first time accounts for 75-90% of the total amount of the solvent.

[0013] In the technical solution of the present invention, the amount of the initiator added dropwise for the first time accounts for 70-90% of the total amount of the initiator.

[0014] In the second aspect, the present invention provides a butadiene-modified ethylene-propylene rubber-acrylate polymer elastomer resin prepared by the above preparation method.

[0015] In the third aspect, the present invention further provides the application of the above butadiene-modified ethylene-propylene rubber-acrylate polymer elastomer resin in the field of coatings.

[0016] In the technical solution of the present invention, the coating components include the above butadiene-modified ethylene-propylene rubber-acrylate polymer elastomer resin, isocyanate elastomer, and catalyst.

[0017] In the technical solution of the present invention, the cyano group in the isocyanate elastomer and the hydroxyl group in the butadiene-modified ethylene-propylene rubber-acrylate polymer elastomer resin are proportioned according to the molar ratio NCO / OH = 1.0-1.05:1.

[0018] In the technical solution of the present invention, the catalyst is selected from dibutyltin dilaurate.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] (1) Through the in-situ polymerization reaction of polybutadiene and acrylic monomers, the present invention generates a hydroxyl-containing polybutadiene-acrylate polymer elastomer. Meanwhile, under the action of an initiator, the acrylate monomers can also undergo a copolymerization reaction among the acrylic monomers, forming an interpenetrating structure with hydroxyl polybutadiene to form a hydroxyl polybutadiene-polyacrylate elastomer resin. Since the polybutadiene-acrylate polymer elastomer and the hydroxyl polybutadiene-polyacrylate elastomer resin have good compatibility, the obtained polymer elastomer exhibits excellent performance in terms of the appearance brightness after curing with a crosslinking agent, the cold resistance of the polymer, and the anti-backstickiness at room temperature, which can meet the surface coating protection requirements of aluminum alloy and stainless steel under specific ultra-low temperature conditions, and also has good ultraviolet resistance.

[0021] (2) The present invention prepares a coating varnish by mixing and reacting the prepared polymer elastomer resin with isocyanate and a catalyst, and coats the coating varnish on the surfaces of aluminum alloy and stainless steel. It has good adhesion, and at the same time, the coating also has excellent ultra-low temperature resistance and ultraviolet resistance, and can meet the internal and external surface coating of equipment under ultra-low temperature conditions such as liquid nitrogen. Specific Embodiments

[0022] The following further details the present invention through specific preferred embodiments, but the present invention is not limited to the following embodiments.

[0023] It should be noted that unless otherwise specified, the chemical reagents involved in the present invention are all purchased through commercial channels.

[0024] The model of the butadiene-modified ethylene-propylene rubber used in the embodiments of the present invention: Dow Chemical 4170.

[0025] The grade of the isocyanate elastomer is: N3800.

[0026] The brand of the ethylidene norbornene-modified ethylene-propylene rubber is Mitsui Chemicals, Japan, and the model is EPDM3070H.

[0027] The dicyclopentadiene-modified ethylene-propylene rubber is purchased from Shanghai Sinopec Mitsui Elastomers Co., Ltd.

[0028] The compositions of each material in Examples 1-5 and Comparative Examples 1-2 of the present invention are shown in Table 1 below. Considering that the dienes in commercially available ethylene-propylene-diene rubbers are mainly ethylidene norbornene (ENB) and dicyclopentadiene (DCPD), in order to better illustrate the unique role of butadiene-modified ethylene-propylene rubber, the present invention respectively uses ethylidene norbornene and dicyclopentadiene as the third unit in the ethylene-propylene-diene rubber. Among them, the raw material in Comparative Example 1 is ethylidene norbornene-modified ethylene-propylene rubber, and the raw material in Comparative Example 2 is dicyclopentadiene-modified ethylene-propylene rubber.

[0029] Table 1 Composition of each material (unit: g)

[0030]

[0031]

[0032] Example 1

[0033] Add each material according to the formula in Example 1 of Table 1. The preparation method of butadiene-modified ethylene-propylene rubber-acrylate polymer elastomer resin is as follows:

[0034] Add butadiene-modified ethylene-propylene rubber and 40 g of solvent xylene to the reactor, stir until the rubber powder is completely dissolved, heat up to 130 °C, then dropwise add acrylate monomer and 0.8 g of initiator, and finish dropping in 3 h. After the dropping is completed, keep the temperature at 130 °C for heat preservation reaction for 60 min. Subsequently, add the remaining solvent and the remaining initiator, continue the heat preservation reaction at 130 °C for 4 h. After the reaction is completed, cool down to 60 °C and filter to obtain butadiene-modified ethylene-propylene rubber-acrylate polymer elastomer resin.

[0035] Example 2

[0036] Add each material according to the formula in Example 2 of Table 1. The preparation method of butadiene-modified ethylene-propylene rubber-acrylate polymer elastomer resin is as follows:

[0037] Add butadiene-modified ethylene-propylene rubber and 40 g of solvent xylene to the reactor, stir until the rubber powder is completely dissolved, heat up to 130 °C, then dropwise add acrylate monomer and 0.8 g of initiator, and finish dropping in 3 h. After the dropping is completed, keep the temperature at 130 °C for heat preservation reaction for 60 min. Subsequently, add the remaining solvent and the remaining initiator, continue the heat preservation reaction at 130 °C for 4 h. After the reaction is completed, cool down to 60 °C and filter to obtain butadiene-modified ethylene-propylene rubber-acrylate polymer elastomer resin.

[0038] Example 3

[0039] Add each material according to the formula in Example 3 of Table 1. The preparation method of butadiene-modified ethylene-propylene rubber-acrylate polymer elastomer resin is as follows:

[0040] Add butadiene-modified ethylene-propylene rubber and 40 g of solvent xylene to the reactor, stir until the rubber powder is completely dissolved, heat up to 130 °C, then dropwise add acrylate monomer and 1.0 g of initiator, and finish dropping in 3 h. After the dropping is completed, keep the temperature at 130 °C for heat preservation reaction for 60 min. Subsequently, add the remaining solvent and the remaining initiator, continue the heat preservation reaction at 130 °C for 4 h. After the reaction is completed, cool down to 60 °C and filter to obtain butadiene-modified ethylene-propylene rubber-acrylate polymer elastomer resin.

[0041] Example 4

[0042] Add each material according to the formula in Example 4 in Table 1. The preparation method of the butadiene-modified ethylene-propylene rubber-acrylate polymer elastomer resin is as follows:

[0043] Add butadiene-modified ethylene-propylene rubber and 40 g of solvent xylene to the reactor, stir until the rubber powder is completely dissolved, heat up to 130 °C, then dropwise add acrylate monomer and 1.2 g of initiator, and finish dropping in 3 h. After the dropping is completed, keep the temperature at 130 °C for heat preservation reaction for 60 min. Subsequently, add the remaining solvent and the remaining initiator, continue the heat preservation reaction at 130 °C for 4 h. After the reaction is completed, cool down to 60 °C and filter to obtain the butadiene-modified ethylene-propylene rubber-acrylate polymer elastomer resin.

[0044] Example 5

[0045] Add each material according to the formula in Example 5 in Table 1. The preparation method of the butadiene-modified ethylene-propylene rubber-acrylate polymer elastomer resin is as follows:

[0046] Add butadiene-modified ethylene-propylene rubber and 40 g of solvent xylene to the reactor, stir until the rubber powder is completely dissolved, heat up to 130 °C, then dropwise add acrylate monomer and 0.8 g of initiator, and finish dropping in 3 h. After the dropping is completed, keep the temperature at 130 °C for heat preservation reaction for 60 min. Subsequently, add the remaining solvent and the remaining initiator, continue the heat preservation reaction at 130 °C for 4 h. After the reaction is completed, cool down to 60 °C and filter to obtain the butadiene-modified ethylene-propylene rubber-acrylate polymer elastomer resin.

[0047] Comparative Example 1

[0048] Add each material according to the formula in Comparative Example 1 in Table 1. The preparation method of the polymer elastomer resin is as follows:

[0049] Add ethylidene norbornene-modified ethylene-propylene rubber and 40 g of solvent xylene to the reactor, stir until the rubber powder is completely dissolved, heat up to 130 °C, then dropwise add acrylate monomer and 0.8 g of initiator, and finish dropping in 3 h. After the dropping is completed, keep the temperature at 130 °C for heat preservation reaction for 60 min. Subsequently, add the remaining solvent and the remaining initiator, continue the heat preservation reaction at 130 °C for 4 h. After the reaction is completed, cool down to 60 °C and filter to obtain the polymer elastomer resin.

[0050] Comparative Example 2

[0051] Add each material according to the formula in Comparative Example 2 in Table 1. The preparation method of the polymer elastomer resin is as follows:

[0052] Add dicyclopentadiene-modified ethylene-propylene rubber and 40 g of solvent xylene into the reactor, stir until the rubber powder is completely dissolved, heat up to 130 °C, then dropwise add acrylate monomer and 0.8 g of initiator, and finish the dropping within 3 h. After the dropping is completed, keep the temperature at 130 °C for 60 min of heat preservation reaction. Subsequently, add the remaining solvent and the remaining initiator, continue the heat preservation reaction at 130 °C for 4 h. After the reaction is completed, cool down to 60 °C, and filter to obtain the polymer elastomer resin.

[0053] Weigh the polymer elastomer resins prepared in Examples 1-5 and Comparative Examples 1-3 respectively and mix them evenly with dibutyltin dilaurate to obtain a mixture. The mass fraction of the polymer elastomer resin in the mixture is 99.94%, and the mass fraction of dibutyltin dilaurate is 0.06%. Then mix the mixture with the isocyanate elastomer, and carry out the ratio according to the molar ratio of NCO / OH = 1.05:1 of the cyano group in the isocyanate elastomer and the hydroxyl group in the polymer elastomer resin to obtain a coating. Then coat the coating on the surface of a 304 stainless steel plate to form a coating film with a thickness of 40 μm, and test the performance of the coating film. The results are shown in Table 2.

[0054] Table 2 Test results of the performance of the coating film

[0055]

[0056] It can be seen from the data in Table 2 above that the coating varnish obtained by mixing the polybutadiene-modified ethylene-propylene rubber-hydroxyacrylate elastomer resin, isocyanate elastomer and a specific catalyst prepared by the present invention in a certain proportion and coating the stainless steel surface adheres more firmly to the surface of the stainless steel compared with other ethylene-propylene rubber-modified acrylic monomer polymers, and at the same time has better ultra-low temperature resistance characteristics, and can meet the surface coating of equipment in ultra-low temperature states such as liquid nitrogen and liquid hydrogen.

[0057] Finally, it should be noted that the above embodiments do not limit the present invention in any form. For those skilled in the art, based on the present invention, some modifications and improvements can be made. Therefore, any modification or improvement made without departing from the spirit of the present invention falls within the scope of protection required by the present invention.

Claims

1. A preparation method of a butadiene-modified ethylene-propylene rubber-acrylate polymer elastomer resin, characterized in that, The steps include: adding butadiene-modified ethylene-propylene rubber and a part of the solvent into a reactor, stirring until the rubber powder is completely dissolved, heating to 100 - 135 °C, then dropping acrylate monomers and a part of the initiator, maintaining the temperature for reaction for 50 - 70 min after the dropping is completed, subsequently adding the remaining solvent and the remaining initiator, continuing to maintain the temperature for reaction for 3.5 - 4 h, cooling to 50 - 60 °C after the reaction is completed, and filtering to obtain butadiene-modified ethylene-propylene rubber-acrylate polymer elastomer resin.

2. The preparation method according to claim 1, characterized in that, Based on the mass fraction of the preparation raw materials, it includes: 5 - 15 parts of butadiene-modified ethylene-propylene rubber, 35 - 45 parts of acrylate monomers, 0.5 - 2 parts of initiator, and 40 - 50 parts of solvent.

3. The preparation method according to claim 1, characterized in that The glass transition temperature of the butadiene-modified ethylene-propylene rubber is lower than -50 °C.

4. The preparation method according to claim 1, characterized in that, The acrylate monomers are selected from at least two of butyl methacrylate, acrylic acid, hydroxypropyl acrylate, hydroxybutyl acrylate, butyl acrylate, isooctyl acrylate, lauryl methacrylate, and isobornyl acrylate.

5. The preparation method according to claim 1, characterized in that, The initiator is selected from at least one of benzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide, and di-tert-amyl peroxide.

6. The preparation method according to claim 1, wherein, The solvent is selected from hydrocarbon solvents, ketone solvents, ester solvents, or ether solvents.

7. The preparation method according to claim 1, characterized in that, The amount of the solvent added for the first time accounts for 75 - 90% of the total amount of the solvent used.

8. The preparation method according to claim 1, wherein, The amount of the initiator added for the first time accounts for 70 - 90% of the total amount of the initiator used.

9. The butadiene-modified ethylene-propylene rubber-acrylate polymer elastomer resin prepared by the preparation method according to any one of claims 1 - 8.

10. The application of the butadiene-modified ethylene-propylene rubber-acrylate polymer elastomer resin according to claim 9 in the field of coatings.

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