CN115418156B - Benzothiazole modified polyaspartate polyurea antifouling paint and preparation method and application thereof - Google Patents

Benzothiazole modified polyaspartate polyurea antifouling paint and preparation method and application thereof Download PDF

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CN115418156B
CN115418156B CN202211153694.3A CN202211153694A CN115418156B CN 115418156 B CN115418156 B CN 115418156B CN 202211153694 A CN202211153694 A CN 202211153694A CN 115418156 B CN115418156 B CN 115418156B
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benzothiazole
component
parts
modified
weight
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CN115418156A (en
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陈蓉蓉
王昊天
刘培礼
李茹民
于静
朱佳慧
刘琦
刘婧媛
王君
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Harbin Engineering University
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Harbin Engineering University
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/02—Polyureas
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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    • C08G18/40—High-molecular-weight compounds
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    • C08G18/40—High-molecular-weight compounds
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
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    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance

Abstract

The invention discloses benzothiazole modified polyaspartic ester polyurea antifouling paint, a preparation method and application thereof, wherein the antifouling paint is prepared by mixing a component A and a component B, and the component A comprises the following components in parts by weight: 166-196 parts of benzothiazole-bonded isocyanate prepolymer, 40-48 parts of solvent and 0.1-0.5 part of catalyst; the component B comprises the following components in parts by weight: 75-82 parts of polyaspartic acid ester, 0.15-0.5 part of flatting agent and 0.15-0.5 part of defoaming agent; the component A and the component B are mixed according to the weight ratio of (206.1-244.5) to (75.3-83). The benzothiazole group is introduced, so that the original polyaspartate polyurea system without antifouling property can obtain certain antifouling capacity, and the generated ureido structure can enhance adhesive force through hydrogen bond or chemical bond, so that the wear resistance and cleaning resistance of the polyaspartate polyurea system are ensured.

Description

Benzothiazole modified polyaspartate polyurea antifouling paint and preparation method and application thereof
Technical Field
The invention relates to the technical field of marine antifouling coatings, in particular to a benzothiazole modified polyaspartate polyurea antifouling coating and a preparation method and application thereof.
Background
Marine biofouling refers to biofouling formed by the continuous adhesion and propagation of marine microorganisms, plants and animals on the surfaces of facilities submerged in seawater, which has a number of adverse effects on marine transportation and exploration, development and utilization of marine resources. In order to ensure that the surface of the ship bottom or the underwater structure is clean, the influence of adhering/fixing marine organisms on the ship navigation, the strength of the structure and the like is avoided, and meanwhile, the protection mode of adopting manual underwater cleaning or underwater robot cleaning and high-efficiency environment-friendly antifouling paint is adopted as the policy release in the aspect that the ship with the clean ship bottom is required to enter the port along with all large international ports has become the future development trend.
The main antifouling paints on the market at present are classified into self-polishing type antifouling paints and fouling release type antifouling paints. The self-polishing type antifouling paint mainly comprises zinc acrylate and copper acrylate serving as matrix resin, an antifouling agent and functional filler, wherein the antifouling agent is released by decomposing the matrix resin in water, so that the aim of inhibiting marine organism adhesion is fulfilled. However, the continuously updated coating cannot ensure the wear resistance and the cleaning resistance of the coating. The fouling release type antifouling paint generally does not contain an antifouling agent, takes modified organic silicon or organic fluorine as matrix resin, mainly weakens bioadhesion through low surface energy, has the advantages of low surface energy and no release of organic matters, is more environment-friendly, but has weak adhesive force to a base material, poor mechanical property and difficult guarantee of wear resistance and cleaning resistance.
Chinese patent document CN112759965A (patent No. 202011552060.6) discloses a preparation method of a wear-resistant and anti-fouling coating, which comprises the steps of carboxylating nano-diamond, grafting the nano-diamond onto the surface of a treated substrate, and finally grafting quaternary ammonium salt onto the diamond to obtain the wear-resistant and anti-fouling nano-film.
Chinese patent document CN106854412a (patent No. 201611133840.0) discloses a preparation method of a wear-resistant and anti-fouling two-component polyurethane coating, which adopts polyurethane and acrylic ester as film forming substances, enhances the wear resistance of the coating by adding pigment and filler such as fine powder of white corundum, white graphite, aluminum titanate and the like, and enhances the anti-fouling performance of the coating by adding dipropylene glycol dibenzoate and tridecafluorooctyl triethoxysilane.
The invention develops a novel polyurea wear-resistant antifouling paint from the design point of high-performance wear-resistant antifouling resin.
Disclosure of Invention
In view of the above, the invention aims to provide a benzothiazole modified polyaspartic ester polyurea antifouling paint with antifouling and wear-resisting properties, and a preparation method and application thereof. The antifouling paint provided by the invention has antifouling performance and wear-resistant and cleaning-resistant functions.
The adopted technical scheme is as follows:
the benzothiazole modified polyaspartate polyurea antifouling paint is characterized by being prepared by mixing a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
166-196 parts of benzothiazole-bonded isocyanate prepolymer,
40-48 parts of a solvent,
0.1-0.5 part of catalyst;
the component B comprises the following components in parts by weight:
75-82 parts of polyaspartic acid ester,
0.15 to 0.5 part of flatting agent,
0.15-0.5 part of defoaming agent;
the component A and the component B are mixed according to the weight ratio of (206.1-244.5) to (75.3-83).
Further, the benzothiazole-bonded isocyanate prepolymer is prepared by the following steps:
s1, dissolving 2-mercaptobenzothiazole in ethyl acetate, then dropwise adding isophorone diisocyanate, mixing, and fully reacting at 60-65 ℃ to obtain a modified benzothiazole solution;
s2, mixing polyoxypropylene glycol and polytetramethylene glycol, and dehydrating to obtain mixed polyol;
s3, mixing the mixed polyol of S2 and the modified benzothiazole solution of S1 with isophorone diisocyanate, and performing a prepolymerization reaction at 80-85 ℃ to obtain a benzothiazole-bonded isocyanate prepolymer.
Further, in S1, the 2-mercaptobenzothiazole solution is prepared by the following steps: and (3) reacting the dibenzothiazyl disulfide with mercaptoethanol in chloroform at the reaction temperature of 25+/-5 ℃ at room temperature for 5-8 hours to obtain the 2-mercaptobenzothiazole.
Further, in S1, the weight ratio of the 2-mercaptobenzothiazole, the ethyl acetate and the isophorone diisocyanate is (2-6.7): 35-50): 3.9-8.9.
Further, in S2, the molecular weight of the polyoxypropylene glycol is 2000-3000, and the molecular weight of the polytetramethylene glycol is 1000-2000; the weight ratio of the polyoxypropylene glycol to the polytetramethylene glycol is 60 (30-50).
Further, in S3, the weight ratio of the mixed polyol, the isocyanate containing modified benzothiazole and isophorone diisocyanate is 100 (38-66) (35-50).
Further, in S1, the rate of dripping isophorone diisocyanate can be selected to be 1.2-2.4mL/min;
further, the solvent is one or more of ethyl acetate, butyl acetate and xylene. The solvent can dissolve the benzothiazole-bonded isocyanate prepolymer, so that the isocyanate prepolymer can fully react with the component B and reduce the viscosity of the system.
Further, the catalyst comprises one or more of dibutyl tin dilaurate, triethylamine, cobalt naphthenate and N-ethylmorpholine. The catalyst is capable of accelerating the reaction.
In the present invention, the leveling agent and the defoaming agent may be selected from commercially available leveling agents and defoaming agents, including, but not limited to, one of commercially available German Pick BYK-306, BYK-307, BYK-330, and one of commercially available German Pick BY 066-N, BYK-141, BYK-071, BYK-060N, for example.
In the invention, polyaspartic acid ester is an isocyanate curing agent containing a secondary amine structure, compared with primary amine, the reaction speed is slower and controllable, the operation time is longer, the hardness of the coating can be increased due to the ester group and the aliphatic characteristic contained in the structure, and the coating has excellent impact resistance and wear resistance due to the combination of the polyaspartic acid ester and the benzothiazole-bonded isocyanate prepolymer in the component A. The introduction of benzothiazole bond in the benzothiazole bonded isocyanate prepolymer of the component A ensures that the paint obtains antifouling performance, and simultaneously, the addition of benzene rings also ensures that the rigidity of chain segments is increased, and the mechanical performance of the paint is improved so as to ensure the wear resistance and cleaning resistance of the paint.
The invention relates to a preparation method of benzothiazole modified polyaspartate polyurea antifouling paint, which comprises the following steps:
s10, uniformly mixing 166-196 parts of benzothiazole-bonded isocyanate prepolymer, 40-48 parts of solvent and 0.1-0.5 part of catalyst by weight to obtain a component A;
s20, uniformly mixing 75-82 parts of polyaspartic acid ester, 0.15-0.5 part of flatting agent and 0.15-0.5 part of defoaming agent in parts by weight to obtain a component B;
s30, mixing the component A and the component B according to the weight ratio of (206.1-244.5) to (75.3-83).
The application of the benzothiazole modified polyaspartate polyurea antifouling paint in the marine antifouling coating is characterized in that the benzothiazole modified polyaspartate polyurea antifouling paint is coated on a substrate and cured.
The invention is not particularly limited as long as the components A and B can be mixed sufficiently.
After the component A and the component B are mixed, the mixed system is preferably defoamed, and the defoamation method is not particularly limited and only needs to completely remove bubbles.
In the present invention, the material of the base material includes one or more of glass, steel, wood, plastic, and bakelite, and more preferably steel.
In the present invention, the thickness of the antifouling paint coated on the substrate is not particularly limited, and the thickness may be set as required.
In the invention, the curing temperature is preferably 80+/-2 ℃, and the curing time is not particularly limited, and only the coating is required to be formed into a dry film.
In the invention, when the antifouling paint is applied to marine antifouling, the antifouling paint is preferably coated on the surface of marine equipment, and the thickness of the antifouling paint coated on the surface of the marine equipment is not particularly limited and can be set according to actual conditions.
In summary, the invention has the following beneficial effects:
(1) The 2-mercaptobenzothiazole as an antifouling agent added in the polyaspartic acid ester polyurea system (namely the benzothiazole modified polyaspartic acid ester polyurea antifouling paint) is introduced into a resin matrix in a chemical bonding mode, belongs to a non-leaching type antifouling agent, can be stably fixed in the resin matrix, and has the benzothiazole group which enables the polyaspartic acid ester polyurea system without antifouling performance to obtain antifouling capability.
(2) The polyaspartic acid ester is a secondary amine chain extender, the prepared benzothiazole modified polyaspartic acid ester polyurea antifouling paint has higher hydrogen bond density, good mechanical property, higher wear resistance and excellent toughness, and a large number of hydrogen bonds exist to ensure that the polyaspartic acid ester polyurea antifouling paint has high adhesive force and is not easy to fall off from a matrix, so that the benzothiazole modified polyaspartic acid ester polyurea antifouling paint can cope with complex marine environment in application as a marine antifouling coating, and the service life is prolonged.
Detailed Description
The present invention will be described in detail by way of specific examples, but the purpose and purpose of these exemplary embodiments are merely to illustrate the present invention, and are not intended to limit the actual scope of the present invention in any way.
Unless otherwise specified, "parts" in the following examples are parts by weight.
Example 1
A benzothiazole modified polyaspartate polyurea antifouling paint comprises an A component and a B component which are independently packaged, wherein the A component comprises 170 parts of benzothiazole bonded isocyanate prepolymer, 45 parts of solvent and 0.2 part of catalyst.
The preparation method of the 2-mercaptobenzothiazole comprises the following steps: adding 3.32 parts of dibenzothiazyl disulfide and 45 parts of chloroform into a reaction device, dripping 3.12 parts of beta-mercaptoethanol at the temperature of 25+/-5 ℃ at room temperature, reacting for 5 hours under stirring, removing the solvent by rotary evaporation, cleaning for 2-3 times by deionized water (15 mL), and vacuum drying for 24 hours to obtain yellow needle-shaped crystals, namely the 2-mercaptobenzothiazole.
A method for preparing a benzothiazole-bonded isocyanate prepolymer comprising the steps of: a. 2.91 parts of 2-mercaptobenzothiazole is dissolved in 35 parts of ethyl acetate, a reaction device is added, 3.91 parts of isophorone diisocyanate is added at 50+/-5 ℃, after uniform mixing, the temperature is raised to 60-65 ℃ and the reaction is carried out for 2 hours, thus obtaining a modified benzothiazole solution;
b. adding the modified benzothiazole solution obtained in the step a into a reaction device containing dehydrated 60 parts of polyoxypropylene glycol, 40 parts of polytetramethylene glycol and 0.2 part of dibutyl tin dilaurate mixture, uniformly mixing, dropwise adding 47.97 parts of isophorone diisocyanate, dropwise adding the mixture at 50+/-5 ℃, uniformly mixing, heating to 80-85 ℃, and reacting for 2.5 hours to obtain the benzothiazole-bonded isocyanate prepolymer.
The component B comprises 76.32 parts of polyaspartic acid ester NH1220, 0.5 part of defoaming agent and 0.5 part of leveling agent.
215.2 parts of the component A and 77.32 parts of the component B are mixed and stirred uniformly, the anti-fouling paint is obtained through vacuum defoaming, and then the anti-fouling paint is coated on a steel substrate and cured at the temperature of 80+/-2 ℃ to obtain the anti-fouling coating.
The abrasion loss ratio of the obtained antifouling coating was measured according to GB/T25262, and abrasion resistance was measured by a coating abrasion tester, the rotating speed of the turntable at the time of the measurement was set to 60r/min, the rotating speed was 500r, and the abrasion loss was represented by the difference between the mass of the samples before and after the experiment. The results were: 0.1479g.
Inhibition of diatom attachment rate test: taking a blank glass sheet as a control, soaking the prepared sample and the glass sheet in a chlorella solution at the same time, culturing for seven days, taking out, measuring ultraviolet absorption at 680nm by an ultraviolet-visible spectrophotometer, and the inhibition rate is expressed by the ratio of the absorbance of the algae liquid for soaking the sample to the absorbance of the algae liquid for soaking the blank glass sheet; the results were: 95%.
Mussel attachment rate test: taking a blank glass sheet as a control, simultaneously placing a sample and the glass sheet into a glass jar with the common mussel, and observing the number of the foot filaments of the glass and the coating after two days of placing, wherein the inhibition rate is expressed by the ratio of the difference between the number of the foot filaments on the sample and the number of the foot filaments on the glass sheet to the number of the foot filaments on the glass sheet, and the result is as follows: 57%.
Example 2
Referring to example 1, the difference from example 1 is: 4.82 parts of 2-mercaptobenzothiazole are added.
The test was performed according to the test method of example 1, with the following results: an abrasion loss of 0.1293g, which suppresses the sticking rate of diatom: 97.2%; the mussel adhesion rate is inhibited by 66.32 percent.
Example 3
Referring to example 1, the difference from example 1 is: 6.71 parts of 2-mercaptobenzothiazole are added.
The test was performed according to the test method of example 1, with the following results: an abrasion loss of 0.0609g; the diatom adhesion rate is inhibited by 98.3 percent, and the mussel adhesion rate is inhibited by 73.24 percent.
Example 4
Referring to example 1, the difference from example 1 is: 8.80 parts of 2-mercaptobenzothiazole are added.
The test method according to example 1 gave the following results: abrasion loss of 0.0601g, and the adhesion rate of diatom is inhibited: 98.36% inhibition of mussel attachment rate: 73.72%.
Comparative example 1
Referring to example 1, the difference from example 1 is: no 2-mercaptobenzothiazole was added. The benzothiazole-bonded isocyanate prepolymer is replaced with an isocyanate prepolymer that is not benzothiazole-bonded.
The test method according to example 1 gave the following results: the abrasion loss was 0.1821g.
Has no inhibiting effect on diatom adhesion.
The above list of detailed descriptions is only specific to practical embodiments of the present invention, and they are not intended to limit the scope of the present invention, and all equivalent embodiments or modifications that do not depart from the spirit of the present invention should be included in the scope of the present invention.

Claims (5)

1. The benzothiazole modified polyaspartate polyurea antifouling paint is characterized by being prepared by mixing an A component and a B component, wherein:
the component A comprises the following components in parts by weight:
166-196 parts of benzothiazole-bonded isocyanate prepolymer,
40-48 parts of a solvent,
0.1-0.5 part of catalyst;
the component B comprises the following components in parts by weight:
75-82 parts of polyaspartic acid ester,
0.15 to 0.5 part of flatting agent,
0.15-0.5 part of defoaming agent;
the component A and the component B are mixed according to the weight ratio of (206.1-244.5) to (75.3-83); the benzothiazole-bonded isocyanate prepolymer is prepared by the following steps:
s1, dissolving 2-mercaptobenzothiazole in ethyl acetate, then dropwise adding isophorone diisocyanate, mixing, and fully reacting at 60-65 ℃ to obtain a modified benzothiazole solution;
s2, mixing polyoxypropylene glycol and polytetramethylene glycol, and dehydrating to obtain mixed polyol;
s3, mixing the mixed polyol of S2 and the modified benzothiazole solution of S1 with isophorone diisocyanate, and performing a prepolymerization reaction at 80-85 ℃ to obtain a benzothiazole-bonded isocyanate prepolymer;
in S1, the 2-mercaptobenzothiazole solution is prepared by the following steps: reacting dibenzothiazyl disulfide with mercaptoethanol in chloroform at a room temperature of 25+/-5 ℃ for 5-8 hours to obtain 2-mercaptobenzothiazole;
in S1, the weight ratio of the 2-mercaptobenzothiazole to the ethyl acetate to the isophorone diisocyanate is (2-6.7): 35-50): 3.9-8.9;
in S2, the molecular weight of the polyoxypropylene glycol is 2000-3000, and the molecular weight of the polytetramethylene glycol is 1000-2000; the weight ratio of the polyoxypropylene glycol to the polytetramethylene glycol is 60 (30-50);
in S3, the weight ratio of the mixed polyol to the isocyanate containing the modified benzothiazole to the isophorone diisocyanate is 100 (38-66) (35-50).
2. The benzothiazole modified polyaspartate polyurea anti-fouling coating of claim 1 wherein the solvent is one or more of ethyl acetate, butyl acetate, xylene.
3. The benzothiazole modified polyaspartate polyurea anti-fouling coating of claim 1 wherein the catalyst comprises one or more of dibutyltin dilaurate, triethylamine, cobalt naphthenate, N-ethylmorpholine.
4. A method for preparing the benzothiazole modified polyaspartic ester polyurea antifouling paint according to any one of claims 1 to 3, comprising the following steps:
s10, uniformly mixing 166-196 parts of benzothiazole-bonded isocyanate prepolymer, 40-48 parts of solvent and 0.1-0.5 part of catalyst by weight to obtain a component A;
s20, uniformly mixing 75-82 parts of polyaspartic acid ester, 0.15-0.5 part of flatting agent and 0.15-0.5 part of defoaming agent in parts by weight to obtain a component B;
s30, mixing the component A and the component B according to the weight ratio of (206.1-244.5) to (75.3-83).
5. Use of the benzothiazole modified polyaspartate polyurea antifouling paint according to any of claims 1-3 as marine antifouling coating, wherein the benzothiazole modified polyaspartate polyurea antifouling paint is coated on a substrate and cured.
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