CN109734916B - Main-chain silicon-zinc polycondensate, hydrolysable antifouling paint and preparation method thereof - Google Patents
Main-chain silicon-zinc polycondensate, hydrolysable antifouling paint and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of marine antifouling paints, and particularly relates to a main chain type silicon acrylate-zinc polycondensate, a hydrolysable antifouling paint and a preparation method thereof. The main chain type silicon-zinc acrylate polycondensate provided by the invention is prepared by synthesizing organosilicone acrylic acid and preparing the main chain type silicon-zinc acrylate polycondensate through the synthesized organosilicone acrylic acid, the obtained main chain type silicon-zinc acrylate polycondensate can keep the surface to be stably hydrolyzed in seawater for a long time, and a coating prepared by using the polymer as a film forming matter has the advantages of low antifouling agent content/low resistance, and the surface roughness is low and smoother after seawater abrasion, so that the coating is beneficial to reducing the resistance of seawater to the coating and has important application value.
Description
Technical Field
The invention belongs to the technical field of marine antifouling paints, and particularly relates to a main chain type silicon-zinc polycondensate, a hydrolysable antifouling paint and a preparation method thereof.
Background
The antifouling paint can save fuel oil and reduce carbon emission for ships, and the antifouling paint added with the antifouling agent is an economic, feasible and effective method. However, the common hydrolysis type copolymer is used as a film forming material of the coating, and a large amount of antifouling agent is usually contained in the formula, so that the cost of the coating and the burden of marine environment are increased, and the roughness of the surface of the coating is increased, so that the oil consumption of ships is increased. It is therefore of great interest to find a low antifouling agent content/low resistance antifouling coating, and the key technical-functional polymer as an antifouling coating is the most effective means to achieve this goal.
US5795374, published: 19980818 discloses a ship antifouling paint made of a triorganosilyl group-containing polymer, but the polymer film produced has a very low hydrolysis rate and cannot satisfy the use requirements of a film-forming material for a low antifouling agent/low-drag antifouling paint.
EP0802243B1, published: 20010627, discloses a marine antifouling paint having an organosilyl acrylate based polymer binder and a rosin compound for improving the rate of hydrolysis of the paint. But over a longer period of time the painted surface will crack and peel, mainly due to changes in the painted surface.
EP1208167B1, published: 30/07/2003, and EP1476509a2, publication date: in 11/17/2004, the mechanical properties of the antifouling paint were improved by adding fibers and methacrylate polymer, respectively. However, it was found that the polishing and antifouling properties were difficult to maintain for a long period of time, and the surface coating had relatively large roughness due to the side chain hydrolysis characteristics and the addition of fibers.
CN103131289B, published: in 2013, 06 and 05, the self-polishing and low-surface-performance matrix resin is obtained by copolymerizing organic silyl acrylate and fluorine-containing (methyl) acrylate, and is hydrophobic and oleophobic, but the antifouling paint prepared by the resin matrix is seriously dependent on ship speed, and has short antifouling period and unsatisfactory static antifouling effect.
US7045560B2, published: in 2006, 05, 16, the metal-containing resin was used as a film-forming material, and the static antifouling effect was good, but the amount of the antifouling agent added was large, and the surface of the coating was rough and could not satisfy the film-forming material requirements for the low antifouling agent/low resistance antifouling coating.
The hydrolytic polymers in the patents are difficult to maintain stable and uniform hydrolytic property for a long time, and the surface of the coating using the resin as a film forming material is rough after seawater washing for a period of time, which is not beneficial to preparing energy-saving drag-reduction antifouling coatings.
Disclosure of Invention
In order to solve the above problems in the background art, the present invention provides a main chain type silicon-zinc polycondensate, the structural formula of which is shown below:
wherein R is1Is alkylene having 1 to 10 carbon atoms, alkylene containing hydroxyl, alkylene containing carboxyl or oxyalkylene having up to 8 carbon atoms;
R2is alkyl, aryl or alkenyl, R in different positions2May be the same or different;
R3、R4alkyl, aryl, capped or uncapped polyoxyalkylene, aryl, aralkylene, and alkenyl;
R5is an alkylene group having 1 to 14 carbon atoms;
a is an integer of 0-100, b is an integer of 0-50, and a + b is more than or equal to 0 and less than or equal to 100.
Furthermore, the molecular weight of the main chain type silicon-zinc polycondensate is 10000-60000, the solid content is 45-55%, and the viscosity is 500-5000 mPa.
The invention also provides a preparation method of the main chain type silicon-zinc polycondensate, which comprises the following steps:
step a, dissolving dibasic acid in a solvent B, mixing, adding bis-aminated polysiloxane, heating the obtained solution to 50-110 ℃, refluxing for 4-8 hours, and removing supernatant to obtain subnatant;
step b, synthesizing a main chain type silicon-zinc polycondensate
B, filling the solvent C and zinc oxide into a container, heating to 70-150 ℃, then adding the subnatant obtained in the step a, and keeping the temperature condition for reacting for 6-12 hours to obtain a light yellow transparent substance, namely the main chain type silicon-zinc polycondensate;
wherein, the solvent B and the solvent C are both polar solvents.
Further, the step a comprises the following raw materials in parts by weight:
10-42 parts of dibasic acid
40-80 parts of solvent B
20-50 parts of bis-aminated polysiloxane.
In step a, the dibasic acid is a dibasic acid with a carbon chain number not more than sixteen, and comprises one or more of malonic acid, succinic acid and sebacic acid.
Further, the step b comprises the following raw materials in parts by weight:
20-50 parts of subnatant
10-42 parts of zinc oxide
30-60 parts of a solvent C.
Further, the solvent B and the solvent C comprise one or more of tetrahydrofuran, methanol, ethanol, butanone, N, N-dimethylformamide and dimethyl sulfoxide.
The present invention also provides a hydrolysable antifouling paint which employs a main chain type silicon-zinc polycondensate as described in any of the above.
The preparation method of the hydrolysable antifouling paint comprises the following preparation steps: adding the main chain type silicon-zinc polycondensate, pigments and fillers, an organic solvent, a main antifouling agent, an auxiliary antifouling agent and an auxiliary agent into a dispersion tank together, dispersing at a high speed of 1500-3000 r/min for 20 minutes to obtain a primary coating, grinding the primary coating, and obtaining a hydrolysable antifouling coating when the particle size of the coating is less than or equal to 80 microns;
the main anti-fouling agent is an inorganic anti-fouling agent or an organic anti-fouling agent;
the auxiliary antifouling agent is at least one of copper pyrithione, zinc pyrithione, zineb, triphenylboron pyridinium, sea-Nine211 and bromopyrrolecarbonitrile.
Further, the inorganic antifouling agent comprises at least one of copper powder, cuprous oxide, copper naphthenate, cuprous thiocyanate, basic copper carbonate, and copper hydroxide;
the auxiliary agent comprises at least one of aluminum, calcium, zinc salts of stearic acid, lecithin and alkyl sulfonic acid, polyethylene wax, amide wax, hydrogenated castor oil wax and polyamide wax, synthetic fumed silica and bentonite.
The main chain type silicon-zinc polycondensate provided by the invention can keep the surface to be stably hydrolyzed in seawater for a long time, and the coating using the polymer as a film forming material has low surface roughness and is smoother after being abraded by seawater, thereby being beneficial to reducing the resistance of seawater to the coating and having important application value.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a schematic diagram of the weight loss ratios of examples 1 to 4 and comparative examples 1 to 2 provided by the present invention as a function of time.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following description will clearly and completely describe the embodiments of the present invention, and obviously, the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a main chain type silicon-zinc polycondensate, which has the following structural formula:
wherein R is1Is alkylene having 1 to 10 carbon atoms, alkylene containing hydroxyl, alkylene containing carboxyl or oxyalkylene having up to 8 carbon atoms;
R2is alkyl, aryl or alkenyl, R in different positions2May be the same or different;
R3、R4alkyl, aryl, capped or uncapped polyoxyalkylene, aryl, aralkylene, and alkenyl;
R5is an alkylene group having 1 to 14 carbon atoms;
a is an integer of 0-100, b is an integer of 0-50, and a + b is more than or equal to 0 and less than or equal to 100.
Furthermore, the molecular weight of the main chain type silicon-zinc polycondensate is 10000-60000, the solid content is 45-55%, and the viscosity is 500-5000 mPa.
The invention also provides a preparation method of the main chain type silicon-zinc polycondensate, which comprises the following steps:
step a, dissolving dibasic acid in a solvent B, mixing, adding bis-aminated polysiloxane (DN-PDS for short), heating the obtained solution to 50-110 ℃, refluxing for 4-8 hours, and removing supernatant to obtain subnatant; the dibasic acid has a carbon chain not exceeding sixteen and comprises one or more of malonic acid, succinic acid and sebacic acid.
Wherein, the structural formula of DN-PDS is as follows:
in the above formula, R1Selected from the group consisting of alkyl groups having 1 to 10 carbon atoms, hydroxyalkyl groups, carboxyalkyl groups and oxyalkylene groups having up to 8 carbon atoms;
R2may be the same or different and is selected from alkyl, aryl and alkenyl; r3And R4Can be the same as orAnd is selected from the group consisting of alkyl, aryl, capped or uncapped polyoxyalkylene, aryl, aralkylene, and alkenyl; a is an integer of 0-100, b is an integer of 0-50, a + b is not less than 0 and not more than 100.
Step b, synthesizing a main chain type silicon-zinc polycondensate;
b, filling the solvent C and zinc oxide into a container, heating to 70-150 ℃, then adding the subnatant prepared in the step a, and keeping the temperature condition for reacting for 6-12 hours to obtain a light yellow transparent substance, namely the main chain type silicon-zinc polycondensate;
wherein, the solvent B and the solvent C are both polar solvents, and comprise one or a mixture of tetrahydrofuran, methanol, ethanol, butanone, N, N-dimethylformamide and dimethyl sulfoxide;
according to the above preparation method, the present invention also provides the following examples:
TABLE 1
The main chain type silicon-zinc polycondensate provided in the above example and the corresponding comparative example were subjected to a surface contact angle test, wherein comparative example 1 is a silicon acrylate polymer, and comparative example 2 is a zinc acrylate polymer; the test method comprises the following steps: the full-automatic surface/interfacial tension meter is adopted for testing, and the test results are as follows:
TABLE 2
As can be seen from the comparison of the table above, the initial contact angle of the main chain type zinc-silicon polycondensate provided by the invention is obviously larger than that of the prior art, and the roughness can be obviously reduced, thereby being beneficial to achieving low resistance.
The hydrolysis rate test is carried out on the main chain type silicon-zinc polycondensate provided by the embodiment and the comparative example, the hydrolysis rate evaluation is carried out by adopting the weight loss rate, the test result is shown in figure 1, and as can be seen from the figure, the slope of the weight loss rate image of the main chain type zinc-silicon polycondensate provided by the invention is obviously more stable than the comparative ratio, so that the hydrolysis is more uniform and stable.
The present invention also provides a hydrolysable antifouling paint which employs a main chain type silicon-zinc polycondensate as described in any of the above.
The preparation method of the hydrolysable antifouling paint comprises the following preparation steps: adding the main chain type silicon-zinc polycondensate, pigments and fillers, an organic solvent, a main antifouling agent, an auxiliary antifouling agent and an auxiliary agent into a dispersion tank together, dispersing at a high speed of 1500-3000 r/min for 20 minutes to obtain a primary coating, grinding the primary coating, and obtaining a hydrolysable antifouling coating when the particle size of the coating is less than or equal to 80 microns;
the main anti-fouling agent is an inorganic anti-fouling agent or an organic anti-fouling agent; the auxiliary antifouling agent is at least one of copper pyrithione, zinc pyrithione, zineb, triphenylboron pyridinium, sea-Nine211 and bromopyrrolecarbonitrile. Among the above-mentioned antifouling agents, those can be used alone or in combination, and various antifouling agents other than cuprous oxide are preferably used in combination with cuprous oxide.
Preferably, the inorganic antifouling agent comprises at least one of copper powder, cuprous oxide, copper naphthenate, cuprous thiocyanate, basic copper carbonate and copper hydroxide, preferably cuprous oxide.
The auxiliary agent comprises at least one of aluminum, calcium, zinc salts of stearic acid, lecithin and alkyl sulfonic acid, polyethylene wax, amide wax, hydrogenated castor oil wax and polyamide wax, synthetic fumed silica and bentonite, and preferably polyamide wax and bentonite.
The main chain type zinc-silicon polycondensates prepared according to examples 1 to 4 were prepared according to the above method to obtain corresponding coatings, and after the corresponding coatings were abraded in seawater for 5 months, roughness was measured using a confocal 3d profilometer; the test results are shown below, where comparative example 1 is a silicone acrylate anti-fouling paint and comparative example 2 is a zinc acrylate anti-fouling paint;
TABLE 3
As can be seen from the above table, the antifouling paint prepared by using the main chain type zinc-silicon polycondensate provided by the invention has low surface roughness and is smoother after seawater abrasion compared with the prior art, and is beneficial to reducing the resistance of seawater to the antifouling paint.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A main chain type silicon-zinc polycondensate characterized by the structural formula:
wherein R is1Is alkylene having 1 to 10 carbon atoms, alkylene containing hydroxyl, alkylene containing carboxyl or oxyalkylene having up to 8 carbon atoms;
R2is alkyl, aryl or alkenyl, R in different positions2May be the same or different;
R3、R4alkyl, aryl, capped or uncapped polyoxyalkylene, aryl, aralkylene, and alkenyl;
R5is an alkylene group having 1 to 14 carbon atoms;
a is an integer of 0-100, b is an integer of 0-50, and a + b is more than or equal to 0 and less than or equal to 100.
2. The main chain type silicon-zinc polycondensate according to claim 1, characterized in that: the molecular weight of the main chain type silicon-zinc polycondensate is 10000-60000.
3. A method for producing the main chain type silicon-zinc polycondensate according to claim 1, comprising the steps of:
step a, dissolving dibasic acid in a solvent B, mixing, adding bis-aminated polysiloxane, heating the obtained solution to 50-110 ℃, refluxing for 4-8 hours, and removing supernatant to obtain subnatant;
step b, synthesizing a main chain type silicon-zinc polycondensate
B, filling the solvent C and zinc oxide into a container, heating to 70-150 ℃, then adding the subnatant obtained in the step a, and keeping the temperature condition for reacting for 6-12 hours to obtain a light yellow transparent substance, namely the main chain type silicon-zinc polycondensate;
wherein, the solvent B and the solvent C are both polar solvents.
4. The method for preparing the main chain type silicon-zinc polycondensate according to claim 3, wherein the step a comprises the following raw materials in parts by weight:
10-42 parts of dibasic acid
40-80 parts of solvent B
20-50 parts of bis-aminated polysiloxane.
5. The method for producing a main chain type silicon-zinc polycondensate according to claim 3, characterized in that: in the step a, the dibasic acid is a dibasic acid with a carbon chain number not more than sixteen, and comprises one or more of malonic acid, succinic acid and sebacic acid.
6. The method for preparing the main chain type silicon-zinc polycondensate according to claim 3, wherein the step b comprises the following raw materials in parts by weight:
20-50 parts of subnatant
10-42 parts of zinc oxide
30-60 parts of a solvent C.
7. The method for producing a main chain type silicon-zinc polycondensate according to claim 3, characterized in that: the solvent B and the solvent C comprise one or a mixture of tetrahydrofuran, methanol, ethanol, butanone, N, N-dimethylformamide and dimethyl sulfoxide.
8. A hydrolyzable antifouling coating characterized by: a main chain type silicon-zinc polycondensate produced by the method for producing a main chain type silicon-zinc polycondensate according to any one of claims 1 to 3 or a main chain type silicon-zinc polycondensate according to any one of claims 4 to 7.
9. A method of preparing a hydrolysable antifouling paint according to claim 8, characterized by comprising the following preparation steps: adding the main chain type silicon-zinc polycondensate, pigments and fillers, an organic solvent, a main antifouling agent, an auxiliary antifouling agent and an auxiliary agent into a dispersion tank together, dispersing at a high speed of 1500-3000 r/min for 20 minutes to obtain a primary coating, grinding the primary coating, and obtaining a hydrolysable antifouling coating when the particle size of the coating is less than or equal to 80 microns;
the main anti-fouling agent is an inorganic anti-fouling agent or an organic anti-fouling agent;
the auxiliary antifouling agent is at least one of copper pyrithione, zinc pyrithione, zineb, triphenylboron pyridinium, sea-Nine211 and bromopyrrolecarbonitrile.
10. A process for preparing a hydrolysable antifouling paint according to claim 9, characterized in that:
the inorganic antifouling agent comprises at least one of copper powder, cuprous oxide, copper naphthenate, cuprous thiocyanate, basic copper carbonate and copper hydroxide;
the auxiliary agent comprises at least one of aluminum, calcium, zinc salts of stearic acid, lecithin and alkyl sulfonic acid, polyethylene wax, amide wax, hydrogenated castor oil wax and polyamide wax, synthetic fumed silica and bentonite.
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