CN111848959A - Benzoxazine modified organic silicon resin and preparation method and application thereof - Google Patents

Benzoxazine modified organic silicon resin and preparation method and application thereof Download PDF

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CN111848959A
CN111848959A CN201910352608.3A CN201910352608A CN111848959A CN 111848959 A CN111848959 A CN 111848959A CN 201910352608 A CN201910352608 A CN 201910352608A CN 111848959 A CN111848959 A CN 111848959A
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benzoxazine
organic silicon
silicone resin
silicon resin
modified silicone
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辛忠
周长路
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East China University of Science and Technology
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • 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

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Abstract

The invention discloses a benzoxazine modified organic silicon resin which is prepared by condensation polymerization of benzoxazine functionalized silane and polydimethylsiloxane; the structural formula of the benzoxazine modified organic silicon resin is as follows:

Description

Benzoxazine modified organic silicon resin and preparation method and application thereof
Technical Field
The invention belongs to the technical field of organic silicon resin, and particularly relates to benzoxazine modified organic silicon resin and a preparation method and application thereof.
Background
Aquatic animal-planted microorganisms such as barnacles, oysters, ascidians, sea cabbages and green cortex attached to and grown on the surface of marine facilities cause serious biofouling problems to the marine facilities, so that the use performance of equipment is reduced, and the safe and effective operation of the facilities and materials is remarkably reduced. In the case of ships, biofouling can greatly increase the dynamic resistance of the ship's hull. The friction resistance can be increased by more than 10% by a 100-micron-thick biological film, and the resistance can be increased by 80% by a 1-mm-thick biological film, so that the ship speed is reduced by 15%. When the bottom of the ship is seriously polluted by organisms, the thickness of marine organism adhesion can reach more than ten centimeters, and for large commercial ships or military ships with ship bottoms of nearly ten thousand square meters, the ship speed is obviously reduced, and the energy consumption is increased; fouling organisms are attached to equipment such as ship bottom sonar, so that equipment signals are weakened and even fail; oxygen generated by partial attached bacterial metabolites and algae can accelerate electrochemical corrosion of a metal structure, damage the main structure of the offshore facility and seriously influence the performance exertion and safe operation of the offshore engineering facility. Some heat exchange systems adopt seawater cooling, and the water inlet pipe is attached by marine fouling matters, so that the inflow of seawater is reduced, and the heat exchange efficiency is reduced. Numerous undersea engineering facilities such as struts, harbour facilities, fishing nets, ships, coastal industrial facilities have long been plagued with the problem of biofouling.
Marine microorganisms will start to attach themselves to the surface of the installation by physicochemical means. The outermost layer of the microorganism is wrapped with biomacromolecules such as polypeptide and polysaccharide or generates a layer of glue (the forming materials are similar to the polysaccharide and the polypeptide) which is a main substance for adhesion, and the biomacromolecules have strong polarity and are easily adhered to the surface of equipment containing polar groups through hydrogen bonds. Further the biomacromolecules will react with the surface of the device to form a stronger chemical attachment. Hydrophobic surfaces have a lower affinity for marine microorganisms due to the absence of polar groups, so that only van der waals forces exist between the microorganisms and the hydrophobic surface, which adhesion is very weak.
In the last 50 th century, tributyltin self-polishing antifouling paint (TBT-SPC) appeared, and the TBT-SPC rapidly developed with excellent performance and huge cost advantage, occupied more than 70% of antifouling paint market, and obtained huge social and economic benefits. But after being released, the plant growth and reproduction of organisms are strongly interfered, even biogenetic variation is caused, and the plant can enter human bodies through food chains, so that the human health is directly harmed. Under this severe situation, the use of organic tin antifouling paints is restricted by successive actions of countries in the world, and the related products have been completely banned by the International Maritime Organization (IMO) by 2008. The antifouling paint opens the era of low toxicity and no toxicity, and the development of novel paint technology is accelerated in all countries in the world. Although the subsequent alternative tin-free self-polishing antifouling paint alleviates the contradiction between the antifouling requirement and the environmental problem to a certain extent, the antifouling agent containing organic metal (such as zinc, copper and the like) groups is similar to the organic tin action mechanism, the massive enrichment of the antifouling agent is biohazard, and the environmental safety is questionable and questionable. Therefore, the field is in the key stage that old antifouling paint is eliminated and new products are not yet developed, and the development of novel environment-friendly nontoxic antifouling paint is trending. Therefore, the surface property of the material is changed, a novel non-release antifouling coating material is developed, marine organisms are not beneficial to organism attachment in mutual contact with the material, the problem of biofouling can be fundamentally solved, benefit maximization is realized at the minimum environmental cost, and the development of the technology is undoubtedly significant for promoting the development of industries such as ships, marine products, national defense and the like in China.
As mentioned above, the fouling-release (FR) coating with hydrophobic property does not prevent fouling organisms from attaching, but weakens the acting force between the fouling organisms and the coating surface, so that the fouling is peeled off along with the movement of marine facilities or the water flow shearing force generated by mild "carding" equipment, and has good antifouling performance. As is known from the mechanism of action of FR coatings, the surface free energy is the first factor determining their antifouling properties. Long-term biological medicine and marine antifouling research prove that the biological adhesion amount of the coating surface and the critical surface tension (gamma)c) The empirical relationship between them can be described by a "Baier curve". The analysis curve shows that the lower the surface free energy is, the better the antifouling application is, and the lowest amount of the biofouling is 22 to 24mN · m-1Within the range. Silicone resins with surface free energies around this range were therefore the material of choice for FR coatings, and Robbart first filed a related patent in 1961 (US 2986474). However, the application of the silicone resin is limited by some defects, such as low mechanical strength, and the performance of the silicone resin is damaged and lost by animal shells or ship anchors and the like in the using process; the hydrophilic sites inside the polymer migrate to the surface and lose hydrophobic properties. Modification of silicone resins or formulations is therefore often required to meet practical requirements. The addition of inorganic fillers (CaCO) to silicone coatings is often required for commercial applications 3、SiO2Etc.) or non-reactive silicone oils as a supplement. However, the introduction of these foreign substances causes the loss of the smooth and hydrophobic properties of the coating surface and environmental problems (CaCO3 and silicone oil are gradually dissolved or released into the marine environment). The introduction of organic polymer components such as Polyurethane (PU), epoxy resin, etc. by physical blending or chemical synthesis is another effective way to effectively enhance the performance of silicone resins. The disadvantage of low mechanical strength of the silicone polymer can be overcome while retaining the advantages of low surface energy and high smoothness of the coating (CN205711513U, CN103304762B, etc.). However, the surface energy of the modified materials is high, and the problem of hydrophilic site migration still exists. Based on this, fluorocarbon resin is a strong competitor of modified materials due to good chemical stability, heat resistance, aging resistance and extremely low surface energy (10-20mN · m < -1 >), and fluorosilicone resin has a remarkable effect on enhancing the performance of the coating in all aspects (US6265515B1, WO2007/102741, CN101775144B and CN 103666165B). However, fluoride containing more than 4-CF 2-units is potentially harmful to organisms, the original purpose of green and environment-friendly FR coating is sacrificed, and the high cost also limits the wide range of application.
Therefore, the development of a novel modified organic silicon resin fouling and desorption coating material with low cost, low surface energy, no fluorine and good durability is a key topic derived from national important requirements.
Disclosure of Invention
In order to overcome the problems that the organic silicon resin antifouling material in the prior art is low in mechanical strength and insufficient in hydrophobic durability, and a fluorine-silicon modification mode is high in cost and sacrifices environmental protection, the invention aims to provide the benzoxazine modified organic silicon resin which is low in cost, low in surface energy, green and fluorine-free and good in durability.
The second purpose of the invention is to provide a preparation method of the benzoxazine modified silicone resin.
The third purpose of the invention is to provide an application of the benzoxazine modified organic silicon resin.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a benzoxazine-modified organic silicon resin, which is prepared by condensation polymerization of benzoxazine-functionalized silane and polydimethylsiloxane.
The structural formula of the benzoxazine modified organic silicon resin is as follows:
Figure BDA0002044417110000031
R1is selected from C1～C18Straight, branched or cyclic alkyl, halogen, phenyl, hydrogen or C substituted by amino, halogen, mercapto or epoxy groups 1～C10One of a linear, branched or cyclic alkyl group;
z, z is the number of repeating units from 3 to 200, preferably from 20 to 30, and x is from 5 to 50%, preferably from 10 to 30%, of z; y is 50 to 95%, preferably 70 to 90%, of z.
The structure of the benzoxazine-functional silane is as follows:
Figure BDA0002044417110000032
R1is selected from C1～C18Straight, branched or cyclic alkyl, halogen, phenyl, hydrogen or C substituted by amino, halogen, mercapto or epoxy groups1～C10One of a linear, branched or cyclic alkyl group;
R2selected from methoxy or ethoxy.
The polydimethylsiloxane has the following structure:
Figure BDA0002044417110000041
R3selected from hydrogen, hydroxyl, methoxyl or ethoxyl, and x is 9-30.
The second aspect of the invention provides a preparation method of the benzoxazine-modified silicone resin, which comprises the following steps: dissolving benzoxazine functional silane and polydimethylsiloxane in a molar ratio of (5-100): 1 in an organic solvent, adding water and a catalyst, ultrasonically mixing uniformly, coating on a substrate, and performing a hydrolytic condensation reaction to obtain the benzoxazine modified organic silicon resin.
The organic solvent is selected from at least one of alkanes, substituted alkanes, alcohols, ethers, ketones, esters, amides, pyrrolidones and sulfoxides, and specifically selected from at least one of chloroform, tetrachloroethane, ethanol, N-butanol, diethylene glycol dimethyl ether, tetrahydrofuran, acetone, ethyl acetate, N-dimethylacetamide, N-methylpyrrolidone and dimethylsulfoxide.
The organic solvent is added in an amount of 1-1000% of the benzoxazine-functional silane.
The water is present in a molar amount of 0.01 to 40 times the benzoxazine-functional silane.
The mole number of the catalyst is 0-10 times, preferably 1-10 times that of the benzoxazine functionalized silane.
The ultrasonic mixing temperature is 25-60 ℃, the time is 15-120 minutes, the frequency is 35 or 53kHz, and the power is 30-100%.
The temperature of the hydrolysis condensation reaction is 25-150 ℃, preferably 25-70 ℃, and the time is 1-24 hours, preferably 2-20 hours.
The catalyst is selected from one of acid, hydroxide, ammonia or amine.
The acid is at least one of acetic acid and hydrochloric acid.
The hydroxide is at least one of sodium hydroxide and potassium hydroxide.
The ammonia or amine is at least one of ammonia water, n-butylamine and triethylamine.
The base material is one of metal and glass, and is specifically selected from an aluminum alloy base material, a glass base material and a stainless steel base material.
The third aspect of the invention provides a use of the benzoxazine-modified silicone resin as an antifouling paint.
The use of the benzoxazine-modified silicone resin as an antifouling coating, comprising the steps of: and thermally curing the benzoxazine modified organic silicon resin to obtain the polybenzoxazine modified organic silicon resin coating which is used as an antifouling coating and mainly used for antifouling fouling and desorption coatings of oceans.
The curing temperature of the thermal curing is 150-240 ℃, and preferably 150-200 ℃; the curing time is 0.1 to 24 hours, preferably 0.5 to 5 hours.
The polybenzoxazine modified silicone resin coating has the following repeating structural unit:
Figure BDA0002044417110000051
R1is selected from C1～C18Straight, branched or cyclic alkyl, halogen, phenyl, hydrogen or C substituted by amino, halogen, mercapto or epoxy groups1～C10One of a linear, branched or cyclic alkyl group;
z, z is the number of repeating units from 3 to 200, preferably from 20 to 30, and x is from 5 to 50%, preferably from 10 to 30%, of z; y is 50 to 95%, preferably 70 to 90%, of z.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
compared with the traditional fluorine-silicon modification, the benzoxazine modified organic silicon resin has the characteristics of low surface free energy which is similar to that of a fluorine-containing compound and does not contain any fluorine atom, low cost, environmental friendliness, better mechanical strength and capability of making up the defect of poor mechanical property of organic silicon.
The coating is prepared by performing condensation polymerization reaction on benzoxazine functional silane and polydimethylsiloxane and then performing a thermosetting process. Therefore, the fluorine-free low-cost benzoxazine modified organic silicon resin can be used as antifouling paint, has excellent antifouling and durable performances, has low surface free energy and good antifouling and fouling desorption performances, and can be equivalent to fluorine-silicon modified resin.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
The structure of the benzoxazine-functional silane is as follows:
Figure BDA0002044417110000061
the 3-methyldimethoxysiloxane-n-propyl-3, 4-dihydro-6-methyl-2H-1, 3-benzoxazine (i.e., the compound of the structural formula) was synthesized by the method described in the literature (Langmuir.2011,27(13):8365, 8370), and specifically included the following steps: a250 mL four-neck flask with a mechanical stirring, condenser and thermometer was charged with N2Adding paraformaldehyde (0.1mol) and 50mL of chloroform after about 25-30min, adding 7g of ground calcium hydride, slightly stirring, adding 3-aminopropylmethyldimethoxysilane (0.05mol) when the temperature of the system rises to 65 ℃ and condensate drops, violently stirring and heating, adding p-cresol (0.05mol) when the temperature of the system rises to 85 ℃, refluxing and reacting for 3h after the addition is finished, filtering to remove residues after the reaction is finished, and distilling under reduced pressure to remove the solvent and other volatile impurities to obtain a viscous dark yellow liquid (namely the compound with the structural formula) (MP-mdmos). 1HNMR (400MHz, deuterated chloroform,): 0.10-0.18,0.58-0.67,1.58-1.70,2.20-2.35,2.65-2.75,3.50-3.60,3.85-4.00,4.80-4.90,6.75-7.15.
The paracresol, the paraformaldehyde, the trichloromethane and the calcium hydride are analytically pure and are purchased from Shanghai Linfeng chemical reagent company Limited. The purity of the 3-aminopropyl methyl dimethoxysilane is more than or equal to 98 percent, and the 3-aminopropyl methyl dimethoxysilane is purchased from New chemical materials, Inc. of Dabang, Hubei.
In the second step, the structure of polydimethylsiloxane is as follows:
Figure BDA0002044417110000062
x is 9.
Mixing 2.1mol of MP-mdmos and 0.1mol of polydimethylsiloxane, dissolving the mixture in ethanol (the adding amount of the ethanol is 100 percent of the MP-mdmos), adding water and acetic acid which are 5 times of the mol number of benzoxazine functionalized silane, ultrasonically mixing the mixture for 30 minutes under the conditions of 35kHz, 80 percent of power and 35 ℃ of temperature, coating the mixture on an aluminum alloy substrate, and performing hydrolytic condensation at the temperature of 35 ℃ for 20 hours to prepare the benzoxazine modified organic silicon resin.
The structural formula of the benzoxazine modified organic silicon resin is as follows:
Figure BDA0002044417110000071
R1is a methyl group, and the compound is,
x＝9，y＝21，z＝30。
the polydimethylsiloxane, analytically pure, was purchased from great corporation. The ethanol and acetic acid were analytically pure and purchased from Shanghai Lingfeng Chemicals Co., Ltd. The aluminum alloy substrate, 150X 70X 0.5mm, was purchased from Dageda precision instruments (Guangzhou).
And thirdly, curing the obtained benzoxazine modified organic silicon resin by a thermal curing method at the curing temperature of 180 ℃ for 0.5h to obtain the polybenzoxazine modified organic silicon resin coating which is used as an antifouling coating and mainly used as an antifouling fouling desorption coating for marine antifouling.
The polybenzoxazine modified silicone resin coating has the following repeating structural unit:
Figure BDA0002044417110000072
x＝9，y＝21，z＝30。
example 2
In a first step, the structure of the benzoxazine-functional silane is as follows:
Figure BDA0002044417110000081
3-methyldiethoxysiloxane-n-propyl-3, 4-dihydro-6-dodecyl-2H-1, 3-benzoxazine was prepared in the same manner as in example 1, with p-cresol replaced with 4-dodecylphenol to obtain the desired product (DP-mdeos).1HNMR (400MHz, deuterated chloroform,): 0.10-0.18,0.58-0.67,0.80-0.90,1.20-1.30,1.58-1.70,2.20-2.35,2.65-2.75,3.50-3.60,3.85-4.00,4.80-4.90,6.75-7.15.
The 4-dodecylphenol was analytically pure and purchased from Bailingwei technologies, Inc., Beijing. The purity of the 3-aminopropyl methyl diethoxy silane is more than or equal to 98 percent, and the 3-aminopropyl methyl diethoxy silane is purchased from New chemical materials, Inc. of Depont Hubei.
In the second step, the structure of polydimethylsiloxane is as follows:
Figure BDA0002044417110000082
x is 10.
Mixing 1.0mol of DP-mdeos and 0.1mol of polydimethylsiloxane, dissolving the mixture in chloroform (the adding amount of the chloroform is 50 percent of the DP-mdeos), adding water and hydrochloric acid which are 40 times of the mole number of benzoxazine functionalized silane, ultrasonically mixing for 15 minutes under the conditions of 53kHz, 100 percent of power and 30 ℃, coating the mixture on a glass substrate, and performing hydrolytic condensation at the temperature of 25 ℃ for 10 hours to prepare the benzoxazine modified organic silicon resin.
The structure of the benzoxazine modified organic silicon resin is as follows:
Figure BDA0002044417110000083
x＝10，y＝10，z＝20。
the polydimethylsiloxane, analytically pure, was purchased from great corporation. The chloroform and hydrochloric acid were analytically pure and purchased from Shanghai Lingfeng Chemicals Co., Ltd. The glass substrate, 150X 70X 1mm, was purchased from Dageda precision instruments (Guangzhou).
And thirdly, curing the obtained benzoxazine modified organic silicon resin by a thermal curing method at the curing temperature of 200 ℃ for 1h to obtain the polybenzoxazine modified organic silicon resin coating which is used as an antifouling coating and mainly used for an antifouling fouling desorption coating of the ocean.
The polybenzoxazine modified silicone resin coating has the following repeating structural unit:
Figure BDA0002044417110000091
x＝10，y＝10，z＝20。
example 3
In a first step, the benzoxazine-functional silane has the following structure:
Figure BDA0002044417110000092
3-methyldiethoxysiloxane-n-propyl-3, 4-dihydro-6-n-butyl-2H-1, 3-benzoxazine the preparation method was the same as in example 1, and p-cresol was replaced with 4-n-butylphenol to obtain the objective product (BP-mdeos).1HNMR (400MHz, deuterated chloroform,): 0.10-0.18,0.58-0.67,0.80-0.90,1.20-1.30,1.58-1.70,2.20-2.35,2.65-2.75,3.50-3.60,3.85-4.00,4.80-4.90,6.75-7.15.
The 4-n-butylphenol was analytically pure and purchased from Bailingwei technologies, Inc., Beijing. The purity of the 3-aminopropyl methyl diethoxy silane is more than or equal to 98 percent, and the 3-aminopropyl methyl diethoxy silane is purchased from New chemical materials, Inc. of Depont Hubei.
In the second step, the polydimethylsiloxane structure is as follows:
Figure BDA0002044417110000101
x is 30.
Mixing 7.0mol of BP-mdeos and 0.1mol of polydimethylsiloxane, dissolving the mixture in ethyl acetate (the adding amount of the ethyl acetate is 30 percent of that of the BP-mdeos), adding water and ammonia water which are 1 time of the mole number of benzoxazine functionalized silane and 5 times of that of the ammonia water, ultrasonically mixing for 15 minutes under the conditions of 35kHz, 100 percent of power and 25 ℃, coating the mixture on a 304 stainless steel substrate to perform hydrolytic condensation at the temperature of 25 ℃ for 5 hours, and preparing the benzoxazine modified organic silicon resin.
The structural formula of the benzoxazine modified organic silicon resin is as follows:
Figure BDA0002044417110000102
x＝30，y＝70，z＝100。
the polydimethylsiloxane, analytically pure, was purchased from great corporation. The ethyl acetate and the ammonia water are analytically pure and purchased from Shanghai Lingfeng Chemicals Co. The 304 stainless steel substrate, 150X 70X 0.5mm, was purchased from Dageda precision instruments (Guangzhou).
And thirdly, curing the obtained benzoxazine modified organic silicon resin by a thermal curing method at the curing temperature of 150 ℃ for 5 hours to obtain the polybenzoxazine modified organic silicon resin coating which is used as an antifouling coating and mainly used as an antifouling fouling desorption coating for marine antifouling.
The polybenzoxazine modified silicone resin coating has the following repeating structural unit:
Figure BDA0002044417110000111
x＝30，y＝70，z＝100。
example 4
In the first step, the benzoxazine-functional silane structure was the same as in example 3, BP-mdeos.
Second, polydimethylsiloxane structure:
Figure BDA0002044417110000112
R3is ethoxy and x is 9.
Mixing 2.1mol of BP-mdeos and 0.1mol of polydimethylsiloxane, dissolving the mixture in dimethyl sulfoxide (the addition amount of the dimethyl sulfoxide is 100 percent of that of the BP-mdeos), adding water and sodium hydroxide which are 10 times of the mole number of benzoxazine functionalized silane, ultrasonically mixing the mixture for 60 minutes under the conditions of 53kHz, 100 percent of power and 50 ℃, coating the mixture on a 304 stainless steel substrate, and performing hydrolytic condensation at the temperature of 50 ℃ for 5 hours to prepare the benzoxazine modified organic silicon resin.
The structure of the benzoxazine modified organic silicon resin is as follows:
Figure BDA0002044417110000113
R1n-butyl, x is 10, y is 10, and z is 20.
The polydimethylsiloxane, analytically pure, was purchased from great corporation. The dimethyl sulfoxide and the sodium hydroxide are analytically pure and purchased from Shanghai Lingfeng Chemicals Co. The 304 stainless steel substrate, 150X 70X 0.5mm, was purchased from Dageda precision instruments (Guangzhou).
And thirdly, curing the obtained benzoxazine modified organic silicon resin by a thermal curing method at the curing temperature of 180 ℃ for 2 hours to obtain the polybenzoxazine modified organic silicon resin coating which is used as an antifouling coating and mainly used for antifouling fouling desorption coating of the ocean.
The polybenzoxazine modified silicone resin coating has the following repeating structural unit:
Figure BDA0002044417110000121
R1is a normal butyl group and a N-butyl group,
x＝10，y＝10，z＝20。
example 5
In the first step, the benzoxazine-functional silane structure was the same as example 2, DP-mdeos.
Second, polydimethylsiloxane structure:
Figure BDA0002044417110000122
R3is methoxy and x is 10.
Mixing 1.0mol of DP-mdeos and 0.1mol of polydimethylsiloxane, dissolving the mixture in acetone (the addition of the acetone is 100 percent of the addition of the DP-mdeos), adding water and n-butylamine which are 10 times of the mole number of benzoxazine functionalized silane, ultrasonically mixing the mixture for 30 minutes under the conditions of 53kHz, 100 percent of power and 50 ℃, coating the mixture on an aluminum alloy substrate, and performing hydrolytic condensation at the temperature of 50 ℃ for 2.5 hours to prepare the benzoxazine modified organic silicon resin.
The structure of the benzoxazine modified organic silicon resin is as follows:
Figure BDA0002044417110000131
R1is dodecyl, x is 9, y is 21, and z is 30.
The polydimethylsiloxane, analytically pure, was purchased from great corporation. The acetone and n-butylamine are analytically pure and purchased from Shanghai Lingfeng Chemicals Co. The aluminum alloy substrate, 150X 70X 0.5mm, was purchased from Dageda precision instruments (Guangzhou).
And thirdly, curing the obtained benzoxazine modified organic silicon resin by a thermal curing method at the curing temperature of 180 ℃ for 2 hours to obtain the polybenzoxazine modified organic silicon resin coating which is used as an antifouling coating and mainly used for antifouling fouling desorption coating of the ocean.
The polybenzoxazine modified silicone resin coating has the following repeating structural unit:
Figure BDA0002044417110000132
R1is a dodecyl group, and the dodecyl group is,
x＝9，y＝21，z＝30。
comparative example 1
A coating was obtained in the same manner as in example 1 except that no benzene was addedUse of oxazine-functionalized silanes with R3Polydimethylsiloxane with the methoxy group and x being 30 serves as a coating main body material. The polydimethylsiloxane, analytically pure, was purchased from great corporation.
Comparative example 2
A coating was obtained in the same manner as in example 1 except that dodecafluoroheptylpropylmethyldimethoxysilane was used in place of the benzoxazine-functional silane. The dodecafluoroheptylpropylmethyldimethoxysilane was chemically pure and purchased from north Hu Jinleda chemical Co.
Example 6
Coating surface free energy test
(1) The static contact angles (according to Langmuir,29(2013) 411-416) of water, ethylene glycol and diiodomethane were measured at room temperature by the sitting drop method (needle-in type) (OCA20, Dataphysics) using a test liquid (water, ethylene glycol and diiodomethane) having a volume of 2. mu.L and a dropping rate of 5. mu.L/s, and 5 points were taken for each coating sample and the average value was taken.
(2) The calculation of the surface energy (according to the Langmuir,29(2013)411-416 method) is also carried out by a contact angle measuring instrument (OCA20), and the adopted calculation mode is an OWRK mode and is calculated according to the principle of the Owens three-liquid method. At least one of the test liquids is a nonpolar liquid, the nonpolar liquid is Diiodomethane (DIM), and the polar liquid is water (H) 2O) and Ethylene Glycol (EG), results are shown in table 1:
TABLE 1
Figure BDA0002044417110000141
As can be seen from the data in table 1, the polybenzoxazine modified silicone resin coating has lower surface free energy than the comparative silicone resin, and the performance of the polybenzoxazine modified silicone resin coating is equivalent to or lower than that of the fluorosilicone modified material.
Example 7
Antifouling Property test
Specimens (150X 70X 0.5mm, thickness of coating 50-60 μm) prepared in comparative examples 1-2 and examples 1-5 were immersed in the sea water of the Shanghai mountain (longitude 121.5, latitude 30.8, depth 2 m) for 8 months (4-11 months), examined monthly, washed with water and sponged, and re-immersed, and the results of adhesion are shown in Table 2.
TABLE 2
Moss attaching area (%) Algae attachment area (%)
Comparative example 1 40-50 50-70
Comparative example 2 20-30 40-50
Example 1 20-25 30-40
Example 2 20-25 30-40
Example 3 25-35 40-50
Example 4 20-30 40-50
Example 5 20-30 40-50
As can be seen from the data in Table 2, the antifouling performance of the polybenzoxazine modified organic silicon resin coating is better than that of the comparative example 1, and the antifouling capacity is equivalent to that of the comparative example 2.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. A benzoxazine modified organic silicon resin is characterized in that: is prepared by condensation polymerization of benzoxazine functionalized silane and polydimethylsiloxane;
the structural formula of the benzoxazine modified organic silicon resin is as follows:
Figure FDA0002044417100000011
R1is selected from C1～C18Straight, branched or cyclic alkyl, halogen, phenyl, hydrogen or C substituted by amino, halogen, mercapto or epoxy groups1～C10One of a linear, branched or cyclic alkyl group;
and x + y is z, wherein z is the number of repeating units from 3 to 200, x is from 5 to 50% of z, and y is from 50 to 95% of z.
2. The benzoxazine-modified silicone resin according to claim 1, wherein: the structure of the benzoxazine-functional silane is as follows:
Figure FDA0002044417100000012
R1is selected from C1～C18Straight, branched or cyclic alkyl, halogen, phenyl, hydrogen or C substituted by amino, halogen, mercapto or epoxy groups1～C10One of a linear, branched or cyclic alkyl group;
R2selected from methoxy or ethoxy.
3. The benzoxazine-modified silicone resin according to claim 1, wherein: the polydimethylsiloxane has the following structure:
Figure FDA0002044417100000013
R3selected from hydrogen, hydroxyl, methoxyl or ethoxyl, and x is 9-30.
4. A method for producing the benzoxazine-modified silicone resin according to any one of claims 1 to 3, characterized in that: the method comprises the following steps: dissolving benzoxazine functional silane and polydimethylsiloxane in a molar ratio of (5-100): 1 in an organic solvent, adding water and a catalyst, ultrasonically mixing uniformly, coating on a substrate, and performing a hydrolytic condensation reaction to obtain the benzoxazine modified organic silicon resin.
5. The method for preparing a benzoxazine-modified silicone resin according to claim 4, wherein: the organic solvent is at least one of alkanes, substituted alkanes, alcohols, ethers, ketones, esters, amides, pyrrolidones and sulfoxides;
the mole number of the catalyst is 0-10 times that of the benzoxazine-functionalized silane;
the ultrasonic mixing temperature is 25-60 ℃, the time is 15-120 minutes, the frequency is 35 or 53kHz, and the power is 30-100%.
6. The method for preparing a benzoxazine-modified silicone resin according to claim 4, wherein: the temperature of the hydrolysis condensation reaction is 25-150 ℃, and the time is 1-24 h;
the catalyst is selected from one of acid, hydroxide, ammonia or amine;
the base material is one of metal and glass.
7. Use of a benzoxazine-modified silicone resin according to any one of claims 1 to 3 as an antifouling coating.
8. Use of a benzoxazine-modified silicone resin according to claim 7 as an antifouling coating, characterized in that: the method comprises the following steps: and thermally curing the benzoxazine modified organic silicon resin to obtain the polybenzoxazine modified organic silicon resin coating.
9. Use of a benzoxazine-modified silicone resin according to claim 8 as an antifouling coating, characterized in that: the curing temperature of the thermal curing is 150-240 ℃, and the curing time is 0.1-24 h.
10. Use of a benzoxazine-modified silicone resin according to claim 8 as an antifouling coating, characterized in that: the polybenzoxazine modified silicone resin coating has the following repeating structural unit:
Figure FDA0002044417100000021
R1is selected from C1～C18Straight-chain, branched-chain or cyclic alkyl, halogen, phenyl, hydrogen or from amino, halogenMercapto or epoxy substituted C1～C10One of a linear, branched or cyclic alkyl group;
and x + y is z, wherein z is the number of repeating units from 3 to 200, x is from 5 to 50% of z, and y is from 50 to 95% of z.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022121327A1 (en) * 2020-12-09 2022-06-16 山东大学 Temporary high-temperature-resistant dispersing agent and preparation and use methods therefor
CN115403774A (en) * 2022-10-09 2022-11-29 齐鲁工业大学 Synthesis and reshaping method of reprocessable silicone resin containing dynamic covalent Si-O-Ph bond
CN115725110A (en) * 2022-11-16 2023-03-03 航天特种材料及工艺技术研究所 Silicon resin modified polybenzoxazine aerogel and preparation method thereof
CN115948147A (en) * 2022-12-30 2023-04-11 广州市白云化工实业有限公司 Organic silicon polymer/benzoxazine/epoxy resin packaging adhesive and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102134254A (en) * 2011-01-05 2011-07-27 山东大学 Silicon-containing benzoxazine resin as well as preparation method and application thereof
CN104193999A (en) * 2014-09-09 2014-12-10 济南大学 Method for preparing fluorine-silicon-containing benzoxazine copolymer
CN105801875A (en) * 2016-05-24 2016-07-27 济南大学 Fluorine-silicon segmented copolymer with side chain containing benzoxazine ring, preparation method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102134254A (en) * 2011-01-05 2011-07-27 山东大学 Silicon-containing benzoxazine resin as well as preparation method and application thereof
CN104193999A (en) * 2014-09-09 2014-12-10 济南大学 Method for preparing fluorine-silicon-containing benzoxazine copolymer
CN105801875A (en) * 2016-05-24 2016-07-27 济南大学 Fluorine-silicon segmented copolymer with side chain containing benzoxazine ring, preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
朱春莉: "新型苯并噁嗪树脂的合成及性能研究", 《中国优秀博硕士学位论文全文数据库(博士)工程科技Ⅰ辑》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022121327A1 (en) * 2020-12-09 2022-06-16 山东大学 Temporary high-temperature-resistant dispersing agent and preparation and use methods therefor
CN115403774A (en) * 2022-10-09 2022-11-29 齐鲁工业大学 Synthesis and reshaping method of reprocessable silicone resin containing dynamic covalent Si-O-Ph bond
CN115403774B (en) * 2022-10-09 2023-08-11 齐鲁工业大学 Synthesis and reforming method of reworkable silicone resin containing dynamic covalent Si-O-Ph bond
CN115725110A (en) * 2022-11-16 2023-03-03 航天特种材料及工艺技术研究所 Silicon resin modified polybenzoxazine aerogel and preparation method thereof
CN115725110B (en) * 2022-11-16 2024-03-26 航天特种材料及工艺技术研究所 Silicone resin modified polybenzoxazine aerogel and preparation method thereof
CN115948147A (en) * 2022-12-30 2023-04-11 广州市白云化工实业有限公司 Organic silicon polymer/benzoxazine/epoxy resin packaging adhesive and preparation method thereof

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