CN106928410B - Organic silicon modified acrylic resin with high solid content and low viscosity, preparation method and application - Google Patents

Organic silicon modified acrylic resin with high solid content and low viscosity, preparation method and application Download PDF

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CN106928410B
CN106928410B CN201710167386.9A CN201710167386A CN106928410B CN 106928410 B CN106928410 B CN 106928410B CN 201710167386 A CN201710167386 A CN 201710167386A CN 106928410 B CN106928410 B CN 106928410B
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methacrylate
acrylate
acrylic resin
butyl
solid content
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CN106928410A (en
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张萌
夏天渊
许建华
印维坚
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Langfang Nippon Paint Co Ltd
NIPPON PAINT (GUANGZHOU) CO Ltd
Libang Coatings (china) Co Ltd
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Langfang Nippon Paint Co Ltd
NIPPON PAINT (GUANGZHOU) CO Ltd
Libang Coatings (china) Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C08F283/128—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to reaction products of polysiloxanes having at least one Si-H bond and compounds having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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    • 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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • 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
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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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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 an organic silicon modified acrylic resin with high solid content and low viscosity, which has a structure shown as a general formula I:
Figure DDA0001250203830000011
the definition of each substituent group in the formula is shown in the specification. The organic silicon modified acrylic resin with high solid content and low viscosity can endow varnish paint films with higher friction resistance and smoothness.

Description

Organic silicon modified acrylic resin with high solid content and low viscosity, preparation method and application
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to organic silicon modified acrylic resin with high solid content and low viscosity, a preparation method and application.
Background
As is well known, acrylic resins are widely used in large quantities for the preparation of various high-performance coatings due to their excellent aging resistance and excellent physical and mechanical properties; particularly in the field of automobile finishing, acrylic resins can undergo a crosslinking reaction with amino resins or polyfunctional isocyanates and are therefore used for the preparation of one-component solvent-based acrylic-amino system or two-component solvent-based acrylic-isocyanate system overprint varnishes which are applied over a topcoat to form an outermost protective decorative coating.
With the increasing awareness of people on environmental protection, in 2016, the government officially brings Volatile Organic Compounds (VOCs) into the regulatory scope, which puts more strict requirements on the coating industry. Reducing the content of VOCs in the coating system, i.e., reducing the amount of organic solvent used in the coating system, has a negative impact on the coating application, i.e., the application viscosity of the coating gradually increases with the decrease in the amount of solvent used, thereby affecting the application properties of the coating and the properties of the final coating film. How to improve the construction solid content of a coating system and maintain the basic performance of the original coating unchanged under the condition of ensuring that the construction viscosity of the coating system is not changed becomes a main problem which is urgently needed to be solved at present. Aiming at the current situation that the current paint application manufacturers take single-component varnish as the first choice, the use of the high-solid low-viscosity acrylic resin is the best scheme for solving the current problems.
US4687822 discloses a process for preparing acrylic resin with high solid content and low viscosity. According to the relevant expression in the examples, a series of acrylic resins with number average molecular weight between 1800 and 2800, solid content of 70% and 80%, respectively, and bubble viscosity between Y and Z5 were prepared by using 2, 4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and used to prepare high solid content coatings.
US4985517 discloses a method for preparing a high-solid acrylic resin-based coating. According to the relevant expression in the examples, the patent prepares a series of acrylic resins with number average molecular weight of 2000-3000, solid content of 65-70% and B type rotational viscosity of 0.7-13 Pa.s by using 1-decene as a polymerization monomer.
US6294607 discloses a process for the preparation of a coating based on an ultra-high solids acrylic resin. According to the relevant description mentioned in the patent, this patent uses allyl alcohol propionate and its related derivatives as specific polymerization monomers to prepare specific polyol-containing resins. After the resin is mixed with the traditional acrylic resin, the solid content of a resin system is provided, the viscosity of the system can be greatly reduced, and the solid content of the prepared coating can reach 65-70%.
Azuma et al (Progress in Organic Coatings,1997,32:1-7) copolymerize trimethylsiloxyethyl methacrylate as a monomer with other conventional acrylic monomers to prepare low polarity, low viscosity silane modified acrylic resins. The resin can be used for preparing high-solid content automobile coating.
Slinckx et al (Progress in Organic Coatings,2000,38: 163-. By mixing the reactive diluent with acrylic resin, the acrylic resin with solid content of 68% is prepared, and the acrylic resin can be used for preparing high-solid-content automobile paint.
Petit et al (Progress in Organic Coatings,2001,43:41-49) used glycidyl versatate (CARDURA E10) as a raw material to modify acrylic resin or acrylic monomers to prepare three different types of high-solid acrylic resins. The high-solid acrylic resin has the molecular weight of about 2500, the solid content of 66-70% and the B-type rotational viscosity of 2.5-3.6 Pa.s, and can be used for preparing room-temperature cured automobile repair varnish.
Daniel et al (European Coatings Journal,2004,11:22-32) have synthesized seven different high hydroxyl value acrylic polyol resins with number average molecular weight of 2200 to 2900, solid content of 70 to 100%, rotational viscosity of type B of 5.7 to 30 Pa.s, and glass transition temperature of-52 ℃ to 55 ℃.
The high-solid acrylic resin is prepared by adopting a composite initiator and mixed solvent system and adopting a starvation polymerization process by adopting the Juanjuan et al (university of Nanjing Richardson, 2007,31:129-133), wherein the solid content of the resin can reach 70%, and the viscosity of the resin is moderate.
In the above-disclosed technical documents, various methods for producing a high-solid acrylic resin are mentioned. By analyzing the above documents, only one document mentions the modification of acrylic acid with a small molecule silane monomer, and the rest does not refer to the modification of acrylic resin with a silicone macromer. With the continuous improvement of the requirements of coating manufacturers on the performance of coatings, the coating manufacturers want the varnish coating film to have higher friction resistance and smoothness, and the requirements can be hardly met by simply using the traditional acrylic resin.
In view of the above, there is a need for a silicone-modified acrylic resin with high solid content and low viscosity, which has high abrasion resistance and smoothness, to overcome the shortcomings of the prior art.
Disclosure of Invention
In order to meet the requirements of paint manufacturers on friction resistance and smoothness and make up for the defects of the traditional acrylic resin, the invention aims to provide the organosilicon modified acrylic resin with high friction resistance and smoothness and high solid content and low viscosity.
Another purpose of the invention is to provide a preparation method of the organosilicon modified acrylic resin with high solid content and low viscosity.
Still another object of the present invention is to provide a use of the silicone modified acrylic resin with high solid content and low viscosity.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
one aspect of the present invention provides a high solid content and low viscosity silicone modified acrylic resin, which has a structure shown in general formula I:
Figure BDA0001250203810000031
wherein:
in formula I:
R1selected from aliphatic, alicyclic and aromatic alkyl, alkoxy, acyloxy, hydroxyalkyl and hydroxyalkylene containing 1-20 carbon atoms;
R2、R3、R4、R5each independently selected from a hydrogen atom, an aliphatic, alicyclic or aromatic alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group and a hydroxyalkylene group;
R6is selected from one of the formulas II:
CH2CH2CH2OH CH2CH2CH2CH2OH CH2CH2CH2CH2CH2OH
CH2CH2CH2CH2CH2CH2OH CH2CH2CH2OCH2CH(OH)CH2OCH3
(II)；
R7is selected from one of the formulas III:
CH3CH2CH2CH2CH3CH(CH3)CH2(CH3)3C (CH3)3SiO
(III)；
m>0，n>0，o>0，p>0，q>0，x>0，y>0。
the alkyl group referred to in formula I includes a straight chain or branched chain alkyl group. Aliphatic, alicyclic and aromatic alkyl, alkoxy, acyloxy, hydroxyalkyl and hydroxyalkylene groups of the general formula I are exemplified below: alkyl is ethyl belonging to aliphatic alkyl; alkyl is phenyl belonging to the aromatic group; the alkyl group is a cyclohexane group belonging to alicyclic alkyl groups. Similarly, alkoxy is ethoxy belonging to aliphatic alkoxy; alkoxy is phenoxy belonging to the group of aromatic alkoxy; alkoxy is cyclohexyloxy belongs to cycloaliphatic alkoxy.
The hydroxyl value of the organic silicon modified acrylic resin is between 50 and 250 mgKOH/g; the acid value is between 0 and 20 mgKOH/g; a glass transition temperature (Tg) of between-30 ℃ and +50 ℃; the number average molecular weight is 500-20000, preferably 1500-5000; the solid content is between 70% and 100%, preferably between 75% and 90%; the B-type rotational viscosity is 0.5 to 200 pas (25 ℃), preferably 2 to 25 pas.
The high-solid-content low-viscosity organosilicon modified acrylic resin comprises the following components in parts by weight:
Figure BDA0001250203810000041
the solvent is selected from at least one of aliphatic ester, monohydric alcohol, ketone, dihydric alcohol ether, dihydric alcohol ester, and aromatic hydrocarbon solvent, including but not limited to the following compounds known to those skilled in the art: toluene, xylene, S-100# solvent oil, trimethylbenzene solvent oil, S-150# solvent oil, durene solvent oil, butanone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, ethylene glycol butyl ether acetate, amyl acetate, ethylene glycol ethyl ether propionate, ethylene glycol butyl ether, ethylene glycol, n-propanol, isopropanol, n-butanol and propylene glycol methyl ether acetate.
The monomer containing a carbon-carbon double bond and capable of undergoing copolymerization reaction includes, but is not limited to, at least one of the following compounds known to those skilled in the art: styrene, methyl propylene, allyl alcohol, ethylene versatate, monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, monoisopropyl maleate, mono-n-butyl maleate, mono-sec-butyl maleate, mono-tert-butyl maleate, monopentyl maleate, monohexyl maleate, monoethylhexyl maleate, bis-methyl maleate, bis-ethyl maleate, bis-n-propyl maleate, bis-isopropyl maleate, bis-n-butyl maleate, bis-sec-butyl maleate, bis-tert-butyl maleate, bis-pentyl maleate, bis-hexyl maleate, bis-ethylhexyl maleate.
The derivative of the acrylate and/or methacrylate monomer is selected from at least one of alkyl acrylate, alkyl methacrylate, cycloalkyl acrylate, cycloalkyl methacrylate, including but not limited to at least one of the following compounds known to those skilled in the art: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, 3, 5-trimethylhexyl acrylate, 3, 5-trimethylhexyl methacrylate, octadecyl acrylate, octadecyl methacrylate, dodecyl acrylate, dodecyl methacrylate, cyclopentyl acrylate, cyclopentyl methacrylate, isobornyl acrylate, isobornyl methacrylate, isopropyl methacrylate, isobutyl acrylate, Cyclohexyl acrylate, cyclohexyl methacrylate, glycidyl acrylate and glycidyl methacrylate.
The derivative of the acrylate and/or methacrylate monomer containing hydroxyl group is selected from at least one of hydroxyalkyl acrylate and hydroxyalkyl methacrylate, including but not limited to at least one of the following compounds known to those skilled in the art: 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, condensation products of acrylic acid with glycidyl versatate and condensation products of methacrylic acid with glycidyl versatate.
The derivative of acrylic acid and/or methacrylic acid containing carboxyl is selected from acrylic acid and/or methacrylic acid.
The initiator is selected from at least one of azo-type initiators or peroxy-type initiators, including but not limited to at least one of the following compounds known to those skilled in the art: azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, 1-bis (tert-amylperoxy) cyclane, 1-bis (tert-amylperoxy) -3,3, 5-trimethylcyclohexane, tert-butyl peroxybenzoate, tert-amyl peroxyacetate, 3, 5-trimethylhexanoate, ethyl 3, 3-bis (tert-butylperoxy) butyrate, ethyl 3, 3-bis (tert-amylperoxy) butyrate, dicumyl peroxide, tert-amyl hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, di-tert-amyl peroxide.
The preparation method of the organic silicon macromonomer comprises the following steps:
1) adding hexamethyldisilazane dropwise into unsaturated monohydric alcohol A, heating the system to 90-120 ℃, continuing to react for 4-8 hours (h) at the temperature, and obtaining a trimethylsiloxy unsaturated compound B through hydroxyl protection;
2) adding a catalyst into the trimethylsiloxy unsaturated compound B, and protecting the catalyst by using nitrogen, wherein the reaction temperature is as follows: at the temperature of 80-110 ℃, the reaction time is as follows: 4-12h, and then dropwise adding trimethylcyclotrisiloxane
Figure BDA0001250203810000051
Obtaining trimethylsiloxy alkyl modified cyclotrisiloxane after complete reaction
Figure BDA0001250203810000052
3) Modifying cyclotrisiloxane with trimethylsiloxy alkyl group
Figure BDA0001250203810000061
Hexamethylcyclotrisiloxane D3By non-polarityDissolving an organic solvent and a polar solvent, adding an alkyl lithium initiator, protecting by using argon in the reaction process, and reacting at the temperature: -70 ℃ to 50 ℃, reaction time: adding dimethyl hydrogen chlorosilane for end capping to obtain an organosilicon macromolecule E with a side chain having a hydroxyl protecting group and a single end having a hydrosilation group after 4-12 h;
4) mixing organosilicon macromolecules E with a hydroxyl protecting group on a side chain and a hydrosilyl group at a single end, a polymerization inhibitor and a catalyst, dripping allyl methacrylate, and protecting by nitrogen in the reaction process, wherein the reaction temperature is as follows: at the temperature of 80-110 ℃, the reaction time is as follows: obtaining an organic silicon macromonomer F with a side chain having a hydroxyl protecting group and a single end having a methacrylic group for 4-12 h;
5) adding an organic silicon macromonomer F with a side chain having a hydroxyl protecting group and a methacrylic group at a single end into an alcohol solvent, and reacting by taking weak acid as a catalyst at the reaction temperature of: 65-100 ℃, and the reaction time is as follows: and (4) distilling under reduced pressure for 4-12h to remove alcohol compounds and low-boiling-point substances to obtain the organosilicon macromonomer G with a side chain having a hydroxyl alkyl group and a single end having a methacrylic acid group, namely the organosilicon macromonomer.
The molar ratio of the unsaturated monohydric alcohol A to the hexamethyldisilazane is 2 (1-2), preferably 2 (1-1.1).
The unsaturated monohydric alcohol A is selected from one of the following structures:
A1)CH2＝CHCH2OH A2)CH2＝CHCH2CH2OH A3)CH2＝CHCH2CH2CH2OH
A4)CH2＝CHCH2CH2CH2CH2OH A5)CH2＝CHCH2OCH2CH(OH)CH2OCH3。
the trimethylsiloxy unsaturated compound B is selected from one of the following structures:
B1)CH2＝CHCH2OSi(CH3)3B2)CH2＝CHCH2CH2OSi(CH3)3B3)CH2＝CHCH2CH2CH2OSi(CH3)3
B4)CH2＝CHCH2CH2CH2CH2OSi(CH3)3B5)CH2＝CHCH2OCH2CH[OSi(CH3)3]CH2OCH3。
the catalyst is chloroplatinic acid.
The trimethyl siloxy unsaturated compound B and trimethyl cyclotrisiloxane
Figure BDA0001250203810000062
The molar ratio of (a) to (b) is 3:1 to 6:1, preferably 3:1 to 3.3: 1.
The mass of the catalyst accounts for 0.05-1% of that of the trimethylcyclotrisiloxane.
The trimethylsiloxy alkyl modified cyclotrisiloxane
Figure BDA0001250203810000063
The structure of (a) is as follows:
T1)CH2CH2CH2OSi(CH3)3T2)CH2CH2CH2CH2OSi(CH3)3T3)CH2CH2CH2CH2CH2OSi(CH3)3
T4)CH2CH2CH2CH2CH2CH2OSi(CH3)3T5)CH2CH2CH2OCH2CH[OSi(CH3)3]CH2OCH3。
of the non-polar organic solvent and the polar solventThe mass ratio of the non-polar organic solvent to the polar solvent is 1: 1-1: 5, and the total mass of the non-polar organic solvent and the polar solvent is equal to that of the trimethylsiloxyalkyl modified cyclotrisiloxane
Figure BDA0001250203810000072
Hexamethylcyclotrisiloxane D3And the total mass ratio of the alkyl lithium is 1: 4-4: 1.
The molar ratio of the alkyl lithium initiator to the dimethyl hydrogen chlorosilane is 1: 1-1: 1.2; trimethylsiloxyalkyl-modified cyclotrisiloxanes in the preparation process
Figure BDA0001250203810000073
Hexamethylcyclotrisiloxane D3And alkyllithium the molar ratios of the 3 reactants fed depend on the molecular weight of the final product.
Referring to the molecular structure in example 1, the molecular weight design formula (taking n-butyllithium as an initiator and using 1mol as an example) is as follows:
designed molecular weight of silicone macromolecule E ═ molecular weight of n-butyl (57) + DT 3Molecular weight XDT 3Amount of (n ═ x/3) + D3Molecular weight of (2) XD3Amount of (m) ═ y/3) + (CH3)2The molecular weight of SiH (59), i.e., M57 +60y +190x + 59.
If the molecular weight is about 1000 and x and y in the above reaction formula are 1 and 12 respectively, n and m are about 1/3 and 4 respectively, namely 1mol of initiator and 1/3mol of D are needed for preparing organosilicon macromolecule E with molecular weight of about 1000T 3And 4mol of D3。
The designed molecular weight of the organosilicon macromolecule E with the side chain having a hydroxyl protecting group and the single end having a hydrosilation group is MLithium removal molecular weight of alkyllithium initiators+DT 3Molecular weight XDT 3Amount of substance (c) + D3Molecular weight of (2) XD3Amount of substance(s) + MDimethyl hydrogen chlorosilane。
The non-polar organic solvent is selected from at least one of aliphatic hydrocarbon solvent, alicyclic hydrocarbon solvent and aromatic hydrocarbon solvent, including but not limited to at least one of the following compounds known to those skilled in the art: isopentane, n-pentane, petroleum ether, n-hexane, cyclohexane, isooctane, cyclopentane, trimethylpentane, cyclopentane, heptane, toluene, benzene, xylene.
The alkyl lithium initiator is selected from at least one of n-butyl lithium, sec-butyl lithium, tert-butyl lithium and trimethylsiloxy lithium.
The polar solvent is selected from at least one of aliphatic ketones, alicyclic ketones, aromatic ketones, amides, sulfoxides, nitriles, heterocyclic solvents, including but not limited to at least one of the following compounds known to those skilled in the art: tetrahydrofuran, formamide, acetonitrile, N-dimethylformamide, hexamethylphosphoramide, butanone, dimethyl sulfoxide, acetone, 1, 4-dioxane and pyridine.
The dimethyl hydrochlorosilane is dimethyl monochlorosilane.
The number average molecular weight of the organosilicon macromolecule E with the side chain having a hydroxyl protecting group and the single end having a hydrosilation group is between 500 and 4500, and the organosilicon macromolecule E has the following structure:
Figure BDA0001250203810000081
wherein: y >0, x > 0.
The mass of the polymerization inhibitor accounts for 0.1-5% of the mass of the allyl methacrylate.
The mass of the catalyst accounts for 0.05-1% of that of the organic silicon macromolecule E with a hydroxyl protecting group at a side chain and a hydrosilyl group at a single end.
The molar ratio between the organosilicon macromolecule E with the hydroxyl protecting group on the side chain and the hydrosilyl group at a single end and allyl methacrylate is mainly referred to the molar ratio between an Si-H group in the organosilicon macromolecule E with the hydroxyl protecting group on the side chain and a C ═ C group in allyl methacrylate, namely the molar ratio between the allyl methacrylate and the hydrosilyl group (Si-H) contained in the organosilicon macromolecule E with the hydroxyl protecting group on the side chain and the hydrosilyl group at a single end is 1: 1-2: 1, preferably 1.01: 1-1.05: 1.
The polymerization inhibitor is selected from phenolic and quinone polymerization inhibitors, including but not limited to at least one of the following compounds known to those skilled in the art: hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tertiary butyl hydroquinone and 2, 5-di-tertiary butyl hydroquinone.
The catalyst is selected from chloroplatinic acid.
The organic silicon macromonomer F with a side chain provided with a hydroxyl protecting group and a methacrylic acid group at a single end has the following structure:
Figure BDA0001250203810000091
wherein y >0 and x > 0.
The mass ratio of the organic silicon macromonomer F with the side chain provided with the hydroxyl protecting group and the single end provided with the methacrylic group to the alcohol solvent is 1: 1-1: 4.
The mass of the weak acid accounts for 0.5-5% of that of the organosilicon macromonomer F with a hydroxyl protecting group on a side chain and a methacrylic acid group on a single end.
The alcohol solvent is at least one selected from methanol, ethanol, n-propanol and isopropanol.
The weak acid is at least one selected from formic acid, acetic acid, propionic acid, lactic acid, dimethylolpropionic acid and dimethylolbutyric acid.
Another aspect of the present invention provides a preparation method of the silicone modified acrylic resin with high solid content and low viscosity, including the following steps:
mixing 25-200 parts of a monomer which contains carbon-carbon double bonds and can be subjected to copolymerization reaction, 200-500 parts of a derivative of an acrylate and/or methacrylate monomer, 150-250 parts of a derivative of a hydroxyl-containing acrylate and/or methacrylate monomer, 1-20 parts of a derivative of carboxyl-containing acrylic acid and/or methacrylic acid, 25-100 parts of an organosilicon macromonomer and 14-70 parts of an initiator, adding the mixture into 100-200 parts of a solvent for reaction at the temperature of 80-200 ℃ for 4-20 hours, and obtaining the organosilicon modified acrylic resin with high solid content and low viscosity.
In a further aspect of the invention, the invention provides a use of the high-solid low-viscosity organosilicon modified acrylic resin for preparing a coating.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the main chain of the organic silicon in the organic silicon modified acrylic resin with high solid content and low viscosity is a Si-O-Si bond which is not easy to be decomposed by ultraviolet light and ozone, so that the organic silicon has better irradiation resistance and weather resistance than other high polymer materials, and therefore, the acrylic resin modified by the organic silicon can further improve the weather resistance of the resin and the color and gloss retention of a paint film.
The main chain of the organic silicon in the organic silicon modified acrylic resin with high solid content and low viscosity is very flexible, and the intermolecular action force is much weaker than that of a hydrocarbon compound, so that the organic silicon has the advantage of low viscosity compared with the hydrocarbon compound with the same molecular weight; when the organosilicon chain forging is introduced into acrylic resin molecules, the viscosity of the acrylic resin can be effectively reduced; on the other hand, the flexibility of the acrylic resin can also be adjusted, so that a paint film added with the organic silicon modified acrylic resin has good impact resistance.
The organic silicon modified acrylic resin with high solid content and low viscosity has weak organic silicon surface tension, small surface energy and strong film forming capability, and can endow a paint film with good scratch resistance and stain resistance and simultaneously ensure that the paint film has good smooth hand feeling after the organic silicon modified acrylic resin is added into the paint film.
The organic silicon modified acrylic resin with high solid content and low viscosity has lower surface tension, when the solid content of the organic silicon modified acrylic resin is more than 80%, a resin system can keep lower viscosity, and the resin can be used for preparing a varnish coating with high solid content, low construction viscosity and a solvent type, so that the VOC content of the varnish can be reduced; at the same time, the resin can help to reduce the surface tension of a coating film formed by the varnish coating, and endow the final coating film with excellent smoothness and dry friction resistance.
Drawings
FIG. 1 is an infrared spectrum of allyl alcohol in the present invention;
FIG. 2 is an infrared spectrum of allyloxytrimethylsilane of the present invention;
FIG. 3 is a NMR spectrum of allyloxytrimethylsilane of the present invention;
FIG. 4 is an infrared spectrum of an organosilicon macromolecule E having hydroxyl protecting groups on the side chains and hydrosilyl groups at the single ends according to the present invention;
FIG. 5 is an infrared spectrum of a silicone macromonomer F having a hydroxyl protecting group in the side chain and a methacrylic group at one end in the present invention; and
FIG. 6 is an infrared spectrum of a silicone macromonomer G having a hydroxyalkyl group in the side chain and a methacrylic group at the single terminal in the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
Various aspects of the present invention will be described in detail below, and various starting materials of the present invention are commercially available unless otherwise specified; or prepared according to conventional methods in the art. Unless defined or stated otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention.
The experimental procedures, in which specific conditions are not specified, in the following examples are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
Example 1
The formula of the preparation method of the organosilicon macromonomer G with the side chain containing hydroxyl alkyl and the single end containing methacrylic group is as follows:
Figure BDA0001250203810000111
hydroxyl protection: 338.1g (2.1mol) of hexamethyldisilazane were slowly added dropwise to 232g (4mol) of allyl alcohol in a 1L reactor at room temperature. After the dropwise addition, the reaction system was heated to 100 ℃ and continued to react at this temperature for 6 hours, and then the reaction was stopped. The 98-100 ℃ fraction was collected under normal pressure to obtain 473.2g of allyloxytrimethylsilane (91% yield).
As shown in FIGS. 1 to 3, FIG. 1 is an infrared spectrum of allyl alcohol, wherein: the ordinate transmittince means the Transmittance, the abscissa wavenumbers means the wavenumber, allyl alcohol is at 3332cm-1Has wide hydroxy stretching vibration absorption peaks, 3084, 1646, 993 and 919cm-1The absorption peak at is CH ═ CH2Characteristic absorption peaks of the bonds. FIG. 2 is an infrared spectrum of allyloxytrimethylsilane, wherein: the ordinate transmittince means the Transmittance and the abscissa wavenumbers means the wavenumber, since the hydroxyl group of allyl alcohol reacts with hexamethyldisilazane to form a siloxane bond, it is at 3332cm-1Has no hydroxyl absorption peak and is assigned to-CH ═ CH23083, 1646 and 993cm of key-1Peak sum ascribed to Si-CH31252, 841 and 755cm of key-1The absorption peak still exists, and the Si-O-C bond is increased to 1087cm-1The absorption peak at (c). FIG. 3 is a chart of NMR spectrum of allyloxytrimethylsilane, wherein 6 groups of peaks are shared, and the ratio of peak areas is 6: 9: 2: 1: 1:1. the methyl group where the No. 5 proton is located is connected with Si, and the peak at 0.13ppm can be judged to be the No. 5 proton according to the peak area; the methine group with the 4 th proton is connected with oxygen atom and double bond, so the chemical shift value is about 4.0ppm, the peak at 4.14ppm is the 4 th proton, and the peak area is in accordance with the number of protons in methine; 1.2, 3 protonsIs a proton on a double-bond carbon atom, and the chemical shift of the proton is between 5.0 and 6.0 ppm.
Primary hydrosilylation: in a 1L reactor, 393.9g (3.03mol) of allyloxytrimethylsilane and 0.5g of chloroplatinic acid catalyst (0.5/180 ═ 0.27%) were sequentially charged, and after introducing nitrogen gas for 20min, the reaction system was heated to 100 ℃ and 180g (1mol) of trimethylcyclotrisiloxane was added dropwise thereto and reacted for 8 hours, followed by termination of the reaction. The low boiling point substance was distilled off under reduced pressure to obtain 553g of trimethylsiloxyalkyl-modified cyclotrisiloxane in a yield of 97.0%.
Anionic polymerization: 1mol of n-butyllithium, 740g (3.333mol) of hexamethylcyclotrisiloxane, 190g (0.333mol) of trimethylsiloxyalkyl modified cyclotrisiloxane, 500g of n-hexane and tetrahydrofuran (mass ratio is 1:1) are sequentially added into a 2L reaction kettle after anhydrous and anaerobic treatment, stirred at 25 ℃ for 8 hours, and then added with 1.1mol of dimethylchlorosilane for terminating the reaction. And (3) filtering the reaction liquid to remove the generated lithium chloride, and distilling under reduced pressure to remove low-boiling-point substances to obtain 987g of organosilicon macromolecules with the number average molecular weight of about 1026, wherein the side chains of the organosilicon macromolecules have hydroxyl protecting groups and the single ends of the organosilicon macromolecules have hydrosilyl groups, and the yield is 96.2%.
As shown in fig. 4, fig. 4 is an infrared spectrum of the silicone macromolecule E with a hydroxyl protecting group on the side chain and a hydrosilyl group at the single end, in which: ordinate Transmitance refers to Transmittance, abscissa wavenumbers refers to wavenumber, (1) due to (CH)3)2Increase of SiO chain links, 800cm-1A C-H swing vibration absorption peak appears, which is one of the characteristic peaks of polydimethylsiloxane; (2)1027cm-1And 1092cm-1The dual-strong peak is the stretching vibration absorption peak of Si-O-Si, which is also a characteristic peak of polydimethylsiloxane; (3)1260cm-1The strong peak is a C-H symmetric deformation bending vibration absorption peak; (4)2905cm-1And 2962cm-1The peak appears as the C-H stretching vibration absorption peak; (5)2127cm-1The peak appeared here is the stretching vibration absorption peak of Si-H. Preliminarily proves that n-butyl lithium initiates hexamethylcyclotrisiloxane and trimethylsiloxy alkyl modified cyclotrisiloxane to polymerize through characteristic absorption peaks appearing in a spectrogramThe dimethylmonochlorosilane terminates the polymerization reaction and forms hydrosilyl groups.
Secondary hydrosilylation: 615.6g (0.6mol of Si-H group) of organosilicon macromolecule with a side chain provided with a hydroxyl protecting group and a hydrosilyl group at a single end, 0.38g of p-hydroxyanisole polymerization inhibitor and 1g of chloroplatinic acid catalyst are sequentially added into a 1L reaction kettle, after nitrogen is introduced for 20min, the reaction system is heated to 100 ℃, 74.4g (0.6mol of C ═ C double bond group) of allyl methacrylate is dropwise added at the temperature, and the reaction is terminated after 5H of reaction. The low-boiling residue was distilled off under reduced pressure to obtain 662g of an organosilicon macromonomer having a hydroxyl protecting group on the side chain and a methacrylic group at the single end, and the yield was 95.9%. In the above reaction, the molar ratio of allyl methacrylate to hydrosilyl group (Si-H) was 1:1.
As shown in FIG. 5, FIG. 5 is an infrared spectrum of a silicone macromonomer F having a hydroxyl protecting group at a side chain and a methacrylic group at a single terminal, wherein: the ordinate Transmittance refers to the Transmittance, and the abscissa wavenumbers refers to the wavenumber, as can be seen from FIG. 5, 2957cm-1Is an inverse symmetric stretching vibration absorption peak of methyl; 2899cm-1Is a symmetric stretching vibration absorption peak of methyl; 1252cm-1Is Si-CH3A stretching vibration absorption peak; 1097cm-1Is the stretching vibration absorption peak of Si-O-Si, and 2127cm-1The characteristic absorption peak of the silicon-hydrogen bond disappears, and 1725cm is simultaneously used-1And an absorption peak of a C ═ O bond appears, which shows that allyl methacrylate and organosilicon macromolecule E with a hydroxyl protecting group on a side chain and a hydrosilation group on a single end have a hydrosilation addition reaction.
Alcoholysis reaction: 345g of an organosilicon macromonomer with a side chain having a hydroxyl protecting group and a methacrylic acid group at a single end, 500g of methanol and 3g of acetic acid were sequentially added to a 1L reaction kettle. The reaction was stopped after 9h at 65 ℃ under reflux. Acetic acid, excessive methanol and low-boiling-point substances are removed by reduced pressure distillation, 320g of organosilicon macromonomer with side chain of hydroxyalkyl and single end of methacrylic group with number average molecular weight about 1078 is obtained, and the yield is 98.9%. As shown in FIG. 6, FIG. 6 shows a mono-or branched hydroxyalkyl groupThe infrared spectrum of the end-methacrylate group-bearing silicone macromonomer G is shown in the following: the ordinate Transmittance means the Transmittance and the abscissa wavenumbers means the wavenumber, as can be seen from FIG. 6, 3445cm after alcoholysis with methanol-1A stronger hydroxyl absorption peak appears, which indicates that under the reaction condition, the trimethyl silicon protecting group is removed to generate hydroxyl.
Example 2
Hydroxyl protection: 338.1g (2.1mol) of hexamethyldisilazane were slowly added dropwise to 288g (4mol) of 3-buten-1-ol in a 1L reactor at room temperature. After the dropwise addition, the reaction system was heated to 100 ℃ and continued to react at this temperature for 6 hours, and then the reaction was stopped. The 110 ℃ and 115 ℃ fractions were collected at atmospheric pressure to give 558g of vinylbutoxytrimethylsilane in a 96.9% yield.
Primary hydrosilylation: 436.3g (3.03mol) of vinylbutoxytrimethylsilane and 0.5g of chloroplatinic acid catalyst were sequentially added to a 1L reaction vessel, and after introducing nitrogen gas for 20min, the reaction system was heated to 100 ℃ and 180g (1mol) of trimethylcyclotrisiloxane was added dropwise thereto at this temperature to react for 8 hours, and the reaction was terminated. The low boiling point substance was distilled off under reduced pressure to obtain 601g of trimethylsiloxyalkyl-modified cyclotrisiloxane in a yield of 98.2%.
Anionic polymerization: 1mol of n-butyllithium, 518g (2.333mol) of hexamethylcyclotrisiloxane, 408g (0.666mol) of trimethylsiloxyalkyl modified cyclotrisiloxane, 500g of n-hexane and tetrahydrofuran (mass ratio is 1:1) are sequentially added into a 2L reaction kettle after anhydrous and anaerobic treatment, stirred at 25 ℃ for 8 hours and then added with 1.1mol of dimethylchlorosilane for terminating the reaction. The reaction solution was filtered to remove the generated lithium chloride, and after low boiling point substances were removed by distillation under reduced pressure, 975g of an organosilicon macromolecule having a hydroxyl protecting group at a side chain and a hydrosilyl group at a single end of 1022 number average molecular weight was obtained with a yield of 95.4%.
Secondary hydrosilylation: 600g (0.6mol of Si-H group) of organic silicon macromolecule with a hydroxyl protecting group on a side chain and a hydrosilyl group on a single end, 0.38g of p-benzoquinone polymerization inhibitor and 1g of chloroplatinic acid catalyst are sequentially added into a 1L reaction kettle, after nitrogen is introduced for 20min, the reaction system is heated to 100 ℃, 74.4g (0.6mol of C ═ C double bond group) of allyl methacrylate is dropwise added at the temperature, and the reaction is terminated after 5H of reaction. Vacuum distillation is carried out to remove low-boiling-point substances, 640g of organosilicon macromonomer with a side chain having a hydroxyl protecting group and a single end having a methacrylic acid group and a number average molecular weight of about 1146 is obtained, and the yield is 94.9%. The mol ratio of allyl methacrylate to the hydrosilyl group (Si-H) contained in the organosilicon macromolecule E with a hydroxyl protecting group at the side chain and a hydrosilyl group at the single end is 1:1.
Alcoholysis reaction: in a 2L reactor, 458.4g of an organosilicon macromonomer having a hydroxyl-protecting group in the side chain and a methacrylic group at the single terminal, 800g of methanol and 5g of acetic acid were sequentially added. The reaction was stopped after 9h at 65 ℃ under reflux. Acetic acid, excessive methanol and low-boiling-point substances are removed by reduced pressure distillation, 410g of organosilicon macromonomer with a side chain of hydroxyalkyl and a single end of methacrylic group with the number average molecular weight of about 1074 is obtained, and the yield is 95.3%.
Example 3
The allyl alcohol in the hydroxyl group protection reaction of example 1 was changed to 4-penten-1-ol, the amount of the substance of n-butyllithium in the anionic polymerization was changed from 1mol to 0.5mol, the amount of the substance of dimethylmonochlorosilane was changed from 1.1mol to 0.55mol, and other reaction conditions were as described in example 1, to obtain an organosilicon macromonomer having a molecular weight and structure different from those of example 1.
Example 4
By changing n-butyllithium to sec-butyllithium, the amount of the substance of sec-butyllithium from 1mol to 0.75mol, and the amount of the substance of dimethylmonochlorosilane from 1.1mol to 0.825mol in the anionic polymerization in example 2, and other reaction conditions as described in example 2, an organosilicon macromonomer having a molecular weight and structure different from those of example 2 was obtained.
Example 5
Firstly, 125g of a mixed solvent of xylene and propylene glycol monomethyl ether acetate (mass ratio of 1:1) is added into a 1L reaction kettle provided with a stirrer, a thermometer, a nitrogen guide pipe and a reflux condenser, and the temperature of a reaction system is raised to 130-140 ℃. After the reaction temperature is stable, dropwise adding a reaction mixture consisting of 50g of styrene, 225g of n-butyl acrylate, 175g of 2-hydroxyethyl methacrylate, 5g of acrylic acid, 45g of methyl methacrylate, 26.3g of the organosilicon macromonomer prepared in example 1 and 38g of tert-butyl peroxy-2-ethylhexanoate into a reaction kettle by a peristaltic pump, maintaining the reaction temperature at 130-140 ℃ in the dropwise adding process, and controlling the dropwise adding speed to ensure that the dropwise adding of the reaction mixture is completed within 2-4 h. After the dropwise addition, continuously preserving the heat for 2-4 h at 130-140 ℃, and terminating the reaction to obtain the high-solid-content low-viscosity organic silicon modified acrylic resin with the solid content of 80.8%, the hydroxyl value of 143mg KOH/g, the organic silicon content of 5%, the B-type rotational viscosity of 25Pa s and the number average molecular weight of 3000 or so, and the acid value of 7.4 KOH/g; the glass transition temperature (Tg) was-7.6 ℃.
Example 6
Firstly, 125g of a mixed solvent of butyl acetate, xylene and propylene glycol monomethyl ether acetate (mass ratio of 1:3:4) is added into a 1L reaction kettle provided with a stirrer, a thermometer, a nitrogen guide pipe and a reflux condenser, and the temperature of a reaction system is raised to 130-140 ℃. After the reaction temperature is stable, dropwise adding a reaction mixture consisting of 100g of styrene, 200g of n-butyl acrylate, 150g of 2-hydroxyethyl methacrylate, 8g of acrylic acid, 42g of ethylhexyl methacrylate, 55.5g of the organosilicon macromonomer prepared in example 2 and 48g of tert-butyl peroxy-2-ethylhexanoate into a reaction kettle by a peristaltic pump, maintaining the reaction temperature at 120-140 ℃ in the dropwise adding process, and controlling the dropwise adding speed to ensure that the dropwise adding of the reaction mixture is finished within 2-4 h. After the dropwise addition, continuously preserving the heat for 2-4 h at 120-140 ℃, and terminating the reaction to obtain the high-solid-content low-viscosity organic silicon modified acrylic resin with the solid content of 81.6%, the hydroxyl value of 116mg KOH/g, the organic silicon content of 10%, the B-type rotational viscosity of 7.4 Pa.s and the number average molecular weight of 2500 or so, and the acid value of 11.2mg KOH/g; the glass transition temperature (Tg) was-12 ℃.
Example 7
Firstly, 156g of a mixed solvent of butyl acetate and xylene (mass ratio of 7:2) is added into a 1L reaction kettle provided with a stirrer, a thermometer, a nitrogen guide pipe and a reflux condenser, and the temperature of a reaction system is raised to 130-140 ℃. After the reaction temperature is stable, a reaction mixture consisting of 80g of styrene, 220g of n-butyl acrylate, 180g of 2-hydroxyethyl methacrylate, 2g of acrylic acid, 18g of dodecyl methacrylate, 43.5g of the organosilicon macromonomer prepared in example 3 and 53.4g of tert-butyl peroxy-2-ethylhexanoate is dripped into a reaction kettle through a peristaltic pump, the reaction temperature is maintained between 120 and 130 ℃ during the dripping process, and the dripping speed is controlled to ensure that the reaction mixture is dripped within 2 to 4 hours. After the dropwise addition, continuously preserving the heat for 2-4 h at 120-130 ℃, and terminating the reaction to obtain the high-solid-content low-viscosity organic silicon modified acrylic resin with the solid content of 77.7%, the hydroxyl value of 143mg KOH/g, the organic silicon content of 8%, the B-type rotational viscosity of 8.7 Pa.s and the number average molecular weight of 2200 or so, and the acid value of 2.9mg KOH/g; the glass transition temperature (Tg) was-9.5 ℃.
Example 8
Firstly, 125g of a mixed solvent of xylene and propylene glycol monomethyl ether acetate (mass ratio of 1:1) is added into a 1L reaction kettle provided with a stirrer, a thermometer, a nitrogen guide pipe and a reflux condenser, and the temperature of a reaction system is raised to 130-140 ℃. After the reaction temperature is stable, a reaction mixture consisting of 53g of styrene, 220g of n-butyl acrylate, 175g of 2-hydroxyethyl methacrylate, 7g of acrylic acid, 45g of methyl methacrylate, 26.3g of the organosilicon macromonomer prepared in example 4 and 35g of tert-amyl peroxy-2-ethylhexanoate is dripped into a reaction kettle through a peristaltic pump, the reaction temperature is maintained between 130 and 140 ℃ during the dripping process, the dripping speed is controlled, and the reaction mixture is ensured to be dripped within 2 to 4 hours. After the dropwise addition is finished, continuously preserving the heat for 2-4 h at 130-140 ℃, and terminating the reaction to obtain the high-solid-content low-viscosity organic silicon modified acrylic resin with the solid content of 80.8%, the hydroxyl value of 143mg KOH/g, the organic silicon content of 5%, the B-type rotational viscosity of 27.4 Pa.s and the number average molecular weight of 3500, and the acid value of 10.4mg KOH/g; the glass transition temperature (Tg) was-7.1 ℃.
Example 9
Firstly, 125g of a mixed solvent of xylene and propylene glycol monomethyl ether acetate (mass ratio of 2:1) is added into a 1L reaction kettle provided with a stirrer, a thermometer, a nitrogen guide pipe and a reflux condenser, and the temperature of a reaction system is raised to 130-140 ℃. After the reaction temperature is stable, dropwise adding a reaction mixture consisting of 50g of styrene, 175g of n-butyl acrylate, 175g of 2-hydroxyethyl methacrylate, 5g of acrylic acid, 95g of methyl methacrylate, 88g of the organosilicon macromonomer prepared in example 1 and 61g of tert-amyl peroxybenzoate into a reaction kettle by a peristaltic pump, maintaining the reaction temperature between 130 and 140 ℃ in the dropwise adding process, and controlling the dropwise adding rate to ensure that the dropwise adding of the reaction mixture is completed within 2 to 4 hours. After the dropwise addition is finished, continuously preserving the heat for 2-4 h at 130-140 ℃, and terminating the reaction to obtain the high-solid-content low-viscosity organic silicon modified acrylic resin with the solid content of 82.5%, the hydroxyl value of 128mg KOH/g, the organic silicon content of 15%, the B-type rotational viscosity of 5.4 Pa.s and the number average molecular weight of 2000 or so, and the acid value of 6.6mg KOH/g; the glass transition temperature (Tg) was-16.2 ℃.
Example 10
Firstly, 100g of a mixed solvent of butyl acetate and S-100# solvent oil (the mass ratio is 1:4) is added into a 1L reaction kettle provided with a stirrer, a thermometer, a nitrogen guide pipe and a reflux condenser, and the temperature of a reaction system is raised to 130-140 ℃. After the reaction temperature is stable, dropwise adding a reaction mixture consisting of 30g of styrene, 70g of n-butyl acrylate, 70g of tert-butyl methacrylate, 50g of vinyl versatate, 100g of 2-hydroxypropyl methacrylate, 6g of acrylic acid, 74g of isobornyl methacrylate, 20g of the organosilicon macromonomer prepared in example 1 and 14g of di-tert-butyl peroxide into a reaction kettle by a peristaltic pump, maintaining the reaction temperature at 130-140 ℃ in the dropwise adding process, controlling the dropwise adding rate, and ensuring that the dropwise adding of the reaction mixture is completed within 2-4 h. After the dropwise addition, continuously keeping the temperature at 130-140 ℃ for 2-4 h, and terminating the reaction to obtain the high-solid-content low-viscosity organic silicon modified acrylic resin with the solid content of 80.8%, the hydroxyl value of 92mg KOH/g, the organic silicon content of 4.7%, the B-type rotational viscosity of 7.7 Pa.s and the number average molecular weight of about 2200, the acid value of 11mg KOH/g and the Tg of-3.1 ℃.
Example 11
Firstly, 200g of a mixed solvent of butyl acetate, xylene and amyl acetate (mass ratio of 1:4:5) is added into a 1L reaction kettle provided with a stirrer, a thermometer, a nitrogen guide pipe and a reflux condenser, and the temperature of a reaction system is raised to 130-140 ℃. After the reaction temperature is stable, a reaction mixture consisting of 100g of styrene, 150g of n-butyl acrylate, 100g of ethylhexyl methacrylate, 100g of 2-hydroxyethyl methacrylate, 75g of 2-hydroxypropyl methacrylate, 10g of acrylic acid, 10g of methacrylic acid, 100g of dodecyl acrylate, 55g of isobornyl methacrylate, 100g of di-n-butyl maleate, 50g of the organosilicon macromonomer prepared in example 2 and 33g of di-tert-butyl peroxide is dripped into a reaction kettle through a peristaltic pump, the reaction temperature is maintained between 130 and 140 ℃ in the dripping process, the dripping rate is controlled, and the reaction mixture is ensured to be dripped within 2 to 4 hours. After the dropwise addition, continuously keeping the temperature at 130-140 ℃ for 2-4 h, and terminating the reaction to obtain the high-solid-content low-viscosity organosilicon modified acrylic resin with the solid content of 80.9%, the hydroxyl value of 88mg KOH/g, the organosilicon content of 2.4%, the B-type rotational viscosity of 3.3 Pa.s and the number average molecular weight of 1800, the acid value of 17.5mg KOH/g and the Tg of-2.7 ℃.
The silicone modified acrylic resin with high solid content and low viscosity prepared in the above examples can be used in coating and preparation thereof.
The main chain of the organic silicon in the organic silicon modified acrylic resin with high solid content and low viscosity is a Si-O-Si bond which is not easy to be decomposed by ultraviolet light and ozone, so that the organic silicon has better irradiation resistance and weather resistance than other high polymer materials, and therefore, the acrylic resin modified by the organic silicon can further improve the weather resistance of the resin and the color and gloss retention of a paint film.
The main chain of the organic silicon in the organic silicon modified acrylic resin with high solid content and low viscosity is very flexible, and the intermolecular action force is much weaker than that of a hydrocarbon compound, so that the organic silicon has the advantage of low viscosity compared with the hydrocarbon compound with the same molecular weight; when the organosilicon chain forging is introduced into acrylic resin molecules, the viscosity of the acrylic resin can be effectively reduced; on the other hand, the flexibility of the acrylic resin can also be adjusted, so that a paint film added with the organic silicon modified acrylic resin has good impact resistance.
The organic silicon modified acrylic resin with high solid content and low viscosity has weak organic silicon surface tension, small surface energy and strong film forming capability, and can endow a paint film with good scratch resistance and stain resistance and simultaneously ensure that the paint film has good smooth hand feeling after the organic silicon modified acrylic resin is added into the paint film.
The organic silicon modified acrylic resin with high solid content and low viscosity has lower surface tension, when the solid content of the organic silicon modified acrylic resin is more than 80%, a resin system can keep lower viscosity, and the resin can be used for preparing a varnish coating with high solid content, low construction viscosity and a solvent type, so that the VOC content of the varnish can be reduced; at the same time, the resin can help to reduce the surface tension of a coating film formed by the varnish coating, and endow the final coating film with excellent smoothness and dry friction resistance.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the invention and are not to be construed as limiting the embodiments of the present invention, and that various other changes and modifications may be made by those skilled in the art based on the above description. All documents mentioned in this application are incorporated by reference into this application as if each were individually incorporated by reference.

Claims (19)

1. An organosilicon modified acrylic resin with high solid content and low viscosity is characterized in that: the structure is shown in general formula I:
Figure FDA0002213803310000011
wherein:
in formula I:
R1selected from aliphatic, alicyclic and aromatic alkyl, alkoxy and acyloxy groups containing 1-20 carbon atomsA hydroxyalkyl group;
R2、R3、R4、R5each independently selected from hydrogen atoms, aliphatic, alicyclic and aromatic alkyl groups containing 1 to 20 carbon atoms and hydroxyalkyl groups;
R6is selected from one of the formulas II:
-CH2CH2CH2OH -CH2CH2CH2CH2OH -CH2CH2CH2CH2CH2OH
-CH2CH2CH2CH2CH2CH2OH -CH2CH2CH2OCH2CH(OH)CH2OCH3
(II)；
the structure of R7 is selected from one of the formulas III:
CH3CH2CH2CH2- CH3CH(CH3)CH2- (CH3)3C- (CH3)3SiO-
(III)；
m>0，n>0，o>0，p>0，q>0，x>0，y>0；
the organic silicon modified acrylic resin comprises the following components in parts by weight:
Figure FDA0002213803310000012
Figure FDA0002213803310000021
the preparation method of the organic silicon macromonomer comprises the following steps:
1) adding hexamethyldisilazane dropwise into unsaturated monohydric alcohol A, heating the system to 90-120 ℃, continuing to react for 4-8 hours (h) at the temperature, and obtaining a trimethylsiloxy unsaturated compound B through hydroxyl protection;
2) mesityloxyAdding a catalyst into the unsaturated compound B, and protecting by using nitrogen, wherein the reaction temperature is as follows: at the temperature of 80-110 ℃, the reaction time is as follows: 4-12h, and then dropwise adding trimethylcyclotrisiloxane
Figure FDA0002213803310000022
Obtaining trimethylsiloxy alkyl modified cyclotrisiloxane after complete reaction
Figure FDA0002213803310000023
3) Modifying cyclotrisiloxane with trimethylsiloxy alkyl group
Figure FDA0002213803310000024
Hexamethylcyclotrisiloxane D3Dissolving by using a non-polar organic solvent and a polar solvent, adding an alkyl lithium initiator, protecting by using argon in the reaction process, and reacting at the temperature: -70 ℃ to 50 ℃, reaction time: adding dimethyl hydrogen chlorosilane for end capping to obtain an organosilicon macromolecule E with a side chain having a hydroxyl protecting group and a single end having a hydrosilation group after 4-12 h;
4) mixing organosilicon macromolecules E with a hydroxyl protecting group on a side chain and a hydrosilyl group at a single end, a polymerization inhibitor and a catalyst, dripping allyl methacrylate, and protecting by nitrogen in the reaction process, wherein the reaction temperature is as follows: at the temperature of 80-110 ℃, the reaction time is as follows: obtaining an organic silicon macromonomer F with a side chain having a hydroxyl protecting group and a single end having a methacrylic group for 4-12 h;
5) adding an organic silicon macromonomer F with a side chain having a hydroxyl protecting group and a methacrylic group at a single end into an alcohol solvent, and reacting by taking weak acid as a catalyst at the reaction temperature of: 65-100 ℃, and the reaction time is as follows: and (4) distilling under reduced pressure for 4-12h to remove alcohol compounds and low-boiling-point substances, thereby obtaining the organic silicon macromonomer G with the side chain having the hydroxyl alkyl group and the single end having the methacrylic acid group.
2. The silicone-modified acrylic resin with high solid content and low viscosity according to claim 1, wherein: the hydroxyl value of the organic silicon modified acrylic resin is between 50 and 250 mgKOH/g; the acid value is between 0 and 20mg KOH/g; a glass transition temperature (Tg) of between-30 ℃ and +50 ℃; the number average molecular weight is 500-20000; the solid content is between 70 and 100 percent; the B-type rotational viscosity is between 0.5 and 200 pas.
3. The silicone-modified acrylic resin with high solid content and low viscosity according to claim 1, wherein: the solvent is selected from at least one of aliphatic ester, monohydric alcohol, ketone, dihydric alcohol ether, dihydric alcohol ester and aromatic hydrocarbon solvent;
the derivative of the acrylate and/or methacrylate monomer is selected from at least one of alkyl acrylate, alkyl methacrylate, cycloalkyl acrylate and cycloalkyl methacrylate;
the derivative of the acrylate and/or methacrylate monomer containing hydroxyl is selected from at least one of hydroxyalkyl acrylate and hydroxyalkyl methacrylate;
the initiator is selected from at least one of azo initiators or peroxy initiators.
4. The silicone-modified acrylic resin with high solid content and low viscosity according to claim 1, wherein: such solvents include, but are not limited to, the following compounds: at least one of toluene, xylene, S-100# solvent oil, trimethylbenzene solvent oil, S-150# solvent oil, durene solvent oil, butanone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, ethylene glycol butyl ether acetate, amyl acetate, ethylene glycol ethyl ether propionate, ethylene glycol butyl ether, ethylene glycol, n-propanol, isopropanol, n-butanol and propylene glycol methyl ether acetate;
the monomer containing a carbon-carbon double bond and capable of undergoing copolymerization reaction includes, but is not limited to, the following compounds: styrene, methyl propylene, allyl alcohol, ethylene versatate, monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, monoisopropyl maleate, mono-n-butyl maleate, mono-sec-butyl maleate, mono-tert-butyl maleate, monopentyl maleate, monohexyl maleate, monoethylhexyl maleate, bis-methyl maleate, bis-ethyl maleate, bis-n-propyl maleate, bis-isopropyl maleate, bis-n-butyl maleate, bis-sec-butyl maleate, bis-tert-butyl maleate, bis-pentyl maleate, bis-hexyl maleate, bis-ethylhexyl maleate.
5. The silicone-modified acrylic resin with high solid content and low viscosity according to claim 1, wherein: the derivative of the acrylate and/or methacrylate monomer is methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, 3, 5-trimethylhexyl acrylate, 3, 5-trimethylhexyl methacrylate, octadecyl acrylate, octadecyl methacrylate, dodecyl acrylate, dodecyl methacrylate, cyclopentyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, at least one of cyclopentyl methacrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glycidyl acrylate and glycidyl methacrylate.
6. The silicone-modified acrylic resin with high solid content and low viscosity according to claim 1, wherein: the derivative of the acrylic ester and/or methacrylic ester monomer containing hydroxyl is at least one of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, a condensation product of acrylic acid and glycidyl versatate, and a condensation product of methacrylic acid and glycidyl versatate.
7. The silicone-modified acrylic resin with high solid content and low viscosity according to claim 1, wherein: the derivative of acrylic acid and/or methacrylic acid containing carboxyl is selected from acrylic acid and/or methacrylic acid;
the initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, 1-bis (tert-amylperoxy) cyclane, 1-bis (tert-amylperoxy) -3,3, 5-trimethylcyclohexane, tert-butyl peroxybenzoate, tert-amyl peroxyacetate, tert-butyl peroxy-3, 5-trimethylhexanoate, ethyl 3, 3-bis (tert-butylperoxy) butyrate, ethyl 3, 3-bis (tert-amylperoxy) butyrate, dicumyl peroxide, tert-amyl hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide and di-tert-amyl peroxide.
8. The silicone-modified acrylic resin with high solid content and low viscosity according to claim 1, wherein: the molar ratio of the unsaturated monohydric alcohol A to the hexamethyldisilazane is 2 (1-2);
the unsaturated monohydric alcohol A is selected from one of the following structures:
A1)CH2＝CHCH2OH A2)CH2＝CHCH2CH2OH A3)CH2＝CHCH2CH2CH2OH
A4)CH2＝CHCH2CH2CH2CH2OH A5)CH2＝CHCH2OCH2CH(OH)CH2OCH3。
9. the silicone-modified acrylic resin with high solid content and low viscosity according to claim 1, wherein: the catalyst is chloroplatinic acid;
the trimethyl siloxy unsaturated compound B and trimethyl cyclotrisiloxane
Figure FDA0002213803310000041
The molar ratio of (a) to (b) is 3: 1-6: 1;
the mass of the catalyst accounts for 0.05-1% of that of the trimethylcyclotrisiloxane.
10. The silicone-modified acrylic resin with high solid content and low viscosity according to claim 1, wherein: the mass ratio of the nonpolar organic solvent to the polar solvent is 1: 1-1: 5, and the total mass of the nonpolar organic solvent and the polar solvent is equal to that of the trimethylsiloxy alkyl modified cyclotrisiloxane
Figure FDA0002213803310000042
Hexamethylcyclotrisiloxane D3The total mass ratio of the alkyl lithium is 1: 4-4: 1;
the molar ratio of the alkyl lithium initiator to the dimethyl hydrochlorosilane is 1: 1-1: 1.2.
11. The silicone-modified acrylic resin with high solid content and low viscosity according to claim 1, wherein: the nonpolar organic solvent is selected from at least one of aliphatic hydrocarbon solvent, alicyclic hydrocarbon solvent and aromatic hydrocarbon solvent;
the polar solvent is at least one selected from aliphatic ketones, alicyclic ketones, aromatic ketones, amides, sulfoxides, nitriles and heterocyclic solvents.
12. The silicone-modified acrylic resin with high solid content and low viscosity according to claim 1, wherein: the non-polar organic solvent includes, but is not limited to, the following compounds: at least one of isopentane, n-pentane, petroleum ether, n-hexane, cyclohexane, isooctane, cyclopentane, trimethylpentane, cyclopentane, heptane, toluene, benzene and xylene;
the alkyl lithium initiator is selected from at least one of n-butyl lithium, sec-butyl lithium, tert-butyl lithium and trimethylsiloxy lithium;
the polar solvents include, but are not limited to, the following compounds: at least one of tetrahydrofuran, formamide, acetonitrile, N-dimethylformamide, hexamethylphosphoramide, butanone, dimethyl sulfoxide, acetone, 1, 4-dioxane and pyridine.
13. The silicone-modified acrylic resin with high solid content and low viscosity according to claim 1, wherein: the mass of the polymerization inhibitor accounts for 0.1-5% of that of the allyl methacrylate;
the mass of the catalyst accounts for 0.05-1% of that of the organic silicon macromolecule E with a hydroxyl protecting group at a side chain and a hydrosilyl group at a single end;
the mol ratio of allyl methacrylate to the hydrosilyl group contained in the organosilicon macromolecule E with a hydroxyl protecting group on the side chain and a hydrosilyl group at the single end is 1: 1-2: 1.
14. The silicone-modified acrylic resin with high solid content and low viscosity according to claim 1, wherein: the polymerization inhibitor is selected from phenolic polymerization inhibitors and quinone polymerization inhibitors;
the catalyst is selected from chloroplatinic acid.
15. The silicone-modified acrylic resin with high solid content and low viscosity according to claim 14, wherein: the polymerization inhibitor is at least one of hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tertiary butyl hydroquinone and 2, 5-di-tertiary butyl hydroquinone.
16. The silicone-modified acrylic resin with high solid content and low viscosity according to claim 1, wherein: the mass ratio of the organic silicon macromonomer F with the side chain provided with the hydroxyl protecting group and the single end provided with the methacrylic group to the alcohol solvent is 1: 1-1: 4;
the mass of the weak acid accounts for 0.5-5% of that of the organosilicon macromonomer F with a hydroxyl protecting group on a side chain and a methacrylic acid group on a single end.
17. The silicone-modified acrylic resin with high solid content and low viscosity according to claim 1, wherein: the alcohol solvent is selected from at least one of methanol, ethanol, n-propanol and isopropanol;
the weak acid is at least one selected from formic acid, acetic acid, propionic acid, lactic acid, dimethylolpropionic acid and dimethylolbutyric acid.
18. A method for preparing the silicone modified acrylic resin with high solid content and low viscosity as claimed in any one of claims 1 to 17, wherein: the method comprises the following steps:
mixing 25-200 parts of a monomer which contains carbon-carbon double bonds and can be subjected to copolymerization reaction, 200-500 parts of a derivative of an acrylate and/or methacrylate monomer, 150-250 parts of a derivative of a hydroxyl-containing acrylate and/or methacrylate monomer, 1-20 parts of a derivative of carboxyl-containing acrylic acid and/or methacrylic acid, 25-100 parts of an organosilicon macromonomer and 14-70 parts of an initiator, adding the mixture into 100-200 parts of a solvent for reaction at the temperature of 80-200 ℃ for 4-20 hours, and obtaining the organosilicon modified acrylic resin.
19. Use of the silicone-modified acrylic resin with high solids and low viscosity as defined in any one of claims 1 to 17 for the preparation of a coating.
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