CN106928410A - A kind of organosilicon modified crylic acid resin of high-solid lower-viscosity, Preparation method and use - Google Patents
A kind of organosilicon modified crylic acid resin of high-solid lower-viscosity, Preparation method and use Download PDFInfo
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- CN106928410A CN106928410A CN201710167386.9A CN201710167386A CN106928410A CN 106928410 A CN106928410 A CN 106928410A CN 201710167386 A CN201710167386 A CN 201710167386A CN 106928410 A CN106928410 A CN 106928410A
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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
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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
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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
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- 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
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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 kind of organosilicon modified crylic acid resin of high-solid lower-viscosity, structure is as shown in formula I:Each substituted radical is defined in the specification in formula.The organosilicon modified crylic acid resin of high-solid lower-viscosity of the invention can assign varnish paint film compared with high friction resistance and slipping.
Description
Technical field
The invention belongs to technical field of polymer materials, more particularly to a kind of high-solid lower-viscosity organosilicon-modified acrylic tree
Fat, Preparation method and use.
Background technology
It is well known that because acrylic resin has excellent resistance to ag(e)ing and outstanding Physical Mechanical therefore big
Amount ground, it is widely used in and prepares various high-performance coatings;Field especially is covered with paint, lacquer, colour wash, etc. in automobile, acrylic resin can be with amino
Resin or polyfunctional isocyanate crosslink reaction, therefore be used to preparation and be applied on finish paint form most external protection decoration
One-component solvent borne acrylic acid-amino the system or double-component solvent-type acrylic-isocyanate systems coating varnish of coating.
As people gradually step up to environmental protection consciousness, Chinese Government is formal by VOC within 2016
(VOCs) supervision scope is included, this proposes more strict requirements to coating industry.The VOCs contents in coating system are reduced,
That is, reduction coating system uses the amount of organic solvent, but can be negatively affected to coating application, i.e., as solvent makes
The reduction of consumption, the working viscosity of coating gradually increases, so as to influence the application property of coating and the performance of final film.How
In the case of ensureing that coating system working viscosity is constant, the construction for improving coating system contains admittedly, and maintains original coating basic
Performance is constant, as the subject matter for being badly in need of solving at present.With one-component varnish it is first-selected for current coating application producer
Present situation, is a kind of preferred plan for solving existing issue using high-solid lower-viscosity acrylic resin.
United States Patent (USP) US4687822 discloses a kind of preparation method of high-solid lower-viscosity acrylic resin.According in embodiment
Correlation statement, the patent, as chain-transferring agent, is prepared for a series of numbers equal by using 2,4- diphenyl -4-methyl-1-pentene
Between 1800~2800, solid content is respectively 70% and 80%, acrylic acid tree of the bubble viscosity between Y~Z5 to molecular weight
Fat, and above-mentioned resin is used to prepare high-solid-content paint.
United States Patent (USP) US4985517 discloses a kind of preparation method based on the solid acrylic resin paint of height.According to implementation
Related statement in example, the patent by using 1- decene as polymerized monomer, be prepared for a series of number-average molecular weights 2000~
Between 3000, solid content between 65%~70%, acrylic resin of the Type B rotary viscosity between 0.7~13Pas.
United States Patent (USP) US6294607 discloses a kind of preparation method based on ultra high solids part acrylic resin paint.Root
The associated description referred to according to patent, the patent is particular polymeric monomer using allyl alcohol propionic ester and its related derivatives, is prepared
It is special containing polyol resin.After the resin mixes with traditional acrylic resin, while offer resin system contains admittedly, energy
System viscosity is enough substantially reduced, the coating of preparation is admittedly containing up to 65%~70%.
Azuma et al. (Progress in Organic Coatings, 1997,32:1-7) use trimethylsiloxy group ethyl
Methacrylate is monomer, and low polarity, low viscous silane-modified acrylic acid are prepared with other Conventional acrylic monomer copolymerizations
Resin.The resin can be used to prepare the automobile coating of large arch dam.
Slinckx et al. (Progress in Organic Coatings, 2000,38:163-173) shunk with versatic acid
Glyceride (CARDURA E10) is raw material, and three kinds of response type diluents are prepared for by with polyol reaction.Reacted by by this
Type diluent is mixed with acrylic resin, is prepared for the acrylic resin that solid content is up to 68%, and it can be used to prepare height
Admittedly contain car paint.
Petit et al. (Progress in Organic Coatings, 2001,43:41-49) use tertiary carbonic acid glycidyl
Ester (CARDURA E10) is raw material, and acrylic resin or acrylic monomers are modified, and prepares three sections of different large arch dams third
Olefin(e) acid resin.2500 or so, between 66%~70%, Type B revolves solid content the molecular weight of the large arch dam acrylic resin
Turn viscosity between 2.5~3.6Pas, can be used to prepare the car repair varnish of cold curing.
Daniel et al. (European Coatings Journal, 2004,11:22-32) with allyl alcohol homologue with
Acrylic monomers is polymerized, and has synthesized seven kinds of different high hydroxyl value acrylic polyol resins, and their number-average molecular weight is situated between
Between 2200~2900, solid content between 70%~100%, Type B rotary viscosity between 5.7~30Pas, glass
Glass conversion temperature is between -52 DEG C to 55 DEG C.
Sun Zhi beautiful et al. (Institutes Of Technology Of Nanjing's journal, 2007,31:129-133) use composite initiator and mixed solvent
System, large arch dam acrylic resin is prepared for by " starvation method " polymerization technique, and the solid content of the resin is up to 70%, and viscosity
It is moderate.
In technical literature disclosed above, various methods for preparing large arch dam acrylic resin are referred to.By to upper
State document to be analyzed, only one document refers to and being modified acrylic acid using small molecule silane monomer that remaining is not related to
And acrylic resin is modified to silicone macromolecule monomer.As coating is required not coating property using manufacturer
Disconnected to improve, coating wishes that varnish film can have rub resistance and slipping higher using manufacturer, and traditional third is used merely
Olefin(e) acid resin is difficult that such requirement can be met.
In view of this, it is badly in need of a kind of organosilicon-modified acrylic with compared with high friction resistance and the high-solid lower-viscosity of slipping
Resin is making up the deficiencies in the prior art.
The content of the invention
Requirement of the manufacturer to rub resistance and slipping is used in order to meet coating, conventional acrylic resin presence is made up
Defect, it is an object of the invention to provide a kind of organic-silicon-modified propylene of the high-solid lower-viscosity with compared with high friction resistance and slipping
Acid resin.
It is a further object to provide a kind of preparation of the organosilicon modified crylic acid resin of the high-solid lower-viscosity
Method.
It is also another object of the present invention to provide a kind of purposes of the organosilicon modified crylic acid resin of the high-solid lower-viscosity.
To achieve these goals, the technical solution adopted by the present invention is as follows:
One aspect of the present invention provides a kind of organosilicon modified crylic acid resin of high-solid lower-viscosity, structure such as formula I
It is shown:
Wherein:
In formula I:
R1Selected from containing 1~20 aliphatic of carbon atom, alicyclic, aromatic alkyl, alkoxy, acyloxy, hydroxyl alkane
Base, hydroxyl alkylidene;
R2、R3、R4、R5Be each independently selected from hydrogen atom, containing 1~20 aliphatic of carbon atom, alicyclic, aromatic series
Alkyl, hydroxyalkyl, hydroxyl alkylidene;
R6Structure be selected from Formula II in one kind:
CH2CH2CH2OH CH2CH2CH2CH2OH CH2CH2CH2CH2CH2OH
CH2CH2CH2CH2CH2CH2OH CH2CH2CH2OCH2CH(OH)CH2OCH3
(II);
R7Structure be selected from formula III in one kind:
CH3CH2CH2CH2 CH3CH(CH3)CH2 (CH3)3C (CH3)3SiO
(III);
m>0, n>0, o>0, p>0, q>0, x>0, y>0.
Signified alkyl includes straight or branched alkyl in formula I.Aliphatic, alicyclic, aromatic series in following mutual-through type I
Alkyl, alkoxy, acyloxy, hydroxyalkyl, hydroxyl alkylidene be illustrated:Alkyl is that ethyl belongs to aliphatic alkyl;Alkane
Base is that phenyl belongs to aromatic alkyl;Alkyl is that cyclohexyl belongs to alicyclic alkyl group.Similarly, alkoxy is that ethyoxyl belongs to fat
Fat race alkoxy;Alkoxy is that phenoxy group belongs to aromatic series alkoxy;Alkoxy is that hexamethylene alkoxy belongs to alicyclic alkoxy.
The hydroxyl value of the organosilicon modified crylic acid resin is between 50~250mgKOH/g;Acid number is between 0~20mg
Between KOH/g;Glass transition temperature (Tg) is between -30 DEG C to+50 DEG C;Number-average molecular weight between 500~20000,
It is preferred that 1500~5000;Solid content between 70%~100%, preferably 75%~90%;Type B rotary viscosity between 0.5~
Between 200Pas (25 DEG C), preferably 2~25Pas.
The organosilicon modified crylic acid resin of the high-solid lower-viscosity includes the component of following weight portion:
The solvent be selected from aliphatic ester, unary alcohol, ketone, di-alcohols, dihydroxylic alcohols ethers, dihydroxylic alcohols esters,
At least one in aromatic series carbon varsol, including but not limited to following compound known to those skilled in the art:Toluene,
Dimethylbenzene, S-100# solvent naphthas, trimethylbenzene solvent naphtha, S-150# solvent naphthas, durol solvent naphtha, butanone, methyl-isobutyl
Ketone, cyclohexanone, ethyl acetate, butyl acetate, butyl glycol ether acetic acid esters, pentyl acetate, ethylene glycol ethyl ether propionic ester, ethylene glycol
Butyl ether, ethylene glycol, normal propyl alcohol, isopropanol, n-butanol, propylene glycol methyl ether acetate.
The carbon-carbon double bonds and the monomer of copolyreaction can be carried out include but is not limited to following those skilled in the art institute
At least one in the compound known:Styrene, methyl-prop ethene, allyl alcohol, tertiary ethylene carbonate, monomethyl maleate, horse
Come sour mono ethyl ester, maleic acid list n-propyl, maleic acid list isopropyl ester, maleic acid list N-butyl, the secondary butyl ester of maleic acid list, maleic acid
The double methyl esters of single tert-butyl ester, maleic acid list pentyl ester, the own ester of maleic acid list, maleic acid list Octyl Nitrite, maleic acid, the double second of maleic acid
The double n-propyls of ester, maleic acid, the double isopropyl esters of maleic acid, the double N-butyls of maleic acid, the double secondary butyl esters of maleic acid, the double tertiary fourths of maleic acid
The double pentyl esters of ester, maleic acid, the double own esters of maleic acid, the double Octyl Nitrites of maleic acid.
The derivative of the acrylate and/or methacrylate monomers is selected from alkyl acrylate, methacrylic acid
At least one in Arrcostab, acrylate base ester, cycloalkyl methacrylate, including but not limited to following this area skill
At least one in compound known to art personnel:Methyl acrylate, methyl methacrylate, ethyl acrylate, metering system
Acetoacetic ester, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate,
N-BMA, isobutyl acrylate, Isobutyl methacrylate, tert-butyl acrylate, Tert-butyl Methacrylate,
Amyl acrylate, pentylmethacrylate, Hexyl 2-propenoate, hexyl methacrylate, EHA, methacrylic acid
Octyl Nitrite, the own ester of acrylic acid 3,3,5- trimethyls, the own ester of methacrylic acid 3,3,5- trimethyls, octadecyl acrylate,
Octadecyl methacrylate, dodecylacrylate, lauryl methacrylate, acrylic acid cyclopentyl ester, first
Base acrylic acid cyclopentyl ester, isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, methacrylic acid ring
Own ester, glycidyl acrylate, GMA.
The acrylate of the hydroxyl and/or the derivative of methacrylate monomers be selected from acrylic acid hydroxy alkyl ester,
At least one in hydroxyalkyl methacrylate, in including but not limited to following compound known to those skilled in the art
It is at least one:HEA, HEMA, acrylic acid 2- hydroxypropyl esters, methacrylic acid 2-
Hydroxypropyl ester, acrylic acid 3- hydroxypropyl esters, methacrylic acid 3- hydroxypropyl esters, acrylic acid 3- hydroxyls butyl ester, methacrylic acid 3-
The condensation of hydroxyl butyl ester, acrylic acid 4- hydroxyls butyl ester, methacrylic acid 4- hydroxyls butyl ester, acrylic acid and tertiary carbonic acid glycidyl ester is produced
Thing, methacrylic acid and tertiary carbonic acid glycidyl ester condensation product.
The derivative of the carboxylic acrylic acid and/or methacrylic acid is selected from acrylic acid and/or methacrylic acid.
The initiator is selected from least one in azo-initiator or peroxide initiator, including but not limited to following
At least one in compound known to those skilled in the art:Azodiisobutyronitrile, ABVN, benzoyl peroxide first
Double (t-amyl peroxy) the ring group alkane of acyl, the peroxidating 2- ethyl acids tert-butyl ester, peroxidating 2- ethyl acids tert-pentyl ester, 1,1-,
Double (the t-amyl peroxy) -3,3,5- trimethyls thiacyclohexanes of 1,1-, peroxidized t-butyl perbenzoate, peroxide acid tert-amyl acetate,
Peroxidating acetic acid tert-pentyl ester, peroxidating 3,5 ,-trimethyl tert-butyl acrylate, 3,3- double (t-butyl peroxy) ethyl butyrate, 3,3-
Double (t-amyl peroxy) ethyl butyrates, cumyl peroxide, t-amyl peroxy hydrogen, TBHP, peroxidating two
The tert-butyl group, di t-amyl peroxide.
The preparation method of the silicone macromolecule monomer is comprised the following steps:
1) HMDS is added drop-wise in unsaturated monohydric alcohol A, system is warming up to 90~120 DEG C, and herein
At a temperature of continue react 4~8 hours (h), trimethylsiloxy group unsaturated compound B is obtained by hydroxyl protection;
2) toward catalyst is added in trimethylsiloxy group unsaturated compound B, protected with nitrogen, reaction temperature is:
80~110 DEG C, the reaction time is:4~12h, is then added dropwise trimethyl cyclotrisiloxaneTrimethyl is obtained after reaction completely
Siloxyalkyl is modified cyclotrisiloxane
3) by the alkyl-modified cyclotrisiloxane of trimethylsiloxy groupHexamethyl cyclotrisiloxane D3With nonpolar organic molten
Agent and polar solvent are dissolved, and add alkyl lithium initiator, are protected with argon gas in course of reaction, reaction temperature:-70
DEG C~50 DEG C, reaction time:4-12h, is eventually adding dimethyl silicane hydroxide and is blocked, and obtains side chain with hydroxyl protecting group
Group, the single-ended silicone macromolecule E with silicon hydrogen group;
4) side chain is carried into hydroxy-protective group, single-ended silicone macromolecule E, polymerization inhibitor, catalysis with silicon hydrogen group
Agent mixes, and allyl methacrylate is added dropwise, and is protected with nitrogen in course of reaction, and reaction temperature is:80~110 DEG C, instead
It is between seasonable:4~12h, obtains side chain with hydroxy-protective group, the single-ended silicone macromolecule list with methacrylic acid group
Body F;
5) side chain is added with hydroxy-protective group, the single-ended silicone macromolecule monomer F with methacrylic acid group
To in alcohols solvent, with weak acid as catalyst reaction, reaction temperature is:65 DEG C~100 DEG C, the reaction time is:4~12h, decompression
Distillation removal alcohol compound and low-boiling-point substance, obtain side chain big with hydroxyl alkyl, the single-ended organosilicon with methacrylic acid group
Molecule monomer G, i.e., described silicone macromolecule monomer.
The mol ratio of the unsaturated monohydric alcohol A and HMDS is 2:(1~2), preferably 2:(1~1.1).
The unsaturated monohydric alcohol A is selected from the one kind in following structure:
A1)CH2=CHCH2OH A2)CH2=CHCH2CH2OH A3)CH2=CHCH2CH2CH2OH
A4)CH2=CHCH2CH2CH2CH2OH A5)CH2=CHCH2OCH2CH(OH)CH2OCH3。
The trimethylsiloxy group unsaturated compound B is selected from the one kind in following structure:
B1)CH2=CHCH2OSi(CH3)3 B2)CH2=CHCH2CH2OSi(CH3)3 B3)CH2=CHCH2CH2CH2OSi
(CH3)3
B4)CH2=CHCH2CH2CH2CH2OSi(CH3)3 B5)CH2=CHCH2OCH2CH[OSi(CH3)3]CH2OCH3。
The catalyst is chloroplatinic acid.
The trimethylsiloxy group unsaturated compound B and trimethyl cyclotrisiloxaneMol ratio be 3:1~6:1,
It is preferred that 3:1~3.3:1.
The quality of the catalyst accounts for the 0.05%~1% of trimethyl cyclotrisiloxane quality.
The alkyl-modified cyclotrisiloxane of trimethylsiloxy groupStructure it is as follows:
T1)CH2CH2CH2OSi(CH3)3 T2)CH2CH2CH2CH2OSi(CH3)3 T3)CH2CH2CH2CH2CH2OSi(CH3)3
T4)CH2CH2CH2CH2CH2CH2OSi(CH3)3 T5)CH2CH2CH2OCH2CH[OSi(CH3)3]CH2OCH3。
The mass ratio of the non-polar organic solvent and polar solvent is 1:1~1:5, non-polar organic solvent and polarity are molten
The gross mass of agent and the alkyl-modified cyclotrisiloxane of trimethylsiloxy groupHexamethyl cyclotrisiloxane D3, lithium alkylide total matter
Amount is than being 1:4~4:1.
The alkyl lithium initiator is 1 with the molar ratio range of dimethyl silicane hydroxide:1~1:1.2;Three in preparation process
Methyl siloxyalkyl is modified cyclotrisiloxaneHexamethyl cyclotrisiloxane D3This 3 kinds of feeding intake for reactant are rubbed with lithium alkylide
That ratio is depending on the size of final product molecular weight.
With reference to the molecular structure in embodiment 1, (with n-BuLi as initiator, consumption is 1mol to molecular weight design formula
As a example by) as follows:
Molecular weight (57)+D of the design molecular weight=normal-butyl of silicone macromolecule ET 3Molecular weight × DT 3Material amount
(n=x/3)+D3Molecular weight × D3Material amount (m=y/3)+(CH3)2The molecular weight (59) of SiH, i.e. M=57+60y+
190x+59。
If design molecular weight is 1000 or so, x and y are respectively 1 and 12 in above-mentioned reaction equation, then n and m respectively may be about 1/
3 and 4, that is, the silicone macromolecule E that molecular weight is 1000 or so is prepared, about need initiator, the D of 1/3mol of 1molT 3And 4mol
D3。
The side chain carries hydroxy-protective group, the design molecular weight of the single-ended silicone macromolecule E with silicon hydrogen group
=MAlkyl lithium initiator removes the molecular weight of lithium+DT 3Molecular weight × DT 3Material amount+D3Molecular weight × D3Material amount+MDimethyl silicane hydroxide。
The non-polar organic solvent is selected from aliphatic carbon varsol, alicyclic carbon varsol, aromatic series carbon hydro carbons
At least one in solvent, at least one in including but not limited to following compound known to those skilled in the art:Isoamyl
Alkane, pentane, petroleum ether, n-hexane, hexamethylene, isooctane, pentamethylene, trimethylpentane, pentamethylene, heptane, toluene, benzene,
Dimethylbenzene.
The alkyl lithium initiator be selected from n-BuLi, s-butyl lithium, tert-butyl lithium, trimethylsiloxy group lithium at least
It is a kind of.
The polar solvent be selected from aliphatic ketone, alicyclic ketones, aromatic series ketone, amide-type, sulfoxide type, nitrile,
At least one in heterocyclic solvent, in including but not limited to following compound known to those skilled in the art at least one
Kind:Tetrahydrofuran, formamide, acetonitrile, N,N-dimethylformamide, hexamethyl phosphoramide, butanone, dimethyl sulfoxide, acetone, 1,4-
Dioxane, pyridine.
The dimethyl silicane hydroxide is chlorodimethyl silane.
The side chain carries hydroxy-protective group, the number-average molecular weight of the single-ended silicone macromolecule E with silicon hydrogen group
Between 500~4500, and with following structure:
Wherein:y>0, x>0.
The quality of the polymerization inhibitor accounts for the 0.1%~5% of allyl methacrylate quality.
The quality of the catalyst accounts for side chain with hydroxy-protective group, the single-ended silicone macromolecule with silicon hydrogen group
The 0.05%~1% of the quality of E.
The side chain carries hydroxy-protective group, single-ended silicone macromolecule E and methacrylic acid with silicon hydrogen group
Mol ratio Primary Reference side chain between allyl ester carries hydroxy-protective group, the single-ended silicone macromolecule with silicon hydrogen group
In E in Si -- H and allyl methacrylate C=C groups mol ratio, i.e., described allyl methacrylate and side chain
With between hydroxy-protective group, silicon hydrogen group (Si-H) contained by the single-ended silicone macromolecule E with silicon hydrogen group mole
Than being 1:1~2:1, preferably 1.01:1~1.05:1.
The polymerization inhibitor is selected from phenols and quinones polymerization inhibitor, including but not limited to following change known to those skilled in the art
At least one in compound:Hydroquinones, 1,4-benzoquinone, methylnaphthohydroquinone, MEHQ, 2- TBHQs, 2,5-
Di-tert-butyl hydroquinone.
The catalyst is selected from chloroplatinic acid.
The side chain has with hydroxy-protective group, the single-ended silicone macromolecule monomer F with methacrylic acid group
Following structure:
Wherein, y>0, x>0.
The side chain carries hydroxy-protective group, single-ended silicone macromolecule monomer F and alcohol with methacrylic acid group
The mass ratio of class solvent is 1:1~1:4.
The quality of the weak acid accounts for side chain and divides greatly with hydroxy-protective group, the single-ended organosilicon with methacrylic acid group
The 0.5%~5% of sub- monomer F mass.
The alcohols solvent is selected from least one in methyl alcohol, ethanol, normal propyl alcohol, isopropanol.
The weak acid is selected from least in formic acid, acetic acid, propionic acid, lactic acid, dihydromethyl propionic acid, dimethylolpropionic acid
Kind.
Another aspect of the present invention provides a kind of preparation of the organosilicon modified crylic acid resin of the high-solid lower-viscosity
Method, comprises the following steps:
By 25~200 parts of carbon-carbon double bonds and the monomer of copolyreaction, 200~500 parts of acrylate and/or first can be carried out
The derivative of the derivative of base acrylate monomer, the acrylate of 150~250 parts of hydroxyls and/or methacrylate monomers
Thing, the derivative of 1~20 part of carboxylic acrylic acid and/or methacrylic acid, 25~100 parts of silicone macromolecule monomers, 14
~70 parts of initiator mixing, are added to reaction in 100~200 parts of solvents, and reaction temperature is 80~200 DEG C, and the time is 4~20h,
Obtain the organosilicon modified crylic acid resin of the high-solid lower-viscosity.
Another aspect of the invention provides a kind of organosilicon modified crylic acid resin of the high-solid lower-viscosity to be used to make
The purposes of standby coating.
There is advantages below and beneficial effect due to using above-mentioned technical proposal, the present invention:
The main chain of organosilicon is Si-O-Si keys in the organosilicon modified crylic acid resin of high-solid lower-viscosity of the invention, is difficult
Decomposed by ultraviolet light and ozone so that organosilicon has preferably resistance to irradiation and weather-proof ability than other macromolecular materials, because
This, it is organic-silicon-modified after acrylic resin can further be lifted resin weatherability and paint film guarantor's color gloss retention.
The main chain of organosilicon is very submissive in the organosilicon modified crylic acid resin of high-solid lower-viscosity of the invention, and intermolecular
Force ratio hydrocarbon want much weaker, therefore, compared with the hydrocarbon with molecular weight, organosilicon has viscosity low
Advantage;After the forging of organosilicon chain is incorporated into acrylic resin molecule, can effectively lower the viscosity of acrylic resin;Separately
On the one hand, it is also possible to adjust the pliability of acrylic resin so that the paint film of addition organosilicon modified crylic acid resin has good
Good impact resistance.
Organosilyl surface tension force is weak in the organosilicon modified crylic acid resin of high-solid lower-viscosity of the invention, surface can it is small, into
Film ability is strong, after organosilicon modified crylic acid resin is added in paint film, can assign the good scratch resistance of paint film and resistance to
Contamination, while so that paint film has good feel slipping.
The organosilicon modified crylic acid resin of high-solid lower-viscosity of the invention has relatively low surface tension, when organic-silicon-modified
When the solid content of acrylic resin is more than 80%, resin system can keep relatively low viscosity, and the resin can be used to prepare Gao Gu
Containing, low working viscosity, solvent type varnish paint, so as to help reduce the VOC content of varnish;At the same time, the resin can also
Help reduces the surface tension that varnish paint forms film, assigns the excellent slipping of final film and resistance to dry friction.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of allyl alcohol in the present invention;
Fig. 2 is the infrared spectrogram of allyloxy trimethyl silane in the present invention;
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of allyloxy trimethyl silane in the present invention;
Fig. 4 be in the present invention side chain with hydroxy-protective group, the single-ended silicone macromolecule E with silicon hydrogen group it is red
External spectrum figure;
Fig. 5 is that side chain carries hydroxy-protective group, the single-ended silicone macromolecule with methacrylic acid group in the present invention
The infrared spectrogram of monomer F;And
Fig. 6 is that side chain carries hydroxyl alkyl, the single-ended silicone macromolecule monomer G with methacrylic acid group in the present invention
Infrared spectrogram.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is a part of embodiment of the invention, rather than whole embodiments.Based on this hair
Bright embodiment, the every other implementation that those of ordinary skill in the art are obtained under the premise of creative work is not made
Example, belongs to the scope of protection of the invention.
Hereinafter it is described in detail to various aspects of the present invention, as no specific instructions, various raw materials of the invention can lead to
Cross and be commercially available;Or prepared according to the conventional method of this area.Unless otherwise defined or described herein, institute used herein
There is specialty identical with meaning familiar to those skilled in the art institute with scientific words.In addition it is any similar to described content
Or during the method and material of equalization all can be applied to the inventive method.
The experimental technique of unreceipted actual conditions in the following example, generally according to normal condition, or according to manufacturer
Proposed condition is carried out.Unless otherwise indicated, otherwise all of number is weight portion, and all of percentage is weight percent
Than.
Embodiment 1
Side chain carries hydroxyl alkyl, the side of the preparation method of the single-ended silicone macromolecule monomer G with methacrylic acid group
Formula is as follows:
Hydroxyl protection:In the reactor of 1L, 338.1g (2.1mol) HMDS is slowly added dropwise at room temperature
To in 232g (4mol) allyl alcohol.After completion of dropping, reaction system is warming up to 100 DEG C, and it is small to continue reaction 6 in this temperature
When after stop reaction.Normal pressure collects 98-100 DEG C of cut, obtains allyloxy trimethyl silane 473.2g, yield 91%.
As shown in Figures 1 to 3, Fig. 1 is the infrared spectrogram of allyl alcohol, in figure:Ordinate Transmittance refers to transmission
Rate, abscissa wavenumbers refers to wave number, and allyl alcohol is in 3332cm-1There is hydroxyl stretching vibration absworption peak very wide at place,
3084th, 1646,993 and 919cm-1The absworption peak at place is CH=CH2The characteristic absorption peak of key.Fig. 2 is allyloxy trimethyl silicane
The infrared spectrogram of alkane, in figure:Ordinate Transmittance refers to transmissivity, and abscissa wavenumbers refers to wave number,
Because the hydroxyl of allyl alcohol forms silicon oxygen bond with HMDS reaction, so in 3332cm-1Locate no hydroxyl group absorption
Peak, and belong to-CH=CH23083, the 1646 of key and 993cm-1Peak and belong to Si-CH31252, the 841 of key and 755cm-1
The absworption peak at place is still present, and increased Si-O-C keys in 1087cm-1The absworption peak at place.Fig. 3 is allyloxy trimethyl silane
Hydrogen nuclear magnetic resonance spectrogram, 6 groups of peaks are had in figure, by chemical displacement value from small to large, i.e., the order from High-Field to low field, its peak
Area ratio is 6:9:2:1:1:1.Methyl where No. 5 protons is connected with Si, according to its peak area, can conclude that at 0.13ppm
Peak be No. 5 protons;Methine where No. 4 protons is connected with oxygen atom, is also connected with double bond, therefore its chemical displacement value should
In 4.0ppm or so, the peak of Gu4.14ppmChu should be No. 4 protons, and its peak area also complies with the number of proton in methine;1、
2nd, No. 3 protons are the protons on double-linked carbon, and its chemical shift is between 5.0~6.0ppm.
Si―H addition reaction:In the reactor of 1L, 393.9g (3.03mol) allyloxy trimethyl silane is sequentially added
With 0.5g chloroplatinic acid catalysts (0.5/180=0.27%), after being passed through nitrogen 20min, reaction system is warming up to 100 DEG C,
180g (1mol) trimethyl cyclotrisiloxane, terminating reaction after reaction 8h are added dropwise at a temperature of this.Vacuum distillation removes low-boiling-point substance, obtains
To the alkyl-modified cyclotrisiloxane of 553g trimethylsiloxy groups, yield 97.0%.
Anionic polymerisation:In the 2L reactors after being processed by anhydrous and oxygen-free, sequentially add 1mol n-BuLi,
740g (3.333mol) hexamethyl cyclotrisiloxane, the alkyl-modified cyclotrisiloxane of 190g (0.333mol) trimethylsiloxy group,
(mass ratio is 1 for 500g n-hexanes and tetrahydrofuran:1), after stirring reaction 8h at 25 DEG C, the chlorine silicon of 1.1mol dimethyl one is added
Alkane terminating reaction.Reacting liquid filtering is removed the lithium chloride of generation, after vacuum distillation removal low-boiling-point substance, the equal molecule of 987g numbers is obtained
The side chain measured as 1026 or so carries hydroxy-protective group, the single-ended silicone macromolecule with silicon hydrogen group, yield 96.2%.
As shown in figure 4, Fig. 4 is side chain carries hydroxy-protective group, the single-ended silicone macromolecule E with silicon hydrogen group
Infrared spectrogram, in figure:Ordinate Transmittance refers to transmissivity, and abscissa wavenumbers refers to wave number, (1) by
In (CH3)2SiO chain links increase, 800cm-1Place occurs in that the rocking vibration absworption peak of C-H, and this is dimethyl silicone polymer
One of characteristic peak;(2)1027cm-1And 1092cm-1The double strong peak that place occurs is the stretching vibration absworption peak of Si-O-Si, and this is also
One characteristic peak of dimethyl silicone polymer;(3)1260cm-1Locate the strong peak for occurring for the symmetric deformation flexural vibrations of C-H absorb
Peak;(4)2905cm-1And 2962cm-1The peak for locating to occur is the stretching vibration absworption peak of C-H;(5)2127cm-1The peak for locating to occur is
The stretching vibration absworption peak of Si-H.By the characteristic absorption peak occurred in spectrogram, tentatively illustrate that n-BuLi triggers hexamethyl
Cyclotrisiloxane and the alkyl-modified cyclotrisiloxane of trimethylsiloxy group there occurs polymerisation, and chlorodimethyl silane is terminated
Polymerisation simultaneously forms silicon hydrogen group.
Secondary Si―H addition reaction:In the reactor of 1L, 615.6g (0.6mol Si -- Hs) side chain is sequentially added with hydroxyl
Base blocking group, the single-ended silicone macromolecule with silicon hydrogen group, 0.38g MEHQs polymerization inhibitor and 1g chloroplatinic acids are urged
Agent, after being passed through nitrogen 20min, 100 DEG C is warming up to by reaction system, and 74.4g is added dropwise at this temperature, and (0.6mol C=C are double
Key group) allyl methacrylate, terminating reaction after reaction 5h.Vacuum distillation removes low-boiling-point substance, obtains the equal molecule of 662g numbers
The side chain for 1150 or so is measured with hydroxy-protective group, the single-ended silicone macromolecule monomer with methacrylic acid group, is received
Rate 95.9%.In above-mentioned reaction, the mol ratio between allyl methacrylate and silicon hydrogen group (Si-H) is 1:1.
As shown in figure 5, Fig. 5 is side chain dividing greatly with hydroxy-protective group, the single-ended organosilicon with methacrylic acid group
The infrared spectrogram of sub- monomer F, in figure:Ordinate Transmittance refers to transmissivity, and abscissa wavenumbers refers to
Wave number, as seen from Figure 5,2957cm-1It is the inverse symmetrical stretching vibration absworption peak of methyl;2899cm-1Symmetrical flexible for methyl shakes
Dynamic absworption peak;1252cm-1It is Si-CH3Stretching vibration absworption peak;1097cm-1It is the stretching vibration absworption peak of Si-O-Si, and
2127cm-1Place's si-h bond characteristic absorption peak disappears, while 1725cm-1There is the absworption peak of C=O keys in place, illustrates methacrylic acid
Allyl ester and with side chain with hydroxy-protective group, to there is Si―H addition reaction in single-ended silicone macromolecule E with silicon hydrogen group anti-
Should.
Alcoholysis reaction:In the reactor of 1L, 345g side chains are sequentially added with hydroxy-protective group, single-ended with methyl
The silicone macromolecule monomer of acrylic, 500g methyl alcohol and 3g acetic acid.Under 65 DEG C of heated reflux conditions, stop after reaction 9h
Reaction.Vacuum distillation removal acetic acid, excessive methyl alcohol and low-boiling-point substance, obtain the side chain band that 320g number-average molecular weights are 1078 or so
There are hydroxyl alkyl, the single-ended silicone macromolecule monomer with methacrylic acid group, yield 98.9%.As shown in fig. 6, Fig. 6 is side
Chain carries hydroxyl alkyl, the infrared spectrogram of the single-ended silicone macromolecule monomer G with methacrylic acid group, in figure:Ordinate
Transmittance refers to transmissivity, and abscissa wavenumbers refers to wave number, as seen from Figure 6, through Methanolysis after,
3445cm-1Stronger hydroxyl absorption peak is occurred in that, is illustrated at this point in the reaction, trimethyl silicane blocking group is divested, generated
Hydroxyl.
Embodiment 2
Hydroxyl protection:In the reactor of 1L, 338.1g (2.1mol) HMDS is slowly added dropwise at room temperature
To in 288g (4mol) 3- butene-1-ols.After completion of dropping, reaction system is warming up to 100 DEG C, and continued in this temperature anti-
Stop reaction after answering 6 hours.Normal pressure collects 110-115 DEG C of cut, obtains alkene butoxy trimethyl silane 558g, yield
96.9%.
Si―H addition reaction:In the reactor of 1L, 436.3g (3.03mol) alkene butoxy trimethyl silane is sequentially added
With 0.5g chloroplatinic acid catalysts, after being passed through nitrogen 20min, reaction system is warming up to 100 DEG C, 180g is added dropwise at this temperature
(1mol) trimethyl cyclotrisiloxane, terminating reaction after reaction 8h.Vacuum distillation removes low-boiling-point substance, obtains 601g trimethyl silica
The alkyl-modified cyclotrisiloxane of base, yield 98.2%.
Anionic polymerisation:In the 2L reactors after being processed by anhydrous and oxygen-free, sequentially add 1mol n-BuLi,
518g (2.333mol) hexamethyl cyclotrisiloxane, the alkyl-modified cyclotrisiloxane of 408g (0.666mol) trimethylsiloxy group,
(mass ratio is 1 for 500g n-hexanes and tetrahydrofuran:1), after stirring reaction 8h at 25 DEG C, the chlorine silicon of 1.1mol dimethyl one is added
Alkane terminating reaction.Reacting liquid filtering is removed the lithium chloride of generation, after vacuum distillation removal low-boiling-point substance, the equal molecule of 975g numbers is obtained
The side chain measured as 1022 or so carries hydroxy-protective group, the single-ended silicone macromolecule with silicon hydrogen group, yield 95.4%.
Secondary Si―H addition reaction:In the reactor of 1L, 600g (0.6mol Si -- Hs) side chain is sequentially added with hydroxyl
Blocking group, the single-ended silicone macromolecule with silicon hydrogen group, 0.38g 1,4-benzoquinone polymerization inhibitor and 1g chloroplatinic acid catalysts, lead to
After entering nitrogen 20min, reaction system is warming up to 100 DEG C, 74.4g (0.6mol C=C double bonds group) is added dropwise at this temperature
Allyl methacrylate, terminating reaction after reaction 5h.Vacuum distillation removes low-boiling-point substance, and it is 1146 to obtain 640g number-average molecular weights
The side chain of left and right carries hydroxy-protective group, the single-ended silicone macromolecule monomer with methacrylic acid group, yield 94.9%.
Allyl methacrylate and side chain are siliceous with hydroxy-protective group, the single-ended silicone macromolecule E institutes with silicon hydrogen group
Mol ratio between hydrogen group (Si-H) is 1:1.
Alcoholysis reaction:In the reactor of 2L, 458.4g side chains are sequentially added with hydroxy-protective group, single-ended with first
The silicone macromolecule monomer of base acrylic, 800g methyl alcohol and 5g acetic acid.Under 65 DEG C of heated reflux conditions, stop after reaction 9h
Only react.Vacuum distillation removal acetic acid, excessive methyl alcohol and low-boiling-point substance, obtain the side chain that 410g number-average molecular weights are 1074 or so
With hydroxyl alkyl, the single-ended silicone macromolecule monomer with methacrylic acid group, yield 95.3%.
Embodiment 3
Allyl alcohol during the hydroxyl protection of embodiment 1 is reacted is changed to 4- amylene-1-ols, the n-BuLi in anionic polymerisation
The amount of material 0.5mol is changed to by 1mol, the amount of the material of chlorodimethyl silane is changed to 0.55mol by 1.1mol, and other are anti-
Answer condition as described in Example 1, obtain molecular weight and structure is different from the silicone macromolecule monomer of embodiment 1.
Embodiment 4
N-BuLi in anionic polymerisation in embodiment 2 is changed to s-butyl lithium, the amount of the material of s-butyl lithium by
1mol is changed to 0.75mol, and the amount of the material of chlorodimethyl silane is changed to 0.825mol by 1.1mol, and other reaction conditions are strictly according to the facts
Apply described in example 2, obtain molecular weight and structure is different from the silicone macromolecule monomer of embodiment 2.
Embodiment 5
First, by 125g dimethylbenzene and propylene glycol methyl ether acetate, (mass ratio is 1:1) mixed solvent is added to and is equipped with
In the 1L reactors of agitator, thermometer, nitrogen conduit and reflux condenser, and reaction system is warming up to 130~140 DEG C.
After reaction temperature stabilization, will be by 50g styrene, 225g n-butyl acrylates, 175g HEMAs, 5g third
Olefin(e) acid, 45g methyl methacrylates, the silicone macromolecule monomer of the preparation of 26.3g embodiments 1 and 38g peroxidating 2- ethyls are
The reactant mixture of tert-butyl acrylate composition, is added drop-wise in reactor by peristaltic pump, and maintenance reaction temperature is 130 during dropwise addition
Between~140 DEG C, drop rate is controlled, it is ensured that by reactant mixture completion of dropping in 2~4h.After completion of dropping, continue
2~4h is incubated between 130~140 DEG C, terminating reaction obtains solid content for 80.8%, hydroxyl value is 143mg KOH/g, organosilicon
Content be 5%, Type B rotary viscosity for 25Pas, the high-solid lower-viscosity that number-average molecular weight is 3000 or so it is organic-silicon-modified
Acrylic resin, acid number is 7.4KOH/g;Glass transition temperature (Tg) is -7.6 DEG C.
Embodiment 6
First, by 125g butyl acetates, dimethylbenzene and propylene glycol methyl ether acetate, (mass ratio is 1:3:4) mixed solvent
It is added in the 1L reactors equipped with agitator, thermometer, nitrogen conduit and reflux condenser, and reaction system is warming up to
130~140 DEG C.After reaction temperature stabilization, will be by 100g styrene, 200g n-butyl acrylates, 150g methacrylic acids 2-
Hydroxyethyl ester, 8g acrylic acid, 42g ethylhexyl methacrylates, 55.5g embodiments 2 prepare silicone macromolecule monomer and
The reactant mixture of 48g peroxidating 2- ethyl acids tert-butyl ester composition, is added drop-wise in reactor, during dropwise addition by peristaltic pump
Maintenance reaction temperature controls drop rate, it is ensured that by reactant mixture completion of dropping in 2~4h between 120~140 DEG C.
After completion of dropping, continue to be incubated 2~4h between 120~140 DEG C, terminating reaction, obtain solid content for 81.6%, hydroxyl value is
116mg KOH/g, silicone content be 10%, Type B rotary viscosity for 7.4Pas, number-average molecular weight be 2500 or so it is described
The organosilicon modified crylic acid resin of high-solid lower-viscosity, acid number is 11.2mg KOH/g;Glass transition temperature (Tg) is -12 DEG C.
Embodiment 7
First, by 156g butyl acetates and dimethylbenzene, (mass ratio is 7:2) mixed solvent is added to equipped with agitator, temperature
In the 1L reactors of degree meter, nitrogen conduit and reflux condenser, and reaction system is warming up to 130~140 DEG C.Work as reaction temperature
After stabilization, will be by 80g styrene, 220g n-butyl acrylates, 180g HEMAs, 2g acrylic acid, 18g first
Silicone macromolecule monomer and 53.4g peroxidating 2- ethyl acids prepared by base dodecylacrylate, 43.5g embodiments 3
The reactant mixture of tert-butyl ester composition, is added drop-wise in reactor by peristaltic pump, during dropwise addition maintenance reaction temperature 120~
Between 130 DEG C, drop rate is controlled, it is ensured that by reactant mixture completion of dropping in 2~4h.After completion of dropping, continue 120
2~4h is incubated between~130 DEG C, terminating reaction obtains solid content for 77.7%, hydroxyl value is 143mg KOH/g, silicone content
For 8%, Type B rotary viscosity be 8.7Pas, the high-solid lower-viscosity that number-average molecular weight is 2200 or so organic-silicon-modified third
Olefin(e) acid resin, acid number is 2.9mg KOH/g;Glass transition temperature (Tg) is -9.5 DEG C.
Embodiment 8
First, by 125g dimethylbenzene and propylene glycol methyl ether acetate, (mass ratio is 1:1) mixed solvent is added to and is equipped with
In the 1L reactors of agitator, thermometer, nitrogen conduit and reflux condenser, and reaction system is warming up to 130~140 DEG C.
After reaction temperature stabilization, will be by 53g styrene, 220g n-butyl acrylates, 175g HEMAs, 7g third
Olefin(e) acid, 45g methyl methacrylates, the silicone macromolecule monomer of the preparation of 26.3g embodiments 4 and 35g peroxidating 2- ethyls are
The reactant mixture of sour tert-pentyl ester composition, is added drop-wise in reactor by peristaltic pump, and maintenance reaction temperature is 130 during dropwise addition
Between~140 DEG C, drop rate is controlled, it is ensured that by reactant mixture completion of dropping in 2~4h.After completion of dropping, continue
2~4h is incubated between 130~140 DEG C, terminating reaction obtains solid content for 80.8%, hydroxyl value is 143mg KOH/g, organosilicon
Content is 5%, Type B rotary viscosity for 27.4Pas, the organosilicon of the high-solid lower-viscosity that number-average molecular weight is 3500 or so change
Property acrylic resin, acid number be 10.4mg KOH/g between;Glass transition temperature (Tg) is -7.1 DEG C.
Embodiment 9
First, by 125g dimethylbenzene and propylene glycol methyl ether acetate, (mass ratio is 2:1) mixed solvent, is added to and is equipped with
In the 1L reactors of agitator, thermometer, nitrogen conduit and reflux condenser, and reaction system is warming up to 130~140 DEG C.
After reaction temperature stabilization, will be by 50g styrene, 175g n-butyl acrylates, 175g HEMAs, 5g third
Silicone macromolecule monomer and 61g perbenzoic acids uncle penta prepared by olefin(e) acid, 95g methyl methacrylates, 88g embodiments 1
The reactant mixture of ester composition, is added drop-wise in reactor by peristaltic pump, and maintenance reaction temperature is 130~140 during dropwise addition
Between DEG C, drop rate is controlled, it is ensured that by reactant mixture completion of dropping in 2~4h.After completion of dropping, continue 130~
Be incubated 2~4h between 140 DEG C, terminating reaction, obtain solid content for 82.5%, hydroxyl value be that 128mg KOH/g, silicone content are
15%th, Type B rotary viscosity is 5.4Pas, the organic-silicon-modified propylene of the high-solid lower-viscosity that number-average molecular weight is 2000 or so
Acid resin, acid number is between 6.6mg KOH/g;Glass transition temperature (Tg) is -16.2 DEG C.
Embodiment 10
First, by 100g butyl acetates and S-100# solvent naphthas, (mass ratio is 1:4) mixed solvent, is added to be equipped with and stirs
In mixing the 1L reactors of device, thermometer, nitrogen conduit and reflux condenser, and reaction system is warming up to 130~140 DEG C.When
After reaction temperature stabilization, will be by 30g styrene, 70g n-butyl acrylates, 70g Tert-butyl Methacrylates, 50g versatic acid second
Prepared by alkene ester, 100g methacrylic acid 2- hydroxypropyl esters, 6g acrylic acid, 74g isobornyl methacrylates, 20g embodiments 1
The reactant mixture of silicone macromolecule monomer and 14g di-t-butyl peroxides composition, is added drop-wise in reactor by peristaltic pump,
Maintenance reaction temperature controls drop rate, it is ensured that by reactant mixture in 2~4h between 130~140 DEG C during dropwise addition
Completion of dropping.After completion of dropping, continue to be incubated 2~4h between 130~140 DEG C, terminating reaction, obtaining solid content is
80.8%th, hydroxyl value is that 92mg KOH/g, silicone content are that 4.7%, Type B rotary viscosity is that 7.7Pas, number-average molecular weight are
The organosilicon modified crylic acid resin of 2200 or so the high-solid lower-viscosity, acid number is 11mgKOH/g, Tg=-3.1 DEG C.
Embodiment 11
First, by 200g butyl acetates, dimethylbenzene and pentyl acetate, (mass ratio is 1:4:5) mixed solvent, is added to
In 1L reactors equipped with agitator, thermometer, nitrogen conduit and reflux condenser, and reaction system is warming up to 130~140
℃.When reaction temperature stabilization after, will by 100g styrene, 150g n-butyl acrylates, 100g ethylhexyl methacrylates,
100g HEMAs, 75g methacrylic acid 2- hydroxypropyl esters, 10g acrylic acid, 10g methacrylic acids, 100g
Prepared by the double N-butyls of dodecylacrylate, 55g isobornyl methacrylates, 100g maleic acids, 50g embodiments 2 has
The reactant mixture of machine silicon macromonomer and 33g di-t-butyl peroxides composition, is added drop-wise in reactor by peristaltic pump, is dripped
Plus during maintenance reaction temperature between 130~140 DEG C, control drop rate, it is ensured that reactant mixture is dripped in 2~4h
Add complete.After completion of dropping, continue to be incubated 2~4h between 130~140 DEG C, terminating reaction, obtain solid content for 80.9%,
Hydroxyl value is 88mg KOH/g, silicone content is 2.4%, Type B rotary viscosity is 3.3Pas, number-average molecular weight is 1800 or so
The high-solid lower-viscosity organosilicon modified crylic acid resin, acid number is 17.5mgKOH/g, Tg=-2.7 DEG C.
The organosilicon modified crylic acid resin of the high-solid lower-viscosity prepared by above example can be used in coating and its preparation
In.
The main chain of organosilicon is Si-O-Si keys in the organosilicon modified crylic acid resin of high-solid lower-viscosity of the invention, is difficult
Decomposed by ultraviolet light and ozone so that organosilicon has preferably resistance to irradiation and weather-proof ability than other macromolecular materials, because
This, it is organic-silicon-modified after acrylic resin can further be lifted resin weatherability and paint film guarantor's color gloss retention.
The main chain of organosilicon is very submissive in the organosilicon modified crylic acid resin of high-solid lower-viscosity of the invention, and intermolecular
Force ratio hydrocarbon want much weaker, therefore, compared with the hydrocarbon with molecular weight, organosilicon has viscosity low
Advantage;After the forging of organosilicon chain is incorporated into acrylic resin molecule, can effectively lower the viscosity of acrylic resin;Separately
On the one hand, it is also possible to adjust the pliability of acrylic resin so that the paint film of addition organosilicon modified crylic acid resin has good
Good impact resistance.
Organosilyl surface tension force is weak in the organosilicon modified crylic acid resin of high-solid lower-viscosity of the invention, surface can it is small, into
Film ability is strong, after organosilicon modified crylic acid resin is added in paint film, can assign the good scratch resistance of paint film and resistance to
Contamination, while so that paint film has good feel slipping.
The organosilicon modified crylic acid resin of high-solid lower-viscosity of the invention has relatively low surface tension, when organic-silicon-modified
When the solid content of acrylic resin is more than 80%, resin system can keep relatively low viscosity, and the resin can be used to prepare Gao Gu
Containing, low working viscosity, solvent type varnish paint, so as to help reduce the VOC content of varnish;At the same time, the resin can also
Help reduces the surface tension that varnish paint forms film, assigns the excellent slipping of final film and resistance to dry friction.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not right
The restriction of embodiments of the present invention, for those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms, the embodiment cited by the present invention cannot give all of implementation method thoroughly
To the greatest extent, it is every to belong to obvious change or variation that technical scheme extends out still in protection model of the invention
The row for enclosing.The all documents for referring in the present invention are all incorporated as reference in this application, independent just as a document
It is cited as with reference to such.
Claims (21)
1. a kind of organosilicon modified crylic acid resin of high-solid lower-viscosity, it is characterised in that:Structure is as shown in formula I:
Wherein:
In formula I:
R1Selected from containing 1~20 aliphatic of carbon atom, alicyclic, aromatic alkyl, alkoxy, acyloxy, hydroxyalkyl, hydroxyl
Alkylidene;
R2、R3、R4、R5Be each independently selected from hydrogen atom, containing 1~20 aliphatic of carbon atom, alicyclic, aromatic alkane
Base, hydroxyalkyl, hydroxyl alkylidene;
R6Structure be selected from Formula II in one kind:
CH2CH2CH2OH CH2CH2CH2CH2OH CH2CH2CH2CH2CH2OH
CH2CH2CH2CH2CH2CH2OH CH2CH2CH2OCH2CH(OH)CH2OCH3
(II);
R7Structure be selected from formula III in one kind:
CH3CH2CH2CH2 CH3CH(CH3)CH2 (CH3)3C (CH3)3SiO
(III);
m>0, n>0, o>0, p>0, q>0, x>0, y>0.
2. the organosilicon modified crylic acid resin of high-solid lower-viscosity according to claim 1, it is characterised in that:The organosilicon
Acrylic resin modified hydroxyl value is between 50~250mgKOH/g;Acid number is between 0~20mg KOH/g;Gamma transition
Temperature (Tg) is between -30 DEG C to+50 DEG C;Number-average molecular weight is between 500~20000;Solid content between 70%~
Between 100%;Type B rotary viscosity is between 0.5~200Pas.
3. the organosilicon modified crylic acid resin of high-solid lower-viscosity according to claim 1, it is characterised in that:The organosilicon
The acrylic resin modified component including following weight portion:
4. the organosilicon modified crylic acid resin of high-solid lower-viscosity according to claim 3, it is characterised in that:The solvent choosing
From in aliphatic ester, unary alcohol, ketone, di-alcohols, dihydroxylic alcohols ethers, dihydroxylic alcohols esters, aromatic series carbon varsol
At least one;
The derivative of the acrylate and/or methacrylate monomers is selected from alkyl acrylate, methacrylate
At least one in ester, acrylate base ester, cycloalkyl methacrylate;
The acrylate of the hydroxyl and/or the derivative of methacrylate monomers are selected from acrylic acid hydroxy alkyl ester, methyl
At least one in acrylic acid hydroxy alkyl ester;
The initiator is selected from least one in azo-initiator or peroxide initiator.
5. the organosilicon modified crylic acid resin of high-solid lower-viscosity according to claim 4, it is characterised in that:The solvent bag
Include but be not limited to following compound:Toluene, dimethylbenzene, S-100# solvent naphthas, trimethylbenzene solvent naphtha, S-150# solvent naphthas, equal four
Toluene solvant oil, butanone, methyl iso-butyl ketone (MIBK), cyclohexanone, ethyl acetate, butyl acetate, butyl glycol ether acetic acid esters, acetic acid penta
In ester, ethylene glycol ethyl ether propionic ester, butyl glycol ether, ethylene glycol, normal propyl alcohol, isopropanol, n-butanol, propylene glycol methyl ether acetate
At least one;
The carbon-carbon double bonds and the monomer of copolyreaction can be carried out include but is not limited to following compound:Styrene, methyl-prop
Ethene, allyl alcohol, tertiary ethylene carbonate, monomethyl maleate, ethyl maleate, maleic acid list n-propyl, Malaysia monooctyl acid
Propyl ester, maleic acid list N-butyl, the secondary butyl ester of maleic acid list, the maleic acid list tert-butyl ester, maleic acid list pentyl ester, the own ester of maleic acid list,
The double methyl esters of maleic acid list Octyl Nitrite, maleic acid, the double ethyl esters of maleic acid, the double n-propyls of maleic acid, maleic acid double isopropyl ester, Malaysias
Sour double N-butyls, the double secondary butyl esters of maleic acid, the double tert-butyl esters of maleic acid, the double pentyl esters of maleic acid, the double own esters of maleic acid, the double second of maleic acid
At least one in the own ester of base.
6. the organosilicon modified crylic acid resin of high-solid lower-viscosity according to claim 4, it is characterised in that:The acrylic acid
The derivative of ester and/or methacrylate monomers is methyl acrylate, methyl methacrylate, ethyl acrylate, methyl-prop
The positive fourth of olefin(e) acid ethyl ester, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, acrylic acid
The tertiary fourth of ester, n-BMA, isobutyl acrylate, Isobutyl methacrylate, tert-butyl acrylate, methacrylic acid
Ester, amyl acrylate, pentylmethacrylate, Hexyl 2-propenoate, hexyl methacrylate, EHA, methyl-prop
Olefin(e) acid Octyl Nitrite, the own ester of acrylic acid 3,3,5- trimethyls, the own ester of methacrylic acid 3,3,5- trimethyls, octadecyl base
Ester, octadecyl methacrylate, dodecylacrylate, lauryl methacrylate, acrylic acid cyclopentyl ester,
Methacrylic acid cyclopentyl ester, isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, methacrylic acid
At least one in cyclohexyl, glycidyl acrylate, GMA.
7. the organosilicon modified crylic acid resin of high-solid lower-viscosity according to claim 4, it is characterised in that:The hydroxyl
Acrylate and/or methacrylate monomers derivative be HEA, methacrylic acid 2- ethoxys
Ester, acrylic acid 2- hydroxypropyl esters, methacrylic acid 2- hydroxypropyl esters, acrylic acid 3- hydroxypropyl esters, methacrylic acid 3- hydroxypropyls
Ester, acrylic acid 3- hydroxyls butyl ester, methacrylic acid 3- hydroxyls butyl ester, acrylic acid 4- hydroxyls butyl ester, methacrylic acid 4- hydroxyl butyl
In ester, acrylic acid and tertiary carbonic acid glycidyl ester condensation product, methacrylic acid and tertiary carbonic acid glycidyl ester condensation product
It is at least one.
8. the organosilicon modified crylic acid resin of high-solid lower-viscosity according to claim 4, it is characterised in that:It is described containing carboxyl
Acrylic acid and/or methacrylic acid derivative be selected from acrylic acid and/or methacrylic acid;
The initiator is azodiisobutyronitrile, ABVN, benzoyl peroxide, the tertiary fourth of peroxidating 2- ethyl acids
Double (t-amyl peroxy) the ring group alkane of ester, peroxidating 2- ethyl acids tert-pentyl ester, 1,1-, double (t-amyl peroxy) -3,3 of 1,1-,
5- trimethyls thiacyclohexane, peroxidized t-butyl perbenzoate, peroxide acid tert-amyl acetate, peroxidating acetic acid tert-pentyl ester, peroxidating
3,5 ,-trimethyl double (t-amyl peroxy) ethyl butyrates of double (t-butyl peroxy) ethyl butyrates of tert-butyl acrylate, 3,3-, 3,3-,
In cumyl peroxide, t-amyl peroxy hydrogen, TBHP, di-t-butyl peroxide, di t-amyl peroxide
At least one.
9. the organosilicon modified crylic acid resin of high-solid lower-viscosity according to claim 3, it is characterised in that:The organosilicon
The preparation method of macromonomer is comprised the following steps:
1) HMDS is added drop-wise in unsaturated monohydric alcohol A, system is warming up to 90~120 DEG C, and in this temperature
It is lower to continue to react 4~8 hours (h), trimethylsiloxy group unsaturated compound B is obtained by hydroxyl protection;
2) toward catalyst is added in trimethylsiloxy group unsaturated compound B, protected with nitrogen, reaction temperature is:80~
110 DEG C, the reaction time is:4~12h, is then added dropwise trimethyl cyclotrisiloxaneTrimethyl silica is obtained after reaction completely
The alkyl-modified cyclotrisiloxane of base
3) by the alkyl-modified cyclotrisiloxane of trimethylsiloxy groupHexamethyl cyclotrisiloxane D3With non-polar organic solvent and
Polar solvent is dissolved, and adds alkyl lithium initiator, is protected with argon gas in course of reaction, reaction temperature:- 70 DEG C~
50 DEG C, reaction time:4-12h, is eventually adding dimethyl silicane hydroxide and is blocked, obtain side chain with hydroxy-protective group,
The single-ended silicone macromolecule E with silicon hydrogen group;
4) side chain is mixed with hydroxy-protective group, the single-ended silicone macromolecule E with silicon hydrogen group, polymerization inhibitor, catalyst
Close, allyl methacrylate is added dropwise, protected with nitrogen in course of reaction, reaction temperature is:80~110 DEG C, during reaction
Between be:4~12h, obtains side chain with hydroxy-protective group, the single-ended silicone macromolecule monomer F with methacrylic acid group;
5) side chain is added to alcohol with hydroxy-protective group, the single-ended silicone macromolecule monomer F with methacrylic acid group
In class solvent, with weak acid as catalyst reaction, reaction temperature is:65 DEG C~100 DEG C, the reaction time is:4~12h, vacuum distillation
Removal alcohol compound and low-boiling-point substance, obtain side chain with hydroxyl alkyl, the single-ended silicone macromolecule with methacrylic acid group
Monomer G.
10. the organosilicon modified crylic acid resin of high-solid lower-viscosity according to claim 9, it is characterised in that:The insatiable hunger
It is 2 with the mol ratio of monohydric alcohol A and HMDS:(1~2);
The unsaturated monohydric alcohol A is selected from the one kind in following structure:
A1)CH2=CHCH2OH A2)CH2=CHCH2CH2OH A3)CH2=CHCH2CH2CH2OH
A4)CH2=CHCH2CH2CH2CH2OH A5)CH2=CHCH2OCH2CH(OH)CH2OCH3。
The organosilicon modified crylic acid resin of 11. high-solid lower-viscosities according to claim 9, it is characterised in that:The catalysis
Agent is chloroplatinic acid;
The trimethylsiloxy group unsaturated compound B and trimethyl cyclotrisiloxaneMol ratio be 3:1~6:1;
The quality of the catalyst accounts for the 0.05%~1% of trimethyl cyclotrisiloxane quality.
The organosilicon modified crylic acid resin of 12. high-solid lower-viscosities according to claim 9, it is characterised in that:The non-pole
Property organic solvent and polar solvent mass ratio be 1:1~1:5, the gross mass and front three of non-polar organic solvent and polar solvent
Base siloxyalkyl is modified cyclotrisiloxaneHexamethyl cyclotrisiloxane D3, lithium alkylide total mass ratio be 1:4~4:1;
The alkyl lithium initiator is 1 with the molar ratio range of dimethyl silicane hydroxide:1~1:1.2;
The side chain with hydroxy-protective group, the single-ended silicone macromolecule E with silicon hydrogen group design molecular weight=
MAlkyl lithium initiator removes the molecular weight of lithium+DT 3Molecular weight × DT 3Material amount+D3Molecular weight × D3Material amount+MDimethyl silicane hydroxide。
The organosilicon modified crylic acid resin of 13. high-solid lower-viscosities according to claim 9, it is characterised in that:The non-pole
Property organic solvent be selected from aliphatic carbon varsol, alicyclic carbon varsol, aromatic series carbon varsol at least one;
The polar solvent is selected from aliphatic ketone, alicyclic ketones, aromatic series ketone, amide-type, sulfoxide type, nitrile, heterocycle
At least one in class solvent.
The organosilicon modified crylic acid resin of 14. high-solid lower-viscosities according to claim 13, it is characterised in that:The non-pole
Property organic solvent includes but is not limited to following compound:Isopentane, pentane, petroleum ether, n-hexane, hexamethylene, isooctane, ring
At least one in pentane, trimethylpentane, pentamethylene, heptane, toluene, benzene, dimethylbenzene;
The alkyl lithium initiator is selected from least in n-BuLi, s-butyl lithium, tert-butyl lithium, trimethylsiloxy group lithium
Kind;
The polar solvent includes but is not limited to following compound:Tetrahydrofuran, formamide, acetonitrile, N,N-dimethylformamide,
At least one in hexamethyl phosphoramide, butanone, dimethyl sulfoxide, acetone, 1,4- dioxane, pyridine;
The dimethyl silicane hydroxide is chlorodimethyl silane.
The organosilicon modified crylic acid resin of 15. high-solid lower-viscosities according to claim 9, it is characterised in that:The inhibition
The quality of agent accounts for the 0.1%~5% of allyl methacrylate quality;
The quality of the catalyst accounts for side chain with hydroxy-protective group, the single-ended silicone macromolecule E with silicon hydrogen group
The 0.05%~1% of quality;
The allyl methacrylate carries hydroxy-protective group, the single-ended silicone macromolecule with silicon hydrogen group with side chain
Mol ratio between silicon hydrogen group contained by E is 1:1~2:1.
The organosilicon modified crylic acid resin of 16. high-solid lower-viscosities according to claim 9, it is characterised in that:The inhibition
Agent is selected from phenols and quinones polymerization inhibitor;
The catalyst is selected from chloroplatinic acid.
The organosilicon modified crylic acid resin of 17. high-solid lower-viscosities according to claim 16, it is characterised in that:The inhibition
Agent is hydroquinones, 1,4-benzoquinone, methylnaphthohydroquinone, MEHQ, 2- TBHQs, 2,5- di-t-butyls to benzene two
At least one in phenol.
The organosilicon modified crylic acid resin of 18. high-solid lower-viscosities according to claim 9, it is characterised in that:The side chain
Mass ratio with hydroxy-protective group, single-ended silicone macromolecule monomer F and alcohols solvent with methacrylic acid group is
1:1~1:4;
The quality of the weak acid accounts for side chain with hydroxy-protective group, the single-ended silicone macromolecule list with methacrylic acid group
The 0.5%~5% of body F mass.
The organosilicon modified crylic acid resin of 19. high-solid lower-viscosities according to claim 9, it is characterised in that:The alcohols
Solvent is selected from least one in methyl alcohol, ethanol, normal propyl alcohol, isopropanol;
The weak acid is selected from least one in formic acid, acetic acid, propionic acid, lactic acid, dihydromethyl propionic acid, dimethylolpropionic acid.
A kind of preparation method of the organosilicon modified crylic acid resin of any described high-solid lower-viscosity of 20. claims 1 to 19, its
It is characterised by:Comprise the following steps:
By 25~200 parts of carbon-carbon double bonds and the monomer of copolyreaction, 200~500 parts of acrylate and/or methyl-prop can be carried out
Derivative, 1 of the derivative of olefin(e) acid ester monomer, the acrylate of 150~250 parts of hydroxyls and/or methacrylate monomers
The derivative of~20 parts of carboxylic acrylic acid and/or methacrylic acid, 25~100 parts of silicone macromolecule monomers, 14~70
Part initiator mixing, is added to reaction in 100~200 parts of solvents, and reaction temperature is 80~200 DEG C, and the time is 4~20h, acquisition
The organosilicon modified crylic acid resin.
A kind of organosilicon modified crylic acid resin of any described high-solid lower-viscosity of 21. claims 1 to 19 is used to prepare coating
Purposes.
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CN108047451A (en) * | 2017-12-29 | 2018-05-18 | 廊坊立邦涂料有限公司 | A kind of Polycaprolactone modified polysiloxanes, Preparation method and use |
CN109734850A (en) * | 2018-12-14 | 2019-05-10 | 万华化学(宁波)有限公司 | A kind of building primer emulsion and its preparation method and application |
CN113105592A (en) * | 2021-04-01 | 2021-07-13 | 深圳市安品有机硅材料有限公司 | Modified acrylic resin emulsion and preparation method thereof |
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