CN107216419A - A kind of method for preparing high concentration hydroxyl polyacrylic resin and its solidification - Google Patents

A kind of method for preparing high concentration hydroxyl polyacrylic resin and its solidification Download PDF

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Publication number
CN107216419A
CN107216419A CN201710367938.0A CN201710367938A CN107216419A CN 107216419 A CN107216419 A CN 107216419A CN 201710367938 A CN201710367938 A CN 201710367938A CN 107216419 A CN107216419 A CN 107216419A
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branched
acrylate
high concentration
resin
solidification
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CN107216419B (en
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薛小强
蒋必彪
黄文艳
杨宏军
孙佳悦
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Jiangsu Sanyou Pipeline Technology Co ltd
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Changzhou University
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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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate

Abstract

A kind of method for preparing high concentration hydroxyl polyacrylic resin and its solidification, belongs to Polymer Synthesizing, the preparation field of resin material.The present invention uses dimethacrylate Triethylene Glycol for branched monomer, comonomer is used as with methyl acrylate, butyl acrylate, methyl methacrylate and hydroxy-ethyl acrylate, branched p 0 lypropylene acid resin solution is prepared using quick under single electron transfer well-controlled radical polymerization method normal temperature, solids content is 70~80%；Highly filled hydroxyl branched p 0 lypropylene acid resin, 1,6 hexamethylene diisocyanate and catalyst dibutyltin dilaurylate carry out film-forming, and weatherability resin material reduces the discharge of organic solvent.

Description

A kind of method for preparing high concentration hydroxyl polyacrylic resin and its solidification
Technical field
It is branched monomer the present invention relates to dimethacrylate Triethylene Glycol, (25 DEG C) progress single electrons under normal temperature Transfer activity controllable free-radical polymerisation, quickly prepares highly filled hydroxyl branched p 0 lypropylene acid resin, and with double different Cyanate carries out film-forming, with typical weatherability resin material, greatly reduces to organic solvent emission, belongs to high score Son synthesis, coating matrix resin art.
Background technology
In recent years, as environmental protection requirement is constantly strengthened, it is main at present to prepare high concentration coating with matrix resin One of developing way, so as to reduce the consumption of organic solvent, general solution prepares low-molecular weight polymer, reduction solution Viscosity, is made into highly filled cold coating.But the system is influenceed that coating can be limited by construction technology and paint film property etc. Popularization and application.Therefore, the requirement based on composite molecular weight, existing resin highest solid content is 50%~65% (typically not Higher than 70%), solvent load is still higher, is unfavorable for environmental protection, therefore, keeps under polymer molecular weight permanence condition, and exploitation is high Solids content resin, reduces solvent load, is to alleviate one of effective way of coating VOC emission.
Branched polymer is due to its unique three-dimensional globular structure, and therefore, unique bonded mode directly influences macromolecular The mutual winding of interchain and interaction force.The formation of branched structure changes the form of macromolecular, therefore shows different Solution property and melt property, and with the physical property such as the crystallinity different from linear polymer, fusing point, heat endurance and Mechanical performance.This structure makes its molecule interchain be acted on without winding, so as to substantially increase its dissolubility and compatibility, and identical The linear molecule of molecular weight is compared, and super branched molecule is in elliposoidal, and compact conformation, melt and solution viscosity are relatively low, is expected to greatly Ground lifts resin solid content, reduces solvent load.
At present, branched polypropylene acid resin uses the method synthesis that ABx type monomers progressively polymerize, but can occur this reaction Monomer structure type is relatively limited, is that sight is invested active free radical polymerization by this increasing scientist.Nineteen ninety-five, Fr é Chet is proposed by the Self condensation vinyl polymerization thing polymerisation of self-initiating monomer (Inimer) synthesis of super branched polymer (SCVP)(Fréchet J M J,Gitsov I,Aoshima S,et al.Science,1995,269:1080-1083), but It is that not only manufacturing process is cumbersome by the Inimer that must use of the polymerization, and involves great expense.2004, Sherrington DC et al. propose that bifunctional vinyl compound can be used to prepare branched polymer for branched monomer, and are successfully prepared Branched polymethyl methacrylate (Isaurea F, Coemack P A G, Graham S, et al.Chemical Communication,2004,9:1138-1139.).2006, Bannisteri et al. was under the conditions of ATRP, to diene chemical combination The polymerization behavior of thing and common monoene has carried out specific research (Bannnister I, Billingham N C, Armes S P, et al.Macromolecules,2006,39(22):7483-7492).But there is also obvious for ATRP Deficiency, such as polymerization speed are slower, the shortcomings of post processing is troublesome.
Percec proposes a kind of new quasi- active free radical polymerization method and overcomes disadvantage mentioned above, and the polymerization is ordered Entitled single electron transfer radical polymerization (SET-LRP), the mechanism of the polymerization is exactly briefly in Cu (0)/complexant Under catalysis, in intensive polar solvent, with organohalogen compounds (R-X) for initiator, monomer is triggered to enter under room temperature or lower temperature Capable quasi- active free radical polymerization.SET-LRP uses common copper wire or copper powder as catalyst, and polymerization takes copper wire after terminating Go out or filter copper powder.If in addition, using copper wire as catalyst, copper wire can be taken out at any time, polymerization is It can stop, after copper wire is placed into, polymerization may continue to.Therefore, because catalyst system and catalyzing is readily removed, reaction process is easy to control System, the low feature of normal-temperature reaction energy consumption so that SET-LRP has good prospects for commercial application.Research shows, SET-LRP institutes Prepare polymer and often possess higher molecular weight, reach as high as 106, and ATRP obtain the molecular weight of polymer typically can only be 104~105In the range of.Therefore, SET-LRP is received significant attention.Based on its reaction rate is fast, polymerization temperature is low, polymerizing condition temperature And the advantages of, this method can be applied to prepare branched p 0 lypropylene acid resin.
The content of the invention
This patent discloses a kind of method for preparing high concentration hydroxyl polyacrylic resin and its solidification, turned using single electron Free radical polymerisation process is moved, copolymerization is used as with methyl acrylate, butyl acrylate, methyl methacrylate and hydroxy-ethyl acrylate Monomer, dimethacrylate Triethylene Glycol is branched monomer, and dimethylformamide (DMF) is as solvent, (25 under normal temperature DEG C) quickly prepare the hydroxyl branched p 0 lypropylene acid resin of highly filled (70~80% content), and with double isocyanates Film-forming is carried out, with typical weatherability resin material, is greatly reduced to organic solvent emission, effectively reduction VOC rows The target with energy-saving and emission-reduction is put, is widely used in highly filled cold coating material.
Brief description of the drawings
Fig. 1：Branched polymer nuclear magnetic spectrogram (1), H-NMR the peak at 5.58ppm, 5.15ppm corresponds respectively to diethyl Two hydrogen of double bond on alkenyl benzene.With the raising of monomer conversion, the peak corresponding to hydrogen atom in double bond of dangling is continuous Reduce, illustrate that pendency double bond is constantly being consumed, form branched polymer；
Fig. 2：Under the relation of polymer molecular weight and the degree of branching under high conversion, 91% monomer conversion, the branch of polymer Change degree as little as about 0.3, is finally successfully prepared the polymer with highly branched structure；
Fig. 3：The relation of viscosity under the shear rate of different solid content branched polymers, 75% is highly filled branched poly- The viscosity of compound is 11pas, meets coating spray viscosity requirement, prepares highly filled acrylic resin soln.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to further reason of going together The solution present invention, but the invention is not limited in any way.It should be pointed out that for colleague, not departing from present inventive concept On the premise of, some improvement can also be made.These belong to protection scope of the present invention.
Embodiment 1
The preparation of highly filled branched polypropylene acid resin：Weigh methyl acrylate MA (4.30g, 50mmol), acrylic acid Butyl ester BA (5.00g, 50mmol), methyl methacrylate MMA (4.90g, 50mmol) and hydroxy-ethyl acrylate MAH (5.96g, 50mmol), branched monomer dimethacrylate Triethylene Glycol tri-EGDMA (2.29g, 8.0mmol), 2 bromopropionic acid first Ester MBP (1.66g, 10.0mmol), pentamethyl-diethylenetriamine PMDETA (1.73g, 10.0mmol) is added to stirrer 100mL marks mouth pin reaction bulb (tool high vacuum valve) in, add with solvent dimethylformamide 10g, while stirring, Vacuumize, be placed under argon gas protection after logical argon gas 3 times；Copper wire is added in reactor, vacuumizes rapidly plus after rubber stopper, lead to argon Gas 3 times, bottleneck parcel tetrafluoroethene band sealing, reactor is placed in constant temperature (25 DEG C) water-bath and reacted, after reaction terminates, is taken out Copper wire, adds xylene solvent, adjusts resin viscosity, and solid content is up to 75%.
Under embodiment 2, the same terms, change [MA]:[BA]:[MMA]:[MAH]=1:1:1:2,1:1:1:3,1:1:2: 1,1:1:2:2, prepare a series of acrylic resin soln of different components and hydroxy radical content.
Embodiment 3
The curing reaction of highly filled branched polypropylene acid resin, weighs the Hydroxylated acrylic resin solution of 75% solid content 10g, adds 1, hexamethylene-diisocyanate 0.5g, catalyst dibutyltin dilaurylate 0.005g, stirs, and sprays film forming, 70 DEG C of solidification 1h, or normal temperature cure 5h.
Under embodiment 4, the same terms, change acrylic resin and 1, hexamethylene-diisocyanate amount ratio is 10:1,15:1, 30:1,50:1, spray film-forming.

Claims (1)

1. a kind of method for preparing high concentration hydroxyl polyacrylic resin and its solidification, using methyl acrylate, butyl acrylate, Methyl methacrylate and hydroxy-ethyl acrylate are as comonomer, and dimethacrylate Triethylene Glycol is branched list Body, using single electron transfer well-controlled radical polymerization method, lower 25 DEG C of normal temperature quickly prepares hydroxyl branched p 0 lypropylene acid resin Solution, solids content is 70~80%；Dibutyl tin laurate is as catalyst, and 1, hexamethylene-diisocyanate is solidified Film forming, forms weatherability resin material, reduces the discharge of organic solvent, its preparation method is：
(1) methyl acrylate MA, butyl acrylate BA, methyl methacrylate MMA, hydroxy-ethyl acrylate MAH, branched list are weighed Body dimethacrylate Triethylene Glycol tri-EGDMA, 2 bromopropionic acid methyl esters MBP, pentamethyl-diethylenetriamine PMDETA, Dimethylformamide DMF is added in the reaction bulb with stirrer (tool high vacuum valve), while stirring, is vacuumized, is led to It is placed in after argon gas 3 times under argon gas protection, copper wire is added in reactor, is vacuumized rapidly plus after rubber stopper, logical argon gas 3 times, bottle Mouth parcel tetrafluoroethene band sealing；Reactor is placed in constant temperature (25 DEG C) water-bath and reacted, after reaction terminates, dimethylbenzene is added dilute Polymer is released, solid content is 70~80%, is high concentration hydroxyl branched p 0 lypropylene acid resin solution；
(2) the Hydroxylated acrylic resin solution of 75% solid content, 1, hexamethylene-diisocyanate, the fourth of catalyst dibutyltin cinnamic acid two are weighed Ji Xi, stirs, and sprays film forming, heating or normal temperature cure.
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CN108250383A (en) * 2018-01-19 2018-07-06 盐城工学院 More degree of cross linking polyurethane elastomers and preparation method thereof
CN108976368A (en) * 2018-06-07 2018-12-11 复旦大学 A kind of film build method can be used for rapid shaping
CN109535967A (en) * 2018-11-14 2019-03-29 常州大学 A kind of preparation method of environment-friendly type high impact resistance coating
CN111763296A (en) * 2020-06-17 2020-10-13 广东柯力森树脂有限公司 Modified acrylic resin and preparation method thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108250383A (en) * 2018-01-19 2018-07-06 盐城工学院 More degree of cross linking polyurethane elastomers and preparation method thereof
CN108250383B (en) * 2018-01-19 2020-09-08 盐城工学院 Polyurethane elastomer with multiple crosslinking degrees and preparation method thereof
CN108976368A (en) * 2018-06-07 2018-12-11 复旦大学 A kind of film build method can be used for rapid shaping
CN109535967A (en) * 2018-11-14 2019-03-29 常州大学 A kind of preparation method of environment-friendly type high impact resistance coating
CN109535967B (en) * 2018-11-14 2022-01-25 常州大学 Preparation method of environment-friendly high-impact-resistance coating
CN111763296A (en) * 2020-06-17 2020-10-13 广东柯力森树脂有限公司 Modified acrylic resin and preparation method thereof
CN111763296B (en) * 2020-06-17 2022-04-05 广东柯力森树脂有限公司 Modified acrylic resin and preparation method thereof

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