CN107216419B - It is a kind of to prepare high concentration hydroxyl polyacrylic resin and its cured method - Google Patents
It is a kind of to prepare high concentration hydroxyl polyacrylic resin and its cured method Download PDFInfo
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- CN107216419B CN107216419B CN201710367938.0A CN201710367938A CN107216419B CN 107216419 B CN107216419 B CN 107216419B CN 201710367938 A CN201710367938 A CN 201710367938A CN 107216419 B CN107216419 B CN 107216419B
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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
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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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- 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
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- 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
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- 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
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Abstract
It is a kind of to prepare high concentration hydroxyl polyacrylic resin and its cured method, belong to the preparation field of Polymer Synthesizing, resin material.The present invention uses dimethacrylate Triethylene Glycol for branched monomer, use methyl acrylate, butyl acrylate, methyl methacrylate and hydroxy-ethyl acrylate as comonomer, using branched p 0 lypropylene acid resin solution is quickly prepared under single electron transfer well-controlled radical polymerization method room temperature, solid content is 70~80%；Highly filled hydroxyl branched p 0 lypropylene acid resin, 1, hexamethylene-diisocyanate and catalyst dibutyltin dilaurylate carry out film-forming, and weatherability resin material reduces the discharge of organic solvent.
Description
Technical field
It is branched monomer, (25 DEG C) progress single electrons under room temperature the present invention relates to dimethacrylate Triethylene Glycol
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, has typical weatherability resin material, greatly reduces to organic solvent emission, belong to high score
Son synthesis, coating matrix resin art.
Background technique
In recent years, as environmental protection requirement is constantly reinforced, it is main at present for preparing high concentration coating with matrix resin
One of developing way, to reduce the dosage of organic solvent, general solution prepares low-molecular weight polymer, reduces solution
Viscosity is made into highly filled cold coating.But the system is influenced to will limit coating by construction technology and paint film property etc.
It promotes and applies.Therefore, based on the requirement of composite molecular weight, existing resin highest solid content is 50%~65% (generally not
Higher than 70%), solvent usage is still higher, is unfavorable for environmental protection, therefore, keeps under polymer molecular weight permanence condition, exploitation is high
Solid content resin reduces solvent usage, is one of the effective way for alleviating coating VOC emission.
Branched polymer due to its unique three-dimensional globular structure, 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 have the physical properties such as the crystallinity different from linear polymer, fusing point, thermal stability and
Mechanical performance.This structure acts on its molecule interchain without winding, and identical to substantially increase its dissolubility and compatibility
The linear molecule of molecular weight is compared, and super branched molecule is in elliposoidal, and compact-sized, melt and solution viscosity are lower, is expected to greatly
Ground promotes resin solid content, reduces solvent usage.
Currently, branched polypropylene acid resin is mostly used the method synthesis that ABx type monomer gradually polymerize, but this reaction can occur
Monomer structure type is relatively limited, and sight is invested active free radical polymerization by more and more scientists thus.Nineteen ninety-five, Fr é
Chet is proposed by the Self condensation vinyl polymerization object polymerization reaction of self-initiating monomer (Inimer) synthesis of super branched polymer
(SCVP) (Fr é chet 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,
It is that branched monomer prepares branched polymer, and is successfully prepared that bifunctional vinyl compound, which can be used, in Sherrington DC et al. proposition
Branching 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 object 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 apparent for atom transfer radical polymerization
Deficiency post-processes the disadvantages of troublesome if polymerization speed is slower.
Percec proposes the new quasi- active free radical polymerization method of one kind and overcomes disadvantage mentioned above, which is ordered
Entitled single electron transfer free radical polymerization (SET-LRP), the mechanism of the polymerization are briefly exactly in Cu (0)/complexant
Under catalysis, in intensive polar solvent, with organohalogen compounds (R-X) be initiator, cause monomer under room temperature or lower temperature into
Capable quasi- active free radical polymerization.SET-LRP uses common copper wire or copper powder as catalyst, takes copper wire after polymerization
It filters out or by copper powder.In addition, if 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 be may continue to.Therefore, because catalyst system is readily removed, reaction process is easy to control
System, normal-temperature reaction the features such as low energy consumption, so that SET-LRP has good prospects for commercial application.Studies have shown that SET-LRP institute
It prepares polymer and often has higher molecular weight, reach as high as 106, and the molecular weight of the obtained polymer of ATRP generally can only be
104~105In range.Therefore, SET-LRP is received significant attention.Based on its reaction rate is fast, polymerization temperature is low, polymerizing condition temperature
And the advantages that, this method can be applied to prepare branched p 0 lypropylene acid resin.
Summary of the invention
High concentration hydroxyl polyacrylic resin and its cured method are prepared this patent discloses a kind of, is turned using single electron
Free radical polymerisation process is moved, uses methyl acrylate, butyl acrylate, methyl methacrylate and hydroxy-ethyl acrylate as copolymerization
Monomer, dimethacrylate Triethylene Glycol are branched monomer, and dimethylformamide (DMF) is used as solvent, (25 under room 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, there is typical weatherability resin material, greatly reduce to organic solvent emission, VOC row is effectively reduced
The target with energy-saving and emission-reduction is put, is widely used in highly filled cold coating material.
Detailed description of the invention
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, peak corresponding to the hydrogen atom in double bond of dangling is continuous
Reduce, illustrates that pendency double bond is constantly consuming, form branched polymer；
Fig. 2: the relationship of polymer molecular weight and the degree of branching under high conversion, under 91% monomer conversion, the branch of polymer
Change degree is finally successfully prepared the polymer with highly branched structure down to about 0.3；
Fig. 3: the relationship of viscosity under the shear rate of different solid content branched polymers, 75% highly filled branching are poly-
The viscosity for closing object is 11pas, meets coating spray viscosity requirement, prepares highly filled acrylic resin soln.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment 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 not departing from present inventive concept for colleague
Under the premise of, several improvement can also be made.These are all within the scope of protection of the present invention.
Embodiment 1
The preparation of highly filled branched polypropylene acid resin: methyl acrylate MA (4.30g, 50mmol), acrylic acid are weighed
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) are added to stirrer
100mL mark mouth ball bottle reaction flask (tool high vacuum valve) in, add with solvent dimethylformamide 10g, while agitating,
It vacuumizes, be placed under argon gas protection for logical argon gas 3 times；Copper wire is added in reactor, is vacuumized rapidly plus after rubber stopper, logical argon
Gas 3 times, bottleneck wraps up the sealing of tetrafluoroethene band, and reactor is placed in constant temperature (25 DEG C) water-bath and is reacted, and after reaction, takes out
Xylene solvent is added in copper wire, adjusts resin viscosity, and solid content is up to 75%.
Embodiment 2 under the same terms, changes [MA]: [BA]: [MMA]: [MAH]=1:1:1:2,1:1:1:3,1:1:2:
1,1:1:2:2 prepares 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 is added 1, and hexamethylene-diisocyanate 0.5g, catalyst dibutyltin dilaurylate 0.005g are stirred evenly, spraying film forming,
70 DEG C of solidification 1h or normal temperature cure 5h.
Embodiment 4 under the same terms, changes acrylic resin and 1, and hexamethylene-diisocyanate amount ratio is 10:1,15:1,
30:1,50:1 sprays film-forming.
Claims (3)
1. a kind of preparation method of high concentration hydroxyl polyacrylic resin solution, using methyl acrylate, butyl acrylate, methyl
As comonomer, dimethacrylate Triethylene Glycol is branched monomer, benefit for methyl acrylate and hydroxy-ethyl acrylate
With single electron transfer well-controlled radical polymerization method, lower 25 DEG C of room temperature quickly prepares hydroxyl branched p 0 lypropylene acid resin solution,
Solid content is 70~80%；Dibutyl tin dilaurate is as catalyst, and 1, hexamethylene-diisocyanate carries out film-forming,
Weatherability resin material is formed, the discharge of organic solvent, preparation method are reduced are as follows:
(1) methyl acrylate MA, butyl acrylate BA, methyl methacrylate MMA, hydroxy-ethyl acrylate MAH, branching 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 flask with stirrer, while agitating, is vacuumized, is placed on for logical argon gas 3 times
Under argon gas protection, copper wire is added in reactor, vacuumizes rapidly plus after rubber stopper, is argon gas 3 times logical, bottleneck wraps up tetrafluoroethene
Band sealing；Reactor is placed in 25 DEG C of water bath with thermostatic control and is reacted, after reaction, dimethylbenzene diluted polymer is added, obtains
The hydroxyl branched p 0 lypropylene acid resin solution that solid content is 70~80%.
2. a kind of high concentration hydroxyl polyacrylic resin solution, it is characterised in that the preparation method as described in claim 1 obtains
It arrives.
3. a kind of cured method of high concentration hydroxyl polyacrylic resin solution, in the claim 1 for weighing 75% solid content
Then obtained Hydroxylated acrylic resin solution is added 1, hexamethylene-diisocyanate, catalyst dibutyltin dilaurylate stirs
It mixes uniformly, spraying film forming, heating or normal temperature cure.
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| CN108250383B (en) * | 2018-01-19 | 2020-09-08 | 盐城工学院 | Polyurethane elastomer with multiple crosslinking degrees and preparation method thereof |
| CN108976368B (en) * | 2018-06-07 | 2020-07-03 | 复旦大学 | Film forming method for rapid forming |
| CN109535967B (en) * | 2018-11-14 | 2022-01-25 | 常州大学 | Preparation method of environment-friendly high-impact-resistance coating |
| 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 |
| TWI746225B (en) | 2020-10-22 | 2021-11-11 | 碩晨生醫股份有限公司 | Brush roller and its manufacturing method and brush roller mold |
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Effective date of registration: 20230413 Address after: 213000 No.18 nanjiaqiao, Hejia village committee, Benniu Town, Xinbei District, Changzhou City, Jiangsu Province Patentee after: Jiangsu Sanyou Pipeline Technology Co.,Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |