CN110357996A - A kind of polymer and its preparation method and application as levelling agent - Google Patents
A kind of polymer and its preparation method and application as levelling agent Download PDFInfo
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- CN110357996A CN110357996A CN201910702088.4A CN201910702088A CN110357996A CN 110357996 A CN110357996 A CN 110357996A CN 201910702088 A CN201910702088 A CN 201910702088A CN 110357996 A CN110357996 A CN 110357996A
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- alkoxy silane
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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
- C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F130/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F130/08—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/47—Levelling agents
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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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
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
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Abstract
The present invention relates to a kind of polymer and preparation method and application as levelling agent, is reacted with acrylic monomer using hexafluoropropylene oxide, obtains intermediate；Intermediate is reacted with alkoxy silane monomer, obtains alkoxy silane fluorinated acrylate monomer；Alkoxy silane fluorinated acrylate monomer is under the action of initiator, using atom transfer radical polymerization method, and then obtains polyalkoxysilane fluorinated acrylate.Using the smoothness of silica alkyl polymer, it can be used for the levelling agent of coating, ink.
Description
Technical field
The invention belongs to field of polymer material preparing technology, and in particular to a kind of polymer and its system as levelling agent
Preparation Method and application.
Background technique
Levelling agent is a kind of common coating and ink addition agent, can reduce the surface tension of coating, promotes wet film dry
In the process, the stability and homogeneity of surface tension, for improving the smooth and smooth degree of film, so levelling agent needs mostly
Have the function of anti-shrinkage cavity, smooth, levelling etc..
Existing levelling agent is roughly divided into two major classes, and one is work by adjusting paint film viscosity and flow time
, this kind of levelling agent is or mixtures thereof some high boiling organic solvents mostly, as isophorone, diacetone alcohol,
Solvesso150 etc.；Another kind is worked by adjusting surface of the paint film property, and this kind of levelling agent passes through limited compatible
Property migrate to surface of the paint film, influence the surface naturies such as paint film interfacial tension, paint film made to obtain good levelling.According to chemical structure
Difference, this kind of levelling agent mainly has three categories: acrylic compounds, organic silicon and fluorocarbons class.Wherein, organic silicon stream
Flat agent does not have surface state control ability, therefore uses substantially in levelling agent, in terms of being chiefly used in high temperature resistant；Acrylic compounds stream
Flat agent has strong levelability, has more defoaming capacity, does not influence ply adhesion, but the profit of acrylic compounds levelling agent substrate
Moist difference cannot eliminate shrinkage cavity；Fluorine class levelling agent it is substrate wetting good, anti-shrinkage cavity ability is strong, but defoaming capacity and layer
Between poor adhesive force therefore the advantage and disadvantage of fluorine and acrylic acid can be made complementary with the esters of acrylic acid levelling agent of fluorine richness.
Application No. is 201510592088.5 Chinese patents to disclose a kind of fluoro-acrylate copolymer levelling agent
Preparation method by acrylate monomer and contains under the action of rare earth metal complex catalyst or trasition metal coordination catalyst
Fluoroacrylate monomers carry out coordination poly-merization in a solvent, and ring is made with auxiliary agent in decompression removal reaction dissolvent according to the proportion
Border friendly water soluble coating fluorinated acrylate levelling agent can be effectively reduced coating system surface tension, have paint
The features such as levelling speed is fast, nonshrink hole ability is strong.
Application No. is 200810020505.9,201110059353.5 and 201110059479.2 Chinese patents to report
The preparation method of series fluorosurfactants acrylate leveling agent, but these patents are all using conventional free radical polymerization, due to certainly
It is that free radical is caused by heating by base polymerization reaction, free radical causes fastly, fast to increase, a large amount of heat of releasing, in production process
It is easy to happen implode, controllability is poor, and there are certain risk.
Summary of the invention
The purpose of the present invention is to provide a kind of polymer and preparation method thereof as levelling agent, can be used as levelling agent and
Anticrater agent for having both acrylic compounds levelling agent, organosilicon using the levelling agent of the polymer in coating, ink simultaneously
The advantages of levelling agent and fluorine class levelling agent, has the effect of good smoothness, anti-shrinkage cavity and ground wetting.
A kind of polymer as levelling agent has structure as follows:
Wherein, R1~R3、R5It is alkyl, n is 10~200.
A kind of preparation method of the polymer as levelling agent, specifically includes the following steps:
S1, hexafluoropropylene oxide are reacted with acrylic monomer, obtain intermediate；
S2, it is reacted by the intermediate that step S1 is obtained with alkoxy silane monomer, obtains alkoxy silane fluorine-containing propene
Acid ester monomer；
S3, the alkoxy silane fluorinated acrylate monomer obtained by step S2 are under the action of initiator, using original
Sub- transfer radical polymerization method, and then obtain polyalkoxysilane fluorinated acrylate.
Further, acrylic monomer is acrylic or methacrylic acid in the step S1.
Further, the hexafluoropropylene oxide and acrylic monomer molar ratio are 1:1~1.2, and in nitrogen atmosphere
In reacted, reaction temperature be 60~80 DEG C.
Further, alkoxy silane monomer is trimethyl oxysilane, trifluoro propane trimethoxy in the step S2
One of silane or dimethyl siloxane or a variety of mixtures.
Further, the polymer in the step S3 in polymerization reaction according to the poly- alkyl silane fluorinated acrylate of target
The requirement of molecular weight is adjusted the reaction ratio of alkoxy silane fluorinated acrylate monomer and initiator, polymerization reaction
Temperature be 40~70 DEG C.
A kind of polymer as levelling agent is applied in coating or ink, can be used as levelling agent and anticrater agent simultaneously.
The invention has the following beneficial effects:
1, the present invention is reacted using hexafluoropropylene oxide with acrylic monomer, obtains intermediate, the R of intermediate5For alkane
Base, the reaction mechanism is as follows:
Intermediate is reacted with alkoxy silane monomer, obtains alkoxy silane fluorinated acrylate monomer, wherein alkoxy
R in silane monomer1~R4It is identical or different alkyl, the reaction mechanism is as follows:
Alkoxy silane fluorinated acrylate monomer uses atom transfer radical polymerization method, obtains polyalkoxysilane
Fluorinated acrylate, the reaction mechanism is as follows:
2, polyalkoxysilane fluorinated acrylate produced by the present invention has excellent smoothness and shrinkproof pore performance, benefit
Levelling agent is made with it or anti-lockhole agent makes it with splendid levelability and glossiness, utilizes fluorochemical monomer and acrylic compounds
Fluorine-containing acrylic acid ethylene glycol esters are made in monomer reaction, so that there is polymer extremely low surface tension to be suitable for levelling agent
In, it recycles fluorine-containing acrylic acid ethylene glycol esters to react again with alkylsiloxane and is obtained simultaneously using atom transfer radical polymerization
To subject polymer, so that subject polymer has the lubricity and spreadability of alkylsiloxane.
Detailed description of the invention
Fig. 1 is the nuclear-magnetism fluorine spectrogram of polyalkoxysilane fluorinated acrylate produced by the present invention.
Specific embodiment
It is next combined with specific embodiments below that the present invention will be described in detail.
Embodiment 1
The preparation method of alkoxy silane fluorinated acrylate, specifically includes the following steps:
S1, hexafluoropropylene oxide are reacted in the atmosphere of nitrogen with acrylic acid, mole of hexafluoropropylene oxide and acrylic acid
Than for 1:1, reaction temperature is 60 DEG C, intermediate is obtained；
S2, the intermediate obtained by step S1 are reacted with trimethyl oxysilane, obtain alkoxy silane fluorine-containing propene
Acid ester monomer；
S3, the alkoxy silane fluorinated acrylate monomer obtained by step S2 are under the action of initiator, using original
Sub- transfer radical polymerization method, and then polyalkoxysilane fluorinated acrylate is obtained, polymeric reaction temperature is 40 DEG C.
Further, anti-to polymerizeing according to the requirement of the polymer molecular weight of the poly- alkyl silane fluorinated acrylate of target
The reaction ratio of middle alkoxy silane fluorinated acrylate monomer and initiator is answered to be adjusted, the corresponding height of an initiator
The formation of molecule, if monomer is more, initiator is fewer, and the molecular weight of resulting polymers is bigger, conversely, monomer is fewer, draws
Hair agent is more, and molecular weight is with regard to smaller.
Embodiment 2
The preparation method of alkoxy silane fluorinated acrylate, specifically includes the following steps:
S1, hexafluoropropylene oxide are reacted in the atmosphere of nitrogen with methacrylic acid, hexafluoropropylene oxide and metering system
The molar ratio of acid is 1:1.1, and reaction temperature is 80 DEG C, obtains intermediate；
The mixture of S2, the intermediate obtained by step S1 and trifluoro propane trimethoxy silane or dimethyl siloxane
Reaction, obtains alkoxy silane fluorinated acrylate monomer；
S3, the alkoxy silane fluorinated acrylate monomer obtained by step S2 are under the action of initiator, using original
Sub- transfer radical polymerization method, and then polyalkoxysilane fluorinated acrylate is obtained, polymeric reaction temperature is 70 DEG C.
Embodiment 3
The preparation method of alkoxy silane fluorinated acrylate, specifically includes the following steps:
S1, hexafluoropropylene oxide are reacted in the atmosphere of nitrogen with methacrylic acid, hexafluoropropylene oxide and metering system
The molar ratio of acid is 1:1.2, and reaction temperature is 70 DEG C, obtains intermediate；
S2, the intermediate obtained by step S1 are reacted with trifluoro propane trimethoxy silane, are obtained alkoxy silane and are contained
Fluoroacrylate monomers；
S3, the alkoxy silane fluorinated acrylate monomer obtained by step S2 are under the action of initiator, using original
Sub- transfer radical polymerization method, and then polyalkoxysilane fluorinated acrylate is obtained, polymeric reaction temperature is 60 DEG C.
In conclusion alkoxy silane fluorinated acrylate made of preparation method by embodiment 1-3 can be simultaneously
As levelling agent and anticrater agent in coating, ink.
Performance test:
Using the influence after sample prepared by embodiment 1-3 is used for oil paint as levelling agent for properties of product,
Wherein, GB/T 21782.12-2010 is measured compatibility according to national standards, levelability GB1750-89 according to national standards
(79) it is measured, smoothness is indicated by friction co-efficient value, by MXS-05A can coating surface smoothness tester
It is detected, foam stability is measured using Roche foam meter, and glossiness is tested using XD-1050 glossiness tester.
The performance test of 1 polyalkoxysilane fluorinated acrylate of table
Influence of the 2 polyalkoxysilane fluorinated acrylate of table to coating property
| Test sample | Compatibility | Levelability | Shrinkage cavity degree | Foam stability |
| Embodiment 1 | It is transparent | It is good | Without shrinkage cavity | Defoaming |
| Embodiment 2 | It is transparent | It is good | Object shrinkage cavity | Defoaming |
| Embodiment 3 | It is transparent | It is good | Without shrinkage cavity | Defoaming |
As can be seen from Table 1 and Table 2, polyalkoxysilane fluorinated acrylate produced by the present invention is used as levelling agent
In oil paint, the surface tension, surface viscosity and coefficient of friction of coating are reduced, while improving the glossiness of coating,
Final coating obtained all has preferable compatibility, levelability and foam stability, can prevent shrinkage cavity.
It is the nuclear-magnetism fluorine spectrogram of polyalkoxysilane fluorinated acrylate referring to attached drawing 1, mainly passes through chemical potential in spectrogram
Shifting value judges difference group present in polymer obtained, and in low field area, the peak value of polymer appearance meets-CF3、-
CF2And the chemical displacement value of-OCF- group, wherein-CF3Chemical displacement value in -52~-87ppm range,-CF2Change
Displacement study is in -80~-120ppm range, and the chemical displacement value of-OCF- is in -125~-150ppm range.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks
Domain is included within the scope of the present invention.
Claims (7)
1. a kind of polymer as levelling agent, it is characterised in that: have structure as follows:
Wherein, R1~R3、R5It is alkyl, n is 10~200.
2. the polymer as levelling agent is applied in coating or ink as described in claim 1, it can be used as levelling agent simultaneously
And anticrater agent.
3. a kind of preparation method of the polymer as levelling agent as described in claim 1, which is characterized in that specifically include with
Lower step:
S1, hexafluoropropylene oxide are reacted with acrylic monomer, obtain intermediate；
S2, it is reacted by the intermediate that step S1 is obtained with alkoxy silane monomer, obtains alkoxy silane fluorinated acrylate
Monomer；
S3, the alkoxy silane fluorinated acrylate monomer obtained by step S2 are turned under the action of initiator using atom
Free radical polymerisation process is moved, and then obtains polyalkoxysilane fluorinated acrylate.
4. a kind of preparation method of the polymer as levelling agent as claimed in claim 3, it is characterised in that: the step S1
Middle acrylic monomer is acrylic or methacrylic acid.
5. a kind of preparation method of the polymer of levelling agent as claimed in claim 3, it is characterised in that: the Hexafluoropropylene third
Alkane and acrylic monomer molar ratio are 1:1~1.2, and are reacted in nitrogen atmosphere, and reaction temperature is 60~80 DEG C.
6. a kind of preparation method of the polymer as levelling agent as claimed in claim 3, it is characterised in that: the step S2
Middle alkoxy silane monomer be one of trimethyl oxysilane, trifluoro propane trimethoxy silane or dimethyl siloxane or
A variety of mixtures.
7. a kind of preparation method of the polymer as levelling agent as claimed in claim 3, it is characterised in that: the step S3
The temperature of middle polymerization reaction is 40~70 DEG C.
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| CN201910702088.4A CN110357996B (en) | 2019-07-31 | 2019-07-31 | Polymer used as leveling agent and preparation method and application thereof |
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| CN201910702088.4A CN110357996B (en) | 2019-07-31 | 2019-07-31 | Polymer used as leveling agent and preparation method and application thereof |
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| CN110357996B CN110357996B (en) | 2021-11-09 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0157218A1 (en) * | 1984-03-09 | 1985-10-09 | Daikin Industries, Limited | Fluorine-containing silane compounds and method of preparing them |
| CN1571822A (en) * | 2001-10-17 | 2005-01-26 | 埃弗卡添加剂股份有限公司 | Levelling agent and anti-cratering agent |
| CN101952379A (en) * | 2008-02-22 | 2011-01-19 | 巴斯夫欧洲公司 | Fluoro levelling agents |
| CN103524651A (en) * | 2013-10-12 | 2014-01-22 | 三明学院 | Levelling agent or used as anticratering agent |
| CN107964063A (en) * | 2017-09-29 | 2018-04-27 | 三明学院 | A kind of polymer without PFOA and preparation method thereof, purposes |
-
2019
- 2019-07-31 CN CN201910702088.4A patent/CN110357996B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0157218A1 (en) * | 1984-03-09 | 1985-10-09 | Daikin Industries, Limited | Fluorine-containing silane compounds and method of preparing them |
| CN1571822A (en) * | 2001-10-17 | 2005-01-26 | 埃弗卡添加剂股份有限公司 | Levelling agent and anti-cratering agent |
| CN101952379A (en) * | 2008-02-22 | 2011-01-19 | 巴斯夫欧洲公司 | Fluoro levelling agents |
| CN103524651A (en) * | 2013-10-12 | 2014-01-22 | 三明学院 | Levelling agent or used as anticratering agent |
| CN107964063A (en) * | 2017-09-29 | 2018-04-27 | 三明学院 | A kind of polymer without PFOA and preparation method thereof, purposes |
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