CN108129601A - A kind of synthetic method of microgel - Google Patents
A kind of synthetic method of microgel Download PDFInfo
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- CN108129601A CN108129601A CN201711397752.6A CN201711397752A CN108129601A CN 108129601 A CN108129601 A CN 108129601A CN 201711397752 A CN201711397752 A CN 201711397752A CN 108129601 A CN108129601 A CN 108129601A
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- Prior art keywords
- microgel
- vinyl
- mass ratio
- synthetic method
- methyl
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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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a kind of synthetic methods of microgel, it selects based on mono-vinyl unsaturated compound, three kinds of collocation vinyl aromatic monomers, (methyl) methyl acrylate and (methyl) acrylate ester different monomers, it can reach soft or hard suitable, micro-gel surface will not be too hard or too soft；Adding more vinyl unsaturated compounds can allow microgel inside to form reticular structure as crosslinking agent, and overall structure is made more to stablize；Addition water soluble vinyl unsaturated compound can make microgel have certain hydrophily, when microgel is used in coating industry, can improve the adhesive force with coated base material.
Description
Technical field
The present invention relates to a kind of synthetic methods of microgel, belong to functional high polymer material field.
Background technology
Microgel belongs to functional high molecule material, belongs to micron-sized gel particle.In coating industry, painted improving
Film flow, durability and mechanical properties have significant advantage, have excellent processing performance and workability.It should be in the moon
When in the electrophoretic coating priming paint of pole, corrosion resistance is greatly improved；In building coating field, microgel compounds together with resin
It uses, fine and close film can be formed to prevent the infiltration of water point, moisture in capped concrete can also be made to extending out
It dissipates；It applies in such as laptop computer mobile phone when on the electronic product often with human contact, face coat can provide preferably
Acid-resisting and oil-resisting, particularly ethanol-tolerant solvent resistance, the in addition also scratch-resistant appearance for injuring high glaze high-leveling.
The preparation method of microgel is typically now：Inverse emulsion polymerization and the precipitation method, but both methods has one
Determine defect, for example inverse emulsion polymerization easily produces the unstable microgel of performance, and the precipitation method can not synthesize specific ruler
Very little microgel.
Invention content
Easily generation performance is unstable in order to solve the problems, such as above-mentioned microgel preparation by the present invention, provides a kind of microgel
Synthetic method.
To achieve the above object, the technical solution adopted by the present invention is：A kind of synthetic method of microgel, by below into
It is grouped as：
A. mono-vinyl unsaturated compounds, shared mass ratio >=85%, glass transition temperature Tg >=
100℃；
B. more vinyl unsaturated compounds, shared mass ratio≤7%；
C. water soluble vinyl unsaturated compound, shared mass ratio≤3%；
D. there is the vinyl unsaturated compound of functional group, shared mass ratio≤5%.
Prepared by present invention selection seeded emulsion polymerization, need to add surfactant, surfactant accounts for entire lotion weight
The 0.001%~10% of amount, surfactant can be cation, anion or non-ionic, and surfactant can be
Be not involved in response type or participate in response type.Such as anionic surfactant can be bay alcohol sulfuric ester
Sodium salt, cumene potassium participate in such as acrylic acid -2- sulfoethyl ester sodium salts of response type.
The present invention selects initiator used in seeded emulsion polymerization as azo, peroxide or persulfide
Class initiator.
Present invention selection microgel diameter is between 50~500nm, preferably 80~300nm.
The vinyl aromatic compounds optimization styrene class monomer that the present invention selects.
(methyl) alkyl-acrylates that the present invention selects are the compounds of similar (methyl) methyl acrylate.
(methyl) acrylate esters that the present invention selects are the compounds of similar (methyl) isobornyl acrylate.
More vinyl unsaturated compounds that the present invention selects, preferably two (methyl) acrylic ester monomers.
The water soluble vinyl unsaturated compound that the present invention selects refers to that mass ratio can be dissolved at 25 DEG C in water
7%, such as methacrylic acid.
The vinyl unsaturated compound with functional group that the present invention selects, refers to react with additional crosslink agent
Group, such as isocyanate-hydroxyl, acetoacetate-amine, amine-isocyanates, amine-epoxy, carboxylic acid-epoxy etc..
Advantages of the present invention：It selects based on mono-vinyl unsaturated compound, collocation vinyl aromatic monomers, (first
Base) three kinds of different monomers of methyl acrylate and (methyl) acrylate ester, it can reach soft or hard suitable, micro-gel surface
It will not be too hard or too soft；Adding more vinyl unsaturated compounds can allow microgel inside to form reticular structure as crosslinking agent,
Overall structure is made more to stablize；Addition water soluble vinyl unsaturated compound can make microgel have certain hydrophily, when
When microgel is used in coating industry, the adhesive force with coated base material can be improved.
Specific embodiment
Embodiment 1
By in the reaction bulb equipped with stirring, 20g dodecyl sodium sulfates are added in, add in the deionized water dissolving of 400mL.It rises
Temperature adds in vinyl compound, emulsifier mixture (300mL deionized waters, the 19g dodecyl sulphurs of each component to 50 DEG C
Sour sodium, 130g styrene, 350g methyl methacrylates, 57g isobornyl methacrylates, 9.5g methacrylic acids, 100g
Ethylene glycol monomethyl ether), it is emulsified 15 minutes after being added dropwise, persulfate aqueous solution is added dropwise, and (1.8g potassium peroxydisulfates are dissolved in 8mL deionizations
In water), it is 3 hours to cause polymerization time, 80 DEG C of constant temperature, the constant 300r/min of mixing speed.Cooled down after reaction
Drainage is washed, and obtains microgel.
Embodiment 2
By in the reaction bulb equipped with stirring, 20g lauryl sodium sulfate is added in, adds in the deionized water dissolving of 400mL.It rises
Temperature adds in vinyl compound, emulsifier mixture (300mL deionized waters, the 15g dodecyl sulphur of each component to 50 DEG C
Sour sodium, 125g styrene, 393g methyl methacrylates, 11g ethylene glycol dimethacrylates, 9.4g methacrylic acids,
100g ethylene glycol monomethyl ethers), it is emulsified 15 minutes after being added dropwise, persulfate aqueous solution is added dropwise, and (1.5g Ammonium Persulfate 98.5s are dissolved in 5mL and go
In ionized water), it is 2 hours to cause polymerization time, 80 DEG C of constant temperature, the constant 300r/min of mixing speed.It drops after reaction
Temperature filtering washing, obtains microgel.
Embodiment 3
By in the reaction bulb equipped with stirring, 13g lauric monoglycerides are added in, add in the deionized water dissolving of 400mL.It rises
Temperature is to 50 DEG C, and adding in vinyl compound, the emulsifier mixture of each component, (300mL deionized waters, 25g lauric acid lists are sweet
Grease, 130g styrene, 320g methyl methacrylates, 12g 2-EHAs, 55g isobornyl methacrylates,
10g methacrylic acids, 100g ethylene glycol monomethyl ethers), it is emulsified 15 minutes after being added dropwise, azo-bis-isobutyl cyanide aqueous solution was added dropwise
(2g crosses azo-bis-isobutyl cyanide in 10mL deionized waters), it is 2 hours to cause polymerization time, 80 DEG C of constant temperature, mixing speed
Constant 300r/min.Cooling filtering washing after reaction, obtains microgel.
Embodiment 4
By in the reaction bulb equipped with stirring, 30g methyl glycol fatty acid esters are added in, add in the deionized water dissolving of 400mL.It rises
Temperature adds in vinyl compound, emulsifier mixture (300mL deionized waters, the 10g propylene glycol fatties of each component to 50 DEG C
Acid esters, 130g styrene, 302g methyl methacrylates, 55g isobornyl methacrylates, 9.5g methacrylic acids, 11g second
Diol dimethacrylate, 100g ethylene glycol monomethyl ethers), it is emulsified 15 minutes after being added dropwise, it is molten that dibenzoyl peroxide is added dropwise
Liquid (2g dibenzoyl peroxides are dissolved in 10mL deionized waters), it is 5 hours to cause polymerization time, 90 DEG C of constant temperature, stirring
Constant airspeed 350r/min.Cooling filtering washing after reaction, obtains microgel.
Although embodiments of the present invention are illustrated in specification, these embodiments are intended only as prompting,
It should not limit protection scope of the present invention.It is equal that various omission, substitution, and alteration are carried out without departing from the spirit and scope of the present invention
It should include within the scope of the present invention.
Claims (7)
1. a kind of synthetic method of microgel, it is characterised in that：The microgel is prepared by following components：
A. mono-vinyl unsaturated compounds, shared mass ratio >=85%, glass transition temperature Tg >=100 DEG C；
B. more vinyl unsaturated compounds, shared mass ratio≤7%；
C. water soluble vinyl unsaturated compound, shared mass ratio≤3%；
D. there is the vinyl unsaturated compound of functional group, shared mass ratio≤5%.
2. the synthetic method of microgel according to claim 1, which is characterized in that the mono-vinyl class unsaturation
It is composed of the following components to close object：
A. vinyl aromatic compounds, shared mass ratio is between 10%~40%, glass transition temperature Tg >=100
℃；
B. (methyl) alkyl-acrylates, shared mass ratio is between 50%~80%, glass transition temperature Tg >=100
℃；
C. (methyl) acrylate esters, shared mass ratio is between 1%~20%, glass transition temperature Tg >=95
℃。
3. the synthetic method of microgel according to claim 1, it is characterised in that：More vinyl unsaturation chemical combination
Object is two (methyl) acrylic ester monomers.
4. the synthetic method of microgel according to claim 1, it is characterised in that：The water soluble vinyl is unsaturated
Compound refers to that mass ratio 10% and above monomer can be dissolved at 25 DEG C.
5. the synthetic method of microgel according to claim 1, it is characterised in that：The second with functional groups
Alkenyl unsaturated compound refers to the vinyl unsaturated compound containing epoxy group.
6. the synthetic method of microgel according to claim 1, it is characterised in that：The diameter of microgel is in 50~500nm
Between.
7. the synthetic method of microgel according to claim 1, it is characterised in that：It is obtained by seeded emulsion polymerization.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711397752.6A CN108129601A (en) | 2017-12-21 | 2017-12-21 | A kind of synthetic method of microgel |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711397752.6A CN108129601A (en) | 2017-12-21 | 2017-12-21 | A kind of synthetic method of microgel |
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| CN108129601A true CN108129601A (en) | 2018-06-08 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838370A (en) * | 2010-02-12 | 2010-09-22 | 长兴化学工业(中国)有限公司 | Aqueous concoction, aqueous polymer emulsion prepared from same and application thereof |
| CN102516446A (en) * | 2011-12-02 | 2012-06-27 | 佛山市南海高拓包装材料有限公司 | Aqueous acrylic resin, and preparation method and application thereof |
| CN105131172A (en) * | 2015-09-18 | 2015-12-09 | 四川绿创环阅环保科技有限公司 | Preparation method of water-based acrylate emulsion |
| CN105837757A (en) * | 2016-04-06 | 2016-08-10 | 北京金汇利应用化工制品有限公司 | Microgel aqueous acrylic acid shell-core resin emulsion and preparation method thereof |
-
2017
- 2017-12-21 CN CN201711397752.6A patent/CN108129601A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838370A (en) * | 2010-02-12 | 2010-09-22 | 长兴化学工业(中国)有限公司 | Aqueous concoction, aqueous polymer emulsion prepared from same and application thereof |
| CN102516446A (en) * | 2011-12-02 | 2012-06-27 | 佛山市南海高拓包装材料有限公司 | Aqueous acrylic resin, and preparation method and application thereof |
| CN105131172A (en) * | 2015-09-18 | 2015-12-09 | 四川绿创环阅环保科技有限公司 | Preparation method of water-based acrylate emulsion |
| CN105837757A (en) * | 2016-04-06 | 2016-08-10 | 北京金汇利应用化工制品有限公司 | Microgel aqueous acrylic acid shell-core resin emulsion and preparation method thereof |
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Application publication date: 20180608 |