CN106674410A - Preparation method of polyvinyl acetate water dispersion - Google Patents
Preparation method of polyvinyl acetate water dispersion Download PDFInfo
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- CN106674410A CN106674410A CN201710015897.9A CN201710015897A CN106674410A CN 106674410 A CN106674410 A CN 106674410A CN 201710015897 A CN201710015897 A CN 201710015897A CN 106674410 A CN106674410 A CN 106674410A
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- polyvinyl acetate
- sodium
- methyl
- aqueous dispersion
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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
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Medicinal Preparation (AREA)
Abstract
The invention relates to a preparation method of a polyvinyl acetate water dispersion. The polyvinyl acetate water dispersion is prepared by carrying out free-radical polymerization on vinyl acetate in a surfactant-protective agent system in the presence of sodium (methyl) acrylate or a sodium (methyl) acrylate-(methyl) acrylic acid mixture. The amount of the sodium (methyl) acrylate or the amount of the sodium (methyl) acrylate-(methyl) acrylic acid mixture does not exceed 10% of the total amount of the vinyl acetate monomer. The polyvinyl acetate water dispersion prepared by the method has the advantages of small particle size and high storage stability, and can be used as a material for preparations.
Description
Technical field
The present invention relates to macromolecule material preparation area, and in particular to a kind of preparation side of polyvinyl acetate ester aqueous dispersion
Method.
Background technology
Polyvinyl acetate is a kind of common macromolecular material, with relatively low vitrification point, good film-forming property, clothing film
Slow releasing function do not affected by medium pH, with fabulous pliability, be commonly used for moistureproof taste masking and the sustained release coating of solid preparation
Material, is mainly used in the fields such as medicine, health product.
Polymer powders redispersible or polymer beads are refer in the 532A of DE 197 09 is used for drug coating
Purposes, wherein powder or granule comprising 10-95 weight % polyvinyl acetate and 5-90 weight % containing N- vinylpyridines
The polymer of pyrrolidone and suitable other additives.
Liu Yu et al. in the medicine of Anhui《The preparation of metformin hydrochloride osmotic pump preparation and the research of Release infactor》
In mention achievable stable zero that metformin hydrochloride osmotic pump controlled release tablet is obtained with polyvinyl acetate ester aqueous dispersion coating
Level release.
Wang Fang et al. in polymer material science and engineering《Polyvinyl acetate nano emulsion intercalation method》Document
Mentioning can be had using sodium lauryl sulphate (SDS)/octyl phenyl polyoxyethylene ether (OP-10) complexed surfactant system
Effect improves the bin stability and Calcium ion stability of vinylacetate nanoemulsions, but surfactant usage amount is too high,
When as coating material, internal release and effect performance of medicine is have impact on.
A kind of polyvinyl acetate with high shear stability is mentioned in BASF European Co., Ltd patent CN 101253225A
Ester aqueous dispersion, the method is prepared with vinyl acetate radical polymerization by acrylic or methacrylic acid or its mixture
Aqueous polymer dispersion with good shear stability, but, the preparation method has only used anion surfactant, in reality
Border easily produces precipitation during preparing, while the less stable of storage.
The content of the invention
The invention discloses a kind of method for preparing polyvinyl acetate ester aqueous dispersion, the poly-vinegar acid that the inventive method is obtained
Ethylene ester aqueous dispersion, particle diameter is little, stable storing, can make formulating materials.
The technical solution used in the present invention is as follows：
A kind of preparation method of polyvinyl acetate ester aqueous dispersion, it is characterised in that：By a certain amount of water, surface activity
Agent, protective agent, initiator, (methyl) sodium acrylate or (methyl) sodium acrylate and (methyl) acrylic acid mixture, input reaction
In container, stir 30-40 minutes at 75~80 DEG C, under keeping warm mode, be slowly added dropwise Vinyl Acetate Monomer, carry out free radical
Polymerization be obtained, described surfactant be by anionic surfactant and nonionic surfactant by a certain percentage
It is obtained by mixing, the mixing quality ratio of the two is (1-5)：(5-1) quality of, described (methyl) sodium acrylate is less than acetic acid second
The quality of the 10% of allyl ester monomer gross mass, (methyl) sodium acrylate and (methyl) acrylic acid mixture is less than acetic acid second
The 10% of allyl ester monomer gross mass.
Described anion surfactant selected from dodecyl sodium sulfate, benzene sulfonic acid sodium salt, sodium laurate, sodium sorbate,
One or more mixing in sodium alkyl sulfonate, described anionic surfactant accounts for Vinyl Acetate Monomer gross mass
0.6~2% (w/w).
Described nonionic surfactant is selected from OPEO, tween, NPE, fat
One or more mixing in fat polyoxyethylenated alcohol, described nonionic surfactant accounts for the total matter of Vinyl Acetate Monomer
0.6~2% (w/w) of amount.
One or more in polyvinyl alcohol, polyvinylpyrrolidone, the hydroxypropyl methylcellulose of the protective agent is mixed
Close, protective agent consumption is 0.5~5% (w/w) of monomer total amount.
Described initiator selected from azodiisobutyronitrile, benzoyl peroxide, sodium peroxydisulfate, Ammonium persulfate., potassium peroxydisulfate,
One or more mixing in azo-bis-iso-dimethyl；Initiator amount is 0.5~1% (w/w) of monomer total amount.
In terms of polyvinyl acetate solid, the solid content of the polyvinyl acetate ester aqueous dispersion is 20~35%.
Described surfactant is dodecyl sodium sulfate and the mixture of OPEO, the mixing of the two
Mass ratio is 1:1, total amount is monomer total amount 2% (w/w).
The vinylacetate feed way is semi-continuous charging, is added in 1-5h, preferably 2-3h.
The mean diameter of the dispersion particle is 100~500nm, preferably 200~300nm.
The technical problem underlying that the present invention is solved is, with vinylacetate as raw material, through one-step polymerization dispersion poly-vinegar to be obtained
Vinyl acetate aqueous dispersion.
Beneficial effects of the present invention：
1st, anion surfactant and non-ionic surfactant mixture be present invention employs, it is to avoid single type
The defect of surfactant, improves the stability of emulsifying systems, it is ensured that dispersibility of the vinylacetate in the decorum, and
Precipitation is not produced in polymerization process, and storage stability is high.Meanwhile, present invention employs a small amount of (methyl) acrylates and vinegar
Vinyl acetate copolymerization so that the product aqueous dispersion narrow diameter distribution obtained by polymerization, slow release and taste masking performance are high.
2nd, this method allows the emulsifying agent of addition as dispersing aid using pharmacopeia, and additive dosage is less, reduces work
For the application risk of pharmaceutic adjuvant.
3rd, only has a small amount of waste water in this method production process, production technology is environmentally friendly.
4th, method of the present invention reaction condition is relatively mild, simple to operate, is suitable to industrialized production.
In a word, the present invention is deposited by a certain percentage in anion surfactant and nonionic surfactant with protective agent
In aqueous polymer dispersion prepared by the lower radical polymerization by vinylacetate, by the combination matching of various different auxiliary agents
The scattered effect of one-step polymerization is reached, production process is greatly simplify, the polyvinyl acetate ester aqueous dispersion that this method is obtained,
Particle diameter is little, and the mean diameter of the dispersion particle is 200~300nm, and stable storing can make formulating materials.
Specific embodiment
The present invention is further explained below by specific embodiment, they are understood not to limit this by any way
The scope of invention.
Embodiment 1
Weigh 140g purified water, 0.6g dodecyl sodium sulfates, 0.6g OPEOs, 1.8g polyvinyl pyrroles
Alkanone, 0.54g azodiisobutyronitriles, 1.2g Sodium methacrylate .s are added in there-necked flask, are placed in 80 DEG C of heating in water bath stirrings
0.5h.60g vinylacetates are added and is slowly added dropwise to there-necked flask in constant pressure funnel, continue to react after being added dropwise to complete
2h, then cooling obtains polyvinyl acetate ester aqueous dispersion.Testing result is as follows：
| Detection project | Standard specifies | Testing result |
| Solid content | 20-35% | 29.5% |
| Viscosity | Less than 100mpas | 45mpa·s |
| Vinyl Acetate Monomer | Less than 100ppm | Conformance with standard |
| Particle diameter | 100-500nm | 242nm |
Embodiment 2
Weigh 140g purified water, 0.6g benzene sulfonic acid sodium salts, 1.8g tweens, 1.8g polyvinylpyrrolidones, 0.6g azos two different
Butanoic acid dimethyl ester, 0.45g Sodium methacrylate .s are added in there-necked flask, are placed in 75 DEG C of heating in water bath stirring 0.5h.By 15g acetic acid
Vinyl acetate adds there-necked flask reaction 0.5h, then adds remaining 45g vinylacetates and slowly drips in constant pressure funnel
Add in there-necked flask, continue to react 2h after being added dropwise to complete, then cooling obtains polyvinyl acetate ester aqueous dispersion.Detection knot
Fruit is as follows：
| Detection project | Standard specifies | Testing result |
| Solid content | 20-35% | 30.8% |
| Viscosity | Less than 100mpas | 68mpa·s |
| Vinyl Acetate Monomer | Less than 100ppm | Conformance with standard |
| Particle diameter | 100-500nm | 278nm |
Embodiment 3
Weigh 120g purified water, 1.6g sodium lauryl sulphates, 0.4g NPEs, 0.6g polyvinyl alcohol,
0.3g sodium peroxydisulfates, 0.9g sodium acrylate are added in there-necked flask, are placed in 75 DEG C of heating in water bath stirring 0.5h.By 60g acetic acid second
Alkene ester is added and is slowly added dropwise to there-necked flask in constant pressure funnel, and 20g purified water and 0.3g are added to there-necked flask after 0.5h
Ammonium persulfate solution, continues Deca vinylacetate, continues to react 2h after being added dropwise to complete, and then cooling obtains polyvinyl acetate
Aqueous dispersion.Testing result is as follows：
| Detection project | Standard specifies | Testing result |
| Solid content | 20-35% | 30.5% |
| Viscosity | Less than 100mpas | 24mpa·s |
| Vinyl Acetate Monomer | Less than 100ppm | Conformance with standard |
| Particle diameter | 100-500nm | 156nm |
Embodiment 4
Weigh 140g purified water, 0.4g sodium laurates, 2.0g fatty alcohol-polyoxyethylene ether, 0.9g hydroxypropyl methylcellulose,
0.6g benzoyl peroxides, 1.8g acrylic acid and sodium acrylate mixture are added in there-necked flask, are placed in 75 DEG C of heating in water bath and are stirred
Mix 0.5h.30g vinylacetates are added to there-necked flask, 1h is reacted, then 30g acetic acid second is slowly added dropwise with constant pressure funnel
Alkene ester, continues to react 1h, then cooling discharge after being added dropwise to complete, and static a period of time occurs precipitation, and aqueous dispersion system is not
It is stable.Testing result is as follows：
Embodiment 5
Weigh 140g purified water, 0.9g sodium sorbates, 0.3g OPEOs, 1.8g polyvinylpyrrolidones,
0.54g azodiisobutyronitriles, 0.6g sodium acrylate are added in there-necked flask, are placed in 75 DEG C of heating in water bath stirring 0.5h.By 60g vinegar
Vinyl acetate is added and is slowly added dropwise to there-necked flask in constant pressure funnel, continues to react 2h after being added dropwise to complete, and is then lowered the temperature
Obtain polyvinyl acetate ester aqueous dispersion.Testing result is as follows：
| Detection project | Standard specifies | Testing result |
| Solid content | 20-35% | 27.5% |
| Viscosity | Less than 100mpas | 32mpa·s |
| Vinyl Acetate Monomer | Less than 100ppm | Conformance with standard |
| Particle diameter | 100-500nm | 214nm |
Embodiment 6
Weigh 140g purified water, 0.9g sodium alkyl sulfonates, 0.3g OPEOs, 0.8g polyvinyl alcohol, 0.3g
Methacrylic acid and 0.3g Sodium methacrylate .s are added in there-necked flask, are placed in 75 DEG C of heating in water bath stirring 0.5h.Add 0.6g
Azodiisobutyronitrile, then 60g vinylacetates are added be slowly added dropwise to there-necked flask in constant pressure funnel, wait to drip
Continue to react 2h into rear, then cooling obtains polyvinyl acetate ester aqueous dispersion.Testing result is as follows：
Claims (7)
1. a kind of preparation method of polyvinyl acetate ester aqueous dispersion, it is characterised in that：By a certain amount of water, surfactant,
Protective agent, initiator,（Methyl）Sodium acrylate or（Methyl）Sodium acrylate and（Methyl）Acrylic acid mixture, puts into reaction vessel
In, stir 30-40 minutes at 75~80 DEG C, under keeping warm mode, Vinyl Acetate Monomer is slowly added dropwise, carry out radical polymerization
It is obtained, described surfactant is mixed by a certain percentage by anionic surfactant and nonionic surfactant
And obtain, the mixing quality ratio of the two is（1-5）：（5-1）, it is described（Methyl）The quality of sodium acrylate is less than vinylacetate
The 10% of monomer gross mass, it is described（Methyl）Sodium acrylate and（Methyl）The quality of acrylic acid mixture is less than vinylacetate
The 10% of monomer gross mass.
2. the preparation method of polyvinyl acetate ester aqueous dispersion according to claim 1, it is characterised in that：
Described anion surfactant is selected from dodecyl sodium sulfate, benzene sulfonic acid sodium salt, sodium laurate, sodium sorbate, alkyl
One or more mixing in sodium sulfonate, described anionic surfactant accounts for the 0.6 of Vinyl Acetate Monomer gross mass
~2%（w/w）.
3. the preparation method of polyvinyl acetate ester aqueous dispersion according to claim 1, it is characterised in that：
Described nonionic surfactant is selected from OPEO, tween, NPE, fatty alcohol
One or more mixing in polyoxyethylene ether, described nonionic surfactant accounts for Vinyl Acetate Monomer gross mass
0.6~2%（w/w）.
4. the preparation method of polyvinyl acetate ester aqueous dispersion according to claim 1, it is characterised in that：
One or more mixing of the protective agent in polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl methylcellulose, protects
Shield agent consumption is the 0.5~5% of monomer total amount（w/w）.
5. the preparation method of polyvinyl acetate ester aqueous dispersion according to claim 1, it is characterised in that：Described initiation
Agent is selected from azodiisobutyronitrile, benzoyl peroxide, sodium peroxydisulfate, Ammonium persulfate., potassium peroxydisulfate, azo-bis-iso-dimethyl
In one or more mixing；Initiator amount is the 0.5~1% of monomer total amount（w/w）.
6. the preparation method of polyvinyl acetate ester aqueous dispersion according to claim 1, it is characterised in that：
In terms of polyvinyl acetate solid, the solid content of the polyvinyl acetate ester aqueous dispersion is 20~35%.
7. the preparation method of polyvinyl acetate ester aqueous dispersion according to claim 1, it is characterised in that：
Described surfactant is dodecyl sodium sulfate and the mixture of OPEO, the mixing quality of the two
Than for 1:1, total amount is monomer total amount 2%（w/w）.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710015897.9A CN106674410A (en) | 2017-01-10 | 2017-01-10 | Preparation method of polyvinyl acetate water dispersion |
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| CN201710015897.9A CN106674410A (en) | 2017-01-10 | 2017-01-10 | Preparation method of polyvinyl acetate water dispersion |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101253225A (en) * | 2005-09-02 | 2008-08-27 | 巴斯夫欧洲公司 | Aqueous polyvinyl acetate dispersions having high shearing stability |
| CN104892821A (en) * | 2015-05-27 | 2015-09-09 | 合肥卓元科技服务有限公司 | Preparation method of vinyl acetate-vinyl versatate copolymer emulsion |
-
2017
- 2017-01-10 CN CN201710015897.9A patent/CN106674410A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101253225A (en) * | 2005-09-02 | 2008-08-27 | 巴斯夫欧洲公司 | Aqueous polyvinyl acetate dispersions having high shearing stability |
| CN104892821A (en) * | 2015-05-27 | 2015-09-09 | 合肥卓元科技服务有限公司 | Preparation method of vinyl acetate-vinyl versatate copolymer emulsion |
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Application publication date: 20170517 |
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