CN110698583A - Environment-friendly reactive emulsifier acrylate soap-free emulsion and preparation method thereof - Google Patents
Environment-friendly reactive emulsifier acrylate soap-free emulsion and preparation method thereof Download PDFInfo
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- CN110698583A CN110698583A CN201911009270.8A CN201911009270A CN110698583A CN 110698583 A CN110698583 A CN 110698583A CN 201911009270 A CN201911009270 A CN 201911009270A CN 110698583 A CN110698583 A CN 110698583A
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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
- 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
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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
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
- C08F220/22—Esters containing halogen
Abstract
The invention discloses a preparation method of acrylate soap-free emulsion based on an environment-friendly reactive emulsifier, which comprises the following specific steps of firstly, sequentially adding a (methyl) acrylate main monomer and a functional monomer into an aqueous solution containing a part of the reactive emulsifier to obtain pre-emulsion, then sequentially adding a part of the pre-emulsion and a part of an initiator solution into a deionized water base solution containing a stabilizer and the rest of the reactive emulsifier, heating to 65-90 ℃, keeping the temperature for 5-30 min, simultaneously slowly adding the rest of the pre-emulsion and the initiator solution into the base solution for reaction for 1.5-8 h, keeping the temperature for 0.5-2.5 h, and then discharging; the dosage of each component is calculated according to the mass of the main monomer, wherein the dosage of the functional monomer is 0.1-50%, the total dosage of the reactive emulsifier is 1-20%, the dosage of the deionized water is 100-1000%, the dosage of the stabilizer is 0.01-10%, and the dosage of the initiator is 0.01-30%.
Description
Technical Field
The invention relates to an application of a reactive emulsifier in acrylate emulsion, in particular to an environment-friendly reactive emulsifier without phenol groups, belonging to the field of soap-free emulsion polymerization.
Background
Since the 30's of the 20 th century, polymer emulsions have been the focus of attention in both academic and industrial sectors. Polymer emulsions are traditionally used in the coatings, adhesives, inks, paper, leather, and other industries. Among the numerous polymerization processes, suspension dispersion and emulsion polymerization are the most widespread methods for preparing polymer particles of various sizes. The emulsion polymerization is a unique method for preparing nano-scale particle polymers, and has the advantages of simple operation, high polymerization rate, high molecular weight, high conversion rate and the like. Typical emulsion polymerization systems consist of water, monomers, surfactants (emulsifiers) and initiators. Generally, the polymerized monomers have low solubility in water and form a water-insoluble polymer during polymerization, whereby emulsification with surfactants is used in small amounts, but plays a crucial role in emulsion polymerization, the surfactants forming a large number of micelles in solution, whereas polymerization occurs mainly in the monomer-swollen micelles. Because the traditional surfactant does not participate in polymerization reaction, the traditional surfactant is attached to the surface of the polymer only in a physical adsorption mode and is finally carried into a product; the surface migration phenomenon can occur in the process of film forming and drying of the polymer, and the electrical property, the optical property, the surface property, the water resistance and the like of the emulsion polymer are influenced, so that the application of the emulsion polymer is limited. The soap-free emulsion has good monodispersity and clean surface, eliminates the influence of a low molecular weight surfactant on the performance of the emulsion, and improves the physical and chemical properties and the bonding property of a polymer coating film, particularly the water resistance and the solvent resistance, so that the soap-free emulsion has special application in many fields. Thus, studies on soap-free emulsion polymerization have been conducted around the inside and outside.
Currently, common soap-free emulsion polymerization methods are: initiator fragmentation, water-soluble monomer copolymerization, reactive emulsifier copolymerization, and ultrasonic emulsifier-free emulsion polymerization. The preparation method is characterized in that the lamivudine is prepared into the monodisperse PMMA microspheres by a soap-free emulsion polymerization method by using azobisisobutylamidine hydrochloride (AMPMDHC) as an initiator. The results show that: the more the initiator is used, the smaller the sphere diameter of the PMMA microsphere is, but the influence on the distribution of the sphere diameter of the microsphere is smaller. However, such systems generally give emulsions having a solids content of only about 10%. Tangguang and the like successfully prepare the soap-free acrylate emulsion with the solid content of up to 60 percent by adding hydrophilic polymerizable ionic monomer 3-allyloxy-2-hydroxy-sodium propanesulfonate (AHPS). The emulsion has low viscosity, obviously improved storage stability, water resistance and peel strength, but has larger particle size of emulsion particles, generally about 500nm compared with the conventional emulsion. In the general soap-free emulsion polymerization method, the emulsion product has low solid content or the emulsion particle size is too large, so the application of the soap-free emulsion polymerization method is limited to a certain extent. The reactive emulsifier copolymerization method is characterized in that a double bond capable of participating in polymerization is grafted on the traditional surfactant and is copolymerized to the surface of a polymer in a chemical bond mode, so that the adverse effects of migration and the like caused by independently adding an emulsifier are overcome, and the surface tension of the polymer is reduced, so that the stability and the solid content of the polymer emulsion are greatly improved. Xuwei ring, Li Shao Xiang uses allyloxy nonyl phenol polyoxyethylene ether ammonium sulfate (DNS-86), allyloxy nonyl phenol polyoxyethylene ether, etc. as reactive emulsifier, Butyl Acrylate (BA), styrene (St), Methyl Methacrylate (MMA) as monomer, and synthesizes acrylate soap-free emulsion by emulsion polymerization method. The results show that: when the allyloxy nonyl phenol polyoxyethylene ether ammonium sulfate (DNS-86) is used independently, the emulsion has the best performances, and when the content of the DNS-86 is 2.5-3%, the emulsion has good comprehensive performance. Along with the rapid development of economy in recent years, the international attention on environmental protection and reasonable resource application is higher and higher, and in order to respond to the requirement of domestic and foreign environmental protection, the invention provides an environmentally-friendly reactive emulsifier soap-free emulsion polymerization method without nonylphenyl phenol.
The technical problem to be solved is as follows: the invention synthesizes the acrylate soap-free emulsion by adopting a semicontinuous seed emulsion polymerization method through the environment-friendly reactive emulsifier, and solves the problems of low solid content, large latex particle size and the like of the common soap-free emulsion.
Technical scheme
The invention discloses a preparation method of an environment-friendly reactive emulsifier soap-free emulsion, which comprises the following polymerization processes:
firstly, sequentially adding a (methyl) acrylate main monomer and a functional monomer into an aqueous solution containing a part of reactive emulsifier to obtain a pre-emulsion, then sequentially adding a part of the pre-emulsion and a part of an initiator solution into a deionized water base solution containing a stabilizer and the rest of the reactive emulsifier, heating to 65-90 ℃, keeping the temperature for 5-30 min, simultaneously slowly adding the rest of the pre-emulsion and the initiator solution into the base solution, reacting for 1.5-8 h, keeping the temperature for 0.5-2.5 h, and then discharging;
the dosage of each component is calculated by the mass of the main monomer, wherein the dosage of the functional monomer is 0.1-50%, the total dosage of the reactive emulsifier is 1-20%, the total dosage of the deionized water is 100-1000%, the dosage of the stabilizer is 0.01-10%, and the total dosage of the initiator is 0.01-30%.
The (meth) acrylate main monomer is one or more of alkyl methacrylate, alkyl acrylate and fluorine-containing alkyl acrylate, wherein the number of carbon atoms of the alkyl is 1-22, and the number of fluorine atoms is 1-18.
The environment-friendly reactive emulsifier is one or more of SR-10, ER-10 and JS-20, and its state is liquid.
The functional monomer is one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, itaconic acid, monobutyl itaconate, maleic acid, glycidyl methacrylate, linoleic acid, trimethylolpropane triacrylate, diallyl phthalate, 2-dimethylaminoethyl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, N-methylolacrylamide, N-hydroxyethyl acrylamide and N-octadecylamide monomaleate.
The initiator is one or a mixture of more of ammonium persulfate, potassium persulfate, sodium persulfate, azodiisobutyronitrile and benzamide peroxide.
The stabilizer is Na2HPO4、Na2CO3、NaHCO3、Na2SO3、NaHSO3And one or a mixture of more of NaOH.
Advantageous effects
The invention discloses a reactive emulsifier for acrylate soap-free emulsion polymerization, which is characterized by comprising the following components in percentage by weight:
(1) compared with the traditional acrylate emulsion, the acrylate soap-free emulsion has no free migration phenomenon of the micromolecule emulsifier on the surface of the polymer, and improves the electrolyte resistance, the water resistance and the solvent resistance of the polymer film.
(2) The acrylate soap-free emulsion has the outstanding advantages of high solid content, small particle size, safety, environmental protection, high stability and the like, and expands the commercial application thereof.
Drawings
FIG. 1 is a schematic diagram of a reactive emulsifier structure.
Detailed Description
The preparation method of the environment-friendly reactive emulsifier acrylate soap-free emulsion comprises the following specific steps:
firstly, sequentially adding a (methyl) acrylate main monomer and a functional monomer into an aqueous solution containing a part of reactive emulsifier to obtain a pre-emulsion, then sequentially adding a part of the pre-emulsion and a part of an initiator solution into a deionized water base solution containing a stabilizer and the rest of the reactive emulsifier, heating to 65-90 ℃, then preserving heat for 5-30 min, simultaneously slowly adding the rest of the pre-emulsion and the initiator solution into the base solution for reaction for 1.5-8 h, preserving heat for 0.5-2.5 h, and then discharging;
the dosage of each component is calculated by the mass of the main monomer, wherein the dosage of the functional monomer is 0.1-50%, the total dosage of the reactive emulsifier is 1-20%, the total dosage of the deionized water is 100-1000%, the dosage of the stabilizer is 0.01-10%, and the total dosage of the initiator is 0.01-30%.
The effects of the present invention will be further illustrated by the following specific examples:
the embodiments are implemented on the premise of the technical scheme of the invention, and the technical means used is conventional means well known to those skilled in the art, and the technical scheme is not to be construed as limiting the invention.
Example 1
(1) Preparation of pre-emulsion: 43.55g of methyl methacrylate, 43.55g of butyl acrylate and 2g of monobutyl itaconate are weighed and mixed in a beaker at normal temperature; weighing 1.54g of a reactive emulsifier JS-20 and 40g of deionized water, placing the mixture in a 250ml three-neck flask with a stirring device, dropwise adding a mixed monomer into the flask at a constant speed when the reactive emulsifier JS-20 is fully dissolved in the water, and continuously stirring for 0.5h after the monomer is dropwise added to prepare a pre-emulsion for later use.
(2) Preparing a base solution: 0.77g of a reaction type emulsifier JS-20, 40g of deionized water and 0.2g of a stabilizer disodium hydrogen phosphate are weighed at normal temperature, mixed and placed in a four-neck flask with a mechanical stirring device, a condensation reflux device and a thermometer, and fully dissolved.
(3) Preparing a seed emulsion: weighing 0.45g of initiator ammonium persulfate to dissolve in 30g of deionized water for later use; and (3) placing the four-neck flask filled with the base solution into a water bath kettle, heating the four-neck flask in the water bath kettle, taking 10g of the pre-emulsion and 1/3 of the initiator solution when the reaction temperature reaches 75 ℃, simultaneously pouring the 10g of the pre-emulsion and the 1/3 of the initiator solution into the four-neck flask, and continuing heating and reacting.
(4) Polymerization reaction: and when the reaction temperature reaches 85 ℃, dropwise adding the rest pre-emulsion and the initiator solution at a constant speed, reacting for 4 hours, preserving the temperature for 1 hour, and discharging.
Example 2
(1) Preparation of pre-emulsion: weighing 42.65g of ethyl methacrylate, 42.65g of butyl acrylate and 2g of hydroxyethyl methacrylate at normal temperature, and mixing in a beaker; weighing 1.54g of a reactive emulsifier JS-20 and 40g of deionized water, placing the mixture in a 250ml three-neck flask with a stirring device, dropwise adding a mixed monomer into the flask at a constant speed when the reactive emulsifier JS-20 is fully dissolved in the water, and continuously stirring for 0.5h after the monomer is dropwise added to prepare a pre-emulsion for later use.
(2) Preparing a base solution: 0.77g of a reaction type emulsifier JS-20, 40g of deionized water and 0.2g of a stabilizer disodium hydrogen phosphate are weighed at normal temperature, mixed and placed in a four-neck flask with a mechanical stirring device, a condensation reflux device and a thermometer, and fully dissolved.
(3) Preparing a seed emulsion: weighing 0.45g of initiator ammonium persulfate to dissolve in 30g of deionized water for later use; and (3) placing the four-neck flask filled with the base solution into a water bath kettle, heating the four-neck flask in the water bath kettle, taking 10g of the pre-emulsion and 1/3 of the initiator solution when the reaction temperature reaches 75 ℃, simultaneously pouring the 10g of the pre-emulsion and the 1/3 of the initiator solution into the four-neck flask, and continuing heating and reacting.
(4) Polymerization reaction: and when the reaction temperature reaches 80 ℃, dropwise adding the rest pre-emulsion and the initiator solution at a constant speed, reacting for 5 hours, preserving the temperature for 1 hour, and discharging.
Example 3
(1) Preparation of pre-emulsion: weighing 41.75g g g of trifluoro ethyl acrylate, 41.75g of butyl acrylate and 2g of N-hydroxyethyl acrylamide at normal temperature, and mixing in a beaker; 3.0g of reactive emulsifier SR-10 and 40g of deionized water are weighed and placed in a 250ml three-neck flask with a stirring device, when the reactive emulsifier is fully dissolved in the water, mixed monomers are dropwise added into the flask at a constant speed, and the stirring is continued for 0.5h after the dropwise addition of the monomers is finished, so as to prepare the pre-emulsion for later use.
(2) Preparing a base solution: 1.5g of reactive emulsifier ER-10, 40g of deionized water and 0.2g of stabilizer disodium hydrogen phosphate are weighed at normal temperature, mixed and placed in a four-neck flask with a mechanical stirring device, a condensation reflux device and a thermometer, and fully dissolved.
(3) Preparing a seed emulsion: 0.45g of initiator ammonium persulfate is weighed and dissolved in 30g of deionized water for standby: and (3) placing the four-neck flask filled with the base solution into a water bath kettle, heating the four-neck flask in the water bath kettle, taking 10g of the pre-emulsion and 1/3 of the initiator solution when the reaction temperature reaches 75 ℃, simultaneously pouring the 10g of the pre-emulsion and the 1/3 of the initiator solution into the four-neck flask, and continuing heating and reacting.
(4) Polymerization reaction: and when the reaction temperature reaches 85 ℃, dropwise adding the rest pre-emulsion and the initiator solution at a constant speed, reacting for 4 hours, preserving the temperature for 1 hour, and discharging.
Example 4
(1) Preparation of pre-emulsion: weighing 42.65g of ethyl trifluoroacetate, 42.65g of butyl acrylate and 2g of triethylene glycol dimethacrylate and mixing in a beaker at normal temperature; 3.0g of reactive emulsifier SR-10 and 40g of deionized water are weighed and placed in a 250ml three-neck flask with a stirring device, when the reactive emulsifier is fully dissolved in the water, mixed monomers are dropwise added into the flask at a constant speed, and the stirring is continued for 0.5h after the dropwise addition of the monomers is finished, so as to prepare the pre-emulsion for later use.
(2) Preparing a base solution: 1.5g of reactive emulsifier SR-10, 40g of deionized water and 0.2g of stabilizer sodium bicarbonate are weighed at normal temperature, mixed and placed in a four-neck flask with mechanical stirring, condensation reflux and a thermometer, and fully dissolved.
(3) Preparing a seed emulsion: weighing 0.45g of initiator ammonium persulfate to dissolve in 30g of deionized water for later use; and (3) placing the four-neck flask filled with the base solution into a water bath kettle, heating the four-neck flask in the water bath kettle, taking 10g of the pre-emulsion and 1/3 of the initiator solution when the reaction temperature reaches 75 ℃, simultaneously pouring the 10g of the pre-emulsion and the 1/3 of the initiator solution into the four-neck flask, and continuing heating and reacting.
(4) Polymerization reaction: and when the reaction temperature reaches 85 ℃, dropwise adding the rest pre-emulsion and the initiator solution at a constant speed, reacting for 4 hours, preserving the temperature for 1 hour, and discharging.
Claims (6)
1. A preparation method of acrylate soap-free emulsion based on an environment-friendly reactive emulsifier is characterized by comprising the following steps of firstly, sequentially adding a (methyl) acrylate main monomer and a functional monomer into an aqueous solution containing a part of the reactive emulsifier to obtain pre-emulsion, then sequentially adding a part of the pre-emulsion and a part of an initiator solution into a deionized water base solution containing a stabilizer and the rest of the reactive emulsifier, heating to 65-90 ℃, keeping the temperature for 5-30 min, simultaneously slowly adding the rest of the pre-emulsion and the initiator solution into the base solution, reacting for 1.5-8 h, keeping the temperature for 0.5-2.5 h, and discharging;
the dosage of each component is calculated by the mass of the main monomer, wherein the dosage of the functional monomer is 0.1-50%, the total dosage of the reactive emulsifier is 1-20%, the total dosage of the deionized water is 100-1000%, the dosage of the stabilizer is 0.01-10%, and the total dosage of the initiator is 0.01-30%.
2. The method for preparing the acrylate soap-free emulsion according to claim 1, wherein: the (methyl) acrylate main monomer is one or more of alkyl methacrylate, alkyl acrylate and fluorine-containing alkyl acrylate, wherein the carbon number of the alkyl is 1-22, and the fluorine number is 1-18.
3. The method for preparing the acrylate soap-free emulsion according to claim 1, wherein: the environment-friendly reactive emulsifier is one or more of SR-10, ER-10 and JS-20, and the state of the emulsifier is liquid.
4. The method for preparing the acrylate soap-free emulsion according to claim 1, wherein: the functional monomer is one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, itaconic acid, monobutyl itaconate, maleic acid, glycidyl methacrylate, linoleic acid, trimethylolpropane triacrylate, diallyl phthalate, 2-dimethylaminoethyl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, N-methylolacrylamide, N-hydroxyethyl acrylamide and N-octadecylamide monomaleate.
5. The method for preparing the acrylate soap-free emulsion according to claim 1, wherein: the initiator is one or a mixture of more of ammonium persulfate, potassium persulfate, sodium persulfate, azodiisobutyronitrile and benzamide peroxide.
6. The method for preparing the acrylate soap-free emulsion according to claim 1, wherein: the stabilizer is Na2HPO4、Na2CO3、NaHCO3、NaHSO3、Na2SO3And one or a mixture of more of NaOH.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112279967A (en) * | 2020-10-29 | 2021-01-29 | 广东衡光新材料科技有限公司 | Preparation method of oleic acid modified soap-free acrylic emulsion |
| CN112321775A (en) * | 2020-12-02 | 2021-02-05 | 陕西科技大学 | Reactive polysiloxane modified polyacrylate soap-free emulsion and preparation method thereof |
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| CN103524669A (en) * | 2013-11-04 | 2014-01-22 | 常州天马集团有限公司（原建材二五三厂） | Acrylate emulsion and preparing method thereof |
| CN105949378A (en) * | 2016-05-17 | 2016-09-21 | 佛山市加恩新材料有限公司 | Water-based acrylic emulsion resin, water-based coating emulsion and preparation method |
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2019
- 2019-10-21 CN CN201911009270.8A patent/CN110698583A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524669A (en) * | 2013-11-04 | 2014-01-22 | 常州天马集团有限公司（原建材二五三厂） | Acrylate emulsion and preparing method thereof |
| CN105949378A (en) * | 2016-05-17 | 2016-09-21 | 佛山市加恩新材料有限公司 | Water-based acrylic emulsion resin, water-based coating emulsion and preparation method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112279967A (en) * | 2020-10-29 | 2021-01-29 | 广东衡光新材料科技有限公司 | Preparation method of oleic acid modified soap-free acrylic emulsion |
| CN112321775A (en) * | 2020-12-02 | 2021-02-05 | 陕西科技大学 | Reactive polysiloxane modified polyacrylate soap-free emulsion and preparation method thereof |
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Application publication date: 20200117 |