CN105622831A - Preparation method of acrylic acid organic silicon soap-free copolymerization emulsion - Google Patents
Preparation method of acrylic acid organic silicon soap-free copolymerization emulsion Download PDFInfo
- Publication number
- CN105622831A CN105622831A CN201610058775.3A CN201610058775A CN105622831A CN 105622831 A CN105622831 A CN 105622831A CN 201610058775 A CN201610058775 A CN 201610058775A CN 105622831 A CN105622831 A CN 105622831A
- Authority
- CN
- China
- Prior art keywords
- emulsion
- soap
- acrylic acid
- weight
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Abstract
The invention discloses a preparation method of acrylic acid organic silicon soap-free copolymerization emulsion. Unsaturated monomers, organic silicon, a reactive emulsifier, an initiator and water are adopted as raw materials, temperature of a reaction kettle is controlled by virtue of core-shell polymerization and soap-free polymerization technologies, then treatment is carried out for removing residual monomers, and a neutralizing agent is added for neutralization, so that emulsion is obtained. By virtue of the soap-free polymerization technology, better water white resistance can be realized with less expensive organic silicon monomer, and water absorption of a paint film is reduced. By virtue of the core-shell polymerization technology, a core layer with high glass transition temperature and a shell layer with lower glass transition temperature are obtained, so that synthetic emulsion has lower film formation temperature under the condition that the average glass transition temperature is the same with a homopolymerization technology, usage amount of a coalescing agent is reduced, and influence of solvent volatilization on atmospheric environment is reduced. The acrylic acid organic silicon soap-free copolymerization emulsion product does not contain a free emulsifying agent, so that influence of the acrylic acid organic silicon soap-free copolymerization emulsion product on the environment is greatly reduced, and the acrylic acid organic silicon soap-free copolymerization emulsion product is environmentally friendly; and the acrylic acid organic silicon soap-free copolymerization emulsion has excellent weather resistance, water resistance and pollution resistance.
Description
Technical field
The preparation method that the present invention relates to a kind of polymer emulsion, particularly relates to a kind of acrylic acid organosilicon preparation method without soap copolymer emulsion.
Background technology
The research and development of emulsion polymerization technology originate in early stage in last century, and the emulsion polymerization technology just existing similar with current factory formula the latter stage twenties occurs. Emulsion is polymerized more perfect definition and is regarded as: emulsion polymerization be with water or other liquid as in the emulsion of medium, generate emulsion particle isolated each other by micelle mechanism or oligomer mechanism, and carry out radical addition polymerization wherein or ion addition polymerization produces a kind of polymerization of high polymer.
Emulsion is polymerized the main feature produced: 1) polymerization speed is fast, and molecular weight is high; 2) with water for medium, cost is low, and reaction system viscosity is little, excellent in stability, and reaction heat is easily derived, and can operate continuously; 3) latex product can directly as coating and binding agent, and powder particles is little, is suitable for some Special use occasion; 4) owing to using emulsifying agent, polymer is impure, and post processing is complicated, and cost is high.
Soap-free polymerization refers to be not added with emulsifying agent or add trace emulsifying agent (lower than CMC concentration value) or adopt the emulsion polymerization process of reactive emulsifier. Technique is that emulsion is polymerized the difficult problem mainly captured in recent years, owing to common emulsion polymerization uses emulsifying agent, causes that the purity of polymer finally given is on the low side, causes that the compactness of polymeric film lowers significantly, polymer performance has obvious reduction.
Summary of the invention
It is an object of the invention to the deficiency overcoming prior art to exist, there is provided a kind of have relatively low surface can, the acrylic acid organosilicon of excellent adhesive force, excellent water-fast and weather resistance without the preparation method of soap copolymer emulsion, the polymer emulsion of preparation can be applicable to the fields such as outer wall building coating, water-in-water multicolor coating and thermal insulation coatings.
The purpose of the present invention is achieved through the following technical solutions:
Acrylic acid organosilicon is without the preparation method of soap copolymer emulsion, it is characterized as being: employing raw material is unsaturated monomer, organosilicon, reactive emulsifier, initiator and water, by hud polymerization, soap-free polymerization technique, control temperature of reaction kettle, residual monomer is removed again through aftertreatment technology, and add nertralizer neutralization, prepare acrylic acid organosilicon without soap copolymer emulsion.
Further, above-mentioned acrylic acid organosilicon, without the preparation method of soap copolymer emulsion, comprises the following steps:
1) in pre-emulsification tank, addition 240��270 weight parts waters, 15��20 weight portion reactive emulsifiers, 3��5 parts by weight propylene amide carry out dispersion and emulsion, it is then slowly added into 80��260 parts by weight of methylmethacrylate, 110��180 parts by weight propylene acid butyl esters, 80��240 different monooctyl esters of parts by weight of acrylic acid, 1��4 weight parts of methacrylic acid, prepares stratum nucleare pre-emulsion;
2) in emulsion tank, add 220��260 weight parts waters, 10��15 weight portion reactive emulsifiers, 5��8 weight portion N-[2-(2-methyl-4-oxopentyl)s, 300��400 different monooctyl esters of parts by weight of acrylic acid, 150��300 parts by weight of methylmethacrylate, 2��5 weight parts of methacrylic acid, 10��30 weight portion organic silicon monomers, prepare shell pre-emulsion;
3) in reactor, 300��330 parts by weight of deionized water, 2��5 weight portion reactive emulsifiers are added, heating is to 82��84 DEG C, again by the step 1 of 1��5% weight portion) prepared by stratum nucleare pre-emulsion and initiator solution put in reactor, keep reaction temperature at 84��86 DEG C, react 10��20 minutes, prepare seed emulsion;
4) dropping step 1) prepared by stratum nucleare pre-emulsion to reactor, keep temperature of reaction kettle be 85��87 DEG C, prepare stratum nucleare emulsion;
5) drip step 2 again) prepared by shell pre-emulsion to reactor, the temperature keeping reactor is 85��87 DEG C, after being added dropwise to complete, continues insulation 1��2 hour;
6) temperature of reaction kettle is down to 65��70 DEG C, is subsequently adding 1.1��1.5 weight portion H2O2With 0.7��1.3 weight portion reducing agent, be incubated 30��60 minutes, eliminate residual demonomerization;
7) emulsion temperature in reactor is down to less than 40 DEG C, it is subsequently adding 6��8 weight portion pH value regulators, 0.5��1.5 weight portion defoamer, 0.5��2 weight portion antibacterial, 2��5 parts by weight of crosslinking agent, finally it is filtered, it is thus achieved that acrylic acid organosilicon is without soap copolymer emulsion.
Further, above-mentioned acrylic acid organosilicon is without the preparation method of soap copolymer emulsion, wherein, described reactive emulsifier is one or more in allyl alkyl ether alcohol sulfate SR-1025, Methacrylamide isopropyl sulfonic acid AMPS-2404, allyl alkyl sulfosuccinate ester salt M-12S, 1-propenyloxy group 2-hydroxypropanesulfonic acid sodium UCAN-1, sodium vinyl sulfonate SVS.
Further, above-mentioned acrylic acid organosilicon is without the preparation method of soap copolymer emulsion, wherein, and step 2) in, described organic silicon monomer is one or several in A-174, A-171, A-151 silane coupler.
Further, above-mentioned acrylic acid organosilicon is without the preparation method of soap copolymer emulsion, wherein, and step 3) in, described initiator solution is one or more in Ammonium persulfate., sodium peroxydisulfate, potassium peroxydisulfate.
Further, above-mentioned acrylic acid organosilicon is without the preparation method of soap copolymer emulsion, and wherein, the addition of described initiator solution is 40��60 weight portions.
Further, above-mentioned acrylic acid organosilicon is without the preparation method of soap copolymer emulsion, wherein, and step 4) in, time for adding controls at 1.5��2.5 hours, after being added dropwise to complete, is incubated 10��15 minutes in 85��87 DEG C.
Further, above-mentioned acrylic acid organosilicon is without the preparation method of soap copolymer emulsion, wherein, and step 5) in, time for adding controls at 1��1.5 hour, after being added dropwise to complete, is incubated 1��2 hour in 86��88 DEG C.
Yet further, above-mentioned acrylic acid organosilicon is without the preparation method of soap copolymer emulsion, wherein, and step 6) in, described reducing agent is the emulsion polymerization novel reducer FF of sodium formaldehyde sulfoxylate, vitamin C, Brueggemann company of Germany6In one or several.
Yet further, above-mentioned acrylic acid organosilicon is without the preparation method of soap copolymer emulsion, wherein, step 7) in, described pH value regulator is one or more in AMP-95PH regulator, ammonia, ethanolamine, described defoamer is one or more in WBA defoamer, 681F defoamer, NXZ defoamer, described antibacterial is one or more in Kazon antibacterial, DE-109 antibacterial, D7-10 antibacterial, and described cross-linking agent is one or more in adipic dihydrazide, triethanolamine, isoniazid.
Substantive distinguishing features and significant progress that technical solution of the present invention is prominent are mainly reflected in:
1. the technique such as emulsifier-free emulsion polymerization, core-shell emulsion polymerization is utilized to prepare, multiple insatiable hunger conjunction monomer, organic silicon monomer, reactive emulsifier, initiator is adopted to make, especially with soap-free polymerization technique, make the emulsion made does not contain free emulsifying agent, the very high purity of film, greatly improves product resistance to water, and the polymer performance obtained is not affected by emulsifying agent, the organic silicon monomer using less costliness can realize good water-whitening resistance, reduces the water absorption rate of paint film.
2. have employed hud polymerization technique, obtain the shell that the higher stratum nucleare of vitrification point, vitrification point are relatively low, when making the average glass transition temperature identical with equal polymerizing technology, the emulsion synthesized has less film-forming temperature, reduce the consumption of coalescents, reduce the solvent volatilization impact on atmospheric environment.
3. owing to product not containing free emulsifying agent, make product be substantially reduced for the impact of environment, belong to environmentally friendly product. There is extraordinary weatherability, resistance to water and antifouling property, not easy to leak, do not break, can be applicable to the fields such as outer wall building coating, water-repellent paint, heat insulation coating, meet the multiple requirement such as insulation, energy-conservation, decoration.
Detailed description of the invention
The present invention takes to use reactive emulsifier, the emulsifying agent containing alkene key in the course of the polymerization process can form micelle by emulsified monomer, ensure being normally carried out of emulsion polymerization, the alkene key that it contains can participate in again polymerization, it is grafted on the group of acrylic monomers, it is ensured that final polymer does not contain free emulsifying agent; Additionally acrylic ester monomer and the organic silicon monomer containing double bond are also taked the mode of hud polymerization by the present invention, by in whole for organic silicon monomer graft copolymerizations to the shell of acrylic resin, greatly improve the silicone content on acrylic resin surface, have the excellent weatherability of acrylic resin and the adhesion of base material and the gloss retention of organic siliconresin and UV resistant performance simultaneously concurrently.
Employing raw material is unsaturated monomer, organosilicon, reactive emulsifier, potassium peroxydisulfate and water, by hud polymerization, soap-free polymerization technique, control temperature of reaction kettle, then pass through aftertreatment technology and remove residual monomer, and add nertralizer neutralization, obtain the acrylic acid organosilicon of relatively low film-forming temperature and water resistance excellence without soap copolymer emulsion.
Embodiment 1:
Pre-emulsification tank (A) adds 120kg deionized water, 10.8kg allyl alkyl ether alcohol sulfate SR-1025,2kg acrylamide, be subsequently adding 2.4kg methacrylic acid (AA), 55kg butyl acrylate (BA), 130kg methyl methacrylate (MMA) carry out high speed dispersion, prepare pre-emulsion A.
Emulsion tank (B) adds 48.5kg deionized water, 2.34kg allyl alkyl ether alcohol sulfate SR-1025,1.04kg Methacrylamide isopropyl sulfonic acid AMPS-2404,1.2kg N-[2-(2-methyl-4-oxopentyl) (DAAM), 72.1kg Isooctyl acrylate monomer (2-EHA), 31.2kg methyl methacrylate (MMA), 0.78 methacrylic acid, 5.72kg ��-methacryloxypropyl trimethoxy silane (A-174), prepares shell pre-emulsion (B).
Add 304.2kg deionized water, 4.2kgSR-1025 in a kettle., it is then heated to 82��84 DEG C, ready 12.5kg pre-emulsion (A) and 0.44kg initiator potassium persulfate (KPS)+8.3kg deionized water solution are joined in reactor, keep reaction temperature at 84��86 DEG C, course of reaction controls at 10 minutes, prepares seed emulsion.
Dropping stratum nucleare pre-emulsion (A), to reactor, continues to ensure the temperature 85��87 DEG C of reactor, and dropping controlled at 2 hours. After being added dropwise to complete, it is incubated 10 minutes in 85��87 DEG C.
Dropping shell pre-emulsion (B), to reactor, continues to ensure the temperature 85��86 DEG C of reactor, and dropping controlled at 1 hour. After being added dropwise to complete, continue insulation 1 hour in 86��88 DEG C.
Cool the temperature to 65��70 DEG C, be subsequently adding 0.78kgH2O2And 0.55kgFF6, it is incubated 30 minutes, eliminates residual demonomerization.
Adopt circulating water cooling to 40 DEG C, be subsequently adding 6.5kgPH regulator (AMP-95), 0.6kgWBA defoamer, 0.8kg Kazon antibacterial, 3.3kg adipic dihydrazide, be then filtered, it is thus achieved that acrylic acid organosilicon is without soap copolymer emulsion.
Embodiment 2:
Pre-emulsification tank (A) adds 120kg deionized water, 10.8kg allyl alkyl ether alcohol sulfate SR-1025,2kg acrylamide, be subsequently adding 2.4kg methacrylic acid (AA), 55kg butyl acrylate (BA), 130kg methyl methacrylate (MMA) carry out high speed dispersion, prepare pre-emulsion A.
Emulsion tank (B) adds 48.5kg deionized water, 2.34kg allyl alkyl ether alcohol sulfate SR-1025,1.04kg Methacrylamide isopropyl sulfonic acid AMPS-2404,1.2kg N-[2-(2-methyl-4-oxopentyl) (DAAM), 72.1kg Isooctyl acrylate monomer (2-EHA), 31.2kg methyl methacrylate (MMA), 0.78 methacrylic acid, 5.72kg vinyltrimethoxy silane (A-171), prepares shell pre-emulsion (B).
Add 304.2kg deionized water, 4.2kgSR-1025 in a kettle., it is then heated to 82��84 DEG C, ready 12.5kg pre-emulsion (A) and 0.44kg initiator potassium persulfate (KPS)+8.3kg deionized water solution are joined in reactor, keep reaction temperature at 84��86 DEG C, course of reaction controls at 20 minutes, prepares seed emulsion.
Dropping stratum nucleare pre-emulsion (A), to reactor, continues to ensure the temperature 85��87 DEG C of reactor, and dropping controlled at 2 hours. After being added dropwise to complete, it is incubated 15 minutes in 85��87 DEG C.
Dropping shell pre-emulsion (B), to reactor, continues to ensure the temperature 85��86 DEG C of reactor, and dropping controlled at 1 hour. After being added dropwise to complete, continue insulation 1 hour in 86��88 DEG C.
Cool the temperature to 65��70 DEG C, be subsequently adding 0.78kgH2O2And 0.55kgFF6, it is incubated 30 minutes, eliminates residual demonomerization.
Adopt circulating water cooling to 40 DEG C, be subsequently adding 6.5kgPH regulator (AMP-95), 0.6kgWBA defoamer, 0.8kg Kazon antibacterial, 3.3kg adipic dihydrazide, be then filtered, it is thus achieved that acrylic acid organosilicon is without soap copolymer emulsion.
Embodiment 3:
Pre-emulsification tank (A) adds 120kg deionized water, 10.8kg allyl alkyl sulfosuccinate ester salt M-12S, 2kg acrylamide, be subsequently adding 2.4kg methacrylic acid (AA), 55kg butyl acrylate (BA), 130kg methyl methacrylate (MMA) carry out high speed dispersion, prepare pre-emulsion A.
Emulsion tank (B) adds 48.5kg deionized water, 2.34kg allyl alkyl sulfosuccinate ester salt M-12S, 1.04kg Methacrylamide isopropyl sulfonic acid AMPS-2404,1.2kg N-[2-(2-methyl-4-oxopentyl) (DAAM), 72.1kg Isooctyl acrylate monomer (2-EHA), 31.2kg methyl methacrylate (MMA), 0.78 methacrylic acid, 5.72kg ��-methacryloxypropyl trimethoxy silane (A-174), prepares shell pre-emulsion (B).
Add 304.2kg deionized water, 4.2kg allyl alkyl sulfosuccinate ester salt M-12S in a kettle., it is then heated to 82��84 DEG C, ready 12.5kg pre-emulsion (A) and 0.44kg initiator sodium peroxydisulfate+8.3kg deionized water solution are joined in reactor, keep reaction temperature at 84��86 DEG C, course of reaction controls at 15 minutes, prepares seed emulsion.
Dropping stratum nucleare pre-emulsion (A), to reactor, continues to ensure the temperature 85��87 DEG C of reactor, and dropping controlled at 1.5 hours. After being added dropwise to complete, it is incubated 15 minutes in 85��87 DEG C.
Dropping shell pre-emulsion (B), to reactor, continues to ensure the temperature 85��87 DEG C of reactor, and dropping controlled at 1 hour. After being added dropwise to complete, continue insulation 1 hour in 86��88 DEG C.
Cool the temperature to 65��70 DEG C, be subsequently adding 0.78kgH2O2With 0.55kg sodium formaldehyde sulfoxylate, be incubated 60 minutes, eliminate residual demonomerization.
Adopt circulating water cooling to 40 DEG C, be subsequently adding 6.5kgPH regulator (ammonia), 0.6kg681F defoamer, 0.8kgDE-109 antibacterial, 3.3kg triethanolamine, be then filtered, it is thus achieved that acrylic acid organosilicon is without soap copolymer emulsion.
Embodiment 4:
Pre-emulsification tank (A) adds 120kg deionized water, 10.8kg sodium vinyl sulfonate SVS, 2kg acrylamide, be subsequently adding 2.4kg methacrylic acid (AA), 55kg butyl acrylate (BA), 130kg methyl methacrylate (MMA) carry out high speed dispersion, prepare pre-emulsion A.
Emulsion tank (B) adds 48.5kg deionized water, 2.34kg sodium vinyl sulfonate SVS, 1.04kg Methacrylamide isopropyl sulfonic acid AMPS-2404,1.2kg N-[2-(2-methyl-4-oxopentyl) (DAAM), 72.1kg Isooctyl acrylate monomer (2-EHA), 31.2kg methyl methacrylate (MMA), 0.78 methacrylic acid, 5.72kg silane coupler (A-151), prepares shell pre-emulsion (B).
Add 304.2kg deionized water, 4.2kg sodium vinyl sulfonate SVS in a kettle., it is then heated to 82��84 DEG C, ready 12.5kg pre-emulsion (A) and 0.44kg initiator ammonium persulfate+8.3kg deionized water solution are joined in reactor, keep reaction temperature at 84��86 DEG C, course of reaction controls at 10 minutes, prepares seed emulsion.
Dropping stratum nucleare pre-emulsion (A), to reactor, continues to ensure the temperature 85��87 DEG C of reactor, and dropping controlled at 2.5 hours. After being added dropwise to complete, it is incubated 10 minutes in 85��87 DEG C.
Dropping shell pre-emulsion (B), to reactor, continues to ensure the temperature 85��87 DEG C of reactor, and dropping controlled at 2 hours. After being added dropwise to complete, continue insulation 2 hours in 86��88 DEG C.
Cool the temperature to 65��70 DEG C, be subsequently adding 0.78kgH2O2With 0.55kg vitamin C, be incubated 45 minutes, eliminate residual demonomerization.
Adopt circulating water cooling to 40 DEG C, be subsequently adding 6.5kgPH regulator (ethanolamine), 0.6kgNXZ defoamer, 0.8kgD7-10 antibacterial, 3.3kg isoniazid, be then filtered, it is thus achieved that acrylic acid organosilicon is without soap copolymer emulsion.
Wherein, allyl alkyl ether alcohol sulfate SR-1025 produces for Chinese mugwort Dicon A/S, Methacrylamide isopropyl sulfonic acid AMPS-2404 is Shanghai loyalty Company, allyl alkyl sulfosuccinate ester salt M-12S is Shanghai loyalty Company, 1-propenyloxy group 2-hydroxypropanesulfonic acid sodium UCAN-1 is Shanghai loyalty Company, sodium vinyl sulfonate SVS is Shanghai loyalty Company.
The performance test results such as following table of the obtained product of above-described embodiment:
The acrylic acid organosilicon that the present invention obtains as can be seen here is without soap copolymer emulsion, high comprehensive performance, and technical specification meets or exceeds market like product. Owing to have employed soap-free polymerization technique so that not containing free emulsifying agent, the very high purity of film in finished emulsion, the polymer performance obtained is not affected by emulsifying agent; Owing to have employed hud polymerization technique, use the organic silicon monomer of less costliness just can reach good performance.
By soap-free polymerization technique, use the organic silicon monomer of less costliness can realize good water-whitening resistance, reduce the water absorption rate of paint film.
By hud polymerization technique, obtain the shell that the higher stratum nucleare of vitrification point, vitrification point are relatively low, when making the average glass transition temperature identical with equal polymerizing technology, the emulsion synthesized has less film-forming temperature, reduce the consumption (coalescents is all high boiling solvent under normal circumstances) of coalescents, reduce the solvent volatilization impact on atmospheric environment.
In sum, the technique such as emulsifier-free emulsion polymerization, core-shell emulsion polymerization is utilized to prepare, multiple insatiable hunger conjunction monomer, organic silicon monomer, reactive emulsifier, initiator is adopted to make, especially with soap-free polymerization technique, make the emulsion made does not contain free emulsifying agent, the very high purity of film, greatly improves product resistance to water, and the polymer performance obtained is not affected by emulsifying agent; Owing to have employed hud polymerization technique, use the organic silicon monomer of less costliness just can reach good performance. Additionally due to product does not contain free emulsifying agent, make product be substantially reduced for the impact of environment, belong to environmentally friendly product. There is extraordinary weatherability, resistance to water and antifouling property, not easy to leak, do not break, can be applicable to the fields such as outer wall building coating, water-repellent paint, heat insulation coating, meet the multiple requirement such as insulation, energy-conservation, decoration.
It is to be understood that: the above is only the preferred embodiment of the present invention; for those skilled in the art; under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. acrylic acid organosilicon is without the preparation method of soap copolymer emulsion, it is characterized in that: employing raw material is unsaturated monomer, organosilicon, reactive emulsifier, initiator and water, by hud polymerization, soap-free polymerization technique, control temperature of reaction kettle, residual monomer is removed again through aftertreatment technology, and add nertralizer neutralization, prepare acrylic acid organosilicon without soap copolymer emulsion.
2. acrylic acid organosilicon according to claim 1 is without the preparation method of soap copolymer emulsion, it is characterised in that comprise the following steps:
1) in pre-emulsification tank, addition 240��270 weight parts waters, 15��20 weight portion reactive emulsifiers, 3��5 parts by weight propylene amide carry out dispersion and emulsion, it is then slowly added into 80��260 parts by weight of methylmethacrylate, 110��180 parts by weight propylene acid butyl esters, 80��240 different monooctyl esters of parts by weight of acrylic acid, 1��4 weight parts of methacrylic acid, prepares stratum nucleare pre-emulsion;
2) in emulsion tank, add 220��260 weight parts waters, 10��15 weight portion reactive emulsifiers, 5��8 weight portion N-[2-(2-methyl-4-oxopentyl)s, 300��400 different monooctyl esters of parts by weight of acrylic acid, 150��300 parts by weight of methylmethacrylate, 2��5 weight parts of methacrylic acid, 10��30 weight portion organic silicon monomers, prepare shell pre-emulsion;
3) in reactor, 300��330 parts by weight of deionized water, 2��5 weight portion reactive emulsifiers are added, heating is to 82��84 DEG C, again by the step 1 of 1��5% weight portion) prepared by stratum nucleare pre-emulsion and initiator solution put in reactor, keep reaction temperature at 84��86 DEG C, react 10��20 minutes, prepare seed emulsion;
4) dropping step 1) prepared by stratum nucleare pre-emulsion to reactor, keep temperature of reaction kettle be 85��87 DEG C, prepare stratum nucleare emulsion;
5) drip step 2 again) prepared by shell pre-emulsion to reactor, the temperature keeping reactor is 85��87 DEG C, after being added dropwise to complete, continues insulation 1��2 hour;
6) temperature of reaction kettle is down to 65��70 DEG C, is subsequently adding 1.1��1.5 weight portion H2O2With 0.7��1.3 weight portion reducing agent, be incubated 30��60 minutes, eliminate residual demonomerization;
7) emulsion temperature in reactor is down to less than 40 DEG C, it is subsequently adding 6��8 weight portion pH value regulators, 0.5��1.5 weight portion defoamer, 0.5��2 weight portion antibacterial, 2��5 parts by weight of crosslinking agent, finally it is filtered, it is thus achieved that acrylic acid organosilicon is without soap copolymer emulsion.
3. acrylic acid organosilicon according to claim 2 is without the preparation method of soap copolymer emulsion, it is characterised in that: described reactive emulsifier is one or more in allyl alkyl ether alcohol sulfate SR-1025, Methacrylamide isopropyl sulfonic acid AMPS-2404, allyl alkyl sulfosuccinate ester salt M-12S, 1-propenyloxy group 2-hydroxypropanesulfonic acid sodium UCAN-1, sodium vinyl sulfonate SVS.
4. acrylic acid organosilicon according to claim 2 is without the preparation method of soap copolymer emulsion, it is characterised in that: step 2) in, described organic silicon monomer is one or several in A-174, A-171, A-151 silane coupler.
5. acrylic acid organosilicon according to claim 2 is without the preparation method of soap copolymer emulsion, it is characterised in that: step 3) in, described initiator solution is one or more in Ammonium persulfate., sodium peroxydisulfate, potassium peroxydisulfate.
6. the acrylic acid organosilicon according to claim 2 or 5 is without the preparation method of soap copolymer emulsion, it is characterised in that: the addition of described initiator solution is 40��60 weight portions.
7. acrylic acid organosilicon according to claim 2 is without the preparation method of soap copolymer emulsion, it is characterised in that: step 4) in, time for adding controls at 1.5��2.5 hours, after being added dropwise to complete, is incubated 10��15 minutes in 85��87 DEG C.
8. acrylic acid organosilicon according to claim 2 is without the preparation method of soap copolymer emulsion, it is characterised in that: step 5) in, time for adding controls at 1��1.5 hour, after being added dropwise to complete, is incubated 1��2 hour in 86��88 DEG C.
9. acrylic acid organosilicon according to claim 2 is without the preparation method of soap copolymer emulsion, it is characterised in that: step 6) in, described reducing agent is the emulsion polymerization novel reducer FF of sodium formaldehyde sulfoxylate, vitamin C, Brueggemann company of Germany6In one or several.
10. acrylic acid organosilicon according to claim 2 is without the preparation method of soap copolymer emulsion, it is characterized in that: step 7) in, described pH value regulator is one or more in AMP-95PH regulator, ammonia, ethanolamine, described defoamer is one or more in WBA defoamer, 681F defoamer, NXZ defoamer, described antibacterial is one or more in Kazon antibacterial, DE-109 antibacterial, D7-10 antibacterial, and described cross-linking agent is one or more in adipic dihydrazide, triethanolamine, isoniazid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610058775.3A CN105622831A (en) | 2016-01-28 | 2016-01-28 | Preparation method of acrylic acid organic silicon soap-free copolymerization emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610058775.3A CN105622831A (en) | 2016-01-28 | 2016-01-28 | Preparation method of acrylic acid organic silicon soap-free copolymerization emulsion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105622831A true CN105622831A (en) | 2016-06-01 |
Family
ID=56038208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610058775.3A Pending CN105622831A (en) | 2016-01-28 | 2016-01-28 | Preparation method of acrylic acid organic silicon soap-free copolymerization emulsion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105622831A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749857A (en) * | 2016-12-27 | 2017-05-31 | 广东衡光化工有限公司 | One kind is for PVC acrylic emulsions used for water color ink and preparation method thereof |
| CN109265625A (en) * | 2018-09-25 | 2019-01-25 | 赵家栋 | A kind of dedicated acrylic emulsion of lacquer and its preparation method and application |
| CN110283283A (en) * | 2019-04-24 | 2019-09-27 | 武汉仕全兴新材料科技股份有限公司 | A kind of preparation method of soap-free core-shell hydroxyl acrylic emulsion |
| CN110698606A (en) * | 2019-09-24 | 2020-01-17 | 湖北工业大学 | Preparation method of high-elongation soap-free emulsion polymer |
| CN111116940A (en) * | 2019-11-29 | 2020-05-08 | 扬州工业职业技术学院 | Emulsifier for chlorinated polyolefin external emulsification and preparation method thereof |
| CN111793401A (en) * | 2020-07-09 | 2020-10-20 | 西卡(上海)管理有限公司 | Waterproof coating and preparation method thereof |
| CN111875756A (en) * | 2020-08-13 | 2020-11-03 | 广州市祥枫化工科技有限公司 | Preparation method and formula of soap-free synthetic aqueous acrylic acid dispersion resin |
| CN112048034A (en) * | 2020-08-17 | 2020-12-08 | 广东恒和永盛实业有限公司 | Antibacterial acrylic emulsion for water-based pigment and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772617A (en) * | 2014-01-21 | 2014-05-07 | 山东圣光化工集团有限公司 | Silicone-acrylate copolymer emulsion and preparation method thereof |
-
2016
- 2016-01-28 CN CN201610058775.3A patent/CN105622831A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772617A (en) * | 2014-01-21 | 2014-05-07 | 山东圣光化工集团有限公司 | Silicone-acrylate copolymer emulsion and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 赵陈超等编著: "《有机硅树脂及其应用》", 31 October 2011, 化学工业出版社 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749857A (en) * | 2016-12-27 | 2017-05-31 | 广东衡光化工有限公司 | One kind is for PVC acrylic emulsions used for water color ink and preparation method thereof |
| CN109265625A (en) * | 2018-09-25 | 2019-01-25 | 赵家栋 | A kind of dedicated acrylic emulsion of lacquer and its preparation method and application |
| CN109265625B (en) * | 2018-09-25 | 2021-02-26 | 浙江科力森化学有限公司 | Acrylic emulsion special for real stone paint and preparation method and application thereof |
| CN110283283A (en) * | 2019-04-24 | 2019-09-27 | 武汉仕全兴新材料科技股份有限公司 | A kind of preparation method of soap-free core-shell hydroxyl acrylic emulsion |
| CN110698606A (en) * | 2019-09-24 | 2020-01-17 | 湖北工业大学 | Preparation method of high-elongation soap-free emulsion polymer |
| CN111116940A (en) * | 2019-11-29 | 2020-05-08 | 扬州工业职业技术学院 | Emulsifier for chlorinated polyolefin external emulsification and preparation method thereof |
| CN111116940B (en) * | 2019-11-29 | 2022-11-29 | 扬州工业职业技术学院 | Emulsifier for chlorinated polyolefin external emulsification and preparation method thereof |
| CN111793401A (en) * | 2020-07-09 | 2020-10-20 | 西卡(上海)管理有限公司 | Waterproof coating and preparation method thereof |
| CN111875756A (en) * | 2020-08-13 | 2020-11-03 | 广州市祥枫化工科技有限公司 | Preparation method and formula of soap-free synthetic aqueous acrylic acid dispersion resin |
| CN112048034A (en) * | 2020-08-17 | 2020-12-08 | 广东恒和永盛实业有限公司 | Antibacterial acrylic emulsion for water-based pigment and preparation method thereof |
| CN112048034B (en) * | 2020-08-17 | 2022-11-08 | 广东恒和永盛集团有限公司 | Antibacterial acrylic emulsion for water-based pigment and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105622831A (en) | Preparation method of acrylic acid organic silicon soap-free copolymerization emulsion | |
| CN102649835B (en) | Organic-inorganic hybrid high-silicon-content acrylic ester emulsion and preparation method thereof | |
| CN102731735B (en) | Organosilicon modified silica sol/polyacrylate composite emulsion and its preparation method | |
| CN104530302B (en) | A kind of Ludox/polyacrylate dispersion of high silicon content and preparation method thereof | |
| CN102898578B (en) | Self-crosslinking silicone-acrylate copolymer emulsion and preparation method | |
| CN112280043B (en) | Silicon dioxide/polyacrylate/polysiloxane composite emulsion, preparation method and application thereof | |
| CN107118650B (en) | Silica sol/polyacrylate emulsion containing hydroxyl-amino resin baking varnish and preparation method thereof | |
| CN101831230A (en) | Method for preparing polyacrylate/nano-SiO2 compound coating agent by using reactive emulsifier | |
| CN104877089A (en) | Preparation method of modified fluorine-containing acrylic superhydrophobic resin emulsion | |
| US10214641B2 (en) | Aqueous organic silicon fluoro-containing polymer dispersion and method for manufacturing the same | |
| CN103012665A (en) | Ultraviolet cross-linked organosilicone modified acrylate copolymer emulsion | |
| CN101434674A (en) | Fluorine-containing water-dilutable resin prepared by nucleocapsid emulsion multicomponent copolymerization and coating thereof | |
| CN103382236B (en) | Silicon-acralyte latex of a kind of high silicone content and preparation method thereof | |
| CN110627950A (en) | Aqueous fluorine modified acrylic emulsion and preparation method and application thereof | |
| CN103772617A (en) | Silicone-acrylate copolymer emulsion and preparation method thereof | |
| CN101735541A (en) | Environmental-friendly type emulsion for heat insulating material and preparation method thereof | |
| CN104403042A (en) | Salt-fog-resistant vinylidene chloride copolymer latex and preparation method thereof | |
| KR101886395B1 (en) | New and stable aqueous hybrid binder | |
| CN103232566B (en) | Preparation method of high-solid-content low-viscosity acrylate emulsion for sealing gum | |
| CN106632791A (en) | Primer styrene-acrylic emulsion resistant to fresh cement efflorescence and preparation method of primer styrene-acrylic emulsion | |
| CN105968252A (en) | Solid acrylic resin and preparation method thereof | |
| CN113563503A (en) | Preparation method of environment-friendly water-resistant yellowing-resistant copolymer emulsion | |
| CN108424488B (en) | Anti-fouling and water-resistant silicone-acrylate emulsion and preparation method thereof | |
| JPH1180486A (en) | Acrylic-silicone emulsion composition | |
| CN107556429B (en) | Silicone-acrylic emulsion and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160601 |
|
| RJ01 | Rejection of invention patent application after publication |