CN110922541A - Preparation method of ACR elastic resin with core-shell structure - Google Patents

Preparation method of ACR elastic resin with core-shell structure Download PDF

Info

Publication number
CN110922541A
CN110922541A CN201911182989.1A CN201911182989A CN110922541A CN 110922541 A CN110922541 A CN 110922541A CN 201911182989 A CN201911182989 A CN 201911182989A CN 110922541 A CN110922541 A CN 110922541A
Authority
CN
China
Prior art keywords
core
polysiloxane
acr
preparation
emulsion
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
Application number
CN201911182989.1A
Other languages
Chinese (zh)
Inventor
石晓林
严国银
魏欣煜
王万萍
缑可贞
谢濠江
徐慧远
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
YIBIN HAIFENG HERUI CO Ltd
Yibin Tianyuan Group Co Ltd
Original Assignee
YIBIN HAIFENG HERUI CO Ltd
Yibin Tianyuan Group Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by YIBIN HAIFENG HERUI CO Ltd, Yibin Tianyuan Group Co Ltd filed Critical YIBIN HAIFENG HERUI CO Ltd
Priority to CN201911182989.1A priority Critical patent/CN110922541A/en
Publication of CN110922541A publication Critical patent/CN110922541A/en
Pending legal-status Critical Current

Links

Images

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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Abstract

The invention discloses a core-shell junctionThe preparation method of the ACR elastic resin comprises the steps of obtaining the ACR elastic resin comprising a polysiloxane core layer and a polyacrylate shell layer by a core-shell emulsion polymerization method, mixing an organic silicon monomer, a silane coupling agent, a catalyst, deionized water and an emulsifier, emulsifying, introducing nitrogen to remove oxygen, carrying out polymerization reaction, and adjusting the pH to 6-8 after the reaction is finished to obtain the polysiloxane core emulsion. The invention enables the polysiloxane latex particles to have more excellent elasticity at low temperature; simultaneously, the organosilicon monomer in the preparation stage of the polysiloxane nuclear emulsion comprises methyltrimethoxysilane, and acrylate silane coupling agent which is respectively formed inside and outside the elastic particles of the polysiloxane emulsion in the polymerization reaction process
Figure DDA0002291757550000011
And a cross-linked structure which improves the elastic properties of the polysiloxane at low temperatures below-25 ℃ on the basis of ensuring the ductility of the polysiloxane.

Description

Preparation method of ACR elastic resin with core-shell structure
Technical Field
The invention relates to the field of organic silicon modified ACR resin, in particular to a preparation method of ACR elastic resin with a core-shell structure.
Background
Acrylate (ACR) resin is a high molecular polymer produced by radical polymerization of acrylate or methacrylate, and has excellent oil resistance, thermal stability, ozone resistance, and ultraviolet resistance, so that it has been widely used in the fields of thermoplastic resins, paints, impact modifiers, and the like. However, the ACR resin has poor temperature resistance, water resistance and air permeability, and further application of the ACR resin is limited to a certain extent. The organic silicon Polymer (PSi) has extremely low surface energy, the Si-O bond has very high bond energy which is far greater than the C-O bond energy of the C-C bond energy, the Si-O-Si has strong flexibility and lower glass transition temperature, so that the organic silicon polymer has excellent performances of water resistance, high and low temperature resistance, weather resistance, flexibility, impact resistance, air permeability and the like.
Therefore, the acrylate and the siloxane which have different polarities and different reactivities and compatibilities are copolymerized into the composite material with excellent comprehensive performance through emulsion polymerization, and the method has important theoretical research and development application values. However, the toughening and modification effects are affected by compatibility issues between the matrix resin and the rubber phase. If the rubber polymer is used as the core layer and the hard polymer is used as the shell layer, the interfacial compatibility between the rubber polymer and the matrix resin can be obviously improved, and the toughening modification effect of the rubber polymer is improved. Such composite particles having a hard-shell soft core structure are therefore widely used in impact modifiers and toughening agents for polymeric materials. In the existing research, the toughening effect of the rubber particles with the three-layer structure is more effective than that of the rubber particles with the two layers. Wherein the first layer is a Polysiloxane (PSi) which has the property of having excellent elasticity at low temperatures; the second layer is an acrylate rubber phase which forms a composite rubber phase with polysiloxane, so that the extensibility and the flexibility of the polysiloxane are improved; the third layer is polymethacrylate (MMA) as a coating layer, and the inner layer elastic particles are coated, so that the problem that the inner layer elastic particles are condensed to lose the stable structure of the nano particles after demulsification is avoided. The rubber particles with the three-layer structure have a toughening effect on PMMA shells more effectively than the rubber particles with the two-layer structure, and the PMMA shells used as the shells of the core-shell organic silica gel particles eliminate the blending defect caused by poor compatibility of PSi and PVC interfaces, so that the improvement of the impact resistance of PVC is facilitated, and the low-temperature toughening effect of the core-shell Acrylate (ACR) particles in PVC modification is also improved. But the elasticity is lost at the low temperature of below 25 ℃ below zero, the ACR resin can not be used as a processing aid to toughen the high polymer resin, the application range of the organic silicon modified ACR resin is limited, and the application requirement of PVC hard products in the low temperature field can not be met.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of the ACR elastic resin with the core-shell structure, and solving the problem that the ACR elastic resin loses elasticity at the low temperature of minus 25 ℃.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of an ACR elastic resin with a core-shell structure comprises the steps of obtaining the ACR elastic resin comprising a polysiloxane core layer and a polyacrylate shell layer by a core-shell emulsion polymerization method, wherein the core-layer polysiloxane core emulsion is prepared by the steps of mixing an organic silicon monomer, a silane coupling agent, a catalyst, deionized water and an emulsifier, emulsifying, introducing nitrogen to remove oxygen, carrying out a polymerization reaction, and adjusting the pH to 6-8 after the reaction is finished to obtain a polysiloxane core emulsion;
the emulsifier is a compound mixture of sodium dodecyl benzene sulfonate and alkylphenol ethoxylates or fatty alcohol polyoxyethylene ether; the organic silicon monomer comprises methyl trimethoxy silane, and the silane coupling agent is acrylate silane coupling agent.
Further, the organosilicon monomer also comprises octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane or a mixture of the octamethylcyclotetrasiloxane and the hexamethylcyclotrisiloxane.
Further, the mass ratio of the sodium dodecyl benzene sulfonate to the alkylphenol polyoxyethylene ether or the fatty alcohol polyoxyethylene ether in the emulsifier is 1-6: 2.
Further, the general formula of the silane coupling agent is CH2＝CH-COOR-Si(OR)3Wherein R is ethanediyl or propanediyl.
Further, the polysiloxane core emulsion has the general formula (R)2SiO2/2)x·(RSiO3/2)y·(CH2＝CH-COOR-SiO3/2)zThe main chain Structure Is (SiR)2-O)nWherein R is methyl.
Further, the polymerization reaction temperature is 65-95 ℃, and the reaction time is 8-40 h.
Further, the mass ratio of the organosilicon monomer to the silane coupling agent to the emulsifier is 100: 3-20: 1.5-5.0, the mass of the silane coupling agent is 3% -20% of that of the organosilicon monomer, and the mass of the emulsifier is 1.5% -5.0% of that of the organosilicon monomer. The usage amount of the organosilicon monomer is 10% -80% of the total mass of the core monomer, wherein the mass ratio of the organosilicon monomer to the acrylate monomer is 1-8: 2-9.
Further, stirring is carried out in the polymerization reaction process, the stirring speed is 150 r/min-400 r/min, and the solid content of the obtained polysiloxane core emulsion is 15% -40%. Under the reaction condition, the particle size of the obtained polysiloxane core emulsion is 90-130 nm, the elasticity and the ductility of the polysiloxane at a low temperature below-25 ℃ are further ensured, if the particle size is small, the elasticity is poor, and if the particle size is too large, the elasticity is poor due to the poor ductility.
Further, the catalyst is hydrochloric acid or sulfuric acid, and H is generated in the polymerization reaction process+The ion concentration is 0.05-0.30 mol/L.
Further, the preparation method of the core-shell structure ACR elastic resin further comprises the following steps:
(1) mixing an acrylate monomer, an emulsifier, a cross-linking agent and deionized water, emulsifying, adding the mixture into the obtained polysiloxane core emulsion, and adding an initiator to carry out polymerization reaction to obtain polysiloxane modified outer core emulsion;
(2) mixing methacrylate monomers, a cross-linking agent, an emulsifier and deionized water, emulsifying, adding the mixture into the polysiloxane modified outer core emulsion obtained in the step (1), and adding an initiator to carry out polymerization reaction to obtain the ACR composite emulsion with the core-shell structure;
(3) and demulsifying and drying the ACR composite emulsion with the core-shell structure to obtain the ACR elastic resin with the core-shell structure.
The general formula of the acrylate monomer is CH2CH-COOR, wherein R is ethyl, propyl, butyl, isooctyl and other saturated alkyl; the general formula of the methacrylate monomer is CH2＝C(CH3) -COOR, wherein R is methyl, ethyl, propyl or other saturated alkyl.
The crosslinking agents in the steps (1) and (2) are Allyl Methacrylate (AMA), divinyl benzene (DVB), 1, 4-butanediol diacrylate (BDDA) and other organic matters with two C ═ C bonded double bond structures; the initiator is water soluble sulfate, such as potassium persulfate, ammonium persulfate, and sodium persulfate.
The emulsifier in the steps (1) and (2) is a compound emulsifier of an anionic emulsifier and a nonionic emulsifier, wherein the anionic emulsifier is Sodium Dodecyl Benzene Sulfonate (SDBS), and the nonionic emulsifier is Alkylphenol Polyoxyethylene Ether (APEO) and fatty alcohol polyoxyethylene ether (AEO).
The mass ratio of the organosilicon monomer to the acrylate monomer is 1-8: 2-9, the dosage of the cross-linking agent is 0.5-1.5% of the mass of the acrylate monomer, and the dosage of the emulsifier is 0.5-4.0% of the mass of the acrylate monomer; the using amount of the initiator persulfate is 0.2-0.8 percent of the mass of the acrylate monomer, the free radical polymerization reaction temperature is 50-100 ℃, the reaction time is 1.0-5.0 h, the stirring speed is 150-400 r/min, and the solid content of the outer core emulsion is 25-40 percent;
the amount of the methacrylate monomer in the step (2) accounts for 30-50% of the total monomer mass, and the total monomer comprises an organosilicon monomer, an acrylate monomer and methacrylate; the dosage of the cross-linking agent is 0.25 to 2.0 percent of the mass of the methacrylate monomer, and the dosage of the emulsifying agent is 1.0 to 4.0 percent of the mass of the methacrylate monomer; the using amount of the initiator persulfate is 0.15-0.8 percent of that of the methacrylate monomer, the free radical polymerization reaction temperature is 50-100 ℃, the reaction time is 2.0-6.0 h, the stirring speed is 150-400 r/min, and the solid content of the ACR composite emulsion is 30-40 percent.
The invention has the beneficial effects that: according to the emulsifier compounded by the sodium dodecyl benzene sulfonate and the alkylphenol polyoxyethylene or the fatty alcohol polyoxyethylene ether, siloxane obtained by methyl trimethoxy silane, octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane or a mixture of octamethylcyclotetrasiloxane and hexamethylcyclotrisiloxane has a Si-O-Si linear structure with high polymerization degree, so that polysiloxane latex particles have excellent elasticity at low temperature; simultaneously, the organosilicon monomer in the preparation stage of the polysiloxane nuclear emulsion comprises methyltrimethoxysilane, and acrylate silane coupling agent which is respectively arranged inside and outside the elastic particles of the polysiloxane emulsion in the polymerization reaction processTo (RSiO)3/2) A cross-linked structure which improves the elastic properties of the polysiloxane at low temperatures below-25 ℃ on the basis of ensuring the ductility of the polysiloxane;
the acrylate silane coupling agent introduces reactive double bonds on the surface of polysiloxane emulsion particles, and the reactive double bonds and acrylate improve free radical polymerization to form a polysiloxane-polyacrylate crosslinking structure, so that the compatibility of polysiloxane and polyacrylate is effectively improved, the elastic properties of polysiloxane and polyacrylate are improved, and the core-shell structure ACR elastic resin with excellent low-temperature performance is formed.
Drawings
FIG. 1 is a transmission electron microscope image of the ACR composite emulsion obtained in the example after dyeing.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
Synthesis of polysiloxane core emulsion
The raw materials selected comprise methyltrimethoxysilane (MTMS), octamethylcyclotetrasiloxane (D4), hexamethylcyclotrisiloxane (D3), gamma-methacryloxy trimethoxysilane (KH-570), Sodium Dodecyl Benzene Sulfonate (SDBS), Alkylphenol Polyoxyethylene Ether (APEO), fatty alcohol polyoxyethylene ether (AEO), concentrated hydrochloric acid with mass concentration of 31%, deionized water
TABLE 1 examples starting materials for the preparation of silicone core emulsions
Figure BDA0002291757530000041
TABLE 2 example proportioning by weight of raw materials for preparing polysiloxane core emulsion
MTMS D4 D3 KH-570 SDBS APEO AEO Catalyst and process for preparing same Deionized water
Example 1 1 40 - 1.2 0.8 0.2 - 1.2 100
Example 2 0.6 30 - 1.8 0.6 0.2 - 0.7 90
Example 3 0.3 60 - 6 1.5 0.5 - 1.5 150
Example 4 0.5 50 20 2.0 1.2 - 0.4 1.2 100
Comparative example 1 - 30 20 4.0 1.5 - - 1.0 100
Comparative example 2 - 50 20 1.4 - 1.5 - 1.4 120
Comparative example 3 0.6 60 - 1.8 1.8 - - 1.5 120
Synthesis of di-polysiloxane modified outer core emulsion
The raw materials selected include Butyl Acrylate (BA), Sodium Dodecyl Benzene Sulfonate (SDBS), Alkylphenol Polyoxyethylene (APEO), divinyl benzene (DVB), Allyl Methacrylate (AMA), 1, 4-butanediol diacrylate (BDDA), potassium persulfate and deionized water.
TABLE 3 example proportioning by weight of raw materials for preparing polysiloxane modified outer core emulsion
BA SDBS APEO DVB AMA Potassium persulfate Deionized water
Example 1 60 0.9 0.3 0.5 - 0.24 120
Example 2 70 1.2 0.4 - 0.75 0.18 180
Example 3 40 0.6 0.2 - - 0.2 80
Example 4 50 1.2 0.3 - 0.5 0.2 130
Comparative example 1 60 0.9 0.3 0.5 - 0.24 120
Comparative example 2 60 0.9 0.3 0.5 - 0.24 120
Comparative example 3 60 0.9 0.3 0.5 - 0.24 120
Synthesis of ACR composite emulsion
The raw materials comprise Methyl Methacrylate (MMA), Allyl Methacrylate (AMA), 1, 4-butanediol diacrylate (BDDA), divinyl benzene (DVB), Sodium Dodecyl Benzene Sulfonate (SDBS), Alkylphenol Polyoxyethylene Ether (APEO), potassium persulfate, deionized water
Table 4 example the mass ratio of raw materials for preparing ACR composite emulsion
MMA SDBS APEO DVB AMA BDDA Potassium persulfate Deionized water
Example 1 50 1 0.3 0.3 - - 0.2 120
Example 2 60 0.9 0.4 - 0.4 - 0.3 150
Example 3 60 1.2 0.4 - - 0.3 0.18 150
Example 4 75 0.8 0.4 - 0.3 - 0.24 180
Comparative example 1 50 1 0.3 0.3 - - 0.2 120
Comparative example 2 50 1 0.3 0.3 - - 0.2 120
Comparative example 3 50 1 0.3 0.3 - - 0.2 120
Example 1:
(a) synthesis of Silicone core emulsions
Mixing 40 parts of octamethylcyclotetrasiloxane, 1.0 part of methyltrimethoxysilane, 1.2 parts of gamma-methacryloxy trimethoxysilane, 100 parts of deionized water, 1.2 parts of 31% concentrated hydrochloric acid, 0.8 part of sodium dodecyl benzene sulfonate and 0.2 part of alkylphenol polyoxyethylene ether at normal temperature, pre-emulsifying for 10min by a high-shear emulsifying machine, introducing nitrogen to remove oxygen, reacting for 25.0h under the conditions that the temperature is 80 ℃ and the stirring rate is 250r/min, and adding 10% of sodium hydroxide solution to adjust the pH value to 7 to obtain polysiloxane core emulsion, wherein the particle size of the polysiloxane seed emulsion is 108 nm;
(b) synthesis of polysiloxane-modified outer core emulsion
Mixing 60 parts of butyl acrylate, 0.9 part of sodium dodecyl sulfate, 0.3 part of alkylphenol polyoxyethylene, 0.5 part of divinylbenzene and 120 parts of deionized water, pre-emulsifying for 10min by using a high-shear emulsifier, adding the mixture into the polysiloxane seed emulsion obtained in the step (a), simultaneously adding 0.24 part of potassium persulfate, and reacting for 2.0h at the stirring speed of 200r/min and the temperature of 70 ℃ to obtain the polysiloxane modified outer core emulsion with the particle size of 136 nm;
(c) synthesis of ACR Elastomeric resins
50 parts of methyl methacrylate, 0.3 part of divinylbenzene, 1 part of sodium dodecyl sulfate, 0.3 part of alkylphenol polyoxyethylene and 120 parts of deionized water are pre-emulsified for 10min by a high-shear emulsifier, added into the polysiloxane modified outer core emulsion in the step (b), and continuously added with 0.2 part of potassium persulfate, reacted for 4.0h at the stirring rate of 200r/min and the temperature of 70 ℃ to obtain the ACR composite emulsion with the core-shell structure and the particle size of 157nm, and the ACR elastic resin is obtained after demulsification and drying.
Example 2:
(a) synthesis of Silicone core emulsions
Mixing 30 parts of octamethylcyclotetrasiloxane, 0.6 part of methyltrimethoxysilane, 1.8 parts of gamma-methacryloxy trimethoxysilane, 90 parts of deionized water, 0.7 part of 31% concentrated hydrochloric acid, 0.6 part of sodium dodecyl benzene sulfonate and 0.2 part of alkylphenol polyoxyethylene ether at normal temperature, pre-emulsifying for 10min by a high-shear emulsifying machine, introducing nitrogen to remove oxygen, reacting for 35.0h under the conditions that the temperature is 65 ℃ and the stirring rate is 250r/min, and adding 10% of sodium hydroxide solution to adjust the pH value to 8 to obtain polysiloxane core emulsion, wherein the particle size of the polysiloxane seed emulsion is 126 nm;
(b) synthesis of polysiloxane-modified outer core emulsion
Mixing 70 parts of butyl acrylate, 1.2 parts of sodium dodecyl sulfate, 0.4 part of alkylphenol polyoxyethylene, 0.75 part of allyl methacrylate and 180 parts of deionized water, pre-emulsifying for 10min by using a high-shear emulsifier, adding the mixture into the polysiloxane seed emulsion obtained in the step (a), simultaneously adding 0.18 part of potassium persulfate, and reacting for 2.0h at the temperature of 80 ℃ at the stirring rate of 200r/min to obtain the polysiloxane modified outer core emulsion with the particle size of 142 nm;
(c) synthesis of ACR Elastomeric resins
60 parts of methyl methacrylate, 0.4 part of allyl methacrylate, 0.9 part of sodium dodecyl sulfate, 0.4 part of alkylphenol polyoxyethylene, and 150 parts of deionized water are pre-emulsified for 10min by a high-shear emulsifier, added into the polysiloxane modified outer core emulsion in the step (b), continuously added with 0.2 part of potassium persulfate, reacted for 4.0h at the stirring rate of 200r/min and the temperature of 80 ℃ to obtain the ACR composite emulsion with the core-shell structure and the particle size of 165nm, and the ACR elastic resin is obtained after demulsification and drying.
Example 3:
(a) synthesis of Silicone core emulsions
Mixing 60 parts of octamethylcyclotetrasiloxane, 0.3 part of methyltrimethoxysilane, 6 parts of gamma-methacryloxy trimethoxysilane, 150 parts of deionized water, 1.5 parts of 31% concentrated hydrochloric acid, 1.5 parts of sodium dodecyl benzene sulfonate and 0.5 part of alkylphenol polyoxyethylene ether at normal temperature, pre-emulsifying for 10min by a high-shear emulsifying machine, introducing nitrogen to remove oxygen, reacting for 24.0h under the conditions that the temperature is 70 ℃ and the stirring rate is 210r/min, adding 10% sodium hydroxide solution to adjust the pH value to 6, and obtaining polysiloxane core emulsion, wherein the particle size of the polysiloxane seed emulsion is 116 nm;
(b) synthesis of polysiloxane-modified outer core emulsion
Mixing 40 parts of butyl acrylate, 0.6 part of sodium dodecyl sulfate, 0.2 part of alkylphenol polyoxyethylene, 0.32 part of 1, 4-butanediol diacrylate and 80 parts of deionized water, pre-emulsifying for 10min by using a high-shear emulsifier, adding the mixture into the polysiloxane seed emulsion obtained in the step (a), simultaneously adding 0.20 part of potassium persulfate, and reacting for 2.0h at the stirring speed of 250r/min and the temperature of 75 ℃ to obtain the polysiloxane modified outer core emulsion with the particle size of 138 nm;
(c) synthesis of ACR Elastomeric resins
60 parts of methyl methacrylate, 0.3 part of 1, 4-butanediol diacrylate, 1.2 parts of sodium dodecyl sulfate, 0.4 part of alkylphenol polyoxyethylene and 150 parts of deionized water are pre-emulsified for 10min by a high-shear emulsifier, added into the polysiloxane modified outer core emulsion in the step (b), and continuously added with 0.18 part of potassium persulfate, and reacted for 4.0h at the stirring speed of 250r/min and the temperature of 75 ℃ to obtain the ACR composite emulsion with the core-shell structure and the particle size of 159nm, and the ACR elastic resin is obtained after demulsification and drying.
Example 4:
(a) synthesis of Silicone core emulsions
Mixing 50 parts of octamethylcyclotetrasiloxane, 0.5 part of methyltrimethoxysilane, 20 parts of hexamethylcyclotrisiloxane, 2.0 parts of gamma-methacryloxy trimethoxysilane, 100 parts of deionized water, 1.2 parts of 31% concentrated sulfuric acid, 1.2 parts of sodium dodecyl benzene sulfonate and 0.4 part of fatty alcohol-polyoxyethylene ether at normal temperature, pre-emulsifying for 10min by a high-shear emulsifying machine, introducing nitrogen to remove oxygen, reacting for 24.0h under the conditions that the temperature is 70 ℃ and the stirring rate is 250r/min, adding 10% of sodium hydroxide solution to adjust the pH value to 7, and obtaining polysiloxane core emulsion, wherein the particle size of the polysiloxane seed emulsion is 118 nm;
(b) synthesis of polysiloxane-modified outer core emulsion
Mixing 50 parts of butyl acrylate, 1.2 parts of sodium dodecyl sulfate, 0.3 part of alkylphenol polyoxyethylene, 0.5 part of allyl methacrylate and 130 parts of deionized water, pre-emulsifying for 10min by using a high-shear emulsifier, adding the mixture into the polysiloxane seed emulsion obtained in the step (a), simultaneously adding 0.20 part of potassium persulfate, and reacting for 2.0h at the stirring speed of 300r/min and the temperature of 80 ℃ to obtain the polysiloxane modified outer core emulsion with the particle size of 147 nm;
(c) synthesis of ACR Elastomeric resins
And (2) pre-emulsifying 75 parts of methyl methacrylate, 0.3 part of allyl methacrylate, 0.8 part of sodium dodecyl sulfate, 0.4 part of alkylphenol polyoxyethylene ether and 180 parts of deionized water by using a high-shear emulsifier for 10min, adding the pre-emulsified mixture into the polysiloxane modified outer core emulsion obtained in the step (b), continuously adding 0.24 part of potassium persulfate, reacting for 3.0h at the stirring speed of 300r/min and the temperature of 80 ℃ to obtain the ACR composite emulsion with the core-shell structure and the particle size of 168nm, and demulsifying and drying to obtain the ACR elastic resin.
Comparative example 1:
(a) synthesis of Silicone core emulsions
Mixing 30 parts of octamethylcyclotetrasiloxane, 20 parts of hexamethylcyclotrisiloxane, 4.0 parts of gamma methacryloxy trimethoxysilane, 100 parts of deionized water, 1.0 part of 31% concentrated hydrochloric acid and 1.5 parts of sodium dodecyl benzene sulfonate at normal temperature, pre-emulsifying for 10min by a high-shear emulsifying machine, introducing nitrogen to remove oxygen, reacting for 25.0h at the temperature of 80 ℃ and the stirring rate of 250r/min, adding 10% sodium hydroxide solution to adjust the pH value to 7, and thus obtaining polysiloxane core emulsion, wherein the particle size of the polysiloxane seed emulsion is 40 nm;
(b) synthesis of polysiloxane-modified outer core emulsion
Mixing 60 parts of butyl acrylate, 0.9 part of sodium dodecyl sulfate, 0.3 part of alkylphenol polyoxyethylene, 0.5 part of divinylbenzene and 120 parts of deionized water, pre-emulsifying for 10min by using a high-shear emulsifier, adding the mixture into the polysiloxane seed emulsion obtained in the step (a), simultaneously adding 0.24 part of potassium persulfate, and reacting for 2.0h at the temperature of 70 ℃ at the stirring speed of 200r/min to obtain the polysiloxane modified outer core emulsion with the particle size of 95 nm;
(c) synthesis of ACR Elastomeric resins
50 parts of methyl methacrylate, 0.3 part of divinylbenzene, 1 part of sodium dodecyl sulfate, 0.3 part of alkylphenol polyoxyethylene and 120 parts of deionized water are pre-emulsified for 10min by a high-shear emulsifier, added into the polysiloxane modified outer core emulsion in the step (b), and continuously added with 0.2 part of potassium persulfate, reacted for 4.0h at the stirring rate of 200r/min and the temperature of 70 ℃ to obtain the ACR composite emulsion with the core-shell structure and the particle size of 118nm, and the ACR elastic resin is obtained after demulsification and drying.
Comparative example 2:
(a) synthesis of Silicone core emulsions
Mixing 50 parts of octamethylcyclotetrasiloxane, 20 parts of hexamethylcyclotrisiloxane, 1.4 parts of gamma methacryloxy trimethoxysilane, 120 parts of deionized water, 1.4 parts of 31% concentrated hydrochloric acid and 1.5 parts of alkylphenol polyoxyethylene ether at normal temperature, pre-emulsifying for 10min by using a high-shear emulsifying machine, introducing nitrogen to remove oxygen, reacting for 25.0h under the conditions that the temperature is 80 ℃ and the stirring rate is 250r/min, and adding 10% sodium hydroxide solution to adjust the pH value to 7 to obtain polysiloxane nuclear emulsion, wherein the particle size of the polysiloxane seed emulsion is 98 nm;
(b) synthesis of polysiloxane-modified outer core emulsion
Mixing 60 parts of butyl acrylate, 0.9 part of sodium dodecyl sulfate, 0.3 part of alkylphenol polyoxyethylene, 0.5 part of divinylbenzene and 120 parts of deionized water, pre-emulsifying for 10min by using a high-shear emulsifier, adding the mixture into the polysiloxane seed emulsion obtained in the step (a), simultaneously adding 0.24 part of potassium persulfate, and reacting for 2.0h at the stirring speed of 200r/min and the temperature of 70 ℃ to obtain the polysiloxane modified outer core emulsion with the particle size of 117 nm;
(c) synthesis of ACR Elastomeric resins
50 parts of methyl methacrylate, 0.3 part of divinylbenzene, 1 part of sodium dodecyl sulfate, 0.3 part of alkylphenol polyoxyethylene and 120 parts of deionized water are pre-emulsified for 10min by a high-shear emulsifier, added into the polysiloxane modified outer core emulsion in the step (b), and continuously added with 0.2 part of potassium persulfate, reacted for 4.0h at the stirring rate of 200r/min and the temperature of 70 ℃ to obtain the ACR composite emulsion with the core-shell structure and the particle size of 145nm, and the ACR elastic resin is obtained after demulsification and drying.
Comparative example 3:
(a) synthesis of Silicone core emulsions
Mixing 60 parts of octamethylcyclotetrasiloxane, 0.6 part of methyltrimethoxysilane, 1.8 parts of gamma-methacryloxy trimethoxysilane, 120 parts of deionized water, 1.5 parts of 31% concentrated hydrochloric acid and 1.8 parts of sodium dodecyl benzene sulfonate at normal temperature, pre-emulsifying for 10min by a high-shear emulsifying machine, introducing nitrogen to remove oxygen, reacting for 25.0h at the temperature of 80 ℃ and at the stirring rate of 250r/min, adding 10% sodium hydroxide solution to adjust the pH value to 7, and thus obtaining polysiloxane core emulsion, wherein the particle size of the polysiloxane seed emulsion is 105 nm;
(b) synthesis of polysiloxane-modified outer core emulsion
Mixing 60 parts of butyl acrylate, 0.9 part of sodium dodecyl sulfate, 0.3 part of alkylphenol polyoxyethylene, 0.5 part of divinylbenzene and 120 parts of deionized water, pre-emulsifying for 10min by using a high-shear emulsifier, adding the mixture into the polysiloxane seed emulsion obtained in the step (a), simultaneously adding 0.24 part of potassium persulfate, and reacting for 2.0h at the temperature of 70 ℃ at the stirring speed of 200r/min to obtain the polysiloxane modified outer core emulsion with the particle size of 137 nm;
(c) synthesis of ACR Elastomeric resins
50 parts of methyl methacrylate, 0.3 part of divinylbenzene, 1 part of sodium dodecyl sulfate, 0.3 part of alkylphenol polyoxyethylene and 120 parts of deionized water are pre-emulsified for 10min by a high-shear emulsifier, added into the polysiloxane modified outer core emulsion in the step (b), and continuously added with 0.2 part of potassium persulfate, reacted for 4.0h at the stirring rate of 200r/min and the temperature of 70 ℃ to obtain the ACR composite emulsion with the core-shell structure and the particle size of 166nm, and the ACR elastic resin is obtained after demulsification and drying.
Fourthly, performance test
The performance tests of the ACR elastic resins obtained in examples 1 to 4 and comparative examples 1, 2 and 3 were carried out, and the specific test procedures were as follows: the results of the notch impact strength tests at normal temperature and low temperature (-25 ℃) after blending, open milling and sample preparation of 15 parts of ACR elastic resin, 100 parts of PVC resin, 2 parts of stabilizer and 1.2 parts of calcium stearate are shown in the following table, and it can be seen that the notch impact strength at low temperature-25 ℃ of the examples is improved by more than one time as compared with the comparative examples.
Results of performance test of the ACR elastic resin obtained in Table 5
Normal temperature notch impact strength/kJ/m2 Notched impact strength/kJ/m at low temperature of-25 DEG C2
Example 1 31.0 7.10
Example 2 35.5 7.50
Example 3 36.8 7.60
Example 4 39.6 8.10
Comparative example 1 16.0 3.40
Comparative example 2 12.00 2.80
Comparative example 3 21.0 3.70
TABLE 6 emulsion particle size during preparation
Figure BDA0002291757530000091
Figure BDA0002291757530000101
For ACR elastic resin, if the particle diameter is small, the elasticity is poor, and if the particle diameter is too large, the elasticity is poor due to poor ductility, the particle diameter of the polysiloxane core emulsion obtained by the invention is 90-130 nm, and the elasticity performance and ductility of the polysiloxane at a low temperature below minus 25 ℃ are further ensured.

Claims (10)

1. A preparation method of ACR elastic resin with a core-shell structure is provided, which obtains the ACR elastic resin comprising a polysiloxane core layer and a polyacrylate shell layer by a core-shell emulsion polymerization method, and is characterized in that: the preparation method of the core-layer polysiloxane core emulsion comprises the steps of mixing an organic silicon monomer, a silane coupling agent, a catalyst, deionized water and an emulsifier, emulsifying, introducing nitrogen to remove oxygen, carrying out polymerization reaction, and adjusting the pH to 6-8 after the reaction is finished to obtain the polysiloxane core emulsion;
the emulsifier is a compound mixture of sodium dodecyl benzene sulfonate and alkylphenol ethoxylates or fatty alcohol polyoxyethylene ether; the organic silicon monomer comprises methyl trimethoxy silane, and the silane coupling agent is acrylate silane coupling agent.
2. The preparation method of the ACR elastic resin with the core-shell structure according to claim 1, wherein the preparation method comprises the following steps: the organosilicon monomer also comprises octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane or a mixture of the octamethylcyclotetrasiloxane and the hexamethylcyclotrisiloxane.
3. The preparation method of the ACR elastic resin with the core-shell structure according to claim 1, wherein the preparation method comprises the following steps: the mass ratio of the sodium dodecyl benzene sulfonate to the alkylphenol polyoxyethylene ether or the fatty alcohol polyoxyethylene ether in the emulsifier is 1-6: 2.
4. The ACR elastic tree with core-shell structure as claimed in claim 1A method for producing a fat, characterized by: the general formula of the silane coupling agent is CH2＝CH-COOR-Si(OR)3Wherein R is ethanediyl or propanediyl.
5. The preparation method of the ACR elastic resin with the core-shell structure according to claim 1, wherein the preparation method comprises the following steps: the general formula of polysiloxane in the polysiloxane core emulsion is (R)2SiO2/2)x·(RSiO3/2)y·(CH2＝CH-COOR-SiO3/2)zThe main chain Structure Is (SiR)2-O)nWherein R is methyl.
6. The preparation method of the ACR elastic resin with the core-shell structure according to claim 1, wherein the preparation method comprises the following steps: the polymerization reaction temperature is 65-95 ℃, and the reaction time is 8-40 h.
7. The method for preparing the ACR elastic resin with the core-shell structure according to claim 1 or 6, wherein the method comprises the following steps: the mass ratio of the organosilicon monomer to the silane coupling agent to the emulsifier is 100: 3-20: 1.5-5.0.
8. The preparation method of the ACR elastic resin with the core-shell structure according to claim 7, wherein the preparation method comprises the following steps: stirring is carried out in the polymerization reaction process, the stirring speed is 150 r/min-400 r/min, and the solid content of the obtained polysiloxane core emulsion is 15% -40%.
9. The preparation method of the ACR elastic resin with the core-shell structure according to claim 1, wherein the preparation method comprises the following steps: the catalyst is hydrochloric acid or sulfuric acid, and H is generated in the polymerization reaction process+The ion concentration is 0.05-0.30 mol/L.
10. The preparation method of the ACR elastic resin with the core-shell structure according to claim 1, wherein the preparation method comprises the following steps: the method comprises the following steps:
(1) mixing an acrylate monomer, an emulsifier, a cross-linking agent and deionized water, emulsifying, adding the mixture into the obtained polysiloxane core emulsion, and adding an initiator to carry out polymerization reaction to obtain polysiloxane modified outer core emulsion;
(2) mixing methacrylate monomers, a cross-linking agent, an emulsifier and deionized water, emulsifying, adding the mixture into the polysiloxane modified outer core emulsion obtained in the step (1), and adding an initiator to carry out polymerization reaction to obtain the ACR composite emulsion with the core-shell structure;
(3) and demulsifying and drying the ACR composite emulsion with the core-shell structure to obtain the ACR elastic resin with the core-shell structure.
CN201911182989.1A 2019-11-27 2019-11-27 Preparation method of ACR elastic resin with core-shell structure Pending CN110922541A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911182989.1A CN110922541A (en) 2019-11-27 2019-11-27 Preparation method of ACR elastic resin with core-shell structure

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911182989.1A CN110922541A (en) 2019-11-27 2019-11-27 Preparation method of ACR elastic resin with core-shell structure

Publications (1)

Publication Number Publication Date
CN110922541A true CN110922541A (en) 2020-03-27

Family

ID=69846674

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911182989.1A Pending CN110922541A (en) 2019-11-27 2019-11-27 Preparation method of ACR elastic resin with core-shell structure

Country Status (1)

Country Link
CN (1) CN110922541A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112724334A (en) * 2020-12-29 2021-04-30 铨盛聚碳科技股份有限公司 Organic silicon acrylate impact modifier and preparation method thereof
CN113278115A (en) * 2021-05-27 2021-08-20 英德侗富贵科技材料有限公司 Core-shell polymer and preparation method and application thereof
CN114478952A (en) * 2022-01-25 2022-05-13 深圳市骏鼎达新材料股份有限公司 Preparation method of epoxy group-containing polysiloxane-acrylate elastomer and application of epoxy group-containing polysiloxane-acrylate elastomer in low-temperature toughening nylon tube
CN114773788A (en) * 2022-05-11 2022-07-22 泉州师范学院 Photosensitive resin composition based on nano silicon rubber core-shell structure polymer toughened epoxy resin and application of photosensitive resin composition in 3D printing
CN114853959A (en) * 2022-05-11 2022-08-05 泉州师范学院 Preparation method of clean nano organosilicon core-shell toughening powder

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0827347A (en) * 1994-07-15 1996-01-30 Nisshin Chem Ind Co Ltd Alkoxysilyl-containing acrylic emulsion
JP2002038057A (en) * 2000-07-28 2002-02-06 Dainippon Ink & Chem Inc Water-base coating material composition containing silicone resin
CN101121771A (en) * 2006-08-11 2008-02-13 汉高股份两合公司 Acryloxyalkoxysilicane modified acrylic acid ester polymerization emulsion and its preparation method and application
CN101456936A (en) * 2007-12-10 2009-06-17 华南理工大学 Flame-retardant interfacial modifier and preparation method and flame retardant polycarbonate composition
CN102464784A (en) * 2010-11-19 2012-05-23 北京佳盛世纪科技有限公司 Synthesis method of organic silicon modified acrylate copolymer
CN102516450A (en) * 2011-12-02 2012-06-27 陕西科技大学 Method for preparing water-resistant and cold-resistant leather coating agent with high solid content with pre-emulsified core-shell emulsion polymerization method
CN103483493A (en) * 2013-09-18 2014-01-01 广州中国科学院工业技术研究院 Silicone modified acrylic ester emulsion and preparation method thereof
JP2015140361A (en) * 2014-01-27 2015-08-03 三菱レイヨン株式会社 Impact strength modifier for aliphatic polyester resin, aliphatic polyester resin composition and molded article thereof
CN106146755A (en) * 2015-04-09 2016-11-23 泉州市合创涂料科技有限公司 A kind of preparation method of high solids content silicone acrylic emulsion
CN106866971A (en) * 2017-04-10 2017-06-20 广东优科艾迪高分子材料有限公司 A kind of weather-proof low-temperature type organosilicon impact modifier and preparation method and application
CN107151296A (en) * 2017-04-18 2017-09-12 华南理工大学 The preparation method of big particle diameter core shell structure silicone acrylates/styrol copolymer
CN107226883A (en) * 2017-07-03 2017-10-03 南昌大学 A kind of core shell structure aqueous silicone acrylic emulsion and preparation method thereof

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0827347A (en) * 1994-07-15 1996-01-30 Nisshin Chem Ind Co Ltd Alkoxysilyl-containing acrylic emulsion
JP2002038057A (en) * 2000-07-28 2002-02-06 Dainippon Ink & Chem Inc Water-base coating material composition containing silicone resin
CN101121771A (en) * 2006-08-11 2008-02-13 汉高股份两合公司 Acryloxyalkoxysilicane modified acrylic acid ester polymerization emulsion and its preparation method and application
CN101456936A (en) * 2007-12-10 2009-06-17 华南理工大学 Flame-retardant interfacial modifier and preparation method and flame retardant polycarbonate composition
CN102464784A (en) * 2010-11-19 2012-05-23 北京佳盛世纪科技有限公司 Synthesis method of organic silicon modified acrylate copolymer
CN102516450A (en) * 2011-12-02 2012-06-27 陕西科技大学 Method for preparing water-resistant and cold-resistant leather coating agent with high solid content with pre-emulsified core-shell emulsion polymerization method
CN103483493A (en) * 2013-09-18 2014-01-01 广州中国科学院工业技术研究院 Silicone modified acrylic ester emulsion and preparation method thereof
JP2015140361A (en) * 2014-01-27 2015-08-03 三菱レイヨン株式会社 Impact strength modifier for aliphatic polyester resin, aliphatic polyester resin composition and molded article thereof
CN106146755A (en) * 2015-04-09 2016-11-23 泉州市合创涂料科技有限公司 A kind of preparation method of high solids content silicone acrylic emulsion
CN106866971A (en) * 2017-04-10 2017-06-20 广东优科艾迪高分子材料有限公司 A kind of weather-proof low-temperature type organosilicon impact modifier and preparation method and application
CN107151296A (en) * 2017-04-18 2017-09-12 华南理工大学 The preparation method of big particle diameter core shell structure silicone acrylates/styrol copolymer
CN107226883A (en) * 2017-07-03 2017-10-03 南昌大学 A kind of core shell structure aqueous silicone acrylic emulsion and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
SUN PING等: "Properties of composite organic silicone modified styrene acrylic emulsion", 《ELECTROPLATING & FINISHING》 *
任淑英: "ACR抗冲击改性剂的合成及其在聚乳酸改性中的应用研究", 《中国塑料》 *
李鲜英: "抗冲改性剂有机硅改性ACR的合成及其在PC中的应用", 《塑料助剂》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112724334A (en) * 2020-12-29 2021-04-30 铨盛聚碳科技股份有限公司 Organic silicon acrylate impact modifier and preparation method thereof
CN113278115A (en) * 2021-05-27 2021-08-20 英德侗富贵科技材料有限公司 Core-shell polymer and preparation method and application thereof
CN114478952A (en) * 2022-01-25 2022-05-13 深圳市骏鼎达新材料股份有限公司 Preparation method of epoxy group-containing polysiloxane-acrylate elastomer and application of epoxy group-containing polysiloxane-acrylate elastomer in low-temperature toughening nylon tube
CN114773788A (en) * 2022-05-11 2022-07-22 泉州师范学院 Photosensitive resin composition based on nano silicon rubber core-shell structure polymer toughened epoxy resin and application of photosensitive resin composition in 3D printing
CN114853959A (en) * 2022-05-11 2022-08-05 泉州师范学院 Preparation method of clean nano organosilicon core-shell toughening powder
CN114853959B (en) * 2022-05-11 2023-05-26 泉州师范学院 Preparation method of clean nano organic silicon core-shell toughening powder
CN114773788B (en) * 2022-05-11 2023-09-19 泉州师范学院 Photosensitive resin composition based on nano silicone rubber core-shell structure polymer toughened epoxy resin and application of photosensitive resin composition in 3D printing

Similar Documents

Publication Publication Date Title
CN110922541A (en) Preparation method of ACR elastic resin with core-shell structure
CN108300407B (en) Low modR vulcanization neutral silicone weather proofing sealant of a kind of one-component de-oxime type and preparation method thereof
CN106632816B (en) A kind of colorful continuous phase silicone acrylic emulsion and preparation method thereof reacted with protective glue
CN101781390B (en) Preparation method of nuclear shell structure high-silicon silicone acrylic emulsion used for building exterior wall
JP5242805B2 (en) Epoxy resin containing siloxane mixture, process for producing the same and use thereof
CN110305621A (en) A kind of dealcoholized cold curing organosilicon sealant and preparation method thereof
CN1654533A (en) Nano silicon dioxide/acrylate composite emulsion and process for preparing same
CN101724326A (en) Waterborne organic silicon-acrylic acid self-stratifying coating
CN104213465B (en) Refreshing UV paper gloss oil of release effect, superslide and preparation method thereof is had after a kind of UV ultraviolet light polymerization
CN110577747A (en) room temperature vulcanized fluorosilicone rubber and preparation method thereof
CN110387128B (en) Self-adhesive single-component addition type silicone rubber and preparation method thereof
CN110818860A (en) Preparation method of acrylate modified organic silicon resin
CN107033295B (en) A kind of micro-nano emulsion of organosilicon-modified acrylic and preparation method thereof
CN110511385A (en) A kind of polysiloxanes/polysilsesquioxane core-shell emulsion and preparation method thereof
CN1517373A (en) Composition of elastic organic silicon phenylpropyl resin emulsion for paint and its preparation method
CN114044847B (en) High-water-resistance and dirt-resistance acrylate emulsion and preparation method thereof
CN1546542A (en) Method for preparing organic silicon modified polyacrylic acid (polyacrylate) emulsion
CN102617812B (en) Preparation method of anionic water-based polyurethane/poly (phenethylene-acrylate-acrylonitrile) hybrid emulsion
CN102093563A (en) Preparation method of negative ion hydrophilic organic silicon emulsion
CN106380763A (en) Organosilicon-modified PVC composite material
JP2010528165A (en) Reactive resin containing core-shell particles, method for producing the same and use thereof
CN110885399B (en) Acrylic emulsion adhesive and preparation method thereof
CN109504267B (en) Organic silicon modified water-based composite wood coating and preparation method and application thereof
CN114790342B (en) Silane modified carbon black composite filler and preparation method thereof
CN108003623B (en) Single-component silicone rubber for acrylic bonding and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20200327

RJ01 Rejection of invention patent application after publication