CN107151296B - Big partial size core-shell structure polysiloxanes-acrylate/styrol copolymer preparation method - Google Patents
Big partial size core-shell structure polysiloxanes-acrylate/styrol copolymer preparation method Download PDFInfo
- Publication number
- CN107151296B CN107151296B CN201710252485.7A CN201710252485A CN107151296B CN 107151296 B CN107151296 B CN 107151296B CN 201710252485 A CN201710252485 A CN 201710252485A CN 107151296 B CN107151296 B CN 107151296B
- Authority
- CN
- China
- Prior art keywords
- acrylate
- polysiloxanes
- shell structure
- added
- core
- 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.)
- Active
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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- 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
- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/18—Increasing the size of the dispersed particles
-
- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/22—Coagulation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Silicon Polymers (AREA)
Abstract
本发明公开了大粒径核壳结构聚硅氧烷‑丙烯酸酯/苯乙烯共聚物的制备方法。该制备方法是向聚硅氧烷‑丙烯酸丁酯乳液中加入聚丙烯酸酯类附聚剂，附聚得到聚硅氧烷‑丙烯酸酯核乳液；温度调至60℃～80℃，加入无机过氧类引发剂与碳酸钠，调节pH值，加入甲基丙烯酸甲酯和苯乙烯，反应，得到核壳结构聚硅氧烷‑丙烯酸酯/苯乙烯共聚物乳液；加水稀释，控制固含量为15％～19％，加入无机盐水溶液，室温搅拌，熟化，再冷却、离心分离、洗涤，将所得沉淀干燥。本发明所得聚硅氧烷‑丙烯酸酯/苯乙烯共聚物产物粒子核壳结构明显，平均粒径400nm～600nm，对工程塑料聚碳酸酯有明显的低温增韧作用。
The invention discloses a preparation method of a large particle size core-shell structure polysiloxane-acrylate/styrene copolymer. The preparation method includes adding a polyacrylate agglomeration agent to a polysiloxane-butyl acrylate emulsion, and agglomerating to obtain a polysiloxane-acrylate core emulsion; adjusting the temperature to 60°C to 80°C, adding inorganic peroxygen A similar initiator and sodium carbonate, adjust the pH value, add methyl methacrylate and styrene, and react to obtain a core-shell structure polysiloxane-acrylate/styrene copolymer emulsion; add water to dilute, and control the solid content to 15% ~19%, add an aqueous inorganic salt solution, stir at room temperature, mature, then cool, centrifuge, wash, and dry the resulting precipitate. The polysiloxane-acrylate/styrene copolymer product obtained by the invention has an obvious core-shell structure and an average particle size of 400nm-600nm, and has obvious low-temperature toughening effect on engineering plastic polycarbonate.
Description
Technical field
The present invention relates to a kind of big partial size core-shell structure polysiloxanes-acrylate/styrol copolymer preparation method,
Specifically, be related to a kind of latex particle size 400nm~600nm has nucleocapsid structure polysiloxanes-acrylate/benzene
The preparation method of ethylene copolymer.
Background technique
Polysiloxane rubber polarity is small, and flexibility is good, has excellent high temperature resistant, durability in oxidative degradation；Polyacrylate
Rubber and polar polymer interaction force are strong, are widely used as the impact modifier of thermoplastic resin and its alloy.Poly- silicon oxygen
Alkane-acrylic acid esters co-polymer combines the very big polymer of polysiloxanes and two class polarity spectrum of polyacrylate, simultaneous
Advantage in both tools performance can assign thermoplastic resin and its better low temperature impact effect of alloy.Emulsion polymerization is commonly used to
Polysiloxanes-acrylic acid esters co-polymer is prepared, since the increase of partial size will affect the stability of polymer emulsion, leads to lotion
The phenomenon that generating a large amount of gels in synthesis process or even being demulsified, polymerization process is difficult to control, so existing emulsion polymerisation process system
Polysiloxanes-acrylic acid esters co-polymer latex particle the partial size obtained is mostly in 200nm or less.Increase polysiloxanes-acrylic acid
It ester copolymer latex particle partial size and is allowed to that core-shell structure is presented, is being used as thermoplastic resin such as polycarbonate (PC) and its benzene
Ethylene-butylene-acrylonitrile copolymer (ABS) alloy it is impact-resistant modified when effect it is bigger, therefore develop big partial size core-shell structure
Polysiloxanes-acrylic acid esters co-polymer is of great significance.
South China Science & Engineering University Feng Meng is in its master's thesis (nucleocapsid structure polysiloxanes-acrylate elastomer system
Standby and its toughening PC/ABS alloy research) in disclose a kind of substep emulsion polymerizing preparation silicon-acrylate elastomer
Method, this method is using octamethylcy-clotetrasiloxane, γ-methacryloxypropyl trimethoxy silane as silane monomer system
Standby polysiloxanes core lotion, then distinguish graft copolymerization with butyl acrylate, methyl methacrylate obtains latex particle and is averaged grain
Diameter is polysiloxanes-acrylate copolymer emulsion of 193.8nm, and methyl methacrylate polymerization step is not only added in this method
It is easy demulsification, and final product is not fairly obvious to PC toughening effect.The patent of invention of General Electric Company
(CN99813947.5) emulsion polymerization is used, by reducing the dosage of emulsifier, increasing the methods of the reaction time for poly- silicon oxygen
The size controlling of alkane core lotion is in 400nm or more, and then grafted acrylate class again, obtains silicone-acrylate rubber punching
Modifying agent is hit, but polysiloxanes core lotion obtained by this method is very sticky, the problems such as unstable lotion, layering occurs.
In conclusion there has been no prepare big partial size well, have nucleocapsid structure polysiloxanes-acrylic acid for the prior art
The method of ester copolymer.
Summary of the invention
The object of the present invention is to provide a kind of emulsion-stabilizing, latex particle partial sizes to reach 400nm~600nm, has core-shell structure copolymer
Structure polysiloxanes-acrylate/styrol copolymer preparation method.
In order to achieve the above object, the present invention uses polyacrylate to polysiloxanes-butyl acrylate copolymer lotion
The method of class agglomeration passes through the soft micelle Surface charge layer of local failure polysiloxanes-butyl acrylate copolymer latex
Stability overcomes the repulsive force of surfactant emulsion agent, makes between particle that interface is close, adhesion, from containing polysiloxanes-butyl acrylate
The short grained stable emulsifying state of copolymer is changed into another stable state of the bulky grain containing copolymer, latex particle partial size from
100nm or so increases to 300nm or more as core；With the two kinds of hard monomer graft copolymerizations of methyl methacrylate and styrene, polymerization
Process is stablized, and copolymer of methyl methacrylatestyrene shell is superscribed outside it, and the final average grain diameter that obtains is in 400nm
Polysiloxanes-acrylate/styrene copolymer latexes of~600nm, core-shell structure, what is obtained after inorganic salts are demulsified is poly-
Silicon-acrylate/styrol copolymer has good toughening effect to polycarbonate and its with the copolymer of ABS, especially
It is obvious to polycarbonate low temperature toughening effect.
The object of the invention is achieved through the following technical solutions:
Big partial size core-shell structure polysiloxanes-acrylate/styrol copolymer preparation method, comprising the following steps:
(1) polyacrylate agglomerant is added into polysiloxanes-polybutylacrylate latex, in 30 DEG C~70 DEG C of temperature
Degree lower stirring agglomeration 30~120 minutes, obtain polysiloxanes-acrylate core lotion；Every 100 mass parts dry weight polysiloxanes-
1~5 mass parts dry weight polyacrylate agglomerant is added in polybutylacrylate latex；
(2) polysiloxanes-acrylate core lotion temperature obtained by step (1) is adjusted to 60 DEG C~80 DEG C, be added inorganic
PH value is adjusted to 9~11 by peroxide initiator and sodium carbonate, adds methyl methacrylate and benzene that mass ratio is 1~3:1
Ethylene reacts 3~6 hours, and obtaining latex particle is 400nm~600nm, core-shell structure polysiloxanes-acrylate/styrene
The solid content control of copolymer emulsion, lotion is 30~37%, the gross mass dosage of methyl methacrylate and styrene and dry
Reunion silicon-acrylate core quality of the emulsion ratio is 20~45:55~80；
(3) polysiloxanes-acrylate/styrene copolymer latexes obtained by step (2) are diluted with water, control solid content
It is 15%~19%, inorganic salt solution is added, it is stirred at room temperature 15~after sixty minutes, it is warming up to 80 DEG C~90 DEG C curings 30~60
Minute, then cooling, centrifuge separation, washing, gained is precipitated into drying, obtains white solid, is the poly- silicon oxygen of big partial size core-shell structure
Alkane-acrylate/styrol copolymer.
To further realize the present invention, it is preferable that the preparation side of step (1) polysiloxanes-polybutylacrylate latex
Method are as follows: at 60 DEG C~90 DEG C, first by two degree of functionality organosilans, tri-alkoxy organosilan existing for the anion emulsifier
Polymerization reaction 1~3 hour in aqueous solution, then thereto be added include water, anion emulsifier, two degree of functionality organosilans,
The pre-emulsion mixture of tri-alkoxy organosilan and end-capping reagent hydrolyzes copolycondensation 2~5 hours, obtains polysiloxanes cream
Liquid, control solid content are 28%~35%；
Deionized water, mixed emulsifier, inorganic peroxy class initiator and carbonic acid are added into the polysiloxane emulsion
PH value is adjusted to 9~11 by sodium, and at 60 DEG C~80 DEG C, the mixture of butyl acrylate and crosslinking agent is added using semi-continuous process,
It is reacted again 2~5 hours after the completion of charging, obtains polysiloxanes-polybutylacrylate latex；
The gross mass and acrylic acid fourth of two kinds of organosilane monomers of two degree of functionality organosilans and tri-alkoxy organosilan
The mass ratio of ester is 5~25:75~95；Two degree of functionality organosilans both account for the 90%~95% of organosilan gross mass, and three
Alkoxy silane accounts for the 5%~10% of two kinds of organosilan gross masses；Both two kinds of organosilane monomers are added in two portions, keep
Mass ratio it is constant, for the first time addition both gross mass 20-30%, add remaining 70-80% for the second time.
Crosslinking agent is allyl methacrylate or ethylene glycol dimethacrylate, and quality dosage is butyl acrylate
The 2%~4% of quality；Solid content is controlled 30~38%.
Preferably, the two degrees of functionality organosilan is octamethylcy-clotetrasiloxane, and the trialkoxy silane is ethylene
Base trimethoxy silane, vinyltriethoxysilane or γ-methacryloxypropyl trimethoxy silane；The sealing end
Agent is hexamethyldisiloxane, and dosage is the 0.1%~0.3% of two kinds of organosilan gross masses.
Preferably, the anion emulsifier is by C12~16At least one of alkyl benzene sulphonate and C12~18In sodium alkyl sulfate
At least one is constituted, and the mass ratio of two kinds of emulsifiers is 1~2:1, and the dosage of anion emulsifier is two kinds of organosilane monomers
The 2%~5% of gross mass, keep both mass ratio it is constant, be added in two portions, for the first time be added quality dosage 50%~
75%.
Preferably, the mixed emulsifier is by C12~18At least one of sodium alkyl sulfate and nonylphenol polyoxyethylenes
Ether is constituted, and for the mass ratio of two kinds of emulsifiers in 1:2 between 2:1, dosage is the 1%~5% of butyl acrylate quality.
Preferably, the inorganic peroxy class initiator is potassium peroxydisulfate or ammonium persulfate, and dosage is butyl acrylate quality
0.1%~0.5%；The dosage of sodium carbonate is the 0.5%~1.5% of butyl acrylate quality；It is described that pH value is adjusted to 9~11
It is to be adjusted by sodium hydroxide solution.
Preferably, the polyacrylate agglomerant the preparation method comprises the following steps: to including deionized water, C12~18Alkyl
Mass ratio is added in two portions in the system of at least one of sodium sulphate emulsifier, molecular weight regulator and inorganic peroxy class initiator
For the butyl acrylate and acrylic acid of 60~90:10~40, is reacted 2~4 hours at 60 DEG C~90 DEG C, obtain polyacrylate
Class agglomerant, control solid content are 31%~35%, are used after dilution；The mass ratio of control butyl acrylate and acrylic acid is not
Become, the 10% of both additions gross mass, adds remaining 90% for the second time for the first time, is all made of semi-continuous process addition.
Preferably, the inorganic peroxy class initiator is potassium peroxydisulfate or ammonium persulfate, and dosage is butyl acrylate and third
The 1%~2% of olefin(e) acid gross mass；The C12~18Sodium alkyl sulfate emulsifier is butyl acrylate and acrylic acid gross mass
0.5%~3%；The molecular weight regulator is lauryl mercaptan, and dosage is butyl acrylate and acrylic acid gross mass
0.5%~2%.
Preferably, step (2) the inorganic peroxy class initiator is potassium peroxydisulfate or ammonium persulfate, and dosage is metering system
The 0.1%~0.5% of sour methyl esters and styrene gross mass；Sodium carbonate amount is methyl methacrylate and styrene gross mass
1%~3%；Step (2) is described, which to be adjusted to 9~11 for pH value, is adjusted by sodium hydroxide solution.
Preferably, step (3) inorganic salts are one of magnesium sulfate, calcium chloride and aluminum sulfate, inorganic salt solution
Mass percentage concentration is that polysiloxanes-acrylate of every 100 mass parts dry weight/styrene copolymerized is controlled between 5%~25%
20~120 mass parts inorganic salts are added in object；Drying described in step (3) is will to be deposited in drying 8~10 hours at 80 DEG C.
Compared with the prior art, the present invention has the advantage that
(1) using polyacrylate to polysiloxanes-soft particle agglomeration of butyl acrylate copolymer latex, latex particle
Partial size increases to 300nm or more from 100nm or so, and the time is 30~120 minutes, and the time is short, and method is simple, high-efficient, and partial size
It is adjustable, the core emulsion-stabilizing of formation；
(2) using the two kinds of hard monomer graft copolymerizations of methyl methacrylate and styrene in polysiloxanes-butyl acrylate
The method that hard shell is formed outside copolymer, polymerization process good emulsion stability；Exclusive use methacrylic acid is overcome well
Methylmethacrylate monomer generates the problems such as being demulsified since polymerization rate is fast；
(3) gained polysiloxanes-acrylate/styrol copolymer product particles core-shell structure is obvious, average grain diameter
400nm~600nm has apparent low temperature toughening effect to engineering plastics polycarbonate.
Detailed description of the invention
Fig. 1 is 1 gained polysiloxanes of embodiment-acrylate core emulsion latex particle diameter size distribution figure；
Fig. 2 is 1 gained polysiloxanes of embodiment-acrylate/styrenic copolymer latex particle diameter size distribution figure；
Fig. 3 is 1 gained polysiloxanes of embodiment-acrylate/styrenic copolymer latex particle TEM photo；
Fig. 4 is 1 gained polysiloxanes of comparative example-acrylate/styrenic copolymer latex particle diameter size distribution figure；
Fig. 5 is 1 gained polysiloxanes of comparative example-acrylate/styrenic copolymer latex particle TEM photo.
Specific embodiment
For a better understanding of the invention, the present invention is further illustrated with reference to the accompanying drawings and examples, but this hair
Bright embodiment is unlimited so.
Embodiment 1
The preparation of polysiloxanes-polybutylacrylate latex: in 250ml reaction flask be added 0.3g dodecyl benzene sulfonic acid,
0.3g lauryl sodium sulfate and 50g deionized water are heated to 60 DEG C after mixing evenly, add four silicon of 9.0g prestox ring
Oxygen alkane and 1.0g γ-methacryloxypropyl trimethoxy silane are kept for 60 DEG C react 3 hours；By 20g deionized water,
0.1g dodecyl benzene sulfonic acid, 0.1g lauryl sodium sulfate, 27g octamethylcy-clotetrasiloxane, 3.0g γ-methacryloxypropyl
Base propyl trimethoxy silicane and 0.04g hexamethyldisiloxane are layered by homogeneous blender high-speed stirred to without obvious, 2
In hour, which is added drop-wise in above-mentioned reaction flask, is reacted 5 hours at 60 DEG C, obtaining solid content is 33.8%
Polysiloxane emulsion；
The above-mentioned polysiloxane emulsion of 8.9g is taken, 80g deionized water, 0.6g alkyl phenol polyoxyethylene ether and 0.6g 12 is added
Sodium alkyl sulfate stirs evenly in another 250ml reaction flask, is warming up to 60 DEG C；31.18g is added and contains 0.28g potassium peroxydisulfate
With the aqueous solution of 0.9g sodium carbonate, its pH is adjusted to 11 with the sodium hydroxide solution that mass concentration is 5%, then is dripped in 2 hours
Adding the mixture of 57g butyl acrylate and 1.14g allyl methacrylate, reacts 5 hours, reaction temperature is maintained at 60 DEG C,
Polysiloxanes-polybutylacrylate latex that solid content is 33.7% is obtained, using the BI- of Brooker Hai Wen instrument company of the U.S.
It is 140nm that 90Plus type Zeta potential meter Particle Size Analyzer (following partial size is all measured with the instrument), which measures average grain diameter,；
The preparation of polyacrylate agglomerant: 180g deionized water, 3.0g 12 are sequentially added into 250ml reaction flask
Sodium alkyl sulfate and 2.0g lauryl mercaptan stir and are warming up to 60 DEG C, add the over cure that 8.0g mass concentration is 10%
The mixture of 8.0g butyl acrylate and 2.0g acrylic acid is added dropwise in 0.5 hour, reacts 1.5 at 60 DEG C for sour aqueous solutions of potassium
Hour, then be added 12.0g mass concentration be 10% persulfate aqueous solution, in 2 hours be added dropwise 72g butyl acrylate and
The mixture of 18g acrylic acid reacts 2.5 hours at 60 DEG C, obtains the polyacrylate agglomerant that solid content is 32.1%；
Polysiloxanes-acrylate/styrene copolymer latexes preparation: the above-mentioned polysiloxanes-butyl acrylate of 90g is taken
Lotion is added in another 250ml reaction flask, adds after the above-mentioned polyacrylate agglomerant of 1.9g is diluted with 17.1g deionized water
Enter, stir at 30 °C for 2 hours, obtains polysiloxanes-acrylate core lotion, latex particle particle size distribution situation is such as
Attached drawing 1, average grain diameter 310nm；60 DEG C are raised the temperature to, 10.7g is added and contains 0.1g potassium peroxydisulfate and 0.6g sodium carbonate
Aqueous solution, with mass concentration be 3% sodium hydroxide solution its pH is adjusted to 11, in 2 hours be added dropwise 15g methacrylic acid
Methyl esters and 5g styrene mixture, and cooled down after being reacted 6 hours at 60 DEG C, obtain stable polysiloxanes-acrylate/benzene
Ethylene copolymer emulsion, solid content 36.9%, gained latex particle particle size distribution situation such as attached drawing 2, average grain diameter are
410nm, and narrowly distributing；Latex particle uses the TECNAIG of FEI electron-optical company of Holland after being dyed with phosphotungstic acid2- 12 types are saturating
Radio mirror (TEM) observation, gained photo such as attached drawing 3, it can be seen that latex particle size about 410nm, is presented apparent from figure
Core-shell structure.
Demulsification: the above-mentioned polysiloxanes-acrylate/styrene copolymer latexes of 100g are taken, it is dilute to pour into 100g deionized water
It releases, is slowly added to the aluminum sulfate aqueous solution that 148g mass concentration is 5% at room temperature, persistently stirs 15 minutes, temperature is increased
It to 80 DEG C and is kept for 60 minutes, then cooling, centrifugation, washing, it is 8 hours dry at 80 DEG C, obtain the big poly- silicon of partial size core-shell structure
Oxygen alkane-acrylate/styrol copolymer white solid.
Embodiment 2
The preparation of polysiloxanes-polybutylacrylate latex: in 250ml reaction flask be added 0.4g dodecyl benzene sulfonic acid,
0.4g lauryl sodium sulfate and 60g deionized water are heated to 70 DEG C after mixing evenly, add four silicon of 9.5g prestox ring
Oxygen alkane and 0.5g γ-methacryloxypropyl trimethoxy silane are kept for 70 DEG C react 3 hours；By 30g deionized water,
0.2g dodecyl benzene sulfonic acid, 0.2g lauryl sodium sulfate, 28.5g octamethylcy-clotetrasiloxane, 1.5g vinyl trimethoxy
Base silane and the mixture of 0.08g hexamethyldisiloxane were layered by homogeneous blender high-speed stirred to without obvious, at 2 hours
It is interior, which is added drop-wise in reaction flask, is reacted 3 hours at 70 DEG C, the poly- silicon oxygen that solid content is 28.6% is obtained
Alkane lotion；
The above-mentioned polysiloxane emulsion of 25g is taken, 100g deionized water, 0.4g alkyl phenol polyoxyethylene ether and 0.2g 12 is added
Sodium alkyl sulfate stirs evenly in another 250ml reaction flask, is warming up to 70 DEG C；30.73g is added and contains 0.13g ammonium persulfate
With the aqueous solution of 0.6g sodium carbonate, its pH is adjusted to 11 with the sodium hydroxide solution that mass concentration is 2%, then is dripped in 2 hours
Add the mixture of 63g butyl acrylate and 1.26g ethylene glycol dimethacrylate, reacts 4 hours, reaction temperature is maintained at 70
DEG C, obtain polysiloxanes-polybutylacrylate latex that solid content is 31.3%, partial size 140nm；
The preparation of polyacrylate agglomerant: 180g deionized water, 1.0g 16 are sequentially added into 250ml reaction flask
Sodium alkyl sulfate and 1.0g lauryl mercaptan stir and are warming up to 90 DEG C, add the persulfuric acid that 8.0g mass concentration is 5%
The mixture of 9.0g butyl acrylate and 1.0g acrylic acid is added dropwise in aqueous solutions of potassium in 0.5 hour, and it is small that 0.5 is reacted at 90 DEG C
When, then be added 12.0g mass concentration be 5% persulfate aqueous solution, then in 2 hours be added dropwise 81g butyl acrylate and
The mixture of 9g acrylic acid reacts 1.5 hours at 90 DEG C, obtains the polyacrylate agglomerant that solid content is 31.3%；
Polysiloxanes-acrylate/styrene copolymer latexes preparation: the above-mentioned polysiloxanes of 110g-acrylic acid fourth is taken
Ester lotion adds after diluting the above-mentioned polyacrylate agglomerant of 5.6g with 30.4g deionized water in another 250ml reaction flask
Enter, stirred 1 hour at 50 DEG C, obtain polysiloxanes-acrylate core lotion, the partial size for measuring latex particle is 360nm；It will
Temperature is increased to 70 DEG C, and the aqueous solution that 10.33g contains 0.03g ammonium persulfate and 0.3g sodium carbonate is added, is with mass concentration
Its pH is adjusted to 11 by 4% sodium hydroxide solution, and 10g methyl methacrylate and 5g styrene mixture are added dropwise in 2 hours,
And it is cooling after being reacted 5 hours at 70 DEG C, stable polysiloxanes-acrylate/styrene copolymer latexes are obtained, admittedly contain
Amount is 30.1%, average grain diameter 450nm；
Demulsification: the above-mentioned polysiloxanes-acrylate/styrene copolymer latexes of 100g are taken, it is dilute to pour into 100g deionized water
It releases, is slowly added to the calcium chloride water that 144g mass concentration is 25% at room temperature, persistently stirs 15 minutes, temperature is increased
It to 80 DEG C and is kept for 60 minutes, then cooling, centrifugation, washing, it is 9 hours dry at 80 DEG C, obtain the big poly- silicon of partial size core-shell structure
Oxygen alkane-acrylate/styrol copolymer white solid.
Embodiment 3
The preparation of polysiloxanes-polybutylacrylate latex: in 250ml reaction flask be added 0.4g myristyl benzene sulfonic acid,
0.4g sodium hexadecyl sulfate and 60g deionized water are heated to 80 DEG C after mixing evenly, add four silicon of 9.5g prestox ring
Oxygen alkane and 0.5g γ-methacryloxypropyl trimethoxy silane are kept for 80 DEG C react 2 hours；By 20g deionized water,
0.4g myristyl benzene sulfonic acid, 0.4g sodium hexadecyl sulfate, 28.5g octamethylcy-clotetrasiloxane, 1.5g vinyl trimethoxy
Base silane and the mixture of 0.08g hexamethyldisiloxane were layered by homogeneous blender high-speed stirred to without obvious, at 2 hours
It is interior, which is added drop-wise in reaction flask, is reacted 3 hours at 80 DEG C, the poly- silicon oxygen that solid content is 31.4% is obtained
Alkane lotion；
The above-mentioned polysiloxane emulsion of 29g is taken, 100g deionized water, 0.8g alkyl phenol polyoxyethylene ether and 0.8g 12 is added
Sodium alkyl sulfate stirs evenly in another 250ml reaction flask, is warming up to 70 DEG C；30.55g is added and contains 0.15g ammonium persulfate
With the aqueous solution of 0.5g sodium carbonate, its pH is adjusted to 10 with the sodium hydroxide solution that mass concentration is 1%, is added dropwise in 2 hours
The mixture of 51g butyl acrylate and 1.5g allyl methacrylate reacts 3 hours, and reaction temperature is maintained at 70 DEG C, obtains
Polysiloxanes-polybutylacrylate latex that solid content is 29.9%, average grain diameter 130nm；
The preparation of polyacrylate agglomerant: 160g deionized water, 1.0g 16 are sequentially added into 250ml reaction flask
Sodium alkyl sulfate and 1.0g lauryl mercaptan stir and are warming up to 70 DEG C, add the persulfuric acid that 8.0g mass concentration is 5%
Aqueous solutions of potassium, then the mixture of 7.0g butyl acrylate and 3.0g acrylic acid is added dropwise in 0.5 hour, react 1 small at 70 DEG C
When, then be added 12.0g mass concentration be 5% persulfate aqueous solution, then in 2 hours be added dropwise 63g butyl acrylate and
The mixture of 27g acrylic acid reacts 2 hours at 70 DEG C, obtains the polyacrylate agglomerant that solid content is 33.5%；
Polysiloxanes-acrylate/styrene copolymer latexes preparation: the above-mentioned polysiloxanes of 102g-acrylic acid fourth is taken
Ester lotion adds after diluting the above-mentioned polyacrylate agglomerant of 2.7g with 24.3g deionized water in another 250ml reaction flask
Enter, stirred 1 hour at 50 DEG C, obtain polysiloxanes-acrylate core lotion, the partial size for measuring latex particle is 380nm；It will
Temperature is increased to 70 DEG C, and the aqueous solution that 10.46g contains 0.06g potassium peroxydisulfate and 0.4g sodium carbonate is added, is with mass concentration
Its pH is adjusted to 10 by 3% sodium hydroxide solution, and 13.3g methyl methacrylate and the mixing of 6.7g styrene are added dropwise in 2 hours
Object, and cooled down after being reacted 4 hours at 70 DEG C, stable polysiloxanes-acrylate/styrene copolymer latexes are obtained,
Solid content is 33.1%, and the partial size for measuring latex particle is 600nm；
Demulsification: the above-mentioned polysiloxanes-acrylate/styrene copolymer latexes of 100g are taken, it is dilute to pour into 100g deionized water
It releases, is slowly added to the calcium chloride water that 132g mass concentration is 20% at room temperature, persistently stirs 30 minutes, temperature is increased
It to 80 DEG C and is kept for 40 minutes, then cooling, centrifugation, washing, it is 10 hours dry at 80 DEG C, obtain the big poly- silicon of partial size core-shell structure
Oxygen alkane-acrylate/styrol copolymer white solid.
Embodiment 4
The preparation of polysiloxanes-polybutylacrylate latex: in 250ml reaction flask be added 1.0g myristyl benzene sulfonic acid,
0.5g sodium hexadecyl sulfate and 50g deionized water are heated to 90 DEG C after mixing evenly, add four silicon of 9.0g prestox ring
Oxygen alkane and 1.0g vinyltriethoxysilane are kept for 90 DEG C react 1 hour；By 20g deionized water, 0.33g Tetradecylbenzene
Sulfonic acid, 0.17g sodium hexadecyl sulfate, 27g octamethylcy-clotetrasiloxane, 3.0g vinyltriethoxysilane and 0.12g six
The mixture of tetramethyldisiloxane, to without obvious layering, in 2 hours, which is mixed by homogeneous blender high-speed stirred
It closes object to be added drop-wise in reaction flask, be reacted 2 hours at 90 DEG C, obtain the polysiloxane emulsion that solid content is 34.9%；
The above-mentioned polysiloxane emulsion of 40g is taken, 80g deionized water, 0.6g alkyl phenol polyoxyethylene ether and 1.1g 16 is added
Sodium alkyl sulfate stirs evenly in another 250ml reaction flask, is warming up to 80 DEG C；30.36g is added and contains 0.06g ammonium persulfate
With the aqueous solution of 0.3g sodium carbonate, its pH is adjusted to 10 with the sodium hydroxide solution that mass concentration is 5%, then is dripped in 2 hours
Add the mixture of 56g butyl acrylate and 2.24g ethylene glycol dimethacrylate, reacts 2 hours, reaction temperature is maintained at 80
DEG C, obtain polysiloxanes-polybutylacrylate latex that solid content is 33.7%, average grain diameter 120nm；
The preparation of polyacrylate agglomerant: 150g deionized water, 0.5g 18 are sequentially added into 250ml reaction flask
Sodium alkyl sulfate and 0.5g lauryl mercaptan stir and are warming up to 80 DEG C, add the over cure that 8.0g mass concentration is 10%
Sour aqueous ammonium, then in 0.5 hour be added dropwise 6.0g butyl acrylate and 4.0g acrylic acid mixture, reacted at 80 DEG C
0.5 hour, the ammonium persulfate aqueous solution that 12.0g mass concentration is 10% is then added, then 54g acrylic acid is added dropwise in 2 hours
The mixture of butyl ester and 36g acrylic acid reacts 1.5 hours at 80 DEG C, obtains the polyacrylate that solid content is 34.9%
Agglomerant；
Polysiloxanes-acrylate/styrene copolymer latexes preparation: the above-mentioned polysiloxanes of 105g-acrylic acid fourth is taken
Ester lotion adds after diluting the above-mentioned polyacrylate agglomerant of 2.0g with 18g deionized water in another 250ml reaction flask
Enter, stirred 0.5 hour at 70 DEG C, obtain polysiloxanes-acrylate core lotion, the partial size for measuring latex particle is 330nm；
80 DEG C are raised the temperature to, the aqueous solution that 10.165g contains 0.015g ammonium persulfate and 0.15g sodium carbonate is added, it is dense with quality
Its pH is adjusted to 10 for 1% sodium hydroxide solution by degree, and 7.5g methyl methacrylate is added dropwise in 2 hours and 7.5g styrene is mixed
Object is closed, and is cooled down after being reacted 3 hours at 80 DEG C, stable polysiloxanes-acrylate/styrene copolymer latexes are obtained,
Its solid content is 34.1%, and the partial size for measuring latex particle is 400nm；
Demulsification: the above-mentioned polysiloxanes-acrylate/styrene copolymer latexes of 100g are taken, it is dilute to pour into 100g deionized water
It releases, is slowly added to the magnesium sulfate solution that 272g mass concentration is 15% at room temperature, persistently stirs 30 minutes, temperature is increased
It to 90 DEG C and is kept for 40 minutes, then cooling, centrifugation, washing, it is 9 hours dry at 80 DEG C, obtain the big poly- silicon of partial size core-shell structure
Oxygen alkane-acrylate/styrol copolymer white solid.
Embodiment 5
The preparation of polysiloxanes-polybutylacrylate latex: in 250ml reaction flask be added 0.3g cetyl benzenesulfonic acid,
0.3g sodium stearyl sulfate and 50g deionized water are heated to 60 DEG C after mixing evenly, add four silicon of 9.0g prestox ring
Oxygen alkane and 1.0g γ-methacryloxypropyl trimethoxy silane are kept for 60 DEG C react 3 hours；By 20g deionized water,
0.1g cetyl benzenesulfonic acid, 0.1g sodium stearyl sulfate, 27g octamethylcy-clotetrasiloxane, 3.0g γ-methacryloxypropyl
Base propyl trimethoxy silicane and the mixture of 0.04g hexamethyldisiloxane are obvious to nothing by homogeneous blender high-speed stirred
Layering, in 2 hours, which is added drop-wise in reaction flask, is reacted 5 hours at 60 DEG C, obtaining solid content is
33.8% polysiloxane emulsion；
The above-mentioned polysiloxane emulsion of 59g is taken, 60g deionized water, 2.0g alkyl phenol polyoxyethylene ether and 1.0g 18 is added
Sodium alkyl sulfate stirs evenly in another 250ml reaction flask, is warming up to 80 DEG C；30.36g is added and contains 0.06g potassium peroxydisulfate
With the aqueous solution of 0.3g sodium carbonate, its pH is adjusted to 9 with the sodium hydroxide solution that mass concentration is 1%, then is added dropwise in 2 hours
The mixture of 60g butyl acrylate and 2.4g allyl methacrylate reacts 2 hours, and reaction temperature is maintained at 80 DEG C, obtains
Polysiloxanes-polybutylacrylate latex that solid content is 38.0%, average grain diameter 110nm；
The preparation of polyacrylate agglomerant: 180g deionized water, 2.0g 12 are sequentially added into 250ml reaction flask
Sodium alkyl sulfate and 1.0g lauryl mercaptan stir and are warming up to 60 DEG C, add the over cure that 8.0g mass concentration is 10%
Sour aqueous solutions of potassium, then in 0.5 hour be added dropwise 8.0g butyl acrylate and 2.0g acrylic acid mixture, reacted at 60 DEG C
1.5 hours, the persulfate aqueous solution that 12.0g mass concentration is 10% is then added, then 72g acrylic acid is added dropwise in 2 hours
The mixture of butyl ester and 18g acrylic acid obtains the polyacrylate agglomeration that solid content is 31.8% 2.5 hours at 60 DEG C
Agent；
Polysiloxanes-acrylate/styrene copolymer latexes preparation: the above-mentioned polysiloxanes of 107g-acrylic acid fourth is taken
Ester lotion adds after diluting the above-mentioned polyacrylate agglomerant of 2.5g with 22.5g deionized water in another 250ml reaction flask
Enter, stir at 30 °C for 2 hours, obtain polysiloxanes-acrylate core lotion, the partial size for measuring latex particle is 380nm；It will
Temperature is increased to 80 DEG C, and the aqueous solution that 10.11g contains 0.01g potassium peroxydisulfate and 0.1g sodium carbonate is added, is with mass concentration
Its pH is adjusted to 9 by 3% sodium hydroxide solution, dropwise addition 5g methyl methacrylate and 5g styrene mixture in 2 hours, and
It is cooling after being reacted 3 hours at 80 DEG C, stable polysiloxanes-acrylate/styrene copolymer latexes are obtained, solid content is
33.9%, the partial size for measuring latex particle is 560nm；
Demulsification: the above-mentioned polysiloxanes-acrylate/styrene copolymer latexes of 100g are taken, it is dilute to pour into 100g deionized water
It releases, is slowly added to the aluminum sulfate aqueous solution that 271g mass concentration is 10% at room temperature, persistently stirs 60 minutes, temperature is increased
It to 90 DEG C and is kept for 30 minutes, then cooling, centrifugation, washing, it is 8 hours dry at 80 DEG C, obtain the big poly- silicon of partial size core-shell structure
Oxygen alkane-acrylate/styrol copolymer white solid.
Comparative example 1
Polysiloxanes-polybutylacrylate latex is prepared in the same manner as in Example 1, but gained lotion directly carries out first
Then the graft copolymerization of base methyl acrylate and styrene carries out agglomeration using polyacrylate, to obtained polysiloxanes-
Acrylate/styrene copolymer latexes carry out particle size determination, and gained particle size distribution situation such as attached drawing 4 can from Fig. 4
It arrives, particle diameter distribution is wider, average grain diameter 200nm, solid content 38.7%；TEM after latex particle is dyed with phosphotungstic acid shines
Piece such as attached drawing 5, it can be seen that core-shell structure is presented in latex particle from Fig. 5, but particle is smaller, and diameter only has about 200nm；Using
Same as Example 1 method demulsification, dry etc., obtain polysiloxanes-acrylate/styrol copolymer white solid and oppose
Compare sample.
The product obtained with embodiment 1 and comparative example 1 is used for the toughening modifying of polycarbonate, by mass percentage for
94.8% polycarbonate (Samsung of South Korea, model SC-1100R), 5% polysiloxanes-acrylate/styrene copolymerized
After object, 0.2% antioxidant B215 carry out mixing, pass through dual-screw-stem machine melting, extrusion, cooling, dry, pelletizing and packaging；It is used
Double screw extruder model LTE26/40 (German LabTech company), each zone temperature of barrel are as follows: the first 210 DEG C of area, second
245 DEG C of area, 250 DEG C of third area, the 4th 255 DEG C of area, the 5th 260 DEG C of area, the 6th 260 DEG C of area, 260 DEG C of District 7, Section Eight 265
DEG C, the 9th 265 DEG C of area, 255 DEG C of head, engine speed 150r/min, rate of feeding: 25r/min；Prepared pellet presses standard
Size is molded into the standard batten of test, according to ASTMD638 canonical measure tensile strength and elongation at break, according to
ASTMD790 measures bending strength；Injection molding gained band notch standard impulse batten is freezed 2 in -40 DEG C of cryogenic freezing casees in advance
Hour, according to GB/T 1843-2008 canonical measure notch impact strength, test result such as table 1.
The raw material proportioning and test result of table 1 embodiment 1 and comparative example 1
As can be seen from Table 1, the big partial size core-shell structure polysiloxanes-acrylate/styrol copolymer of the present invention is to poly-
Carbonic ester has good low temperature toughening effect, and compared to pure polycarbonate, the notch impact strength at -40 DEG C increases more than 1 times, and
Tensile strength is only declined slightly with bending strength；In addition, agglomeration method is used for methyl methacrylate and benzene in preparation process
The product i.e. comparative sample obtained after Vinyl Graft copolymerization is smaller to polycarbonate low temperature toughening effect.Therefore the present invention is using poly-
Esters of acrylic acid to after polysiloxanes-soft particle agglomeration of butyl acrylate copolymer latex be used as core lotion, emulsion preparation process
Stablize, latex particle partial size increasing method is simple, and the time is short, high-efficient, gained polysiloxanes-acrylate/styrene copolymerized
Object product particle core-shell structure is obvious, and 400~600nm of average grain diameter has obviously engineering plastics polycarbonate and its ABS alloy
Low temperature toughening effect, have a good application prospect.
Claims (10)
1. big partial size core-shell structure polysiloxanes-acrylate/styrol copolymer preparation method, it is characterised in that including with
Lower step:
(1) into polysiloxanes-polybutylacrylate latex be added polyacrylate agglomerant, 30 DEG C~70 DEG C at a temperature of
Stirring agglomeration 30~120 minutes, obtains polysiloxanes-acrylate core lotion；Every 100 mass parts dry weight polysiloxanes-propylene
1~5 mass parts dry weight polyacrylate agglomerant is added in acid butyl ester lotion；
(2) polysiloxanes-acrylate core lotion temperature obtained by step (1) is adjusted to 60 DEG C~80 DEG C, inorganic peroxy is added
PH value is adjusted to 9~11 by class initiator and sodium carbonate, adds methyl methacrylate and benzene second that mass ratio is 1~3:1
Alkene reacts 3~6 hours, and it is total for 400nm~600nm, core-shell structure polysiloxanes-acrylate/styrene to obtain latex particle
The solid content control of copolymer emulsion, lotion is 30~37%, the gross mass dosage and dry weight of methyl methacrylate and styrene
Polysiloxanes-acrylate core quality of the emulsion ratio is 20~45:55~80；
(3) polysiloxanes-acrylate/styrene copolymer latexes obtained by step (2) are diluted with water, control solid content is
15%~19%, inorganic salt solution is added, it is stirred at room temperature 15~after sixty minutes, it is warming up to 80 DEG C~90 DEG C and cures 30~60 points
Clock, then cooling, centrifuge separation, washing, precipitate drying for gained, obtain white solid, are big partial size core-shell structure polysiloxanes-
Acrylate/styrol copolymer.
2. big partial size core-shell structure polysiloxanes-acrylate/styrol copolymer preparation side according to claim 1
Method, which is characterized in that step (1) polysiloxanes-polybutylacrylate latex the preparation method comprises the following steps: at 60 DEG C~90 DEG C,
The first polymerization reaction 1~3 in the aqueous solution existing for anion emulsifier by two degree of functionality organosilans, tri-alkoxy organosilan
Hour, then being added thereto includes water, anion emulsifier, two degree of functionality organosilans, tri-alkoxy organosilan and envelope
The pre-emulsion mixture of agent to be held, hydrolyzes copolycondensation 2~5 hours, obtains polysiloxane emulsion, control solid content is 28%~
35%；
Deionized water, mixed emulsifier, inorganic peroxy class initiator and sodium carbonate are added into the polysiloxane emulsion, it will
PH value is adjusted to 9~11, and at 60 DEG C~80 DEG C, the mixture of butyl acrylate and crosslinking agent, charging are added using semi-continuous process
It reacts again after the completion 2~5 hours, obtains polysiloxanes-polybutylacrylate latex；
The gross mass of two kinds of organosilane monomers of two degree of functionality organosilans and tri-alkoxy organosilan and butyl acrylate
Mass ratio is 5~25:75~95；Two degree of functionality organosilans account for the 90%~95% of the two organosilan gross mass, three alcoxyls
Base silane accounts for the 5%~10% of two kinds of organosilan gross masses；Two kinds of organosilane monomers are added in two portions, and keep the matter of the two
Amount is than constant, and the 20-30% of both additions gross mass, adds remaining 70-80% for the second time for the first time；
Crosslinking agent is allyl methacrylate or ethylene glycol dimethacrylate, and quality dosage is butyl acrylate quality
2%~4%；Controlling polysiloxanes-polybutylacrylate latex solid content is 30~38%.
3. big partial size core-shell structure polysiloxanes-acrylate/styrol copolymer preparation side according to claim 2
Method, which is characterized in that the two degrees of functionality organosilan is octamethylcy-clotetrasiloxane, and the trialkoxy silane is vinyl
Trimethoxy silane, vinyltriethoxysilane or γ-methacryloxypropyl trimethoxy silane；The end-capping reagent
For hexamethyldisiloxane, dosage is the 0.1%~0.3% of two kinds of organosilan gross masses.
4. big partial size core-shell structure polysiloxanes-acrylate/styrol copolymer preparation side according to claim 2
Method, which is characterized in that the anion emulsifier is by C12~16At least one of alkyl benzene sulphonate and C12~18In sodium alkyl sulfate extremely
A kind of few composition, the mass ratio of two kinds of emulsifiers are 1~2:1, and the dosage of anion emulsifier is that two kinds of organosilane monomers are total
The 2%~5% of quality keeps the two mass ratio constant, is added in two portions, the 50%~75% of quality dosage is added for the first time.
5. big partial size core-shell structure polysiloxanes-acrylate/styrol copolymer preparation side according to claim 2
Method, which is characterized in that the mixed emulsifier is by C12~18At least one of sodium alkyl sulfate and nonylphenol polyoxyethylenes ether
It constitutes, for the mass ratio of two kinds of emulsifiers in 1:2 between 2:1, dosage is the 1%~5% of butyl acrylate quality.
6. big partial size core-shell structure polysiloxanes-acrylate/styrol copolymer preparation side according to claim 2
Method, which is characterized in that the inorganic peroxy class initiator is potassium peroxydisulfate or ammonium persulfate, and dosage is butyl acrylate quality
0.1%~0.5%；The dosage of sodium carbonate is the 0.5%~1.5% of butyl acrylate quality；It is described pH value is adjusted to 9~11 to be
It is adjusted by sodium hydroxide solution.
7. big partial size core-shell structure polysiloxanes-acrylate/styrol copolymer preparation side according to claim 1
Method, which is characterized in that the polyacrylate agglomerant the preparation method comprises the following steps: to including deionized water, C12~18Alkyl sulfide
Mass ratio, which is added in two portions, in the system of at least one of sour sodium emulsifier, molecular weight regulator and inorganic peroxy class initiator is
The butyl acrylate and acrylic acid of 60~90:10~40 react 2~4 hours at 60 DEG C~90 DEG C, obtain polyacrylate
Agglomerant, control solid content are 31%~35%, are used after dilution；The mass ratio for controlling butyl acrylate and acrylic acid is constant,
The 10% of both additions gross mass for the first time, adds remaining 90% for the second time, is all made of semi-continuous process addition.
8. big partial size core-shell structure polysiloxanes-acrylate/styrol copolymer preparation side according to claim 7
Method, which is characterized in that the inorganic peroxy class initiator is potassium peroxydisulfate or ammonium persulfate, and dosage is butyl acrylate and propylene
The 1%~2% of sour gross mass；The C12~18Sodium alkyl sulfate emulsifier is butyl acrylate and acrylic acid gross mass
0.5%~3%；The molecular weight regulator is lauryl mercaptan, and dosage is butyl acrylate and acrylic acid gross mass
0.5%~2%.
9. big partial size core-shell structure polysiloxanes-acrylate/styrol copolymer preparation side according to claim 1
Method, wherein step (2) the inorganic peroxy class initiator is potassium peroxydisulfate or ammonium persulfate, and dosage is methyl methacrylate
With the 0.1%~0.5% of styrene gross mass；Sodium carbonate amount be methyl methacrylate and styrene gross mass 1%~
3%；Step (2) is described, which to be adjusted to 9~11 for pH value, is adjusted by sodium hydroxide solution.
10. big partial size core-shell structure polysiloxanes-acrylate/styrol copolymer preparation according to claim 1
Method, wherein step (3) inorganic salts are one of magnesium sulfate, calcium chloride and aluminum sulfate, inorganic salt solution quality hundred
Dividing concentration is that polysiloxanes-acrylate/styrol copolymer addition of every 100 mass parts dry weight is controlled between 5%~25%
20~120 mass parts inorganic salts；Drying described in step (3) is will to be deposited in drying 8~10 hours at 80 DEG C.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710252485.7A CN107151296B (en) | 2017-04-18 | 2017-04-18 | Big partial size core-shell structure polysiloxanes-acrylate/styrol copolymer preparation method |
| PCT/CN2017/113367 WO2018192222A1 (en) | 2017-04-18 | 2017-11-28 | Preparation method for polysiloxane-acrylate/styrene copolymer with large particle size and core-shell structure |
| ZA2019/04575A ZA201904575B (en) | 2017-04-18 | 2019-07-12 | Method for preparing polysiloxane-acrylate/styrene copolymer with a large particle size and a core-shell structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710252485.7A CN107151296B (en) | 2017-04-18 | 2017-04-18 | Big partial size core-shell structure polysiloxanes-acrylate/styrol copolymer preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107151296A CN107151296A (en) | 2017-09-12 |
| CN107151296B true CN107151296B (en) | 2019-01-29 |
Family
ID=59794205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710252485.7A Active CN107151296B (en) | 2017-04-18 | 2017-04-18 | Big partial size core-shell structure polysiloxanes-acrylate/styrol copolymer preparation method |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN107151296B (en) |
| WO (1) | WO2018192222A1 (en) |
| ZA (1) | ZA201904575B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107151296B (en) * | 2017-04-18 | 2019-01-29 | 华南理工大学 | Big partial size core-shell structure polysiloxanes-acrylate/styrol copolymer preparation method |
| CN110511385A (en) * | 2018-05-21 | 2019-11-29 | 北京化工大学 | A kind of polysiloxane/polysilsesquioxane core-shell emulsion and preparation method thereof |
| CN109021237B (en) * | 2018-06-29 | 2021-05-25 | 郑勇 | Large-particle-size organic siloxane rubber emulsion and plastic toughening modifier prepared from same |
| EP3830150A1 (en) * | 2018-07-27 | 2021-06-09 | Rohm and Haas Company | Polymerization process for silicone and acrylic monomers |
| JP7523423B2 (en) * | 2018-07-27 | 2024-07-26 | ローム アンド ハース カンパニー | Dual silicone-acrylic polymer particles |
| KR102802870B1 (en) * | 2018-07-27 | 2025-05-07 | 다우 실리콘즈 코포레이션 | Polymerization of silicone and acrylic monomers |
| WO2020023815A1 (en) * | 2018-07-27 | 2020-01-30 | Rohm And Haas Company | Silicone-acrylic polymer particles |
| CN110922541A (en) * | 2019-11-27 | 2020-03-27 | 宜宾天原集团股份有限公司 | Preparation method of ACR elastic resin with core-shell structure |
| CN111154180A (en) * | 2019-12-17 | 2020-05-15 | 会通新材料股份有限公司 | Polypropylene glass fiber material with good appearance and low warpage and preparation method thereof |
| CN112724335B (en) * | 2020-12-29 | 2023-04-18 | 铨盛聚碳科技股份有限公司 | Matte organic silicon high-impact-resistance toughening agent and preparation method thereof |
| CN113583154B (en) * | 2021-09-07 | 2022-06-28 | 河北工业大学 | Preparation method of polyacrylate latex particles with large particle size |
| CN114015257B (en) * | 2021-12-01 | 2022-09-30 | 南京清研高分子新材料有限公司 | Preparation method of high-impact-resistance liquid crystal polymer composite material |
| 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 |
| 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 its application in 3D printing |
| CN117327233B (en) * | 2023-10-10 | 2024-04-05 | 嘉鱼县宇威新材料科技有限公司 | Cold-resistant silicone-acrylate toughening agent with core-shell structure and preparation method thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5106908A (en) * | 1988-11-14 | 1992-04-21 | General Electric Company | Polyorganosiloxane/polyvinyl-based graft (meth)acrylate polymers |
| CA2266506C (en) * | 1997-07-29 | 2005-09-27 | Kaneka Corporation | Graft copolymer particles and thermoplastic resin compositions |
| JP4702998B2 (en) * | 2000-12-05 | 2011-06-15 | 株式会社カネカ | Rubber-modified resin and thermoplastic resin composition containing the same |
| US20040162399A1 (en) * | 2003-02-14 | 2004-08-19 | Reddy Poreddy Narsi | Silicone-acrylate impact modifier |
| KR100528771B1 (en) * | 2003-08-02 | 2005-11-15 | 주식회사 엘지화학 | Acryl-silicones Complex Impact-Modifier and Method for Preparing the Same, and Vinyl Chloride Resin Composition Having the Same |
| KR100836731B1 (en) * | 2005-10-13 | 2008-06-10 | 주식회사 엘지화학 | Acryl-silicone rubber composite polymer, preparation method and use thereof |
| CN102372824A (en) * | 2010-08-25 | 2012-03-14 | 广州熵能聚合物技术有限公司 | Impact modifier formed by organo-silioxane crosslinked elastic polymer, and preparation method and application thereof |
| CN106519144B (en) * | 2016-08-31 | 2019-06-04 | 广州熵能创新材料股份有限公司 | The preparation method of ethylene base system graft copolymer and resin combination and ethylene base system graft copolymer containing it |
| CN107151296B (en) * | 2017-04-18 | 2019-01-29 | 华南理工大学 | Big partial size core-shell structure polysiloxanes-acrylate/styrol copolymer preparation method |
-
2017
- 2017-04-18 CN CN201710252485.7A patent/CN107151296B/en active Active
- 2017-11-28 WO PCT/CN2017/113367 patent/WO2018192222A1/en not_active Ceased
-
2019
- 2019-07-12 ZA ZA2019/04575A patent/ZA201904575B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ZA201904575B (en) | 2020-02-26 |
| CN107151296A (en) | 2017-09-12 |
| WO2018192222A1 (en) | 2018-10-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107151296B (en) | Big partial size core-shell structure polysiloxanes-acrylate/styrol copolymer preparation method | |
| JP3643830B2 (en) | Method for producing thermoplastic transparent resin | |
| CN109897141B (en) | Preparation method of high-strength ASA resin for building materials | |
| KR101288752B1 (en) | Rubber polymer latex, method of preparing the same, and ABS graft copolymer comprising the same | |
| EP3118258A1 (en) | Thermoplastic resin composition, preparation method therefor, and molded product comprising same | |
| CN105418835B (en) | A kind of preparation method of makrolon toughness reinforcing core shell structure acrylate-functional polymer particle | |
| KR101115798B1 (en) | Thermoplastic Resin Composition Having Good Coloring and Mechanical Properties | |
| CN109054570A (en) | A kind of environment protection type high-strength elastic coating and preparation method thereof | |
| CN112724335A (en) | Matte organic silicon high-impact-resistance toughening agent and preparation method thereof | |
| CA1184691A (en) | Thermoplastic molding material including a crosslinked acrylate rubber grafted with styrene and acrylonitrile | |
| CN102863726A (en) | Synthetic method of PVC modifier | |
| CN101864120B (en) | Preparation method of polyacrylate/nano-CaCO3 composite material | |
| CN108239239A (en) | A kind of preparation method of polyvinyl chloride copolymer resins composite material | |
| CN108129613A (en) | A kind of preparation method of siliceous nucleocapsid vinyl chloride copolymer | |
| EP3363863B1 (en) | Thermoplastic transparent resin and preparation method therefor | |
| CN108997534A (en) | A kind of preparation method of low-temperature transparent high-impact MBS resin | |
| KR20050040592A (en) | Rubber latex and preparing method thereof | |
| CN117304411B (en) | Preparation method of ASA high-glue powder | |
| KR102602114B1 (en) | Thermoplastic compositions containing multistage copolymers as melt strength process aids with lubricating properties | |
| KR100385729B1 (en) | Thermoplastic resin composition having superior coloring properties | |
| CN105884962A (en) | Emulsion for stonelike paint and stonelike paint with emusion as film forming matter | |
| KR20000014173A (en) | Thermoplastic resin composition and method for preparing it | |
| CN107556429B (en) | Silicone-acrylic emulsion and preparation method thereof | |
| CN113388066B (en) | Polybutadiene latex and preparation method thereof | |
| CN112625187A (en) | PTFE (Polytetrafluoroethylene) coated particles with core-shell structure 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191218 Address after: 511442 No. 4-1, He Xi Road, Nan Cao Tang Village, Panyu District South Village, Guangzhou, Guangdong Patentee after: Guangzhou Guanghua Plastic Pipe Co. Ltd. Address before: 510640 Tianhe District, Guangdong, No. five road, No. 381, Patentee before: South China University of Technology |