CN109438633A - A kind of organosilicon toughener and its synthetic method with anti-drop effect - Google Patents

A kind of organosilicon toughener and its synthetic method with anti-drop effect Download PDF

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CN109438633A
CN109438633A CN201811056556.7A CN201811056556A CN109438633A CN 109438633 A CN109438633 A CN 109438633A CN 201811056556 A CN201811056556 A CN 201811056556A CN 109438633 A CN109438633 A CN 109438633A
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dispersing agent
monomer
weight ratio
mixture
ethyl
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王启瑶
冯猛
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EVERSUN POLYCARBON SCI & TECH Corp.
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Guangdong Youke Aidi Polymer Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides
    • 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
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • 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
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer

Abstract

The present invention relates to pluronic polymer technical fields, and in particular to a kind of organosilicon toughener and its synthetic method with anti-drop effect, which includes: the synthesis of organopolysiloxane core lotion；The synthesis of organosilicon toughener with anti-drop effect.Synthetic method of the invention is by by organosilicon and PTFE polymerization, then successively coats soft monomer and hard monomer, and organosilicon toughener obtained had not only improved the impact strength of material, but also had excellent anti-dripping melt performance, simple process and low cost.

Description

A kind of organosilicon toughener and its synthetic method with anti-drop effect
Technical field
The present invention relates to pluronic polymer technical fields, and in particular to it is a kind of with it is anti-drop effect organosilicon toughener and Its synthetic method.
Background technique
Polycarbonate (PC) is a kind of tough thermoplastic resin, and realizes and industrialize in early 1960s, 90 years Large-scale industrial production is realized at generation end, is the second largest engineering plastics that yield is only second to polyamide.It has excellent machinery Performance, but to notch sensitive, notch toughness is subject to certain restrictions.The toughener for being related to engineering plastics PC resin at present is main There are MBS resin, ACR resin, maleic anhydride graft copolymer (EVA-g-MAH), nano inorganic particle etc., but all exists Problem, such as due to containing butadiene in the molecular structure of MBS resin, carbon-carbon double bond unsaturated structure makes its exposure in air Or it is easy to happen aging phenomenon under ultraviolet irradiation, cause the weatherability of MBS resin poor.The lower temperature resistance of ACR resin Energy, anti-pollution characteristic are poor, and water penetration and water imbibition are also higher, and there is the phenomenon that " hot sticky cold crisp ".
In plastic flame modified system, to improve plastic flame grade, improving burning drippage deficiency, need to be properly added Anti-dripping agent.Anti-dripping agent is using fibrosis of the polytetrafluoroethylene polymer in plastic processing, and heat shrinkable plays anti-drop Effect is fallen, the sprawling of flame is reduced；Furthermore, it is possible to increase the melt strength and slump resistance of polymer.Therefore, it is necessary to grind Send out a kind of with the anti-organosilicon toughener for dripping effect.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide one kind to have anti-drop effect The synthetic method of the organosilicon toughener of fruit, the synthetic method is by then successively coating soft monomer for organosilicon and PTFE polymerization And hard monomer, organosilicon toughener obtained had not only improved the impact strength of material, but also had excellent anti-dripping melt performance, technique letter It is single, it is at low cost.
Another object of the present invention is to provide a kind of organosilicon toughener with anti-drop effect, the organosilicon toughener When in toughening PC system, the notched Izod impact hit intensity of PC both can be improved, it may have certain anti-dripping effects.
The purpose of the invention is achieved by the following technical solution: a kind of synthesis of the organosilicon toughener with anti-drop effect Method includes the following steps:
A, the synthesis of organopolysiloxane core lotion:
A1, organosiloxane monomer is uniformly mixed, using homogenizer under 8000~12000rpm revolving speed high speed shear 5 ~20min, obtains mixed liquor；
A2, mixed liquor is added in the aqueous solution dissolved with catalyst and emulsifier, is reacted at a temperature of 85~100 DEG C 6~12h obtains organopolysiloxane core lotion；Wherein, the gross mass of organosiloxane monomer be water quality 40%~ 60%, the dosage of catalyst is the 1%~5% of organosiloxane monomer mass, and the dosage of emulsifier is organosiloxane monomer The 1%~20% of quality；
B, the synthesis of the organosilicon toughener with anti-drop effect:
B1, organopolysiloxane core lotion, PTFE emulsion, dispersing agent and distilled water are added in reaction kettle together, 5~25min of high shear agitation, obtains reaction solution under 1000~2000rpm revolving speed；Wherein, the dosage of PTFE emulsion is organic The 10%-50% of polysiloxanes core quality of the emulsion, the dosage of dispersing agent are the 1%-5% of organopolysiloxane core quality of the emulsion；
B2, reaction solution lye is adjusted into pH value to 9~12, soft monomer is then added, adds initiator and crosslinking agent, It is stirred to react 5-10h at a temperature of 50~90 DEG C, obtains the polymer emulsion of organopolysiloxane grafting soft monomer；Wherein, soft The dosage of monomer is the 5%-15% of organopolysiloxane core quality of the emulsion, and the dosage of initiator is organopolysiloxane core lotion The 0.1%-0.8% of quality, the dosage of crosslinking agent are the 0.2%-0.6% of organopolysiloxane core quality of the emulsion；
B3, hard monomer is then added, adds initiator and crosslinking agent, is stirred to react 5-10h at a temperature of 50~90 DEG C, Obtain the polymer emulsion with core-shell structure；Wherein, the dosage of hard monomer is the 25%- of organopolysiloxane core quality of the emulsion 45%, the dosage of initiator is the 0.1%-0.8% of organopolysiloxane core quality of the emulsion, and the dosage of crosslinking agent is organic poly- silicon The 0.2%-0.6% of oxygen alkane core quality of the emulsion；
B4, demulsifier demulsification is added, dries pulverizing is after centrifugation to get the organosilicon toughening with anti-drop effect Agent；Wherein, the dosage of demulsifier is 0.5-3 times of polymer emulsion quality.
In the step A1, organosiloxane monomer is by cyclic siloxane monomer, function groups siloxanyl monomers and second The mixture that alkenyl siloxane monomer is formed with weight ratio 20-60:0.1-1.0:0.5-1.5.
The present invention is by using cyclic siloxane monomer, function groups siloxanyl monomers and vinylsiloxane monomer conduct Organosiloxane monomer complex uses, and controlling its weight ratio is 20-60:0.1-1.0:0.5-1.5, and the anti-of resin can be improved It is impact property, waterproofness, grease proofness, anti-fog properties, soil resistance, soil release performance, moisture-proof, lubricity, abrasion performance, antistick characteristic, resistance to Chemicals and marresistance.
Preferably, the structural formula of the function groups siloxanyl monomers are as follows:Wherein, R1、R2、R3And R4 Appointing respectively in hydrogen, methyl, ethyl, propyl, vinyl, acrylic, acetenyl, propinyl, methoxyl group, ethyoxyl and phenyl Anticipate one kind, and R1、R2、R3And R4In at least one methoxy or ethoxy.
Preferably, the function groups siloxanyl monomers are methyltrimethoxysilane, methyltriethoxysilane, ethyl Trimethoxy silane, ethyl triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, tetramethoxy Silane, tetraethoxysilane, phenyltrimethoxysila,e, dimethoxydiphenylsilane, triphenylmethoxy silane, methylbenzene Base dimethoxysilane, ethylphenyl dimethoxysilane, propyl phenyidimethoxysilane, ethenylphenyl dimethoxy silicon Alkane, acrylic phenyidimethoxysilane, ethynyl phenyl dimethoxysilane, propinyl phenyidimethoxysilane, methyl Diphenylmethyl oxysilane, ethyl diphenyl methoxy silane, propyl diphenylmethyl oxysilane, vinyl diphenyl methoxyl group Silane, acrylic diphenylmethyl oxysilane, acetenyl diphenylmethyl oxysilane, propinyl diphenylmethyl oxysilane, two Methyl phenyl methoxy silane, diethylbenzene methoxylsilane, dipropyl phenylmethoxysilane, divinyl phenyl methoxy Base silane, diallyl phenylmethoxysilane, diacetylene phenylmethoxysilane, dipropyl alkynyl phenyl methoxy silane, Methylethyl phenylmethoxysilane, methyl-propyl phenylmethoxysilane, ethyl propyl phenylmethoxysilane, ethylene methacrylic Base phenylmethoxysilane, ethyl propylene base phenylmethoxysilane, methylacetylenyl phenylmethoxysilane, ethyl propinyl Phenylmethoxysilane, phenyl triethoxysilane, diphenyl diethoxy silane, triphenyl Ethoxysilane, aminomethyl phenyl Diethoxy silane, Ethylphenyldiethoxysandne, propyl phenyl diethoxy silane, ethenylphenyl diethoxy silicon Alkane, acrylic phenyl diethoxy silane, ethynyl phenyl diethoxy silane, propinyl diethylamino phenyl oxysilane, methyl Diphenyl Ethoxysilane, ethyl diphenyl Ethoxysilane, propyl diphenyl Ethoxysilane, vinyl diphenyl ethyoxyl Silane, acrylic diphenyl Ethoxysilane, acetenyl diphenyl Ethoxysilane, propinyl diphenyl Ethoxysilane, two Aminomethyl phenyl Ethoxysilane, diethyl phenyl Ethoxysilane, dipropyl phenyl ethoxy silane, divinyl phenyl ethoxy Base silane, diallyl phenyl ethoxy silane, diacetylene phenyl ethoxy silane, dipropyl alkynyl phenyl Ethoxysilane, Methylethyl phenyl ethoxy silane, methyl-propyl phenyl ethoxy silane, ethyl propyl phenyl ethoxy silane, ethylene methacrylic Base phenyl ethoxy silane, ethyl propylene base phenyl ethoxy silane, methylacetylenyl phenyl ethoxy silane, ethyl propinyl Phenyl ethoxy silane, 1,3- bis- [2- (dimethoxy-methyl silicyl) ethyl] benzene, the bis- [2- (dimethoxy-methyls of Isosorbide-5-Nitrae- Silicyl) ethyl] benzene, bis- [1- (dimethoxy-methyl silicyl) ethyl] benzene of 1,3-, bis- [1- (the dimethoxy first of Isosorbide-5-Nitrae- Base silicyl) ethyl] benzene, 1- [1_ (dimethoxy-methyl silicyl) ethyl] -3- [2- (dimethoxy-methyl monosilane Base) ethyl] benzene and 1- [1_ (dimethoxy-methyl silicyl) ethyl] -4- [2- dimethoxy-methyl silicyl) ethyl] At least one of benzene.
The present invention can be used as crosslinking agent use by using above-mentioned multi-functional siloxanyl monomers, promote or adjust polymerization Object molecule interchain covalent bonds or ionic bond are formed, so that multiple linear molecules is made to be mutually bonded the substance for being cross-linked into reticular structure, The shock resistance and anti-flammability of resin can be improved.More preferably, the multi-functional siloxanyl monomers are by aminomethyl phenyl Dimethoxysilane, phenyltrimethoxysila,e and vinyltrimethoxysilane are with weight ratio 1:0.4-0.8:0.8-1.2 group At mixture.
The structural formula of the polymerized monomer of the cyclic siloxane monomer isWherein R5And R6Respectively Any one in hydrogen, methyl, ethyl, propyl, vinyl, acrylic, acetenyl, propinyl and phenyl, the ring-type silicon oxygen Polymerization degree n=3-6 of alkane monomer.The substituent group R of each polymerized monomer5And R6It may be the same or different.
Preferably, the cyclic siloxane monomer is hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, decamethyl ring Five siloxanes, ten diformazan basic rings, six siloxanes, hexaetcycletrisiloxane, octaethyl cyclotetrasiloxane, ten ethyl rings, five silicon oxygen Alkane, ten diethyl basic rings, six siloxanes, hexaphenyl cyclotrisiloxane, octaphenylcyclotetrasiloxane, ten phenyl cyclopentasiloxanes, 12 Six siloxanes of benzyl ring, six vinyl cyclotrisiloxane, eight vinyl cyclotetrasiloxanes, ten vinyl cyclopentasiloxanes, 12 Six siloxanes of ethylene basic ring, three hydrogen trimethyl cyclotrisiloxane, trimethyl triethyl group cyclotrisiloxane, trimethyl triphenyl ring three Siloxanes, triethyl group triphenyl cyclotrisiloxane, trimethyl trivinyl cyclotrisiloxane, three silicon oxygen of trivinyl triphen basic ring Alkane, diethyl tetramethyl-ring trisiloxanes, dimethyl tetraethyl cyclotrisiloxane, divinyl tetramethyl-ring trisiloxanes, two Methyl tetravinyl cyclotrisiloxane, diphenyltetramethyl cyclotrisiloxane, dimethyl tetraphenyl cyclotrisiloxane, vinyl five Methyl cyclotrisiloxane, five vinyl cyclotrisiloxane of methyl, phenyl pentamethyl cyclotrisiloxane, five benzyl ring of methyl, three silicon oxygen Alkane, tetrahydro tetramethyl-ring tetrasiloxane, tetramethyl tetraethyl cyclotetrasiloxane, tetramethyl tetraphenyl cyclotetrasiloxane, tetraethyl Tetraphenyl cyclotetrasiloxane, t etram-ethyltetravinylcyclotetrasiloxane, tetravinyl tetraphenyl cyclotetrasiloxane, diethyl pregnancy Basic ring tetrasiloxane, dimethyl Hexaethyl cyclotetrasiloxane, divinyl hexamethyl cyclotetrasiloxane, six ethylene basic ring of dimethyl Tetrasiloxane, diphenyl hexamethyl cyclotetrasiloxane, dimethyl hexaphenyl cyclotetrasiloxane, seven methyl ring of vinyl, four silicon oxygen In alkane, seven phenyl cyclotetrasiloxane of seven vinyl cyclotetrasiloxane of methyl, phenyl heptamethylcyclotetrasiloxane and methyl at least It is a kind of.
The present invention can control the partial size of polymer by using above-mentioned cyclic siloxane monomer, to improve resin Anti-flammability and impact strength.More preferably, the cyclic siloxane monomer is by trimethyl triethyl group cyclotrisiloxane, two The mixing that six vinyl cyclotetrasiloxane of methyl and seven phenyl cyclotetrasiloxane of methyl are formed with weight ratio 2-4:0.5-1.5:1 Object.
The structural formula of the vinylsiloxane monomer are as follows:Wherein, R7, R8, R9 and R10 are respectively Hydrogen, methyl, ethyl, propyl, vinyl, acrylic, styryl, γ-methacryloxypropyl, styryl, 2- are (right Ethenylphenyl) ethyl, 3- (to vinylbenzoyl oxygroup) propyl, acetenyl, propinyl, methoxyl group, ethyoxyl and phenyl In any one, and R7, R8, R9 and R10 at least one be vinyl, acrylic, styryl, γ-methacryl Oxygroup propyl, styryl, 2- (to ethenylphenyl) ethyl or 3- (to vinylbenzoyl oxygroup) propyl, at least one For methoxy or ethoxy.
Preferably, the vinylsiloxane monomer is vinyltrimethoxysilane, vinyltriethoxysilane, two Vinyl dimethoxysilane, divinyl diethoxy silane, vinyl methyl dimethoxysilane, vinyl methyl diethyl Oxysilane, vinyl ethyldimethoxysilane, vinyl ethyl diethoxy silane, vinyl dimethylamine oxygroup silicon Alkane, vinyl propyl diethoxy silane, to vinyl phenylmethyl methoxy silane, to vinyl phenylmethyl ethyoxyl silicon Alkane, to ethenylphenyl ethyl methoxy silane, to ethenylphenyl ethyl Ethoxysilane, styryl trimethoxy silicon Alkane, styryl triethoxysilane, 2- (to ethenylphenyl) ethyl-methyl dimethoxysilane, 2- (to ethenylphenyl) Ethyl-methyl diethoxy silane, 3- (to vinylbenzoyl oxygroup) hydroxypropyl methyl dimethoxysilane, 3- are (to vinyl benzene Formyloxy) hydroxypropyl methyl diethoxy silane, acrylic trimethoxy silane, acrylic triethoxysilane, acrylic first Base dimethoxysilane, propenylmethyl diethoxy silane, acrylic ethyldimethoxysilane, acrylic ethyl diethoxy Base silane, acrylic propyldimethoxy-silane, acrylic propyl diethoxy silane, γ-mercaptopropyi methyl dimethoxy oxygroup Silane, γ-methacryloxypropyl methoxyl group dimethylsilane, γ-methacryloxypropyl dimethoxy-methyl Silane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl ethyoxyl dimethylsilane, γ-methacryloxypropyl diethoxymethylsilane, γ-methacryloxypropyl morpholine silane, γ-methacryloxypropyl dimethoxy-ethyl silane, γ-methacryloxypropyl ethyoxyl diethylsilane, In γ-methacryloxypropyl diethoxy ethylsilane and γ-methacryloxypropyl It is at least one.
The present invention can be used as coupling agent use, in organic poly- silicon by using above-mentioned vinylsiloxane monomer The side chain of oxygen alkane or end import the ingredient of vinyl polymerized functional group, the vinyl polymerized functional group as with by being copolymerized Monomer formed copolymerized polymer chemical bonding when grafting active site and play a role.More preferably, the vinyl silicon Oxygen alkane monomer be by vinyl propyldimethoxy-silane, to vinyl phenylmethyl Ethoxysilane and 3- (to vinyl benzene Formyloxy) mixture that is formed with weight ratio 2-4:1.5-2.5:1 of hydroxypropyl methyl diethoxy silane.
Preferably, in the step A2, the structural formula of catalyst are as follows:Wherein, R ' is for carbon atom number Alkyl, alkenyl, aromatic radical or the carbon atom number of 1-10 is the naphthenic base of 3-10, cycloalkenyl.
Specifically, the catalyst is methane sulfonic acid, trifluoromethane sulfonic acid, methylol sulfonic acid, ethylsulfonic acid, trifluoroethyl Sulfonic acid, isethionic acid, propyl sulfonic acid, hydroxypropyl sulfonic acid, 1- butyl sulfonic acid, vinyl sulfonic acid, propene sulfonic acid, metering system sulphur Acid, ethyl propylene sulfonic acid, benzene sulfonic acid, toluenesulfonic acid, ethyl phenenyl azochlorosulfonate acid, acid dimethyl, diethylbenzene sulfonic acid and 12 At least one of alkyl benzene sulphonate.
The present invention is easy to make the particle diameter distribution of organic polysiloxane emulsion narrow by using above-mentioned catalyst, in addition, being easy Reduction the phenomenon that resin bad order, can also improve resin in low temperature as caused by the emulsifier component of organopolysiloxane Impact strength.More preferably, the catalyst is by methylol sulfonic acid, trifluoroethyl sulfonic acid and hydroxypropyl sulfonic acid with weight Than the mixture of 1:0.8-1.2:0.4-0.8 composition.
In the step A2, emulsifier is by cationic surfactant, anionic surfactant and non-ionic surface The mixture that activating agent is formed with weight ratio 0.4-0.8:1:0.2-0.6.
Preferably, the cationic surfactant is by dialkyl dimethyl quaternary ammonium salt, benzalkonium dimethyl quaternary ammonium The mixture that salt and monoalkyl quaternary ammonium salts are formed with weight ratio 1:1.2-1.6:1.8-2.6；The anionic surfactant is By polyoxyethylene alkyl ether hydrogen sulfuric acid ester, alkyl diphenyl base ether disulfonate and polyoxyethylene alkyl ether ester with weight ratio 1:0.5- 1.5:1.4-2.2 the mixture of composition；The nonionic surfactant is by isomeric alcohol polyethenoxy ether, sorbitan The mixture that aliphatic ester and polyoxyethylene hardened castor oil aliphatic ester are formed with weight ratio 1.6-2.4:1:0.8-1.2.This The type, multiple that invention passes through strict control cationic surfactant, anionic surfactant and nonionic surfactant Match and match, emulsifying effectiveness is good, is conducive to the emulsion dispersion of organosiloxane monomer, accelerates reaction and carries out.
In the step B1, the average molecular weight of PTFE emulsion is 1,000,000-1,000 ten thousand, and solid content is in 58%-62%, cream Liquid partial size is at 0.01-0.30 μm, viscosity 10-40*10-3Pa.S.The present invention passes through the mean molecule of strict control PTFE emulsion Amount, solid content, emulsion particle diameter and viscosity, can improve plastic melt intensity and bending modulus, and flame-retardant anti-dropping effect makes thermoplastic materials Reach higher flame-retardant standard.
In the step B2, soft monomer is by ethyl acrylate, Isooctyl acrylate monomer and lauryl methacrylate with weight Measure the mixture formed than 2-4:1-2:1.The present invention passes through the type of strict control esters of acrylic acid soft monomer, compounds and match Than, with lower glass transition temperature, polymerization forms grafting layer, and anti-dripping agent obtained has excellent weather resistance, and Resistance to low temperature is excellent.
In the step B3, hard monomer is by methyl acrylate, ethyl methacrylate and vinylacetate with weight ratio 1:0.8-1.2:1.5-2.5 the mixture of composition.The present invention by the type of strict control esters of acrylic acid hard monomer, compounding and Proportion, glass transition temperature with higher, polymerization form shell, and anti-dripping agent anti-dripping effects obtained is good.
In the step B2 and the step B3, initiator is by isopropyl benzene hydroperoxide, azodiisobutyronitrile and tetrem The mixture that alkene imines is formed with weight ratio 1:0.5-1.5:1.5-2.5.The present invention passes through the type of strict control initiator, answers Match and match, initiation effect is good, can trigger free radical polymerization and copolymerization, can improve rate of polymerization.
In the step B2 and the step B3, crosslinking agent be by diallyl fumarate, dimethacrylate -1,6- oneself The mixture that diol ester and Pehanorm trimethyl acrylic ester are formed with weight ratio 1:0.8-1.2:1.4-2.2.This hair Bright type, compounding and proportion by strict control crosslinking agent can promote or adjust polymerization in intermolecular bridging action of line style Object molecule interchain covalent bonds or ionic bond are formed, so that multiple linear molecules is made to be mutually bonded the substance for being cross-linked into reticular structure, The anti-flammability and shock resistance of resin can be improved.
In the step B4, demulsifier is made of sodium chloride, potassium acetate and ammonium sulfate with weight ratio 2-4:1.4-2.2:1 Mixture.The present invention passes through compounding, compounding and the proportion of strict control demulsifier, and demulsification is good, can destroy reaction solution Emulsified state, convenient for isolating and purifying for reaction product.
Preferably, in the step B1, dispersing agent is inorganic dispersing agent and/or organic dispersing agent；
The inorganic dispersing agent be natural silicate, Sulfates, carbonate, Oxalates, hydroxide species and It is at least one of oxide-based；
The natural silicate is at least one of talcum, bentonite, diatomite and kaolin；The Sulfates are Calcium sulfate and/or barium sulfate；The carbonate is at least one of calcium carbonate, barium carbonate and magnesium carbonate；The oxalates Class is calcium oxalate；The hydroxide species are at least one of aluminium hydroxide, magnesium hydroxide and calcium hydroxide；The oxide Class is titanium dioxide and/or zinc oxide；
The organic dispersing agent is natural polymer subclass dispersing agent, protein-based macromolecule dispersing agent, cellulose family spread out Biological species dispersing agent, synthesis high score subclass dispersing agent, the synthesis of class containing carboxyl macromolecule dispersing agent, the synthesis macromolecule dispersion of nitrogenous class At least one of agent and ester-containing base class synthesis macromolecule dispersing agent；
The natural polymer subclass dispersing agent is at least one of carbohydrate starch, pectin, natural plant gum and seaweed glue；It is described Protein-based macromolecule dispersing agent is gelatin and/or Fish protein；The cellulose derivative class dispersing agent be methylcellulose, At least one of methylhydroxypropylcellulose, hydroxyethyl cellulose and hydroxypropyl cellulose；The synthesis high score subclass dispersion Agent is hydroxyl class partial alcoholysis polyvinyl alcohol；The synthesis macromolecule dispersing agent of class containing carboxyl is total for phenylethylene/maleic anhydride Polymers, vinyl acetate/copolymer-maleic anhydride and at least one of acrylic copolymer and methacrylic copolymer； The nitrogenous class synthesis macromolecule dispersing agent is polyvinylpyrrolidone；The ester-containing base class synthesis macromolecule dispersing agent is poly- Ethylene oxide fatty acid esters and/or sorbitan fatty acid.
For the present invention by using above-mentioned dispersing agent, dispersion effect is good, is conducive to organopolysiloxane core lotion and PTFE The dispersion of lotion is accelerated reaction and is carried out.More preferably, the dispersing agent is by diatomite, calcium carbonate, methylhydroxypropyl The mixture that element and sorbitan fatty acid are formed with weight ratio 1-2:0.5-1.5:1:0.8-1.2.
A kind of organosilicon toughener with anti-drop effect, the organosilicon toughener is according to preparation method described above It is made.
A kind of toughened polycarbonate material using the organosilicon toughener with anti-drop effect described above, the increasing Tough makrolon material includes the raw material of following parts by weight: 80-120 parts of polycarbonate, 20-40 parts of glass fibre, organic silicon rigidity-increasing Tough dose 1-10 parts, it is 4-8 parts of modifying agent, auxiliary agent 1-10 parts other；
Wherein, the modifying agent is more created by macromolecule modified nanometer calcium carbonate, hyperbranched polyester amide and 4- allyl The mixture that the wooden phenol modified dimethyl polysiloxane is formed with weight ratio 2-6:0.1-1.0:0.5-1.5.
Flame-retardant polycarbonate material of the invention can be improved the intensity of material, pass through addition by the way that glass fibre is added The toughness of material can be improved in organosilicon toughener, and by the way that modifying agent is added, processing heat stability, the machine of material can be improved Tool mechanical property and appearance.
Preferably, the preparation method of the macromolecule modified nanometer calcium carbonate includes the following steps:
(1) 15-25g nanometer calcium carbonate and 0.3-0.7g calgon dispersing agent are added into 300-500mL distilled water, Disperse 20-28h；60-100g Polymeric quaternary ammonium salts are dissolved in 200-400mL tetrahydrofuran simultaneously, dispersion 20-28h is spare；
(2) the addition 200-400mL tetrahydrofuran into scattered nanometer calcium carbonate system, high speed dispersion 0.3-0.7h, Then slurries are transferred in there-necked flask, polymeric quartenary ammonium salting liquid is slowly added dropwise under stirring, system constantly generates white flock Precipitating；
(3) after completion of dropwise addition, system is warming up to 75-85 DEG C, after reacting 20-28h, then slurries is filtered, 55-65 DEG C of vacuum Dry 24-48h, obtains macromolecule modified nanometer calcium carbonate；
Wherein, in the step (1), Polymeric quaternary ammonium salts be brominated polyphenylether stearyl dimethyl benzyl ammonium chloride, Dimethyl diallyl ammonium chloride-acrylamide copolymer, polydimethyl diallyl ammonium chloride, chlorination -2- hydroxyl -3- (three Methylamino) propyl polyethylene oxide cellulose ether and N, N, N- trimethyl-2- (2- methyl-1-oxo-2- acrylic oxygroup) second At least one of ammonium chloride-acrylamide copolymer.
The present invention passes through raw material, preparation step and the technological parameter of stringent macromolecule modified nanometer calcium carbonate, height obtained The processing heat stability and mechanical property of polycarbonate can be improved in molecular modification nanometer calcium carbonate.Preferably, the polymer Quaternary ammonium salt is by brominated polyphenylether stearyl dimethyl benzyl ammonium chloride, chlorination -2- hydroxyl -3- (dimethylamino) propyl polycyclic Oxidative ethane cellulose ether and N, N, N- trimethyl-2- (2- methyl-1-oxo-2- acrylic oxygroup) ethyl ammonium chloride-acryloyl The mixture that amine copolymer object is formed with weight ratio 2-4:1.5-2.5:1.
Preferably, the synthetic method of the hyperbranched polyester amide are as follows: under nitrogen protection, successively by 0.8-1.2mol tri- Ethanol amine, 0.8-1.2mol 1,2,4- trimellitic anhydride and 0.005-0.015mol Catalyzed by p-Toluenesulfonic Acid agent are added three mouthfuls Round-bottomed flask is placed in heating oil bath, and stirring is gradually warming up to 210-230 DEG C, after raw material is uniformly mixed bleach, Continue to be stirred to react 2-4h at a temperature of 210-230 DEG C, be then cooled to room temperature, obtains yellow transparent solid body i.e. hyper-branched polyester acyl Amine.
The present invention passes through the raw material of stringent hyperbranched polyester amide, preparation step and technological parameter, hyperbranched poly obtained Esteramides can not only improve the processing fluidity of polycarbonate, while can also improve the mechanical performance and surface smoothness of product, And the variation of polycarbonate color will not be caused.
Preferably, the synthetic method of the 4- allyl guaiacol modified dimethyl polysiloxane are as follows: temperature is being housed It counts, in the there-necked flask of blender, sequentially adds 230-270g dimethyl silicone polymer, 23-27g 4- allyl at room temperature and more create The wooden phenol forms the suspension of White-opalescent after stirring；Add the chlorine platinum that 0.5-1.0mL platinum mass fraction is 1.5-2.5% The octanol solution of acid；Continue to stir, is warming up to 90-100 DEG C under logical nitrogen, reacts 2-4h.
Raw material, preparation step and the technique that the present invention passes through stringent 4- allyl guaiacol modified dimethyl polysiloxane The tensile strength of polycarbonate, bending can be improved in parameter, 4- allyl guaiacol modified dimethyl polysiloxane obtained Intensity, impact strength and elongation at break.
Preferably, the melt index of the polycarbonate is bisphenol A-type poly- carbonic acid of the melt index in 10-50g/10min At least one of ester, polyester-type polycarbonate and hexamethylene bisphenol A polycarbonate.
The present invention is by using above-mentioned polycarbonate, and the melt index of strict control polycarbonate is that melt index exists 10-50g/10min, so that polycarbonate has high-intensitive and coefficient of elasticity, high impact, use temperature range wide, forming Shrinking percentage is low, and dimensional stability is good, and fatigue durability and weatherability are good, and electrical characteristic is excellent, colorless and odorless, safety and environmental protection.More Preferably, the polycarbonate is by bisphenol A polycarbonate, polyester-type polycarbonate and hexamethylene bisphenol A polycarbonate The mixture formed with weight ratio 1-2:0.8-1.2:1.
The glass fibre be fibre diameter 5-15 μm, fibre length 1-10mm alkali-free short glass fiber.
The present invention by using fibre diameter 5-15 μm, fibre length 1-10mm alkali-free short glass fiber, Good insulating, heat resistance is strong, and corrosion resistance is good, high mechanical strength, and the intensity of plastics can be improved.
Other described auxiliary agents are at least one of antioxidant, UV resistant agent, lubricant, smoke suppressant and Vitrified powder.This The antioxygenic property, anti-ultraviolet property, processability of makrolon material can be improved by using other above-mentioned auxiliary agents in invention Can, flame-retardant smoke inhibition effect is good.More preferably, other described auxiliary agents are by antioxidant, UV resistant agent, lubricant, smoke suppressant The mixture formed with Vitrified powder with weight ratio 0.4-0.8:0.6-1.0:1:0.5-1.5:0.8-1.2.
Preferably, the antioxidant is by β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three The mixing that [2.4- di-tert-butyl-phenyl] phosphite ester and the double lauryls of thio-2 acid are formed with weight ratio 1-2:0.8-1.2:1 Object.The present invention passes through type, compounding and the weight proportion of strict control antioxidant, can delay or inhibit material oxidation process It carries out, to prevent the aging of material and prolong its service life.
Preferably, the UV resistant agent is by 2- (2 '-hydroxyls -5 '-aminomethyl phenyl) benzotriazole, 2- hydroxyl -4- The mixture that methoxy benzophenone and hexamethylphosphoramide are formed with weight ratio 0.5-1.5:1.4-2.2:1.The present invention is logical The type, compounding and weight proportion for crossing strict control ultraviolet absorbing agent, can absorb ultraviolet light strongly, imitate with excellent collaboration It answers.
Preferably, the lubricant is by oxidized polyethylene wax, glycerin monostearate and stearic amide with weight ratio 1-2:0.4-0.8:1 the mixture of composition.The present invention passes through type, compounding and the proportion of strict control lubricant, can make material Material improves the mobility of material and the release property of product in process, can reduce difficulty of processing, saves energy consumption.
Preferably, the smoke suppressant is by ferrocene, antimony oxide and ammonium octamolybdate with weight ratio 0.5-1.5:1.5- 2.5:1 the mixture of composition.For the present invention by type, compounding and the proportion of strict control smoke suppressant, smoke suppressing effect is good, can be with Reduce toxic gas and smog that thermoplastic polyurethane is generated in burning.
Preferably, the Vitrified powder is by attapulgite, zinc borate, silicate glass powder with weight ratio 2-4:0.5-1.5: The mixture of 1 composition.The present invention by type, compounding and the proportion of strict control Vitrified powder, it is moldable can be at 600-1000 DEG C Fine and close ceramic product is formed in range, the ceramic product of formation has good elevated temperature strength and heat resistanceheat resistant stream impact energy Power also has good mechanical property at normal temperature.
The beneficial effects of the present invention are: synthetic methods of the invention by by organosilicon and PTFE polymerization, then successively wraps Soft monomer and hard monomer are covered, organosilicon toughener obtained had not only improved the impact strength of material, but also had excellent anti-dripping melt Can, simple process and low cost.
When organosilicon toughener of the invention is in toughening PC system, the notched Izod impact hit intensity of PC both can be improved, Also there is certain anti-dripping effects.
Specific embodiment
For the ease of the understanding of those skilled in the art, below with reference to embodiment, the present invention is further illustrated, real The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of synthetic method of the organosilicon toughener with anti-drop effect, includes the following steps:
A, the synthesis of organopolysiloxane core lotion:
A1, organosiloxane monomer is uniformly mixed, using homogenizer under 8000rpm revolving speed high speed shear 20min, obtain To mixed liquor；
A2, mixed liquor is added in the aqueous solution dissolved with catalyst and emulsifier, reacts 12h at a temperature of 85 DEG C, Obtain organopolysiloxane core lotion；Wherein, the gross mass of organosiloxane monomer is the 40% of water quality, the dosage of catalyst It is the 1% of organosiloxane monomer mass, the dosage of emulsifier is the 1% of organosiloxane monomer mass；
B, the synthesis of the organosilicon toughener with anti-drop effect:
B1, organopolysiloxane core lotion, PTFE emulsion, dispersing agent and distilled water are added in reaction kettle together, High shear agitation 25min, obtains reaction solution under 1000rpm revolving speed；Wherein, the dosage of PTFE emulsion is organopolysiloxane core The 10% of quality of the emulsion, the dosage of dispersing agent are the 1% of organopolysiloxane core quality of the emulsion；
B2, reaction solution lye is adjusted into pH value to 9, soft monomer is then added, adds initiator and crosslinking agent, in 50 It is stirred to react 10h at a temperature of DEG C, obtains the polymer emulsion of organopolysiloxane grafting soft monomer；Wherein, the dosage of soft monomer It is the 5% of organopolysiloxane core quality of the emulsion, the dosage of initiator is the 0.1% of organopolysiloxane core quality of the emulsion, is handed over The dosage for joining agent is the 0.2% of organopolysiloxane core quality of the emulsion；
B3, hard monomer is then added, adds initiator and crosslinking agent, is stirred to react 10h at a temperature of 50 DEG C, is had There is the polymer emulsion of core-shell structure；Wherein, the dosage of hard monomer is the 25% of organopolysiloxane core quality of the emulsion, initiator Dosage be the 0.1% of organopolysiloxane core quality of the emulsion, the dosage of crosslinking agent is organopolysiloxane core quality of the emulsion 0.2%；
B4, demulsifier demulsification is added, dries pulverizing after centrifugation had both obtained the organosilicon toughening with anti-drop effect Agent；Wherein, the dosage of demulsifier is 0.5 times of polymer emulsion quality.
In the step A1, organosiloxane monomer is by cyclic siloxane monomer, function groups siloxanyl monomers and second The mixture that alkenyl siloxane monomer is formed with weight ratio 20:0.1:0.5.
The function groups siloxanyl monomers are methyltrimethoxysilane, methyltriethoxysilane, ethyl trimethoxy Base silane, ethyl triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, tetramethoxy-silicane, four Ethoxysilane, phenyltrimethoxysila,e, dimethoxydiphenylsilane or triphenylmethoxy silane.
The cyclic siloxane monomer is hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, five silicon oxygen of decamethyl ring Alkane, ten diformazan basic rings, six siloxanes, hexaetcycletrisiloxane, octaethyl cyclotetrasiloxane, ten ethyl cyclopentasiloxanes, 12 Six siloxanes of ethyl ring, hexaphenyl cyclotrisiloxane, octaphenylcyclotetrasiloxane, ten phenyl cyclopentasiloxanes, ten hexichol basic rings Six siloxanes, six vinyl cyclotrisiloxane or eight vinyl cyclotetrasiloxanes.
The vinylsiloxane monomer is vinyltrimethoxysilane, vinyltriethoxysilane, divinyl Dimethoxysilane, divinyl diethoxy silane, vinyl methyl dimethoxysilane, vinyl methyl diethoxy silicon Alkane, vinyl ethyldimethoxysilane, vinyl ethyl diethoxy silane, vinyl propyldimethoxy-silane, ethylene Base propyl diethoxy silane or to vinyl phenylmethyl methoxy silane.
In the step A2, catalyst is methane sulfonic acid, trifluoromethane sulfonic acid, methylol sulfonic acid or ethylsulfonic acid；
In the step A2, emulsifier is by cationic surfactant, anionic surfactant and non-ionic surface The mixture that activating agent is formed with weight ratio 0.4:1:0.2；
In the step B1, the average molecular weight of PTFE emulsion is 1,000,000, and solid content is 58%, and emulsion particle diameter is in 0.01 μ M, viscosity 10*10-3Pa.S；
In the step B2, soft monomer is by ethyl acrylate, Isooctyl acrylate monomer and lauryl methacrylate with weight Measure the mixture formed than 2:1:1；
In the step B3, hard monomer is by methyl acrylate, ethyl methacrylate and vinylacetate with weight ratio 1:0.8:1.5 the mixture of composition；
In the step B2 and the step B3, initiator is by isopropyl benzene hydroperoxide, azodiisobutyronitrile and tetrem The mixture that alkene imines is formed with weight ratio 1:0.5:1.5；
In the step B2 and the step B3, crosslinking agent be by diallyl fumarate, dimethacrylate -1,6- oneself The mixture that diol ester and Pehanorm trimethyl acrylic ester are formed with weight ratio 1:0.8:1.4；
In the step B4, mixing that demulsifier is made of sodium chloride, potassium acetate and ammonium sulfate with weight ratio 2:1.4:1 Object.
In the step B1, dispersing agent is inorganic dispersing agent；
The inorganic dispersing agent is natural silicate, Sulfates, carbonate or Oxalates；
The natural silicate is talcum, bentonite, diatomite or kaolin；The Sulfates are calcium sulfate or sulfuric acid Barium；The carbonate is calcium carbonate, barium carbonate or magnesium carbonate；The Oxalates are calcium oxalate.
A kind of organosilicon toughener with anti-drop effect, the organosilicon toughener is according to preparation method described above It is made.
A kind of toughened polycarbonate material using the organosilicon toughener with anti-drop effect described above, the increasing Tough makrolon material includes the raw material of following parts by weight: 80 parts of polycarbonate, 20 parts of glass fibre, 1 part of organosilicon toughener, 4 parts of modifying agent, 1 part of other auxiliary agents；
Wherein, the modifying agent is more created by macromolecule modified nanometer calcium carbonate, hyperbranched polyester amide and 4- allyl The mixture that the wooden phenol modified dimethyl polysiloxane is formed with weight ratio 2:0.1:0.5.
The preparation method of the macromolecule modified nanometer calcium carbonate includes the following steps:
(1) 15g nanometer calcium carbonate and 0.3g calgon dispersing agent are added into 300mL distilled water, disperses 20h；Together When 60g Polymeric quaternary ammonium salts are dissolved in 200mL tetrahydrofuran, dispersion 20h it is spare；
(2) 200mL tetrahydrofuran, high speed dispersion 0.3h, then slurry are added into scattered nanometer calcium carbonate system Liquid is transferred in there-necked flask, and polymeric quartenary ammonium salting liquid is slowly added dropwise under stirring, and system constantly generates white flock precipitate；
(3) after completion of dropwise addition, system is warming up to 75 DEG C, after reacting 20h, then slurries is filtered, 55 DEG C of vacuum drying for 24 hours, Obtain macromolecule modified nanometer calcium carbonate；
Wherein, in the step (1), Polymeric quaternary ammonium salts are brominated polyphenylether stearyl dimethyl benzyl ammonium chloride.
The synthetic method of the hyperbranched polyester amide are as follows: under nitrogen protection, successively by 0.8mol triethanolamine, 0.8mol 1,2,4- trimellitic anhydride and 0.005mol Catalyzed by p-Toluenesulfonic Acid agent are added three neck round bottom flask and are placed in heating In oil bath, stirring is gradually warming up to 210 DEG C, after raw material is uniformly mixed bleach, continues to be stirred to react at a temperature of 210 DEG C 2h is then cooled to room temperature, and obtains yellow transparent solid body i.e. hyperbranched polyester amide.
The synthetic method of the 4- allyl guaiacol modified dimethyl polysiloxane are as follows: equipped with thermometer, stirring In the there-necked flask of device, 230g dimethyl silicone polymer, 23g 4- allyl guaiacol are sequentially added at room temperature, is formed after stirring The suspension of White-opalescent；Add the octanol solution for the chloroplatinic acid that 0.5mL platinum mass fraction is 1.5%；Continue to stir, lead to It is warming up to 90 DEG C under nitrogen, reacts 2h.
The melt index of the polycarbonate is bisphenol A polycarbonate of the melt index in 10g/10min；The glass Fiber be fibre diameter 5 μm, fibre length 1mm alkali-free short glass fiber；Other described auxiliary agents are antioxidant.
Embodiment 2
A kind of synthetic method of the organosilicon toughener with anti-drop effect, includes the following steps:
A, the synthesis of organopolysiloxane core lotion:
A1, organosiloxane monomer is uniformly mixed, using homogenizer under 9000rpm revolving speed high speed shear 15min, obtain To mixed liquor；
A2, mixed liquor is added in the aqueous solution dissolved with catalyst and emulsifier, reacts 10h at a temperature of 88 DEG C, Obtain organopolysiloxane core lotion；Wherein, the gross mass of organosiloxane monomer is the 45% of water quality, the dosage of catalyst It is the 2% of organosiloxane monomer mass, the dosage of emulsifier is the 5% of organosiloxane monomer mass；
B, the synthesis of the organosilicon toughener with anti-drop effect:
B1, organopolysiloxane core lotion, PTFE emulsion, dispersing agent and distilled water are added in reaction kettle together, High shear agitation 10min, obtains reaction solution under 1200rpm revolving speed；Wherein, the dosage of PTFE emulsion is organopolysiloxane core The 20% of quality of the emulsion, the dosage of dispersing agent are the 2% of organopolysiloxane core quality of the emulsion；
B2, reaction solution lye is adjusted into pH value to 10, soft monomer is then added, adds initiator and crosslinking agent, in It is stirred to react 9h at a temperature of 60 DEG C, obtains the polymer emulsion of organopolysiloxane grafting soft monomer；Wherein, the dosage of soft monomer It is the 8% of organopolysiloxane core quality of the emulsion, the dosage of initiator is the 0.3% of organopolysiloxane core quality of the emulsion, is handed over The dosage for joining agent is the 0.3% of organopolysiloxane core quality of the emulsion；
B3, hard monomer is then added, adds initiator and crosslinking agent, is stirred to react 9h at a temperature of 60 DEG C, is had There is the polymer emulsion of core-shell structure；Wherein, the dosage of hard monomer is the 30% of organopolysiloxane core quality of the emulsion, initiator Dosage be the 0.3% of organopolysiloxane core quality of the emulsion, the dosage of crosslinking agent is organopolysiloxane core quality of the emulsion 0.3%；
B4, demulsifier demulsification is added, dries pulverizing after centrifugation had both obtained the organosilicon toughening with anti-drop effect Agent；Wherein, the dosage of demulsifier is 1 times of polymer emulsion quality.
In the step A1, organosiloxane monomer is by cyclic siloxane monomer, function groups siloxanyl monomers and second The mixture that alkenyl siloxane monomer is formed with weight ratio 30:0.3:0.8.
The function groups siloxanyl monomers are aminomethyl phenyl dimethoxysilane, ethylphenyl dimethoxysilane, third Base phenyidimethoxysilane, ethenylphenyl dimethoxysilane, acrylic phenyidimethoxysilane, ethynyl phenyl two Methoxy silane, propinyl phenyidimethoxysilane, methyldiphenyl methoxylsilane, ethyl diphenyl methoxy silane, Propyl diphenylmethyl oxysilane, vinyl diphenyl methoxy silane, acrylic diphenylmethyl oxysilane, acetenyl hexichol Methoxylsilane, propinyl diphenylmethyl oxysilane, dimethyl benzene methoxylsilane, diethylbenzene ylmethoxy silicon Alkane, dipropyl phenylmethoxysilane, divinyl phenylmethoxysilane, diallyl phenylmethoxysilane, diacetylene Base phenylmethoxysilane, dipropyl alkynyl phenyl methoxy silane, Methylethyl phenylmethoxysilane, methyl-propyl phenyl first Oxysilane, ethyl propyl phenylmethoxysilane, methyl vinyl phenyl methoxy silane, ethyl propylene base Phenylmethoxy Silane, methylacetylenyl phenylmethoxysilane or ethyl propinyl phenylmethoxysilane.
The cyclic siloxane monomer is ten vinyl cyclopentasiloxanes, ten divinyl basic rings, six siloxanes, three hydrogen front threes Basic ring trisiloxanes, trimethyl triethyl group cyclotrisiloxane, trimethyl triphenyl cyclotrisiloxane, three silicon of triethyl group triphen basic ring Oxygen alkane, trimethyl trivinyl cyclotrisiloxane, trivinyl triphenyl cyclotrisiloxane, diethyl tetramethyl-ring trisiloxanes Or dimethyl tetraethyl cyclotrisiloxane.
The vinylsiloxane monomer is to vinyl phenylmethyl Ethoxysilane, to ethenylphenyl ethyl methoxy Base silane, to ethenylphenyl ethyl Ethoxysilane, styryltrimethoxysilane, styryl triethoxysilane, 2- (to ethenylphenyl) ethyl-methyl dimethoxysilane or 2- (to ethenylphenyl) ethyl-methyl diethoxy silane.
In the step A2, catalyst is trifluoroethyl sulfonic acid, isethionic acid, propyl sulfonic acid, hydroxypropyl sulfonic acid or 1- Butyl sulfonic acid；
In the step A2, emulsifier is by cationic surfactant, anionic surfactant and non-ionic surface The mixture that activating agent is formed with weight ratio 0.5:1:0.3；
In the step B1, the average molecular weight of PTFE emulsion is 3,000,000, and solid content is 59%, and emulsion particle diameter is in 0.05 μ M, viscosity 20*10-3Pa.S；
In the step B2, soft monomer is by ethyl acrylate, Isooctyl acrylate monomer and lauryl methacrylate with weight Measure the mixture formed than 2.5:1.2:1；
In the step B3, hard monomer is by methyl acrylate, ethyl methacrylate and vinylacetate with weight ratio 1:0.9:1.8 the mixture of composition；
In the step B2 and the step B3, initiator is by isopropyl benzene hydroperoxide, azodiisobutyronitrile and tetrem The mixture that alkene imines is formed with weight ratio 1:0.8:1.8；
In the step B2 and the step B3, crosslinking agent be by diallyl fumarate, dimethacrylate -1,6- oneself The mixture that diol ester and Pehanorm trimethyl acrylic ester are formed with weight ratio 1:0.9:1.6；
In the step B4, demulsifier is made of sodium chloride, potassium acetate and ammonium sulfate with weight ratio 2.5:1.6:1 mixed Close object.
In the step B1, dispersing agent is inorganic dispersing agent；
The inorganic dispersing agent is hydroxide species or oxide-based；
The hydroxide species are aluminium hydroxide, magnesium hydroxide or calcium hydroxide；It is described it is oxide-based for titanium dioxide or Zinc oxide.
A kind of organosilicon toughener with anti-drop effect, the organosilicon toughener is according to preparation method described above It is made.
A kind of toughened polycarbonate material using the organosilicon toughener with anti-drop effect described above, the increasing Tough makrolon material includes the raw material of following parts by weight: 90 parts of polycarbonate, 25 parts of glass fibre, 3 parts of organosilicon toughener, 5 parts of modifying agent, 3 parts of other auxiliary agents；
Wherein, the modifying agent is more created by macromolecule modified nanometer calcium carbonate, hyperbranched polyester amide and 4- allyl The mixture that the wooden phenol modified dimethyl polysiloxane is formed with weight ratio 3:0.3:0.8.
The preparation method of the macromolecule modified nanometer calcium carbonate includes the following steps:
(1) 18g nanometer calcium carbonate and 0.4g calgon dispersing agent are added into 350mL distilled water, disperses 22h；Together When 70g Polymeric quaternary ammonium salts are dissolved in 250mL tetrahydrofuran, dispersion 22h it is spare；
(2) 250mL tetrahydrofuran, high speed dispersion 0.4h, then slurry are added into scattered nanometer calcium carbonate system Liquid is transferred in there-necked flask, and polymeric quartenary ammonium salting liquid is slowly added dropwise under stirring, and system constantly generates white flock precipitate；
(3) after completion of dropwise addition, system is warming up to 78 DEG C, after reacting 22h, then slurries is filtered, 58 DEG C of vacuum drying 30h, Obtain macromolecule modified nanometer calcium carbonate；
Wherein, in the step (1), Polymeric quaternary ammonium salts are dimethyl diallyl ammonium chloride-acrylamide copolymer.
The synthetic method of the hyperbranched polyester amide are as follows: under nitrogen protection, successively by 0.9mol triethanolamine, 0.9mol1,2,4- trimellitic anhydride and 0.008mol Catalyzed by p-Toluenesulfonic Acid agent are added three neck round bottom flask and are placed in heating In oil bath, stirring is gradually warming up to 215 DEG C, after raw material is uniformly mixed bleach, continues to be stirred to react at a temperature of 215 DEG C 2.5h is then cooled to room temperature, and obtains yellow transparent solid body i.e. hyperbranched polyester amide.
The synthetic method of the 4- allyl guaiacol modified dimethyl polysiloxane are as follows: equipped with thermometer, stirring In the there-necked flask of device, 240g dimethyl silicone polymer, 24g 4- allyl guaiacol are sequentially added at room temperature, is formed after stirring The suspension of White-opalescent；Add the octanol solution for the chloroplatinic acid that 0.6mL platinum mass fraction is 1.8%；Continue to stir, lead to It is warming up to 92 DEG C under nitrogen, reacts 2.5h.
The melt index of the polycarbonate is polyester-type polycarbonate of the melt index in 20g/10min；The glass Fiber be fibre diameter 8 μm, fibre length 3mm alkali-free short glass fiber；Other described auxiliary agents are UV resistant agent.
Embodiment 3
A kind of synthetic method of the organosilicon toughener with anti-drop effect, includes the following steps:
A, the synthesis of organopolysiloxane core lotion:
A1, organosiloxane monomer is uniformly mixed, using homogenizer under 10000rpm revolving speed high speed shear 12min, Obtain mixed liquor；
A2, mixed liquor is added in the aqueous solution dissolved with catalyst and emulsifier, reacts 9h at a temperature of 92 DEG C, obtains To organopolysiloxane core lotion；Wherein, the gross mass of organosiloxane monomer is the 50% of water quality, and the dosage of catalyst is The 3% of organosiloxane monomer mass, the dosage of emulsifier are the 10% of organosiloxane monomer mass；
B, the synthesis of the organosilicon toughener with anti-drop effect:
B1, organopolysiloxane core lotion, PTFE emulsion, dispersing agent and distilled water are added in reaction kettle together, High shear agitation 15min, obtains reaction solution under 1500rpm revolving speed；Wherein, the dosage of PTFE emulsion is organopolysiloxane core The 30% of quality of the emulsion, the dosage of dispersing agent are the 3% of organopolysiloxane core quality of the emulsion；
B2, reaction solution lye is adjusted into pH value to 10.5, soft monomer is then added, adds initiator and crosslinking agent, It is stirred to react 8h at a temperature of 70 DEG C, obtains the polymer emulsion of organopolysiloxane grafting soft monomer；Wherein, the use of soft monomer Amount is the 10% of organopolysiloxane core quality of the emulsion, and the dosage of initiator is the 0.5% of organopolysiloxane core quality of the emulsion, The dosage of crosslinking agent is the 0.4% of organopolysiloxane core quality of the emulsion；
B3, hard monomer is then added, adds initiator and crosslinking agent, is stirred to react 8h at a temperature of 65 DEG C, is had There is the polymer emulsion of core-shell structure；Wherein, the dosage of hard monomer is the 35% of organopolysiloxane core quality of the emulsion, initiator Dosage be the 0.5% of organopolysiloxane core quality of the emulsion, the dosage of crosslinking agent is organopolysiloxane core quality of the emulsion 0.4%；
B4, demulsifier demulsification is added, dries pulverizing after centrifugation had both obtained the organosilicon toughening with anti-drop effect Agent；Wherein, the dosage of demulsifier is 1.5 times of polymer emulsion quality.
In the step A1, organosiloxane monomer is by cyclic siloxane monomer, function groups siloxanyl monomers and second The mixture that alkenyl siloxane monomer is formed with weight ratio 40:0.5:1.
The function groups siloxanyl monomers are phenyl triethoxysilane, diphenyl diethoxy silane or triphenyl second Oxysilane.
The cyclic siloxane monomer is divinyl tetramethyl-ring trisiloxanes, three silicon oxygen of dimethyl tetravinyl ring Alkane, diphenyltetramethyl cyclotrisiloxane, dimethyl tetraphenyl cyclotrisiloxane, vinyl pentamethyl cyclotrisiloxane, methyl Five benzyl ring trisiloxanes of five vinyl cyclotrisiloxane, phenyl pentamethyl cyclotrisiloxane or methyl.
The vinylsiloxane monomer is 3- (to vinylbenzoyl oxygroup) hydroxypropyl methyl dimethoxysilane, 3- (to vinylbenzoyl oxygroup) hydroxypropyl methyl diethoxy silane, acrylic trimethoxy silane, propylene ethyl triethoxy silicane Alkane, propenylmethyl dimethoxysilane, propenylmethyl diethoxy silane, acrylic ethyldimethoxysilane, propylene Base ethyl diethoxy silane, acrylic propyldimethoxy-silane or acrylic propyl diethoxy silane.
In the step A2, catalyst be vinyl sulfonic acid, propene sulfonic acid, methacrylic sulfonic acid, ethyl propylene sulfonic acid or Benzene sulfonic acid；
In the step A2, emulsifier is by cationic surfactant, anionic surfactant and non-ionic surface The mixture that activating agent is formed with weight ratio 0.6:1:0.4；
In the step B1, the average molecular weight of PTFE emulsion is 5,000,000, and solid content is 60%, and emulsion particle diameter is in 0.15 μ M, viscosity 25*10-3Pa.S；
In the step B2, soft monomer is by ethyl acrylate, Isooctyl acrylate monomer and lauryl methacrylate with weight Measure the mixture formed than 3:1.5:1；
In the step B3, hard monomer is by methyl acrylate, ethyl methacrylate and vinylacetate with weight ratio The mixture of 1:1:2 composition；
In the step B2 and the step B3, initiator is by isopropyl benzene hydroperoxide, azodiisobutyronitrile and tetrem The mixture that alkene imines is formed with weight ratio 1:1:2；
In the step B2 and the step B3, crosslinking agent be by diallyl fumarate, dimethacrylate -1,6- oneself The mixture that diol ester and Pehanorm trimethyl acrylic ester are formed with weight ratio 1:1:1.8；
In the step B4, mixing that demulsifier is made of sodium chloride, potassium acetate and ammonium sulfate with weight ratio 3:1.8:1 Object.
In the step B1, dispersing agent is organic dispersing agent；
The organic dispersing agent is that natural polymer subclass dispersing agent, protein-based macromolecule dispersing agent or cellulose family spread out Biological species dispersing agent；
The natural polymer subclass dispersing agent is carbohydrate starch, pectin, natural plant gum or seaweed glue；The protein-based high score Sub- dispersing agent is gelatin or Fish protein；The cellulose derivative class dispersing agent is methylcellulose, methylhydroxypropyl Element, hydroxyethyl cellulose or hydroxypropyl cellulose.
A kind of organosilicon toughener with anti-drop effect, the organosilicon toughener is according to preparation method described above It is made.
A kind of toughened polycarbonate material using the organosilicon toughener with anti-drop effect described above, the increasing Tough makrolon material includes the raw material of following parts by weight: 100 parts of polycarbonate, 30 parts of glass fibre, organosilicon toughener 5 Part, 6 parts of modifying agent, 5 parts of other auxiliary agents；
Wherein, the modifying agent is more created by macromolecule modified nanometer calcium carbonate, hyperbranched polyester amide and 4- allyl The mixture that the wooden phenol modified dimethyl polysiloxane is formed with weight ratio 4:0.5:1.
The preparation method of the macromolecule modified nanometer calcium carbonate includes the following steps:
(1) 20g nanometer calcium carbonate and 0.5g calgon dispersing agent are added into 400mL distilled water, dispersion is for 24 hours；Together When 80g Polymeric quaternary ammonium salts are dissolved in 300mL tetrahydrofuran, disperse it is spare for 24 hours；
(2) 300mL tetrahydrofuran, high speed dispersion 0.5h, then slurry are added into scattered nanometer calcium carbonate system Liquid is transferred in there-necked flask, and polymeric quartenary ammonium salting liquid is slowly added dropwise under stirring, and system constantly generates white flock precipitate；
(3) after completion of dropwise addition, system is warming up to 80 DEG C, after reaction for 24 hours, then slurries is filtered, 60 DEG C of vacuum drying 36h, Obtain macromolecule modified nanometer calcium carbonate；
Wherein, in the step (1), Polymeric quaternary ammonium salts are polydimethyl diallyl ammonium chloride.
The synthetic method of the hyperbranched polyester amide are as follows: under nitrogen protection, successively by 1mol triethanolamine, 1mol 1,2,4- trimellitic anhydride and 0.01mol Catalyzed by p-Toluenesulfonic Acid agent are added three neck round bottom flask and are placed in heating oil bath, Stirring, is gradually warming up to 220 DEG C, after raw material is uniformly mixed bleach, continues to be stirred to react 3h at a temperature of 220 DEG C, then It is cooled to room temperature, obtains yellow transparent solid body i.e. hyperbranched polyester amide.
The synthetic method of the 4- allyl guaiacol modified dimethyl polysiloxane are as follows: equipped with thermometer, stirring In the there-necked flask of device, 250g dimethyl silicone polymer, 25g 4- allyl guaiacol are sequentially added at room temperature, is formed after stirring The suspension of White-opalescent；Add the octanol solution for the chloroplatinic acid that 0.8mL platinum mass fraction is 2%；Continue to stir, leads to nitrogen It is warming up to 95 DEG C under gas, reacts 3h.
The melt index of the polycarbonate is hexamethylene bisphenol A polycarbonate of the melt index in 30g/10min；Institute State glass fibre be fibre diameter 10 μm, fibre length 5mm alkali-free short glass fiber；Other described auxiliary agents are lubrication Agent.
Embodiment 4
A kind of synthetic method of the organosilicon toughener with anti-drop effect, includes the following steps:
A, the synthesis of organopolysiloxane core lotion:
A1, organosiloxane monomer is uniformly mixed, using homogenizer under 11000rpm revolving speed high speed shear 8min, obtain To mixed liquor；
A2, mixed liquor is added in the aqueous solution dissolved with catalyst and emulsifier, reacts 8h at a temperature of 96 DEG C, obtains To organopolysiloxane core lotion；Wherein, the gross mass of organosiloxane monomer is the 55% of water quality, and the dosage of catalyst is The 4% of organosiloxane monomer mass, the dosage of emulsifier are the 15% of organosiloxane monomer mass；
B, the synthesis of the organosilicon toughener with anti-drop effect:
B1, organopolysiloxane core lotion, PTFE emulsion, dispersing agent and distilled water are added in reaction kettle together, High shear agitation 20min, obtains reaction solution under 1800rpm revolving speed；Wherein, the dosage of PTFE emulsion is organopolysiloxane core The 40% of quality of the emulsion, the dosage of dispersing agent are the 4% of organopolysiloxane core quality of the emulsion；
B2, reaction solution lye is adjusted into pH value to 11, soft monomer is then added, adds initiator and crosslinking agent, in It is stirred to react 6h at a temperature of 80 DEG C, obtains the polymer emulsion of organopolysiloxane grafting soft monomer；Wherein, the dosage of soft monomer It is the 12% of organopolysiloxane core quality of the emulsion, the dosage of initiator is the 0.6% of organopolysiloxane core quality of the emulsion, is handed over The dosage for joining agent is the 0.5% of organopolysiloxane core quality of the emulsion；
B3, hard monomer is then added, adds initiator and crosslinking agent, is stirred to react 6h at a temperature of 80 DEG C, is had There is the polymer emulsion of core-shell structure；Wherein, the dosage of hard monomer is the 40% of organopolysiloxane core quality of the emulsion, initiator Dosage be the 0.6% of organopolysiloxane core quality of the emulsion, the dosage of crosslinking agent is organopolysiloxane core quality of the emulsion 0.5%；
B4, demulsifier demulsification is added, dries pulverizing after centrifugation had both obtained the organosilicon toughening with anti-drop effect Agent；Wherein, the dosage of demulsifier is 2 times of polymer emulsion quality.
In the step A1, organosiloxane monomer is by cyclic siloxane monomer, function groups siloxanyl monomers and second The mixture that alkenyl siloxane monomer is formed with weight ratio 50:0.8:1.2.
The function groups siloxanyl monomers are aminomethyl phenyl diethoxy silane, Ethylphenyldiethoxysandne, third Base diethylamino phenyl oxysilane, ethenylphenyl diethoxy silane, acrylic phenyl diethoxy silane, ethynyl phenyl two Ethoxysilane, propinyl diethylamino phenyl oxysilane, methyldiphenylethoxysilane, ethyl diphenyl Ethoxysilane, Propyl diphenyl Ethoxysilane, vinyl diphenyl Ethoxysilane, acrylic diphenyl Ethoxysilane, acetenyl hexichol Base oxethyl silane, propinyl diphenyl Ethoxysilane, 3,5-dimethylphenyl Ethoxysilane, diethylbenzene base oxethyl silicon Alkane, dipropyl phenyl ethoxy silane, divinyl phenyl ethoxy silane, diallyl phenyl ethoxy silane, diacetylene Base phenyl ethoxy silane, dipropyl alkynyl phenyl Ethoxysilane, Methylethyl phenyl ethoxy silane, methyl-propyl phenyl second Oxysilane, ethyl propyl phenyl ethoxy silane, methyl vinyl phenyl Ethoxysilane, ethyl propylene base phenyl ethoxy Silane, methylacetylenyl phenyl ethoxy silane or ethyl propinyl phenyl ethoxy silane.
The cyclic siloxane monomer is tetrahydro tetramethyl-ring tetrasiloxane, tetramethyl tetraethyl cyclotetrasiloxane, tetramethyl Base tetraphenyl cyclotetrasiloxane, tetraethyl tetraphenyl cyclotetrasiloxane, t etram-ethyltetravinylcyclotetrasiloxane, tetravinyl four Phenyl cyclotetrasiloxane, diethyl hexamethyl cyclotetrasiloxane, dimethyl Hexaethyl cyclotetrasiloxane or divinyl hexamethyl Cyclotetrasiloxane.
The vinylsiloxane monomer is γ-mercapto propyl methyl dimethoxy silane, γ-methacryloxy third Ylmethoxy dimethylsilane, γ-methacryloxypropyl dimethoxymethylsilane, γ-methacryloxy third Base trimethoxy silane, γ-methacryloxypropyl ethyoxyl dimethylsilane or γ-methacryloxypropyl two (ethoxymethyl) base silane.
In the step A2, catalyst is toluenesulfonic acid, ethyl phenenyl azochlorosulfonate acid or acid dimethyl；
In the step A2, emulsifier is by cationic surfactant, anionic surfactant and non-ionic surface The mixture that activating agent is formed with weight ratio 0.7:1:0.5；
In the step B1, the average molecular weight of PTFE emulsion is 8,000,000, and solid content is 61%, and emulsion particle diameter is in 0.2 μ M, viscosity 30*10-3Pa.S；
In the step B2, soft monomer is by ethyl acrylate, Isooctyl acrylate monomer and lauryl methacrylate with weight Measure the mixture formed than 3.5:1.8:1；
In the step B3, hard monomer is by methyl acrylate, ethyl methacrylate and vinylacetate with weight ratio 1:1.1:2.2 the mixture of composition；
In the step B2 and the step B3, initiator is by isopropyl benzene hydroperoxide, azodiisobutyronitrile and tetrem The mixture that alkene imines is formed with weight ratio 1:1.2:2.2；
In the step B2 and the step B3, crosslinking agent be by diallyl fumarate, dimethacrylate -1,6- oneself The mixture that diol ester and Pehanorm trimethyl acrylic ester are formed with weight ratio 1:1.1:2；
In the step B4, mixing that demulsifier is made of sodium chloride, potassium acetate and ammonium sulfate with weight ratio 3.5:2:1 Object.
In the step B1, dispersing agent is organic dispersing agent；
The organic dispersing agent is that synthesis high score subclass dispersing agent or class containing carboxyl synthesize macromolecule dispersing agent；
The synthesis high score subclass dispersing agent is hydroxyl class partial alcoholysis polyvinyl alcohol；The class containing carboxyl synthesizes high score Sub- dispersing agent is phenylethylene/maleic anhydride copolymer, vinyl acetate/copolymer-maleic anhydride and acrylic copolymer or methyl Acrylic copolymer.
A kind of organosilicon toughener with anti-drop effect, the organosilicon toughener is according to preparation method described above It is made.
A kind of toughened polycarbonate material using the organosilicon toughener with anti-drop effect described above, the increasing Tough makrolon material includes the raw material of following parts by weight: 110 parts of polycarbonate, 35 parts of glass fibre, organosilicon toughener 8 Part, 7 parts of modifying agent, 8 parts of other auxiliary agents；
Wherein, the modifying agent is more created by macromolecule modified nanometer calcium carbonate, hyperbranched polyester amide and 4- allyl The mixture that the wooden phenol modified dimethyl polysiloxane is formed with weight ratio 5:0.8:1.2.
The preparation method of the macromolecule modified nanometer calcium carbonate includes the following steps:
(1) 22g nanometer calcium carbonate and 0.6g calgon dispersing agent are added into 450mL distilled water, disperses 26h；Together When 80g Polymeric quaternary ammonium salts are dissolved in 350mL tetrahydrofuran, dispersion 26h it is spare；
(2) 350mL tetrahydrofuran, high speed dispersion 0.6h, then slurry are added into scattered nanometer calcium carbonate system Liquid is transferred in there-necked flask, and polymeric quartenary ammonium salting liquid is slowly added dropwise under stirring, and system constantly generates white flock precipitate；
(3) after completion of dropwise addition, system is warming up to 82 DEG C, after reacting 26h, then slurries is filtered, 62 DEG C of vacuum drying 42h, Obtain macromolecule modified nanometer calcium carbonate；
Wherein, in the step (1), Polymeric quaternary ammonium salts are chlorination -2- hydroxyl -3- (dimethylamino) propyl polycyclic oxygen second Alkoxy cellulose ether.
The synthetic method of the hyperbranched polyester amide are as follows: under nitrogen protection, successively by 1.1mol triethanolamine, 1.1mol1,2,4- trimellitic anhydride and 0.012mol Catalyzed by p-Toluenesulfonic Acid agent are added three neck round bottom flask and are placed in heating In oil bath, stirring is gradually warming up to 225 DEG C, after raw material is uniformly mixed bleach, continues to be stirred to react at a temperature of 225 DEG C 3.5h is then cooled to room temperature, and obtains yellow transparent solid body i.e. hyperbranched polyester amide.
The synthetic method of the 4- allyl guaiacol modified dimethyl polysiloxane are as follows: equipped with thermometer, stirring In the there-necked flask of device, 260g dimethyl silicone polymer, 26g 4- allyl guaiacol are sequentially added at room temperature, is formed after stirring The suspension of White-opalescent；Add the octanol solution for the chloroplatinic acid that 0.9mL platinum mass fraction is 2.2%；Continue to stir, lead to It is warming up to 98 DEG C under nitrogen, reacts 3.5h.
The melt index of the polycarbonate is bisphenol A polycarbonate of the melt index in 40g/10min；The glass Fiber be fibre diameter 12 μm, fibre length 8mm alkali-free short glass fiber；Other described auxiliary agents are smoke suppressant.
Embodiment 5
A kind of synthetic method of the organosilicon toughener with anti-drop effect, includes the following steps:
A, the synthesis of organopolysiloxane core lotion:
A1, organosiloxane monomer is uniformly mixed, using homogenizer under 12000rpm revolving speed high speed shear 5min, obtain To mixed liquor；
A2, mixed liquor is added in the aqueous solution dissolved with catalyst and emulsifier, reacts 6h at a temperature of 100 DEG C, Obtain organopolysiloxane core lotion；Wherein, the gross mass of organosiloxane monomer is the 60% of water quality, the dosage of catalyst It is the 5% of organosiloxane monomer mass, the dosage of emulsifier is the 20% of organosiloxane monomer mass；
B, the synthesis of the organosilicon toughener with anti-drop effect:
B1, organopolysiloxane core lotion, PTFE emulsion, dispersing agent and distilled water are added in reaction kettle together, High shear agitation 5min, obtains reaction solution under 2000rpm revolving speed；Wherein, the dosage of PTFE emulsion is organopolysiloxane core The 50% of quality of the emulsion, the dosage of dispersing agent are the 5% of organopolysiloxane core quality of the emulsion；
B2, reaction solution lye is adjusted into pH value to 12, soft monomer is then added, adds initiator and crosslinking agent, in It is stirred to react 5h at a temperature of 90 DEG C, obtains the polymer emulsion of organopolysiloxane grafting soft monomer；Wherein, the dosage of soft monomer It is the 15% of organopolysiloxane core quality of the emulsion, the dosage of initiator is the 0.8% of organopolysiloxane core quality of the emulsion, is handed over The dosage for joining agent is the 0.6% of organopolysiloxane core quality of the emulsion；
B3, hard monomer is then added, adds initiator and crosslinking agent, is stirred to react 5h at a temperature of 90 DEG C, is had There is the polymer emulsion of core-shell structure；Wherein, the dosage of hard monomer is the 45% of organopolysiloxane core quality of the emulsion, initiator Dosage be the 0.8% of organopolysiloxane core quality of the emulsion, the dosage of crosslinking agent is organopolysiloxane core quality of the emulsion 0.6%；
B4, demulsifier demulsification is added, dries pulverizing after centrifugation had both obtained the organosilicon toughening with anti-drop effect Agent；Wherein, the dosage of demulsifier is 3 times of polymer emulsion quality.
In the step A1, organosiloxane monomer is by cyclic siloxane monomer, function groups siloxanyl monomers and second The mixture that alkenyl siloxane monomer is formed with weight ratio 60:1.0:1.5.
The function groups siloxanyl monomers are bis- [2- (dimethoxy-methyl silicyl) ethyl] benzene of 1,3-, Isosorbide-5-Nitrae-is bis- [2- (dimethoxy-methyl silicyl) ethyl] benzene, 1,3- bis- [1- (dimethoxy-methyl silicyl) ethyl] benzene, Isosorbide-5-Nitrae- Bis- [1- (dimethoxy-methyl silicyl) ethyl] benzene, 1- [1_ (dimethoxy-methyl silicyl) ethyl] -3- [2- (two Methoxy silicyl) ethyl] benzene or 1- [1_ (dimethoxy-methyl silicyl) ethyl] -4- [2- dimethoxy first Base silicyl) ethyl] benzene.
The cyclic siloxane monomer be six vinyl cyclotetrasiloxane of dimethyl, diphenyl hexamethyl cyclotetrasiloxane, Dimethyl hexaphenyl cyclotetrasiloxane, vinyl heptamethylcyclotetrasiloxane, seven vinyl cyclotetrasiloxane of methyl, seven first of phenyl Seven phenyl cyclotetrasiloxane of basic ring tetrasiloxane or methyl.
The vinylsiloxane monomer is γ-methacryloxypropyl morpholine silane, γ-methyl-prop Alkene acryloxypropylethoxysilane dimethoxy-ethyl silane, γ-methacryloxypropyl ethyoxyl diethylsilane, γ-methyl-prop Alkene acryloxypropylethoxysilane diethoxy ethylsilane or γ-methacryloxypropyl.
In the step A2, catalyst is diethylbenzene sulfonic acid or dodecyl benzene sulfonic acid；
In the step A2, emulsifier is by cationic surfactant, anionic surfactant and non-ionic surface The mixture that activating agent is formed with weight ratio 0.8:1:0.6；
In the step B1, the average molecular weight of PTFE emulsion is 10,000,000, and solid content is 62%, and emulsion particle diameter is 0.30 μm, viscosity 40*10-3Pa.S；
In the step B2, soft monomer is by ethyl acrylate, Isooctyl acrylate monomer and lauryl methacrylate with weight Measure the mixture formed than 4:2:1；
In the step B3, hard monomer is by methyl acrylate, ethyl methacrylate and vinylacetate with weight ratio 1:1.2:2.5 the mixture of composition；
In the step B2 and the step B3, initiator is by isopropyl benzene hydroperoxide, azodiisobutyronitrile and tetrem The mixture that alkene imines is formed with weight ratio 1:1.5:2.5；
In the step B2 and the step B3, crosslinking agent be by diallyl fumarate, dimethacrylate -1,6- oneself The mixture that diol ester and Pehanorm trimethyl acrylic ester are formed with weight ratio 1:1.2:2.2；
In the step B4, mixing that demulsifier is made of sodium chloride, potassium acetate and ammonium sulfate with weight ratio 4:2.2:1 Object.
In the step B1, dispersing agent is organic dispersing agent；
The organic dispersing agent is that nitrogenous class synthesizes macromolecule dispersing agent or ester-containing base class synthesizes macromolecule dispersing agent；
The nitrogenous class synthesis macromolecule dispersing agent is polyvinylpyrrolidone；The ester-containing base class synthesis macromolecule point Powder is polyethyleneoxide fatty acid esters or sorbitan fatty acid.
A kind of organosilicon toughener with anti-drop effect, the organosilicon toughener is according to preparation method described above It is made.
A kind of toughened polycarbonate material using the organosilicon toughener with anti-drop effect described above, the increasing Tough makrolon material includes the raw material of following parts by weight: 120 parts of polycarbonate, 40 parts of glass fibre, organosilicon toughener 10 Part, 8 parts of modifying agent, 10 parts of other auxiliary agents；
Wherein, the modifying agent is more created by macromolecule modified nanometer calcium carbonate, hyperbranched polyester amide and 4- allyl The mixture that the wooden phenol modified dimethyl polysiloxane is formed with weight ratio 6:1.0:1.5.
The preparation method of the macromolecule modified nanometer calcium carbonate includes the following steps:
(1) 25g nanometer calcium carbonate and 0.7g calgon dispersing agent are added into 500mL distilled water, disperses 28h；Together When 100g Polymeric quaternary ammonium salts are dissolved in 400mL tetrahydrofuran, dispersion 28h it is spare；
(2) 400mL tetrahydrofuran, high speed dispersion 0.7h, then slurry are added into scattered nanometer calcium carbonate system Liquid is transferred in there-necked flask, and polymeric quartenary ammonium salting liquid is slowly added dropwise under stirring, and system constantly generates white flock precipitate；
(3) after completion of dropwise addition, system is warming up to 85 DEG C, after reacting 28h, then slurries is filtered, 65 DEG C of vacuum drying 48h, Obtain macromolecule modified nanometer calcium carbonate；
Wherein, in the step (1), Polymeric quaternary ammonium salts N, N, N- trimethyl-2- (2- methyl-1-oxo-2- propylene Base oxygroup) ethyl ammonium chloride-acrylamide copolymer.
The synthetic method of the hyperbranched polyester amide are as follows: under nitrogen protection, successively by 1.2mol triethanolamine, 1.2mol1,2,4- trimellitic anhydride and 0.015mol Catalyzed by p-Toluenesulfonic Acid agent are added three neck round bottom flask and are placed in heating In oil bath, stirring is gradually warming up to 230 DEG C, after raw material is uniformly mixed bleach, continues to be stirred to react at a temperature of 230 DEG C 4h is then cooled to room temperature, and obtains yellow transparent solid body i.e. hyperbranched polyester amide.
The synthetic method of the 4- allyl guaiacol modified dimethyl polysiloxane are as follows: equipped with thermometer, stirring In the there-necked flask of device, 270g dimethyl silicone polymer, 27g 4- allyl guaiacol are sequentially added at room temperature, is formed after stirring The suspension of White-opalescent；Add the octanol solution for the chloroplatinic acid that 1.0mL platinum mass fraction is 2.5%；Continue to stir, lead to It is warming up to 100 DEG C under nitrogen, reacts 4h.
The melt index of the polycarbonate is polyester-type polycarbonate of the melt index in 50g/10min；The glass Fiber be fibre diameter 15 μm, fibre length 10mm alkali-free short glass fiber；Other described auxiliary agents are Vitrified powder.
Embodiment 6
The present embodiment and above-described embodiment 1 the difference is that:
The multi-functional siloxanyl monomers are by aminomethyl phenyl dimethoxysilane, phenyltrimethoxysila,e and vinyl The mixture that trimethoxy silane is formed with weight ratio 1:0.4:0.8.
The cyclic siloxane monomer is by trimethyl triethyl group cyclotrisiloxane, six vinyl cyclotetrasiloxane of dimethyl The mixture formed with seven phenyl cyclotetrasiloxane of methyl with weight ratio 2:0.5:1.
The vinylsiloxane monomer is by vinyl propyldimethoxy-silane, to vinyl phenylmethyl ethyoxyl The mixture that silane and 3- (to vinylbenzoyl oxygroup) hydroxypropyl methyl diethoxy silane are formed with weight ratio 2:1.5:1.
The catalyst is by methylol sulfonic acid, trifluoroethyl sulfonic acid and hydroxypropyl sulfonic acid with weight ratio 1:0.8:0.4 group At mixture.
The cationic surfactant is by dialkyl dimethyl quaternary ammonium salt, benzalkonium dimethyl quaternary ammonium and single alkane The mixture that based quaternary ammonium salt is formed with weight ratio 1:1.2:1.8；The anionic surfactant is by polyoxyethylene alkyl ether The mixture that hydrogen sulfuric acid ester, alkyl diphenyl base ether disulfonate and polyoxyethylene alkyl ether ester are formed with weight ratio 1:0.5:1.4； The nonionic surfactant is by isomeric alcohol polyethenoxy ether, sorbitan fatty acid esters and polyoxyethylene hardened castor The mixture that sesame oil aliphatic ester is formed with weight ratio 1.6:1:0.8.
The Polymeric quaternary ammonium salts are by brominated polyphenylether stearyl dimethyl benzyl ammonium chloride, chlorination -2- hydroxyl -3- (dimethylamino) propyl polyethylene oxide cellulose ether and N, N, N- trimethyl-2- (2- methyl-1-oxo-2- acrylic oxygroup) The mixture that ethyl ammonium chloride-acrylamide copolymer is formed with weight ratio 2:1.5:1.
The polycarbonate is by bisphenol A polycarbonate, polyester-type polycarbonate and hexamethylene bisphenol A polycarbonate The mixture formed with weight ratio 1:0.8:1.
Other described auxiliary agents are by antioxidant, UV resistant agent, lubricant, smoke suppressant and Vitrified powder with weight ratio 0.4: The mixture of 0.6:1:0.5:0.8 composition.
The antioxidant is by β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [bis- uncles of 2.4- Butyl phenyl] mixture that is formed with weight ratio 1:0.8:1 of the double lauryls of phosphite ester and thio-2 acid.
The UV resistant agent is by 2- (2 '-hydroxyls -5 '-aminomethyl phenyl) benzotriazole, 2- hydroxyl -4- methoxyl group two The mixture that Benzophenone and hexamethylphosphoramide are formed with weight ratio 0.5:1.4:1.
The lubricant is by oxidized polyethylene wax, glycerin monostearate and stearic amide with weight ratio 1:0.4:1 The mixture of composition.
The mixing that the smoke suppressant is made of ferrocene, antimony oxide and ammonium octamolybdate with weight ratio 0.5:1.5:1 Object.
The mixing that the Vitrified powder is made of attapulgite, zinc borate, silicate glass powder with weight ratio 2:0.5:1 Object.
Embodiment 7
The present embodiment and above-described embodiment 2 the difference is that:
The multi-functional siloxanyl monomers are by aminomethyl phenyl dimethoxysilane, phenyltrimethoxysila,e and vinyl The mixture that trimethoxy silane is formed with weight ratio 1:0.5:0.9.
The cyclic siloxane monomer is by trimethyl triethyl group cyclotrisiloxane, six vinyl cyclotetrasiloxane of dimethyl The mixture formed with seven phenyl cyclotetrasiloxane of methyl with weight ratio 2.5:0.8:1.
The vinylsiloxane monomer is by vinyl propyldimethoxy-silane, to vinyl phenylmethyl ethyoxyl The mixing that silane and 3- (to vinylbenzoyl oxygroup) hydroxypropyl methyl diethoxy silane are formed with weight ratio 2.5:1.8:1 Object.
The catalyst is by methylol sulfonic acid, trifluoroethyl sulfonic acid and hydroxypropyl sulfonic acid with weight ratio 1:0.9:0.5 group At mixture.
The cationic surfactant is by dialkyl dimethyl quaternary ammonium salt, benzalkonium dimethyl quaternary ammonium and single alkane The mixture that based quaternary ammonium salt is formed with weight ratio 1:1.3:2；The anionic surfactant is by polyoxyethylene alkyl ether sulphur The mixture that sour hydrogen ester, alkyl diphenyl base ether disulfonate and polyoxyethylene alkyl ether ester are formed with weight ratio 1:0.8:1.6；Institute Stating nonionic surfactant is by isomeric alcohol polyethenoxy ether, sorbitan fatty acid esters and polyoxyethylene hardened castor-oil plant The mixture that oil and fat acid esters is formed with weight ratio 1.8:1:0.9.
The Polymeric quaternary ammonium salts are by brominated polyphenylether stearyl dimethyl benzyl ammonium chloride, chlorination -2- hydroxyl -3- (dimethylamino) propyl polyethylene oxide cellulose ether and N, N, N- trimethyl-2- (2- methyl-1-oxo-2- acrylic oxygroup) The mixture that ethyl ammonium chloride-acrylamide copolymer is formed with weight ratio 2.5:1.8:1.
The polycarbonate is by bisphenol A polycarbonate, polyester-type polycarbonate and hexamethylene bisphenol A polycarbonate The mixture formed with weight ratio 1.2:0.9:1.
Other described auxiliary agents are by antioxidant, UV resistant agent, lubricant, smoke suppressant and Vitrified powder with weight ratio 0.5: The mixture of 0.7:1:0.8:0.9 composition.
The antioxidant is by β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [bis- uncles of 2.4- Butyl phenyl] mixture that is formed with weight ratio 1.2:0.9:1 of the double lauryls of phosphite ester and thio-2 acid.
The UV resistant agent is by 2- (2 '-hydroxyls -5 '-aminomethyl phenyl) benzotriazole, 2- hydroxyl -4- methoxyl group two The mixture that Benzophenone and hexamethylphosphoramide are formed with weight ratio 0.8:1.6:1.
The lubricant is by oxidized polyethylene wax, glycerin monostearate and stearic amide with weight ratio 1.2:0.5: The mixture of 1 composition.
The mixing that the smoke suppressant is made of ferrocene, antimony oxide and ammonium octamolybdate with weight ratio 0.8:1.8:1 Object.
The mixing that the Vitrified powder is made of attapulgite, zinc borate, silicate glass powder with weight ratio 2.5:0.8:1 Object.
Embodiment 8
The present embodiment and above-described embodiment 3 the difference is that:
The multi-functional siloxanyl monomers are by aminomethyl phenyl dimethoxysilane, phenyltrimethoxysila,e and vinyl The mixture that trimethoxy silane is formed with weight ratio 1:0.6:1.
The cyclic siloxane monomer is by trimethyl triethyl group cyclotrisiloxane, six vinyl cyclotetrasiloxane of dimethyl The mixture formed with seven phenyl cyclotetrasiloxane of methyl with weight ratio 3:1:1.
The vinylsiloxane monomer is by vinyl propyldimethoxy-silane, to vinyl phenylmethyl ethyoxyl The mixture that silane and 3- (to vinylbenzoyl oxygroup) hydroxypropyl methyl diethoxy silane are formed with weight ratio 3:2:1.
The catalyst is made of methylol sulfonic acid, trifluoroethyl sulfonic acid and hydroxypropyl sulfonic acid with weight ratio 1:1:0.6 Mixture.
The cationic surfactant is by dialkyl dimethyl quaternary ammonium salt, benzalkonium dimethyl quaternary ammonium and single alkane The mixture that based quaternary ammonium salt is formed with weight ratio 1:1.4:2.2；The anionic surfactant is by polyoxyethylene alkyl ether The mixture that hydrogen sulfuric acid ester, alkyl diphenyl base ether disulfonate and polyoxyethylene alkyl ether ester are formed with weight ratio 1:1:1.8；Institute Stating nonionic surfactant is by isomeric alcohol polyethenoxy ether, sorbitan fatty acid esters and polyoxyethylene hardened castor-oil plant The mixture that oil and fat acid esters is formed with weight ratio 2:1:1.
The Polymeric quaternary ammonium salts are by brominated polyphenylether stearyl dimethyl benzyl ammonium chloride, chlorination -2- hydroxyl -3- (dimethylamino) propyl polyethylene oxide cellulose ether and N, N, N- trimethyl-2- (2- methyl-1-oxo-2- acrylic oxygroup) The mixture that ethyl ammonium chloride-acrylamide copolymer is formed with weight ratio 3:2:1.
The polycarbonate is by bisphenol A polycarbonate, polyester-type polycarbonate and hexamethylene bisphenol A polycarbonate The mixture formed with weight ratio 1.5:1:1.
Other described auxiliary agents are by antioxidant, UV resistant agent, lubricant, smoke suppressant and Vitrified powder with weight ratio 0.6: The mixture of 0.8:1:1:1 composition.
The antioxidant is by β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [bis- uncles of 2.4- Butyl phenyl] mixture that is formed with weight ratio 1.5:1:1 of the double lauryls of phosphite ester and thio-2 acid.
The UV resistant agent is by 2- (2 '-hydroxyls -5 '-aminomethyl phenyl) benzotriazole, 2- hydroxyl -4- methoxyl group two The mixture that Benzophenone and hexamethylphosphoramide are formed with weight ratio 1:1.8:1.
The lubricant is by oxidized polyethylene wax, glycerin monostearate and stearic amide with weight ratio 1.5:0.6: The mixture of 1 composition.
The mixture that the smoke suppressant is made of ferrocene, antimony oxide and ammonium octamolybdate with weight ratio 1:2:1.
The mixture that the Vitrified powder is made of attapulgite, zinc borate, silicate glass powder with weight ratio 3:1:1.
Embodiment 9
The present embodiment and above-described embodiment 4 the difference is that:
The multi-functional siloxanyl monomers are by aminomethyl phenyl dimethoxysilane, phenyltrimethoxysila,e and vinyl The mixture that trimethoxy silane is formed with weight ratio 1:0.7:1.1.
The cyclic siloxane monomer is by trimethyl triethyl group cyclotrisiloxane, six vinyl cyclotetrasiloxane of dimethyl The mixture formed with seven phenyl cyclotetrasiloxane of methyl with weight ratio 3.5:1.2:1.
The vinylsiloxane monomer is by vinyl propyldimethoxy-silane, to vinyl phenylmethyl ethyoxyl The mixing that silane and 3- (to vinylbenzoyl oxygroup) hydroxypropyl methyl diethoxy silane are formed with weight ratio 3.5:2.2:1 Object.
The catalyst is by methylol sulfonic acid, trifluoroethyl sulfonic acid and hydroxypropyl sulfonic acid with weight ratio 1:1.1:0.7 group At mixture.
The cationic surfactant is by dialkyl dimethyl quaternary ammonium salt, benzalkonium dimethyl quaternary ammonium and single alkane The mixture that based quaternary ammonium salt is formed with weight ratio 1:1.5:2.4；The anionic surfactant is by polyoxyethylene alkyl ether The mixture that hydrogen sulfuric acid ester, alkyl diphenyl base ether disulfonate and polyoxyethylene alkyl ether ester are formed with weight ratio 1:1.2:2；Institute Stating nonionic surfactant is by isomeric alcohol polyethenoxy ether, sorbitan fatty acid esters and polyoxyethylene hardened castor-oil plant The mixture that oil and fat acid esters is formed with weight ratio 2.2:1:1.1.
The Polymeric quaternary ammonium salts are by brominated polyphenylether stearyl dimethyl benzyl ammonium chloride, chlorination -2- hydroxyl -3- (dimethylamino) propyl polyethylene oxide cellulose ether and N, N, N- trimethyl-2- (2- methyl-1-oxo-2- acrylic oxygroup) The mixture that ethyl ammonium chloride-acrylamide copolymer is formed with weight ratio 3.5:2.2:1.
The polycarbonate is by bisphenol A polycarbonate, polyester-type polycarbonate and hexamethylene bisphenol A polycarbonate The mixture formed with weight ratio 1.8:1.1:1.
Other described auxiliary agents are by antioxidant, UV resistant agent, lubricant, smoke suppressant and Vitrified powder with weight ratio 0.7: The mixture of 0.9:1:1.2:1.1 composition.
The antioxidant is by β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [bis- uncles of 2.4- Butyl phenyl] mixture that is formed with weight ratio 1.8:1.1:1 of the double lauryls of phosphite ester and thio-2 acid.
The UV resistant agent is by 2- (2 '-hydroxyls -5 '-aminomethyl phenyl) benzotriazole, 2- hydroxyl -4- methoxyl group two The mixture that Benzophenone and hexamethylphosphoramide are formed with weight ratio 1.2:2:1.
The lubricant is by oxidized polyethylene wax, glycerin monostearate and stearic amide with weight ratio 1.8:0.7: The mixture of 1 composition.
The mixing that the smoke suppressant is made of ferrocene, antimony oxide and ammonium octamolybdate with weight ratio 1.2:2.2:1 Object.
The mixing that the Vitrified powder is made of attapulgite, zinc borate, silicate glass powder with weight ratio 3.5:1.2:1 Object.
Embodiment 10
The present embodiment and above-described embodiment 5 the difference is that:
The multi-functional siloxanyl monomers are by aminomethyl phenyl dimethoxysilane, phenyltrimethoxysila,e and vinyl The mixture that trimethoxy silane is formed with weight ratio 1:0.8:1.2.
The cyclic siloxane monomer is by trimethyl triethyl group cyclotrisiloxane, six vinyl cyclotetrasiloxane of dimethyl The mixture formed with seven phenyl cyclotetrasiloxane of methyl with weight ratio 4:1.5:1.
The vinylsiloxane monomer is by vinyl propyldimethoxy-silane, to vinyl phenylmethyl ethyoxyl The mixture that silane and 3- (to vinylbenzoyl oxygroup) hydroxypropyl methyl diethoxy silane are formed with weight ratio 4:2.5:1.
The catalyst is by methylol sulfonic acid, trifluoroethyl sulfonic acid and hydroxypropyl sulfonic acid with weight ratio 1:1.2:0.8 group At mixture.
The cationic surfactant is by dialkyl dimethyl quaternary ammonium salt, benzalkonium dimethyl quaternary ammonium and single alkane The mixture that based quaternary ammonium salt is formed with weight ratio 1:1.6:2.6；The anionic surfactant is by polyoxyethylene alkyl ether The mixture that hydrogen sulfuric acid ester, alkyl diphenyl base ether disulfonate and polyoxyethylene alkyl ether ester are formed with weight ratio 1:1.5:2.2； The nonionic surfactant is by isomeric alcohol polyethenoxy ether, sorbitan fatty acid esters and polyoxyethylene hardened castor The mixture that sesame oil aliphatic ester is formed with weight ratio 2.4:1:1.2.
The Polymeric quaternary ammonium salts are by brominated polyphenylether stearyl dimethyl benzyl ammonium chloride, chlorination -2- hydroxyl -3- (dimethylamino) propyl polyethylene oxide cellulose ether and N, N, N- trimethyl-2- (2- methyl-1-oxo-2- acrylic oxygroup) The mixture that ethyl ammonium chloride-acrylamide copolymer is formed with weight ratio 4:2.5:1.
The polycarbonate is by bisphenol A polycarbonate, polyester-type polycarbonate and hexamethylene bisphenol A polycarbonate The mixture formed with weight ratio 2:1.2:1.
Other described auxiliary agents are by antioxidant, UV resistant agent, lubricant, smoke suppressant and Vitrified powder with weight ratio 0.8: 1.0:1:1.5:1.2 the mixture of composition.
The antioxidant is by β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [bis- uncles of 2.4- Butyl phenyl] mixture that is formed with weight ratio 2:1.2:1 of the double lauryls of phosphite ester and thio-2 acid.
The UV resistant agent is by 2- (2 '-hydroxyls -5 '-aminomethyl phenyl) benzotriazole, 2- hydroxyl -4- methoxyl group two The mixture that Benzophenone and hexamethylphosphoramide are formed with weight ratio 1.5:2.2:1.
The lubricant is by oxidized polyethylene wax, glycerin monostearate and stearic amide with weight ratio 2:0.8:1 The mixture of composition.
The mixing that the smoke suppressant is made of ferrocene, antimony oxide and ammonium octamolybdate with weight ratio 1.5:2.5:1 Object.
The mixing that the Vitrified powder is made of attapulgite, zinc borate, silicate glass powder with weight ratio 4:1.5:1 Object.
Organosilicon toughener produced by the present invention had not only improved the impact strength of material, but also had excellent anti-dripping melt performance, After tested, Izod notched impact strength can achieve 63KJ/m2More than, the Izod notched impact with existing polycarbonate Intensity can be improved 1-2.5 times, and toughness is preferable, and it is 2-4s that anti-dripping melt, which tests t1, t2 2-4s, and no dropping ignites absorbent cotton, Reach V0 standard.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way, Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.

Claims (10)

1. a kind of synthetic method of the organosilicon toughener with anti-drop effect, characterized by the following steps:
A, the synthesis of organopolysiloxane core lotion:
A1, organosiloxane monomer is uniformly mixed, using homogenizer under 8000~12000rpm revolving speed high speed shear 5~ 20min obtains mixed liquor；
A2, mixed liquor is added in the aqueous solution dissolved with catalyst and emulsifier, at a temperature of 85~100 DEG C react 6~ 12h obtains organopolysiloxane core lotion；
B, the synthesis of the organosilicon toughener with anti-drop effect:
B1, organopolysiloxane core lotion, PTFE emulsion, dispersing agent and distilled water are added in reaction kettle together, 1000 5~25min of high shear agitation under~2000rpm revolving speed, obtains reaction solution；
B2, reaction solution lye is adjusted into pH value to 9~12, soft monomer is then added, adds initiator and crosslinking agent, in 50 It is stirred to react 5-10h at a temperature of~90 DEG C, obtains the polymer emulsion of organopolysiloxane grafting soft monomer；
B3, hard monomer is then added, adds initiator and crosslinking agent, is stirred to react 5-10h at a temperature of 50~90 DEG C, obtains Polymer emulsion with core-shell structure；
B4, demulsifier demulsification is added, dries pulverizing is after centrifugation to get the organosilicon toughener with anti-drop effect；
In the step A1, organosiloxane monomer is by cyclic siloxane monomer, function groups siloxanyl monomers and vinyl The mixture that siloxanyl monomers are formed with weight ratio 20-60:0.1-1.0:0.5-1.5.
2. a kind of synthetic method of organosilicon toughener with anti-drop effect according to claim 1, it is characterised in that: The structural formula of the function groups siloxanyl monomers are as follows:Wherein, R1、R2、R3And R4Respectively hydrogen, methyl, Any one in ethyl, propyl, vinyl, acrylic, acetenyl, propinyl, methoxyl group, ethyoxyl and phenyl, and R1、R2、 R3And R4In at least one methoxy or ethoxy；
The structural formula of the polymerized monomer of the cyclic siloxane monomer isWherein R5And R6Respectively hydrogen, first Any one in base, ethyl, propyl, vinyl, acrylic, acetenyl, propinyl and phenyl, the cyclic siloxane monomer Polymerization degree n=3-6；
The structural formula of the vinylsiloxane monomer are as follows:Wherein, R7, R8, R9 and R10 are respectively hydrogen, first Base, ethyl, propyl, vinyl, acrylic, styryl, γ-methacryloxypropyl, styryl, 2- are (to ethylene Base phenyl) ethyl, in 3- (to vinylbenzoyl oxygroup) propyl, acetenyl, propinyl, methoxyl group, ethyoxyl and phenyl Any one, and R7, R8, R9 and R10 at least one be vinyl, acrylic, styryl, γ-methacryloxy Propyl, styryl, 2- (to ethenylphenyl) ethyl or 3- (to vinylbenzoyl oxygroup) propyl, at least one is first Oxygroup or ethyoxyl.
3. a kind of synthetic method of organosilicon toughener with anti-drop effect according to claim 1, it is characterised in that: In the step A2, the structural formula of catalyst are as follows:Wherein, R ' be carbon atom number be 1-10 alkyl, alkenyl, Aromatic radical or carbon atom number are the naphthenic base of 3-10, cycloalkenyl；
In the step A2, emulsifier is by cationic surfactant, anionic surfactant and non-ionic surface active The mixture that agent is formed with weight ratio 0.4-0.8:1:0.2-0.6；
In the step B1, the average molecular weight of PTFE emulsion is 1,000,000-1,000 ten thousand, and solid content is in 58%-62%, lotion grain Diameter is at 0.01-0.30 μm, viscosity 10-40*10-3Pa.S；
In the step B2, soft monomer is by ethyl acrylate, Isooctyl acrylate monomer and lauryl methacrylate with weight ratio The mixture of 2-4:1-2:1 composition；
In the step B3, hard monomer is by methyl acrylate, ethyl methacrylate and vinylacetate with weight ratio 1: The mixture of 0.8-1.2:1.5-2.5 composition；
In the step B2 and the step B3, initiator is sub- by isopropyl benzene hydroperoxide, azodiisobutyronitrile and four ethylene The mixture that amine is formed with weight ratio 1:0.5-1.5:1.5-2.5；
In the step B2 and the step B3, crosslinking agent is by diallyl fumarate, dimethacrylate -1,6- hexylene glycol The mixture that ester and Pehanorm trimethyl acrylic ester are formed with weight ratio 1:0.8-1.2:1.4-2.2；
In the step B4, demulsifier is made of sodium chloride, potassium acetate and ammonium sulfate with weight ratio 2-4:1.4-2.2:1 mixed Close object.
4. a kind of synthetic method of organosilicon toughener with anti-drop effect according to claim 1, it is characterised in that: In the step B1, dispersing agent is inorganic dispersing agent and/or organic dispersing agent；
The inorganic dispersing agent is natural silicate, Sulfates, carbonate, Oxalates, hydroxide species and oxidation At least one of species；
The natural silicate is at least one of talcum, bentonite, diatomite and kaolin；The Sulfates are sulfuric acid Calcium and/or barium sulfate；The carbonate is at least one of calcium carbonate, barium carbonate and magnesium carbonate；The Oxalates are Calcium oxalate；The hydroxide species are at least one of aluminium hydroxide, magnesium hydroxide and calcium hydroxide；It is described oxide-based to be Titanium dioxide and/or zinc oxide；
The organic dispersing agent is natural polymer subclass dispersing agent, protein-based macromolecule dispersing agent, cellulose derivative Class dispersing agent, synthesis high score subclass dispersing agent, class containing carboxyl synthesis macromolecule dispersing agent, nitrogenous class synthesize macromolecule dispersing agent and At least one of ester-containing base class synthesis macromolecule dispersing agent；
The natural polymer subclass dispersing agent is at least one of carbohydrate starch, pectin, natural plant gum and seaweed glue；The albumen Matter class macromolecule dispersing agent is gelatin and/or Fish protein；The cellulose derivative class dispersing agent is methylcellulose, methyl At least one of hydroxypropyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose；The synthesis high score subclass dispersing agent is Hydroxyl class partial alcoholysis polyvinyl alcohol；The class containing carboxyl synthesis macromolecule dispersing agent be phenylethylene/maleic anhydride copolymer, Vinyl acetate/copolymer-maleic anhydride and at least one of acrylic copolymer and methacrylic copolymer；It is described Nitrogenous class synthesis macromolecule dispersing agent is polyvinylpyrrolidone；The ester-containing base class synthesis macromolecule dispersing agent is polycyclic oxygen Ethane aliphatic ester and/or sorbitan fatty acid.
5. a kind of organosilicon toughener with anti-drop effect, it is characterised in that: the organosilicon toughener is according to claim The described in any item preparation methods of 1-4 are made.
6. a kind of toughened polycarbonate material using the organosilicon toughener with anti-drop effect described in claim 5, Be characterized in that: the toughened polycarbonate material includes the raw material of following parts by weight:
Wherein, the modifying agent is by macromolecule modified nanometer calcium carbonate, hyperbranched polyester amide and 4- allyl guaiacol The mixture that modified dimethyl polysiloxane is formed with weight ratio 2-6:0.1-1.0:0.5-1.5.
7. a kind of toughened polycarbonate material according to claim 6, it is characterised in that: the macromolecule modified nano-sized carbon The preparation method of sour calcium includes the following steps:
(1) 15-25g nanometer calcium carbonate and 0.3-0.7g calgon dispersing agent, dispersion are added into 300-500mL distilled water 20-28h；60-100g Polymeric quaternary ammonium salts are dissolved in 200-400mL tetrahydrofuran simultaneously, dispersion 20-28h is spare；
(2) the addition 200-400mL tetrahydrofuran into scattered nanometer calcium carbonate system, high speed dispersion 0.3-0.7h, then Slurries are transferred in there-necked flask, polymeric quartenary ammonium salting liquid is slowly added dropwise under stirring, system constantly generates white flock precipitate；
(3) after completion of dropwise addition, system is warming up to 75-85 DEG C, after reacting 20-28h, then slurries is filtered, 55-65 DEG C of vacuum drying 24-48h obtains macromolecule modified nanometer calcium carbonate；
Wherein, in the step (1), Polymeric quaternary ammonium salts are brominated polyphenylether stearyl dimethyl benzyl ammonium chloride, diformazan Base diallyl ammonium chloride-acrylamide copolymer, polydimethyl diallyl ammonium chloride, chlorination -2- hydroxyl -3- (front three ammonia Base) propyl polyethylene oxide cellulose ether and N, N, N- trimethyl-2- (2- methyl-1-oxo-2- acrylic oxygroup) ethyl chloride Change at least one of ammonium-acrylamide copolymer.
8. a kind of toughened polycarbonate material according to claim 6, it is characterised in that: the hyperbranched polyester amide Synthetic method are as follows: under nitrogen protection, successively by 0.8-1.2mol triethanolamine, 0.8-1.2mol 1,2,4- trimellitic anhydride And 0.005-0.015mol Catalyzed by p-Toluenesulfonic Acid agent is added three neck round bottom flask and is placed in heating oil bath, stirring, gradually It is warming up to 210-230 DEG C, after raw material is uniformly mixed bleach, continues to be stirred to react 2-4h at a temperature of 210-230 DEG C, then It is cooled to room temperature, obtains yellow transparent solid body i.e. hyperbranched polyester amide.
9. a kind of toughened polycarbonate material according to claim 6, it is characterised in that: the 4- allyl guaiacol The synthetic method of modified dimethyl polysiloxane are as follows: in the there-necked flask equipped with thermometer, blender, sequentially add at room temperature 230-270g dimethyl silicone polymer, 23-27g 4- allyl guaiacol form the suspension of White-opalescent after stirring； Add the octanol solution for the chloroplatinic acid that 0.5-1.0mL platinum mass fraction is 1.5-2.5%；Continue to stir, heat up under logical nitrogen To 90-100 DEG C, 2-4h is reacted.
10. a kind of toughened polycarbonate material according to claim 6, it is characterised in that: the melting of the polycarbonate Index is that bisphenol A polycarbonate, polyester-type polycarbonate and hexamethylene bisphenol A-type of the melt index in 10-50g/10min are poly- At least one of carbonic ester；The glass fibre is that fibre diameter is chopped in 5-15 μm, alkali-free of the fibre length in 1-10mm Glass fibre；Other described auxiliary agents are at least one of antioxidant, UV resistant agent, lubricant, smoke suppressant and Vitrified powder.
CN201811056556.7A 2018-09-11 2018-09-11 A kind of organosilicon toughener and its synthetic method with anti-drop effect Pending CN109438633A (en)

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CN112876829A (en) * 2021-01-15 2021-06-01 万华化学(四川)有限公司 Electroplating PC/ABS alloy material and preparation method thereof
CN113105622A (en) * 2021-04-19 2021-07-13 中山大学 Modified polyphenyl ether, thermosetting polyphenyl ether composition and application thereof

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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
CN106947035A (en) * 2017-04-10 2017-07-14 广东优科艾迪高分子材料有限公司 A kind of anti-dripping melt type organic sesqui siloxane fire retardant and preparation method and application

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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
CN106947035A (en) * 2017-04-10 2017-07-14 广东优科艾迪高分子材料有限公司 A kind of anti-dripping melt type organic sesqui siloxane fire retardant and preparation method and application

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109928666A (en) * 2019-03-06 2019-06-25 陕西腾强新材料有限公司 A kind of preparation method of reinforcing type polycarboxylic acid high-performance water reducing agent
CN112876829A (en) * 2021-01-15 2021-06-01 万华化学(四川)有限公司 Electroplating PC/ABS alloy material and preparation method thereof
CN113105622A (en) * 2021-04-19 2021-07-13 中山大学 Modified polyphenyl ether, thermosetting polyphenyl ether composition and application thereof
CN113105622B (en) * 2021-04-19 2022-05-13 中山大学 Modified polyphenyl ether, thermosetting polyphenyl ether composition and application thereof

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