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CN109320674A - A kind of anti-dripping agent and preparation method thereof containing PTFE and organosilicon - Google Patents

A kind of anti-dripping agent and preparation method thereof containing PTFE and organosilicon Download PDF

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Publication number
CN109320674A
CN109320674A CN201811055660.4A CN201811055660A CN109320674A CN 109320674 A CN109320674 A CN 109320674A CN 201811055660 A CN201811055660 A CN 201811055660A CN 109320674 A CN109320674 A CN 109320674A
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dispersing agent
dripping
phenyl
monomer
weight ratio
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Inventor
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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Priority to CN201811055660.4A priority Critical patent/CN109320674A/en
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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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • 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
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to pluronic polymer technical fields, and in particular to a kind of anti-dripping agent and preparation method thereof containing PTFE and organosilicon, the preparation method include: the synthesis of organopolysiloxane core lotion；The preparation of anti-dripping agent containing PTFE and organosilicon.Preparation method of the invention is polymerize by the way that cladding monomer is added in organopolysiloxane core lotion and PTFE emulsion, and anti-dripping agent obtained had not only had preferable flame retardant property, but also had excellent anti-dripping melt performance, simple process and low cost.

Description

A kind of anti-dripping agent and preparation method thereof containing PTFE and organosilicon
Technical field
The present invention relates to pluronic polymer technical fields, and in particular to a kind of anti-dripping agent containing PTFE and organosilicon and its Preparation method.
Background technique
Due to the unique structure of organosilicon, have both the performance of inorganic material and organic material, has surface tension low, viscous The fundamental propertys such as warm coefficient is small, compressibility is high, gas permeability is high, and there is high-low temperature resistant, electric insulation, resistance to oxidation to stablize The excellent characteristics such as property, weatherability, fire retardant, hydrophobic, corrosion-resistant, non-toxic and tasteless and physiological inertia, be widely used in aerospace, The industries such as electric, building, transport, chemical industry, weaving, food, light industry, medical treatment.
In addition, organosilicon is assigning except the excellent flame retardant property of substrate, moreover it is possible to improve processing performance, the mechanicalness of substrate Energy, heat resistance etc., ecology is friendly, and the recycling effect of fire proofing is preferable, is able to satisfy people and strictly wants to fire retardant It asks, but existing organic silicon fibre retardant does not have anti-dripping melt performance.
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 containing PTFE and to have The preparation method of the anti-dripping agent of machine silicon, the preparation method is by being added cladding for organopolysiloxane core lotion and PTFE emulsion Monomer is polymerize, and anti-dripping agent obtained had not only had preferable flame retardant property, 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 anti-dripping agent containing PTFE and organosilicon, the anti-dripping agent can mention The flame-retardant anti-dropping performance of high material, it is more efficient to reach flame-retardant standard, and the dosage of core fire retardant can be reduced.
The purpose of the invention is achieved by the following technical solution: a kind of preparation side of the anti-dripping agent containing PTFE and organosilicon Method includes the following steps:
A, the synthesis of organopolysiloxane core lotion:
Organosiloxane monomer is uniformly mixed, is added in the aqueous solution dissolved with catalyst and emulsifier, 30~ 5~10h is reacted at a temperature of 80 DEG C, obtains organopolysiloxane core lotion；Wherein, the gross mass of organosiloxane monomer is water quality The 40%~60% of amount, the dosage of catalyst are the 1%~5% of organosiloxane monomer mass, and the dosage of emulsifier is organic The 1%~20% of siloxanyl monomers quality；
B, the preparation of the anti-dripping agent containing PTFE and organosilicon:
B1, organopolysiloxane core lotion, PTFE emulsion, dispersing agent and distilled water are added in reaction kettle together, 5~25min of high shear agitation under 1000~2000rpm revolving speed；Wherein, the dosage of PTFE emulsion is organopolysiloxane core cream The 10%-50% of liquid quality, the dosage of dispersing agent are the 1%-5% of organopolysiloxane core quality of the emulsion；
B2, cladding monomer is added, adds emulsifier and initiator, reacts 6-10h at a temperature of 50~80 DEG C；Wherein, The dosage for coating monomer is the 30%-70% of organopolysiloxane core quality of the emulsion, and the dosage of emulsifier is organopolysiloxane The 1%~20% of core quality of the emulsion, the dosage of initiator are the 0.1%-0.8% of organopolysiloxane core quality of the emulsion；
B3, reaction product washed, is centrifuged, drying drying, the anti-dripping agent containing PTFE and organosilicon is made.
Preferably, in the step A, organosiloxane monomer be by phenyl siloxane monomer, cyclic siloxane monomer and The mixture that vinylsiloxane monomer is formed with weight ratio 4-8:2-6:0.1-1.0.
The present invention is by using phenyl siloxane monomer, cyclic siloxane monomer and vinylsiloxane monomer as organic Siloxanyl monomers are used in compounding, and controlling its weight ratio is 4-8:2-6:0.1-1.0, and anti-flammability, the waterproof of resin can be improved Property, grease proofness, anti-fog properties, soil resistance, soil release performance, moisture-proof, lubricity, abrasion performance, antistick characteristic, chemical resistance and resistance to It is scratch resistance.
The structural formula of the phenyl siloxane monomer are as follows:Wherein, R1、R2、R3And R4Respectively hydrogen, first Any one in base, ethyl, propyl, vinyl, acrylic, acetenyl, propinyl, methoxyl group, ethyoxyl and phenyl, and R1、R2、R3And R4In at least one be phenyl, at least one methoxy or ethoxy.
Preferably, the phenyl siloxane monomer is phenyltrimethoxysila,e, dimethoxydiphenylsilane, triphenyl Methoxy silane, aminomethyl phenyl dimethoxysilane, ethylphenyl dimethoxysilane, propyl phenyidimethoxysilane, second Alkenyl phenyidimethoxysilane, acrylic phenyidimethoxysilane, ethynyl phenyl dimethoxysilane, propinyl phenyl Dimethoxysilane, methyldiphenyl methoxylsilane, ethyl diphenyl methoxy silane, propyl diphenylmethyl oxysilane, Vinyl diphenyl methoxy silane, acrylic diphenylmethyl oxysilane, acetenyl diphenylmethyl oxysilane, propinyl two Phenylmethoxysilane, dimethyl benzene methoxylsilane, diethylbenzene methoxylsilane, dipropyl Phenylmethoxy silicon Alkane, divinyl phenylmethoxysilane, diallyl phenylmethoxysilane, diacetylene phenylmethoxysilane, dipropyl Alkynyl phenyl methoxy silane, Methylethyl phenylmethoxysilane, methyl-propyl phenylmethoxysilane, ethyl propyl phenyl Methoxy silane, methyl vinyl phenyl methoxy silane, ethyl propylene base phenylmethoxysilane, methylacetylenyl phenyl first Oxysilane, ethyl propinyl phenylmethoxysilane, phenyl triethoxysilane, diphenyl diethoxy silane, triphenyl Ethoxysilane, aminomethyl phenyl diethoxy silane, Ethylphenyldiethoxysandne, propyl phenyl diethoxy silane, second Alkenyl phenyl diethoxy silane, acrylic phenyl diethoxy silane, ethynyl phenyl diethoxy silane, propinyl phenyl Diethoxy silane, methyldiphenylethoxysilane, ethyl diphenyl Ethoxysilane, propyl diphenyl Ethoxysilane, Vinyl diphenyl Ethoxysilane, acrylic diphenyl Ethoxysilane, acetenyl diphenyl Ethoxysilane, propinyl two Phenyl ethoxy silane, 3,5-dimethylphenyl Ethoxysilane, diethyl phenyl Ethoxysilane, dipropyl phenyl ethoxy silicon Alkane, divinyl phenyl ethoxy 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 Ethoxysilane, methyl vinyl phenyl Ethoxysilane, ethyl propylene base phenyl ethoxy silane, methylacetylenyl phenyl second At least one of oxysilane and ethyl propinyl phenyl ethoxy silane.
The flame retardant property of resin can be improved by using above-mentioned phenyl siloxane monomer in the present invention, can also improve tree Oxidation stability, heat resistance, flame resistance, ultraviolet-resistent property and the chemical resistance of rouge.More preferably, the phenyl siloxane monomer The mixture being made of aminomethyl phenyl dimethoxysilane and aminomethyl phenyl diethoxy silane with weight ratio 2-4:1.
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 A, the structural formula of catalyst are as follows:Wherein, it is 1- that R ', which is carbon atom number, 10 alkyl, alkenyl, aromatic radical or carbon atom number 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 A and the step B2, emulsifier be by cationic surfactant, anionic surfactant and The mixture that nonionic surfactant 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, cladding monomer is by α-methylstyrene, methacrylonitrile, 2-EHA, first Base isobornyl acrylate, fumaric acid and N- methylmaleimido are with weight ratio 1.5-2.5:1-2:0.5-1.5:1:0.4- The mixture of 0.8:0.2-0.6 composition.The present invention coats type, compounding and the proportion of monomer, cladding effect by strict control Fruit is good, and with organopolysiloxane core emulsion polymerization, the anti-flammability, heat resistance and shock resistance of resin can be improved.
In the step B2, initiator is by isopropyl benzene hydroperoxide, azodiisobutyronitrile and four aziridines with weight Than the mixture of 1:0.5-1.5:1.5-2.5 composition.The present invention passes through type, compounding and the proportion of strict control initiator, It is good to cause effect, can trigger free radical polymerization and copolymerization, rate of polymerization can be improved.
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 anti-dripping agent containing PTFE and organosilicon, the anti-dripping agent are made according to preparation method described above.
It is a kind of using anti-dripping melt makrolon material made from the anti-dripping agent described above containing PTFE and organosilicon, institute State the raw material that anti-dripping melt makrolon material includes following parts by weight:
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 flame retardant property and anti-dripping melt performance of material can be improved in fire retardant and anti-dripping agent, and by the way that modifying agent is added, material can be improved Processing heat stability, mechanical mechanics property and the appearance of material.
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: preparation method of the invention passes through organopolysiloxane core lotion and PTFE is newborn Liquid is added cladding monomer and is polymerize, and anti-dripping agent obtained had not only had preferable flame retardant property, but also had excellent anti-dripping melt Performance, simple process and low cost.
Anti-dripping agent of the invention in PTFE by being added organic element silicon, so that anti-dripping agent is in addition to PTFE's Outside anti-dripping melt performance, organosilicon high-low temperature resistant, electric insulation, resistance to oxidation stability, weatherability, fire retardant, hydrophobic, resistance to has also been had both Burn into is non-toxic and tasteless and the excellent characteristics such as physiological inertia.
Anti-dripping agent of the invention has both the excellent performance of both organosilicon and PTFE, can significantly improve the fire-retardant anti-of material Dropping performance has outstanding high temperature resistance, chemical resistance and solvent resistance, while having good dispersibility, with base Body resin compatible is good；And the highly effective flame-retardant anti-dripping agent can more effectively assist user to reach UL94V-0 standard, while can subtract The dosage of few core fire retardant.
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 preparation method of the anti-dripping agent containing PTFE and organosilicon, includes the following steps:
A, the synthesis of organopolysiloxane core lotion:
Organosiloxane monomer is uniformly mixed, is added in the aqueous solution dissolved with catalyst and emulsifier, at 30 DEG C At a temperature of react 10h, obtain organopolysiloxane core lotion；Wherein, the gross mass of organosiloxane monomer is water quality 40%, the dosage of catalyst is the 1% of organosiloxane monomer mass, and the dosage of emulsifier is organosiloxane monomer mass 1%；
B, the preparation of the anti-dripping agent containing PTFE and organosilicon:
B1, organopolysiloxane core lotion, PTFE emulsion, dispersing agent and distilled water are added in reaction kettle together, High shear agitation 25min under 1000rpm revolving speed；Wherein, the dosage of PTFE emulsion is organopolysiloxane core quality of the emulsion 10%, the dosage of dispersing agent is the 1% of organopolysiloxane core quality of the emulsion；
B2, cladding monomer is added, adds emulsifier and initiator, reacts 10h at 50 °C；Wherein, cladding is single The dosage of body is the 30% of organopolysiloxane core quality of the emulsion, and the dosage of emulsifier is organopolysiloxane core quality of the emulsion 1%, the dosage of initiator is the 0.1% of organopolysiloxane core quality of the emulsion；
B3, reaction product washed, is centrifuged, drying drying, the anti-dripping agent containing PTFE and organosilicon is made.
In the step A, organosiloxane monomer is by phenyl siloxane monomer, cyclic siloxane monomer and vinyl silicon The mixture that oxygen alkane monomer is formed with weight ratio 4:2:0.1；
The phenyl siloxane monomer is phenyltrimethoxysila,e, dimethoxydiphenylsilane, triphenylmethoxy Silane, aminomethyl phenyl dimethoxysilane, ethylphenyl dimethoxysilane, propyl phenyidimethoxysilane, vinyl benzene Base dimethoxysilane, acrylic phenyidimethoxysilane, ethynyl phenyl dimethoxysilane, propinyl phenyl dimethoxy Base silane, methyldiphenyl methoxylsilane, ethyl diphenyl methoxy silane or propyl diphenylmethyl oxysilane.
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 A, catalyst is methane sulfonic acid, trifluoromethane sulfonic acid, methylol sulfonic acid or ethylsulfonic acid；
In the step A and the step B2, emulsifier be by cationic surfactant, anionic surfactant and The mixture that nonionic surfactant 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, cladding monomer is by α-methylstyrene, methacrylonitrile, 2-EHA, first Base isobornyl acrylate, fumaric acid and N- methylmaleimido are formed mixed with weight ratio 1.5:1:0.5:1:0.4:0.2 Close object；
In the step B2, initiator is by isopropyl benzene hydroperoxide, azodiisobutyronitrile and four aziridines with weight Than the mixture of 1:0.5:1.5 composition.
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 anti-dripping agent containing PTFE and organosilicon, the anti-dripping agent are made according to preparation method described above.
It is a kind of using anti-dripping melt makrolon material made from the anti-dripping agent described above containing PTFE and organosilicon, institute State the raw material that anti-dripping melt makrolon material includes following parts by weight:
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, 0.8mol1,2,4- 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 preparation method of the anti-dripping agent containing PTFE and organosilicon, includes the following steps:
A, the synthesis of organopolysiloxane core lotion:
Organosiloxane monomer is uniformly mixed, is added in the aqueous solution dissolved with catalyst and emulsifier, at 40 DEG C At a temperature of react 9h, obtain organopolysiloxane core lotion；Wherein, the gross mass of organosiloxane monomer is water quality 45%, the dosage of catalyst is the 2% of organosiloxane monomer mass, and the dosage of emulsifier is organosiloxane monomer mass 5%；
B, the preparation of the anti-dripping agent containing PTFE and organosilicon:
B1, organopolysiloxane core lotion, PTFE emulsion, dispersing agent and distilled water are added in reaction kettle together, High shear agitation 10min under 1200rpm revolving speed；Wherein, the dosage of PTFE emulsion is organopolysiloxane core quality of the emulsion 20%, the dosage of dispersing agent is the 2% of organopolysiloxane core quality of the emulsion；
B2, cladding monomer is added, adds emulsifier and initiator, reacts 9h at a temperature of 60 DEG C；Wherein, monomer is coated Dosage be the 40% of organopolysiloxane core quality of the emulsion, the dosage of emulsifier is organopolysiloxane core quality of the emulsion 5%, the dosage of initiator is the 0.3% of organopolysiloxane core quality of the emulsion；
B3, reaction product washed, is centrifuged, drying drying, the anti-dripping agent containing PTFE and organosilicon is made.
The phenyl siloxane monomer is vinyl diphenyl methoxy silane, acrylic diphenylmethyl oxysilane, second Alkynyl diphenylmethyl oxysilane, propinyl diphenylmethyl oxysilane, dimethyl benzene methoxylsilane, diethyl phenyl first Oxysilane, dipropyl phenylmethoxysilane, divinyl phenylmethoxysilane, diallyl phenylmethoxysilane, Diacetylene phenylmethoxysilane, dipropyl alkynyl phenyl methoxy silane, Methylethyl phenylmethoxysilane, methyl-propyl Phenylmethoxysilane, ethyl propyl phenylmethoxysilane or methyl vinyl phenyl methoxy silane.
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 A, catalyst is trifluoroethyl sulfonic acid, isethionic acid, propyl sulfonic acid, hydroxypropyl sulfonic acid or 1- fourth Base sulfonic acid；
In the step A and the step B2, emulsifier be by cationic surfactant, anionic surfactant and The mixture that nonionic surfactant 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, cladding monomer is by α-methylstyrene, methacrylonitrile, 2-EHA, first What base isobornyl acrylate, fumaric acid and N- methylmaleimido were formed with weight ratio 1.8:1.2:0.8:1:0.5:0.3 Mixture；
In the step B2, initiator is by isopropyl benzene hydroperoxide, azodiisobutyronitrile and four aziridines with weight Than the mixture of 1:0.8:1.8 composition.
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 anti-dripping agent containing PTFE and organosilicon, the anti-dripping agent are made according to preparation method described above.
It is a kind of using anti-dripping melt makrolon material made from the anti-dripping agent described above containing PTFE and organosilicon, institute State the raw material that anti-dripping melt makrolon material includes following parts by weight:
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 preparation method of the anti-dripping agent containing PTFE and organosilicon, includes the following steps:
A, the synthesis of organopolysiloxane core lotion:
Organosiloxane monomer is uniformly mixed, is added in the aqueous solution dissolved with catalyst and emulsifier, at 50 DEG C At a temperature of react 8h, obtain organopolysiloxane core lotion；Wherein, the gross mass of organosiloxane monomer is water quality 50%, the dosage of catalyst is the 3% of organosiloxane monomer mass, and the dosage of emulsifier is organosiloxane monomer mass 10%；
B, the preparation of the anti-dripping agent containing PTFE and organosilicon:
B1, organopolysiloxane core lotion, PTFE emulsion, dispersing agent and distilled water are added in reaction kettle together, High shear agitation 15min under 1500rpm revolving speed；Wherein, the dosage of PTFE emulsion is organopolysiloxane core quality of the emulsion 30%, the dosage of dispersing agent is the 3% of organopolysiloxane core quality of the emulsion；
B2, cladding monomer is added, adds emulsifier and initiator, reacts 8h at a temperature of 65 DEG C；Wherein, monomer is coated Dosage be the 50% of organopolysiloxane core quality of the emulsion, the dosage of emulsifier is organopolysiloxane core quality of the emulsion 10%, the dosage of initiator is the 0.5% of organopolysiloxane core quality of the emulsion；
B3, reaction product washed, is centrifuged, drying drying, the anti-dripping agent containing PTFE and organosilicon is made.
In the step A, organosiloxane monomer is by phenyl siloxane monomer, cyclic siloxane monomer and vinyl silicon The mixture that oxygen alkane monomer is formed with weight ratio 6:3:0.5；
The phenyl siloxane monomer is ethyl propylene base phenylmethoxysilane, methylacetylenyl Phenylmethoxy silicon Alkane, ethyl propinyl phenylmethoxysilane, phenyl triethoxysilane, diphenyl diethoxy silane, triphen base oxethyl Silane, aminomethyl phenyl diethoxy silane, Ethylphenyldiethoxysandne, propyl phenyl diethoxy silane, vinyl benzene Base diethoxy silane or acrylic phenyl diethoxy silane.
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 A, catalyst is vinyl sulfonic acid, propene sulfonic acid, methacrylic sulfonic acid, ethyl propylene sulfonic acid or benzene Sulfonic acid；
In the step A and the step B2, emulsifier be by cationic surfactant, anionic surfactant and The mixture that nonionic surfactant 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, cladding monomer is by α-methylstyrene, methacrylonitrile, 2-EHA, first The mixing that base isobornyl acrylate, fumaric acid and N- methylmaleimido are formed with weight ratio 2:1.5:1:1:0.6:0.4 Object；
In the step B2, initiator is by isopropyl benzene hydroperoxide, azodiisobutyronitrile and four aziridines with weight Than the mixture of 1:1:2 composition.
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 anti-dripping agent containing PTFE and organosilicon, the anti-dripping agent are made according to preparation method described above.
It is a kind of using anti-dripping melt makrolon material made from the anti-dripping agent described above containing PTFE and organosilicon, institute State the raw material that anti-dripping melt makrolon material includes following parts by weight:
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 preparation method of the anti-dripping agent containing PTFE and organosilicon, includes the following steps:
A, the synthesis of organopolysiloxane core lotion:
Organosiloxane monomer is uniformly mixed, is added in the aqueous solution dissolved with catalyst and emulsifier, at 70 DEG C At a temperature of react 6h, obtain organopolysiloxane core lotion；Wherein, the gross mass of organosiloxane monomer is water quality 55%, the dosage of catalyst is the 4% of organosiloxane monomer mass, and the dosage of emulsifier is organosiloxane monomer mass 15%；
B, the preparation of the anti-dripping agent containing PTFE and organosilicon:
B1, organopolysiloxane core lotion, PTFE emulsion, dispersing agent and distilled water are added in reaction kettle together, High shear agitation 20min under 1800rpm revolving speed；Wherein, the dosage of PTFE emulsion is organopolysiloxane core quality of the emulsion 40%, the dosage of dispersing agent is the 4% of organopolysiloxane core quality of the emulsion；
B2, cladding monomer is added, adds emulsifier and initiator, reacts 7h at a temperature of 70 DEG C；Wherein, monomer is coated Dosage be the 60% of organopolysiloxane core quality of the emulsion, the dosage of emulsifier is organopolysiloxane core quality of the emulsion 15%, the dosage of initiator is the 0.6% of organopolysiloxane core quality of the emulsion；
B3, reaction product washed, is centrifuged, drying drying, the anti-dripping agent containing PTFE and organosilicon is made.
In the step A, organosiloxane monomer is by phenyl siloxane monomer, cyclic siloxane monomer and vinyl silicon The mixture that oxygen alkane monomer is formed with weight ratio 7:5:0.8；
The phenyl siloxane monomer is ethynyl phenyl diethoxy silane, propinyl diethylamino phenyl oxysilane, first Base diphenyl Ethoxysilane, ethyl diphenyl Ethoxysilane, propyl diphenyl Ethoxysilane, vinyl diphenyl ethoxy Base silane, acrylic diphenyl Ethoxysilane, acetenyl diphenyl Ethoxysilane, propinyl diphenyl Ethoxysilane, 3,5-dimethylphenyl Ethoxysilane, diethyl phenyl Ethoxysilane or dipropyl 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 A, catalyst is toluenesulfonic acid, ethyl phenenyl azochlorosulfonate acid or acid dimethyl；
In the step A and the step B2, emulsifier be by cationic surfactant, anionic surfactant and The mixture that nonionic surfactant 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 0.20 μ M, viscosity 30*10-3Pa.S；
In the step B2, cladding monomer is by α-methylstyrene, methacrylonitrile, 2-EHA, first What base isobornyl acrylate, fumaric acid and N- methylmaleimido were formed with weight ratio 2.2:1.8:1.2:1:0.7:0.5 Mixture；
In the step B2, initiator is by isopropyl benzene hydroperoxide, azodiisobutyronitrile and four aziridines with weight Than the mixture of 1:1.2:2.2 composition.
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 anti-dripping agent containing PTFE and organosilicon, the anti-dripping agent are made according to preparation method described above.
It is a kind of using anti-dripping melt makrolon material made from the anti-dripping agent described above containing PTFE and organosilicon, institute State the raw material that anti-dripping melt makrolon material includes following parts by weight:
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 preparation method of the anti-dripping agent containing PTFE and organosilicon, includes the following steps:
A, the synthesis of organopolysiloxane core lotion:
Organosiloxane monomer is uniformly mixed, is added in the aqueous solution dissolved with catalyst and emulsifier, at 80 DEG C At a temperature of react 5h, obtain organopolysiloxane core lotion；Wherein, the gross mass of organosiloxane monomer is water quality 60%, the dosage of catalyst is the 5% of organosiloxane monomer mass, and the dosage of emulsifier is organosiloxane monomer mass 20%；
B, the preparation of the anti-dripping agent containing PTFE and organosilicon:
B1, organopolysiloxane core lotion, PTFE emulsion, dispersing agent and distilled water are added in reaction kettle together, High shear agitation 25min under 2000rpm revolving speed；Wherein, the dosage of PTFE emulsion is organopolysiloxane core quality of the emulsion 50%, the dosage of dispersing agent is the 5% of organopolysiloxane core quality of the emulsion；
B2, cladding monomer is added, adds emulsifier and initiator, reacts 6h at a temperature of 80 DEG C；Wherein, monomer is coated Dosage be the 70% of organopolysiloxane core quality of the emulsion, the dosage of emulsifier is organopolysiloxane core quality of the emulsion 20%, the dosage of initiator is the 0.8% of organopolysiloxane core quality of the emulsion；
B3, reaction product washed, is centrifuged, drying drying, the anti-dripping agent containing PTFE and organosilicon is made.
In the step A, organosiloxane monomer is by phenyl siloxane monomer, cyclic siloxane monomer and vinyl silicon The mixture that oxygen alkane monomer is formed with weight ratio 8:6:1.0；
The phenyl siloxane monomer is divinyl phenyl ethoxy silane, diallyl phenyl ethoxy silane, two Ethynyl phenyl Ethoxysilane, dipropyl alkynyl phenyl Ethoxysilane, Methylethyl phenyl ethoxy silane, methyl-propyl benzene Base oxethyl silane, ethyl propyl phenyl ethoxy silane, methyl vinyl phenyl Ethoxysilane, ethyl propylene base phenyl second Oxysilane, methylacetylenyl phenyl ethoxy silane or ethyl propinyl phenyl ethoxy silane.
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 A, catalyst is diethylbenzene sulfonic acid or dodecyl benzene sulfonic acid；
In the step A and the step B2, emulsifier be by cationic surfactant, anionic surfactant and The mixture that nonionic surfactant 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 62%, emulsion particle diameter exists solid content 00.30 μm, viscosity 40*10-3Pa.S；
In the step B2, cladding monomer is by α-methylstyrene, methacrylonitrile, 2-EHA, first Base isobornyl acrylate, fumaric acid and N- methylmaleimido are formed mixed with weight ratio 2.5:2:1.5:1:0.8:0.6 Close object；
In the step B2, initiator is by isopropyl benzene hydroperoxide, azodiisobutyronitrile and four aziridines with weight Than the mixture of 1:1.5:2.5 composition.
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 anti-dripping agent containing PTFE and organosilicon, the anti-dripping agent are made according to preparation method described above.
It is a kind of using anti-dripping melt makrolon material made from the anti-dripping agent described above containing PTFE and organosilicon, institute State the raw material that anti-dripping melt makrolon material includes following parts by weight:
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 phenyl siloxane monomer is by aminomethyl phenyl dimethoxysilane and aminomethyl phenyl diethoxy silane with weight Measure the mixture formed than 2:1.
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 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 dispersing agent is by diatomite, calcium carbonate, methylhydroxypropylcellulose and sorbitan fatty acid with weight Measure the mixture formed than 1:0.5:1:0.8.
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 phenyl siloxane monomer is by aminomethyl phenyl dimethoxysilane and aminomethyl phenyl diethoxy silane with weight Measure the mixture formed than 2.5:1.
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 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 dispersing agent is by diatomite, calcium carbonate, methylhydroxypropylcellulose and sorbitan fatty acid with weight Measure the mixture formed than 1.2:0.8:1:0.9.
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 phenyl siloxane monomer is by aminomethyl phenyl dimethoxysilane and aminomethyl phenyl diethoxy silane with weight Measure the mixture formed than 3:1.
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 dispersing agent is by diatomite, calcium carbonate, methylhydroxypropylcellulose and sorbitan fatty acid with weight Measure the mixture formed than 1.5:1:1:1.
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 3:2:1.
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 phenyl siloxane monomer is by aminomethyl phenyl dimethoxysilane and aminomethyl phenyl diethoxy silane with weight Measure the mixture formed than 3.5:1.
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 dispersing agent is by diatomite, calcium carbonate, methylhydroxypropylcellulose and sorbitan fatty acid with weight Measure the mixture formed than 1.8:1.2:1:1.1.
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 phenyl siloxane monomer is by aminomethyl phenyl dimethoxysilane and aminomethyl phenyl diethoxy silane with weight Measure the mixture formed than 4:1.
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 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 dispersing agent is by diatomite, calcium carbonate, methylhydroxypropylcellulose and sorbitan fatty acid with weight Measure the mixture formed than 2:1.5:1:1.2.
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.
After tested, anti-dripping agent made from embodiment 1-10 is applied in polycarbonate, both has preferable flame retardant property, There is excellent anti-dripping melt performance again, flame retardant property test can achieve 1.6mmUL94V-0 grades, and good flame retardation effect, anti-dripping melt is surveyed Examination t1 is 2-3s, t2 2-4s, and no dropping ignites absorbent cotton, reaches 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 preparation method of the anti-dripping agent containing PTFE and organosilicon, characterized by the following steps:
A, the synthesis of organopolysiloxane core lotion:
Organosiloxane monomer is uniformly mixed, is added in the aqueous solution dissolved with catalyst and emulsifier, at 30~80 DEG C At a temperature of react 5~10h, obtain organopolysiloxane core lotion；
B, the preparation of the anti-dripping agent containing PTFE and organosilicon:
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；
B2, cladding monomer is added, adds emulsifier and initiator, reacts 6-10h at a temperature of 50~80 DEG C；
B3, reaction product washed, is centrifuged, drying drying, the anti-dripping agent containing PTFE and organosilicon is made.
2. a kind of preparation method of anti-dripping agent containing PTFE and organosilicon according to claim 1, it is characterised in that: institute State in step A, organosiloxane monomer be by phenyl siloxane monomer, cyclic siloxane monomer and vinylsiloxane monomer with The mixture of weight ratio 4-8:2-6:0.1-1.0 composition；
The structural formula of the phenyl siloxane monomer 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 be phenyl, 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 preparation method of anti-dripping agent containing PTFE and organosilicon according to claim 1, it is characterised in that: institute It states in step A, the structural formula of catalyst are as follows:Wherein, R ' be carbon atom number be 1-10 alkyl, alkenyl, virtue Perfume base or carbon atom number are the naphthenic base of 3-10, cycloalkenyl；
In the step A and the step B2, emulsifier be by cationic surfactant, anionic surfactant and it is non-from The mixture that sub- surfactant 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, cladding monomer is by α-methylstyrene, methacrylonitrile, 2-EHA, methyl-prop Olefin(e) acid isobornyl thiocyanoacetate, fumaric acid and N- methylmaleimido are with weight ratio 1.5-2.5:1-2:0.5-1.5:1:0.4-0.8: The mixture of 0.2-0.6 composition；
In the step B2, initiator is by isopropyl benzene hydroperoxide, azodiisobutyronitrile and four aziridines with weight ratio 1: The mixture of 0.5-1.5:1.5-2.5 composition.
4. a kind of preparation method of anti-dripping agent containing PTFE and organosilicon according to claim 1, it is characterised in that: institute It states in 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 anti-dripping agent containing PTFE and organosilicon, it is characterised in that: the anti-dripping agent is -4 any according to claim 1 Preparation method described in is made.
6. anti-dripping melt polycarbonate material made from a kind of anti-dripping agent containing PTFE and organosilicon using described in claim 5 Material, it is characterised in that: the anti-dripping melt makrolon 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 anti-dripping melt makrolon material according to claim 6, it is characterised in that: the macromolecule modified nanometer The preparation method of calcium carbonate 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 anti-dripping melt makrolon 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 acid Acid anhydride and 0.005-0.015mol Catalyzed by p-Toluenesulfonic Acid agent are added three neck round bottom flask and are placed in heating oil bath, stirring, by Step 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, so After be cooled to room temperature, obtain yellow transparent solid body i.e. hyperbranched polyester amide.
9. a kind of anti-dripping melt makrolon material according to claim 6, it is characterised in that: the 4- allyl guaiaci lignum The synthetic method of phenol 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 anti-dripping melt makrolon material according to claim 6, it is characterised in that: the polycarbonate melts Melting index is bisphenol A polycarbonate, polyester-type polycarbonate and hexamethylene bisphenol A-type of the melt index in 10-50g/10min At least one of polycarbonate；The glass fibre be fibre diameter 5-15 μm, alkali-free of the fibre length in 1-10mm it is short Cut glass fibre；Other described auxiliary agents are at least one of antioxidant, UV resistant agent, lubricant, smoke suppressant and Vitrified powder.
CN201811055660.4A 2018-09-11 2018-09-11 A kind of anti-dripping agent and preparation method thereof containing PTFE and organosilicon Pending CN109320674A (en)

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CN112625383A (en) * 2020-12-12 2021-04-09 安徽新辰光学新材料有限公司 Anti-yellowing LED lamp film and preparation method thereof
CN113372679A (en) * 2021-07-02 2021-09-10 衢州市中通化工有限公司 Preparation method of environment-friendly silane flame-retardant anti-dripping agent
CN114149541A (en) * 2021-11-18 2022-03-08 万华化学（宁波）有限公司 Acrylic ester and acrylamide grafted polytetrafluoroethylene and high-gloss mirror-surface wear-resistant flame-retardant polycarbonate material
CN116003800A (en) * 2023-01-11 2023-04-25 江苏涌新材料科技有限公司 A kind of organosilicon-based polycarbonate flame retardant and its application
CN116173621A (en) * 2023-02-16 2023-05-30 江苏奥凯环境技术有限公司 Aramid fiber filter material for ultralow emission and production process thereof
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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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CN112625383A (en) * 2020-12-12 2021-04-09 安徽新辰光学新材料有限公司 Anti-yellowing LED lamp film and preparation method thereof
CN113372679A (en) * 2021-07-02 2021-09-10 衢州市中通化工有限公司 Preparation method of environment-friendly silane flame-retardant anti-dripping agent
CN114149541A (en) * 2021-11-18 2022-03-08 万华化学（宁波）有限公司 Acrylic ester and acrylamide grafted polytetrafluoroethylene and high-gloss mirror-surface wear-resistant flame-retardant polycarbonate material
CN114149541B (en) * 2021-11-18 2023-09-19 万华化学（宁波）有限公司 Acrylic ester and acrylamide grafted polytetrafluoroethylene and high-optical-surface wear-resistant flame-retardant polycarbonate material
CN116003800A (en) * 2023-01-11 2023-04-25 江苏涌新材料科技有限公司 A kind of organosilicon-based polycarbonate flame retardant and its application
CN116173621A (en) * 2023-02-16 2023-05-30 江苏奥凯环境技术有限公司 Aramid fiber filter material for ultralow emission and production process thereof
CN116173621B (en) * 2023-02-16 2023-09-29 江苏奥凯环境技术有限公司 Aramid fiber filter material for ultralow emission and production process thereof
CN117209673A (en) * 2023-10-11 2023-12-12 铨盛聚碳科技股份有限公司 Flame-retardant low-temperature toughening synergistic anti-dripping agent and preparation method thereof
CN117209673B (en) * 2023-10-11 2024-04-26 铨盛聚碳科技股份有限公司 Flame-retardant low-temperature toughening synergistic anti-dripping agent and preparation method thereof

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