CN109293853A - A kind of organic silicon fibre retardant and preparation method thereof containing epoxy group - Google Patents
A kind of organic silicon fibre retardant and preparation method thereof containing epoxy group Download PDFInfo
- Publication number
- CN109293853A CN109293853A CN201811055650.0A CN201811055650A CN109293853A CN 109293853 A CN109293853 A CN 109293853A CN 201811055650 A CN201811055650 A CN 201811055650A CN 109293853 A CN109293853 A CN 109293853A
- Authority
- CN
- China
- Prior art keywords
- monomer
- weight ratio
- phenyl
- mixture
- organic silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The present invention relates to pluronic polymer technical fields, and in particular to a kind of organic silicon fibre retardant and preparation method thereof containing epoxy group, the preparation method include: the synthesis of organopolysiloxane core lotion;The synthesis of organic silicon fibre retardant containing epoxy group.Preparation method of the invention has excellent increase-volume chain extension effect, simple process and low cost by introducing GMA monomer, organic silicon fibre retardant obtained in organopolysiloxane core lotion.
Description
Technical field
The present invention relates to pluronic polymer technical fields, and in particular to a kind of organic silicon fibre retardant containing epoxy group and its
Preparation method.
Background technique
For the high polymer alloy and polymer composite of heterogeneous structure, the compatibility between different component is directly affected
The degree of scatter and morphosis of bond strength and dispersed phase between phase and phase, to influence the mechanical property of material and hot
Energy.
Glycidyl methacrylate (GMA) double bond containing C=C and epoxy group, double bond containing C=C can be with other monomers
Copolymerization, or be grafted with macromolecular chain, and epoxy group can be reacted with carboxyl, hydroxyl, amino groups.Polyamide, polyester etc. contain
Carboxyl, amino, hydroxyl isoreactivity group polymer when being blended with other polymers, carry out increasing reaction using GMA.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide one kind to contain epoxy group
Organic silicon fibre retardant preparation method, the preparation method by organopolysiloxane core lotion introduce GMA monomer, be made
Organic silicon fibre retardant have excellent increase-volume chain extension effect, simple process and low cost.
Another object of the present invention is to provide a kind of organic silicon fibre retardant containing epoxy group, which is used
There is excellent increase-volume chain extension effect in the materials such as polyester, polyamide.
The purpose of the invention is achieved by the following technical solution: a kind of preparation side of the organic silicon fibre retardant containing epoxy group
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 synthesis of the organic silicon fibre retardant containing epoxy group:
B1, the pH value for adjusting organopolysiloxane core lotion to neutrality, be added in system initiator, GMA monomer and its
Its acrylic ester monomer is warming up to 70-90 DEG C, reacts 3-6h;Wherein, the dosage of GMA monomer is organopolysiloxane core cream
The 1%-30% of liquid quality, the dosage of other acrylic ester monomers are the 10%-30% of organopolysiloxane core quality of the emulsion,
The dosage of initiator is the 0.1%-0.8% of organopolysiloxane core quality of the emulsion;
B2, GMA monomer and other acrylic ester monomers are added, the reaction was continued at a temperature of 70-90 DEG C 3-6h;Its
In, the dosage of GMA monomer is the 1%-30% of organopolysiloxane core quality of the emulsion, and the dosage of other acrylic ester monomers is
The 10%-30% of organopolysiloxane core quality of the emulsion;
B3, demulsifier demulsification cohesion is added, centrifugation washing, dries pulverizing is to get the organosilicon resistance containing epoxy group
Fire agent;Wherein, the dosage of demulsifier is 0.5-3 times of reaction solution quality.
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, emulsifier is living by cationic surfactant, anionic surfactant and non-ionic surface
The mixture that property agent is formed with weight ratio 0.4-0.8:1:0.2-0.6.
Preferably, the cationic surfactant is by dialkyl dimethyl quaternary ammonium salt, benzalkonium dimethyl quaternary ammonium
The mixture that salt and monoalkyl quaternary ammonium salts are formed with weight ratio 1:1.2-1.6:1.8-2.6;The anionic surfactant is
By polyoxyethylene alkyl ether hydrogen sulfuric acid ester, alkyl diphenyl base ether disulfonate and polyoxyethylene alkyl ether ester with weight ratio 1:0.5-
1.5:1.4-2.2 the mixture of composition;The nonionic surfactant is by isomeric alcohol polyethenoxy ether, sorbitan
The mixture that aliphatic ester and polyoxyethylene hardened castor oil aliphatic ester are formed with weight ratio 1.6-2.4:1:0.8-1.2.This
The type, multiple that invention passes through strict control cationic surfactant, anionic surfactant and nonionic surfactant
Match and match, emulsifying effectiveness is good, is conducive to the emulsion dispersion of organosiloxane monomer, accelerates reaction and carries out.
Preferably, in the step B1, initiator is by isopropyl benzene hydroperoxide, azodiisobutyronitrile and four aziridines
The mixture formed with weight ratio 1:0.5-1.5:1.5-2.5;The present invention passes through the type of strict control initiator, compounds and match
Than initiation effect is good, can trigger free radical polymerization and copolymerization, can improve rate of polymerization.
In the step B1 and the step B2, GMA monomer is that density exists in 1.072-1.076g/mL, glass transition temperature
40-48 DEG C of glycidyl methacrylate.The present invention passes through the density and glass transition temperature of strict control GMA monomer, system
The organic silicon fibre retardant obtained has excellent increase-volume chain extension effect.
In the step B1 and the step B2, other acrylic ester monomers are by butyl acrylate, methacrylic acid
Methyl esters, α-methylstyrene, methacrylonitrile, 2-EHA and isobornyl methacrylate are with weight ratio 1.5-
2.5:1-2:0.5-1.5:1:0.4-0.8:0.2-0.6 the mixture of composition.The present invention passes through the other acrylate of strict control
Type, compounding and the proportion of class monomer, covered effect is good, and with organopolysiloxane core emulsion polymerization, resin can be improved
Anti-flammability, heat resistance and shock resistance.
In the step B3, demulsifier is made of sodium chloride, potassium acetate and ammonium sulfate with weight ratio 2-4:1.4-2.2:1
Mixture.The present invention passes through compounding, compounding and the proportion of strict control demulsifier, and demulsification is good, can destroy reaction solution
Emulsified state, convenient for isolating and purifying for reaction product.
A kind of organic silicon fibre retardant containing epoxy group, the organic silicon fibre retardant is according to preparation method system described above
?.
It is a kind of using flame-retardant polycarbonate material made from the organic silicon fibre retardant described above containing epoxy group, it is described
Flame-retardant polycarbonate material includes the raw material of 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 of material can be improved in organic silicon fibre retardant, and by the way that modifying agent is added, the processing thermostabilization of material can be improved
Property, mechanical mechanics property and appearance.
Preferably, the preparation method of the macromolecule modified nanometer calcium carbonate includes the following steps:
(1) 15-25g nanometer calcium carbonate and 0.3-0.7g calgon dispersing agent are added into 300-500mL distilled water,
Disperse 20-28h;60-100g Polymeric quaternary ammonium salts are dissolved in 200-400mL tetrahydrofuran simultaneously, dispersion 20-28h is spare;
(2) the addition 200-400mL tetrahydrofuran into scattered nanometer calcium carbonate system, high speed dispersion 0.3-0.7h,
Then slurries are transferred in there-necked flask, polymeric quartenary ammonium salting liquid is slowly added dropwise under stirring, system constantly generates white flock
Precipitating;
(3) after completion of dropwise addition, system is warming up to 75-85 DEG C, after reacting 20-28h, then slurries is filtered, 55-65 DEG C of vacuum
Dry 24-48h, obtains macromolecule modified nanometer calcium carbonate;
Wherein, in the step (1), Polymeric quaternary ammonium salts be brominated polyphenylether stearyl dimethyl benzyl ammonium chloride,
Dimethyl diallyl ammonium chloride-acrylamide copolymer, polydimethyl diallyl ammonium chloride, chlorination -2- hydroxyl -3- (three
Methylamino) propyl polyethylene oxide cellulose ether and N, N, N- trimethyl-2- (2- methyl-1-oxo-2- acrylic oxygroup) second
At least one of ammonium chloride-acrylamide copolymer.
The present invention passes through raw material, preparation step and the technological parameter of stringent macromolecule modified nanometer calcium carbonate, height obtained
The processing heat stability and mechanical property of polycarbonate can be improved in molecular modification nanometer calcium carbonate.Preferably, the polymer
Quaternary ammonium salt is by brominated polyphenylether stearyl dimethyl benzyl ammonium chloride, chlorination -2- hydroxyl -3- (dimethylamino) propyl polycyclic
Oxidative ethane cellulose ether and N, N, N- trimethyl-2- (2- methyl-1-oxo-2- acrylic oxygroup) ethyl ammonium chloride-acryloyl
The mixture that amine copolymer object is formed with weight ratio 2-4:1.5-2.5:1.
Preferably, the synthetic method of the hyperbranched polyester amide are as follows: under nitrogen protection, successively by 0.8-1.2mol tri-
Ethanol amine, 0.8-1.2mol 1,2,4- trimellitic anhydride and 0.005-0.015mol Catalyzed by p-Toluenesulfonic Acid agent are added three mouthfuls
Round-bottomed flask is placed in heating oil bath, and stirring is gradually warming up to 210-230 DEG C, after raw material is uniformly mixed bleach,
Continue to be stirred to react 2-4h at a temperature of 210-230 DEG C, be then cooled to room temperature, obtains yellow transparent solid body i.e. hyper-branched polyester acyl
Amine.
The present invention passes through the raw material of stringent hyperbranched polyester amide, preparation step and technological parameter, hyperbranched poly obtained
Esteramides can not only improve the processing fluidity of polycarbonate, while can also improve the mechanical performance and surface smoothness of product,
And the variation of polycarbonate color will not be caused.
Preferably, the synthetic method of the 4- allyl guaiacol modified dimethyl polysiloxane are as follows: temperature is being housed
It counts, in the there-necked flask of blender, sequentially adds 230-270g dimethyl silicone polymer, 23-27g 4- allyl at room temperature and more create
The wooden phenol forms the suspension of White-opalescent after stirring;Add the chlorine platinum that 0.5-1.0mL platinum mass fraction is 1.5-2.5%
The octanol solution of acid;Continue to stir, is warming up to 90-100 DEG C under logical nitrogen, reacts 2-4h.
Raw material, preparation step and the technique that the present invention passes through stringent 4- allyl guaiacol modified dimethyl polysiloxane
The tensile strength of polycarbonate, bending can be improved in parameter, 4- allyl guaiacol modified dimethyl polysiloxane obtained
Intensity, impact strength and elongation at break.
Preferably, the melt index of the polycarbonate is bisphenol A-type poly- carbonic acid of the melt index in 10-50g/10min
At least one of ester, polyester-type polycarbonate and hexamethylene bisphenol A polycarbonate.
The present invention is by using above-mentioned polycarbonate, and the melt index of strict control polycarbonate is that melt index exists
10-50g/10min, so that polycarbonate has high-intensitive and coefficient of elasticity, high impact, use temperature range wide, forming
Shrinking percentage is low, and dimensional stability is good, and fatigue durability and weatherability are good, and electrical characteristic is excellent, colorless and odorless, safety and environmental protection.More
Preferably, the polycarbonate is by bisphenol A polycarbonate, polyester-type polycarbonate and hexamethylene bisphenol A polycarbonate
The mixture formed with weight ratio 1-2:0.8-1.2:1.
The glass fibre be fibre diameter 5-15 μm, fibre length 1-10mm alkali-free short glass fiber.
The present invention by using fibre diameter 5-15 μm, fibre length 1-10mm alkali-free short glass fiber,
Good insulating, heat resistance is strong, and corrosion resistance is good, high mechanical strength, and the intensity of plastics can be improved.
Other described auxiliary agents are at least one of antioxidant, UV resistant agent, lubricant, smoke suppressant and Vitrified powder.This
The antioxygenic property, anti-ultraviolet property, processability of makrolon material can be improved by using other above-mentioned auxiliary agents in invention
Can, flame-retardant smoke inhibition effect is good.More preferably, other described auxiliary agents are by antioxidant, UV resistant agent, lubricant, smoke suppressant
The mixture formed with Vitrified powder with weight ratio 0.4-0.8:0.6-1.0:1:0.5-1.5:0.8-1.2.
Preferably, the antioxidant is by β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three
The mixing that [2.4- di-tert-butyl-phenyl] phosphite ester and the double lauryls of thio-2 acid are formed with weight ratio 1-2:0.8-1.2:1
Object.The present invention passes through type, compounding and the weight proportion of strict control antioxidant, can delay or inhibit material oxidation process
It carries out, to prevent the aging of material and prolong its service life.
Preferably, the UV resistant agent is by 2- (2 '-hydroxyls -5 '-aminomethyl phenyl) benzotriazole, 2- hydroxyl -4-
The mixture that methoxy benzophenone and hexamethylphosphoramide are formed with weight ratio 0.5-1.5:1.4-2.2:1.The present invention is logical
The type, compounding and weight proportion for crossing strict control ultraviolet absorbing agent, can absorb ultraviolet light strongly, imitate with excellent collaboration
It answers.
Preferably, the lubricant is by oxidized polyethylene wax, glycerin monostearate and stearic amide with weight ratio
1-2:0.4-0.8:1 the mixture of composition.The present invention passes through type, compounding and the proportion of strict control lubricant, can make material
Material improves the mobility of material and the release property of product in process, can reduce difficulty of processing, saves energy consumption.
Preferably, the smoke suppressant is by ferrocene, antimony oxide and ammonium octamolybdate with weight ratio 0.5-1.5:1.5-
2.5:1 the mixture of composition.For the present invention by type, compounding and the proportion of strict control smoke suppressant, smoke suppressing effect is good, can be with
Reduce toxic gas and smog that thermoplastic polyurethane is generated in burning.
Preferably, the Vitrified powder is by attapulgite, zinc borate, silicate glass powder with weight ratio 2-4:0.5-1.5:
The mixture of 1 composition.The present invention by type, compounding and the proportion of strict control Vitrified powder, it is moldable can be at 600-1000 DEG C
Fine and close ceramic product is formed in range, the ceramic product of formation has good elevated temperature strength and heat resistanceheat resistant stream impact energy
Power also has good mechanical property at normal temperature.
The beneficial effects of the present invention are: preparation method of the invention in organopolysiloxane core lotion by introducing
GMA monomer, organic silicon fibre retardant obtained have excellent increase-volume chain extension effect, simple process and low cost.
Organic silicon fibre retardant of the invention is for having excellent increase-volume chain extension effect in the materials such as polyester, polyamide.
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 organic silicon fibre retardant containing epoxy group, 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 synthesis of the organic silicon fibre retardant containing epoxy group:
B1, the pH value for adjusting organopolysiloxane core lotion to neutrality, be added in system initiator, GMA monomer and its
Its acrylic ester monomer is warming up to 70 DEG C, reacts 6h;Wherein, the dosage of GMA monomer is organopolysiloxane core quality of the emulsion
1%, the dosages of other acrylic ester monomers is the 10% of organopolysiloxane core quality of the emulsion, and the dosage of initiator is to have
The 0.1% of machine polysiloxanes core quality of the emulsion;
B2, GMA monomer and other acrylic ester monomers are added, the reaction was continued at a temperature of 70 DEG C 6h;Wherein, GMA
The dosage of monomer is the 1% of organopolysiloxane core quality of the emulsion, and the dosage of other acrylic ester monomers is organic poly- silicon oxygen
The 10% of alkane core quality of the emulsion;
B3, demulsifier demulsification cohesion is added, centrifugation washing, dries pulverizing is to get the organosilicon resistance containing epoxy group
Fire agent;Wherein, the dosage of demulsifier is 0.5 times of reaction solution quality.
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, emulsifier is living by cationic surfactant, anionic surfactant and non-ionic surface
The mixture that property agent is formed with weight ratio 0.4:1:0.2.
In the step B1, 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 and the step B2, GMA monomer is for density in 1.072g/mL, glass transition temperature at 40 DEG C
Glycidyl methacrylate;
In the step B1 and the step B2, other acrylic ester monomers are by butyl acrylate, methacrylic acid
Methyl esters, α-methylstyrene, methacrylonitrile, 2-EHA and isobornyl methacrylate are with weight ratio 1.5:
1:0.5:1:0.4:0.2 the mixture of composition;
In the step B3, mixing that demulsifier is made of sodium chloride, potassium acetate and ammonium sulfate with weight ratio 2:1.4:1
Object.
A kind of organic silicon fibre retardant containing epoxy group, the organic silicon fibre retardant is according to preparation method system described above
?.
It is a kind of using flame-retardant polycarbonate material made from the organic silicon fibre retardant described above containing epoxy group, it is described
Flame-retardant polycarbonate material includes the raw material of 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 organic silicon fibre retardant containing epoxy group, 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 synthesis of the organic silicon fibre retardant containing epoxy group:
B1, the pH value for adjusting organopolysiloxane core lotion to neutrality, be added in system initiator, GMA monomer and its
Its acrylic ester monomer is warming up to 75 DEG C, reacts 5h;Wherein, the dosage of GMA monomer is organopolysiloxane core quality of the emulsion
5%, the dosages of other acrylic ester monomers is the 15% of organopolysiloxane core quality of the emulsion, and the dosage of initiator is to have
The 0.3% of machine polysiloxanes core quality of the emulsion;
B2, GMA monomer and other acrylic ester monomers are added, the reaction was continued at a temperature of 75 DEG C 5h;Wherein, GMA
The dosage of monomer is the 5% of organopolysiloxane core quality of the emulsion, and the dosage of other acrylic ester monomers is organic poly- silicon oxygen
The 15% of alkane core quality of the emulsion;
B3, demulsifier demulsification cohesion is added, centrifugation washing, dries pulverizing is to get the organosilicon resistance containing epoxy group
Fire agent;Wherein, the dosage of demulsifier is 1 times of reaction solution quality.
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 5:3:0.3;
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, emulsifier is living by cationic surfactant, anionic surfactant and non-ionic surface
The mixture that property agent is formed with weight ratio 0.5:1:0.3.
In the step B1, 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 and the step B2, GMA monomer is for density in 1.073g/mL, glass transition temperature at 42 DEG C
Glycidyl methacrylate;
In the step B1 and the step B2, other acrylic ester monomers are by butyl acrylate, methacrylic acid
Methyl esters, α-methylstyrene, methacrylonitrile, 2-EHA and isobornyl methacrylate are with weight ratio 1.8:
1.2:0.8:1:0.6:0.3 the mixture of composition;
In the step B3, demulsifier is made of sodium chloride, potassium acetate and ammonium sulfate with weight ratio 2.5:1.6:1 mixed
Close object.
A kind of organic silicon fibre retardant containing epoxy group, the organic silicon fibre retardant is according to preparation method system described above
?.
It is a kind of using flame-retardant polycarbonate material made from the organic silicon fibre retardant described above containing epoxy group, it is described
Flame-retardant polycarbonate material includes the raw material of 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 organic silicon fibre retardant containing epoxy group, 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 synthesis of the organic silicon fibre retardant containing epoxy group:
B1, the pH value for adjusting organopolysiloxane core lotion to neutrality, be added in system initiator, GMA monomer and its
Its acrylic ester monomer is warming up to 80 DEG C, reacts 4.5h;Wherein, the dosage of GMA monomer is organopolysiloxane core lotion matter
The 15% of amount, the dosage of other acrylic ester monomers are the 20% of organopolysiloxane core quality of the emulsion, the dosage of initiator
It is the 0.5% of organopolysiloxane core quality of the emulsion;
B2, GMA monomer and other acrylic ester monomers are added, the reaction was continued at a temperature of 80 DEG C 4.5h;Wherein,
The dosage of GMA monomer is the 15% of organopolysiloxane core quality of the emulsion, and the dosage of other acrylic ester monomers is organic poly-
The 20% of siloxanes core quality of the emulsion;
B3, demulsifier demulsification cohesion is added, centrifugation washing, dries pulverizing is to get the organosilicon resistance containing epoxy group
Fire agent;Wherein, the dosage of demulsifier is 1.5 times of reaction solution quality.
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 6:4:0.5;
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, emulsifier is living by cationic surfactant, anionic surfactant and non-ionic surface
The mixture that property agent is formed with weight ratio 0.6:1:0.4.
In the step B1, initiator is by isopropyl benzene hydroperoxide, azodiisobutyronitrile and four aziridines with weight
Than the mixture of 1:1:2 composition;
In the step B1 and the step B2, GMA monomer is for density in 1.074g/mL, glass transition temperature at 44 DEG C
Glycidyl methacrylate;
In the step B1 and the step B2, other acrylic ester monomers are by butyl acrylate, methacrylic acid
Methyl esters, α-methylstyrene, methacrylonitrile, 2-EHA and isobornyl methacrylate are with weight ratio 2:
1.5:1:1:0.6:0.4 the mixture of composition;
In the step B3, mixing that demulsifier is made of sodium chloride, potassium acetate and ammonium sulfate with weight ratio 3:1.8:1
Object.
A kind of organic silicon fibre retardant containing epoxy group, the organic silicon fibre retardant is according to preparation method system described above
?.
It is a kind of using flame-retardant polycarbonate material made from the organic silicon fibre retardant described above containing epoxy group, it is described
Flame-retardant polycarbonate material includes the raw material of 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 organic silicon fibre retardant containing epoxy group, 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 synthesis of the organic silicon fibre retardant containing epoxy group:
B1, the pH value for adjusting organopolysiloxane core lotion to neutrality, be added in system initiator, GMA monomer and its
Its acrylic ester monomer is warming up to 85 DEG C, reacts 4h;Wherein, the dosage of GMA monomer is organopolysiloxane core quality of the emulsion
25%, the dosages of other acrylic ester monomers is the 25% of organopolysiloxane core quality of the emulsion, and the dosage of initiator is
The 0.6% of organopolysiloxane core quality of the emulsion;
B2, GMA monomer and other acrylic ester monomers are added, the reaction was continued at a temperature of 85 DEG C 4h;Wherein, GMA
The dosage of monomer is the 25% of organopolysiloxane core quality of the emulsion, and the dosage of other acrylic ester monomers is organic poly- silicon oxygen
The 25% of alkane core quality of the emulsion;
B3, demulsifier demulsification cohesion is added, centrifugation washing, dries pulverizing is to get the organosilicon resistance containing epoxy group
Fire agent;Wherein, the dosage of demulsifier is 2 times of reaction solution quality.
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, emulsifier is living by cationic surfactant, anionic surfactant and non-ionic surface
The mixture that property agent is formed with weight ratio 0.7:1:0.3.
In the step B1, 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 and the step B2, GMA monomer is for density in 1.075g/mL, glass transition temperature at 46 DEG C
Glycidyl methacrylate;
In the step B1 and the step B2, other acrylic ester monomers are by butyl acrylate, methacrylic acid
Methyl esters, α-methylstyrene, methacrylonitrile, 2-EHA and isobornyl methacrylate are with weight ratio 2.2:
1.8:1.2:1:0.7:0.5 the mixture of composition;
In the step B3, mixing that demulsifier is made of sodium chloride, potassium acetate and ammonium sulfate with weight ratio 3.5:2:1
Object.
A kind of organic silicon fibre retardant containing epoxy group, the organic silicon fibre retardant is according to preparation method system described above
?.
It is a kind of using flame-retardant polycarbonate material made from the organic silicon fibre retardant described above containing epoxy group, it is described
Flame-retardant polycarbonate material includes the raw material of 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 organic silicon fibre retardant containing epoxy group, 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 synthesis of the organic silicon fibre retardant containing epoxy group:
B1, the pH value for adjusting organopolysiloxane core lotion to neutrality, be added in system initiator, GMA monomer and its
Its acrylic ester monomer is warming up to 90 DEG C, reacts 3h;Wherein, the dosage of GMA monomer is organopolysiloxane core quality of the emulsion
30%, the dosages of other acrylic ester monomers is the 30% of organopolysiloxane core quality of the emulsion, and the dosage of initiator is
The 0.8% of organopolysiloxane core quality of the emulsion;
B2, GMA monomer and other acrylic ester monomers are added, the reaction was continued at a temperature of 90 DEG C 3h;Wherein, GMA
The dosage of monomer is the 30% of organopolysiloxane core quality of the emulsion, and the dosage of other acrylic ester monomers is organic poly- silicon oxygen
The 30% of alkane core quality of the emulsion;
B3, demulsifier demulsification cohesion is added, centrifugation washing, dries pulverizing is to get the organosilicon resistance containing epoxy group
Fire agent;Wherein, the dosage of demulsifier is 3 times of reaction solution quality.
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, emulsifier is living by cationic surfactant, anionic surfactant and non-ionic surface
The mixture that property agent is formed with weight ratio 0.8:1:0.6.
In the step B1, 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 and the step B2, GMA monomer is for density in 1.076g/mL, glass transition temperature at 48 DEG C
Glycidyl methacrylate;
In the step B1 and the step B2, other acrylic ester monomers are by butyl acrylate, methacrylic acid
Methyl esters, α-methylstyrene, methacrylonitrile, 2-EHA and isobornyl methacrylate are with weight ratio 2.5:
2:1.5:1:0.8:0.6 the mixture of composition;
In the step B3, mixing that demulsifier is made of sodium chloride, potassium acetate and ammonium sulfate with weight ratio 4:2.2:1
Object.
A kind of organic silicon fibre retardant containing epoxy group, the organic silicon fibre retardant is according to preparation method system described above
?.
It is a kind of using flame-retardant polycarbonate material made from the organic silicon fibre retardant described above containing epoxy group, it is described
Flame-retardant polycarbonate material includes the raw material of 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 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 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 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 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 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, organic silicon fibre retardant made from embodiment 1-10 is applied in polycarbonate, expands with excellent increase-volume
Chain effect, flame retardant property test can achieve 1.6mmUL94V-0 grades, good flame retardation effect, and not influence high molecular material high polymer
Mechanical property, moreover it is possible to improve mechanical property and heat resistance of matrix resin etc..
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 organic silicon fibre retardant containing epoxy group, 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 synthesis of the organic silicon fibre retardant containing epoxy group:
Initiator, GMA monomer and other third is added to neutrality in B1, the pH value for adjusting organopolysiloxane core lotion in system
Olefin(e) acid esters monomer is warming up to 70-90 DEG C, reacts 3-6h;
B2, GMA monomer and other acrylic ester monomers are added, the reaction was continued at a temperature of 70-90 DEG C 3-6h;
B3, demulsifier demulsification cohesion is added, centrifugation washing, dries pulverizing is to get the organic silicon fibre retardant containing epoxy group.
2. a kind of preparation method of organic silicon fibre retardant containing epoxy group 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,
Any one in methyl, ethyl, propyl, vinyl, acrylic, acetenyl, propinyl and phenyl, the annular siloxane list
Polymerization degree n=3-6 of body;
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 organic silicon fibre retardant containing epoxy group 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, emulsifier is by cationic surfactant, anionic surfactant and nonionic surfactant
The mixture formed with weight ratio 0.4-0.8:1:0.2-0.6.
4. a kind of preparation method of organic silicon fibre retardant containing epoxy group according to claim 1, it is characterised in that: institute
It states in step B1, initiator is by isopropyl benzene hydroperoxide, azodiisobutyronitrile and four aziridines with weight ratio 1:0.5-
1.5:1.5-2.5 the mixture of composition;
In the step B1 and the step B2, GMA monomer is for density in 1.072-1.076g/mL, glass transition temperature in 40-48
DEG C glycidyl methacrylate;
In the step B1 and the step B2, other acrylic ester monomers be by butyl acrylate, methyl methacrylate,
α-methylstyrene, methacrylonitrile, 2-EHA and isobornyl methacrylate are with weight ratio 1.5-2.5:
1-2:0.5-1.5:1:0.4-0.8:0.2-0.6 the mixture of composition;
In the step B3, demulsifier is made of sodium chloride, potassium acetate and ammonium sulfate with weight ratio 2-4:1.4-2.2:1 mixed
Close object.
5. a kind of organic silicon fibre retardant containing epoxy group, it is characterised in that: the organic silicon fibre retardant according to claim 1-4
Described in any item preparation methods are made.
6. flame-retardant polycarbonate material made from a kind of organic silicon fibre retardant containing epoxy group using described in claim 5,
It is characterized by: the flame-retardant polycarbonate material includes the raw material of following parts by weight:
Wherein, the modifying agent is by macromolecule modified nanometer calcium carbonate, hyperbranched polyester amide and 4- allyl guaiacol
The mixture that modified dimethyl polysiloxane is formed with weight ratio 2-6:0.1-1.0:0.5-1.5.
7. a kind of flame-retardant polycarbonate material according to claim 6, it is characterised in that: the macromolecule modified nano-sized carbon
The preparation method of sour calcium includes the following steps:
(1) 15-25g nanometer calcium carbonate and 0.3-0.7g calgon dispersing agent, dispersion are added into 300-500mL distilled water
20-28h;60-100g Polymeric quaternary ammonium salts are dissolved in 200-400mL tetrahydrofuran simultaneously, dispersion 20-28h is spare;
(2) the addition 200-400mL tetrahydrofuran into scattered nanometer calcium carbonate system, high speed dispersion 0.3-0.7h, then
Slurries are transferred in there-necked flask, polymeric quartenary ammonium salting liquid is slowly added dropwise under stirring, system constantly generates white flock precipitate;
(3) after completion of dropwise addition, system is warming up to 75-85 DEG C, after reacting 20-28h, then slurries is filtered, 55-65 DEG C of vacuum drying
24-48h obtains macromolecule modified nanometer calcium carbonate;
Wherein, in the step (1), Polymeric quaternary ammonium salts are brominated polyphenylether stearyl dimethyl benzyl ammonium chloride, diformazan
Base diallyl ammonium chloride-acrylamide copolymer, polydimethyl diallyl ammonium chloride, chlorination -2- hydroxyl -3- (front three ammonia
Base) propyl polyethylene oxide cellulose ether and N, N, N- trimethyl-2- (2- methyl-1-oxo-2- acrylic oxygroup) ethyl chloride
Change at least one of ammonium-acrylamide copolymer.
8. a kind of flame-retardant polycarbonate material according to claim 6, it is characterised in that: the hyperbranched polyester amide
Synthetic method are as follows: under nitrogen protection, successively by 0.8-1.2mol triethanolamine, 0.8-1.2mol 1,2,4- trimellitic anhydride
And 0.005-0.015mol Catalyzed by p-Toluenesulfonic Acid agent is added three neck round bottom flask and is placed in heating oil bath, stirring, gradually
It is warming up to 210-230 DEG C, after raw material is uniformly mixed bleach, continues to be stirred to react 2-4h at a temperature of 210-230 DEG C, then
It is cooled to room temperature, obtains yellow transparent solid body i.e. hyperbranched polyester amide.
9. a kind of flame-retardant polycarbonate material according to claim 6, it is characterised in that: the 4- allyl guaiacol
The synthetic method of modified dimethyl polysiloxane are as follows: in the there-necked flask equipped with thermometer, blender, sequentially add at room temperature
230-270g dimethyl silicone polymer, 23-27g 4- allyl guaiacol form the suspension of White-opalescent after stirring;
Add the octanol solution for the chloroplatinic acid that 0.5-1.0mL platinum mass fraction is 1.5-2.5%;Continue to stir, heat up under logical nitrogen
To 90-100 DEG C, 2-4h is reacted.
10. a kind of flame-retardant polycarbonate material according to claim 6, it is characterised in that: the melting of the polycarbonate
Index is that bisphenol A polycarbonate, polyester-type polycarbonate and hexamethylene bisphenol A-type of the melt index in 10-50g/10min are poly-
At least one of carbonic ester;The glass fibre is that fibre diameter is chopped in 5-15 μm, alkali-free of the fibre length in 1-10mm
Glass fibre;Other described auxiliary agents are at least one of antioxidant, UV resistant agent, lubricant, smoke suppressant and Vitrified powder.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811055650.0A CN109293853A (en) | 2018-09-11 | 2018-09-11 | A kind of organic silicon fibre retardant and preparation method thereof containing epoxy group |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811055650.0A CN109293853A (en) | 2018-09-11 | 2018-09-11 | A kind of organic silicon fibre retardant and preparation method thereof containing epoxy group |
Publications (1)
Publication Number | Publication Date |
---|---|
CN109293853A true CN109293853A (en) | 2019-02-01 |
Family
ID=65166749
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811055650.0A Pending CN109293853A (en) | 2018-09-11 | 2018-09-11 | A kind of organic silicon fibre retardant and preparation method thereof containing epoxy group |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109293853A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110105576A (en) * | 2019-04-10 | 2019-08-09 | 广州摩库乐化工材料技术有限公司 | One kind sulfonate of polysilsesquioxane containing epoxy group and its preparation method and application |
CN110627974A (en) * | 2019-09-30 | 2019-12-31 | 铨盛聚碳科技股份有限公司 | High-heat-resistance phosphorus-silicon flame retardant, and preparation method and application thereof |
CN115819950A (en) * | 2022-12-20 | 2023-03-21 | 上海品诚控股集团有限公司 | High-performance, low-smoke-density and low-heat-release-rate polycarbonate composition and preparation method thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060135709A1 (en) * | 2003-06-20 | 2006-06-22 | Nobuhiro Hasegawa | Curing composition |
CN104962064A (en) * | 2015-07-30 | 2015-10-07 | 苏州荣昌复合材料有限公司 | Polycarbonate modified plastic |
CN106947031A (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 novel fluorine siloxane flame retardant and preparation method and application |
-
2018
- 2018-09-11 CN CN201811055650.0A patent/CN109293853A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060135709A1 (en) * | 2003-06-20 | 2006-06-22 | Nobuhiro Hasegawa | Curing composition |
CN104962064A (en) * | 2015-07-30 | 2015-10-07 | 苏州荣昌复合材料有限公司 | Polycarbonate modified plastic |
CN106947031A (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 novel fluorine siloxane flame retardant and preparation method and application |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110105576A (en) * | 2019-04-10 | 2019-08-09 | 广州摩库乐化工材料技术有限公司 | One kind sulfonate of polysilsesquioxane containing epoxy group and its preparation method and application |
CN110627974A (en) * | 2019-09-30 | 2019-12-31 | 铨盛聚碳科技股份有限公司 | High-heat-resistance phosphorus-silicon flame retardant, and preparation method and application thereof |
CN115819950A (en) * | 2022-12-20 | 2023-03-21 | 上海品诚控股集团有限公司 | High-performance, low-smoke-density and low-heat-release-rate polycarbonate composition and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109293856A (en) | A kind of the organosilicon toughener and its synthetic method of polymer overmold nano-inorganic substance | |
CN109320674A (en) | A kind of anti-dripping agent and preparation method thereof containing PTFE and organosilicon | |
CN109320772A (en) | A kind of anti-dripping agent and preparation method thereof containing organosilicon and inorganic silicon | |
CN1325548C (en) | Flame retardant resinous compositions and method | |
CN109293853A (en) | A kind of organic silicon fibre retardant and preparation method thereof containing epoxy group | |
TWI689559B (en) | Coating agent for leather and leather formed with the coating agent | |
JP4308668B2 (en) | Impact-resistant molding material and molded body | |
CN101400763B (en) | Halogen-free polycarbonate compositions and articles formed therefrom | |
CN106519144B (en) | The preparation method of ethylene base system graft copolymer and resin combination and ethylene base system graft copolymer containing it | |
CN1802394B (en) | Polyorganosiloxane-containing graft copolymer, resin compositions containing the same and process for production of polyorganosiloxane emulsions | |
CN109280135A (en) | A kind of anti-dripping agent and preparation method thereof with superior compatibility | |
CN109438633A (en) | A kind of organosilicon toughener and its synthetic method with anti-drop effect | |
CN101874073A (en) | Polycarbonate composition having improved impact, flammability and surface appearance, method of making, and articles prepared therefrom | |
CN103339198A (en) | Non-halogenated flame retardant polycarbonate compositions | |
CN106947031B (en) | A kind of flucride siloxane fire retardant and the preparation method and application thereof | |
CN103073724B (en) | Long-chain siloxy ethenyl siloxane, modified (methyl) acrylic ester polymer emulsion thereof, and preparation method | |
JP7318759B2 (en) | Polyorganosiloxane-containing graft copolymer, thermoplastic resin composition and molded article | |
CN100348627C (en) | Method for preparing organic silicon modified propenoic ester copolymer emusion by fine emulsion polymerizing method | |
CN109306169A (en) | A kind of hydridization organic matter and the organic silicon fibre retardant of nano silica and preparation method thereof | |
CN103391952B (en) | Graft copolymer and manufacture method, resin combination and products formed | |
CN109233160A (en) | A kind of organic silicon fibre retardant and preparation method thereof containing PTFE and nano silica | |
CN103827217A (en) | Novel polyorganosiloxane, polycarbonate resin composition comprising same, and modified polycarbonate resin | |
CN102268138A (en) | Aqueous organosilicon grafted (methyl) acrylic polymer and preparation method of emulsion thereof | |
CN105229075B (en) | Impact strength modifier for chlorine-containing resin, chlorine-containing resin composition, and molded article thereof | |
US4988788A (en) | Room temperature-curable coating composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190201 |