CN106947035A - A kind of anti-dripping melt type organic sesqui siloxane fire retardant and preparation method and application - Google Patents
A kind of anti-dripping melt type organic sesqui siloxane fire retardant and preparation method and application Download PDFInfo
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- 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
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- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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Abstract
The present invention relates to plastic additive technical field, and in particular to a kind of anti-dripping melt type organic sesqui siloxane fire retardant and preparation method and application, the preparation method comprises the following steps：（1）Organosiloxane monomer is well mixed, is added to and is dissolved with the aqueous solution of catalyst and emulsifying agent, reacts, obtains organopolysiloxane core emulsion；（2）Organopolysiloxane core emulsion, ptfe emulsion, dispersant and distilled water are added in reactor together, high shear agitation；（3）Cladding monomer is added, emulsifying agent and initiator is added, reacts, reaction product is washed, centrifuged, drying is dried, the anti-dripping melt type organic sesqui siloxane fire retardant is made.Anti-dripping melt type organic sesqui siloxane fire retardant produced by the present invention has excellent anti-dripping effects and fire resistance concurrently, and does not influence macromolecular material high polymer mechanical property, moreover it is possible to improve mechanical property and heat resistance of matrix resin etc..
Description
Technical field
The present invention relates to plastic additive technical field, and in particular to a kind of anti-dripping melt type organic sesqui siloxane fire retardant and
Its preparation method and application.
Background technology
Thermoplastic have the advantages that lightly, be easy to manufacture and industrialized production, in the side of our daily production and living
There is its figure in aspect face, and the development to the mankind brings huge power, but is due to thermoplastic easy firing, is heated easy
Softening transform, or even drop, need addition fire retardant to make it have the bigger scope of application, at present, plastics in process of production
The verified intensity for being capable of retarded combustion and reduction burning by adding fire retardant of flame-retardant modified research and application of product.But
It is that plastic products are during burning, in addition to own combustion, can also produces drippage and ignite other combustibles, cause the intensity of a fire
Spread, this often more serious consequence of producing ratio plastic products own combustion.Therefore, during flame retardance of polymer, only
Only addition fire retardant is inadequate, often also needs to add the drippage that auxiliary agent prevents polymer in combustion process.
The content of the invention
In order to overcome shortcoming and defect present in prior art, have it is an object of the invention to provide a kind of anti-dripping melt type
The preparation method of machine silsesquioxane fire retardant, the preparation method uses the monomer feed postition of batch process, simplifies polymerization anti-
Process is answered, W-response efficiency is improved, step is simple, convenient operation and control, and steady quality can large-scale industrial production.
It is an object of the invention to provide a kind of anti-dripping melt type organic sesqui siloxane fire retardant, organic times of the anti-dripping melt type
Half siloxane flame retardant has excellent anti-dripping effects and fire resistance concurrently, and does not influence macromolecular material high polymer mechanical property
Can, moreover it is possible to improve mechanical property and heat resistance of matrix resin etc..
It is an object of the invention to provide a kind of application of anti-dripping melt type organic sesqui siloxane fire retardant, the anti-dripping melt type
Organic sesqui siloxane fire retardant can be obviously improved the anti-dripping effects and fire resistance of matrix resin applied to makrolon.
The purpose of the present invention is achieved through the following technical solutions：A kind of system of anti-dripping melt type organic sesqui siloxane fire retardant
Preparation Method, comprises the following steps：
（1）Organosiloxane monomer is well mixed, is added to and is dissolved with the aqueous solution of catalyst and emulsifying agent, 30~80
5~10h is reacted at a temperature of DEG C, organopolysiloxane core emulsion is obtained；Wherein, the gross mass of organosiloxane monomer is water quality
40%~60%, the consumption of catalyst is the 1%~5% of organosiloxane monomer mass, and the consumption of emulsifying agent is organosiloxane
The 1%~20% of monomer mass；
（2）Organopolysiloxane core emulsion, ptfe emulsion, dispersant and distilled water are added in reactor together,
5~25min of high shear agitation under 1000~2000rpm rotating speeds；Wherein, the consumption of ptfe emulsion is organic poly- silicon
The 10%-50% of oxygen alkane core quality of the emulsion, the consumption of dispersant is the 1%-5% of organopolysiloxane core quality of the emulsion；
（3）Cladding monomer is added, emulsifying agent and initiator is added, 6-10h is reacted at a temperature of 50~80 DEG C, to reaction product
Washed, centrifuged, dry drying, the anti-dripping melt type organic sesqui siloxane fire retardant is made；Wherein, the use of monomer is coated
Measure as the 30%-70% of organopolysiloxane core quality of the emulsion, the consumption of emulsifying agent is the 1% of organopolysiloxane core quality of the emulsion
~20%, the consumption of initiator is the 0.1%-0.8% of organopolysiloxane core quality of the emulsion.
It is preferred that, the step（1）In, organosiloxane monomer is by phenyl siloxane monomer, cyclic siloxane monomer
4-8 is compared with weight with vinylsiloxane monomer：2-6：The mixture of 0.1-1.0 compositions.
The present invention is by using phenyl siloxane monomer, cyclic siloxane monomer and vinylsiloxane monomer as organic
Siloxanyl monomers compounding use, and it is 4-8 to control its weight ratio：2-6：0.1-1.0, can improve the water proofing property, grease proofing of resin
Property, anti-fog properties, soil resistance, soil release performance, moisture-proof, lubricity, abrasion performance, antistick characteristic, chemical proofing and marresistance.
It is preferred that, the phenyl siloxane monomer is phenyltrimethoxysila,e, dimethoxydiphenylsilane, triphenyl
At least one in methoxy silane, phenyl triethoxysilane, diphenyl diethoxy silane and triphenyl Ethoxysilane.
The present invention can improve the oxidation stability, heat resistance, resistance to combustion of resin by using above-mentioned phenyl siloxane monomer
Property, ultraviolet-resistent property and chemical resistance.It is preferred that, the phenyl siloxane monomer is phenyltrimethoxysila,e, diphenyl diformazan
At least one in TMOS, phenyl triethoxysilane and diphenyl diethoxy silane.It is more highly preferred to, the phenyl
Siloxanyl monomers are to compare 0.5-1.5 by phenyltrimethoxysila,e and phenyl triethoxysilane with weight：The mixing of 1 composition
Thing.
The cyclic siloxane monomer is hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, the silica of decamethyl ring five
Alkane, the siloxanes of ten diformazan basic ring six, three hydrogen trimethyl cyclotrisiloxane, trimethyl triphenyl cyclotrisiloxane, the second of trimethyl three
Alkenyl cyclotrisiloxane, trivinyl triphenyl cyclotrisiloxane, tetrahydrochysene tetramethyl-ring tetrasiloxane, tetramethyl tetraphenyl ring four
Siloxanes, t etram-ethyltetravinylcyclotetrasiloxane, tetravinyl tetraphenyl cyclotetrasiloxane, octaphenylcyclotetrasiloxane, eight
Vinyl cyclotetrasiloxane, diethyl hexamethyl cyclotetrasiloxane, divinyl hexamethyl cyclotetrasiloxane, diphenyl hexamethyl
At least one in cyclotetrasiloxane, vinyl heptamethylcyclotetrasiloxane and phenyl heptamethylcyclotetrasiloxane.
The present invention can control the particle diameter of polymer, so as to improve resin by using above-mentioned cyclic siloxane monomer
Anti-flammability and impact strength.It is preferred that, the cyclic siloxane monomer is hexamethyl cyclotrisiloxane, the silica of prestox ring four
At least one in alkane, decamethylcyclopentaandoxane and the siloxanes of ten diformazan basic ring six.It is more highly preferred to, the annular siloxane
Monomer is by hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxane, with weight compares 1：1.5-2.5：
The mixture of 0.8-1.2 compositions.
The vinylsiloxane monomer is vinyltrimethoxy silane, VTES, divinyl
Dimethoxysilane, divinyl diethoxy silane, vinyl methyl dimethoxysilane, vinyl methyl diethoxy silicon
Alkane, vinyl ethyldimethoxysilane, vinyl ethyl diethoxy silane, to vinyl phenylmethyl methoxy silane,
It is (right to ethenylphenyl ethyl methoxy silane, (1- acrylic) trimethoxy silane, styryl trimethoxy silane, 2-
Ethenylphenyl）Ethyl-methyl dimethoxysilane, 3- are (to vinylbenzoyl epoxide）Hydroxypropyl methyl dimethoxysilane, alkene
Propyl trimethoxy silicane, allyltriethoxysilane, allyl methyl dimethoxysilane, allyl methyl diethoxy
Silane, pi-allyl ethyldimethoxysilane, pi-allyl ethyl diethoxy silane, γ-mercaptopropyi methyl dimethoxy epoxide silicon
Alkane, γ-methacryloxypropyl methoxyl group dimethylsilane, γ-methacryloxypropyl dimethoxy-methyl silicon
Alkane, 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, in organic poly- silicon by using above-mentioned vinylsiloxane monomer as coupling agent
The side chain of oxygen alkane or end import the composition of vinyl polymerized functional group, the vinyl polymerized functional group as with by coating
Monomer formation copolymerized polymer chemical bond when grafting active site and play a role.It is preferred that, the vinylsiloxane
Monomer is vinyltrimethoxy silane, styryl trimethoxy silane, allyltrimethoxysilanis, γ-metering system
At least one in acryloxypropylethoxysilane methoxyl group dimethylsilane and γ-methacryloxypropyl ethyoxyl diethylsilane
Kind.It is more highly preferred to, the vinylsiloxane monomer is by vinyltrimethoxy silane, γ-methacryloxy third
Ylmethoxy dimethylsilane and γ-methacryloxypropyl ethyoxyl diethylsilane are with weight ratio 1：1.5-2.5：2-
The mixture of 4 compositions.
It is preferred that, the step（1）In, catalyst is acidic catalyst, and the acidic catalyst is alkyl sulfonic acid class, alkene
At least one in base sulphonic acids, aryl sulfonic acid class, inorganic acids and other organic acids；The alkyl sulfonic acid class is methyl sulphur
At least one in acid, trifluoromethane sulfonic acid, ethylsulfonic acid, isethionic acid, propyl sulfonic acid and 1- butyl sulfonic acids；The alkenyl
Sulphonic acids are at least one in vinyl sulfonic acid, propene sulfonic acid and methacrylic sulfonic acid；The aryl sulfonic acid class be benzene sulfonic acid,
Toluene sulfonic acide, acid dimethyl, ethyl phenenyl azochlorosulfonate acid, at least one of diethylbenzene sulfonic acid and DBSA；Institute
State at least one of the inorganic acids for hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid and phosphoric acid；Other organic acids are formic acid, second
Acid, hydroxyacetic acid, lactic acid, malonic acid, at least one of fumaric acid and maleic acid.
The present invention easily makes the particle diameter distribution of organic polysiloxane emulsion narrow by using above-mentioned acidic catalyst, in addition,
The phenomenon of the resin bad order as caused by the emulsifier component of organopolysiloxane is easily reduced, resin can also be improved low
Impact strength when warm.It is preferred that, the acidic catalyst is pyrovinic acid, vinyl sulfonic acid, benzene sulfonic acid, toluene sulfonic acide and ten
At least one in dialkyl benzene sulfonic acids.It is more highly preferred to, the acidic catalyst is by pyrovinic acid, toluene sulfonic acide and ten
Dialkyl benzene sulfonic acids compare 0.4-0.8 with weight：0.8-1.2：The mixture of 1 composition.
The step（2）In, dispersant is calcium carbonate, montmorillonite, anhydrous sodium metasilicate, diatomite, white carbon and zeolite
In at least one.
The present invention is by using above-mentioned dispersant, and its dispersion effect is good, is easy to organopolysiloxane core emulsion and polytetrafluoro
The high speed shear of vac emulsion.It is preferred that, the dispersant be calcium carbonate, anhydrous sodium metasilicate, diatomite and zeolite in extremely
Few one kind.It is more highly preferred to, the dispersant is to compare 1-2 by calcium carbonate, anhydrous sodium metasilicate and zeolite with weight：0.5-1.5：
The mixture of 1 composition.
It is preferred that, the step（2）In, cladding monomer is styrene monomer, acrylonitrile monomer, esters of acrylic acid list
At least one in body, methacrylate-based monomer, alkenyl class monomer, unsaturated carboxylic acid class monomer and maleimide monomer
Kind.
The present invention polymerize by using above-mentioned cladding monomer with organic polysiloxane emulsion, ptfe emulsion, can be with
Improve anti-flammability, heat resistance and the shock resistance of resin.It is preferred that, the cladding monomer is styrene monomer, acrylonitrile
At least one in class monomer, acrylic ester monomer and methacrylate-based monomer.
The styrene monomer is styrene, α-methylstyrene, α-ethyl styrene, p-methylstyrene and adjacent uncle
At least one in butylstyrene；The acrylonitrile monomer is acrylonitrile and/or methacrylonitrile；The esters of acrylic acid
Monomer be methyl acrylate, ethyl acrylate, n-propyl, n-butyl acrylate, acrylic acid n-pentyl ester, acrylic acid just oneself
At least one in ester, 2-EHA and lauryl acrylate；The methacrylate-based monomer is methyl-prop
E pioic acid methyl ester, EMA, propyl methacrylate, n-BMA, n-amylmethacrylate, methyl
In the just own ester of acrylic acid, 2-Ethylhexyl Methacrylate, isobornyl methacrylate and lauryl methacrylate extremely
Few one kind；The alkenyl class monomer is ethene, propylene, butadiene, isoprene and 5- vinyl -2- ENBs, acryloyl
Amine, N methacrylamide, vinyl imidazole, vinyl acetate, vinyl alkyl ethers, vinyl furan, N- vinyl carbazoles,
Vinylpyridine, ethenyl pyrrolidone, vinyl acetate, vinyl alkyl ethers, allyl methacrylate, the allyl of cyanuric acid three
Ester, triallyl isocyanurate, GDMA, diallyl maleate, vinylacetate, phthalic acid
At least one in diallyl and 1,3-BDO dimethylacrylate；The unsaturated carboxylic acid class monomer be acrylic acid,
At least one in methacrylic acid, maleic acid, fumaric acid and itaconic acid；The maleimide monomer is maleimide
Amine, N- methylmaleimidos, N-phenylmaleimide, N- (2- aminomethyl phenyls) maleimide, N- (4- hydroxy phenyls)
At least one in maleimide and N- N-cyclohexylmaleimides.
The present invention is by using above-mentioned styrene monomer, acrylonitrile monomer, acrylic ester monomer, methacrylic acid
Esters monomer, alkenyl class monomer, unsaturated carboxylic acid class monomer and maleimide monomer, with organopolysiloxane core emulsion,
Ptfe emulsion polymerize, and can improve the anti-flammability, heat resistance and shock resistance of resin.
Be more highly preferred to, it is described cladding monomer be by styrene, acrylonitrile, methyl acrylate and methyl methacrylate with
Weight compares 1：0.4-0.8：1.5-2.5：The mixture of 2-4 compositions.
It is preferred that, the step（1）With the step（3）In, emulsifying agent is cationic surfactant, anionic surface
At least one in activating agent and nonionic surfactant.
The present invention is by using mentioned emulsifier, and its emulsifying effectiveness is good, is conducive to organopolysiloxane core emulsion, polytetrafluoro
The emulsion dispersion of vac emulsion and cladding monomer, accelerates reaction and carries out.It is preferred that, the emulsifying agent is anion surfactant
And/or nonionic surfactant.It is more highly preferred to, the emulsifying agent is by anion surfactant and non-ionic surface work
Property agent compares 1-2 with weight：The mixture of 1 composition.
The cationic surfactant is alkyl trimethyl quaternary ammonium salt, dialkyl dimethyl quaternary ammonium salt, benzalkonium two
Methyl quaternary ammonium, monoalkyl quaternary ammonium salts, alkylphenol-polyethenoxy based quaternary ammonium salt, N- alkyldiethanolamines salt, polyethylene polyamines salt,
At least one in pyridiniujm, imidazoline and morpholine.
The present invention is by using above-mentioned cationic surfactant, and its emulsifying effectiveness is good, is conducive to organopolysiloxane core
Emulsion, ptfe emulsion and the emulsion dispersion for coating monomer, accelerate reaction and carry out.It is preferred that, the cationic surface is lived
Property agent be alkyl trimethyl quaternary ammonium salt, monoalkyl quaternary ammonium salts, alkylphenol-polyethenoxy based quaternary ammonium salt and N- alkyldiethanolamine salt
In at least one.It is more highly preferred to, the cationic surfactant is by alkyl trimethyl quaternary ammonium salt, alkyl phenol polyoxy second
Alkenyl quaternary ammonium salt and N- alkyldiethanolamines salt compare 1.2-1.6 with weight：1.8-2.6：The mixture of 1 composition.
The anion surfactant be alkyl sulfate, alkylbenzenesulfonate, soap, alkyl hydrogen sulfate,
Polyoxyethylene alkyl ether hydrogen sulfuric acid ester, polyoxyethylene alkyl phenyl ether hydrogen sulfuric acid ester, N- acyl taurines, alkyl benzene sulfonic acid ester,
Polyoxyethylene alkyl phenyl ether sulphonic acid ester, α-olefin sulfonate, alkyl naphthalene sulfonic acid ester, alkyl diphenyl base ether disulfonate, sulfo group
Dialkyl succinate, sulfosuccinic acid monoalkyl ester, polyoxyethylene alkyl ether ester, N- acyl aminos hydrochlorate and alkyl phosphate
In at least one.
The present invention is by using above-mentioned anion surfactant, and its emulsifying effectiveness is good, is conducive to organopolysiloxane core
Emulsion, ptfe emulsion and the emulsion dispersion for coating monomer, accelerate reaction and carry out.It is preferred that, the anionic surface is lived
Property agent be alkylbenzenesulfonate, alkyl benzene sulfonic acid ester, polyoxyethylene alkyl phenyl ether sulphonic acid ester and sulfosuccinic acid monoalkyl ester
In at least one.It is more highly preferred to, the anion surfactant is by alkylbenzenesulfonate, polyoxyethylene alkylphenyl
Ether sulfonic acid ester and sulfosuccinic acid monoalkyl ester compare 0.5-1.5 with weight：1.4-2.2：The mixture of 1 composition.
The nonionic surfactant is isomeric alcohol polyethenoxy ether, fatty acid methyl ester APEO, trimethyl nonyl
Alcohol APEO, glycerine mono-acid stearate, aliphatic acid polyethenoxy acid esters, sorbitan fatty acid esters, polyoxy second
Alkene sorbitan fatty acid ester, glycerin fatty vinegar, polyglyceryl fatty acid ester, methyl glycol fatty acid ester, polyoxyethylene hardened castor
At least one in sesame oil fatty acid ester and polyoxyethylene-modified organopolysiloxane.
The present invention is by using above-mentioned nonionic surfactant, and its emulsifying effectiveness is good, is conducive to organopolysiloxane core
Emulsion, ptfe emulsion and the emulsion dispersion for coating monomer, accelerate reaction and carry out.It is preferred that, the non-ionic surface is lived
Property agent be fatty acid methyl ester APEO, glycerine mono-acid stearate, polyoxyethylene sorbitol fatty acid ester and polyoxy second
At least one in the organopolysiloxane that alkene is modified.It is more highly preferred to, the nonionic surfactant is by fatty acid methyl
Ester APEO, glycerine mono-acid stearate and polyoxyethylene-modified organopolysiloxane are with weight ratio 1：0.8-1.2：
The mixture of 1.6-2.4 compositions.
It is preferred that, the step（3）In, initiator is organic peroxide evocating agent, inorganic peroxide initiator, idol
At least one in nitrogen class initiator and redox initiator.
The present invention is by using above-mentioned initiator, and it triggers effect good, can trigger radical polymerization and copolymerization,
Organopolysiloxane core emulsion, ptfe emulsion and the rate of polymerization for coating monomer can be improved.It is preferred that, the initiator
For organic peroxide evocating agent and/or inorganic peroxide initiator.
Organic peroxide evocating agent is benzoyl peroxide, lauroyl peroxide, isopropyl benzene hydroperoxide, tert-butyl group mistake
Hydrogen oxide, di-t-butyl peroxide, cumyl peroxide, peroxidized t-butyl perbenzoate, peroxidating trimethylacetic acid tertiary butyl ester,
In methyl ethyl ketone peroxide, cyclohexanone peroxide, di-isopropyl peroxydicarbonate and di-cyclohexylperoxy di-carbonate at least
It is a kind of；Inorganic peroxide initiator is at least one in potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate；Azo-initiator
It is double for azodiisobutyronitrile, ABVN, azo-bis-iso-dimethyl and 2,2'- azos（2,4- methyl pentane nitriles）In
At least one；Redox initiator is benzoyl peroxide/sucrose, TBHP/rongalite, t-butyl peroxy
Change hydrogen/sodium pyrosulfite, ammonium persulfate/sodium hydrogensulfite, potassium peroxydisulfate/sodium hydrogensulfite, hydrogen peroxide/tartaric acid, peroxide
Change hydrogen/sodium formaldehyde sulfoxylate, ammonium persulfate/ferrous sulfate, hydrogen peroxide/sulfuric acid ferrous iron, benzoyl peroxide/DMA,
Benzoyl peroxide //N, N- diethylanilines, benzoyl peroxide/ferrous pyrophosphate, potassium peroxydisulfate/silver nitrate, persulfuric acid
Salt/mercaptan, isopropyl benzene hydroperoxide/frerrous chloride, potassium peroxydisulfate/frerrous chloride, hydrogen peroxide/frerrous chloride and isopropylbenzene mistake
At least one in the aziridine of hydrogen oxide/tetra-.
The present invention is by using above-mentioned organic peroxide evocating agent, inorganic peroxide initiator, azo-initiator
And redox initiator, it triggers effect good, can trigger radical polymerization and copolymerization, improves organopolysiloxane
Core emulsion, ptfe emulsion and the rate of polymerization for coating monomer.
It is more highly preferred to, the initiator is to compare 1.5- by benzoyl peroxide, potassium peroxydisulfate and ammonium persulfate with weight
2.5：1：The mixture of 0.8-1.2 compositions.
A kind of anti-dripping melt type organic sesqui siloxane fire retardant, the anti-dripping melt type organic sesqui siloxane fire retardant according to
Preparation method described above is made.
A kind of application of anti-dripping melt type organic sesqui siloxane fire retardant, the anti-dripping melt type organic sesqui siloxane is fire-retardant
Agent is applied to makrolon.
It is preferred that, the addition of the anti-dripping melt type organic sesqui siloxane fire retardant is the 0.1- of makrolon gross mass
0.5wt%。
The beneficial effects of the present invention are：The preparation method of the present invention uses the monomer feed postition of batch process, simplifies
Polymerization process, improves W-response efficiency, and step is simple, convenient operation and control, and steady quality can heavy industrialization
Production.
The anti-dripping melt type organic sesqui siloxane fire retardant of the present invention has excellent anti-dripping effects and fire resistance concurrently, and
Macromolecular material high polymer mechanical property is not influenceed, moreover it is possible to improve mechanical property and heat resistance of matrix resin etc..
The fire retardant of the present invention anti-dripping melt when can improve burning, is prevented from heat by using polytetrafluoroethylene (PTFE)
The excellent mixed effects such as fire spreading when plastic resin formed body burns.
The anti-dripping melt type organic sesqui siloxane fire retardant of the present invention can be obviously improved matrix tree applied to makrolon
The anti-dripping effects and fire resistance of fat.
Embodiment
For the ease of the understanding of those skilled in the art, with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying is referred to not limitation of the invention.
Embodiment 1
A kind of preparation method of anti-dripping melt type organic sesqui siloxane fire retardant, comprises the following steps：
（1）Organosiloxane monomer is well mixed, is added to and is dissolved with the aqueous solution of catalyst and emulsifying agent, in 30 DEG C of temperature
The lower reaction 10h of degree, obtains organopolysiloxane core emulsion；Wherein, the gross mass of organosiloxane monomer is the 40% of water quality,
The consumption of catalyst is the 1% of organosiloxane monomer mass, and the consumption of emulsifying agent is the 1% of organosiloxane monomer mass；
（2）Organopolysiloxane core emulsion, ptfe emulsion, dispersant and distilled water are added in reactor together,
The high shear agitation 25min under 1000rpm rotating speeds；Wherein, the consumption of ptfe emulsion is organopolysiloxane core breast
The 10% of liquid quality, the consumption of dispersant is the 1% of organopolysiloxane core quality of the emulsion；
（3）Cladding monomer is added, emulsifying agent and initiator is added, reacts 6h at a temperature of 50 DEG C, reaction product is washed
Wash, centrifuge, dry drying, the anti-dripping melt type organic sesqui siloxane fire retardant is made；Wherein, the consumption of cladding monomer is to have
The 30% of machine polysiloxanes core quality of the emulsion, the consumption of emulsifying agent is the 1% of organopolysiloxane core quality of the emulsion, the use of initiator
Measure as the 0.1% of organopolysiloxane core quality of the emulsion.
The step（1）In, organosiloxane monomer is by phenyl siloxane monomer, cyclic siloxane monomer and vinyl
Siloxanyl monomers compare 4 with weight：2：The mixture of 0.1 composition.
The phenyl siloxane monomer is phenyltrimethoxysila,e；
The cyclic siloxane monomer is hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxane, ten
The siloxanes of diformazan basic ring six or three hydrogen trimethyl cyclotrisiloxane；
The vinylsiloxane monomer is vinyltrimethoxy silane, VTES, divinyl diformazan
TMOS, divinyl diethoxy silane, vinyl methyl dimethoxysilane, vinyl methyl diethoxy silane or
Vinyl ethyldimethoxysilane.
The step（1）In, catalyst is acidic catalyst, and the acidic catalyst is alkyl sulfonic acid class；The alkyl
Sulphonic acids are pyrovinic acid, trifluoromethane sulfonic acid, ethylsulfonic acid, isethionic acid, propyl sulfonic acid or 1- butyl sulfonic acids；The step
Suddenly（2）In, dispersant is calcium carbonate.
The step（2）In, cladding monomer is styrene monomer；The styrene monomer is styrene, α-first
Base styrene, α-ethyl styrene, p-methylstyrene, o-tert-butyl styrene, smell styrene, chlorostyrene or trichloro-benzenes second
Alkene.
The step（1）With the step（3）In, emulsifying agent is cationic surfactant；The cationic surface is lived
Property agent be alkyl trimethyl quaternary ammonium salt, dialkyl dimethyl quaternary ammonium salt, benzalkonium dimethyl quaternary ammonium, monoalkyl quaternary ammonium salts,
Alkylphenol-polyethenoxy based quaternary ammonium salt, N- alkyldiethanolamines salt, polyethylene polyamines salt, pyridiniujm, imidazoline or morpholine.
The step（3）In, initiator is organic peroxide evocating agent；Organic peroxide evocating agent is benzoyl peroxide
Formyl, lauroyl peroxide, isopropyl benzene hydroperoxide, TBHP, di-t-butyl peroxide, peroxidating diisopropyl
Benzene, peroxidized t-butyl perbenzoate, peroxidating trimethylacetic acid tertiary butyl ester, methyl ethyl ketone peroxide, cyclohexanone peroxide, peroxidating two
Diisopropyl carbonate or di-cyclohexylperoxy di-carbonate.
A kind of anti-dripping melt type organic sesqui siloxane fire retardant, the anti-dripping melt type organic sesqui siloxane fire retardant according to
Preparation method described above is made.
A kind of application of anti-dripping melt type organic sesqui siloxane fire retardant, the anti-dripping melt type organic sesqui siloxane is fire-retardant
Agent is applied to makrolon.
The addition of the anti-dripping melt type organic sesqui siloxane fire retardant is the 0.1wt% of makrolon gross mass.
Embodiment 2
A kind of preparation method of anti-dripping melt type organic sesqui siloxane fire retardant, comprises the following steps：
（1）Organosiloxane monomer is well mixed, is added to and is dissolved with the aqueous solution of catalyst and emulsifying agent, in 40 DEG C of temperature
The lower reaction 8h of degree, obtains organopolysiloxane core emulsion；Wherein, the gross mass of organosiloxane monomer is the 45% of water quality, is urged
The consumption of agent is the 2% of organosiloxane monomer mass, and the consumption of emulsifying agent is the 5% of organosiloxane monomer mass；
（2）Organopolysiloxane core emulsion, ptfe emulsion, dispersant and distilled water are added in reactor together,
The high shear agitation 20min under 1200rpm rotating speeds；Wherein, the consumption of ptfe emulsion is organopolysiloxane core breast
The 20% of liquid quality, the consumption of dispersant is the 2% of organopolysiloxane core quality of the emulsion；
（3）Cladding monomer is added, emulsifying agent and initiator is added, reacts 8h at a temperature of 60 DEG C, reaction product is washed
Wash, centrifuge, dry drying, the anti-dripping melt type organic sesqui siloxane fire retardant is made；Wherein, the consumption of cladding monomer is to have
The 40% of machine polysiloxanes core quality of the emulsion, the consumption of emulsifying agent is the 5% of organopolysiloxane core quality of the emulsion, the use of initiator
Measure as the 0.3% of organopolysiloxane core quality of the emulsion.
The step（1）In, organosiloxane monomer is by phenyl siloxane monomer, cyclic siloxane monomer and vinyl
Siloxanyl monomers compare 5 with weight：3：The mixture of 0.3 composition.
The phenyl siloxane monomer is dimethoxydiphenylsilane；
The cyclic siloxane monomer is trimethyl triphenyl cyclotrisiloxane, trimethyl trivinyl cyclotrisiloxane, three second
Alkenyl triphenyl cyclotrisiloxane or tetrahydrochysene tetramethyl-ring tetrasiloxane；
The vinylsiloxane monomer be vinyl ethyl diethoxy silane, to vinyl phenylmethyl methoxy silane,
It is (right to ethenylphenyl ethyl methoxy silane, (1- acrylic) trimethoxy silane, styryl trimethoxy silane or 2-
Ethenylphenyl）Ethyl-methyl dimethoxysilane.
The step（1）In, catalyst is acidic catalyst, and the acidic catalyst is olefin sulfonic acid class；The alkenyl
Sulphonic acids are vinyl sulfonic acid, propene sulfonic acid or methacrylic sulfonic acid；The step（2）In, dispersant is montmorillonite.
The step（2）In, cladding monomer is acrylonitrile monomer；The acrylonitrile monomer is acrylonitrile and/or first
Base acrylonitrile.
The step（1）With the step（3）In, emulsifying agent is anion surfactant；The anionic surface is lived
Property agent be alkyl sulfate, it is alkylbenzenesulfonate, soap, alkyl hydrogen sulfate, polyoxyethylene alkyl ether hydrogen sulfuric acid ester, poly-
Oxygen vinyl alkyl phenyl ether hydrogen sulfuric acid ester, N- acyl taurines, alkyl benzene sulfonic acid ester or polyoxyethylene alkyl phenyl ether sulfonic acid
Ester.
The step（3）In, initiator is inorganic peroxide initiator；Inorganic peroxide initiator is persulfuric acid
At least one in potassium, sodium peroxydisulfate or ammonium persulfate.
A kind of anti-dripping melt type organic sesqui siloxane fire retardant, the anti-dripping melt type organic sesqui siloxane fire retardant according to
Preparation method described above is made.
A kind of application of anti-dripping melt type organic sesqui siloxane fire retardant, the anti-dripping melt type organic sesqui siloxane is fire-retardant
Agent is applied to makrolon.
The addition of the anti-dripping melt type organic sesqui siloxane fire retardant is the 0.2wt% of makrolon gross mass.
Embodiment 3
A kind of preparation method of anti-dripping melt type organic sesqui siloxane fire retardant, comprises the following steps：
（1）Organosiloxane monomer is well mixed, is added to and is dissolved with the aqueous solution of catalyst and emulsifying agent, in 55 DEG C of temperature
The lower reaction 7h of degree, obtains organopolysiloxane core emulsion；Wherein, the gross mass of organosiloxane monomer is the 50% of water quality, is urged
The consumption of agent is the 3% of organosiloxane monomer mass, and the consumption of emulsifying agent is the 10% of organosiloxane monomer mass；
（2）Organopolysiloxane core emulsion, ptfe emulsion, dispersant and distilled water are added in reactor together,
The high shear agitation 15min under 1500rpm rotating speeds；Wherein, the consumption of ptfe emulsion is organopolysiloxane core breast
The 30% of liquid quality, the consumption of dispersant is the 3% of organopolysiloxane core quality of the emulsion；
（3）Cladding monomer is added, emulsifying agent and initiator is added, reacts 8h at a temperature of 65 DEG C, reaction product is washed
Wash, centrifuge, dry drying, the anti-dripping melt type organic sesqui siloxane fire retardant is made；Wherein, the consumption of cladding monomer is to have
The 50% of machine polysiloxanes core quality of the emulsion, the consumption of emulsifying agent is the 10% of organopolysiloxane core quality of the emulsion, initiator
Consumption is the 0.5% of organopolysiloxane core quality of the emulsion.
The step（1）In, organosiloxane monomer is by phenyl siloxane monomer, cyclic siloxane monomer and vinyl
Siloxanyl monomers compare 6 with weight：4：The mixture of 0.5 composition.
The phenyl siloxane monomer is triphenylmethoxy silane；
The cyclic siloxane monomer is tetramethyl tetraphenyl cyclotetrasiloxane, t etram-ethyltetravinylcyclotetrasiloxane, tetrem
Alkenyl tetraphenyl cyclotetrasiloxane or octaphenylcyclotetrasiloxane；
The vinylsiloxane monomer is 3- (to vinylbenzoyl epoxide）Hydroxypropyl methyl dimethoxysilane, pi-allyl three
Methoxy silane, allyltriethoxysilane, allyl methyl dimethoxysilane, allyl methyl diethoxy silane,
Pi-allyl ethyldimethoxysilane or pi-allyl ethyl diethoxy silane.
The step（1）In, catalyst is acidic catalyst, and the acidic catalyst is aryl sulfonic acid class；The aryl
Sulphonic acids are benzene sulfonic acid, toluene sulfonic acide, acid dimethyl, ethyl phenenyl azochlorosulfonate acid, diethylbenzene sulfonic acid or detergent alkylate sulphur
Acid；The step（2）In, dispersant is anhydrous sodium metasilicate.
The step（2）In, cladding monomer is acrylic ester monomer；The acrylic ester monomer is acrylic acid first
Ester, ethyl acrylate, n-propyl, n-butyl acrylate, acrylic acid n-pentyl ester, the just own ester of acrylic acid, acrylic acid 2- second
The own ester of base or lauryl acrylate.
The step（1）With the step（3）In, emulsifying agent is anion surfactant；The anionic surface is lived
Property agent be α-alkene sulfonic acid ester, alkyl naphthalene sulfonic acid ester, alkyl diphenyl base ether disulfonate, dialkyl sulfosuccinate, sulfo group
Succinic acid monoalkyl esters, polyoxyethylene alkyl ether ester, N- acyl aminos hydrochlorate or alkyl phosphate.
The step（3）In, initiator is azo-initiator；Azo-initiator is azodiisobutyronitrile, azo two
Different heptonitrile, azo-bis-iso-dimethyl or 2,2'- azos are double（2,4- methyl pentane nitriles）.
A kind of anti-dripping melt type organic sesqui siloxane fire retardant, the anti-dripping melt type organic sesqui siloxane fire retardant according to
Preparation method described above is made.
A kind of application of anti-dripping melt type organic sesqui siloxane fire retardant, the anti-dripping melt type organic sesqui siloxane is fire-retardant
Agent is applied to makrolon.
The addition of the anti-dripping melt type organic sesqui siloxane fire retardant is the 0.3wt% of makrolon gross mass.
Embodiment 4
A kind of preparation method of anti-dripping melt type organic sesqui siloxane fire retardant, comprises the following steps：
（1）Organosiloxane monomer is well mixed, is added to and is dissolved with the aqueous solution of catalyst and emulsifying agent, in 60 DEG C of temperature
The lower reaction 6h of degree, obtains organopolysiloxane core emulsion；Wherein, the gross mass of organosiloxane monomer is the 55% of water quality, is urged
The consumption of agent is the 4% of organosiloxane monomer mass, and the consumption of emulsifying agent is the 15% of organosiloxane monomer mass；
（2）Organopolysiloxane core emulsion, ptfe emulsion, dispersant and distilled water are added in reactor together,
The high shear agitation 10min under 1800rpm rotating speeds；Wherein, the consumption of ptfe emulsion is organopolysiloxane core breast
The 40% of liquid quality, the consumption of dispersant is the 4% of organopolysiloxane core quality of the emulsion；
（3）Cladding monomer is added, emulsifying agent and initiator is added, reacts 9h at a temperature of 70 DEG C, reaction product is washed
Wash, centrifuge, dry drying, the anti-dripping melt type organic sesqui siloxane fire retardant is made；Wherein, the consumption of cladding monomer is to have
The 60% of machine polysiloxanes core quality of the emulsion, the consumption of emulsifying agent is the 15% of organopolysiloxane core quality of the emulsion, initiator
Consumption is the 0.5% of organopolysiloxane core quality of the emulsion.
The step（1）In, organosiloxane monomer is by phenyl siloxane monomer, cyclic siloxane monomer and vinyl
Siloxanyl monomers compare 7 with weight：5：The mixture of 0.8 composition.
The phenyl siloxane monomer is phenyl triethoxysilane；
The cyclic siloxane monomer is octaphenylcyclotetrasiloxane, eight vinyl cyclotetrasiloxanes, diethyl pregnancy basic ring four
Siloxanes or divinyl hexamethyl cyclotetrasiloxane；
The vinylsiloxane monomer is γ-mercaptopropyi methyl dimethoxysilane, γ-methacryloxypropyl first
Epoxide dimethylsilane, γ-methacryloxypropyl dimethoxymethylsilane, γ-methacryloxypropyl three
Methoxy silane, γ-methacryloxypropyl ethyoxyl dimethylsilane or γ-methacryloxypropyl diethoxy
Butyldimethylsilyl.
The step（1）In, catalyst is acidic catalyst, and the acidic catalyst is inorganic acids；The inorganic acid
Class is hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid or phosphoric acid；The step（2）In, dispersant is diatomite.
The step（2）In, cladding monomer is methacrylate-based monomer；The methacrylate-based monomer is first
Base methyl acrylate, EMA, propyl methacrylate, n-BMA, n-amylmethacrylate,
The just own ester of methacrylic acid, 2-Ethylhexyl Methacrylate, isobornyl methacrylate or lauryl methacrylate.
The step（1）With the step（3）In, emulsifying agent is nonionic surfactant；The non-ionic surface is lived
Property agent be that isomeric alcohol polyethenoxy ether, fatty acid methyl ester APEO, Exxal 12 APEO, glycerine mono-acid are stearic
Acid esters or aliphatic acid polyethenoxy acid esters.
The step（3）In, initiator is redox initiator；Redox initiator is benzoyl peroxide/sugarcane
Sugar, TBHP/rongalite, TBHP/sodium pyrosulfite, ammonium persulfate/sodium hydrogensulfite, persulfuric acid
Potassium/sodium hydrogensulfite, hydrogen peroxide/tartaric acid, hydrogen peroxide/sodium formaldehyde sulfoxylate, ammonium persulfate/ferrous sulfate or hydrogen peroxide/sulphur
It is sour ferrous.
A kind of anti-dripping melt type organic sesqui siloxane fire retardant, the anti-dripping melt type organic sesqui siloxane fire retardant according to
Preparation method described above is made.
A kind of application of anti-dripping melt type organic sesqui siloxane fire retardant, the anti-dripping melt type organic sesqui siloxane is fire-retardant
Agent is applied to makrolon.
The addition of the anti-dripping melt type organic sesqui siloxane fire retardant is the 0.4wt% of makrolon gross mass.
Embodiment 5
A kind of preparation method of anti-dripping melt type organic sesqui siloxane fire retardant, comprises the following steps：
（1）Organosiloxane monomer is well mixed, is added to and is dissolved with the aqueous solution of catalyst and emulsifying agent, in 80 DEG C of temperature
The lower reaction 5h of degree, obtains organopolysiloxane core emulsion；Wherein, the gross mass of organosiloxane monomer is the 60% of water quality, is urged
The consumption of agent is the 5% of organosiloxane monomer mass, and the consumption of emulsifying agent is the 20% of organosiloxane monomer mass；
（2）Organopolysiloxane core emulsion, ptfe emulsion, dispersant and distilled water are added in reactor together,
The high shear agitation 5min under 2000rpm rotating speeds；Wherein, the consumption of ptfe emulsion is organopolysiloxane core emulsion
The 50% of quality, the consumption of dispersant is the 5% of organopolysiloxane core quality of the emulsion；
（3）Cladding monomer is added, emulsifying agent and initiator is added, reacts 6h at a temperature of 80 DEG C, reaction product is washed
Wash, centrifuge, dry drying, the anti-dripping melt type organic sesqui siloxane fire retardant is made；Wherein, the consumption of cladding monomer is to have
The 60% of machine polysiloxanes core quality of the emulsion, the consumption of emulsifying agent is the 20% of organopolysiloxane core quality of the emulsion, initiator
Consumption is the 0.8% of organopolysiloxane core quality of the emulsion.
The step（1）In, organosiloxane monomer is by phenyl siloxane monomer, cyclic siloxane monomer and vinyl
Siloxanyl monomers compare 8 with weight：6：The mixture of 1.0 compositions.
The phenyl siloxane monomer is diphenyl diethoxy silane or triphenyl Ethoxysilane；
The cyclic siloxane monomer is diphenyl hexamethyl cyclotetrasiloxane, vinyl heptamethylcyclotetrasiloxane or phenyl seven
Methyl cyclotetrasiloxane；
The vinylsiloxane monomer is γ-methacryloxypropyl morpholine silane, γ-methacryl
Epoxide dimethylamine epoxide ethylsilane, γ-methacryloxypropyl ethyoxyl diethylsilane, γ-methacryl
Epoxide propyl group diethoxy ethylsilane or γ-methacryloxypropyl.
The step（1）In, catalyst is acidic catalyst, and the acidic catalyst is other organic acids；It is described its
Its organic acid is formic acid, acetic acid, hydroxyacetic acid, lactic acid, malonic acid, fumaric acid or maleic acid；The step（2）In, disperse
Agent is white carbon or zeolite.
The step（2）In, cladding monomer is alkenyl class monomer, unsaturated carboxylic acid class monomer or maleimide list
Body；The alkenyl class monomer be ethene, propylene, butadiene, isoprene and 5- vinyl -2- ENBs, acrylamide,
N methacrylamide, vinyl imidazole, vinyl acetate, vinyl alkyl ethers, vinyl furan, N- vinyl carbazoles, second
Alkenyl pyridine, ethenyl pyrrolidone, vinyl acetate, vinyl alkyl ethers, allyl methacrylate, the allyl of cyanuric acid three
Ester, triallyl isocyanurate, GDMA, diallyl maleate, vinylacetate, phthalic acid
Diallyl or 1,3-BDO dimethylacrylate；The unsaturated carboxylic acid class monomer is acrylic acid, methacrylic acid, horse
Come sour, fumaric acid or itaconic acid；The maleimide monomer is maleimide, N- methylmaleimidos, N- phenyl
Maleimide, N- (2- aminomethyl phenyls) maleimide, N- (4- hydroxy phenyls) maleimides or N- cyclohexyl Malaysia acyl
Imines.
The step（1）With the step（3）In, emulsifying agent is nonionic surfactant；The non-ionic surface is lived
Property agent be sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid ester, glycerin fatty vinegar, polyglycerol fatty acid
Ester, methyl glycol fatty acid ester, polyoxyethylene hardened castor oil fatty acid ester or polyoxyethylene-modified organopolysiloxane.
The step（3）In, initiator is redox initiator；Redox initiator is benzoyl peroxide/N,
Accelerine, benzoyl peroxide //N, N- diethylanilines, benzoyl peroxide/ferrous pyrophosphate, potassium peroxydisulfate/nitre
Sour silver, persulfate/mercaptan, isopropyl benzene hydroperoxide/frerrous chloride, potassium peroxydisulfate/frerrous chloride, hydrogen peroxide/protochloride
The aziridine of iron or isopropyl benzene hydroperoxide/tetra-.
A kind of anti-dripping melt type organic sesqui siloxane fire retardant, the anti-dripping melt type organic sesqui siloxane fire retardant according to
Preparation method described above is made.
A kind of application of anti-dripping melt type organic sesqui siloxane fire retardant, the anti-dripping melt type organic sesqui siloxane is fire-retardant
Agent is applied to makrolon.
The addition of the anti-dripping melt type organic sesqui siloxane fire retardant is the 0.5wt% of makrolon gross mass.
Embodiment 6
The difference of the present embodiment and above-described embodiment 1 is：
The phenyl siloxane monomer is with weight ratio 0.5 by phenyltrimethoxysila,e and phenyl triethoxysilane：1 composition
Mixture.
The cyclic siloxane monomer is by hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, the silicon of decamethyl ring five
Oxygen alkane, with weight compare 1：1.5：The mixture of 0.8 composition.
The vinylsiloxane monomer is by vinyltrimethoxy silane, γ-methacryloxypropyl methoxy
Base dimethylsilane and γ-methacryloxypropyl ethyoxyl diethylsilane are with weight ratio 1：1.5：The mixing of 2 compositions
Thing.
The acidic catalyst is with weight ratio 0.4 by pyrovinic acid, toluene sulfonic acide and DBSA：0.8：
The mixture of 1 composition.
The dispersant is with weight ratio 1 by calcium carbonate, anhydrous sodium metasilicate and zeolite：0.5：The mixture of 1 composition.
The cladding monomer is with weight ratio 1 by styrene, acrylonitrile, methyl acrylate and methyl methacrylate：
0.4：1.5：The mixture of 2 compositions.
The emulsifying agent is with weight ratio 1 by anion surfactant and nonionic surfactant：The mixing of 1 composition
Thing.The anion surfactant is by alkylbenzenesulfonate, polyoxyethylene alkyl phenyl ether sulphonic acid ester and sulfosuccinic acid
Monoalkyl ester compares 0.5 with weight：1.4：The mixture of 1 composition.The nonionic surfactant is by fatty acid methyl ester polyoxy
Vinethene, glycerine mono-acid stearate and polyoxyethylene-modified organopolysiloxane are with weight ratio 1：0.8：1.6 compositions it is mixed
Compound.
The initiator is with weight ratio 1.5 by benzoyl peroxide, potassium peroxydisulfate and ammonium persulfate：1：0.8 composition
Mixture.
Embodiment 7
The difference of the present embodiment and above-described embodiment 2 is：
The phenyl siloxane monomer is with weight ratio 0.8 by phenyltrimethoxysila,e and phenyl triethoxysilane：1 composition
Mixture.
The cyclic siloxane monomer is by hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, the silicon of decamethyl ring five
Oxygen alkane, with weight compare 1：1.8：The mixture of 0.9 composition.
The vinylsiloxane monomer is by vinyltrimethoxy silane, γ-methacryloxypropyl methoxy
Base dimethylsilane and γ-methacryloxypropyl ethyoxyl diethylsilane are with weight ratio 1：1.8：2.5 compositions it is mixed
Compound.
The acidic catalyst is with weight ratio 0.5 by pyrovinic acid, toluene sulfonic acide and DBSA：0.9：
The mixture of 1 composition.
The dispersant is with weight ratio 1.2 by calcium carbonate, anhydrous sodium metasilicate and zeolite：0.8：The mixture of 1 composition.
The cladding monomer is with weight ratio 1 by styrene, acrylonitrile, methyl acrylate and methyl methacrylate：
0.5：1.8：The mixture of 2.5 compositions.
The emulsifying agent is with weight ratio 1.2 by anion surfactant and nonionic surfactant：1 composition it is mixed
Compound.The anion surfactant is by alkylbenzenesulfonate, polyoxyethylene alkyl phenyl ether sulphonic acid ester and sulfosuccinic
Sour monoalkyl ester compares 0.8 with weight：1.6：The mixture of 1 composition.The nonionic surfactant is gathered by fatty acid methyl ester
Oxygen vinethene, glycerine mono-acid stearate and polyoxyethylene-modified organopolysiloxane are with weight ratio 1：0.9：1.8 compositions
Mixture.
The initiator is with weight ratio 1.8 by benzoyl peroxide, potassium peroxydisulfate and ammonium persulfate：1：0.9 composition
Mixture.
Embodiment 8
The difference of the present embodiment and above-described embodiment 3 is：
The phenyl siloxane monomer is with weight ratio 1 by phenyltrimethoxysila,e and phenyl triethoxysilane：1 composition
Mixture.
The cyclic siloxane monomer is by hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, the silicon of decamethyl ring five
Oxygen alkane, with weight compare 1：2：The mixture of 1 composition.
The vinylsiloxane monomer is by vinyltrimethoxy silane, γ-methacryloxypropyl methoxy
Base dimethylsilane and γ-methacryloxypropyl ethyoxyl diethylsilane are with weight ratio 1：2：The mixture of 3 compositions.
The acidic catalyst is with weight ratio 0.6 by pyrovinic acid, toluene sulfonic acide and DBSA：1：1
The mixture of composition.
The dispersant is with weight ratio 1.5 by calcium carbonate, anhydrous sodium metasilicate and zeolite：1：The mixture of 1 composition.
The cladding monomer is with weight ratio 1 by styrene, acrylonitrile, methyl acrylate and methyl methacrylate：
0.6：2：The mixture of 3 compositions.
The emulsifying agent is with weight ratio 1.5 by anion surfactant and nonionic surfactant：1 composition it is mixed
Compound.The anion surfactant is by alkylbenzenesulfonate, polyoxyethylene alkyl phenyl ether sulphonic acid ester and sulfosuccinic
Sour monoalkyl ester compares 1 with weight：1.8：The mixture of 1 composition.The nonionic surfactant is by fatty acid methyl ester polyoxy
Vinethene, glycerine mono-acid stearate and polyoxyethylene-modified organopolysiloxane are with weight ratio 1：1：The mixture of 2 compositions.
The initiator is with weight ratio 2 by benzoyl peroxide, potassium peroxydisulfate and ammonium persulfate：1：The mixing of 1 composition
Thing.
Embodiment 9
The difference of the present embodiment and above-described embodiment 4 is：
The phenyl siloxane monomer is with weight ratio 1.2 by phenyltrimethoxysila,e and phenyl triethoxysilane：1 composition
Mixture.
The cyclic siloxane monomer is by hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, the silicon of decamethyl ring five
Oxygen alkane, with weight compare 1：2.2：The mixture of 1.1 compositions.
The vinylsiloxane monomer is by vinyltrimethoxy silane, γ-methacryloxypropyl methoxy
Base dimethylsilane and γ-methacryloxypropyl ethyoxyl diethylsilane are with weight ratio 1：2.2：3.5 compositions it is mixed
Compound.
The acidic catalyst is with weight ratio 0.7 by pyrovinic acid, toluene sulfonic acide and DBSA：1.1：
The mixture of 1 composition.
The dispersant is with weight ratio 1.8 by calcium carbonate, anhydrous sodium metasilicate and zeolite：1.2：The mixture of 1 composition.
The cladding monomer is with weight ratio 1 by styrene, acrylonitrile, methyl acrylate and methyl methacrylate：
0.7：2.2：The mixture of 3.5 compositions.
The emulsifying agent is with weight ratio 1.8 by anion surfactant and nonionic surfactant：1 composition it is mixed
Compound.The anion surfactant is by alkylbenzenesulfonate, polyoxyethylene alkyl phenyl ether sulphonic acid ester and sulfosuccinic
Sour monoalkyl ester compares 1.2 with weight：2：The mixture of 1 composition.The nonionic surfactant is by fatty acid methyl ester polyoxy
Vinethene, glycerine mono-acid stearate and polyoxyethylene-modified organopolysiloxane are with weight ratio 1：1.1：2.2 compositions it is mixed
Compound.
The initiator is with weight ratio 2.2 by benzoyl peroxide, potassium peroxydisulfate and ammonium persulfate：1：1.1 compositions
Mixture.
Embodiment 10
The difference of the present embodiment and above-described embodiment 5 is：
The phenyl siloxane monomer is with weight ratio 1.5 by phenyltrimethoxysila,e and phenyl triethoxysilane：1 composition
Mixture.
The cyclic siloxane monomer is by hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, the silicon of decamethyl ring five
Oxygen alkane, with weight compare 1：2.5：The mixture of 1.2 compositions.
The vinylsiloxane monomer is by vinyltrimethoxy silane, γ-methacryloxypropyl methoxy
Base dimethylsilane and γ-methacryloxypropyl ethyoxyl diethylsilane are with weight ratio 1：2.5：The mixing of 4 compositions
Thing.
The acidic catalyst is with weight ratio 0.8 by pyrovinic acid, toluene sulfonic acide and DBSA：1.2：
The mixture of 1 composition.
The dispersant is with weight ratio 2 by calcium carbonate, anhydrous sodium metasilicate and zeolite：1.5：The mixture of 1 composition.
The cladding monomer is with weight ratio 1 by styrene, acrylonitrile, methyl acrylate and methyl methacrylate：
0.8：2.5：The mixture of 4 compositions.
The emulsifying agent is with weight ratio 2 by anion surfactant and nonionic surfactant：The mixing of 1 composition
Thing.The anion surfactant is by alkylbenzenesulfonate, polyoxyethylene alkyl phenyl ether sulphonic acid ester and sulfosuccinic acid
Monoalkyl ester compares 1.5 with weight：2.2：The mixture of 1 composition.The nonionic surfactant is by fatty acid methyl ester polyoxy
Vinethene, glycerine mono-acid stearate and polyoxyethylene-modified organopolysiloxane are with weight ratio 1：1.2：2.4 compositions it is mixed
Compound.
The initiator is with weight ratio 2.5 by benzoyl peroxide, potassium peroxydisulfate and ammonium persulfate：1：1.2 compositions
Mixture.
The anti-dripping melt type organic sesqui siloxane fire retardant of the present invention is applied in makrolon, and anti-dripping effects is good, resistance
Combustion performance test can reach 1.6mmUL94V-0 grades, have excellent anti-dripping effects and fire resistance concurrently, and do not influence high score
Sub- 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 present invention preferably implementation, and in addition, the present invention can be realized with other manner,
Any obvious replacement is within protection scope of the present invention on the premise of not departing from present inventive concept.
Claims (10)
1. a kind of preparation method of anti-dripping melt type organic sesqui siloxane fire retardant, it is characterised in that：Comprise the following steps：
（1）Organosiloxane monomer is well mixed, is added to and is dissolved with the aqueous solution of catalyst and emulsifying agent, 30~80
5~10h is reacted at a temperature of DEG C, organopolysiloxane core emulsion is obtained；Wherein, the gross mass of organosiloxane monomer is water quality
40%~60%, the consumption of catalyst is the 1%~5% of organosiloxane monomer mass, and the consumption of emulsifying agent is organosiloxane
The 1%~20% of monomer mass；
（2）Organopolysiloxane core emulsion, ptfe emulsion, dispersant and distilled water are added in reactor together,
5~25min of high shear agitation under 1000~2000rpm rotating speeds；Wherein, the consumption of ptfe emulsion is organic poly- silicon
The 10%-50% of oxygen alkane core quality of the emulsion, the consumption of dispersant is the 1%-5% of organopolysiloxane core quality of the emulsion；
（3）Cladding monomer is added, emulsifying agent and initiator is added, 6-10h is reacted at a temperature of 50~80 DEG C, to reaction product
Washed, centrifuged, dry drying, the anti-dripping melt type organic sesqui siloxane fire retardant is made；Wherein, the use of monomer is coated
Measure as the 30%-70% of organopolysiloxane core quality of the emulsion, the consumption of emulsifying agent is the 1% of organopolysiloxane core quality of the emulsion
~20%, the consumption of initiator is the 0.1%-0.8% of organopolysiloxane core quality of the emulsion.
2. a kind of preparation method of anti-dripping melt type organic sesqui siloxane fire retardant according to claim 1, its feature exists
In：The step（1）In, organosiloxane monomer is by phenyl siloxane monomer, cyclic siloxane monomer and vinyl silica
Alkane monomer compares 4-8 with weight：2-6：The mixture of 0.1-1.0 compositions.
3. a kind of preparation method of anti-dripping melt type organic sesqui siloxane fire retardant according to claim 2, its feature exists
In：The phenyl siloxane monomer be phenyltrimethoxysila,e, dimethoxydiphenylsilane, triphenylmethoxy silane,
At least one in phenyl triethoxysilane, diphenyl diethoxy silane and triphenyl Ethoxysilane；
The cyclic siloxane monomer is hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxane, ten
The siloxanes of diformazan basic ring six, three hydrogen trimethyl cyclotrisiloxane, trimethyl triphenyl cyclotrisiloxane, trimethyl triethylene basic ring
Trisiloxanes, trivinyl triphenyl cyclotrisiloxane, tetrahydrochysene tetramethyl-ring tetrasiloxane, the silica of tetramethyl tetraphenyl ring four
Alkane, t etram-ethyltetravinylcyclotetrasiloxane, tetravinyl tetraphenyl cyclotetrasiloxane, octaphenylcyclotetrasiloxane, eight ethene
Basic ring tetrasiloxane, diethyl hexamethyl cyclotetrasiloxane, divinyl hexamethyl cyclotetrasiloxane, diphenyl pregnancy basic ring four
At least one in siloxanes, vinyl heptamethylcyclotetrasiloxane and phenyl heptamethylcyclotetrasiloxane；
The vinylsiloxane monomer is vinyltrimethoxy silane, VTES, divinyl diformazan
TMOS, divinyl diethoxy silane, vinyl methyl dimethoxysilane, vinyl methyl diethoxy silane,
Vinyl ethyldimethoxysilane, vinyl ethyl diethoxy silane, to vinyl phenylmethyl methoxy silane, to second
Alkenyl phenylethyl methoxy silane, (1- acrylic) trimethoxy silane, styryl trimethoxy silane, 2- are (to ethene
Base phenyl）Ethyl-methyl dimethoxysilane, 3- are (to vinylbenzoyl epoxide）Hydroxypropyl methyl dimethoxysilane, pi-allyl
Trimethoxy silane, allyltriethoxysilane, allyl methyl dimethoxysilane, allyl methyl diethoxy silicon
Alkane, pi-allyl ethyldimethoxysilane, pi-allyl ethyl diethoxy silane, γ-mercaptopropyi methyl dimethoxysilane,
γ-methacryloxypropyl methoxyl group dimethylsilane, γ-methacryloxypropyl dimethoxymethylsilane,
γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl ethyoxyl dimethylsilane, γ-first
Base acryloxypropyl diethoxymethylsilane, γ-methacryloxypropyl morpholine silane, γ-first
Base acryloxypropyl dimethoxy-ethyl silane, γ-methacryloxypropyl ethyoxyl diethylsilane, γ-first
At least one in base acryloxypropyl diethoxy ethylsilane and γ-methacryloxypropyl
Kind.
4. a kind of preparation method of anti-dripping melt type organic sesqui siloxane fire retardant according to claim 1, its feature exists
In：The step（1）In, catalyst is acidic catalyst, and the acidic catalyst is alkyl sulfonic acid class, olefin sulfonic acid class, virtue
At least one in base sulphonic acids, inorganic acids and other organic acids；The alkyl sulfonic acid class is pyrovinic acid, trifluoromethyl
At least one in sulfonic acid, ethylsulfonic acid, isethionic acid, propyl sulfonic acid and 1- butyl sulfonic acids；The olefin sulfonic acid class is second
At least one in olefin sulfonic acid, propene sulfonic acid and methacrylic sulfonic acid；The aryl sulfonic acid class is benzene sulfonic acid, methylbenzene sulphur
Acid, acid dimethyl, ethyl phenenyl azochlorosulfonate acid, at least one of diethylbenzene sulfonic acid and DBSA；The inorganic acid
Class is at least one of pyrovinic acid, vinyl sulfonic acid, benzene sulfonic acid, toluene sulfonic acide and DBSA；Described other have
Machine acids is at least one of formic acid, acetic acid, hydroxyacetic acid, lactic acid, malonic acid, fumaric acid and maleic acid.
5. a kind of preparation method of anti-dripping melt type organic sesqui siloxane fire retardant according to claim 1, its feature exists
In：The step（2）In, cladding monomer is styrene monomer, acrylonitrile monomer, acrylic ester monomer, metering system
At least one in esters of gallic acid monomer, alkenyl class monomer, unsaturated carboxylic acid class monomer and maleimide monomer；The benzene second
Vinyl monomer be styrene, α-methylstyrene, α-ethyl styrene, p-methylstyrene and o-tert-butyl styrene in extremely
Few one kind；The acrylonitrile monomer is acrylonitrile and/or methacrylonitrile；The acrylic ester monomer is acrylic acid first
Ester, ethyl acrylate, n-propyl, n-butyl acrylate, acrylic acid n-pentyl ester, the just own ester of acrylic acid, acrylic acid 2- second
At least one in the own ester of base and lauryl acrylate；The methacrylate-based monomer is methyl methacrylate, methyl
Ethyl acrylate, propyl methacrylate, n-BMA, n-amylmethacrylate, the just own ester of methacrylic acid,
At least one in 2-Ethylhexyl Methacrylate, isobornyl methacrylate and lauryl methacrylate；The alkene
Base class monomer is ethene, propylene, butadiene, isoprene and 5- vinyl -2- ENBs, acrylamide, N- metering systems
Acid amides, vinyl imidazole, vinyl acetate, vinyl alkyl ethers, vinyl furan, N- vinyl carbazoles, vinylpyridine, second
Alkenyl pyrrolidines, vinyl acetate, vinyl alkyl ethers, allyl methacrylate, triallyl cyanurate, isocyanuric acid three
Allyl ester, GDMA, diallyl maleate, vinylacetate, diallyl phthalate and 1,
At least one in 3- butanediol dimethylacrylates；The unsaturated carboxylic acid class monomer is acrylic acid, methacrylic acid, horse
At least one come in sour, fumaric acid and itaconic acid；The maleimide monomer is maleimide, N- methyl Malaysia acyl
Imines, N-phenylmaleimide, N- (2- aminomethyl phenyls) maleimide, N- (4- hydroxy phenyls) maleimides and N- rings
At least one in hexyl maleimide.
6. a kind of preparation method of anti-dripping melt type organic sesqui siloxane fire retardant according to claim 1, its feature exists
In：The step（1）With the step（3）In, emulsifying agent be cationic surfactant, anion surfactant and it is non-from
At least one in sub- surfactant；The cationic surfactant is alkyl trimethyl quaternary ammonium salt, dialkyl dimethyl
Quaternary ammonium salt, benzalkonium dimethyl quaternary ammonium, monoalkyl quaternary ammonium salts, alkylphenol-polyethenoxy based quaternary ammonium salt, N- alkyl diethanols
At least one in amine salt, polyethylene polyamines salt, pyridiniujm, imidazoline and morpholine；The anion surfactant is alkyl
It is sulfate, alkylbenzenesulfonate, soap, alkyl hydrogen sulfate, polyoxyethylene alkyl ether hydrogen sulfuric acid ester, polyxyethylated
Phenyl ether hydrogen sulfuric acid ester, N- acyl taurines, alkyl benzene sulfonic acid ester, polyoxyethylene alkyl phenyl ether sulphonic acid ester, alpha-olefin sulfonic acid
It is ester, alkyl naphthalene sulfonic acid ester, alkyl diphenyl base ether disulfonate, dialkyl sulfosuccinate, sulfosuccinic acid monoalkyl ester, poly-
At least one in oxygen vinyl alkyl ether-ether, N- acyl aminos hydrochlorate and alkyl phosphate；The nonionic surfactant is
Isomeric alcohol polyethenoxy ether, fatty acid methyl ester APEO, Exxal 12 APEO, glycerine mono-acid stearate,
Aliphatic acid polyethenoxy acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid ester, glycerine fatty acid
Vinegar, polyglyceryl fatty acid ester, methyl glycol fatty acid ester, polyoxyethylene hardened castor oil fatty acid ester and polyoxyethylene-modified have
At least one in machine polysiloxanes.
7. a kind of preparation method of anti-dripping melt type organic sesqui siloxane fire retardant according to claim 1, its feature exists
In：The step（3）In, initiator be organic peroxide evocating agent, inorganic peroxide initiator, azo-initiator and
At least one in redox initiator；Organic peroxide evocating agent is benzoyl peroxide, lauroyl peroxide, isopropyl
Benzene hydrogen peroxide, TBHP, di-t-butyl peroxide, cumyl peroxide, peroxidized t-butyl perbenzoate, mistake
Aoxidize trimethylacetic acid tertiary butyl ester, methyl ethyl ketone peroxide, cyclohexanone peroxide, di-isopropyl peroxydicarbonate and the carbon of peroxidating two
At least one in sour dicyclohexyl maleate；Inorganic peroxide initiator be potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate in extremely
Few one kind；Azo-initiator is azodiisobutyronitrile, ABVN, azo-bis-iso-dimethyl and 2,2'- azos
It is double（2,4- methyl pentane nitriles）In at least one；Redox initiator is benzoyl peroxide/sucrose, tert-butyl hydroperoxide
Hydrogen/rongalite, TBHP/sodium pyrosulfite, ammonium persulfate/sodium hydrogensulfite, potassium peroxydisulfate/sodium hydrogensulfite,
Hydrogen peroxide/tartaric acid, hydrogen peroxide/sodium formaldehyde sulfoxylate, ammonium persulfate/ferrous sulfate, hydrogen peroxide/sulfuric acid are ferrous, benzoyl peroxide
Formyl/DMA, benzoyl peroxide //N, N- diethylanilines, benzoyl peroxide/ferrous pyrophosphate, over cure
Sour potassium/silver nitrate, persulfate/mercaptan, isopropyl benzene hydroperoxide/frerrous chloride, potassium peroxydisulfate/frerrous chloride, hydrogen peroxide/
At least one in the aziridine of frerrous chloride and isopropyl benzene hydroperoxide/tetra-.
8. a kind of anti-dripping melt type organic sesqui siloxane fire retardant, it is characterised in that：The anti-dripping melt type organic sesqui siloxane
Preparation method of the fire retardant according to claim any one of 1-7 is made.
9. a kind of application of anti-dripping melt type organic sesqui siloxane fire retardant as claimed in claim 8, it is characterised in that：It is described
Anti-dripping melt type organic sesqui siloxane fire retardant is applied to makrolon.
10. a kind of application of anti-dripping melt type organic sesqui siloxane fire retardant according to claim 9, it is characterised in that：
The addition of the anti-dripping melt type organic sesqui siloxane fire retardant is the 0.1-0.5wt% of makrolon gross mass.
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