CN100497446C - Antidrip agent in thermoplastic resin, preparation and method of use - Google Patents
Antidrip agent in thermoplastic resin, preparation and method of use Download PDFInfo
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- CN100497446C CN100497446C CNB2005100365637A CN200510036563A CN100497446C CN 100497446 C CN100497446 C CN 100497446C CN B2005100365637 A CNB2005100365637 A CN B2005100365637A CN 200510036563 A CN200510036563 A CN 200510036563A CN 100497446 C CN100497446 C CN 100497446C
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- antidrip agent
- tetrafluoroethylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
Abstract
This invention relates to a method for preparing a dropping-preventing agent for flammable thermoplastic resin. The method comprises: (1) agglomerating and polymerizing between the core emulsion and the shell monomer in an electrolyte solution to obtain microparticles with an average size of 0.1-1 mum; (2) agglomerating to obtain agglomerates with particle sizes of 1 mum to 5 mm; (3) washing with water, and drying to obtain particles of the dropping-preventing agent. The dropping-preventing agent can be directly mixed with thermoplastic resin and flame retardant to obtain flame retardant resin, which has better dropping-preventing performance, higher fire-retarding grade and good appearance.
Description
[affiliated technical field]
The present invention relates to a kind of can giving and resist Antidrip agent and the preparation and the using method of dripping performance when the inflammableness thermoplastic resin burns, Antidrip agent is the altered contents that is used for thermoplastic resin, a kind of additive of the flame-retardant anti-dropping performance in the time of improving the thermoplastic resin burning belongs to polymkeric substance type material synthetic technology and physical and chemical modified field.
[background technology]
Light, easily manufactured, easy dyeing that thermoplastic material has, be convenient to the characteristics of scale operation, various environment such as family, office, factory, communal facility have been widely used at present, especially make electronics, electrical equipment, automobile, communication, instrument, toy as engineering plastics, article such as office testing installation.Thermoplastic material has inflammableness, self be heated and softening transform takes place easily even hang, people can obtain flame retardant properties by adding one or more fire retardants when making thermoplastic material, wherein fire retardant comprises halogenated flame retardant, the inorganic phosphorus flame retardant, organophosphate and derivative, organic sulfonate, metal hydroxidess etc. typically have: red phosphorus, Al
2(OH)
3, Mg (OH)
2, RDP, Polybrominated biphenyl, ammonium polyphosphate, melamine and Sb
2O
3Deng synergist.These materials can effectively suppress burning, but are preventing that effect is limited aspect the melt drippage.Also can discharge toxic gas when Polybrominated biphenyl (PBBs) wherein, halogen containing flame-retardant burning that clorafin etc. are widely used, be limited gradually to use.The flame retardant resistance of synthetic resins is based on U.S. insurance industry laboratory bulletin 94 (Underwriters Laboratories Inc., Bulletin 94) " materials classification combustion test " (below be referred to as UL94), combustion time of extinguishing naturally after catching fire by test piece in the UL94 evaluation test and follow incendiary melt drippage to estimate flame retardant resistance, there not be the material of drippage and combustion time weak point to reach high flame retardant rating.Concrete test method is: will grow 127 millimeters, the test film of 12.7 millimeters of width, 1.6 millimeters of thickness and be placed vertically, and in flame ignition 10 seconds of its lower end with test furnace, afterwards flame be removed, and measure test piece and catch fire time of self-gravitation.Catch fire extinguish in, begin igniting in secondary 10 seconds immediately, similarly measure the time of the self-gravitation of catching fire.And, whether catch fire by the cotton layer under the kindling material evaluation test simultaneously sheet that falls.From for the first time and secondary combustion time, cotton catch fire and have or not sustained combustion, according to the above-mentioned UL-94V specification evaluation grade of burning.The burning grade is promptly put out from fire with twice combustion, and does not have drippage and be the highest V-0 level, and other is according to combustion time and drippage situation being divided into V-1, V-2 level, its flame retardant properties reduction.
For reaching the performance requriements of anti-drippage, some have the existing report of document that the high molecular polymer that is subjected to heat shrinkability characteristic is used to improve the melt drippage.For example: the patent CN96195311 of German BASF AG, introduced a kind of aromatic vinyl polymer; Japanese Patent 3-190958 discloses the resin combination of silicon rubber as anti-dripping agent, but it can form volatile cyclisation siloxanes in component end item, and can cause the damage of electricity point.Recently the fluorine resin that has the fibrillation tendency becomes the development main flow as Antidrip agent, and existing various trials use fluoropolymer to improve the fire-retardant anti-drippage performance of synthetic resins.
Adding pure teflon resin (PTFE is categorized as ASTMD-1457 TYPE 3) with fibre-forming performance is openly added in the synthetic resins PC/ABS alloy as Antidrip agent by USP4463130,4786686,5109044,5276078 etc. and improves flame retardant effect.But the technology of the addition means and the formation fine-fibered of resin is not disclosed.The defective of pure tetrafluoroethylene is to add inconvenient operation simultaneously, and surface imperfection is arranged during moulding, and mechanical strength descends.Other modified Teflons have following several as the method that Antidrip agent is used for synthetic resins:
(1) physical blending: CN02805583 has introduced the rigid polymer particulate of fine grain size as the thicker teflon resin of separant parcel particle diameter, and by easy mixing, and the method for mixture extruding pelletization is improved the dispersing property of tetrafluoroethylene.But fibre-forming performance is limited in one's ability with the solution surface imperfection.
(2) condense altogether with other emulsions: USP4810739,5061745 disclose with aqueous dispersions of polytetrafluoroethylhaving with condense modified Teflon altogether and partly solved interpolation and surface imperfection problem after AS or ABS resin emulsion are mixed.
(3) shell structure emulsion polymerization: WO94/1475, CN95192785 disclose the unrestricted flow PTFE particulate that uses the letex polymerization of nucleocapsid method to obtain the surface parcel and have been used as dripping inhibitor, and part has solved interpolation and surface imperfection problem.
(4) solid particles surface coating: EP483510 disclose with the ABS resin particle be immersed in after drying in the aqueous dispersions of polytetrafluoroethylhaving obtain the surface applied polytetrafluoroethylparticle particle as dripping inhibitor, part has solved interpolation and surface imperfection problem, but polytetrafluoroethylene content is difficult to determine.
(5) mixed atomizing drying: EP718346 discloses the spray-dired method of the mixture of a kind of thermoplastic resin solution and aqueous dispersions of polytetrafluoroethylhaving has been removed solvent and water, product improves the dispersiveness of tetrafluoroethylene, prevent particle condensation, improve products appearance.
(6) polytetrafluoroethylene aqueous dispersion: CN98106922 discloses at forcing machine increase vaccum exhaust outlet method adding polytetrafluoroethylene aqueous dispersion and has obtained bigger fine-fibered of length-to-diameter ratio and local cross network structure, but part has solved interpolation and surface imperfection problem fiberizability effect instability, and moisture has detrimentally affect to resin mechanical properties such as PET, PC, PA simultaneously.
More than can not effectively remove impurity such as emulsifying agent in the emulsion building-up process, initiator, stopper by the emulsion modified method of PTFE water-dispersion (method 2～6), processing causes detrimentally affect to back segment.All these methods or anti-drippage are limited in one's ability, the defective that perhaps aftertreatment difficulty can't suitability for industrialized production.At present commercial have only GE speciality chemical company (existing Compton company) emulsion to be total to coacervation prod Blendex B449 and mitsubishi rayon mixed atomizing exsiccant product Metablen A3800, can only reach 50% but these product P TFE content is the highest, the high-content tetrafluoroethylene disperses bad and anti-drippage effect undesirable, while particle diameter form irregularity, free-flowing property is poor, is not easy to store and manipulate.
[summary of the invention]
The purpose of this invention is to provide a kind of Antidrip agent and preparation thereof and using method, improve the anti-drippage performance of inflammableness thermoplastic resin when burning, and can suitability for industrialized production.
We find in experiment, can destroy the interface balance after the adding organic phase in the stable emulsion of vinyl polymer, because interfacial tension difference, the organic phase bag is attached to polymer surfaces.This physicochemical change provides thinking for us, after the surface in situ polyreaction, script softish amorphous polymer being coated on the inside in the organic monomer introducing emulsion, electronic microscope photos and solubility test analysis find that reaction forms the tiny ball-type particulate with hard monomer polymkeric substance parcel.The present invention utilizes this principle, by polymer surface modification, generates spheric Antidrip agent particulate, and yield reaches more than 90%.Antidrip agent of the present invention can add makes flame retardant resin in the thermoplastic resin, the PTFE microballoon that can dissociate when being heated and discharge initial size 0.05-1um, PTFE microballoon be fibrillation in extruding with under shearing, and the multiple spot intersection constitutes network structure.During burning, the dendritic structure of PTFE particulate produces and shrinks, and crossover network tightens up, the tension resin melt, and starvation, thus quicken resin carbonation, have good fire-retardant anti-drippage effect.
The median size that Antidrip agent of the present invention is made up of core and shell portion is that the particle diameter that the micropartical aggegation of 0.01～1um forms is 1um～5mm aggregate.This atomic core is the high molecular fluoro ethene polymers that protofibril forms property, or this polymkeric substance and other vinyl polymers mix mixture.The standard specific gravity of the high molecular weight polytetrafluoroethyldispersions of the protofibril of core formation property is below 2.230, the weight percent of core and shell portion is preferably 95:5～5:95, preferred 90:10～30:70, if the core in this weight ratio is less than 5%, then fibrillation is insufficient, and if anti-drippage DeGrain is greater than 95%, then fibrillation surplus, bad dispersibility and molding degraded appearance.Shell portion is one or more polymers of vinyl monomers.The aggregate particle diameter is 1um～5mm.If particle diameter less than 1um, is unfavorable for drying, store and use, particle diameter becomes fine effect bad greater than 5mm redispersion difficulty then, and anti-drippage effect descends.
Core high molecular fluoro vinyl polymer can be a chlorotrifluoroethylene, R 1216, tetrafluoroethylene, Fluorine containing olefine homopolymerization or multipolymers such as fluoroalkyl ethene, fluoroalkyl fluorovinyl ether, fluorinated polymers such as tetrafluoroethylene, R 1216 TFE copolymer F46, ethylene tetrafluoroethylene copolymer F40, tetrafluoroethylene vinyl ether co-polymer for example, the modified Teflon that one or more vinyl monomer copolymerization of preferred pure tetrafluoroethylene or pure tetrafluoroethylene and 0.001～1% form.The standard specific gravity of high molecular weight polytetrafluoroethyldispersions (ASTM D-1457) is below 2.230, is generally 2.130～2.230, preferred 2.130～2.210, this standard specific gravity is more little, and the expression molecular weight is high more, if surpass 2.210, particularly 2.230, then fibrillation is insufficient.The upper limit of the molecular weight of high molecular weight polytetrafluoroethyldispersions without limits.The number-average molecular weight of high molecular PTFE is pressed following formula: log
10(number-average molecular weight)=31.83-11.58 * (standard specific gravity) calculates, but this molecular weight ranges is very difficult to measure, and is not tight numerical value.Standard specific gravity is that 2.149～2.200 PTFE number-average molecular weight is about 22 * 10
5～9 * 10
6If after the PTFE lower molecular weightization then lose the ability of fibrillation, can not use as Antidrip agent.Can carry out fibrillation can determine by the pasty state extrusion test.If in the pasty state extrusion test, can not obtain the successive extrudate then can be judged as lower molecular weight PTFE.
The vinyl polymer that core mixes is for the product of one or more vinyl monomers through free-radical emulsion polymerization, and is preferred: AS emulsion, PMMA emulsion, PS emulsion, ABS emulsion, benzene emulsion, acrylic ester emulsion, styrene-butadiene emulsion, butyronitrile emulsion, or organosilicon crylic acid latex.Core adds the redispersion performance that the vinyl polymer that mixes can improve Antidrip agent, improves and the thermoplastic resin consistency, can also provide thermoplastic resin essential physical and chemical performance, and for example shock strength is heat-resisting, chemical resistant properties etc.The amount of the vinyl polymer that mixes is the 0-200% of high molecular fluoro ethene polymers consumption.Higher addition can reduce Antidrip agent core high molecular fluoro ethene polymers content, influences the anti-drippage of goods effect.
Shell portion is polyfunctional monomer homopolymerization or multipolymers such as difunctional monomers such as monofunctional monomer, divinyl, Vinylstyrene, dicyclopentadiene, trihydroxy-propane triacrylate, epoxy acrylate, unsaturated polyester such as alkene series, oleic series, methacrylic acid series, silicon propylene series, vinyl cyanide series or vinyl ether, allyl ethers, MALEIC ANHYDRIDE, vinylchlorid.
The alkene series monomers can be ethene, propylene, butylene, iso-butylene etc.; The oleic series monomer can be vinylformic acid, methyl acrylate, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, different monooctyl ester, higher alkyl esters, glycidyl ester, isobornyl thiocyanoacetate, Mono Methyl Ethanol Amine ester etc.; The metha crylic body of itemizing can be methacrylic acid, methyl methacrylate, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, different monooctyl ester, higher alkyl esters, glycidyl ester, isobornyl thiocyanoacetate, Mono Methyl Ethanol Amine ester etc.The monomer of preferred oleic series, methacrylic acid series, phenylethylene or vinyl cyanide series, most preferable methyl acrylate, vinyl cyanide, vinylbenzene etc. have one or more monomer mixtures than high glass transition temperature.The monomer that uses can use dissolution with solvents earlier as being solid-state, and employed solvent is varsols such as toluene, dimethylbenzene; Or esters solvents such as vinyl acetic monomer, butyl ester; Or ketones solvents such as butanone, pimelinketone; Or alcoholic solvent or above solvent mixtures such as ethanol, butanols.
Antidrip agent of the present invention needs equipment such as reaction kettle body, agitator and heating unit in preparation process.At first reaction initiator is dissolved in the monomer or its solution of making shell portion, initiator content is the 0.01-5% of monomer or its solution, preferred 0.1-2%.In reactor, add the ionogen mother liquor earlier, add core emulsion and shell portion emulsion then while stirring, then be warmed up to temperature of reaction 50-100 degree centigrade, preferred 60-100 degree centigrade, remained on this temperature stirring reaction 2-24 hour, preferred 4-12 hour, last centrifugal residual monomer and the moisture removed, drying makes water content less than 5%, preferably less than 1%, obtains the finished product Antidrip agent.
The reaction initiator that the present invention uses can be radical polymerization initiator or ionic polymerization initiator.Radical polymerization initiator commonly used comprises but does not limit benzoyl peroxide, Diisopropyl azodicarboxylate, hydrogen phosphide cumene, hydrogen peroxide di-t-butyl, peroxy dicarbonate second propyl ester, tert butyl peroxy benzoate, Potassium Persulphate, hydrogen peroxide etc.; The ionic polymerization initiator comprises but does not limit aluminum alkyls, normal-butyl sodium, boron trifluoride, zinc chloride, hydrogen iodide etc.Radical polymerization initiators such as preferred benzoyl peroxide, Diisopropyl azodicarboxylate, hydrogen phosphide cumene, hydrogen peroxide di-t-butyl.The ionogen mother liquor that the present invention uses is basic metal or alkaline-earth metal water-soluble salt, for example: one or more inorganic salt or mixing solutionss such as sodium-chlor, magnesium chloride, calcium chloride, sodium sulfate, sal epsom, sodium phosphate, calcium phosphate, the final concentration of electrolyte solution is the 1-5% (concentration expressed in percentage by volume) of the total solution of reaction.According to different emulsions, be used for effectively controlling separating out of emulsion.The ionogen mother liquor can be prepared or use the recovery mother liquor to filter before use and use.
Separate out and the polymeric process for effective control, guarantee the stable and size distribution of precipitation particles, can regulate the pH value of ionogen mother liquor in advance, add low quantity of surfactant, and behind adding core and shell portion solution, add the part separant.The pH value of regulating the ionogen mother liquor is 2-11, and preferred 4-8 can control and separate out and the polymeric process.Mineral acids such as sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid or ammoniacal liquor, trolamine, AMP95 etc. are preferred pH value conditioning agent and stablizer.Add tensio-active agent and can guarantee the stable and size distribution of precipitation particles, polyoxyethylenated alcohol, fatty alcohol-polyoxyethylene ether, oxyethane propane multipolymer or contain negatively charged ion and nonionogenic tenside such as fluoroalkyl ether in sulfonate commonly used or alkyl benzene sulfonate, alkylphosphonic, alkylphenol polyoxyethylene, the mountain.Add separant and can avoid free monomer to be clamminess, stirring rake and kettle are damaged, and stable particle.The separant that uses in the building-up process can be inorganic or organic separants such as lime carbonate, talcum powder, kaolin, calcium phosphate, calcium sulfate, barium sulfate, methylene blue, silicone oil, silicon powder, Mierocrystalline cellulose, pectin, guar gum, polyvinyl alcohol, poly-Sodium Propionate, and add-on is the 0.01-10% of reaction-ure mixture.
Antidrip agent of the present invention can be mixed and made into flame retardant resin with fire retardant and inflammableness thermoplastic resin.The usage quantity of Antidrip agent of the present invention and inflammableness thermoplastic resin is: corresponding to per 100 parts of resins (weight part, below identical), dripping inhibitor is 0.01～5 part, preferred 0.03～2 part, if be less than 0.01 part, then is difficult to obtain desired antidrip property.As surpassing 5 parts, though can improve antidrip property, melt viscosity raises and is unfavorable for injection moulding.Can the butt state mix or to disperse the several different methods such as state mixing of thing, for example: in advance with fire retardant with after dripping inhibitor of the present invention mixes, add forcing machine with resin and make flame retardant resin, or be the method for mixing aqueous dispersion of the present invention or organosol shape in the inflammableness thermoplastic resin of aqueous dispersion or organosol at part or all.Except that dripping inhibitor, can also add known additive as required in the flame retardant resin of the present invention combination, for example UV light absorber, antioxidant, face material, lubricant, shaping additive, lime carbonate, glass fibre etc.
Dripping inhibitor of the present invention is used to improve the fire-retardant anti-drippage performance of inflammableness thermoplastic resin.Used inflammableness thermoplastic resin can be polyolefin-based resins (polyethylene, polypropylene, polymethylpentene etc.), polyvinyl chloride, polystyrene resin (polystyrene, impact resistant polystyrene, AS, ABS etc.), polycarbonate-based (PC) resin, polyamide-based resin (nylon 6, nylon 66, nylon 10 etc.); Polyester based resin (PBT, PET); The inflammableness thermoplastic resins such as alloy of acrylic ester resin (PMMA etc.) and above polymkeric substance.Particularly household electrical appliances, OA instrument, IT product etc. are to fire-retardant polycarbonate of having relatively high expectations, polystyrene resin, polybutylene terephthalate, nylon, resins such as polyphenylene oxide.
[description of drawings]
Accompanying drawing 1: the electromicroscopic photograph of Antidrip agent.Under electron microscope as seen, Antidrip agent surfacing, smooth, size is 1um～5mm.
[embodiment]
Embodiment 1: Antidrip agent A
Have thermometer, add 25 gram deionized waters in the 250ml there-necked flask of reflux and whipping appts, 2 gram NaCl, 0.02OP10 gram, with dilute hydrochloric acid pH value is adjusted to 5, add 0.25 gram methylene blue ethanolic soln (0.5%), start to stir and add vinyl cyanide and the vinylbenzene mix monomer (mass ratio 7/3 that 15g is dissolved with the 0.75g hydrogen phosphide cumene, the refining stopper that takes off of industrial goods) controlled temperature is lower than 50 degree, drip the 50ml tetrafluoroethylene in 1 hour and concentrate dispersion liquid, after dripping end, add active calcium phosphate 1.5 grams, slowly feed nitrogen flooding and remove oxygen, speed with 4 degrees celsius/minute is raised to 50 degree with temperature, be incubated 2 hours, be warmed up to 70 degree insulations 4 hours again, be warmed up to 90 degree insulations 3 hours at last, treat to remove after particle precipitation is come out nitrogen feeding water vapour and made the particle slaking in 30 minutes and drive unreacted monomer away.Product through washing, centrifuge dehydration, be dried to water content＜0.5%, obtain dripping inhibitor 42.8 gram at last, be white microballoon, wherein polytetrafluoroethylene content 65%.
Get above-mentioned Antidrip agent 0.45g and 99.2g thermoplastic resin polycarbonate and 0.35g fire retardant potassium diphenylsulfone sulfonate is used the twin screw extruder extruding pelletization after high-speed mixing, pellet is injected into the flame retardant resin of 127 * 12 * 1.6mm (1/16), measures flame retardant properties according to the fire retardant, classified requirement of UL94.The result shows that this Antidrip agent very easily is dispersed in polycarbonate and the potassium diphenylsulfone sulfonate, and the injected articles surfacing is smooth, and fire-retardant rank is the V0 level during burning, does not have the melt drip phenomenon.
Embodiment 2: Antidrip agent B
Manufacturing process changes shell portion solvent into 12 gram methyl methacrylates with embodiment 1, and initiator uses 0.15 gram Diisopropyl azodicarboxylate, and ionogen is tertiary sodium phosphate 3.3 grams.Reaction product obtains Antidrip agent 43.6 grams through washing, and wherein polytetrafluoroethylene content 72%.Get above-mentioned Antidrip agent 0.3g and 70g polycarbonate and 20g ABS and 9.7g RDP and after high-speed mixing, use the twin screw extruder extruding pelletization, pellet is injected into the flame retardant resin of 127 * 12 * 1.6mm (1/16), measures flame retardant properties according to the fire retardant, classified requirement of UL94.The result shows, this Antidrip agent very easily is dispersed in polycarbonate and RDP, the ABS hybrid resin, and the injected articles surfacing is smooth, and flame retardant rating is the V0 level during burning, does not have the melt drip phenomenon.
Embodiment 3: Antidrip agent C
Manufacturing process changes shell portion solvent into 15 gram vinylbenzene with embodiment 1, and initiator uses benzoyl peroxide 0.15 gram. and ionogen is calcium chloride 2.8 grams.Reaction product obtains Antidrip agent 44.3 grams through washing, and wherein polytetrafluoroethylene content 65%.Get above-mentioned Antidrip agent 0.5g and 95g PBT and 4.5g RDP and use the twin screw extruder extruding pelletization after high-speed mixing, pellet is injected into the flame retardant resin of 127 * 12 * 1.6mm (1/16), measures flame retardant properties according to the fire retardant, classified requirement of UL94.The result shows that this Antidrip agent very easily is dispersed in the hybrid resin of PBT and RDP, and the injected articles surfacing is smooth, and flame retardant rating is the V0 level during burning, does not have the melt drip phenomenon.
Embodiment 4: Antidrip agent D
Manufacturing process concentrates dispersion liquid with the core solvent with 15ml benzene emulsion and 35ml tetrafluoroethylene and replaces with embodiment 1, and ionogen is calcium chloride 2.8 grams.Reaction product obtains Antidrip agent 39.8 grams through washing, and wherein polytetrafluoroethylene content 50%.Get above-mentioned Antidrip agent 0.1g and 80g HIPS, 15g decabromodiphenyl oxide and 4.9g SB
2O
3Use the twin screw extruder extruding pelletization after high-speed mixing, pellet is injected into the flame retardant resin of 127 * 12 * 1.6mm (1/16), measures flame retardant properties according to the fire retardant, classified requirement of UL94.The result shows that this Antidrip agent very easily is dispersed in HIPS and PBBs, SB
2O
3Hybrid resin in, the injected articles surfacing is smooth, flame retardant rating is the V0 level during burning, does not have the melt drip phenomenon.
Embodiment 5: Antidrip agent E
The same embodiment A of manufacturing process concentrates dispersion liquid with the core solvent with 25m styrene-butadiene emulsion and 25ml tetrafluoroethylene and replaces, and ionogen is calcium chloride 2.8 grams.Product gets dripping inhibitor 40.1 grams through washing, and wherein polytetrafluoroethylene content 35%.Get above-mentioned Antidrip agent 0.2g and 79.8g ABS, 15g decabromodiphenyl oxide and 5g SB
2O
3Use the twin screw extruder extruding pelletization after high-speed mixing, pellet is injected into 127 * 12 * 1.6mm (1/16) " new resin, measure flame retardant properties according to the fire retardant, classified requirement of UL94.The result shows that this Antidrip agent very easily is dispersed in ABS and PBBs, SB
2O
3Hybrid resin in, the injected articles surfacing is smooth, flame retardant rating is the V0 level during burning, does not have the melt drip phenomenon.
Comparative example 1-5: the fire-retardant contrast experiment of commercially available Antidrip agent
Use commercially available Antidrip agent to replace dripping inhibitor of the present invention, make batten according to the method for embodiment 1-5 respectively, the test flame retardant properties.The result shows: comparative example 1,3, though 5 also can reach the burning behavior of V0 level, the Antidrip agent that uses needs stored under refrigeration, and also needs special equipment to prevent that excessive fibrillation from twining agitator and screw rod, disperses bad in the use; Comparative example 2,4 directly uses ptfe emulsion, needs the outlet of extruder exhaust equipment, and the introducing of moisture simultaneously causes the resin degraded, and physicals significantly descends, and flame retardant resistance descends, and concrete outcome sees Table 1.
Table 1
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Polycarbonate | 99.2 | 70 | |||
| ABS | 20 | 79.8 | |||
| PBT | 95 | ||||
| HIPS | 80 | ||||
| RDP | 9.7 | 4.5 | |||
| DBBs | 15 | 15 |
| KSS | 0.35 | ||||
| SB2O3 | 4.8 | 5 | |||
| Commercially available Antidrip agent 1 | 0.3 | 0.5 | |||
| Commercially available Antidrip agent 2 | 0.45 | 0.2 | 0.2 | ||
| Dispersed | Sticking screw rod | Easier | Sticking screw rod | Easier | Sticking screw rod |
| Burning behavior | V0 | V1 | V0 | V1 | V0 |
| Surface effect | Brilliant point is coarse | More smooth | Brilliant point is coarse | More smooth | Brilliant point is coarse |
Claims (10)
1, a kind of Antidrip agent of thermoplastic resin, the median size that is formed by core and shell portion is that the micropartical further aggegation formation particle diameter of 0.01～1 μ m is the aggregate of 1 μ m～5mm, this atomic core is the high molecular fluoro ethene polymers of protofibril formation property, the proportion of core and shell portion is 95:5～5:95, it is characterized in that shell portion serves as reasons to be selected from homopolymerization or the multipolymer that methyl methacrylate, vinyl cyanide and cinnamic one or more monomers are made.
2, the described Antidrip agent of claim 1, wherein the high molecular fluoro ethene polymers of the protofibril of core formation property is homopolymerization or the multipolymer that is selected from the Fluorine containing olefine of a chlorotrifluoroethylene, R 1216, tetrafluoroethylene, fluoroalkyl ethene, fluoroalkyl fluorovinyl ether, or is selected from the fluorinated polymer of tetrafluoroethylene, R 1216-TFE copolymer, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-vinyl ether co-polymer.
3, claim 1 or 2 described Antidrip agents, wherein the high molecular fluoro ethene polymers of core is that pure tetrafluoroethylene or pure tetrafluoroethylene and percentage composition are the modified Teflon that 0.001～1% vinyl monomer copolymerization forms.
4, the described Antidrip agent of claim 3, wherein the standard specific gravity of the tetrafluoroethylene of the protofibril of core formation property is 2.130-2.230.
5, the preparation method of the described Antidrip agent of a kind of claim 1, earlier reaction initiator is dissolved in the shell portion monomer solution, initiator content is the 0.01-5% of shell portion solution, in reactor, add basic metal or alkaline-earth metal ionogen mother liquor then, then add core emulsion and shell portion solution while stirring, last conditioned reaction temperature is 50-100 ℃, stirs after 2-24 hour, removes residual monomer, and drying forms.
6, the described preparation method of claim 5, wherein the reaction initiator that adds in the preparation process is the ionic polymerization initiator that is selected from the radical polymerization initiator of benzoyl peroxide, Diisopropyl azodicarboxylate, hydrogen phosphide cumene, hydrogen peroxide di-t-butyl, peroxy dicarbonate second propyl ester, tert butyl peroxy benzoate, Potassium Persulphate, hydrogen peroxide or is selected from aluminum alkyls, normal-butyl sodium, boron trifluoride, zinc chloride, hydrogen iodide.
7, the described preparation method of claim 5, wherein the ionogen that uses in the preparation process is to be selected from the basic metal of sodium-chlor, magnesium chloride, calcium chloride, sodium sulfate, sal epsom, sodium phosphate, calcium phosphate or one or more mixed solutions in the alkaline-earth metal aqueous solution, and the final concentration of electrolyte solution is the 1-5% of total reaction volume.
8, the using method of the described Antidrip agent of a kind of claim 1, wherein Antidrip agent and fire retardant and inflammableness thermoplastic resin are mixed and made into flame retardant resin, and usage quantity is to add Antidrip agent 0.01～5 weight part in per 100 weight part inflammableness thermoplastic resins.
9, the described using method of claim 8, wherein Antidrip agent and fire retardant and inflammableness thermoplastic resin are mixed and made into and can also add the additive that is selected from UV light absorber, antioxidant, Yan material, shapes auxiliary agent, lime carbonate, glass fibre in the flame retardant resin composition process.
10, the described using method of claim 8, wherein the inflammableness thermoplastic resin is the alloy of polyolefin-based resins, polyvinyl chloride, polystyrene resin, polycarbonate-based resin, polyamide-based resin, polyester based resin, acrylic ester resin and above polymkeric substance.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100365637A CN100497446C (en) | 2005-08-18 | 2005-08-18 | Antidrip agent in thermoplastic resin, preparation and method of use |
| PCT/IB2005/002981 WO2007020488A1 (en) | 2005-08-18 | 2005-09-16 | Antidrip agent for thermoplastic resins and method for preparing and using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100365637A CN100497446C (en) | 2005-08-18 | 2005-08-18 | Antidrip agent in thermoplastic resin, preparation and method of use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1872899A CN1872899A (en) | 2006-12-06 |
| CN100497446C true CN100497446C (en) | 2009-06-10 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100365637A Ceased CN100497446C (en) | 2005-08-18 | 2005-08-18 | Antidrip agent in thermoplastic resin, preparation and method of use |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN100497446C (en) |
| WO (1) | WO2007020488A1 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337996B (en) * | 2007-07-04 | 2011-01-19 | 上海聚恒聚合物科技有限公司 | Fluor-containing polymer processing aid, silanes cross-linked polyethylene composition with the processing aid and use of the processing aid |
| KR101600107B1 (en) * | 2008-05-26 | 2016-03-04 | 테이진 카세이 가부시키가이샤 | Flame-retardant polycarbonate resin composition |
| CN102234422B (en) * | 2011-05-06 | 2013-01-02 | 深圳市兴盛迪新材料有限公司 | Flame-retardant nylon resin composition and preparation method thereof |
| CN102408651B (en) * | 2011-06-20 | 2014-06-04 | 上海鲁聚聚合物技术有限公司 | Drippage-resisting agent and preparation method thereof as well as thermoplastic resin product containing drippage-resisting agent |
| CN103665247B (en) * | 2013-12-18 | 2016-01-20 | 常熟振氟新材料有限公司 | The preparation method of nano combined tetrafluoroethylene anti-dripping agent |
| CN104130356B (en) * | 2014-06-26 | 2017-06-20 | 衢州市中通化工有限公司 | A kind of preparation method of Antidrip agent emulsion stabilizer |
| CN112876790B (en) * | 2016-07-01 | 2022-04-29 | 浙江新安化工集团股份有限公司 | Coated fluoropolymer particles and polymer blends and polymer compositions |
| CN106496427A (en) * | 2016-10-27 | 2017-03-15 | 四川大学 | A kind of method for preparing surface modification ptfe micropowder |
| CN106947035A (en) * | 2017-04-10 | 2017-07-14 | 广东优科艾迪高分子材料有限公司 | A kind of anti-dripping melt type organic sesqui siloxane fire retardant and preparation method and application |
| CN108192267A (en) * | 2017-12-21 | 2018-06-22 | 宁波凯耀电器制造有限公司 | A kind of crack resistence PC/ABS plastic alloys and its Shooting Technique |
| CN109517328B (en) * | 2018-12-03 | 2022-02-18 | 金发科技股份有限公司 | ABS composition and preparation method thereof |
| CN110042496A (en) * | 2019-04-09 | 2019-07-23 | 安徽申嘉聚合物科技有限公司 | A kind of preparation method of bloom polytetrafluoroethylene (PTFE) anti-dripping melt fiber |
| CN110003394A (en) * | 2019-04-09 | 2019-07-12 | 安徽申嘉聚合物科技有限公司 | A kind of production method of bloom PTFE Antidrip agent |
| CN110655665B (en) * | 2019-09-23 | 2022-09-09 | 铨盛聚碳科技股份有限公司 | Polytetrafluoroethylene anti-dripping agent, preparation method and application thereof |
| WO2021177199A1 (en) * | 2020-03-06 | 2021-09-10 | 三菱エンジニアリングプラスチックス株式会社 | Resin composition, molded article, and electric wire |
| CN111205487A (en) * | 2020-03-29 | 2020-05-29 | 衢州市中通化工有限公司 | Preparation method of organic silicon coated polytetrafluoroethylene anti-dripping agent |
| WO2023142949A1 (en) * | 2022-01-30 | 2023-08-03 | 熵能创新材料(珠海)有限公司 | Anti-dripping agent, preparation method therefor and use thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3742768A1 (en) * | 1987-12-17 | 1989-06-29 | Basf Ag | HALOGEN-FREE FLAME-RESISTANT MOLDING, METHOD FOR THE PRODUCTION AND THEIR USE |
| US6005025A (en) * | 1992-11-17 | 1999-12-21 | General Electric Company | Method of dispersing solid additives in polymers and products made therewith |
| US5521230A (en) * | 1992-11-17 | 1996-05-28 | General Electric Company | Method of dispersing solid additives in polymers and products made therewith |
| WO1995029964A1 (en) * | 1994-04-28 | 1995-11-09 | Daikin Industries, Ltd. | Dripping inhibitor and flame-retardant resin composition |
-
2005
- 2005-08-18 CN CNB2005100365637A patent/CN100497446C/en not_active Ceased
- 2005-09-16 WO PCT/IB2005/002981 patent/WO2007020488A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007020488A1 (en) | 2007-02-22 |
| CN1872899A (en) | 2006-12-06 |
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