CN108727632A - TPE compounding halogen-free flame-retardant system and its application based on dialkyl dithio hypophosphites - Google Patents
TPE compounding halogen-free flame-retardant system and its application based on dialkyl dithio hypophosphites Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/5398—Phosphorus bound to sulfur
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- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a kind of electric wire compounding halogen-free flame-retardant systems of the TPE based on dialkyl dithio hypophosphites, by weight percentage, raw material composition includes dialkyl dithio hypophosphites 30~50%, carbon forming agent 20~30% and diamond compound 20~40%；Shown in dialkyl dithio hypophosphites structural formula such as following formula (I), in formula, R1、R2Independently selected from straight chained alkyl or branched alkyl, M is selected from Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, H or NH4, m is 1~4；The novel halogen-free flame-retardant system has the characteristics that high fire-retardance, resistance to migration, nonhygroscopic, compatible with matrix TPE material, can be applied in TPE, prepares halogen-free flameproof TPE material, is used as the insulating materials in the top grade such as electric wire, electric appliance consumer electronics field.
Description
Technical field
The present invention relates to the technical fields of halogen-free flameproof TPE, and in particular to one kind being based on dialkyl dithio hypophosphites
TPE compounding halogen-free flame-retardant systems and its application.
Background technology
Thermoplastic elastomer (TPE) (TPE) based on SEBS, composition includes SEBS, white oil and thermoplastic resin etc. substantially, is
One kind has general-purpose plastics processing performance, but product has the high molecule alloy material of similar crosslinking rubber performance.SEBS molecules
Double bond in structure is saturated, therefore has ageing-resistant characteristic；It is halogen-free in composition, it is safe and non-toxic, stability is good, matter
Ground is soft, appearance is beautiful, comfortable feel, resilience performance are good and it is very strong prevent it is wet skidding performance；Thermoplastic elastomer (TPE) is also different from common
Rubber cannot be recycled after rubber cross, and thermoplastic elastomer (TPE) has recuperability, therefore have the characteristics that environmental protection；
In addition the TPE based on SEBS also has very high electrical insulating property.Based on these features, TPE material can by with conventional thermoplastic
The similar processing method of material is such as molded, squeezes out processing method, prepares various TPE elastomer products.
TPE is as a kind of polymer composite, in certain special application fields, it is desirable that material has good fire-retardant
Property, for example apply in fields such as electric wire, electric appliances.In terms of the composition of TPE, constituent is all some ignitable components.Cause
This, will reach the flame-retardancy requirements of application field needs, usually be realized by adding fire retardant thereto.TPE all the time
Flame-retardant system is mainly bromide fire retardant, and collaboration antimony oxide.Largely studies have shown that being added with bromide fire retardant
Insulating materials will produce dense smoke and harmful substance in burning, human body can be caused to suffocate.Therefore, be TPE develop it is safe and environment-friendly,
Halogen-free flame-retardant system becomes the hot spot of research, this also becomes the developing direction of flame retardant area.
Currently, the halogen-free flame retardants applied to TPE material includes mainly two major classes primary structure：One kind is inorganic hydroxide
Objects system, including magnesium hydroxide and aluminium hydroxide；Another kind of is high polymerization degree APP system (APP).For inorganic hydrogen-oxygen
Compound system, fire retardation is limited, and in order to reach the requirement of various codes and standards, usual additive amount is very high, sometime up to
The 80% of entire formula system is with a kind of side of filler due to inorganic hydroxide fire retardant and matrix resin and incompatible
Formula is scattered in matrix resin, and therefore, high filler loading capacity will substantially reduce the mechanical property of material.Sometimes for the inorganic hydrogen-oxygen of reduction
The additive amount of compound, also by the way of red phosphorus collaboration, but the application of red phosphorus can have the appearance color of material, Er Qiehong
The burning of phosphorus easy tos produce the toxic gases such as hydrogen phosphide and a large amount of smog, therefore this is nor best solution.For
High polymerization degree APP (APP) flame-retardant system, it belongs to a kind of Intumscent Flame Retardant System, since its anti-flammability is stronger, adds
Dosage will be substantially reduced compared to inorganic hydroxide system, but APP is due to its surface hydrophilic characteristic, with basis material still not phase
Hold, therefore the mechanical strength of the fire-retardant TPE material of APP systems is still very low, more fatal, due to the presence of ammonium ion,
APP is easy the moisture absorption, and TPE product surfaces will substantially reduce the insulation performance of material with the presence of droplet after a period of time, can bring peace
Full hidden danger, secondly APP systems and basis material is incompatible, apparent from material internal to surface migration, as time goes by, interior
The content of portion's fire retardant will reduce, and the flame retardant property of material, which will decline, even to disappear.
Generally speaking, it is applied to major defect existing for the flame-retardant system of TPE material at present：Poor fire, it is easy to migrate,
The problems such as easy moisture absorption and poor compatibility with matrix TPE material.Therefore, it is necessary to research and develop novel to be applied to the novel of TPE material
Halogen-free flame-retardant system.
Invention content
The present invention in view of the above technical problems, develops a kind of novel halogen-free flame-retardant system applied to TPE material, has
High fire-retardance, resistance to the features such as migrating, is nonhygroscopic, compatible with matrix TPE material.It can be applied in TPE, prepare halogen-free flameproof TPE materials
Material is used as the insulating materials in the high-grade consumer electronics such as electric wire, electric appliance field.
Specific technical solution is as follows：
A kind of TPE based on dialkyl dithio hypophosphites compounding halogen-free flame-retardant systems, it is by weight percentage, former
Material forms：
Dialkyl dithio hypophosphites 30~50%；
Carbon forming agent 20~30%；
Diamond compound 20~40%；
The dialkyl dithio hypophosphites, shown in structural formula such as following formula (I)：
In formula, R1、R2Independently selected from straight chained alkyl or branched alkyl, the carbon number of the straight chained alkyl or branched alkyl is 1
~6；
M is selected from Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, H or NH4, m be 1~
4。
The present invention relates to the exploitations of the novel halogen-free flame-retardant system applied to TPE material, using novel based on dioxane
Phosphorus nitrogen sulphur halogen-free flameproof compound system based on base dithiophosphlic acid salt compound, solve existing flame-retardant system additive amount it is big,
With the defect of TPE substrate compatibilities poor, the easy moisture absorption and migration precipitation.The novel flame-retardant system can be well adapted for being based on SEBS
Thermoplastic elastomer (TPE) (TPE), the halogen-free flameproof TPE proprietary materials being had excellent performance.And by controlling the halogen-free flameproof body
The grain diameter of system, and by suitable surface treatment, while ensureing anti-flammability, the mechanics for reducing material is avoided as possible
Performance.By the halogen-free flame-retardant system after above-mentioned specially treated be applied to thermoplastic elastic material, have resistance to migration and
High flame retardant feature can reach the mark of UL94V0 using the flame retardant thermoplastic elastomer composite material prepared by the flame-retardant system
Standard, and the electric wire prepared by the composite material can reach the standard of VW-1.
It will elaborate below to the present invention.
The present invention and is developed new for the purpose of the various defects for solving the existing halogen-free flame-retardant system applied to TPE
The flame-retardant system of type, inventor have made extensive and intensive studies.For existing flame-retardant system asking in fire-retardant TPE material
Topic, has investigated new flame-retardant system, as a result, it has been found that the halogen-free flame-retardant system based on dialkyl dithio hypophosphites can be well
Solve the problems, such as this.
Shown in the structural formula such as above formula (I) of the dialkyl dithio hypophosphites；Preferably, the dialkyl dithio
Hypophosphites, R1、R2Independently selected from methyl, ethyl, n-propyl, normal-butyl, isobutyl group, tertiary butyl, n-pentyl, isopentyl, just
Hexyl or isohesyl；M is selected from Mg, Ca, Al, Sn, Ti or Zn.
Further preferably, the dialkyl dithio hypophosphites is selected from diethyl-dithio hypo-aluminum orthophosphate or diisobutyl
Dithiophosphlic acid aluminium.
The invention also discloses a kind of preparation processes of the dialkyl dithio hypophosphites, to prepare dialkyl disulfides
For generation aluminum phosphate, specially：
(1) dialkyl dithio sodium hypophosphite solution is reacted in acid condition with aluminum sulfate solution, obtains dialkyl group
The suspension of dithiophosphlic acid aluminum precipitation object；
(2) suspension will be filtered, washed and dry, pulverize to certain grain size at 120 DEG C, obtain dialkyl disulfides
For hypo-aluminum orthophosphate combustion inhibitor.
It wherein, can be by commercially available acquisition, or by the following method as the dialkyl dithio sodium hypophosphite of raw material
It prepares：
(a) linear alkene exists in initiator with hydrogen phosphide and free radical can occur under certain temperature and pressure
Addition reaction generates dialkyl group hydrogen phosphide；
(b) dialkyl group hydrogen phosphide and sulfur reaction are generated into dialkyl dithio hypophosphorous acid；
(c) dialkyl dithio hypophosphorous acid is reacted with sodium hydroxide and generates dialkyl dithio hypophosphorous acid soluble easily in water
Sodium salt.
Dialkyl dithio hypophosphites be characterized in phosphorus content height, the also collaboration of element sulphur, good flame resistance, have compared with
High temperature of initial decomposition, water-soluble extremely low, resistance to migration is nonhygroscopic, is that a kind of novel can be applied to the engineerings such as nylon, polyester
In plastics, especially in the engineering plastics of fiberglass reinforced.Applied to TPE material, due to water-soluble extremely low, be not in the moisture absorption and
There is water stain problem, but due to being condensed phase fire retardant mechanism so that TPE material is easy drippage again in burning, reduces fire-retardant
Performance, if reaching flame-retardancy requirements by improving additive amount, can not can cause material by flame-retardancy requirements as defined in standard
The reduction of energy.
It wants development and application in the flame-retardant system based on dialkyl dithio hypophosphites of TPE, needs to reduce flame-retardant system
The temperature of decomposition mechanism is generated, and improves remaining carbon.For phosphorus flame retardant, charcoal source and air source collaboration are usually also needed to,
Preferable effect is can be only achieved, realizes the application in TPE.Charcoal source is carbon forming agent, and effect is easily to be dehydrated charcoal at high temperature
Change, high temperature dehydration process is an endothermic process, can lower the temperature of comburant, and the steam of generation can dilute the dense of oxygen
Degree, and formed layer of charcoal be one layer of compacted zone, can play the role of it is heat-insulated oxygen-impermeable, avoid burning development.
It can be low molecular compound as carbon forming agent, the usually compound of polyhydroxy, can also be macromolecule chemical combination
Object, but require water-soluble small, such as compounds such as pentaerythrite, match gram can also be sometimes for further decreasing water solubility
Hydroxyl shielding in these compounds forms the poly- of high molecular weight by carrying out condensation reaction with polyacid, such as phthalic acid
Ester substance had not only solved the water solubility problems of hydroxyl, but can increase with the compatibility of matrix resin, improve and mechanical property and avoid analysing
It goes wrong, and some high molecular polymers, the carbon forming agent as polyphenylene oxide (PPO) also can be used as TPE use.And in dialkyl disulfides
Generation phosphate flame retardants are applied in the polyester materials such as PET, and substrate polyester material inherently can be used as carbon forming agent use, therefore
There is synergistic effect.
And air source compound is then that can decompose generation non-combustible gas at high temperature, such as nitrogen, ammonia, carbon dioxide.
High-temperature decomposition reaction is typically the endothermic reaction, can reduce the temperature of comburant, is unfavorable for burning, and what is secondly generated largely can not
Combustion gas body can reduce oxygen concentration, while these gases can also allow matrix polymer to generate foaming effect, be formed by foaming
Layer also has iris action, is unfavorable for the diffusion of burning, plays fire-retardant effect.The air source compound used in the present invention for containing
Nitrogen source compound, preferably compound in triazine class, such as melamine, melamine cyanurate (MCA).
Inventor also found that the relative scale of each raw material is very crucial in halogen-free flame-retardant system, is related to cooperateing with by research
Can effect effectively generate.To further increase cooperative flame retardant effect, it is preferable that in the halogen-free flame-retardant system, dialkyl group two
The weight ratio of thio hypophosphites, carbon forming agent and diamond compound is 50%：25%：25%.
The invention also discloses the application of the compounding halogen-free flame-retardant system in preparing halogen-free flameproof TPE, by weight hundred
Divide than meter, the raw material composition of the halogen-free flameproof TPE includes：
The thermoplastic resin is selected from least one of polypropylene, polyethylene, polystyrene.
Preferably, it is described compounding halogen-free flame-retardant system additive amount by account for entire material system weight percent 30~
55%.
The invention also discloses the preparation processes of the halogen-free flameproof TPE, including：
(1) each raw material for compounding halogen-free flame-retardant system is mixed according to the ratio, successively through crushing and being surface-treated；
(2) by step (1) treated compounding halogen-free flame-retardant system mix with surplus stock, it is extruded be granulated obtain described in
Halogen-free flameproof TPE.
For TPE base materials, halogen-free flame-retardant system is a kind of additive flame retardant, is equivalent in matrix resin with filler
Pattern exists, therefore while ensureing anti-flammability, avoids the mechanical property for reducing material as possible.In order to ensure the mechanics of material
Performance, it is also necessary to the processing of two aspects is carried out to flame-retardant system：First, carrying out levigate crushing, the particle of fire retardant is reduced as possible
Grain size；Second is that the surface to fire retardant is handled, increase the lipophile on fire retardant surface.
A kind of filler of the flame-retardant system as matrix resin, the thinner grain graininess the better, but from engineering and application
Angle, if grain graininess reaches nano-scale, processing cost is very high, and is easy to reunite, and is difficult in matrix resin
It is uniformly dispersed；If fruit granule is too thick, then it can become the defect or weak link of material internal when being filled in matrix resin, be easy
Cause stress concentration, the mechanical property for the material that deteriorates significantly, therefore, the average grain diameter of the halogen-free flame-retardant system should be controlled 20
μm hereinafter, preferably 10 μm hereinafter, more preferably 5 μm or less.Meanwhile as filler, the maximum grain in particle should be also paid close attention to
Diameter is applied in thermoplastic elastomer (TPE), the nothing because the largest particles grain size is the key element for determining material mechanical performance
The particle maximum particle diameter of halogen flame-retardant system is controlled at 100 μm hereinafter, it is preferred that at 50 μm hereinafter, more preferably at 30 μm or less.
In the halogen-free flame-retardant system, although there is the alkyl of dialkyl dithio hypophosphites that there is lipophile, metal
Salt still has the hydrophily of part, still insufficient with the compatibility of matrix resin.In order to increase flame retardant constituent and TPE basis materials
Compatibility needs to be surface-treated halogen-free flame-retardant system, and the surfaces such as stearic acid, Aluminate, titanate esters, organosilicon can be selected
Inorganic agent coats, and the additive amount of surface conditioning agent is the 1~5% of halogen-free flame-retardant system total weight, preferably 2%.
For surface treatment process, it is necessary first to which heat up the halogen-free flame-retardant system, removes moisture content therein, because of moisture
Presence, the effect of surface treatment will be influenced, secondly need by adequately stirring, to allow surfactant to be evenly coated at fire-retardant
The surface of system.Its process is：
A) halogen-free flame-retardant system after crushing is warming up to 110 DEG C, be kept stirring, constant temperature 30min, remove the water in material
Point；
B) at such a temperature, surfactant is added, stirs 30min, completes surface treatment.
The halogen-free flameproof TPE material is prepared, also needs halogen-free flame-retardant system to be dispersed in TPE material, needs
Complete that solid-state is dry-mixed and melting mixing in an extruder.Since fire retardant is heat-sensitive substance, it is necessary to processing temperature is controlled, it is double
The maximum temperature of screw rod is no more than 230 DEG C, preferably at 220 DEG C or less.
Compared with prior art, the invention has the advantages that：
The present invention provides a kind of novel halogen-free flame-retardant systems applied to TPE material, based on dialkyl disulfides generation
Phosphorus nitrogen sulphur halogen-free flameproof compound system based on phosphate compounds has high fire-retardance, resistance to migration, nonhygroscopic and matrix TPE materials
Expect the features such as compatible.It can be applied in TPE, the halogen-free flameproof TPE material of preparation can reach the standard of UL94V0, and by the TPE
The electric wire of material preparation can reach the standard of VW-1, be used as in the high-grade consumer electronics such as electric wire, electric appliance field
Insulating materials.
Specific implementation mode
The preparation of diisobutyl dithiophosphlic acid aluminium
The sulphur of diisobutyl the dithiophosphlic acid sodium water solution 1392g and concentration 30wt% of compound concentration 20wt% respectively
Desalted water 1500g is added into reactor, and the sulfuric acid solution 75g of concentration 25wt% is added by sour aluminum solutions 228g, is warming up to 80
DEG C, start to synchronize dropwise addition diisobutyl dithiophosphlic acid sodium water solution and aluminum sulfate solution in proportion into reaction kettle, obtain
Diisobutyl dithiophosphlic acid aluminum precipitation object, is added dropwise to complete for 2 hours, keeps the temperature 1 hour, is then filtered, washed, dries, obtain
Diisobutyl dithiophosphlic acid aluminium fire retardant 254g (yield 97%).
After tested, 350 DEG C of the initial decomposition temperature of product, solubility is 0.02% in water；
Unless otherwise specified, the diisobutyl dithiophosphlic acid aluminium is all made of in following embodiment.
Embodiment 1
(1) compounding of halogen-free flame-retardant system and surface treatment
Levigate each material in the ball mill, about 5 μm of average grain diameter, 40 μm of maximum particle diameter.It is added according to the ratio in kneader
Advance load weighted diisobutyl dithiophosphlic acid aluminium, pentaerythrite and melamine, start stirring, and open heating unit
Material is warming up to 110 DEG C, keeps 30min, removes the moisture content in material, 2% Aluminate of material gross weight is then added, is mixed
Processing 20min is closed, the uniformly mixed compounding flame retardant being surface-treated is obtained.
(2) characterization of compounding flame retardant
Sampling carries out TGA tests, obtains temperature of the compounding flame retardant in weightlessness 2%, 5%, and on DTG curves
Obtain temperature when decomposition mechanism.
(3) performance test of application and material of the compounding flame retardant in TPE
(a) mixture of halogen-free flameproof TPE systems
It is stirred in machine in height and load weighted SEBS in advance is added, started low or first gear, white oil according to the ratio, object are pumped into metering pump
The control of material temperature degree is at 60 DEG C hereinafter, mixing 30min, allows the abundant oil suctions of SEBS, complete the oil-filled of SEBS.It adds according to the ratio in advance
Surface treated compounding flame retardant, polypropylene and the other auxiliary agents weighed up starts high-speed stirred, stirs 10min, completes
The mixture of halogen-free flameproof TPE systems, discharging.
(b) extruding pelletization of material
Each area's temperature setting of double screw extruder in predetermined temperature (215 DEG C of spiro rod plasticizing section maximum temperature), temperature is waited for
After stablizing 20min, the uniform halogen-free flameproof TPE systems of mixture are added from hopper, starts host and feeder, completes material
Extruding pelletization.The material for having made grain is sent into feed bin by blast system, and dries.
(c) application with test of material
The material dried is molded by the standard sample of various testing standard defineds in injection molding machine, and carries out correlation
The test of material property.
Each compounding flame retardant material and proportioning are shown in Table 1 in embodiment, and thermal weight loss characterization result is shown in Table 1.Compositional flame-retardant body
System is shown in Table 1 applied to the performance test results of the obtained composite materials of TPE.
Embodiment 2
Implementation process is same as Example 1, other than the carbon forming agent of flame-retardant system selects match gram.Respectively compounding resistance in embodiment
Combustion system material and proportioning are shown in Table 1, and thermal weight loss characterization result is shown in Table 1.Compounding flame retardant is applied to the obtained composite woods of TPE
The performance test results of material are shown in Table 1.
Embodiment 3
Implementation process is same as Example 1, other than the air source compound of flame-retardant system selects MCA.It is each multiple in embodiment
It is shown in Table 1 with flame-retardant system material and proportioning, thermal weight loss characterization result is shown in Table 1.It is obtained multiple that compounding flame retardant is applied to TPE
The performance test results of condensation material are shown in Table 1.
Embodiment 4
Implementation process is same as Example 1, other than carbon forming agent selects PPO.Each compounding flame retardant material in embodiment
And proportioning is shown in Table 1, thermal weight loss characterization result is shown in Table 1.The performance that compounding flame retardant is applied to the obtained composite materials of TPE is surveyed
Test result is shown in Table 1.
Comparative example 1
Implementation process is same as Example 1, each in this comparative example other than only using diisobutyl dithiophosphlic acid aluminium
Compounding flame retardant material and proportioning are shown in Table 1, and thermal weight loss characterization result is shown in Table 1.It is obtained that compounding flame retardant is applied to TPE
The performance test results of composite material are shown in Table 1.
Comparative example 2
Implementation process is same as Example 1, other than only using pentaerythrite, each compounding flame retardant object in this comparative example
Material and proportioning are shown in Table 1, and thermal weight loss characterization result is shown in Table 1.Compounding flame retardant is applied to the performance of the obtained composite materials of TPE
Test result is shown in Table 1.
Comparative example 3
Implementation process is same as Example 1, other than only using melamine, each compounding flame retardant object in this comparative example
Material and proportioning are shown in Table 1, and thermal weight loss characterization result is shown in Table 1.Compounding flame retardant is applied to the performance of the obtained composite materials of TPE
Test result is shown in Table 1.
Comparative example 4
Implementation process is same as Example 1, other than compounding flame retardant average particle size is 50 μm, in this comparative example
Each compounding flame retardant material and proportioning are shown in Table 1, and thermal weight loss characterization result is shown in Table 1.Compounding flame retardant is applied to obtained by TPE
The performance test results of composite material be shown in Table 1.
Table 1
Claims (10)
1. a kind of TPE based on dialkyl dithio hypophosphites compounding halogen-free flame-retardant systems, which is characterized in that by weight hundred
Divide than meter, raw material composition includes：
Dialkyl dithio hypophosphites 30~50%；
Carbon forming agent 20~30%；
Diamond compound 20~40%；
The dialkyl dithio hypophosphites, shown in structural formula such as following formula (I)：
In formula, R1、R2Independently selected from straight chained alkyl or branched alkyl, the carbon number of the straight chained alkyl or branched alkyl is 1~6；
M is selected from Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, H or NH4, m is 1~4.
2. the TPE according to claim 1 based on dialkyl dithio hypophosphites compounding halogen-free flame-retardant systems, special
Sign is, the dialkyl dithio hypophosphites, R1、R2Independently selected from methyl, ethyl, n-propyl, normal-butyl, isobutyl group,
Tertiary butyl, n-pentyl, isopentyl, n-hexyl or isohesyl；M is selected from Mg, Ca, Al, Sn, Ti or Zn.
3. the TPE according to claim 1 based on dialkyl dithio hypophosphites compounding halogen-free flame-retardant systems, special
Sign is that the carbon forming agent is selected from polyol and/or polyphenylene oxide.
4. the TPE according to claim 1 based on dialkyl dithio hypophosphites compounding halogen-free flame-retardant systems, special
Sign is that the diamond compound is selected from compound in triazine class.
5. a kind of halogen-free flameproof TPE, which is characterized in that use compounding halogen-free flameproof body according to any one of claims 1 to 4
System, which is characterized in that by weight percentage, the raw material composition of the halogen-free flameproof TPE includes：
6. halogen-free flameproof TPE according to claim 5, which is characterized in that the thermoplastic resin is selected from polypropylene, poly- second
At least one of alkene, polystyrene.
7. a kind of preparation process of halogen-free flameproof TPE according to claim 5 or 6, which is characterized in that including：
(1) each raw material for compounding halogen-free flame-retardant system is mixed according to the ratio, successively through crushing and being surface-treated；
(2) by step (1) treated compounding halogen-free flame-retardant system mixed with surplus stock, extruded granulation obtains the Halogen
Fire-retardant TPE.
8. the preparation process of halogen-free flameproof TPE according to claim 7, which is characterized in that in step (1), the compounding
Halogen-free flame-retardant system is crushed to average grain diameter and is less than 20 μm, and maximum particle diameter is less than 100 μm.
9. the preparation process of halogen-free flameproof TPE according to claim 7, which is characterized in that in step (1), the surface
Processing, specially：
First the compounding halogen-free flame-retardant system is dried, then surface-active is added into the compounding halogen-free flame-retardant system after drying
Agent is stirred well to surfactant and is evenly coated at compounding halogen-free flame-retardant system surface；
The surfactant is selected from least one of stearic acid, Aluminate, titanate esters, organosilicon；
The additive amount of the surfactant is the 1~5% of halogen-free flame-retardant system total weight.
10. the preparation process of halogen-free flameproof TPE according to claim 7, which is characterized in that in step (2), the extrusion
Granulation carries out in double screw extruder, and extrusion temperature is not higher than 230 DEG C.
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| CN1735653A (en) * | 2002-12-16 | 2006-02-15 | 通用电气公司 | Method for making fire-retarded glass-filled polycarbonate and related compositions |
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