CN107602924A - A kind of thermoplastic elastomer (TPE) Halogenless composite fire retardant and its application - Google Patents
A kind of thermoplastic elastomer (TPE) Halogenless composite fire retardant and its application Download PDFInfo
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- CN107602924A CN107602924A CN201710744139.0A CN201710744139A CN107602924A CN 107602924 A CN107602924 A CN 107602924A CN 201710744139 A CN201710744139 A CN 201710744139A CN 107602924 A CN107602924 A CN 107602924A
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- fire retardant
- thermoplastic elastomer
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- halogenless composite
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Abstract
The invention discloses a kind of thermoplastic elastomer (TPE) Halogenless composite fire retardant and its application.Organic hypophosphites system heatproof at present, the excellent performance of resistance to precipitation, but it is less efficient with traditional polyhydroxy base class carbon forming agent synergistic, and flame retardant effect is general.The percentage by weight of Halogenless composite fire retardant of the present invention forms：A) 20 40% organic hypophosphites；B) 2 5% Quadrafos；C) 1 5% PP catalysis carbon forming agents；D) 20 35% nanometer inorganic filler；E) 20 35% nitrogen-containing compound.The features such as Halogenless composite fire retardant of the present invention can apply to thermoplastic elastomer (TPE) fire proofing, high with flame retarding efficiency, resistance to migration, and compatibility is good, the thermoplastic elastomer (TPE) prepared using the flame-retardant system meet the standard that material can reach cable VW 1.
Description
Technical field
The present invention relates to composite flame-retardant agent, specifically a kind of thermoplastic elastomer (TPE) of efficient, resistance to migration is answered with Halogen
Close fire retardant and its application in flame-retardant thermoplastic elastomer is prepared.
Background technology
Thermoplastic elastomer (TPE) TPE/TPR, also known as artificial rubber, both possessed the high resiliency, ageing-resistant, resistance to of tradition crosslinking rubber
Oiliness items excellent properties, while but also with the characteristics of common plasticses are easy to process, processing mode is wide, effectively save energy consumption, drop
Low cost, it is the one-time process revolution of rubber materials.
But thermoplastic itself is there is also some shortcomings, wherein most fatal is exactly inflammability, to human life's safety
Very big potential safety hazard is brought, TPE is especially applied to wires and cables industry.In recent years, a large amount of researchers are to thermoplasticity
Elastomer has carried out flame-retardant modified research.From TPE own materials, PP and SEBS belong to ignitable components, therefore to reach
Flame-retardancy requirements, it is necessary to realized by adding fire retardant.Traditional bromine, antimony fire retardant have preferable flame retardant effect, but burn
When can produce substantial amounts of dense smoke and harmful substance, human body can be caused to suffocate.Therefore, to be that current TPE is fire-retardant grind halogen-free flame-retardant system
The important directions studied carefully.
The existing fire retardant additive without halogen applied to TPE is broadly divided into two major classes：(1) using SEBS and PP as base material, PPO makees
For carbon forming agent, then a certain amount of phosphorus, nitrogenated flame retardant are added, UL94V-0 flame-retardant standard can be reached, such as patent US200/
0088502A1, CN100509938C and CN100509938C.This kind of product is excellent into carbon performance because PPO has, to phosphorus,
The requirement of nitrogen systems fire retardant is relatively low, but because PPO itself uvioresistant performances are poor, easy xanthochromia, and processing characteristics is poor, institute
Limitation be present with application.(2) patent CN101629007A, CN101735546A, CN01955626A, CN103694499A,
The documents such as CN102146193A use different types of halogen-free expansion fire retardant, and APP, pentaerythrite system have preferably into carbon
Performance, but heatproof, the poor-performing of resistance to precipitation.Organic hypophosphites system heatproof, the excellent performance of resistance to precipitation, but with traditional polyhydroxy
Base class carbon forming agent synergistic is less efficient, and flame retardant effect is general.
The content of the invention
For problem present in above-mentioned existing TPE halogen-free flameproofs compound system, the present invention provides a kind of efficient, resistance to migration
Thermoplastic elastomer (TPE) Halogenless composite fire retardant.
Therefore, the present invention adopts the following technical scheme that：A kind of thermoplastic elastomer (TPE) Halogenless composite fire retardant, its weight
Percentage forms：A) 20-40% organic hypophosphites；B) 2-5% Quadrafos；C) 1-5% PP catalysis carbon forming agents；
D) 20-35% nanometer inorganic filler；E) 20-35% nitrogen-containing compound.
The present invention is based on the phosphorus-nitrogen type composite flame-retardant agent based on organic hypophosphite compound, it is therefore intended that is solved current
Organic hypophosphites system addition is big, flame retarding efficiency is low, the defects of easily separating out.New system can be well adapted for SEBS and PP
For the thermoplastic elastomer (TPE) of main body, the halogen-free flameproof TPE material of excellent performance is obtained.
The present invention by furtheing investigate the mutual synergistic effect between organic hypophosphites and Quadrafos, carbon forming agent, and
A BACN of exploitation.
Organic hypophosphites and Quadrafos can play fire retardation in condensed phase, promote into carbon, but organic secondary phosphorus
Hydrochlorate decomposition temperature is high, significantly larger than the decomposition temperature at initial stage of TPE base materials, decomposition temperature and the TPE comparison match of Quadrafos,
But due to being limited by Quadrafos structure, easily migrate in the product, by being added on a small quantity in organic hypophosphites
Quadrafos, fire retardant temperature of initial decomposition is reduced, can just participate in reacting when TPE starts and decomposed, improve the anti-flammability of system
Can, while by being screened to Quadrafos and surface modification, improve the hydrolysis property of Quadrafos itself, effectively solve poly-
The problem of phosphate easily separates out.
In existing TPE systems, two components of PP and SEBS all do not contain into the characteristic group of carbon, develop in the market
Halogenless composite fire retardant system all can additional carbon, improve the carbon yield of system, reduce the decomposition rate of product.Carbon source is general
Based on polyol, such as pentaerythritol derivative, match gram compound, this kind of substance decomposition temperature is relatively low, under high temperature
Easily dehydration carbonization, forms one layer of fine and close carbon-coating, plays a part of heat-insulated oxygen barrier.But polyol decomposition temperature is relatively low,
Poor water resistance, discoloration easily occurs in process.The present invention is catalyzed carbon forming agent, catalysis matrix material itself charing by adding PP
Form layer of charcoal and be covered in material surface, thus flammable catabolite is converted into non-flammable carbon-coating, makes combustible substance
Source is reduced, and the fire resistance of polymer also improves, and can effectively improve Flame Retardancy energy.
Nanometer inorganic filler can effectively improve the work of the thermal stability and fire resistance, particularly montmorillonite of polymer
Industry metaplasia is produced, and nano composite material is provided chance for the application of conventional flame retardant.Nanometer inorganic filler fires in composite
Sic acid salt deposit can be formed in material surface during burning, this structure can effectively serve as the transmission barrier of quality and heat,
Simultaneously because the structure has larger specific surface area, be advantageous to polymer catalyzing dehydrogenation and oxidative dehydrogenation and form conjugated alkene,
Suppress imflammable gas to overflow, promote its aromatic ring, charing.
Some nitrogen-containing compounds are added in system simultaneously, synergistic is carried out with organic hypophosphites and Quadrafos, passes through height
Temperature is decomposed, and is produced a large amount of non-combustible gas, can be reduced polymer surfaces oxygen content, while forms foaming layer of charcoal, preferably
The diffusion of heat and material is prevented, plays fire retardation.
As the supplement of above-mentioned technical proposal, described organic hypophosphites structural formula is：
In formula, R1And R2It is respectively and independently selected from C1-C6Straight or branched alkyl or aryl, n be 2 or 3, M be aluminium ion,
Magnesium ion, zinc ion or titanium ion, preferably aluminium ion or zinc ion.
As the supplement of above-mentioned technical proposal, described organic hypophosphites is alkyl hypophosphorous acid aluminium salt, alkyl hypophosphorous acid
Zinc salt or the above two mixture, preferably two base hypophosphorous acid aluminium salt, two base hypophosphorous acid zinc salt or the above two mixtures.
As the supplement of above-mentioned technical proposal, described Quadrafos is II type APPs, and the degree of polymerization is more than 1000, water
Dissolubility is less than 0.1g/100mL.
As the supplement of above-mentioned technical proposal, the PP catalysis carbon-formings agent is solid acid, preferably modified molecular screen, such as H-
Beta molecular sieves or HZSM-5 molecular sieves.
As the supplement of above-mentioned technical proposal, the nanometer inorganic filler is laminar silicic acid salt material, preferably organic to change
Property montmorillonite (OMMT), such as magnesium-based montmorillonite, calcium-base montmorillonite or sodium-based montmorillonite.
As the supplement of above-mentioned technical proposal, described nitrogen-containing compound is that can produce non-combustible gas under certain condition
The compound of (such as nitrogen, ammonia), such as MCA (melamine cyanurate), MPP (polyphosphoric acid melamine).
The Halogenless composite fire retardant is a kind of additive flame retardant, is existed in TPE matrix resins in the form of filler, because
This is when using the flame-retardant system, in addition to ensureing product and having preferable fire resistance, also to ensure that material is kept well
Mechanical property.In order to ensure the mechanical property of material, the fire retardant particle diameter is controlled in the present invention, ensures fire retardant energy
It is evenly dispersed into material, the defects of not causing material internal and weak link, the average grain diameter control of fire retardant is micro- 10
Rice is following, preferably less than 5 microns.
As the supplement of above-mentioned technical proposal, described Halogenless composite fire retardant also includes surface conditioning agent, its addition
Control is within the 5% of Halogenless composite fire retardant gross mass.It is surface-treated using surface conditioning agent, surface conditioning agent can be with
From surface modifiers such as aluminum stearate, aluminium titanates, organosilicon, maleic anhydride grafting compatilizer POE.
, will be above-mentioned it is a further object of the present invention to provide application of the above-mentioned Halogenless composite fire retardant in thermoplastic elastomer (TPE)
Halogenless composite fire retardant is extruded with thermoplastic elastic material mixed melting, and the addition of the Halogenless composite fire retardant is thermoplastic
The 25-50%, preferably 30-40% of property elastomer percentage by weight.
In order to strengthen the anti-aging and processing characteristics of thermoplastic elastomer (TPE), during melting extrusion can also add some adds
Work auxiliary agent, such as antioxidant, ultraviolet absorber, lubricant, the dosage of processing aid according to thermoplastic elastomer (TPE) be formulated into
Row adjustment.
The invention has the advantages that：Halogen-free flame retardants provided by the invention is overcome existing for existing flame-retardant system
Defect, there is high fire-retardance, resistance to migration, great thermotolerance, good with base material TPE compatibilities；The halogen-free flameproof TPE material of preparation,
The high-end consumer electronicses fields such as electric wire, electrical equipment can be used in.
Embodiment
The present invention is further illustrated below by embodiment, following examples are the preferable embodiment party of the present invention
Formula, but embodiments of the present invention are not limited by following embodiments.
Embodiment 1
(1) preparation of Halogenless composite fire retardant
25 parts of aluminum diethylphosphinate, 5 parts of APP, 5 parts of H-beta molecular sieves, 30 parts of (magnesium of organic modification montmonrillonite
Base montmorillonite), MCA35 parts.
It is accurate to weigh said components, then by way of machinery blends, above-mentioned fire retardant is sufficiently mixed uniformly, that is, obtained
Halogenless composite fire retardant.
(2) application of the composite flame retardant system in thermoplastic elastomer (TPE)
A. halogen-free flame-retardant thermoplastic elastomer TPE systems mixture
Add load weighted SEBS (25%), low speed in advance in homogenizer to start to stir, with measuring pump by proportioning
The white oil of suction 18%, 30min is sufficiently mixed, mixture temperature is maintained at 50 DEG C, ensures that white oil is fully absorbed by SEBS, completes
SEBS Oil feeding process.The Halogenless composite fire retardant (35%) and other auxiliary agents for add polypropylene (21%), being sufficiently mixed
(antioxidant 0.2%, silicone lubricant 0.8%), high-speed stirred 10min, complete the mixture of halogen-free flame-retardant thermoplastic elastomer.
B. the extruding pelletization of material
Set each zone temperatures of double screw extruder (120 DEG C of feeding section, 180 DEG C of melt zone, melt conveying zone 180-
190 DEG C, 200 DEG C of mixing section, 190 DEG C of homogenizing zone, 190 DEG C of head metering section), it is after temperature stabilization 20min, mixture is uniform
Halogen-free flame-retardant thermoplastic elastomer is added in hopper, starts main frame and feeding machine, completes the extruding pelletization of material.The particle made
Drying and processing is carried out, ensures that moisture is less than 0.3%.
C. the application of material and test
The material being baked is molded by injection machine the standard specimen of various testing standard defineds, phase is carried out to sample
Close performance test.
Composite flame retardant system is shown in Table 1 applied to the results of property of the composite obtained by TPE in embodiment.
Embodiment 2
Implementation process is same as Example 1, and Halogenless composite fire retardant is as follows：
23 parts of aluminum diethylphosphinate, 10 parts of diethyl phosphinic acids zinc, 2 parts of APP, HZSM-5 modified molecular screens 5
Part, organic modification montmonrillonite 20 parts (calcium-base montmorillonites), MCA40 parts.
The aluminum stearate that Halogenless composite fire retardant sample adds material gross weight 2% is surface-treated, and is warming up to 80 DEG C, height
Speed stirring 30min, obtains Halogen composite flame retardant system.Each material proportion and application the results are shown in Table shown in 1 in embodiment.
Embodiment 3
Implementation process is same as Example 1, and Halogenless composite fire retardant is as follows：
35 parts of aluminum diethylphosphinate, 1 part of APP, 2 parts of HZSM-5 modified molecular screens, 27 parts of organic modification montmonrillonite
(magnesium-based montmorillonite), MPP35 parts.
The maleic anhydride grafting compatilizer POE that Halogenless composite fire retardant sample adds material gross weight 5% is surface-treated,
100 DEG C are warming up to, high-speed stirred 30min, obtains Halogen composite flame retardant system.Each material proportion and application result are shown in embodiment
Shown in table 1.
Embodiment 4
Implementation process is same as Example 2, and Halogenless composite fire retardant is as follows：
20 parts of aluminum diethylphosphinate, 3 parts of APP, 1 part of H-beta modified molecular screens, 35 parts of organic modification montmonrillonite
(magnesium-based montmorillonite), MCA40 parts.
The Aluminate that Halogenless composite fire retardant sample adds material gross weight 1.5% is surface-treated, high-speed stirred
30min, obtain Halogen composite flame retardant system.Each material proportion and application the results are shown in Table shown in 1 in embodiment.
Embodiment 5
Implementation process is same as Example 2, and the composition of Halogenless composite fire retardant is as follows：
32 parts of diethyl phosphinic acids zinc, 4 parts of APP, 3 parts of H-beta modified molecular screens, 35 parts of organic modification montmonrillonite
(sodium-based montmorillonite), MCA26 parts.
Each material proportion and application the results are shown in Table shown in 1 in embodiment.
Embodiment 6
Implementation process is same as Example 4, and the composition of Halogenless composite fire retardant is as follows：
25 parts of aluminum diethylphosphinate, 3 parts of APP, 4 parts of HZSM-5 modified molecular screens, 35 parts of organic modification montmonrillonite
(magnesium-based montmorillonite), MPP35 parts.
The organosilicon modifier that Halogenless composite fire retardant sample adds material gross weight 2% is surface-treated, high-speed stirred
30min, obtain Halogen composite flame retardant system.Each material proportion and application the results are shown in Table shown in 1 in embodiment.
Table 1：Each raw material proportioning of embodiment and application performance
| Raw material proportioning/performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| SEBS | 25 | 27 | 25 | 23 | 24 | 22 |
| PP | 21 | 23 | 21 | 19 | 20 | 19 |
| White oil | 18 | 19 | 18 | 17 | 17 | 16 |
| Other auxiliary agents (antioxidant+lubricant) | 1 | 1 | 1 | 1 | 1 | 1 |
| Halogen composite flame retardant system | 35 | 30 | 35 | 40 | 38 | 42 |
| Fire resistance (UL94,1.6mm) | V0 | V-1 | V0 | V-0 | V-1 | V-0 |
| Tensile strength (MPa) | 13.4 | 14.2 | 13.8 | 13.2 | 13.6 | 13.3 |
| Elongation at break (%) | 396 | 380 | 380 | 420 | 400 | 410 |
| Resistance to migration (85 DEG C of water * 168h) | Without precipitation | Without precipitation | Without precipitation | Without precipitation | Without precipitation | Without precipitation |
Claims (10)
1. a kind of thermoplastic elastomer (TPE) Halogenless composite fire retardant, it is characterised in that its percentage by weight, which forms, is：a)20-
40% organic hypophosphites；B) 2-5% Quadrafos；C) 1-5% PP catalysis carbon forming agents；D) 20-35% nanometer nothing
Machine filler；E) 20-35% nitrogen-containing compound.
2. thermoplastic elastomer (TPE) Halogenless composite fire retardant according to claim 1, it is characterised in that described organic time
Phosphate structure formula is：
In formula, R1And R2It is respectively and independently selected from C1-C6Straight or branched alkyl or aryl, M be aluminium ion, magnesium ion, zinc ion
Or titanium ion, n are 2 or 3.
3. thermoplastic elastomer (TPE) Halogenless composite fire retardant according to claim 2, it is characterised in that described organic time
Phosphate is alkyl hypophosphorous acid aluminium salt, alkyl hypophosphorous acid zinc salt or the above two mixture.
4. thermoplastic elastomer (TPE) Halogenless composite fire retardant according to claim 1, it is characterised in that described polyphosphoric acid
Salt is II type APPs, and the degree of polymerization is more than 1000, and water solubility is less than 0.1g/100mL.
5. thermoplastic elastomer (TPE) Halogenless composite fire retardant according to claim 1, it is characterised in that the PP is catalyzed into
Charcoal agent is solid acid.
6. thermoplastic elastomer (TPE) Halogenless composite fire retardant according to claim 1, it is characterised in that the nano inorganic
Filler is laminar silicic acid salt material.
7. thermoplastic elastomer (TPE) Halogenless composite fire retardant according to claim 1, it is characterised in that described nitrogen
Compound is the compound that can produce non-combustible gas.
8. thermoplastic elastomer (TPE) Halogenless composite fire retardant according to claim 1, it is characterised in that the Halogen is compound
The average grain diameter of fire retardant is controlled within 10 microns.
9. thermoplastic elastomer (TPE) Halogenless composite fire retardant according to claim 1, it is characterised in that at also including surface
Agent is managed, its addition is controlled within the 5% of Halogenless composite fire retardant gross mass.
10. any one of the claim 1-9 Halogenless composite fire retardants are applied to thermoplastic elastomer (TPE), it is characterised in that described
The addition of Halogenless composite fire retardant is the 25-50% of thermoplastic elastomer (TPE) percentage by weight.
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| CN101717560A (en) * | 2009-11-06 | 2010-06-02 | 金发科技股份有限公司 | Halogen-free antiflaming polyester molding compound composite and preparation method thereof |
| US20140336325A1 (en) * | 2011-12-05 | 2014-11-13 | Clariant Finance (Bvi) Limited | Mixtures of Flame Protection Means Containing Flame Protection Means and Aluminium Phosphites, Method for Production and Use Thereof |
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