CN103396640B - A kind of super soft halogen-free flame-retardant thermoplastic elastomer and preparation method thereof - Google Patents
A kind of super soft halogen-free flame-retardant thermoplastic elastomer and preparation method thereof Download PDFInfo
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- CN103396640B CN103396640B CN201310289215.5A CN201310289215A CN103396640B CN 103396640 B CN103396640 B CN 103396640B CN 201310289215 A CN201310289215 A CN 201310289215A CN 103396640 B CN103396640 B CN 103396640B
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Abstract
Open a kind of super soft halogen-free flame-retardant thermoplastic elastomer of the present invention and preparation method thereof.Existing commercial thermoplastic elastomer is difficult to realize halogen-free flameproof and flexible unification.Elastomerics of the present invention is blend, and this blend comprises ethylene vinyl acetate cross-linking agent, ethylene vinyl acetate EVA, peroxide vulcanizing agent, fire retardant.The method is 1000:1000:0.1 ~ 5 by ethylene vinyl acetate EVM, ethylene vinyl acetate EVA and vulcanizing agent according to mass ratio, and 30 ~ 200 DEG C of dynamic vulcanizations are dry, obtained base-material; In base-material, add fire retardant, melt blending at 140 ~ 250 DEG C, discharging obtains elastomerics.Elastomerics of the present invention has flexible, excellent flame retardant properties, not halogen-containing, industry preparation is simple, processing is economical and callable advantage.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of eco-friendly thermoplastic elastic material, specifically a kind of flexibility is high, rebound resilience good and thermoplastic elastomer of halogen-free flameproof and preparation method thereof.
Background technology
Since the 1950's, the purposes of macromolecular material is increasingly extensive, and consumption increases sharply, and the fire hazard brought therefrom increases thereupon, causes the flame retardant regulation of macromolecular material to require also more and more higher.For reducing combustibility and the rate of flame propagation of macromolecular material, fire retardant is developed rapidly.Fire retardant at present for various macromolecular material has become the important macromolecular material additive being only second to softening agent.The inflammableness of reduction macromolecular material and flame propagation velocity are the basic demands to flame-retardant system.According to the burning feature of macromolecular material, various different modes can be adopted to block the carrying out of its combustion processes, thus reach fire-retardant object.
Halogen containing flame-retardant is one of maximum at present fire retardant, and the fire retardant that global electric wire product is used, about has 80 ﹪ to be bromide fire retardant.Fire retardant can meet the complete processing of various macromolecular material and the service requirements of flame retardant products, technical maturity, relative low price, but Halogen flame retarded polymeric material produces a large amount of cigarettes, toxic gas and corrosive gases when meeting fire or high temperature.Therefore, exploitation and use halogen-free flame retardants are the trend of fire retardant researchdevelopment.In the application aspect of inorganic combustion inhibitor, in order to reach good flame retardant effect, high amount of inorganic filler add the mechanical property greatly reducing material, for the practical application of material, had again a lot of difficulties and restriction.
Inorganic combustion inhibitor magnesium hydroxide (Mg (OH)
2) have Heat stability is good, non-volatile, do not separate out, do not produce toxic gas, not corrode processing equipment, smoke elimination effect obviously, the advantage such as low price, because its decomposition temperature is high and smoke elimination good, polyacrylic flame-retarded in there is critical role.But Mg (OH)
2addition more than 40%, just there is good flame retardant effect, high filler loading capacity is comparatively large to the loss of mechanical properties of material, easily produces molten drop when burning.By Mg (OH)
2composite with the fire retardant of Nitrogen-and Phosphorus-containing, utilize separately as the feature of fire retardant, the two self effect can be made, more can give full play to, cooperative flame retardant effect can be embodied.
Thermoplastic elastomer refers to the elasticity at normal temperatures with rubber, has the class elastomer material that plasticization is shaping under high temperature.Thermoplastic elastomer can adopt the complete processing of similar thermoplastic resin to come reprocessabilty and recycling.Thermoplastic elastomer is prepared from through dynamic vulcanization by thermoplastic resin and rubber usually, and rubber generation sulfuration in melt-processed process is also evenly dispersed in the external phase of thermoplastic resin as dispersed particle.Like this, the rubber domain after sulfuration provides elasticity and the flexibility of material, and thermoplastic resin matrix provides the melt-processable of material.Thermoplastic elastomer has the flexible resilient of rubber and the processability of plastics concurrently due to it, is used widely in fields such as electric wire, sealing, fenders.
The fire-retardant research of thermoplastic elastomer of numerous patent and bibliographical information.These researchs are mainly divided into two classes: a class uses traditional halogen flame, although good flame retardation effect, addition is lower, elastomeric performance well keeps, but this kind of material produces a large amount of cigarettes when meeting fire or high temperature, toxic gas and corrosive gases, be difficult to the demand meeting practical application; Another kind of is that the oxyhydroxide of environment for use close friend or nitrogen phosphorus are fire-retardant, but the addition of these fire retardants is very large, and high filler loading capacity is comparatively large to the loss of mechanical properties of material, and elastomeric flexibility is subject to great damage.For this reason, the matrix of the selection thermoplastic elastomer of the present invention's innovation and suitable flame-retardant system, successfully achieve the combination of thermoplastic elastomer flexibility and halogen-free flameproof, prepared a kind of novel super soft halogen-free flame-retardant thermoplastic elastomer.
Summary of the invention
The object of the invention is to be difficult to unified shortcoming for existing thermoplastic elastomer halogen-free flameproof and good mechanical properties (particularly flexible), provide the thermoplastic elastomer of good, flexible excellent, the halogen-free flame-retardance of a kind of mechanical property.
In order to achieve the above object, we select a kind of EVA-EVM thermoplastic elastomer of dynamic vulcanization as matrix, use halogen-free flameproof filler as fire retardant.
The super soft halogen-free flame-retardant thermoplastic elastomer of the present invention is the mixture of ethylene vinyl acetate cross-linking agent, ethylene vinyl acetate EVA, peroxide vulcanizing agent, fire retardant; Wherein the mass ratio of ethylene vinyl acetate cross-linking agent, ethylene vinyl acetate EVA, peroxide vulcanizing agent, fire retardant is (100 ~ 100.5): 100:(0 ~ 0.5): (2 ~ 240);
Described ethylene vinyl acetate cross-linking agent is the irregular multipolymer of structure shown in formula I or general formula II:
Formula I:
General formula II:
Wherein m, n, p, q are 10 ~ 5000; R group is sulphur, silylation or the phenol oligopolymer group containing epoxy group(ing).
Described fire retardant is nitrogen phosphorus expanding fire retardant, expanded graphite (EG), hydroxy silicon oil (HSO), aluminium hydroxide (ATH), magnesium hydroxide (MH), polynite (MMT), zinc borate (FB), silica gel, silicone powder, micro encapsulation process red phosphorus; Nitrogen phosphorus expanding fire retardant is all nitrogen phosphorus expanding fire retardants.
Another object of the present invention is to provide a kind of method preparing this super soft halogen-free flame-retardant thermoplastic elastomer, and the present invention is by having the novel thermoplastic elastomer of flame retardant resistance by fire retardant and the blended preparation of base molten.The method concrete steps are:
Step (1). be 1000:1000:0.1 ~ 5 by ethylene vinyl acetate EVM, ethylene vinyl acetate EVA and vulcanizing agent according to mass ratio, dynamic vulcanization 1 ~ 5 minute at 30 DEG C ~ 200 DEG C, dry, obtained base-material;
In described ethylene vinyl acetate EVM, the mass content of vinyl acetate is 50 ~ 80 ﹪; In described ethylene vinyl acetate EVA, the mass content of vinyl acetate is 5 ~ 40 ﹪;
Described vulcanizing agent is the one in sulphur, peroxide vulcanizing agent, silane containing hydrogen vulcanizing agent, resin curing agent; Wherein peroxide vulcanizing agent is all peroxide vulcanizing agents, and silane containing hydrogen vulcanizing agent is all silane containing hydrogen vulcanizing agents, and resin curing agent is all resin curing agents;
When vulcanizing agent is peroxide vulcanizing agent, peroxide vulcanizing agent just plays merely the effect providing free radical, forms cancellated ethylene vinyl acetate cross-linking agent between ethylene vinyl acetate EVM; When vulcanizing agent is sulphur, resin curing agent or silane containing hydrogen vulcanizing agent, there is graft reaction in this vulcanizing agent and ethylene vinyl acetate EVM, and then forms cancellated ethylene vinyl acetate cross-linking agent;
As preferably, described dynamic vulcanization temperature is 50 DEG C ~ 180 DEG C.
Step (2). in base-material, add fire retardant, melt blending 5 ~ 10min at 140 ~ 250 DEG C, discharging obtains super soft halogen-free flame-retardant thermoplastic elastomer; The mass ratio of ethylene vinyl acetate EVM that wherein fire retardant and step (1) add is 1 ~ 120:50;
Described fire retardant is one or more in nitrogen phosphorus expanding fire retardant, expanded graphite (EG), hydroxy silicon oil (HSO), aluminium hydroxide (ATH), magnesium hydroxide (MH), polynite (MMT), zinc borate (FB), silica gel, silicone powder, micro encapsulation process red phosphorus; Nitrogen phosphorus expanding fire retardant is all nitrogen phosphorus expanding fire retardants;
Described melt blending and dynamic vulcanization all adopt single screw extrusion machine, twin screw extruder, Banbury mixer or reciprocating singe screw pin forcing machine (being called for short Buss machine), the screw speed of screw extrusion press is 60r/min ~ 180r/min, the rotor speed of Banbury mixer is 60r/min ~ 180r/min, and the screw speed of reciprocating singe screw pin forcing machine (being called for short Buss machine) is 60r/min ~ 180r/min.
The matrix of the selection thermoplastic elastomer of novelty of the present invention and suitable flame-retardant system, successfully achieve the combination of thermoplastic elastomer flexibility and halogen-free flameproof, prepared a kind of mechanical property good, the super soft halogen-free flame-retardant thermoplastic elastomer of excellent fireproof performance.Rubber cable is prepared, in multiple fields widespread uses such as electronics, building materials, automobiles by forming technology.The advantage that processing economy and returnability have thermo-setting elastomer incomparable.Elastomerics of the present invention has flexible, excellent flame retardant properties, not halogen-containing, industry preparation is simple, processing is economical and callable advantage.
Accompanying drawing explanation
Fig. 1 is the stress strain diagrm of comparative example 2 and embodiment 1,2,8;
Fig. 2 is the stress strain diagrm of comparative example 2 and embodiment 3,4,5;
Fig. 3 is the comparative example 1 elastomerics heat release rate obtained with embodiment 2,4,7,8 and the graphic representation of time;
Fig. 4 is the comparative example 1 elastomerics total release of heat obtained with embodiment 2,4,7,8 and the graphic representation of time;
Fig. 5 is that the elastomeric mass that comparative example 1 and embodiment 2,4,7,8 obtain loses the graphic representation with the time;
Fig. 6 is the comparative example 1 cigarette rate of release obtained with embodiment 2,4,7,8 and the graphic representation of time;
Fig. 7 is the comparative example 1 CO rate of release obtained with embodiment 2,4,7,8 and the graphic representation of time;
Fig. 7,8 is the CO that comparative example 1 obtains with embodiment 2,4,7,8 respectively
2the graphic representation of rate of release and time.
Embodiment
Below in conjunction with embodiment and accompanying drawing for further analysis to the present invention.
Comparative example 1
At 160 DEG C, 50gEVM, 50gEVA and 0.1g dicumyl peroxide DCP being joined rotor speed is the Banbury mixer dynamic vulcanization of 80r/min after 5 minutes, and discharging obtains thermoplastic elastomer.
In the thermoplastic elastomer that comparative example 1 is obtained, the mass ratio of ethylene vinyl acetate cross-linking agent, ethylene vinyl acetate EVA, dicumyl peroxide DCP is 50:50:0.1.
Comparative example 2
At 160 DEG C, 25gEVA and 25g magnesium hydroxide is joined the Banbury mixer melt blending 5min that rotor speed is 80r/min, discharging obtains bittern-free flame-proof material;
In the bittern-free flame-proof material that comparative example 2 is obtained, the mass ratio of ethylene vinyl acetate EVA, fire retardant magnesium hydroxide is 50:50.
Embodiment 1
Step (1). by 50g ethylene vinyl acetate EVM, 50g ethylene vinyl acetate EVA and 0.01g dicumyl peroxide DCP, at 160 DEG C, join rotor speed is the Banbury mixer dynamic vulcanization of 80r/min after 5 minutes, dry, obtained base-material.
At step (2) .160 DEG C, 25g base-material and 25g aluminium hydroxide are joined the Banbury mixer melt blending 5min that rotor speed is 80r/min, discharging obtains super soft halogen-free flame-retardant thermoplastic elastomer;
In the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 1 is obtained, the mass ratio of ethylene vinyl acetate cross-linking agent, ethylene vinyl acetate EVA, dicumyl peroxide DCP, fire retardant is 50:50:0.01:100; This fire retardant is aluminium hydroxide.
Embodiment 2
Step (1). identical with the experiment condition of embodiment 1, obtained base-material;
At step (2) .160 DEG C, 25g base-material and 25g magnesium hydroxide are joined the Banbury mixer melt blending 5min that rotor speed is 80r/min, discharging obtains super soft halogen-free flame-retardant thermoplastic elastomer;
In the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 2 is obtained, the mass ratio of ethylene vinyl acetate cross-linking agent, ethylene vinyl acetate EVA, dicumyl peroxide DCP, fire retardant is 50:50:0.01:100.This fire retardant is magnesium hydroxide.
Embodiment 3
Step (1). identical with the experiment condition of embodiment 1, obtained base-material;
At step (2) .160 DEG C, 25g base-material, 24g magnesium hydroxide, 1g nitrogen phosphorus expanding fire retardant NP-P20X are joined the Banbury mixer melt blending 5min that rotor speed is 80r/min, and discharging obtains super soft halogen-free flame-retardant thermoplastic elastomer;
In the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 3 is obtained, the mass ratio of ethylene vinyl acetate cross-linking agent, ethylene vinyl acetate EVA, dicumyl peroxide DCP, fire retardant is 50:50:0.01:100; This fire retardant is magnesium hydroxide, nitrogen phosphorus expanding fire retardant NP-P20X.
Embodiment 4
Step (1). identical with the experiment condition of embodiment 1, obtained base-material;
At step (2) .160 DEG C, 25g base-material, 23g magnesium hydroxide, 2g nitrogen phosphorus expanding fire retardant NP-P20X are joined the Banbury mixer melt blending 5min that rotor speed is 80r/min, and discharging obtains super soft halogen-free flame-retardant thermoplastic elastomer;
In the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 4 is obtained, the mass ratio of ethylene vinyl acetate cross-linking agent, ethylene vinyl acetate EVA, dicumyl peroxide DCP, fire retardant is 50:50:0.01:100; This fire retardant is magnesium hydroxide, nitrogen phosphorus expanding fire retardant NP-P20X.
Embodiment 5
Step (1). identical with the experiment condition of embodiment 1, obtained base-material;
At step (2) .160 DEG C, 25g base-material, 20g magnesium hydroxide, 5g nitrogen phosphorus expanding fire retardant NP-P20X are joined the Banbury mixer melt blending 5min that rotor speed is 80r/min, and discharging obtains super soft halogen-free flame-retardant thermoplastic elastomer;
In the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 5 is obtained, the mass ratio of ethylene vinyl acetate cross-linking agent, ethylene vinyl acetate EVA, dicumyl peroxide DCP, fire retardant is 50:50:0.01:100; This fire retardant is magnesium hydroxide, nitrogen phosphorus expanding fire retardant NP-P20X.
Embodiment 6
Step (1). identical with the experiment condition of embodiment 1, obtained base-material;
At step (2) .160 DEG C, 25g base-material, 15g magnesium hydroxide, 10g nitrogen phosphorus expanding fire retardant NP-P20X are joined the Banbury mixer melt blending 5min that rotor speed is 80r/min, and discharging obtains super soft halogen-free flame-retardant thermoplastic elastomer;
In the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 6 is obtained, the mass ratio of ethylene vinyl acetate cross-linking agent, ethylene vinyl acetate EVA, dicumyl peroxide DCP, fire retardant is 50:50:0.01:100; This fire retardant is magnesium hydroxide, nitrogen phosphorus expanding fire retardant NP-P20X.
Embodiment 7
Step (1). identical with the experiment condition of embodiment 1, obtained base-material;
At step (2) .160 DEG C, 25g base-material, 5g magnesium hydroxide, 20g nitrogen phosphorus expanding fire retardant NP-P20X are joined the Banbury mixer melt blending 5min that rotor speed is 80r/min, and discharging obtains super soft halogen-free flame-retardant thermoplastic elastomer;
In the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 7 is obtained, the mass ratio of ethylene vinyl acetate cross-linking agent, ethylene vinyl acetate EVA, dicumyl peroxide DCP, fire retardant is 50:50:0.01:100; This fire retardant is magnesium hydroxide, nitrogen phosphorus expanding fire retardant NP-P20X.
Embodiment 8
Step (1). identical with the experiment condition of embodiment 1, obtained base-material;
At step (2) .160 DEG C, 25g base-material, 25g nitrogen phosphorus expanding fire retardant NP-P20X are joined the Banbury mixer melt blending 5min that rotor speed is 80r/min, and discharging obtains super soft halogen-free flame-retardant thermoplastic elastomer;
In the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 8 is obtained, the mass ratio of ethylene vinyl acetate cross-linking agent, ethylene vinyl acetate EVA, dicumyl peroxide DCP, fire retardant is 50:50:0.01:100; This fire retardant is nitrogen phosphorus expanding fire retardant NP-P20X.
By bittern-free flame-proof material obtained for comparative example 2, the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 1,2,8 obtains is hot pressed into sheet in the thermocompressor of 180 DEG C, carries out Mechanics Performance Testing with standard dog bone punching press cutter preparation standard test batten.
From Fig. 1, table one, the bittern-free flame-proof material elongation at break that comparative example 2 obtains, breaking tenacity are all very low, the elastomerics that embodiment 1,2,8 obtains all has good mechanical property, that elongation at break or breaking tenacity are all well a lot of than comparative example, the elongation at break of the super soft halogen-free flame-retardant thermoplastic elastomer of the present invention is described, breaking tenacity, and the excellence that its flexibility is all suitable.
The tension fracture data sheet of the obtained product of table one embodiment 1,2,8
By bittern-free flame-proof material obtained for comparative example 2, the super soft Halogen composite flame-proof thermoplastic elastomer that embodiment 3,4,5 obtains is hot pressed into sheet in the thermocompressor of 180 DEG C, carries out Mechanics Performance Testing with standard dog bone punching press cutter preparation standard test batten.
From Fig. 2, table two, the bittern-free flame-proof material elongation at break that comparative example 2 obtains, breaking tenacity are all very low, the elastomerics that embodiment 3,4,5 obtains all has fabulous mechanical property, elastomeric mechanical property compared with single a kind of fire retardant gained also will be got well, and illustrates that in the super soft halogen-free flame-retardant thermoplastic elastomer of the present invention, compositional flame-retardant also has good effect.
The tension fracture data sheet of the obtained product of table two embodiment 3,4,5
By comparative example 1, the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 1 ~ 8 obtains makes batten by injection moulding, with the oxygen index of oxygen index measurer test material.
As shown in Table 3, the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 1 ~ 8 is obtained has good flame retardant properties.The limiting oxygen index(LOI) that the present invention with the addition of the super soft halogen-free flame-retardant thermoplastic elastomer of halogen-free flame retardants is significantly improved, and improves 10 more than ﹪; And the flame retardant properties of the super soft halogen-free flame-retardant thermoplastic elastomer of the present invention obtains obvious improvement.
Table three comparative example 1, the limiting oxygen index(LOI) data sheet of the obtained product of embodiment 1 ~ 8
As shown in Table 3, the limiting oxygen index(LOI) of embodiment 3 is the highest.
Fig. 3 is the comparative example 1 elastomerics heat release rate obtained with embodiment 2,4,7,8 and the graphic representation of time, and heat release rate is the important parameter of when characterizing fire generation.Comparative example 1 obtained super soft halogen-free flame-retardant thermoplastic elastomer heat release rate time, and its maximum heat rate of release was all to 295 (kW/M the earliest
2), very easily burn, the super soft halogen-free flame-retardant thermoplastic elastomer heat release rate peak value that embodiment 2,4,7,8 obtains obviously reduces, and is respectively 200 (kW/M
2), 140 (kW/M
2), 147 (kW/M
2), 175 (kW/M
2).Flame retardant effect promotes obviously, and in embodiment 2,4,7,8, the elastomeric peak value of a kind of fire retardant gained that the heat release rate peakedness ratio of the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 4,7 is obtained is single is low, and this flame retardant properties further illustrating again compositional flame-retardant gained thermoplastic elastomer is more excellent.Embodiment 4,7 all adds two kinds of different fire retardants, cooperative flame retardant, and 2 HRR peak values appear in obtained super soft halogen-free flame-retardant thermoplastic elastomer.Occur that 2 HRR peak values are caused by the carbon-coating structure release non-combustible gas due to burning formation.Before the carbon-coating expanded is formed, there is first HRR peak, after carbon-coating is formed, limited thermal source and extraneous releasing, completely cut off the transmission of quality and heat.The formation of carbon-coating act as the effect of a barrier, is a good radiating insulating layer.But there is again a HRR peak afterwards, this is the crack because carbon-coating occurs, or even break, therefore there is again secondary HRR peak, the super soft halogen-free flame-retardant thermoplastic elastomer that comparing embodiment 4,7 is obtained, be no matter its heat release rate, Thermal release total amount or carbon-coating surface, we can find that the flame retardant resistance of embodiment 4 is better than embodiment 7.Relative to comparative example 1, the flame retardant properties of the super soft halogen-free flame-retardant thermoplastic elastomer that the inventive method prepares is significantly improved.
Fig. 4 is the comparative example 1 elastomerics total release of heat obtained with embodiment 2,4,7,8 and the graphic representation of time.The Thermal release total amount of comparative example 1 is quite large as seen from Figure 4, reaching 70(MJ/m2) the Thermal release total amount of super soft halogen-free flame-retardant thermoplastic elastomer for preparing of embodiment 2,4,7,8 is all very low, only has 24.47(MJ/m2 respectively), 24.1(MJ/m2), 27.5(MJ/m2), 27.6(MJ/m2), wherein the Thermal release total amount of embodiment 4 is minimum.Relative to comparative example 1, the flame retardant properties of the super soft halogen-free flame-retardant thermoplastic elastomer that the inventive method prepares is significantly improved.
Fig. 5 is that the elastomeric mass that comparative example 1 and embodiment 2,4,7,8 obtain loses the graphic representation with the time.As seen from the figure, the super soft halogen-free flame-retardant thermoplastic elastomer thermostability that the present invention with the addition of halogen-free flame retardants significantly improves.Embodiment 4 is larger with the residual quantity of embodiment 8, shows that carbon-coating is more closely knit.Further, after 300s, the mass loss of embodiment 4 is also fewer than embodiment 8, shows that the flame retardant properties of embodiment 4 is better than embodiment 8.Relative to comparative example 1, the flame retardant properties of the super soft halogen-free flame-retardant thermoplastic elastomer that the inventive method prepares is significantly improved.
Fig. 6 is the comparative example 1 cigarette rate of release obtained with embodiment 2,4,7,8 and the graphic representation of time.The cigarette rate of release of the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 2,4,7,8 prepares is all very low, and wherein the cigarette rate of release of embodiment 4 is minimum.Relative to comparative example 1, the smoke-suppressing of the super soft halogen-free flame-retardant thermoplastic elastomer that the inventive method prepares is significantly improved.
Fig. 7,8 is the CO that comparative example 1 obtains with embodiment 2,4,7,8, CO respectively
2rate of release and the graphic representation of time, CO, CO of the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 2,4,7,8 prepares
2rate of release is obtained for effective control, and wherein the rate of release of embodiment 2 is minimum.Relative to comparative example 1, the flame retardant properties of the super soft halogen-free flame-retardant thermoplastic elastomer that the inventive method prepares is significantly improved.
The flame retardant properties excellence very of the super soft halogen-free flame-retardant thermoplastic elastomer prepared by the known the present invention in Fig. 3 ~ 8, and when adding the fire retardant of same ratio, good better than the effect of single a kind of fire retardant of the effect of composite flame-proof.
Embodiment 9
Step (1). by 100g ethylene vinyl acetate EVM, 100g ethylene vinyl acetate EVA and 0.01g sulphur, at 30 DEG C, join the single screw extrusion machine dynamic vulcanization 5 minutes that screw speed is 60r/min, dry, obtained base-material;
Step (2). in base-material, add 2g expanded graphite, join the single screw extrusion machine melt blending 10min that screw speed is 60r/min at 140 DEG C, discharging obtains super soft halogen-free flame-retardant thermoplastic elastomer;
In the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 9 is obtained, the mass ratio of ethylene vinyl acetate cross-linking agent, ethylene vinyl acetate EVA, fire retardant is 100.01:100:2; This fire retardant is expanded graphite.
Embodiment 10
Step (1). by 100g ethylene vinyl acetate EVM, 100g ethylene vinyl acetate EVA and 0.1g epoxy resin, at 100 DEG C, join the single screw extrusion machine dynamic vulcanization 3 minutes that screw speed is 100r/min, dry, obtained base-material;
Step (2). in base-material, add 5g hydroxy silicon oil, join the single screw extrusion machine melt blending 8min that screw speed is 100r/min at 200 DEG C, discharging obtains super soft halogen-free flame-retardant thermoplastic elastomer;
In the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 10 is obtained, the mass ratio of ethylene vinyl acetate cross-linking agent, ethylene vinyl acetate EVA, fire retardant is 100.1:100:5; This fire retardant is hydroxy silicon oil.
Embodiment 11
Step (1). by 100g ethylene vinyl acetate EVM, 100g ethylene vinyl acetate EVA and 0.2g two-(tert-butylperoxyiso-propyl) benzene BIPB, the single screw extrusion machine dynamic vulcanization 1 minute that screw speed is 180r/min is joined at 200 DEG C, drying, obtained base-material;
Step (2). in base-material, add 50g polynite, join the single screw extrusion machine melt blending 5min that screw speed is 180r/min at 250 DEG C, discharging obtains super soft halogen-free flame-retardant thermoplastic elastomer;
In the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 11 is obtained, the mass ratio of ethylene vinyl acetate cross-linking agent, ethylene vinyl acetate EVA, fire retardant is 100.2:100:50; This fire retardant is nitrogen phosphorus expanding fire retardant NP-P20X.
Embodiment 12
Step (1). by 100g ethylene vinyl acetate EVM, 100g ethylene vinyl acetate EVA and 0.3g tertiary butyl phenol urea formaldehyde, at 30 DEG C, join the Banbury mixer dynamic vulcanization 5 minutes that rotor speed is 60r/min, dry, obtained base-material;
Step (2). in base-material, add 100g zinc borate, join the Banbury mixer melt blending 10min that rotor speed is 60r/min at 140 DEG C, discharging obtains super soft halogen-free flame-retardant thermoplastic elastomer;
In the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 12 is obtained, the mass ratio of ethylene vinyl acetate cross-linking agent, ethylene vinyl acetate EVA, fire retardant is 100.3:100:100; This fire retardant is zinc borate.
Embodiment 13
Step (1). by 100g ethylene vinyl acetate EVM, 100g ethylene vinyl acetate EVA and 0.4g resol, at 100 DEG C, join the Banbury mixer dynamic vulcanization 3 minutes that rotor speed is 100r/min, dry, obtained base-material;
Step (2). in base-material, add 150g silica gel, join the Banbury mixer melt blending 8min that rotor speed is 100r/min at 200 DEG C, discharging obtains super soft halogen-free flame-retardant thermoplastic elastomer;
In the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 13 is obtained, the mass ratio of ethylene vinyl acetate cross-linking agent, ethylene vinyl acetate EVA, fire retardant is 100.4:100:150; This fire retardant is silica gel.
Embodiment 14
Step (1). by 100g ethylene vinyl acetate EVM, 100g ethylene vinyl acetate EVA and 0.5g epoxy resin, at 200 DEG C, join the Banbury mixer dynamic vulcanization 1 minute that rotor speed is 180r/min, dry, obtained base-material;
Step (2). in base-material, add 200g silicone powder, join the Banbury mixer melt blending 5min that rotor speed is 180r/min at 250 DEG C, discharging obtains super soft halogen-free flame-retardant thermoplastic elastomer;
In the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 14 is obtained, the mass ratio of ethylene vinyl acetate cross-linking agent, ethylene vinyl acetate EVA, fire retardant is 100.5:100:200; This fire retardant is silicone powder.
Embodiment 15
Step (1). by 100g ethylene vinyl acetate EVM, 100g ethylene vinyl acetate EVA and 0.5g sulphur, at 200 DEG C, join the reciprocating singe screw pin forcing machine dynamic vulcanization 1 minute that screw speed is 60r/min, dry, obtained base-material;
Step (2). in base-material, add 240g micro encapsulation process red phosphorus, join the reciprocating singe screw pin forcing machine melt blending 5min that screw speed is 60r/min at 250 DEG C, discharging obtains super soft halogen-free flame-retardant thermoplastic elastomer;
In the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 15 is obtained, the mass ratio of ethylene vinyl acetate cross-linking agent, ethylene vinyl acetate EVA, fire retardant is 100.5:100:240; This fire retardant is micro encapsulation process red phosphorus.
Embodiment 16
Step (1). by 100g ethylene vinyl acetate EVM, 100g ethylene vinyl acetate EVA and 0.5g epoxy resin, the reciprocating singe screw pin forcing machine dynamic vulcanization 3 minutes that screw speed is 100r/min is joined at 100 DEG C, drying, obtained base-material;
Step (2). in base-material, add 23g magnesium hydroxide, 2g polynite (MMT), join the reciprocating singe screw pin forcing machine melt blending 8min that screw speed is 100r/min at 200 DEG C, discharging obtains super soft halogen-free flame-retardant thermoplastic elastomer;
In the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 16 is obtained, the mass ratio of ethylene vinyl acetate cross-linking agent, ethylene vinyl acetate EVA, fire retardant is 100.5:100:25; This fire retardant is magnesium hydroxide, polynite (MMT).
Embodiment 17
Step (1). by 100g ethylene vinyl acetate EVM, 100g ethylene vinyl acetate EVA and 0.1g two-(tert-butylperoxyiso-propyl) benzene BIPB, the reciprocating singe screw pin forcing machine dynamic vulcanization 5 minutes that screw speed is 180r/min is joined at 30 DEG C, drying, obtained base-material;
Step (2). in base-material, add 20g aluminium hydroxide (ATH), 2g expanded graphite (EG), join the reciprocating singe screw pin forcing machine melt blending 10min that screw speed is 180r/min at 140 DEG C, discharging obtains super soft halogen-free flame-retardant thermoplastic elastomer;
In the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 17 is obtained, the mass ratio of ethylene vinyl acetate cross-linking agent, ethylene vinyl acetate EVA, fire retardant is 100.1:100:22; This fire retardant is aluminium hydroxide (ATH), expanded graphite (EG).
Embodiment 18
Step (1). by 100g ethylene vinyl acetate EVM, 100g ethylene vinyl acetate EVA and 0.1g dicumyl peroxide DCP, the twin screw extruder dynamic vulcanization 5 minutes that screw speed is 60r/min is joined at 50 DEG C, drying, obtained base-material;
Step (2). in base-material, add 100g aluminium hydroxide (ATH), 100g magnesium hydroxide (MH), 10g polynite (MMT), join the twin screw extruder melt blending 10min that screw speed is 180r/min at 140 DEG C, discharging obtains super soft halogen-free flame-retardant thermoplastic elastomer;
In the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 18 is obtained, the mass ratio of ethylene vinyl acetate cross-linking agent, ethylene vinyl acetate EVA, dicumyl peroxide DCP, fire retardant is 100:100:0.1:210; This fire retardant is aluminium hydroxide (ATH), magnesium hydroxide (MH), polynite (MMT).
Embodiment 19
Step (1). by 100g ethylene vinyl acetate EVM, 100g ethylene vinyl acetate EVA and 0.5g dicumyl peroxide DCP, the twin screw extruder dynamic vulcanization 2 minutes that screw speed is 180r/min is joined at 180 DEG C, drying, obtained base-material;
Step (2). in base-material, add 20g magnesium hydroxide (MH), 1g polynite (MMT), 1g nitrogen phosphorus expanding fire retardant NP-P20X, join the twin screw extruder melt blending 5min that screw speed is 180r/min at 220 DEG C, discharging obtains super soft halogen-free flame-retardant thermoplastic elastomer;
In the super soft halogen-free flame-retardant thermoplastic elastomer that embodiment 19 is obtained, the mass ratio of ethylene vinyl acetate cross-linking agent, ethylene vinyl acetate EVA, dicumyl peroxide DCP, fire retardant is 100:100:0.5:22; This fire retardant is magnesium hydroxide (MH), polynite (MMT), nitrogen phosphorus expanding fire retardant NP-P20X.
Above-described embodiment EVM used is that bright Sheng is produced, and in EVM, the mass content of vinyl acetate is 50 ﹪, and melt flow rate (MFR) is 10g/min; The model of EVA is the mass content of vinyl acetate in ELVAX750, EVA is 9 ﹪, and melt flow rate (MFR) is 7g/min; The model of nitrogen phosphorus expanding fire retardant is NP-P20X, the halogen-free environment-friendly fire retardant be the up-to-date research and development of Japanese Shen Chuan KCC a kind of being ignition-proof element with phosphorus, nitrogen; The model of flame retardant of magnesium hydroxide is MAGNIFINH-5, Albemarle Corporation of U.S. product; The model of aluminium hydroxide fire retardant is YH-10, from Shandong Zibo credit and Trade Co., Ltd.; Dicumyl peroxide DCP is Shanghai Fang Rui and reaches Chemical Company's production; In embodiment used, the performance test of gained mechanics of elastic bodies uses instrument to be InstronUniversal Testing Machine; Use dumbbell shape sample, test by GB/T-528-98 standard.
Above-described embodiment is not that the present invention is not limited only to above-described embodiment for restriction of the present invention, as long as meet application claims, all belongs to protection scope of the present invention.
Claims (3)
1. a preparation method for super soft halogen-free flame-retardant thermoplastic elastomer, is characterized in that the method is:
Step (1). be 1000:1000:0.1 ~ 5 by ethylene vinyl acetate EVM, ethylene vinyl acetate EVA and vulcanizing agent according to mass ratio, dynamic vulcanization 1 ~ 5 minute at 30 DEG C ~ 200 DEG C, dry, obtained base-material;
In described ethylene vinyl acetate EVM, the mass content of vinyl acetate is 50 ~ 80 ﹪; In described ethylene vinyl acetate EVA, the mass content of vinyl acetate is 5 ~ 40 ﹪;
Step (2). in base-material, add fire retardant, melt blending 5 ~ 10min at 140 ~ 250 DEG C, discharging obtains super soft halogen-free flame-retardant thermoplastic elastomer; The mass ratio of ethylene vinyl acetate EVM that wherein fire retardant and step (1) add is 1 ~ 120:50;
Described vulcanizing agent is the one in sulphur, peroxide vulcanizing agent, silane containing hydrogen vulcanizing agent, resin curing agent;
When vulcanizing agent is peroxide vulcanizing agent, peroxide vulcanizing agent just plays merely the effect providing free radical, forms cancellated ethylene vinyl acetate cross-linking agent between ethylene vinyl acetate EVM; When vulcanizing agent is sulphur, resin curing agent or silane containing hydrogen vulcanizing agent, there is graft reaction in this vulcanizing agent and ethylene vinyl acetate EVM, and then forms cancellated ethylene vinyl acetate cross-linking agent;
Described fire retardant is made up of nitrogen phosphorus expanding fire retardant, magnesium hydroxide.
2. a kind of method preparing super soft halogen-free flame-retardant thermoplastic elastomer as claimed in claim 1, it is characterized in that described melt blending and dynamic vulcanization all adopt single screw extrusion machine, twin screw extruder, Banbury mixer or reciprocating singe screw pin forcing machine, the screw speed of screw extrusion press is 60r/min ~ 180r/min, the rotor speed of Banbury mixer is 60r/min ~ 180r/min, and the screw speed of reciprocating singe screw pin forcing machine is 60r/min ~ 180r/min.
3. a kind of method preparing super soft halogen-free flame-retardant thermoplastic elastomer as claimed in claim 1, is characterized in that described dynamic vulcanization temperature is 50 DEG C ~ 180 DEG C.
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| CN101712777A (en) * | 2008-10-06 | 2010-05-26 | 潍坊中旭高分子材料有限公司 | Halogen-free and phosphorus-free flame-retarding wire and cable material as well as preparation method thereof |
| CN102382358A (en) * | 2011-11-15 | 2012-03-21 | 中天科技装备电缆有限公司 | Halogen-free flame-retardant cable sheath material for railway locomotive and manufacturing method for halogen-free flame-retardant cable sheath material |
| CN103059401A (en) * | 2012-12-21 | 2013-04-24 | 杭州师范大学 | Oil resistance thermoplastic elastomer and preparing method thereof |
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| CN101712777A (en) * | 2008-10-06 | 2010-05-26 | 潍坊中旭高分子材料有限公司 | Halogen-free and phosphorus-free flame-retarding wire and cable material as well as preparation method thereof |
| CN102382358A (en) * | 2011-11-15 | 2012-03-21 | 中天科技装备电缆有限公司 | Halogen-free flame-retardant cable sheath material for railway locomotive and manufacturing method for halogen-free flame-retardant cable sheath material |
| CN103059401A (en) * | 2012-12-21 | 2013-04-24 | 杭州师范大学 | Oil resistance thermoplastic elastomer and preparing method thereof |
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