CN106633420A - Halogen-free flame-retardation thermoplastic dynamic sulfurated ethylene-propylene-diene monomer rubber/polypropylene composition and preparation method thereof - Google Patents
Halogen-free flame-retardation thermoplastic dynamic sulfurated ethylene-propylene-diene monomer rubber/polypropylene composition and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Ethylene-propylene or ethylene-propylene-diene copolymers
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Abstract
The invention discloses a halogen-free flame-retardation thermoplastic dynamic sulfurated ethylene-propylene-diene monomer rubber/polypropylene composition and a preparation method thereof. The ethylene-propylene-diene monomer rubber/polypropylene composition is prepared by ethylene-propylene-diene monomer rubber, polypropylene, coked piperazine phosphate, melamine pyrophosphate, zinc oxide, ethylene-propylene-diene-grafted maleic anhydride, an initiator, a vulcanizing agent, rubber softening oil and a lubricant. The preparation method comprises the following steps: 1) mixing EPDM, PP, coked piperazine phosphate, MPP, ZnO, EPDM-g-MAH and the lubricant, and dispersing the materials; 2) performing melt extrusion on a premix obtained in the step 1) and performing granulation on the premix; and 3) mixing the premix, the initiator, the vulcanizing agent and the rubber softening oil, extruding a mixture, and granulating the mixture. The ethylene-propylene-diene monomer rubber/polypropylene composition has the advantages of heat resistance, aging resistance, excellent mechanical property and flame resistance performance, enables thermoplastic processing, has a production process, and can be widely used for wire and cable compounds with high flame-resistance requirements.
Description
Technical field
The present invention relates to a kind of halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition and its preparation
Method, belongs to thermoplastic dynamic perduren preparation field.
Background technology
Technology of Dynamic Vulcanized is referred to makes the vulcanization of rubber in rubber and thermoplastic molten Blending Processes, because rubber exists
Also constantly mix with thermoplastic while sulfuration, therefore rubber is in thermoplastic continuous phase as dispersed phase distribution
In.The thermoplastic dynamic vulcanized EPT rubber elastomer prepared using Technology of Dynamic Vulcanized, three for having vulcanized
First EP rubbers is dispersed in polypropylene matrix with micron order, and the elastomer not only has sulfuration ethylene propylene diene rubber
High temperature resistant, ageing-resistant, low permanent compression set the advantages of, also with polypropylene material can with thermoplasticity processing, recyclable make
With the characteristics of, conventional thermosetting ethylene propylene diene rubber can be replaced in many fields.
Thermoplastic dynamic vulcanized EPT rubber elastomer is earliest by U.S. Meng Shan all (Monsanto) companies
Manufacture, its patent US4130535 and US4311628 have prepared the bullet with sulphur and phenolic resin as crosslinking agent respectively
Gonosome.However, the elastomer does not possess anti-flammability, its oxygen index (OI) is generally less than 18, it is impossible to apply in the field for having flame-retardancy requirements
Close.
At present, the thermoplastic dynamic vulcanized EPT rubber with fire resistance is had been developed over, is used
Flame-retardant system mainly include：Bromine/stibium flame retardancy system, red phosphorus flame-retardant system, metal hydroxides flame-retardant system etc..Bromine/antimony resistance
The good flame retardation effect of combustion system, but it can produce a large amount of poisonous and mordant gases when burning under the high temperature conditions；Red phosphorus
Flame retarding efficiency is high, but its is inflammable, by extremely toxic hydrogen phosphide is produced during hot-working, harmfulness is big when operating and using；Metal hydrogen-oxygen
Compound asepsis environment-protecting, but because its fire retardant mechanism is by reaching suppression matrix tree by itself release moisture in heating process
The purpose of fat burning, therefore its flame retarding efficiency is low, needs very big addition to can be only achieved certain flame retardant effect, and addition
It is larger to the damage of matrix resin physical and mechanical properties when big.
The preparation method of conventional flame-proofed thermoplastic dynamic vulcanization EPT rubber mainly includes：Twin-screw
Extrusion machine one-step method, double screw extruder three-step approach, mill/vulcanizing press and usage etc..Twin-screw extrusion machine one-step method,
It is that fire retardant and blending extrusion of other materials are obtained into fire proofing, due to ethylene propylene diene rubber melt viscosity greatly, short
It is difficult to be uniformly dispersed under temporary screw dwell time；Double screw extruder three-step approach, is, according to formula composition, according to mixing, to move
State sulfuration, decomposite mode, obtain fire proofing, can the uneven problem of material dispersion that exists of effectively solving one-step method,
But its long the production cycle, high energy consumption；By the way of mill/vulcanizing press, production efficiency is extremely low.
The content of the invention
It is an object of the invention to provide a kind of halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber combination
Thing.
Another object of the present invention is to provide a kind of halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber
The preparation method of composition.
The technical solution used in the present invention is：
A kind of halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition, it is by following mass parts
Raw material is prepared from：
Ethylene propylene diene rubber：100 parts；
Polypropylene：36.5～86.5 parts；
Piperazine pyrophosphate：20～40 parts；
Melamine pyrophosphate：12～26 parts；
Zinc oxide：1.5～3 parts；
Grafting maleic anhydride with ethylene propylene terpolymer：13～27 parts；
Initiator：0.5～1 part；
Vulcanizing agent：4～8 parts；
Rubber softening oil：30～105.5 parts；
Lubricant：1.5～3 parts.
Described ethylene propylene diene rubber is the terpolymer of ethylene-propylene-ENB, ENB
Content is 2.3wt%～5wt%.
Described polypropylene for 11～20g/10min of melt index random polypropylene, test condition be 230 DEG C/
2.16kg。
Content >=the 0.6wt% of maleic anhydride in described grafting maleic anhydride with ethylene propylene terpolymer.
Described initiator is peroxide.
Described peroxide be benzoyl peroxide, the benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide at least
It is a kind of.
Described vulcanizing agent is N, a N '-penylene BMI.
Described lubricant is Tissuemat E, polypropylene wax, zinc stearate, calcium stearate, stearate, stearic acid, second
At least one in support bis-stearamides, silicone powder.
The preparation method of above-mentioned halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition, including with
Lower step：
1) by ethylene propylene diene rubber, polypropylene, piperazine pyrophosphate, melamine pyrophosphate, zinc oxide, ethylene-propylene-diene monomer
Glue grafted maleic anhydride and lubricant add high-speed mixer, are well mixed；
2) by step 1) material that mixes proceeds to double screw extruder, melting extrusion, granulation；
3) by step 2) material that mixes, initiator and vulcanizing agent add high-speed mixer, it be well mixed, then by material
Double screw extruder is proceeded to, adds rubber softening oil, extrusion, granulation to obtain halogen-free combustion-proof thermoplastic dynamic vulcanization EPDM
Rubber/polypropylene composition.
The screw slenderness ratio L/D of described double screw extruder is (48～60):1, screw speed is 200～280rpm,
Extrusion temperature is 80～200 DEG C.
The invention has the beneficial effects as follows：The halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber of the present invention
Composition had both maintained the heat-resisting, ageing-resistant of EPDM rubber, low compression set, again can thermoplasticity processing, and with excellent
Different mechanical property and fire resistance, production process is simple to operation, can be widely applied to the electric wire higher to flame-retardancy requirements
The outer quilt of cable, such as outside automobile and stove ignition lead crust, computer connecting wires crust, submarine cable and high-side signal transmission cable
Skin etc..
1) present invention improves the compatibility between matrix resin and fire retardant, bulking agent using bulking agent EPDM-g-MAH
The anhydride group of EPDM-g-MAH is anti-with the terminal hydroxy group of fire retardant piperazine pyrophosphate and flame-retardants melamine pyrophosphate respectively
Should, EPDM-g-MAH-g- piperazine pyrophosphates and EPDM-g-MAH-g-MPP are generated, enhance matrix resin EPDM, PP and fire-retardant
Interface binding force between agent piperazine pyrophosphate, MPP, improves the compatibility between EPDM, PP and fire retardant；
2) present invention adopts N, a N '-penylene BMI to enter Mobile state to EPDM/PP compositions as vulcanizing agent
Sulfuration, reduces degradation of the conventional peroxide vulcanizing agent to PP；
3) flame-retardant system that the present invention is coordinated using piperazine pyrophosphate/MPP/ZnO, addition is few, and flame retarding efficiency is high, to base
The performance impact of body resin is little, not halogen-containing, asepsis environment-protecting；
4) present invention prepares EPDM/PP compositions using two-step method, both can ensure that the dispersion of fire retardant, in turn ensure that
The abundant dynamic vulcanization of EPDM and dispersion；
5) method that the present invention adopts dynamic vulcanization in situ, in parallel equidirectional two-screw extruder, BPO is in extrusion temperature
Relatively low screw rod leading portion provides free radical, and initiation forms EPDM macromolecular radicals, EPDM macromolecular radicals and N, N '-isophthalic
Double bond addition on support BMI five-membered ring, forms bigger macromolecular radical, then together with other free radicals
Carry out cross-linking reaction.
Description of the drawings
Fig. 1 is the technique stream of the halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition of the present invention
Cheng Tu.
Specific embodiment
A kind of halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition, it is by following mass parts
Raw material is prepared from：
Ethylene propylene diene rubber：100 parts；
Polypropylene：36.5～86.5 parts；
Piperazine pyrophosphate：20～40 parts；
Melamine pyrophosphate：12～26 parts；
Zinc oxide：1.5～3 parts；
Grafting maleic anhydride with ethylene propylene terpolymer：13～27 parts；
Initiator：0.5～1 part；
Vulcanizing agent：4～8 parts；
Rubber softening oil：30～105.5 parts；
Lubricant：1.5～3 parts.
Preferably, described ethylene propylene diene rubber (EPDM) is the terpolymer of ethylene-propylene-ENB,
The content of ENB is 2.3wt%～5wt%.
It is further preferred that described ethylene propylene diene rubber is the ternary that Mitsui company diene content is 2.3wt%
EP rubbers, Exxon Mobil company diene content are ethylene propylene diene rubber, the Exxon Mobil company of 2.8wt%
Diene content for 4.2wt% ethylene propylene diene rubber, the ethylene propylene diene rubber of LG-DOW company diene content 5wt% in extremely
Few one kind.
Preferably, described polypropylene (PP) is the random polypropylene of 11～20g/10min of melt index, and test condition is
230℃/2.16kg。
It is further preferred that it is 15g/ that described polypropylene is the melt index of platform modeling (Ningbo) limited company
The atactic copolymerized polypropene of 10min, 230 DEG C/2.16kg of test condition.
Preferably, in described grafting maleic anhydride with ethylene propylene terpolymer (EPDM-g-MAH) maleic anhydride content >=
0.6wt%.
Preferably, described initiator is peroxide.
It is further preferred that described initiator is benzoyl peroxide, the benzoyl peroxide tert-butyl ester, peroxidating first and second
At least one in ketone.
Still further preferably, described initiator is benzoyl peroxide (BPO).
Still more preferably, described initiator is the trade mark of Akzo Nobel N.V. for Perkadox L-50S's
Benzoyl peroxide.
Preferably, described vulcanizing agent is N, a N '-penylene BMI.
It is further preferred that N, N '-penylene BMI of the described vulcanizing agent for particle diameter≤150 micron.
Still further preferably, described vulcanizing agent is the N that the trade mark of Xi'an span new material Co., Ltd is HVA-2,
A N '-penylene BMI.
Preferably, described lubricant is Tissuemat E, polypropylene wax, zinc stearate, calcium stearate, stearate, hard
At least one in resin acid, ethylene bis stearamide, silicone powder.
It is further preferred that Tissuemat E of the described lubricant for Honeywell Inc. of the U.S..
The preparation method of above-mentioned halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition, including with
Lower step：
1) by ethylene propylene diene rubber, polypropylene, piperazine pyrophosphate, melamine pyrophosphate, zinc oxide, ethylene-propylene-diene monomer
Glue grafted maleic anhydride and lubricant add high-speed mixer, are well mixed；
2) by step 1) material that mixes proceeds to double screw extruder, melting extrusion, granulation；
3) by step 2) material that mixes, initiator and vulcanizing agent add high-speed mixer, it be well mixed, then by material
Double screw extruder is proceeded to, adds rubber softening oil, extrusion, granulation to obtain halogen-free combustion-proof thermoplastic dynamic vulcanization EPDM
Rubber/polypropylene composition.
Preferably, the screw slenderness ratio L/D of described double screw extruder is (48～60):1, screw speed be 200～
280rpm, extrusion temperature is 80～200 DEG C.
Preferably, described double screw extruder is parallel equidirectional two-screw extruder, and screw configuration is single thread, spiral shell
Bar has at least 5 gear block areas, and screw rod has at least 2 left-hand thread areas.
The present invention is made further explanation and description with reference to specific embodiment.
Fig. 1 is the production work of the halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition of the present invention
Skill flow chart, embodiment 1～5 is carried out according to the technological process.
Embodiment 1：
A kind of halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition, its following (matter of raw material composition
Amount number)：
EPDM (diene content 2.3wt%, Mitsui company)：100 parts；
PP：36.5 parts；
Fire retardant piperazine pyrophosphate：40 parts；
Flame-retardants melamine pyrophosphate (MPP)：26 parts；
Fire retarding synergist ZnO：3 parts；
Bulking agent EPDM-g-MAH：27 parts；
Initiator B PO：1 part；
Vulcanizing agent N, a N '-penylene BMI (HVA-2)：8 parts；
Rubber softening oil：105.5 parts；
Lubricant PE waxes：3 parts.
The preparation method of above-mentioned halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition, including such as
Lower step：
1) by EPDM, PP, fire retardant piperazine pyrophosphate, fire-retartant agent MP P, fire retarding synergist ZnO, bulking agent EPDM-g-MAH
High-speed mixer is added with lubricant PE waxes, is well mixed；
2) by step 1) pre-composition that mixes proceeds to parallel equidirectional two-screw extruder, melting extrusion, granulation；
3) by step 2) obtained in rubber blend, initiator B PO and vulcanizing agent N, a N '-penylene BMI
(HVA-2) high-speed mixer is added, is well mixed, then material is proceeded into parallel equidirectional two-screw extruder, granulated, and in double spiral shells
6th area of bar extruder arranges oil filler point, and rubber softening oil is fed into extruder in the way of weight-loss type forced feed, obtains nothing
Halogen flame-proofed thermoplastic dynamic vulcanization EPT rubber composition.
The screw configuration of the parallel equidirectional two-screw extruder is that the ratio of single thread, spiro rod length L and diameter D is
48:1, screw rod has 6 gear block areas, and screw rod has 3 left-hand thread areas, and screw speed is 280rpm, screw zones and head temperature
For 80,140,150,160,170,190,200,200,200,200,200,200,200/195 DEG C.
Embodiment 2：
A kind of halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition, its following (matter of raw material composition
Amount number)：
EPDM (diene content 4.2wt%, Exxon Mobil company)：100 parts；
PP：46 parts；
Piperazine pyrophosphate：40 parts；
MPP：26 parts；
ZnO：3 parts；
EPDM-g-MAH：27 parts；
BPO：1 part；
HVA-2：8 parts；
Rubber softening oil：87 parts；
PE waxes：3 parts.
The preparation method of above-mentioned halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition, including such as
Lower step：
1) by EPDM, PP, fire retardant piperazine pyrophosphate, fire-retartant agent MP P, fire retarding synergist ZnO, bulking agent EPDM-g-MAH
High-speed mixer is added with lubricant PE waxes, is well mixed；
2) by step 1) pre-composition that mixes proceeds to parallel equidirectional two-screw extruder, melting extrusion, granulation；
3) by step 2) obtained in rubber blend, initiator B PO and vulcanizing agent HVA-2 add high-speed mixer machine, mix
Close uniform, then material is proceeded into parallel equidirectional two-screw extruder, granulate, and oiling is set in the 7th area of double screw extruder
Hole, extruder is fed by rubber softening oil in the way of weight-loss type forced feed, obtains halogen-free combustion-proof thermoplastic dynamic vulcanization three
First ethylene-propylene rubber/polypropylene composition.
The screw configuration of the parallel equidirectional two-screw extruder is that the ratio of single thread, spiro rod length L and diameter D is
60:1, screw rod has 7 gear block areas, and screw rod has 3 left-hand thread areas, and screw speed is 280rpm, screw zones and head temperature
For 80,140,150,160,170,190,200,200,200,200,200,200,200/195 DEG C.
Embodiment 3：
A kind of halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition, its following (matter of raw material composition
Amount number)：
EPDM (diene content 4.2wt%, Exxon Mobil company)：100 parts；
PP：86.5 parts；
Piperazine pyrophosphate：40 parts；
MPP：26 parts；
ZnO：3 parts；
EPDM-g-MAH：27 parts；
BPO：1 part；
HVA-2：8 parts；
Rubber softening oil：30 parts；
PE waxes：1.8 parts.
The preparation method of above-mentioned halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition, including such as
Lower step：
1) by EPDM, PP, fire retardant piperazine pyrophosphate, fire-retartant agent MP P, fire retarding synergist ZnO, bulking agent EPDM-g-MAH
High-speed mixer is added with lubricant PE waxes, is well mixed；
2) by step 1) pre-composition that mixes proceeds to parallel equidirectional two-screw extruder, melting extrusion, granulation；
3) by step 2) obtained in rubber blend, initiator B PO and vulcanizing agent HVA-2 add high-speed mixer, mixing
Uniformly, then by material parallel equidirectional two-screw extruder is proceeded to, is granulated, and oil filler point is set in the 8th area of double screw extruder,
Rubber softening oil is fed into extruder in the way of weight-loss type forced feed, halogen-free combustion-proof thermoplastic dynamic vulcanization ternary second is obtained
Third rubber/polypropylene composition.
The screw configuration of the parallel equidirectional two-screw extruder is that the ratio of single thread, spiro rod length L and diameter D is
52:1, screw rod has 5 gear block areas, and screw rod has 2 left-hand thread areas, and screw speed is 250rpm, screw zones and head temperature
For 80,140,150,160,170,190,200,200,200,200,200,200,200/195 DEG C.
Embodiment 4：
A kind of halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition, its following (matter of raw material composition
Amount number)：
EPDM (diene content 4.2wt%, Exxon Mobil company)：100 parts；
PP：36.5 parts；
Piperazine pyrophosphate：30 parts；
MPP：12 parts；
ZnO：1.5 parts；
EPDM-g-MAH：13 parts；
BPO：0.5 part；
HVA-2：4 parts；
Rubber softening oil：105.5 parts；
PE waxes：1.5 parts.
The preparation method of above-mentioned halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition, including such as
Lower step：
1) by EPDM, PP, fire retardant piperazine pyrophosphate, fire-retartant agent MP P, fire retarding synergist ZnO, bulking agent EPDM-g-MAH
High-speed mixer is added with lubricant PE waxes, is well mixed；
2) by step 1) pre-composition that mixes proceeds to parallel equidirectional two-screw extruder, melting extrusion, granulation；
3) by step 2) obtained in rubber blend, initiator B PO and vulcanizing agent HVA-2 add high-speed mixer, mixing
Uniformly, then by material parallel equidirectional two-screw extruder is proceeded to, is granulated, and oil filler point is set in the 8th area of double screw extruder,
Rubber softening oil is fed into extruder in the way of weight-loss type forced feed, halogen-free combustion-proof thermoplastic dynamic vulcanization ternary second is obtained
Third rubber/polypropylene composition.
The screw configuration of the parallel equidirectional two-screw extruder is that the ratio of single thread, spiro rod length L and diameter D is
52:1, screw rod has 5 gear block areas, and screw rod has 2 left-hand thread areas, and screw speed is 250rpm, screw zones and head temperature
For 80,140,150,160,170,190,200,200,200,200,200,200,200/195 DEG C.
Embodiment 5：
A kind of halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition, its following (matter of raw material composition
Amount number)：
EPDM (diene content 5wt%, LG-DOW company)：100 parts；
PP：46 parts；
Piperazine pyrophosphate：20 parts；
MPP：13.5 parts；
ZnO：1.7 parts；
EPDM-g-MAH：20 parts；
BPO：0.8 part；
HVA-2：6 parts；
Rubber softening oil：87 parts；
PE waxes：2 parts.
The preparation method of above-mentioned halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition, including such as
Lower step：
1) by EPDM, PP, fire retardant piperazine pyrophosphate, fire-retartant agent MP P, fire retarding synergist ZnO, bulking agent EPDM-g-MAH
High-speed mixer is added with lubricant PE waxes, is well mixed；
2) by step 1) pre-composition that mixes proceeds to parallel equidirectional two-screw extruder, melting extrusion, granulation；
3) by step 2) obtained in rubber blend, initiator B PO and vulcanizing agent HVA-2 add high-speed mixer, mixing
Uniformly, then by material parallel equidirectional two-screw extruder is proceeded to, is granulated, and oil filler point is set in the 8th area of double screw extruder,
Rubber softening oil is fed into extruder in the way of weight-loss type forced feed, halogen-free combustion-proof thermoplastic dynamic vulcanization ternary second is obtained
Third rubber/polypropylene composition.
The screw configuration of the parallel equidirectional two-screw extruder is that the ratio of single thread, spiro rod length L and diameter D is
60:1, screw rod has 6 gear block areas, and screw rod has 2 left-hand thread areas, and screw speed is 250rpm, screw zones and head temperature
For 80,140,150,160,170,190,200,200,200,200,200,200,200/195 DEG C.
Comparative example 1：
A kind of EPT rubber composition, its raw material composition is following (mass fraction)：
EPDM (diene content 5wt%, LG-DOW company)：100 parts；
PP：46 parts；
Fire retardant magnesium hydroxide：100 parts；
EPDM-g-MAH：20 parts；
BPO：0.8 part；
HVA-2：6 parts；
Rubber softening oil：87 parts；
PE waxes：2 parts.
The preparation method of above-mentioned EPT rubber composition, comprises the steps：
1) EPDM, PP, fire retardant magnesium hydroxide, bulking agent EPDM-g-MAH and lubricant PE waxes are added into mixed at high speed
Machine, is well mixed；
2) by step 1) pre-composition that mixes proceeds to parallel equidirectional two-screw extruder, melting extrusion, granulation；
3) by step 2) obtained in rubber blend, initiator B PO and vulcanizing agent HVA-2 add high-speed mixer, mixing
Uniformly, then by material parallel equidirectional two-screw extruder is proceeded to, is granulated, and oil filler point is set in the 8th area of double screw extruder,
Rubber softening oil is fed into extruder in the way of weight-loss type forced feed, EPT rubber composition is obtained.
The screw configuration of the parallel equidirectional two-screw extruder is that the ratio of single thread, spiro rod length L and diameter D is
60:1, screw rod has 6 gear block areas, and screw rod has 2 left-hand thread areas, and screw speed is 250rpm, screw zones and head temperature
For 80,140,150,160,170,190,200,200,200,200,200,200,200/195 DEG C.
Comparative example 2：
A kind of EPT rubber composition, its raw material composition is following (mass fraction)：
EPDM (diene content 4.2wt%, Exxon Mobil company)：100 parts；
PP：46 parts；
Piperazine pyrophosphate：40 parts；
MPP：26 parts；
ZnO：3 parts；
BPO：1 part；
HVA-2：8 parts；
Rubber softening oil：87 parts；
PE waxes：3 parts.
The preparation method of above-mentioned EPT rubber composition, comprises the steps：
1) EPDM, PP, fire retardant piperazine pyrophosphate, fire-retartant agent MP P, fire retarding synergist ZnO and lubricant PE waxes are added
High-speed mixer, is well mixed；
2) by step 1) pre-composition that mixes proceeds to parallel equidirectional two-screw extruder, melting extrusion, granulation；
3) by step 2) obtained in rubber blend, initiator B PO and vulcanizing agent HVA-2 add high-speed mixer, mixing
Uniformly, then by material parallel equidirectional two-screw extruder is proceeded to, is granulated, and oil filler point is set in the 7th area of double screw extruder,
Rubber softening oil is fed into extruder in the way of weight-loss type forced feed, EPT rubber composition is obtained.
The screw configuration of the parallel equidirectional two-screw extruder is that the ratio of single thread, spiro rod length L and diameter D is
60:1, screw rod has 7 gear block areas, and screw rod has 3 left-hand thread areas, and screw speed is 280rpm, screw zones and head temperature
For 80,140,150,160,170,190,200,200,200,200,200,200,200/195 DEG C.
Comparative example 3：
A kind of EPT rubber composition, its raw material composition is following (mass fraction)：
EPDM (diene content 0.5wt%, LG-DOW company)：100 parts；
PP：46 parts；
Piperazine pyrophosphate：20 parts；
MPP：13.5 parts；
ZnO：1.7 parts；
EPDM-g-MAH：20 parts；
BPO：0.8 part；
HVA-2：6 parts；
Rubber softening oil：87 parts；
PE waxes：2 parts.
The preparation method of above-mentioned EPT rubber composition, comprises the steps：
1) by EPDM, PP, fire retardant piperazine pyrophosphate, fire-retartant agent MP P, fire retarding synergist ZnO, bulking agent EPDM-g-MAH
High-speed mixer is added with lubricant PE waxes, is well mixed；
2) by step 1) pre-composition that mixes proceeds to parallel equidirectional two-screw extruder, melting extrusion, granulation；
3) by step 2) obtained in rubber blend, initiator B PO and vulcanizing agent HVA-2 add high-speed mixer, mixing
Uniformly, then by material parallel equidirectional two-screw extruder is proceeded to, is granulated, and oil filler point is set in the 8th area of double screw extruder,
Rubber softening oil is fed into extruder in the way of weight-loss type forced feed, EPT rubber composition is obtained.
The screw configuration of the parallel equidirectional two-screw extruder is that the ratio of single thread, spiro rod length L and diameter D is
60:1, screw rod has 6 gear block areas, and screw rod has 2 left-hand thread areas, and screw speed is 250rpm, screw zones and head temperature
For 80,140,150,160,170,190,200,200,200,200,200,200,200/195 DEG C.
The raw material composition of the EPT rubber composition of embodiment 1～5 and comparative example 1～3 is as shown in table 1,
The consumption of each component is represented with mass fraction in table 1.
The raw material composition table of the EPT rubber composition of the embodiment 1～5 of table 1 and comparative example 1～3
Test case：
The EPT rubber composition that embodiment 1～5 and comparative example 1～3 are prepared is fabricated to respectively
Pad, then following performance test is carried out, test result is as shown in table 2：
Shore A hardness：By ASTM-D2240 standard testings；
Tensile strength and elongation at break：By ASTM-D412 standard testings, rate of extension 500mm/min；
Fire resistance：By UL94 standard testings, batten thickness is 3mm.
The performance test data of the EPT rubber composition of the embodiment 1～5 of table 2 and comparative example 1～3
From Tables 1 and 2：
1) fire resistance of EPT rubber composition prepared by embodiment 1～5 is UL94-V0 levels, and
The fire resistance of EPT rubber composition prepared by comparative example 1 is less than UL94-V2 levels, and embodiment 1～5 is made
The tensile strength and elongation at break of standby EPT rubber composition is superior to the ternary second of the preparation of comparative example 1
Third rubber/polypropylene composition, is primarily due to embodiment 1～5 and uses piperazine pyrophosphate/melamine pyrophosphoric
Salt/zinc oxide composite flame retardant system, although addition is little, but excellent fireproof performance, and will not be to the mechanical property of matrix resin
Impact, for magnesium hydroxide, addition is big, and fire resistance is undesirable for the fire retardant that comparative example 1 is adopted, and to matrix resin
Effect on Mechanical Properties it is big；
2) tensile strength and elongation at break of EPT rubber composition prepared by embodiment 1～5 are excellent
In EPT rubber composition prepared by comparative example 2, it is primarily due to embodiment 1～5 and adds bulking agent
EPDM-g-MAH compositions, can significantly improve the compatibility between matrix resin and fire retardant, and comparative example 2 is not added with
EPDM-g-MAH compositions, the compatibility between matrix resin and fire retardant is poor；
3) tensile strength of EPT rubber composition prepared by embodiment 1～5, elongation at break and resistance
Combustion performance is superior to the EPT rubber composition of the preparation of comparative example 3, is primarily due to embodiment 1～5 and is adopted
The diene content of EPDM be 2.3wt%～5wt%, and the diene content of the EPDM that comparative example 3 is adopted is only 0.5wt%；
4) content of PP is different in embodiment 1～3, with the increase of PP contents, the EPT rubber for obtaining
The tensile strength of composition and elongation at break are presented increased trend；
5) content of fire retardant is different in embodiment 3～5, even if flame retardant agent content is relatively low, the ethylene propylene diene rubber for obtaining/
The fire resistance of polypropene composition can still reach UL94-V0 levels, excellent fireproof performance, and it is strong still to maintain higher stretching
Degree and elongation at break, mechanical property is unaffected, excellent combination property.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention not by above-described embodiment
Limit, other any Spirit Essences without departing from the present invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition, it is characterised in that：It is by following
The raw material of mass parts is prepared from：
Ethylene propylene diene rubber：100 parts；
Polypropylene：36.5～86.5 parts；
Piperazine pyrophosphate：20～40 parts；
Melamine pyrophosphate：12～26 parts；
Zinc oxide：1.5～3 parts；
Grafting maleic anhydride with ethylene propylene terpolymer：13～27 parts；
Initiator：0.5～1 part；
Vulcanizing agent：4～8 parts；
Rubber softening oil：30～105.5 parts；
Lubricant：1.5～3 parts.
2. halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition according to claim 1, it is special
Levy and be：Described ethylene propylene diene rubber is the terpolymer of ethylene-propylene-ENB, ENB
Content is 2.3wt%～5wt%.
3. halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition according to claim 1, it is special
Levy and be：Described polypropylene for 11～20g/10min of melt index random polypropylene, test condition be 230 DEG C/
2.16kg。
4. halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition according to claim 1, it is special
Levy and be：Content >=the 0.6wt% of maleic anhydride in described grafting maleic anhydride with ethylene propylene terpolymer.
5. halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition according to claim 1, it is special
Levy and be：Described initiator is peroxide.
6. halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition according to claim 5, it is special
Levy and be：Described peroxide is at least in benzoyl peroxide, the benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide
Kind.
7. halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition according to claim 1, it is special
Levy and be：Described vulcanizing agent is N, a N '-penylene BMI.
8. halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber composition according to claim 1, it is special
Levy and be：Described lubricant is Tissuemat E, polypropylene wax, zinc stearate, calcium stearate, stearate, stearic acid, ethylene
At least one in bis-stearamides, silicone powder.
9. the halogen-free combustion-proof thermoplastic dynamic vulcanization EPT rubber group in claim 1～8 described in any one
The preparation method of compound, it is characterised in that：Comprise the following steps：
1）Ethylene propylene diene rubber, polypropylene, piperazine pyrophosphate, melamine pyrophosphate, zinc oxide, ethylene-propylene-diene monomer are glued
Branch maleic anhydride and lubricant add high-speed mixer, are well mixed；
2）By step 1）The material for mixing proceeds to double screw extruder, melting extrusion, granulation；
3）By step 2）Material, initiator and the vulcanizing agent for mixing adds high-speed mixer, is well mixed, then material is proceeded to
Double screw extruder, add rubber softening oil, extrusion, granulation, obtain halogen-free combustion-proof thermoplastic dynamic vulcanization ethylene propylene diene rubber/
Polypropene composition.
10. preparation method according to claim 9, it is characterised in that：The screw slenderness ratio of described double screw extruder
L/D is（48～60）:1, screw speed is 200～280rpm, and extrusion temperature is 80～200 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050290A (en) * | 2007-04-29 | 2007-10-10 | 沈阳化工学院 | Dynamic sulfurated retardant composite material of polypropylene without halogen, and preparation method |
| CN101418102A (en) * | 2008-12-03 | 2009-04-29 | 苏州特威塑胶有限公司 | High temperature halogen-free flame retardant polypropylene/ethylene propylene terpolymer cable material and preparation method thereof |
| CN103992293A (en) * | 2014-05-07 | 2014-08-20 | 金发科技股份有限公司 | Preparation method for halogen-free flame retardant and flame retardant polyolefin composition thereof |
-
2016
- 2016-09-19 CN CN201610831452.3A patent/CN106633420A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050290A (en) * | 2007-04-29 | 2007-10-10 | 沈阳化工学院 | Dynamic sulfurated retardant composite material of polypropylene without halogen, and preparation method |
| CN101418102A (en) * | 2008-12-03 | 2009-04-29 | 苏州特威塑胶有限公司 | High temperature halogen-free flame retardant polypropylene/ethylene propylene terpolymer cable material and preparation method thereof |
| CN103992293A (en) * | 2014-05-07 | 2014-08-20 | 金发科技股份有限公司 | Preparation method for halogen-free flame retardant and flame retardant polyolefin composition thereof |
Non-Patent Citations (1)
| Title |
|---|
| 廖双泉 等主编: "《热塑性弹性体及其应用》", 30 April 2014, 中国石化出版社 * |
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