CN101704976A - Low smoke halogen-free flame retardant ethylene-propylene-diene rubber and preparation method by extrusion molding thereof - Google Patents

Low smoke halogen-free flame retardant ethylene-propylene-diene rubber and preparation method by extrusion molding thereof Download PDF

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CN101704976A
CN101704976A CN200910241605A CN200910241605A CN101704976A CN 101704976 A CN101704976 A CN 101704976A CN 200910241605 A CN200910241605 A CN 200910241605A CN 200910241605 A CN200910241605 A CN 200910241605A CN 101704976 A CN101704976 A CN 101704976A
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rubber
flame retardant
halogen
low
smoke
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CN101704976B (en
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田明
李波
张立群
吕庆
贡健
尤连兴
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Beijing University of Chemical Technology
Jiangyin Haida Rubber and Plastic Co Ltd
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Beijing University of Chemical Technology
Jiangyin Haida Rubber and Plastic Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/397—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using a single screw
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885—Screw or gear
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92904—Die; Nozzle zone

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a low smoke halogen-free flame retardant ethylene-propylene-diene rubber and a preparation method by extrusion molding thereof; the preparation method comprises the following steps: firstly, raw rubber matrix is evenly mixed at 80-100 DEG C by an open mill or a banbury mixer, and then cooled down to the room temperature; carbon black, modified nanometer/micrometer hydroxide, plasticizer, flame retardant synergist, vulcanization accelerator and vulcanizing agent are added in sequence according to the proportion and evenly mixed. Mixed rubber is added into a single screw extrusion machine; the temperature of a machine body, a screw and a machine head is controlled to be 50-90 DEG C; the rotating speed of the screw is within 15-40 r/min to cause that glue stock is continuously squeezed out; and hot air (175-200 DEG C) or microwave (915-2450 MHz) is adopted to cause that the glue stock is continuously vulcanized and molded. The flame retardant ethylene-propylene-diene rubber has excellent mechanical property, low smoke halogen-free flame retardant performance and good extrusion performance, and is applicable to manufacturing of flame retardant gland strips used in doors and windows for building and vehicles.

Description

A kind of low smoke halogen-free flame retardant ethylene-propylene-diene rubber and preparation method by extrusion molding thereof thereof
Technical field
The present invention relates to the preparation method of a kind of low smoke halogen-free flame retardant ethylene-propylene-diene rubber and extrusion moulding thereof, be applicable to and make building doors and windows, the fire-retardant sealed strip of door-window.
Background technology
Terpolymer EP rubber (EPDM) is usually used in making building doors and windows, vehicle doorn window seal, long service life owing to excellent elasticity (sealing property), heat-resisting, anti-weather-aging property.Raising along with the fire safety requirement, now increasing use occasion requires used elastomeric material to have flame retardant resistance, population collection place elastomeric material such as building field, subway bullet train particularly, both required good flame retardant property, LSZH when requiring the elastomeric material burning does not again cause secondary pollution and injury.Terpolymer EP rubber (EPDM) is mainly by hydrocarbon elementary composition, and oxygen index is about 19, and burning must add fire retardant and just can reach certain flame retardant effect easily.Bigger challenge is, terpolymer EP rubber (EPDM) will be fit to extrude continuously production, must add the softening agent of certain consumption, and softening agent can promote to burn, and the smog of generation is bigger.
Traditional effective flame resistant method is to add halogen-sb system.The CN1746213 patent disclosure a kind of elastomeric material of the flame retardant properties excellence with Halogen matrix (any in neoprene latex, viton, the chlorosulfonated polyethylene) preparation, the fire retardant that is adopted is halogen-antimony cooperative flame retardant systems such as clorafin, antimonous oxide.The CN1542042 patent disclosure a kind of Halogen flame retardant rubber, this flame retardant rubber has been owing to adopted halogen-antimony collaboration system (decabromodiphynly oxide/antimonous oxide), thereby has the advantage that loading level is low, flame retardant effect is good, the mechanical property loss is little.Though use traditional Halogen flame-retardant system filled rubber material that many benefits are arranged, dense smoke, the toxic gas that produces during the elastomeric material burning often causes bigger secondary injury, do not meet the Rosh command request of European Union.
Using metal hydroxides at present is the important means of preparation low-smoke and halogen-free fire-retardant rubber.CN1923884 patent " a kind of preparation method of Halogen Free Flame Retardant EPDM " adopts the Non-halogen Flame Retardant Technology of filling a large amount of aluminium hydroxides or flame retardant of magnesium hydroxide that terpolymer EP rubber (EPDM) is carried out fire-retardant finish, and oxygen index can reach 36%; Use unsaturated hydrochlorate magnesinm methacrylate simultaneously, improved the mechanical property of flame retardant rubber by a relatively large margin.CN1546561 patent " halogen-free flameproof dynamic vulcanization EPT rubber/thermoplastic elastomer " discloses a kind of method for preparing Halogen Free Flame Retardant EPDM (EPDM), this invention is to be the cooperative flame retardant system with magnesium hydroxide/red phosphorus, reduced the overall usage quantity of inorganic combustion inhibitor, oxygen index has reached 30%.Use metal hydroxides (as magnesium hydroxide and aluminium hydroxide) to fill terpolymer EP rubber (EPDM), want to reach flame retardant properties preferably, the oxyhydroxide addition is at least 50%～60%, the interpolation of a large amount of fire retardants causes the mechanical property (hardness increase, elasticity and strength degradation) of terpolymer EP rubber (EPDM) and extrudes processing characteristics obviously descending, extrude that the back colloid breaks or defectives such as rough, shark skin shape, laemodipodiform, bubble, spot and water wave appear in sizing material surface, be not suitable as sealing material and use.
The application of expansion type flame retardant provides an important channel also for preparation low smoke and zero halogen environmental protection flame retardant elastomeric material.Hao Jianwei adopts high polymerization to fill ammonium phosphate (APP) at " the expansion type flame-retarding terpolymer EP rubber of high temperature resistant flame " in (CN101220185) to be acid source, to be that charcoal source and source of the gas are filled terpolymer EP rubber (EPDM) matrix with the one-tenth charcoal whipping agent with melt viscosity regulatory function.The overall addition of expansion type flame retardant is lower slightly than oxyhydroxide, be generally 20%～40%, but to the mechanical property of terpolymer EP rubber (EPDM) (hardness increase, elasticity and strength degradation are not suitable for sealing) with extrude processing characteristics remarkably influenced is arranged, can not realize continuous production.
Though above-mentioned fire-retardant rubber material all has higher oxygen index to reach flame retardant properties preferably, do not possess the good mechanical performance simultaneously and extrude processing characteristics.Terpolymer EP rubber (EPDM) belongs to non-from reinforced rubber, self tensile strength only is about 2MPa, so obtain a kind of low smoke halogen-free flame retardant ethylene-propylene-diene rubber of production that is fit to extrude continuously, maximum difficult point is the balance that realizes excellent mechanical property (particularly hardness, elasticity and intensity), flame retardant properties and extrude processing characteristics.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of low smoke halogen-free flame retardant ethylene-propylene-diene rubber and extrusion moulding thereof, adopt terpolymer EP rubber and maleic anhydride graft terpolymer EP rubber or ethylene-octene copolymer elastomerics and usefulness, fill the coarse particle carbon black and the softening agent of certain consumption simultaneously, improve and extrude processing characteristics, adopt micron oxyhydroxide and a small amount of nanometer oxyhydroxide of surface modification also to use, be aided with other fire retarding synergists, can reach enhancing and fire-retardant double effects simultaneously, finally reach excellent mechanical property, the optimum balance of low-smoke non-halogen flame-retardant performance and good extrusion performance.
A kind of low smoke halogen-free flame retardant ethylene-propylene-diene rubber, it is formed and mass fraction is:
100 parts of rubber matrixes
Modified Nano oxyhydroxide and micron hydroxide mixture 100-250 part
(nanometer oxyhydroxide is 1: 2～10 with micron oxyhydroxide mass ratio)
Fire retarding synergist 5-20 part
Carbon black 10-70 part
Softening agent 10-50 part
Vulcanization accelerator 1-5 part
Vulcanizing agent 1-3 part
Described rubber matrix is terpolymer EP rubber and maleic anhydride graft terpolymer EP rubber or the elastomeric mixture of ethylene-octene copolymer.The percentage of grafting of maleic anhydride graft terpolymer EP rubber is 0.8%～1.0%, can improve the consistency of base rubber and oxyhydroxide, helps extrusion moulding.Adding ethylene-octene copolymer elastomerics (massfraction of monomer octene is 20%～30%) can improve the thermoplastic flowability of material, and improvement is extruded apparent.Terpolymer EP rubber (EPDM): maleic anhydride graft terpolymer EP rubber (EPDM-MAH) or ethylene-octene copolymer elastomerics (POE) are suitable and be 80: 20～95: 5 with mass ratio.Maleic anhydride graft terpolymer EP rubber (EPDM-MAH) or ethylene-octene copolymer elastomerics (POE) add-on are too high, and the hardness of material increases, flexibility decrease.
Modified Nano/micron oxyhydroxide that the present invention adopts is micron magnesium hydroxide or the nano-sized magnesium hydroxide of aluminium hydroxide and surface modification or the mixture of aluminium hydroxide of surface modification.Nano-sized magnesium hydroxide or aluminium hydroxide particle diameter 20～50nm adopt to contain many sulfenyls or vinyl silicane coupling agent surface modification, to improve dispersiveness, improve the intensity of material.Micron magnesium hydroxide or aluminium hydroxide particle diameter 2～20 μ m adopt stearic acid, titanic acid ester or contain the silane coupling agent surface modification of amino, epoxy group(ing).The mass ratio of modified Nano/micron oxyhydroxide and usefulness is 1: 2～10, and preferred mass ratio is 1: 3～5.The micron and the method for modifying of nanometer oxyhydroxide are prior art, with properties-correcting agent with acetone diluted after and nanometer or micron oxyhydroxide mix, the after drying that stirs gets final product.What the present invention all adopted is corresponding commercially available prod after the modification.
Nanometer oxyhydroxide can play the dual function of nanometer enhancing and smoke-inhibiting flame retardant, but consumption is too high, and the hardness of material increases obviously, and processing characteristics worsens.
The fire retarding synergist that the present invention adopts is a zinc borate, the red phosphorus of micro encapsulation (red phosphorus of the micro encapsulation that the present invention adopts is the commercially available prod), polydimethylsiloxane (number-average molecular weight is 5000-30000) a kind of or their mixture. zinc borate or polydimethylsiloxane help improving the one-tenth charcoal of EPDM, reducing smog produces. and the red phosphorus of micro encapsulation and oxyhydroxide have good cooperative flame retardant effect, obviously improve the flame retardant properties of terpolymer EP rubber (EPDM). the use of fire retarding synergist, can reduce the addition of oxyhydroxide, help the performance balance of material.
The sooty particle diameter that the present invention adopts can be commercially available N550, N774 or SP-5000 between 40-100nm, the coarse particle sooty adds the processing characteristics of extruding that helps terpolymer EP rubber (EPDM), but consumption is too high, and the hardness of material increases obviously.
The softening agent that the present invention adopts is paraffin oil, naphthenic oil, low-molecular-weight ethylenic propylene copolymer (preferred number average molecular weight 500-2000), low-molecular-weight polyisobutylene (preferred number average molecular weight 800-2500).An amount of softening agent can guarantee that terpolymer EP rubber (EPDM) extrudes processing characteristics, reduce the hardness of material simultaneously, but consumption can not be too high, otherwise the intensity of material and flame retardant properties obviously reduce, and the smog that produces during burning is bigger.
The vulcanizing agent that the present invention adopts is a Sulfur; Vulcanization accelerator is a terpolymer EP rubber promotor commonly used, as being: 2-benzothiazolyl mercaptan (M), dithio-bis-benzothiazole (DM), zinc dibutyl dithiocarbamate (BZ), bis-pentamethylenethiuram tetrasulfide (DPTT), tetramethyl-thiuram disulfide (TMTD) or N-cyclohexyl-2-[4-morpholinodithio base sulphenamide (CZ).
The preparation method by extrusion molding thereof of a kind of low smoke halogen-free flame retardant ethylene-propylene-diene rubber that the present invention also provides, adopt mill or Banbury mixer that the rubber matrix is mixed at 80-100 ℃ earlier, be cooled to room temperature then, again with carbon black, modification oxyhydroxide, softening agent, fire retarding synergist, vulcanizing agent, vulcanization accelerator adds successively in proportion and mixes, then rubber unvulcanizate is added in the single screw extrusion machine, the control fuselage, screw rod, the temperature of head is at 50-90 ℃, the rotating speed of screw rod is in 15-40r/min, sizing material is extruded continuously, again through 175-200 ℃ of warm air endless vulcanization moulding or the moulding of 915-2450MHz microwave continuous vulcanization.
The present invention takes all factors into consideration from aspects such as mechanical property, flame retardant properties and extrusion performances, but has finally determined the optimum formula system of the low smoke halogen-free flame retardant ethylene-propylene-diene rubber of extrusion moulding.
Effect of the present invention: but the low smoke halogen-free flame retardant ethylene-propylene-diene rubber of extrusion moulding of the present invention has excellent mechanical property, low-smoke non-halogen flame-retardant performance and good extrusion performance.Hardness 70 ± 5, tensile strength 〉=8MPa, oxygen index 〉=30%, smoke density (NBS has flame)≤180, extrusion performance press ASTMD2230 hierarchy system B and estimate, and the extrusion performance classification reaches more than the 9A.
Description of drawings
Fig. 1: the embodiment of the invention is extruded the batten photo, and 1#-3# represents the batten that embodiment 1-3 obtains respectively among the figure.
Fig. 2: Comparative Examples of the present invention is extruded the batten photo, and 4#, 5# represent the batten that Comparative Examples 4,5 obtains respectively among the figure.
As can be seen, compare with the Comparative Examples batten from Fig. 1,2, embodiment of the invention batten is extruded apparent obviously smooth, thereby can realize producing with the forcing machine high-efficiency and continuous.
Embodiment
The present invention will be further described below by embodiment, but not as limitation of the present invention.
Embodiment 1
Each component and mass fraction are: 85 parts of terpolymer EP rubbers (EP35), 15 parts of maleic anhydride graft terpolymer EP rubbers (EPDM-MAH), 5 parts in zinc oxide, 2 parts of stearic acid, 5 parts of zinc borates, 15 parts in micro encapsulation red phosphorus, 60 parts of carbon blacks (N550), 15 parts of the magnesium hydroxides of nano level vinyl silicane coupling agent surface modification, 135 parts of the amine silane surface modified magnesium hydroxides of micron order, 40 parts of naphthenic oils (YT-10), captax/TMTD mass fraction is respectively 0.5/1.5,1.3 parts of Sulfurs.
The preparation technology of embodiment 1 is: earlier that the rubber matrix is mixing even on the hot type opening rubber mixing machine, the roller temperature control is at 90-100 ℃; To be adjusted to roll spacing then on opening rubber mixing machine is the following thin-pass of 0.2mm 3 times, afterwards the bag roller is reinforced to about 3mm to strengthen roll spacing then, again with carbon black, modification oxyhydroxide, fire retarding synergist, softening agent, vulcanization accelerator, vulcanizing agent joins in the opening rubber mixing machine in proportion successively, the roller temperature control is at 40-50 ℃, refining is controlled at about 30min the glue time. and the sizing material after mixing is parked adds cold feed extruder after with the abundant heat refining preheating of opening rubber mixing machine, it is 70 ℃ that controlled temperature makes head, fuselage is 60 ℃, shape of the mouth as one speaks temperature is 90 ℃, setting screw speed is that 40r/min extrudes it continuously, and 180 ℃ of following warm air endless vulcanizations.
Embodiment 2
Each component and mass fraction are: 95 parts of terpolymer EP rubbers (EP33), 5 parts on ethylene-octene copolymer elastomerics (POE8180), 5 parts in zinc oxide, 2 parts of stearic acid, 10 parts of zinc borates, 10 parts of polydimethylsiloxanes (PDMS), 50 parts of carbon blacks (N774), 20 parts of the magnesium hydroxides of nano level vinyl silicane coupling agent surface modification, 150 parts of micron order epoxy radicals silicone hydride modified aluminium hydroxides, 40 parts of paraffin oils (KP6030), altax/TMTD/BZ also is respectively 1.5/0.8/2.5,1.5 parts of Sulfurs with mass fraction.
The preparation technology of embodiment 2 is: take Banbury mixer refining glue method, promptly earlier carbon black, modification oxyhydroxide, fire retarding synergist, softening agent and rubber matrix are dropped into the mixing about 10min of mixing chamber pressurization (it is 0.6MPa that the banburying process keeps floating weight pressure) by proportioning successively, dump temperature is controlled at 85-90 ℃, and adding vulcanization accelerator and Sulfur are mixing to even on opening rubber mixing machine then.To add cold feed extruder behind the bin aging, it is 75 ℃ that controlled temperature makes head, and fuselage is 65 ℃, and charging bole is 60 ℃, and setting screw speed is that 30r/min extrudes it continuously, and 180 ℃ of following warm air endless vulcanizations.
Embodiment 3
Each component and mass fraction are: 80 parts of terpolymer EP rubbers (EP33), 20 parts on ethylene-octene copolymer elastomerics (POE8180), 5 parts in zinc oxide, 2 parts of stearic acid, 12 parts of polydimethylsiloxanes, 8 parts in micro encapsulation red phosphorus, 40 parts of carbon blacks (SP-5000), 30 parts in the aluminium hydroxide of many sulfenyls of nano level silane coupling agent surface modification, 130 parts of micron order epoxy radicals silicone hydride modified aluminium hydroxides, 30 parts of polyisobutene (PB680), captax/DPTT/BZ also is respectively 0.5/0.75/1.5,1.3 parts of Sulfurs with mass fraction.
The preparation technology of embodiment 3 is: earlier that the rubber matrix is mixing even on the hot type opening rubber mixing machine, the roller temperature control is at 90-100 ℃; To be adjusted to roll spacing then on opening rubber mixing machine is the following thin-pass of 0.2mm 3 times, afterwards the bag roller is reinforced to about 3mm to strengthen roll spacing then, join in the opening rubber mixing machine successively carbon black, modification oxyhydroxide, fire retarding synergist, softening agent, vulcanization accelerator, vulcanizing agent in proportion again, the roller temperature control is at 40-50 ℃, and the refining glue time is controlled at about 30min.The sizing material mixing is parked the back add cold feed extruder, it is 85 ℃ that controlled temperature makes head, and fuselage is 80 ℃, and charging bole is 65 ℃, and setting screw speed is that 40r/min extrudes it continuously, and selects the microwave continuous vulcanization of 2450MHz for use.
Material performance test method: the mechanical property of measuring material according to GB/T528-1998; Measure its level and vertical combustion experiment according to GB/T2408-1996; Measure the oxygen index of this material according to GB/T 2406-93; Adopt NBS method test smoke density according to ASTME662-83.
The Extrusion Flow property testing: extrusion performance is pressed ASTM D2230 hierarchy system B and is estimated.
Comparative Examples 4:
Repeat patent " a kind of preparation method of Halogen Free Flame Retardant EPDM " (CN1923884) in disclosed prescription, in Banbury mixer, add 1 part of 100 parts of terpolymer EP rubbers (keltan5508), 150 parts of magnesium hydroxides (H5), 5 parts of methacrylic acids and dicumyl peroxide successively, 60 ℃ mixing down even, vulcanized 12 minutes down at 170 ℃ then, obtain Halogen Free Flame Retardant EPDM.
Comparative Examples 5:
In Banbury mixer, add 100 parts of terpolymer EP rubbers (EP33), 5 parts in zinc oxide, 2 parts of stearic acid, 40 parts of carbon blacks (N550), 90 parts of expansion type flame retardants (NP430), 8 parts of trimeric cyanamides, 3.3 parts of promotor (EG-3), 1.3 parts of Sulfurs successively, 70 ℃ mixing down even, vulcanized 10 minutes down at 180 ℃ then, obtain the expansion type flame-retarding terpolymer EP rubber.
Table 1 embodiment of the invention and the contrast of Comparative Examples gained material property data
Embodiment 1 Embodiment 2 Embodiment 3 Comparative Examples 4 Comparative Examples 5
Tensile strength (MPa) ??8.3 ??8.5 ??9.3 ??12.2 ??4.9
Extension at break (%) ??233 ??215 ??208 ??236 ??203
Hardness (Shao A) ??69 ??71 ??72 ??85 ??92
Oxygen index ??34.3％ ??34.4％ ??33.2％ ??30.7％ ??29.8％
Smoke density (flame is arranged) ??170.9 ??178.5 ??169.7 ??-- ??--
Material performance test method: the mechanical property of measuring material according to GB/T528-1998; Carry out level and vertical combustion experiment according to GB/T2408-1996; Measure the oxygen index of this material according to GB/T 2406-93; Adopt NBS method test smoke density according to ASTME662-83.
The difficult point of preparation extrusion type Halogen Free Flame Retardant EPDM (EPDM) material is to extrude the balance of processing characteristics, mechanical property and flame retardant properties.Can find out that from embodiment optimization formula can be realized hardness 70 ± 5 substantially, tensile strength 〉=8MPa, oxygen index 〉=30%, smoke density (NBS has flame)≤180, extrusion performance press ASTM D2230 hierarchy system B and estimate, and the extrusion performance classification reaches more than the 9A.
In sum, the low smoke halogen-free flame retardant ethylene-propylene-diene rubber prescription that the present invention adopts has for the halogen flame-retardant formulations with respect to traditional, does not discharge toxic gas during burning, and smoke density significantly reduces, and has increased the security that this elastomeric material uses.For other halogen-free flameproof prescriptions, satisfying aspect intensity and the flame retardant properties under the situation of service requirements, improve the extrusion moulding performance of material largely, thereby can realize the serialization industrial production.

Claims (7)

1. low smoke halogen-free flame retardant ethylene-propylene-diene rubber, it is formed and mass fraction is:
100 parts of rubber matrixes
Modified Nano/micron oxyhydroxide 100-250 part
Fire retarding synergist 5-20 part
Carbon black 10-70 part
Softening agent 10-50 part
Vulcanizing agent 1-3 part
Vulcanization accelerator 1-5 part
Described rubber matrix is terpolymer EP rubber and maleic anhydride graft terpolymer EP rubber or the elastomeric mixture of ethylene-octene copolymer;
Described modified Nano/micron oxyhydroxide is the surface modified nano magnesium hydroxide of mass ratio 1: 2～10 or the mixture of aluminium hydroxide and surface modification micron magnesium hydroxide or aluminium hydroxide;
Described fire retarding synergist is a kind of in the red phosphorus, polydimethylsiloxane of zinc borate, micro encapsulation or their mixture.
2. low-smoke and halogen-free fire-retardant rubber according to claim 1 is characterized in that: used sooty particle diameter is 40-100nm.
3. low-smoke and halogen-free fire-retardant rubber according to claim 1 and 2 is characterized in that: used carbon black is N550, N774 or SP-5000 carbon black.
4. low-smoke and halogen-free fire-retardant rubber according to claim 1 is characterized in that: softening agent is paraffin oil, naphthenic oil, low-molecular-weight ethylenic propylene copolymer or low-molecular-weight polyisobutylene.
5. low-smoke and halogen-free fire-retardant rubber according to claim 1 is characterized in that: vulcanizing agent is a Sulfur; Vulcanization accelerator is zinc dibutyl dithiocarbamate, bis-pentamethylenethiuram tetrasulfide, tetramethyl-thiuram disulfide or N-cyclohexyl-2-[4-morpholinodithio base sulphenamide.
6. low-smoke and halogen-free fire-retardant rubber according to claim 1 is characterized in that: surface modified nano magnesium hydroxide or aluminium hydroxide particle diameter 20～50nm, adopt the silane coupling agent surface modification that contains many sulfenyls or vinyl; Surface modification micron magnesium hydroxide or aluminium hydroxide particle diameter 2～20 μ m adopt stearic acid, amino or epoxy silane coupling surface modification.
7. described low-smoke and halogen-free fire-retardant rubber preparation method by extrusion molding thereof of claim 1-6, adopt mill or Banbury mixer that the rubber matrix is mixed at 80-100 ℃ earlier, be cooled to room temperature then, again with carbon black, modification oxyhydroxide, softening agent, fire retarding synergist, vulcanizing agent, vulcanization accelerator adds successively in proportion and mixes, then rubber unvulcanizate is added in the single screw extrusion machine, the control head, fuselage, the temperature of the shape of the mouth as one speaks and charging bole is at 50-90 ℃, the rotating speed of screw rod is in 15-40r/min, sizing material is extruded continuously, again through 175-200 ℃ of warm air or the moulding of 915-2450MHz microwave continuous vulcanization.
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