CN105330995B - A kind of environmental protection flame retardant bipeltate and preparation method thereof - Google Patents
A kind of environmental protection flame retardant bipeltate and preparation method thereof Download PDFInfo
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- CN105330995B CN105330995B CN201510928825.4A CN201510928825A CN105330995B CN 105330995 B CN105330995 B CN 105330995B CN 201510928825 A CN201510928825 A CN 201510928825A CN 105330995 B CN105330995 B CN 105330995B
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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—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2411/00—Characterised by the use of homopolymers or copolymers of chloroprene
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention provides a kind of environmental protection flame retardant bipeltate and preparation method thereof, is made successively through being kneaded with sulfur foam by mixed material；In terms of mass fraction, the mixed material includes：60~100 parts of ethylene propylene diene rubber；The neoprene of x parts, 0 ＜ x ＜ 40；5~10 parts of zinc oxide；3~4 parts of magnesia；4~6 parts of stearic acid；10~30 parts of carbon black；10~30 parts of aluminium hydroxide；10~30 parts of magnesium hydroxide；10~20 parts of Firebrake ZB；10~20 parts of calcium carbonate；10~20 parts of antimony oxide；1~2 part of sulphur；4~8 parts of vulcanization accelerator；5~10 parts of foaming agent.The present invention adds the neoprene of high flame retardant in EPDM, avoids the harm that directly addition halogen flame is brought, can realize ingrain fireproofing.More importantly, the present invention is using Firebrake ZB as fire retardant, the effect of cooperative flame retardant is produced with aluminium hydroxide, magnesium hydroxide, calcium carbonate and antimony oxide these fire retardants, so as to solve EPDM expanded materials poor flame retardant properties, not environmentally with mechanical property it is impacted the problems such as.
Description
Technical field
The present invention relates to field of rubber technology, more particularly to a kind of environmental protection flame retardant bipeltate and preparation method thereof.
Background technology
The modernization of society causes rubber industry to flourish, and rubber is widely used in various industries.Rubber pange
It is using rubber and other rubber chemicals, adds foaming agent, foamed shaping obtains product, wherein, ethylene propylene diene rubber
(EPDM) expanded material is because of its excellent resilience, electrical insulating property, the high fillibility of low-density, lower temperature resistance, heat resistance, resistance to ozone
The performance such as property and weatherability, both can be widely used for the less demanding sports goods of environmental condition, all kinds of buildings and system
In the industries such as cold, air-conditioning, the fields such as the auto parts and components higher to environmental requirement, medicine, military project apparatus are can be widely used for again.
Ethylene propylene diene rubber (EPDM) is the copolymer of ethene, propylene and a small amount of non-conjugated diene hydrocarbon, EPDM expanded materials
In generally also include fire retardant, can typically add halogen and phosphorous fire retardant at present, or add that heavy dose of other are inorganic
Fire retardant.But first method does not meet green social trend；Second method is past because amount of flame-retardant agent is more
It is past to reduce other performances of material, and reduce amount of flame-retardant agent and be difficult to ensure that fire resistance.Therefore, it is necessary to develop one kind
The environmental protection flame retardant bipeltate of function admirable.
The content of the invention
In view of this, the application provides a kind of environmental protection flame retardant bipeltate and preparation method thereof, environmental protection provided by the invention
Flame-retardant expanded rubber has preferable fire resistance and mechanical property.
The present invention provides a kind of environmental protection flame retardant bipeltate, is made successively through being kneaded with sulfur foam by mixed material；
In terms of mass fraction, the mixed material includes：
60~100 parts of ethylene propylene diene rubber；
The neoprene of x parts, 0 ＜ x ＜ 40；
5~10 parts of zinc oxide；
3~4 parts of magnesia；
4~6 parts of stearic acid；
10~30 parts of carbon black；
10~30 parts of aluminium hydroxide；
10~30 parts of magnesium hydroxide；
10~20 parts of Firebrake ZB；
10~20 parts of calcium carbonate；
10~20 parts of antimony oxide；
1~2 part of sulphur；
4~8 parts of vulcanization accelerator；
5~10 parts of foaming agent.
Preferably, the ethylene propylene diene rubber is made up of the material including ethene, propylene and ethylidene norbornene.
Preferably, the neoprene includes 80wt%~90wt% anti-form-1, and 4- polychlorobutadienes and 1wt%~
2wt% 1,2- polychlorobutadienes.
Preferably, the vulcanization accelerator includes 1~2 part of Thiourea accelerator, 1~2 part of thiazole accelerator and 2
~4 parts of thuriam acceserator.
Preferably, the vulcanization accelerator include 1~2 part 1,2- ethylene thioureas, 1~2 part of diphenyl disulfide simultaneously
Thiazole and 2~4 parts of curing are double (thiocarbonyl group dimethylamine).
Preferably, the mixed material also includes 1~2 part of age resistor and 5~10 parts of coupling agent.
Preferably, the mixed material also includes 10~15 parts of antiradiation agent and 5~10 parts of waterproofing agent.
The present invention also provides a kind of preparation method of environmental protection flame retardant bipeltate described above, comprises the following steps：
By the oxidation of ethylene propylene diene rubber, carbon black, aluminium hydroxide, magnesium hydroxide, the stearic acid of 1/2 mass and 1/2 mass
Zinc is kneaded, and obtains ethylene propylene diene rubber masterbatch；
The stearic acid of neoprene, magnesia, Firebrake ZB, calcium carbonate, antimony oxide and 1/2 mass is kneaded, obtained
Neoprene masterbatch；
By the ethylene propylene diene rubber masterbatch, the neoprene masterbatch, sulphur, vulcanization accelerator, foaming agent and
The zinc oxide of 1/2 mass is kneaded, and obtains sizing material；
The rubber vulcanization is foamed, obtains environmental protection flame retardant bipeltate.
Preferably, by ethylene propylene diene rubber, carbon black, aluminium hydroxide, magnesium hydroxide, the stearic acid of 1/2 mass and 1/2 mass
Zinc oxide be kneaded temperature≤110 DEG C；
The temperature that the stearic acid of neoprene, magnesia, Firebrake ZB, calcium carbonate, antimony oxide and 1/2 mass is kneaded
≤90℃；
By the ethylene propylene diene rubber masterbatch, the neoprene masterbatch, sulphur, vulcanization accelerator, foaming agent and
Temperature≤70 DEG C that the zinc oxide of 1/2 mass is kneaded.
Preferably, the temperature of the sulfur foam is 170 DEG C~190 DEG C, the pressure of the sulfur foam for 10MPa~
12MPa, the time of the sulfur foam is 10min~15min.
Compared with prior art, the present invention mainly using include ethylene propylene diene rubber, neoprene, zinc oxide, magnesia,
Stearic acid, carbon black, aluminium hydroxide, magnesium hydroxide, Firebrake ZB, calcium carbonate, antimony oxide, sulphur, vulcanization accelerator and foaming
The mixed material of agent, successively through mixing and sulfur foam, environmental protection flame retardant bipeltate is prepared.The present invention is mainly in EPDM
The neoprene of high flame retardant is added, the harm that directly addition halogen flame is brought is avoided, ingrain fireproofing can be realized.It is heavier
Want, the present invention using Firebrake ZB as fire retardant, with aluminium hydroxide, magnesium hydroxide, calcium carbonate and antimony oxide these
Fire retardant produces the effect of cooperative flame retardant, so as to solve EPDM expanded materials poor flame retardant properties, not environmentally with mechanical property by shadow
The problems such as ringing.
Embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below, it is clear that described embodiment
Only part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area
The every other embodiment that art personnel are obtained under the premise of creative work is not made, belong to the model that the present invention protects
Enclose.
The invention provides a kind of environmental protection flame retardant bipeltate, is made successively through being kneaded with sulfur foam by mixed material；
In terms of mass fraction, the mixed material includes：
60~100 parts of ethylene propylene diene rubber；
The neoprene of x parts, 0 ＜ x ＜ 40；
5~10 parts of zinc oxide；
3~4 parts of magnesia；
4~6 parts of stearic acid；
10~30 parts of carbon black；
10~30 parts of aluminium hydroxide；
10~30 parts of magnesium hydroxide；
10~20 parts of Firebrake ZB；
10~20 parts of calcium carbonate；
10~20 parts of antimony oxide；
1~2 part of sulphur；
4~8 parts of vulcanization accelerator；
5~10 parts of foaming agent.
Flame-retardant expanded rubber provided by the invention belongs to the high EPDM flame-retardant foam materials of fire resistance, and with excellent
Mechanical property and it is environmentally friendly the features such as.
Environmental protection flame retardant bipeltate provided by the invention is made through being kneaded with sulfur foam successively by mixed material；With quality
Number meter, the mixed material include 60~100 parts of ethylene propylene diene rubber, preferably include 70~100 parts of ethylene-propylene-diene monomer
Glue.In an embodiment of the present invention, used ethylene propylene diene rubber (EPDM) is a kind of nonpolar, nodeless mesh rubber.Make
To be preferred, EPDM Third monomer is ethylidene norbornene (ENB), i.e., described ethylene propylene diene rubber by including ethene, propylene and
The material of ethylidene norbornene is made.The present invention is not particularly limited to the source of the ethylene propylene diene rubber, can be used commercially available
Product, the ethylene propylene diene rubber EP 35 produced such as Japan SYnthetic Rubber Co. Ltd.
In terms of mass fraction, the mixed material of the environmental protection flame retardant bipeltate includes the neoprene of x parts, 0 ＜ x ＜
40, preferably include 20~30 parts of neoprene.Neoprene also known as chloroprene rubber, it is using chlorobutadiene as primary raw material
Carry out the synthetic rubber for α-be polymerized.The present invention prepares fire-retardant EPDM/CR with EPDM blendings using neoprene (CR) and foamed
Rubber, make it have the premium properties such as preferable anti-flammability, lower temperature resistance, heat-resisting, resistance to ozone and Weather-resistant.In the present invention
Embodiment in, used neoprene is sulphur adjustment type rubber.In an embodiment of the present invention, the neoprene is
Polarity, crystalline rubber.Preferably, the neoprene includes 80wt%~90wt% anti-form-1,4- polychlorobutadienes and
1wt%~2wt% 1,2- polychlorobutadienes.In a preferred embodiment of the invention, the neoprene includes
85wt% anti-form-1,4- polychlorobutadienes and 1.5wt% 1,2- polychlorobutadienes.The present invention comes to the neoprene
Source is not particularly limited, and can use commercially available prod, such as the neoprene CR 126 of German Lang Sheng groups production.
For the embodiment of the present invention on the basis of by the neoprene with high flame resistance and EPDM blendings, it is suitable to add
Halogen-free phosphorus-free inflaming retarding agent, the fire resistance of rubber bubble material is improved, beneficial to environmental protection and application.In terms of mass fraction, the environmental protection resistance
The mixed material of combustion bipeltate includes 10~30 parts of aluminium hydroxide (ATH), preferably includes 10~15 parts of aluminium hydroxide.Institute
Stating mixed material includes 10~30 parts of magnesium hydroxide (MDH), preferably includes 10~15 parts of magnesium hydroxide.In the present invention,
The aluminium hydroxide and magnesium hydroxide can form the flame-retardant system for acting on EPDM.
In terms of mass fraction, the mixed material of the environmental protection flame retardant bipeltate includes 10~20 parts of calcium carbonate
(CaCO3), preferably include 10~15 parts of calcium carbonate.The mixed material includes 10~20 parts of antimony oxide (Sb2O3),
Preferably include 10~15 parts of antimony oxide.In the present invention, the calcium carbonate and antimony oxide can be used as neoprene
Flame-retardant system.In addition, calcium carbonate can also increase the strength of materials and reduce cost.
In terms of mass fraction, the mixed material of the environmental protection flame retardant bipeltate includes 10~20 parts of Firebrake ZB (ZB),
Preferably include 10~15 parts of Firebrake ZB.In the present invention, Firebrake ZB this fire retardant is added, resistance that can respectively with EPDM and CR
The effect of System forming cooperative flame retardant is fired, makes flame-retardant expanded rubber that there is excellent anti-flammability.The present invention is to fire retardant ATH, resistance
Fire agent MDH, fire brake ZB, fire retardant CaCO3With fire retardant Sb2O3Source be not particularly limited, using commercially available prod.
In terms of mass fraction, the mixed material of the environmental protection flame retardant bipeltate include 5~10 parts zinc oxide, 3~4 parts
Magnesia and 4~6 parts of stearic acid.In one embodiment of the invention, the mixed material include 10 parts zinc oxide,
4 parts of magnesia and 6 parts of stearic acid.In the present invention, the zinc oxide, magnesia and stearic acid form the work of the vulcanization of rubber
Property agent system, vulcanization can be made more abundant, can also play a part of ensureing mobility and antioxidant capacity, moreover it is possible to increase the stretching of rubber
Intensity and anti-impact force；The zinc oxide, magnesia and stearic acid use product commonly used in the art.The environmental protection flame retardant
The mixed material of bipeltate includes 10~30 parts of carbon black, preferably includes 15~20 parts of carbon black.The carbon black is this area
Conventional rubber reinforcing filler, the present invention are not particularly limited to it.
In terms of mass fraction, the mixed material of the environmental protection flame retardant bipeltate includes 1~2 part of sulphur, preferably includes
1.4~1.9 parts of sulphur.The sulphur is vulcanizer commonly used in the art, and the present invention is not particularly limited to it.Accordingly
Ground, the mixed material include 4~8 parts of vulcanization accelerator (referred to as accelerator), vulcanizing system are formed with sulphur.The sulphur
It is to be used in combination in Vulcanization Process of Rubber with vulcanizing agent to change accelerator, can shorten cure time, reduces curing temperature, reduces vulcanizing agent
Dosage and a kind of rubber chemicals for improving the physical and mechanical properties of rubber etc., it can be divided into by chemical constitution：Dithiocarbamates first
Barbiturates, guanidine, Thiourea, thiazoles and thiurams etc..
In the present invention, the vulcanization accelerator preferably include 1~2 part Thiourea accelerator, 1~2 part of thiazoles
Accelerator and 2~4 parts of thuriam acceserator such as vulcanization accelerator TMTD.The present invention can be used in mixed way all kinds of vulcanizations and promote
Agent, facilitation effect are more preferable.Wherein, the Thiourea accelerator such as accelerator NA-22 or accelerator ETU；The thiazoles
Accelerator such as accelerator M or altax.In a preferred embodiment of the invention, the vulcanization accelerator includes 1~2 part
1,2- ethylene thioureas, 1~2 part of dibenzothiazyl disulfide and 2~4 parts of curing it is double (thiocarbonyl group dimethylamine).This
Invention is not particularly limited to the source of the vulcanization accelerator, typically using commercially available prod；Wherein, 1,2- ethylene thioureas are
Commercially available accelerator ETU, dibenzothiazyl disulfide are commercially available altax, and curing double (thiocarbonyl group dimethylamine) is commercially available
Vulcanization accelerator TMTD.In one embodiment of the invention, the vulcanization accelerator include 1 part accelerator ETU, 1.2 parts
Altax and 4 parts of Vulcanization accelerator TMTD.In addition, in one embodiment of the invention, and with zinc oxide and accelerator ETU
(NA-22) consumption of the double bond to sulphur in CR can, be reduced.
In terms of mass fraction, the mixed material of the environmental protection flame retardant bipeltate preferably wraps including 5~10 parts of foaming agent
Include 6~9 parts of foaming agent.In the present invention, the foaming agent is engaged with above-mentioned EPDM vulcanizing systems, and environmental protection is prepared
Flame-retardant expanded rubber.The embodiment of the present invention uses blowing agent AC, and the entitled azodicarbonamide of chemistry, its gas forming amount is big, not combustion-supporting,
There is self-extinguishment, beneficial to applied to environmental protection flame retardant bipeltate.
In terms of mass fraction, the mixed material of the environmental protection flame retardant bipeltate preferably also includes 1~2 part of age resistor,
More preferably also include 1~1.4 part of age resistor.The age resistor, which refers to, can prevent or suppress such as oxygen, heat, light, ozone and machinery
The factors such as stress destroy product properties, extend the compounding ingredient of product storage and service life, including the species such as amine and phenols.This
Invention preferably uses amines antioxidants, more preferably using antioxidant 4010NA (N- isopropyls-N '-diphenyl-para-phenylene diamine).It is described
Mixed material preferably also includes 5~10 parts of coupling agent, more preferably also includes 8~10 parts of coupling agent.The present invention can use even
Join inorganic matter and the compatibility before organic polymer in agent increase rubber, improve processing characteristics and mechanical property etc..Institute
Silicon systems, titanium system, aluminium system and chromium system etc., most commonly silane, titanate esters and aluminate coupling agent can be divided into by stating coupling agent.At this
In inventive embodiments, the coupling agent is preferably silane coupler, such as Si69 and Si75.In some embodiments of the present invention
In, the mixed material of the environmental protection flame retardant bipeltate also includes 1~2 part of age resistor and 5~10 parts of coupling agent.
In terms of mass fraction, the mixed material of the environmental protection flame retardant bipeltate preferably also includes 10~15 parts of radiation proof
Agent, more preferably also include 10~12 parts of antiradiation agent (also referred to as anti-irradiation agent), the radiation proof stability of rubber can be improved.It is described
Mixed material preferably also includes 5~10 parts of waterproofing agent, more preferably also includes 8~10 parts of waterproofing agent.In some of the present invention
In embodiment, the mixed material also includes 10~15 parts of antiradiation agent and 5~10 parts of waterproofing agent.In the another of the present invention
In a little embodiments, the mixed material is also including 1~2 part of age resistor, 5~10 parts of coupling agent, 10~15 parts of radiation proof
Agent and 5~10 parts of waterproofing agent.
Environmental protection flame retardant bipeltate of the present invention can be prepared by sulfur foam technique, and its cell size is suitable, divides
Cloth is uniform, and fire resistance is high, and mechanical property is good, also more environmentally friendly.
Correspondingly, the embodiment of the present invention additionally provides a kind of preparation method of environmental protection flame retardant bipeltate described above,
Comprise the following steps：
By the oxidation of ethylene propylene diene rubber, carbon black, aluminium hydroxide, magnesium hydroxide, the stearic acid of 1/2 mass and 1/2 mass
Zinc is kneaded, and obtains ethylene propylene diene rubber masterbatch；
The stearic acid of neoprene, magnesia, Firebrake ZB, calcium carbonate, antimony oxide and 1/2 mass is kneaded, obtained
Neoprene masterbatch；
By the ethylene propylene diene rubber masterbatch, the neoprene masterbatch, sulphur, vulcanization accelerator, foaming agent and
The zinc oxide of 1/2 mass is kneaded, and obtains sizing material；
The rubber vulcanization is foamed, obtains environmental protection flame retardant bipeltate.
The embodiment of the present invention is mixed into neoprene and replaces a part during environmental protection flame retardant bipeltate is prepared
EPDM, and the halogen-free phosphorus-free inflaming retarding agent of two kinds of systems is added, cooperative flame retardant is formed, makes obtained bipeltate fire resistance high,
Mechanical property is good, also more environmentally friendly.
In internal rubber mixer, the embodiment of the present invention using ethylene propylene diene rubber, carbon black, aluminium hydroxide, magnesium hydroxide,
The stearic acid of 1/2 mass and the zinc oxide of 1/2 mass are kneaded, and ethylene propylene diene rubber masterbatch is prepared.The content of each material
As it was noted above, it will not be repeated here.In one embodiment of the invention, the charging for preparing ethylene propylene diene rubber masterbatch is suitable
Sequence is：EPDM → 1/2 part stearic acid → 1/2 part zinc oxide → carbon black → age resistor → coupling agent → ATH and MDH, more specifically：
EPDM → 1/2 part stearic acid → 1/2 part zinc oxide → carbon black N330 → antioxidant 4010NA → silane coupler → ATH and MDH.
Preferably, the oxidation by ethylene propylene diene rubber, carbon black, aluminium hydroxide, magnesium hydroxide, the stearic acid of 1/2 mass and 1/2 mass
Temperature≤110 DEG C that zinc is kneaded, more preferably 80 DEG C~105 DEG C.The time of the mixing is preferably 5min~10min, more excellent
Elect 6min~8min as.
In internal rubber mixer, the embodiment of the present invention is using neoprene, magnesia, Firebrake ZB, calcium carbonate, three oxidations
Two antimony and the stearic acid of 1/2 mass are kneaded, and neoprene masterbatch is prepared.The content of each material is as it was noted above, herein
Repeat no more.In one embodiment of the invention, the charging sequence for preparing neoprene masterbatch is：CR → magnesia → 1/
2 parts of stearic acid → ZB, CaCO3And Sb2O3.Wherein, the material before arrow first adds, plus, the rest may be inferred after the material after arrow.Make
To be preferred, by the temperature of the stearic acid mixing of neoprene, magnesia, Firebrake ZB, calcium carbonate, antimony oxide and 1/2 mass
≤ 90 DEG C, more preferably 70 DEG C~85 DEG C.The time of the mixing is preferably 5min~10min, more preferably 6min~8min.
After obtaining ethylene propylene diene rubber masterbatch and neoprene masterbatch, the embodiment of the present invention is on opening rubber mixing machine
Prepare EPDM/CR elastomeric compounds.The embodiment of the present invention is by the ethylene propylene diene rubber masterbatch, the neoprene masterbatch, sulphur
Sulphur, vulcanization accelerator, the zinc oxide of foaming agent and 1/2 mass are kneaded, and obtain sizing material.
In some embodiments of the invention, on opening rubber mixing machine, by the ethylene propylene diene rubber masterbatch, described
Neoprene masterbatch, sulphur, vulcanization accelerator, the zinc oxide of foaming agent and 1/2 mass, and other rubber chemicals are as anti-
Radiation agent and/or waterproofing agent, are kneaded, and obtain sizing material.The content of each material is as it was noted above, will not be repeated here.At this
In the embodiment of invention, the charging sequence for preparing EPDM/CR elastomeric compounds is：EPDM masterbatch, CR masterbatch → anti-irradiation agent →
Waterproofing agent → 1/2 part zinc oxide → sulphur → accelerator → foaming agent, more specifically：EPDM masterbatch, CR masterbatch → anti-spoke
According to agent → waterproofing agent → 1/2 part zinc oxide → sulphur → accelerator ETU → altax → Vulcanization accelerator TMTD → blowing agent AC.Make
To be preferred, by the ethylene propylene diene rubber masterbatch, the neoprene masterbatch, sulphur, vulcanization accelerator, foaming agent and 1/
Temperature≤70 DEG C that the zinc oxide of 2 mass is kneaded, more preferably 60 DEG C~70 DEG C.The time of the mixing be preferably 5min~
10min, more preferably 6min~8min.In addition, the embodiment of the present invention can be last thin logical 6 times.
After obtaining sizing material, the embodiment of the present invention by sizing material slice, park.In embodiments of the present invention, the sizing material is thin logical
Slice afterwards, thickness can be 0.8cm~1cm.Then, the embodiment of the present invention quality be 5kg weight under normal temperature park 8 hours with
On；It is required that the environment parked is without sunlight is directly shone, humidity is moderate, dustless, ventilation condition is good.
The embodiment of the present invention by sizing material obtained in the previous step or pellet on vulcanizing press, carry out sulfur foam, through into
Type obtains environmental protection flame retardant bipeltate.
In the present invention, the temperature of the sulfur foam is preferably 170 DEG C~190 DEG C, more preferably 175 DEG C~185 DEG C.
The pressure of the sulfur foam is preferably 10MPa~12MPa；The time of the sulfur foam is preferably 10min~15min.Sulphur
After change foaming terminates, the embodiment of the present invention cools down 15min~20min setting under room temperature (25 DEG C), and final products are made.
After obtaining environmental protection flame retardant bipeltate, the present invention carries out performance test to it.The present invention is according to GB/T528-2009
《Vulcanize the measure of rubber or thermoplastic elastomer tensile stress-strain performance》, stretching experiment test is carried out, test equipment is Shenzhen
Newly think carefully the CMT6104 microcomputer controlled electronic universal testing machines of examination of materials Co., Ltd in city.
The present invention is according to ASTM D1056-2007《Spongy or expanded rubber class flexible, porous material specification》, enter
Row compression experiment and density experiment test, test equipment are the CMT6104 microcomputers that examination of materials Co., Ltd is newly thought carefully by Shenzhen
Control almighty test machine.
The present invention is according to GB/T 10707-2008《The measure of rubber combustion performance》, limited oxygen index experiment test is carried out,
Test equipment is the TTech-GBT2406-1 of this safe Tyke (Suzhou) detecting instrument Science and Technology Ltd. intelligent critical oxygen index
Tester.
The present invention is according to GB/T 10707-2008《The measure of rubber combustion performance》, vertical combustion experiment test is carried out, is surveyed
Try the horizontal vertical burning examination for the TTech-GBT2408-002 that equipment is this safe Tyke (Suzhou) detecting instrument Science and Technology Ltd.
Test instrument.
As a result show, the EPDM flame retardant rubber expanded material of the invention being prepared based on above-mentioned forming method is i.e.
EPDM/CR bipeltates, there is higher cell density and excellent mechanical property and fire resistance, its market has larger
Potential is developed, there is good industrial prospect.This environmental protection flame retardant bipeltate of the present invention both can be widely used for environment bar
In the industry such as the less demanding sports goods of part, all kinds of buildings and refrigeration, air-conditioning, it can be widely used for again higher to environmental requirement
The fields such as auto parts and components, medicine, military project apparatus.
In addition, the preparation technology of environmental protection flame retardant bipeltate of the present invention is simple.
For a further understanding of the application, the environmental protection flame retardant bipeltate provided with reference to embodiment the application and its
Preparation method is specifically described.
In following examples, each material number is mass fraction.In following examples and comparative example, EPDM used is
The ethylene propylene diene rubber EP 35 of Japan SYnthetic Rubber Co. Ltd's production；Neoprene is the bright neoprene for containing group production of Germany
CR 126；Carbon black is purchased from Shanxi Fu Li birch Chemical Co., Ltd.；Anti- irradiation agent is the anti-of Town in Shanghai brightness Chemical Co., Ltd. offer
Irradiate agent UV-531；Waterproofing agent is the waterproofing agent potassium methyl silicate that your writing emerging Chemical Co., Ltd. in Jinan provides；Silane coupler
KH-550 is purchased from Guangzhou Heng Yu Chemical Co., Ltd.s.
Embodiment 1
Material formula：20 parts of 80 parts of EPDM, CR, 10 parts of zinc oxide, 4 parts of magnesia, 6 parts of stearic acid, carbon black N330 20
Part, 10 parts of 10 parts of fire retardant ATH, fire retardant MDH, 10 parts of fire brake ZB, fire retardant CaCO310 parts, fire retardant Sb2O310
Part, 1 part of antioxidant 4010NA, anti-10 parts of agent of irradiation, 10 parts of silane coupler, 10 parts of waterproofing agent, 1.4 parts of sulphur, accelerator
1 part of ETU, 1.2 parts of altax, 4 parts of Vulcanization accelerator TMTD, 9 parts of blowing agent AC.
Specifically preparation method is：
(1) in internal rubber mixer, ethylene propylene diene rubber masterbatch is prepared.Charging sequence is：EPDM → 1/2 part tristearin
Acid → 1/2 part of zinc oxide → carbon black N330 → antioxidant 4010NA → silane coupler → ATH and MDH.Temperature：90℃.It is kneaded
Time：8min.
(2) in internal rubber mixer, neoprene masterbatch is prepared.Charging sequence is：CR → magnesia → 1/2 part is hard
Resin acid → ZB, CaCO3And Sb2O3.Temperature：70℃.Mixing time：8min.
(3) on opening rubber mixing machine, EPDM/CR elastomeric compounds are prepared.Charging sequence is：EPDM masterbatch, CR masterbatch
→ it is anti-irradiation agent → waterproofing agent → 1/2 part zinc oxide → sulphur → accelerator ETU → altax → Vulcanization accelerator TMTD → foaming
Agent AC.Temperature：60℃.Mixing time：8min.It is last thin logical 6 times, obtain sizing material.
(4) the thin logical rear slice of sizing material, thickness is 0.8~1.0cm.In the case where quality is 5kg weight, normal temperature is parked 12 hours；
It is required that the environment parked is without sunlight is directly shone, humidity is moderate, dustless, ventilation condition is good.
(5) by pellet obtained in the previous step, sulfur foam is molded on vulcanizing press, and its condition is：Temperature is 180 ± 5
DEG C, pressure 10MPa, time 10min.Then 20min setting is cooled down under room temperature (25 DEG C), final products are made.
Embodiment 2
Material formula：30 parts of 70 parts of EPDM, CR, 10 parts of zinc oxide, 4 parts of magnesia, 6 parts of stearic acid, carbon black N330 20
Part, 10 parts of 10 parts of fire retardant ATH, fire retardant MDH, 10 parts of fire brake ZB, fire retardant CaCO310 parts, fire retardant Sb2O310
Part, 1 part of antioxidant 4010NA, anti-10 parts of agent of irradiation, 10 parts of silane coupler, 10 parts of waterproofing agent, 1.4 parts of sulphur, accelerator
1 part of ETU, 1.2 parts of altax, 4 parts of Vulcanization accelerator TMTD, 9 parts of blowing agent AC.
Specific preparation method is identical with the preparation method of above-described embodiment 1.
Embodiment 3
Material formula：30 parts of 70 parts of EPDM, CR, 10 parts of zinc oxide, 4 parts of magnesia, 6 parts of stearic acid, carbon black N330 20
Part, 15 parts of 15 parts of fire retardant ATH, fire retardant MDH, 15 parts of fire brake ZB, fire retardant CaCO310 parts, fire retardant Sb2O310
Part, 1 part of antioxidant 4010NA, anti-10 parts of agent of irradiation, 10 parts of silane coupler, 10 parts of waterproofing agent, 1.4 parts of sulphur, accelerator
1 part of ETU, 1.2 parts of altax, 4 parts of Vulcanization accelerator TMTD, 9 parts of blowing agent AC.
Specific preparation method is identical with the preparation method of above-described embodiment 1.
Method as described above, the performance of the gained environmental protection flame retardant bipeltate of embodiment 1~3 is tested.Property
It can the results are shown in Table shown in 1, table 1 is the performance test results of the gained environmental protection flame retardant bipeltate of embodiment 1~3.
The performance test results of the gained environmental protection flame retardant bipeltate of 1 embodiment of table 1~3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Tensile strength (MPa) | 3.50 | 3.20 | 3.80 |
| Elongation at break (%) | 190 | 220 | 210 |
| Compress linear elastic modulus (MPa) | 5.6 | 5.0 | 5.4 |
| Density (g/cm3) | 0.19 | 0.19 | 0.20 |
| Limited oxygen index (%) | 32 | 31 | 35 |
| Vertical combustion grade | V1 | V1 | V0 |
Comparative example 1
Material formula：100 parts of EPDM, 8 parts of zinc oxide, 4 parts of magnesia, 3 parts of stearic acid, 20 parts of carbon black N330 are fire-retardant
50 parts of 100 parts of agent ATH, fire retardant MDH, 1 part of antioxidant 4010NA, anti-10 parts of agent of irradiation, 10 parts of silane coupler, waterproof
10 parts of agent, 1.4 parts of sulphur, 1.2 parts of altax, 4 parts of Vulcanization accelerator TMTD, 9 parts of blowing agent AC.
Specific preparation method and step (1) and the charging sequence and compounding conditions of step (3)~(5) in above-described embodiment 1
Etc. identical, CR is not added, flame-retardant expanded rubber is made.
Comparative example 2
Material formula：100 parts of EPDM, 10 parts of zinc oxide, 4 parts of magnesia, 6 parts of stearic acid, 20 parts of carbon black N330 are fire-retardant
100 parts of agent montmorillonite (granularity is 1250 mesh), 30 parts of fire retardant melamine cyanurate (MCA), 1 part of antioxidant 4010NA, prevent
10 parts of agent of irradiation, 10 parts of silane coupler, 10 parts of waterproofing agent, 1.4 parts of sulphur, 1 part of accelerator ETU, 1.2 parts of altax,
4 parts of Vulcanization accelerator TMTD, 9 parts of blowing agent AC.
Specific preparation method and step (1) and the charging sequence and compounding conditions of step (3)~(5) in above-described embodiment 1
Etc. identical, CR is not added, flame-retardant expanded rubber is made.
Comparative example 3
Material formula：30 parts of 70 parts of EPDM, CR, 10 parts of zinc oxide, 4 parts of magnesia, 6 parts of stearic acid, carbon black N330 20
Part, 1 part of antioxidant 4010NA, anti-10 parts of agent of irradiation, 10 parts of silane coupler, 10 parts of waterproofing agent, 1.4 parts of sulphur, accelerator
1 part of ETU, 1.2 parts of altax, 4 parts of Vulcanization accelerator TMTD, 9 parts of blowing agent AC.
Specific preparation method is identical with the preparation method of above-described embodiment 1, does not add fire retardant, and bipeltate is made.
Comparative example 4
Material formula：30 parts of 70 parts of EPDM, CR, 10 parts of zinc oxide, 4 parts of magnesia, 6 parts of stearic acid, carbon black N330 20
Part, 15 parts of 15 parts of fire retardant ATH, fire retardant MDH, fire retardant Sb2O35 parts, 1 part of antioxidant 4010NA, anti-10 parts of agent of irradiation,
10 parts of silane coupler, 10 parts of waterproofing agent, 1.4 parts of sulphur, 1 part of accelerator ETU, 1.2 parts of altax, Vulcanization accelerator TMTD 4
Part, 9 parts of blowing agent AC.
Specific preparation method is identical with the preparation method of above-described embodiment 1, does not add ZB and CaCO3, fire-retardant hair is made
Steep rubber.
Comparative example 5
Material formula：30 parts of 70 parts of EPDM, CR, 10 parts of zinc oxide, 4 parts of magnesia, 6 parts of stearic acid, carbon black N330 20
Part, 15 parts of fire retardant MDH, 15 parts of fire brake ZB, fire retardant Sb2O310 parts, 1 part of antioxidant 4010NA, anti-10 parts of agent of irradiation,
10 parts of silane coupler, 10 parts of waterproofing agent, 1.4 parts of sulphur, 1 part of accelerator ETU, 1.2 parts of altax, Vulcanization accelerator TMTD 4
Part, 9 parts of blowing agent AC.
Specific preparation method is identical with the preparation method of above-described embodiment 1, there is ZB, but does not have ATH and antimony oxide, makes
Obtain flame-retardant expanded rubber.
Comparative example 6
Material formula：30 parts of 70 parts of EPDM, CR, 10 parts of zinc oxide, 4 parts of magnesia, 6 parts of stearic acid, carbon black N330 20
Part, 15 parts of 15 parts of fire retardant ATH, fire retardant MDH, 15 parts of fire brake ZB, 1 part of antioxidant 4010NA, anti-10 parts of agent of irradiation,
10 parts of silane coupler, 10 parts of waterproofing agent, 1.4 parts of sulphur, 1 part of accelerator ETU, 1.2 parts of altax, Vulcanization accelerator TMTD 4
Part, 9 parts of blowing agent AC.
Specific preparation method is identical with the preparation method of above-described embodiment 1, there is ZB and ATH, but does not have antimony oxide, makes
Obtain flame-retardant expanded rubber.
Comparative example 7
Material formula：30 parts of 70 parts of EPDM, CR, 10 parts of zinc oxide, 4 parts of magnesia, 6 parts of stearic acid, carbon black N330 20
Part, 15 parts of fire retardant MDH, 15 parts of fire brake ZB, fire retardant Sb2O310 parts, 1 part of antioxidant 4010NA, anti-10 parts of agent of irradiation,
10 parts of silane coupler, 10 parts of waterproofing agent, 1.4 parts of sulphur, 1 part of accelerator ETU, 1.2 parts of altax, Vulcanization accelerator TMTD 4
Part, 9 parts of blowing agent AC.
Specific preparation method is identical with the preparation method of above-described embodiment 1, there is ZB and antimony oxide, but does not have ATH, makes
Obtain flame-retardant expanded rubber.
Method as described above, the performance of the gained bipeltate of comparative example 1~7 is tested.Results of property is shown in
Shown in table 2, table 2 is the performance test results of the gained bipeltate of comparative example 1~7.
The performance test results of the gained bipeltate of 2 comparative example of table 1~7
Pass through the comparison of above-described embodiment and comparative example, it can be seen that other flame resistant methods, which are difficult to prepare simultaneously, to be had
The EPDM expanded materials of excellent mechanical performances and fire resistance.The method of the present invention can be simple, function admirable with preparation technology
Environmental protection flame retardant EPDM/CR bipeltates, it can solve the problem that EPDM expanded materials poor flame retardant properties, not environmentally impacted with mechanical property
The problems such as.
Claims (6)
1. a kind of environmental protection flame retardant bipeltate, it is made successively through being kneaded with sulfur foam by mixed material；
In terms of mass fraction, the mixed material includes：
60~100 parts of ethylene propylene diene rubber；
The neoprene of x parts, 0 ＜ x ＜ 40；
5~10 parts of zinc oxide；
3~4 parts of magnesia；
4~6 parts of stearic acid；
10~30 parts of carbon black；
10~30 parts of aluminium hydroxide；
10~30 parts of magnesium hydroxide；
10~20 parts of Firebrake ZB；
10~20 parts of calcium carbonate；
10~20 parts of antimony oxide；
1~2 part of sulphur；
4~8 parts of vulcanization accelerator；The vulcanization accelerator includes 1~2 part of Thiourea accelerator, 1~2 part of thiazoles
Accelerator and 2~4 parts of thuriam acceserator；
5~10 parts of foaming agent；
The mixed material also includes 1~2 part of age resistor and 5~10 parts of coupling agent；The mixed material also include 10~
15 parts of antiradiation agent and 5~10 parts of waterproofing agent.
2. environmental protection flame retardant bipeltate according to claim 1, it is characterised in that the ethylene propylene diene rubber is by including second
The material of alkene, propylene and ethylidene norbornene is made.
3. environmental protection flame retardant bipeltate according to claim 1, it is characterised in that the vulcanization accelerator includes 1~2 part
1,2- ethylene thioureas, 1~2 part of dibenzothiazyl disulfide and 2~4 parts of curing it is double (thiocarbonyl group dimethylamine).
4. a kind of preparation method of the environmental protection flame retardant bipeltate described in claim 1, comprises the following steps：
By ethylene propylene diene rubber, carbon black, aluminium hydroxide, magnesium hydroxide, age resistor, coupling agent, the stearic acid of 1/2 mass and 1/2
The zinc oxide of quality is kneaded, and obtains ethylene propylene diene rubber masterbatch；
The stearic acid of neoprene, magnesia, Firebrake ZB, calcium carbonate, antimony oxide and 1/2 mass is kneaded, obtains neoprene
Rubber masterbatch；
The ethylene propylene diene rubber masterbatch, the neoprene masterbatch, anti-irradiation agent, waterproofing agent, sulphur, vulcanization are promoted
The zinc oxide of agent, foaming agent and 1/2 mass is kneaded, and obtains sizing material；
The rubber vulcanization is foamed, obtains environmental protection flame retardant bipeltate.
5. preparation method according to claim 4, it is characterised in that by ethylene propylene diene rubber, carbon black, aluminium hydroxide, hydrogen
Temperature≤110 DEG C that magnesia, age resistor, coupling agent, the zinc oxide of the stearic acid of 1/2 mass and 1/2 mass are kneaded；
Temperature≤90 that the stearic acid of neoprene, magnesia, Firebrake ZB, calcium carbonate, antimony oxide and 1/2 mass is kneaded
℃；
The ethylene propylene diene rubber masterbatch, the neoprene masterbatch, anti-irradiation agent, waterproofing agent, sulphur, vulcanization are promoted
Temperature≤70 DEG C that the zinc oxide of agent, foaming agent and 1/2 mass is kneaded.
6. the preparation method according to claim 4 or 5, it is characterised in that the temperature of the sulfur foam be 170 DEG C~
190 DEG C, the pressure of the sulfur foam is 10MPa~12MPa, and the time of the sulfur foam is 10min~15min.
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| CN107200891A (en) * | 2017-05-09 | 2017-09-26 | 广西桂山特种橡胶制品有限公司 | A kind of fire retardant combination for neoprene |
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| CN111303544B (en) * | 2020-04-14 | 2022-06-21 | 国光电器股份有限公司 | Flame-retardant high-damping rubber composition and preparation method and application thereof |
| CN111423666B (en) * | 2020-05-27 | 2023-07-14 | 厦门麦丰密封件有限公司 | Ethylene propylene diene monomer flushing valve membrane and preparation method thereof |
| CN111944246A (en) * | 2020-08-24 | 2020-11-17 | 四川远星橡胶有限责任公司 | High-temperature-resistant oil-resistant high-flame-retardant environment-friendly foaming adhesive mixture |
| CN113912953A (en) * | 2021-10-29 | 2022-01-11 | 宜兴市玛斯特新型材料有限公司 | Foaming material and method for preparing rubber foaming plate by using same |
| CN114872243B (en) * | 2022-04-28 | 2024-04-23 | 山西新华防化装备研究院有限公司 | Inflatable corner reflector air rib material and preparation method thereof |
| CN115181366A (en) * | 2022-07-15 | 2022-10-14 | 智筑汇创(上海)新材料科技有限公司 | Halogen-free flame-retardant EPDM foam composite material and preparation method thereof |
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