CN108559184A - Environment-friendly type ethylene propylene diene rubber particle and preparation method thereof - Google Patents
Environment-friendly type ethylene propylene diene rubber particle and preparation method thereof Download PDFInfo
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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/06—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene-diene terpolymers
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- 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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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The present invention provides a kind of environment-friendly type ethylene propylene diene rubber particles and preparation method thereof, are related to plastic cement race track filler particles object technical field, are mainly prepared by the following raw material according to the mass fraction：100 parts of EPT rubber composition, 50 80 parts of filler, 13 parts of activator, 13 parts of environmentally friendly accelerating agent, 15 parts of vulcanizing agent, 5 10 parts of reinforcing agent, 13 parts of pigment, wherein, EPT rubber composition is the mixture of ethylene propylene diene rubber, acrylonitrile modified ethylene propylene diene rubber and acrylic acid modified ethylene propylene diene rubber, and the mass ratio of three is (1 3)：(1‑3)：(1 3), preferably 1:2:2, alleviate existing ethylene propylene diene rubber generally all tensile strength, wear-resistant strength and the smaller technical problem of elasticity, reach raising tensile strength, wear-resistant strength, consistency and elasticity, significantly prolonged the service life, reduces the technique effect of the maintenance cost of plastic cement race track.
Description
Technical field
The present invention relates to plastic cement race track filler particles object technical fields, more particularly, to a kind of environment-friendly type ethylene propylene diene rubber
Particle and preparation method thereof.
Background technology
Plastic cement race track refers to being spread with the place for track and field events that the synthetic material elastomer with rubber properties is laid with
Face face layer, the country, which is generally used, at present mats formation to runway using polyurethane as pavement material, occurs in recent years with environment-protective water
Property acrylic resin be pavement material plastic cement race track, but whether which kind of pavement material is all filled out using rubber grain substantially
It fills.
Existing ethylene propylene diene rubber particle is typically all to be prepared using ethylene propylene diene rubber, tensile strength, resistance to
It is smaller to grind intensity, consistency and elasticity, needs to re-pave using 2-3, not only increases the maintenance cost of plastic cement race track,
And waste a large amount of man power and material.
In view of this, special propose the present invention.
Invention content
One of the objects of the present invention is to provide a kind of environment-friendly type ethylene propylene diene rubber particles, to alleviate existing EPDM
Rubber is typically all to be prepared using ethylene propylene diene rubber, and tensile strength, wear-resistant strength and elasticity are smaller, use 2-3
It needs in year to re-pave, component increases the maintenance cost of plastic cement race track, and wastes the skill of a large amount of man power and material
Art problem.
Environment-friendly type ethylene propylene diene rubber particle provided by the invention, mainly by according to the mass fraction the following raw material prepare and
At：100 parts of EPT rubber composition, 50-80 parts of filler, 1-3 parts of activator, environmentally friendly accelerating agent 1-3 parts, vulcanizing agent 1-
5 parts, 5-10 parts of reinforcing agent, 1-3 parts of pigment, wherein EPT rubber composition is ethylene propylene diene rubber, acrylonitrile modified three
The mixture of first EP rubbers and acrylic acid modified ethylene propylene diene rubber, and the mass ratio of three is (1-3)：(1-3)：(1-3),
Preferably 1:2:2.
Further, the environment-friendly type ethylene propylene diene rubber particle mainly by as mass fraction the following raw material prepare and
At：100 parts of EPT rubber composition, 55-65 parts of filler, 1-3 parts of activator, environmentally friendly accelerating agent 1-3 parts, vulcanizing agent 2-
4 parts, 5-10 parts of reinforcing agent, 1-3 parts of pigment, wherein EPT rubber composition is ethylene propylene diene rubber, acrylonitrile modified three
The mixture of first EP rubbers and acrylic acid modified ethylene propylene diene rubber, and the mass ratio of three is (1-3)：(1-3)：(1-3),
Preferably 1:2:2.
Further, the reinforcing agent is selected from least one of graphene, carbon fiber and carbon nanotube；Preferably, institute
The mixture that reinforcing agent is graphene, carbon fiber and carbon nanotube is stated, and the mass ratio of three is (1-2)：(1-2)：(1-2),
More preferably 1:1:1.
Further, the pigment is the Color master batch containing active strong compound, the colour of the active hydrogen-contg compound
The preparation method of master batch, includes the following steps：Active hydrogen-contg compound is added in pigment, adds Color master batch carrier, so
Extruding pelletization afterwards obtains the Color master batch of active hydrogen-contg compound, wherein the active hydrogen-contg compound is polyether polyol
Or polyester polyol.
Further, the preparation method of the acrylonitrile modified ethylene propylene diene rubber, includes the following steps：First by ternary second
Third rubber solution adds acrylonitrile and initiator in toluene solution, under heating conditions, generates acrylonitrile modified ternary
EP rubbers, wherein the mass ratio of acrylonitrile and ethylene propylene diene rubber is 3:(3-4).
Further, the preparation method of the acrylic acid modified ethylene propylene diene rubber includes the following steps：By acrylic acid, three
First EP rubbers and initiator are uniformly mixed, and through double screw extruder extruding pelletization, obtain acrylic acid modified ethylene-propylene-diene monomer
Glue, wherein the mass ratio of acrylic acid and ethylene propylene diene rubber is 1：(12-18).
Further, the filler is selected from least one of calcium carbonate, white carbon, talcum powder, clay and zinc oxide；
The activator is the mixture of organic activator and inorganic activator, and the organic activator is odium stearate and/or tristearin
Sour potassium, the inorganic activator are zinc oxide and/or magnesia.
Further, the environmentally friendly accelerating agent is selected from N- cyclohexyl -2- benzene thiazolyls sulfenamide, dibenzyl dithio ammonia
At least one of base zinc formate, tetra-benzyl thiram disulfide, curing dicaprolactam；The vulcanizing agent be selected from sulphur,
In cumyl peroxide, dual-tert-butyl peroxide propylbenzene, 1,1 di tert butylperoxy 3,3,5 trimethylcyclohexane extremely
Few one kind.
The second object of the present invention is to provide a kind of preparation method of environment-friendly type ethylene propylene diene rubber particle, existing to alleviate
Have ethylene propylene diene rubber be typically all be prepared using ethylene propylene diene rubber, tensile strength, wear-resistant strength and elasticity compared with
It is small, it needs to re-pave using 2-3, component increases the maintenance cost of plastic cement race track, and wastes a large amount of manpower
And the technical issues of material resources.
The preparation method of environment-friendly type ethylene propylene diene rubber particle provided by the invention, includes the following steps：
(a) by EPT rubber composition, filler, activator, environmentally friendly accelerating agent, vulcanizing agent, reinforcing agent and pigment
It is uniformly mixed, is kneaded and is refined successively, obtain refining mixture；
(b) refining mixture is extruded into sheet material, is granulated after sheet material is vulcanized, obtains environment-friendly type ternary second
Third rubber grain.
Further, in step (a), mixing carries out in mixer, and refining carries out in open mill.
Environment-friendly type ethylene propylene diene rubber particle provided by the invention, passes through EPT rubber composition, filler, activation
Agent, environmentally friendly accelerating agent, vulcanizing agent and reinforcing agent and pigment mutually cooperate with, the stretching of environment-friendly type ethylene propylene diene rubber particle obtained
Intensity, wear-resistant strength, consistency and elasticity significantly improve, and service life significantly extends, and can be up to 5 years or more, effectively reduce
The maintenance cost of plastic cement race track, has saved a large amount of man power and material.
The preparation method of environment-friendly type ethylene propylene diene rubber particle provided by the invention, it is simple for process, it is easy to operate, it saves
A large amount of man power and material, is suitable for industrialized production.
Specific implementation mode
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
According to an aspect of the present invention, the present invention provides a kind of environment-friendly type ethylene propylene diene rubber particles, mainly by pressing
The following raw material of mass fraction meter is prepared：100 parts of EPT rubber composition, 50-80 parts of filler, activator 1-3
Part, environmentally friendly accelerating agent 1-3 parts, 1-5 parts of vulcanizing agent, 5-10 parts of reinforcing agent, 1-3 parts of pigment, wherein EPT rubber composition
For ethylene propylene diene rubber, the mixture of acrylonitrile modified ethylene propylene diene rubber and acrylic acid modified ethylene propylene diene rubber, and three
Mass ratio be (1-3)：(1-3)：(1-3), preferably 1:2:2.
Environment-friendly type ethylene propylene diene rubber particle provided by the invention, passes through EPT rubber composition, filler, activation
Agent, environmentally friendly accelerating agent, vulcanizing agent and reinforcing agent and pigment mutually cooperate with, the stretching of environment-friendly type ethylene propylene diene rubber particle obtained
Intensity, wear-resistant strength, consistency and elasticity significantly improve, and service life significantly extends, and can be up to 5 years or more, effectively reduce
The maintenance cost of plastic cement race track, has saved a large amount of man power and material.
In the present invention, the typical but non-limiting mass fraction of filler as 51,52,53,54,55,56,57,
58、59、60、61、62、63、64、65、66、67、68、69、70、71、72、73、74、75、76、77、78、79、80、81、82、
83,84,85,86,87,88,89,90,91,92,93,94,95,96,97,98 or 99 parts.
In the present invention, the typical but non-limiting mass fraction of activator as 1.1,1.2,1.3,1.4,1.5,
1.6,1.7,1.8,1.9,2,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9 or 3 parts.
In the present invention, the typical but non-limiting mass fraction of environmentally friendly accelerating agent as 1.1,1.2,1.3,1.4,
1.5,1.6,1.7,1.8,1.9,2,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9 or 3 parts.
In the present invention, the typical but non-limiting mass fraction of vulcanizing agent as 1.1,1.2,1.3,1.4,1.5,
1.6、1.7、1.8、1.9、2、2.1、2.2、2.3、2.4、2.5、2.6、2.7、2.8、2.9、3、3.1、3.2、3.3、3.4、3.5、
3.6,3.7,3.8,3.9,4,4.1,4.2,4.3,4.4,4.5,4.6,4.7,4.8 or 4.9 parts.
In the present invention, the typical but non-limiting mass fraction of reinforcing agent as 5.1,5.2,5.3,5.4,5.5,
5.6、5.7、5.8、5.9、6、6.1、6.2、6.3、6.4、6.5、6.6、6.7、6.8、6.9、7、7.1、7.2、7.3、7.4、7.5、
7.6、7.7、7.8、7.9、8、8.1、8.2、8.3、8.4、8.5、8.6、8.7、8.8、8.9、9、9.1、9.2、9.3、9.4、9.5、
9.6,9.7,9.8 or 9.9 parts.
In the present invention, the typical but non-limiting mass fraction of pigment as 1.1,1.2,1.3,1.4,1.5,1.6,
1.7,1.8,1.9,2,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8 or 2.9 parts.
In the present invention, when EPT rubber composition is ethylene propylene diene rubber, acrylonitrile modified ethylene propylene diene rubber
With the mixture of acrylic acid modified ethylene propylene diene rubber, and the mass ratio of three be (1-3)：(1-3)：It is obtained when (1-3)
The tensile strength of environment-friendly type ethylene propylene diene rubber particle, wear-resistant strength, consistency and elasticity significantly improve, and comprehensive performance is more excellent
It is different, service life can be significantly improved, especially when the mass ratio of three is 1:2:When 2, obtained environment-friendly type EPDM
Tensile strength, the wear-resistant strength higher of rubber grain, elasticity is more preferable, and comprehensive performance is more excellent.
In a preferred embodiment of the invention, reinforcing agent in graphene, carbon fiber and carbon nanotube at least one
Kind, it is preferred that the reinforcing agent is the mixture of graphene, carbon fiber and carbon nanotube, and the mass ratio of three is (1-2)：
(1-2)：(1-2), more preferably 1:1:1.
In a preferred embodiment of the invention, graphene is modified graphene, passes through graphene and straight chain compound
It is prepared under the catalysis of quaternary ammonium salt, two end groups of wherein branched chain compound are respectively hydroxyl and epoxy group, straight chain compound
Preferably C5-10Straight chain compound.
By the way that reinforcing agent is added in environment-friendly type ethylene propylene diene rubber provided by the invention, the crosslinking of EP rubbers is improved
Density, it is efficient to promote the vulcanization of EP rubbers molecule, effectively increases the tensile strength of ethylene propylene diene rubber particle and wear-resisting
Intensity, while also so that elasticity is more preferable, comprehensive performance is more excellent, especially when reinforcing agent is that graphene, carbon fiber and carbon are received
The mixture of mitron, and the mass ratio of three is (1-2)：(1-2)：(1-2), more preferably 1:1:When 1, obtained environment-friendly type
The comprehensive performance of ethylene propylene diene rubber is more preferably.
In a preferred embodiment of the invention, pigment is the Color master batch of active hydrogen-contg compound, preparation method, packet
Include following steps：Active hydrogen-contg compound is added in pigment, Color master batch carrier is added, then extruding pelletization, obtains
The Color master batch of active hydrogen-contg compound, wherein the active hydrogen-contg compound is polyether polyol or polyester polyol.
In a preferred embodiment of the invention, master batch carrier is resin, preferably EP rubbers particle.
It is female by the colour that active hydrogen-contg compound is added in environment-friendly type ethylene propylene diene rubber particle provided by the invention
Grain so that it can be chemically reacted with polyurethane spreading material, to greatly improve ethylene propylene diene rubber particle and poly- ammonia
The bonding force of ester pavement material makes it be combined with polyurethane spreading material more stable, and using effect is more excellent.
In a preferred embodiment of the invention, the preparation method of acrylonitrile modified ethylene propylene diene rubber, including walk as follows
Suddenly：First ethylene propylene diene rubber is dissolved in toluene solution, adds acrylonitrile and initiator, under heating conditions, is generated
Acrylonitrile modified ethylene propylene diene rubber, wherein the mass ratio of acrylonitrile and ethylene propylene diene rubber is 3:(3-4).
In a preferred embodiment of the invention, used initiator is preferably benzoyl peroxide, in preparation process
In, the temperature for carrying out graft reaction is preferably 60-100 DEG C, more preferably 80 DEG C.
When the mass ratio of acrylonitrile and ethylene propylene diene rubber is 3:When (3-4), graft reaction carries out the most abundant, made
At acrylonitrile modified ethylene propylene diene rubber comprehensive performance it is the most excellent.
In a preferred embodiment of the invention, the preparation method of acrylic acid modified ethylene propylene diene rubber, including walk as follows
Suddenly：Acrylic acid, ethylene propylene diene rubber and initiator are uniformly mixed, through double screw extruder extruding pelletization, obtain acrylic acid
Modified EPT rubber, wherein the mass ratio of acrylic acid and ethylene propylene diene rubber is 1：(12-18).
The acrylic acid modified ethylene propylene diene rubber that the present invention uses is grafted using twin-screw extrusion, is not had using toxic
Evil solvent simplifies technical process, and made acrylic acid modified ethylene propylene diene rubber has excellent mechanics mechanical performance,
Especially when the mass ratio of acrylic acid and ethylene propylene diene rubber is 1：(12-18), more preferably 1:When 15, the acrylic acid that is shortened into
The comprehensive performance of modified EPT rubber is the most excellent.
During preparing acrylic acid modified ethylene propylene diene rubber, odium stearate is preferably added to as activator, to promote
Into the progress of modified-reaction, the efficiency of acrylic acid-grafted ethylene propylene diene rubber is improved.
In a preferred embodiment of the invention, filler is selected from calcium carbonate, white carbon, talcum powder, clay and zinc oxide
At least one of.
In environment-friendly type ethylene propylene diene rubber particle provided by the invention, it can be reduced by the way that filler is added on the one hand
This, still further aspect can also improve mechanics mechanical performance.
In a preferred embodiment of the invention, activator is the mixture of organic activator and inorganic activator, described
Organic activator is odium stearate and/or potassium stearate, and the inorganic activator is zinc oxide and/or magnesia.
In environment-friendly type ethylene propylene diene rubber particle provided by the invention, by the way that organic activator and inorganic activation is added
Agent can be effectively increased between ethylene propylene diene rubber and acrylic acid modified ethylene propylene diene rubber and acrylonitrile ethylene propylene diene rubber
Crosslink density and curingprocess rate, make obtained environment-friendly type ethylene propylene diene rubber particle have superior mechanics mechanical performance and
Resilience performance.
It in a preferred embodiment of the invention, can using odium stearate and/or potassium stearate as organic activator
The viscosity of rubber is reduced, improves processing performance, improves the plasticity of rubber；Contribute to coordinate accelerating agent simultaneously, plays the second rush
Into the effect of agent, accelerate setting rate.
In a preferred embodiment of the invention, stream is primarily served as inorganic active agent using zinc oxide or magnesia
Dynamic property and antioxidant capacity, increase the tensile strength and shock resistance example of rubber, are used as activating agent followed by sulfidation and have
The reaction of machine accelerating agent, stearic acid, sulphur etc. is happened at zinc oxide or aoxidizes the surface of magnesium ion, due to zinc oxide or magnesia
Big to the affinity of electronics, the ability of adsorption enhancer is strong, and the accelerating agent for dissolving in sizing material is generated in the effect of organic activator
Zinc salt or magnesium salts to improve its solubility, and form a kind of complex compound with amine or aliphatic acid, keep accelerating agent more active, sulphur
Agent is added in complex compound, acts on forming very strong vulcanizing agent, in the process, zinc oxide or magnesia table by induced activation
Face is constantly occurring reaction, and grain size constantly reduces, and consumes zinc oxide or magnesia until sizing material full cure, contributes to ternary
Crosslinking curing between EP rubbers and acrylonitrile modified ethylene propylene diene rubber and acrylic acid modified ethylene propylene diene rubber.
In a preferred embodiment of the invention, environmentally friendly accelerating agent is selected from N- cyclohexyl -2- benzene thiazolyls sulfenamide, two
At least one of benzyl dithiocarbamate zinc, tetra-benzyl thiram disulfide, curing dicaprolactam.
By using N- cyclohexyl -2- benzene thiazolyls sulfenamide, zinc dibenzyl dithiocarbamate, four benzyl of curing
At least one of base thiuram, curing dicaprolactam are used as accelerating agent so that N- nitrous is free of in accelerating agent
Amine, and N- nitrosamine is strong carcinogen, and toxic hepatitis and ascites, preferred embodiment for the present invention institute are shown as to human liver
The environmentally friendly accelerating agent used is free of N- nitrosamine, has good safety and environment-friendly type energy.
In a preferred embodiment of the invention, vulcanizing agent is selected from sulphur, cumyl peroxide, dual-tert-butyl peroxide third
At least one of base benzene, 1,1 di tert butylperoxy 3,3,5 trimethylcyclohexane.
Vulcanizing agent is added in environment-friendly type ethylene propylene diene rubber particle provided by the invention, helps to improve rubbery system
The degree of cross linking, to ensure the good comprehensive performance of rubber.
According to another aspect of the present invention, the present invention also provides the preparation sides of above-mentioned environment-friendly type ethylene propylene diene rubber particle
Method includes the following steps：
(a) by EPT rubber composition, filler, activator, environmentally friendly accelerating agent, vulcanizing agent, reinforcing agent and pigment
It is uniformly mixed, is kneaded and is refined successively, obtain refining mixture；
(b) refining mixture is extruded into sheet material, is granulated after sheet material is vulcanized, obtains environment-friendly type ternary second
Third rubber grain.
The preparation method of environment-friendly type ethylene propylene diene rubber particle provided by the invention, it is simple for process, it is easy to operate, it saves
A large amount of man power and material, is suitable for industrialized production.
Double refining is carried out by mixing and mill in environment-friendly type ethylene propylene diene rubber particle provided by the invention, is contributed to
The crosslinking degree for improving rubber, to ensure that vulcanizate has good tensile strength, elongation at break etc., to prepare comprehensive performance
Excellent vulcanizate.
In a preferred embodiment of the invention, in step (a), mixing carries out in mixer, refines in open mill
Middle progress.
In accelerating agent used in environment-friendly type ethylene propylene diene rubber particle provided by the invention, N- nitrosamine is free of, is encountered
When hot weather and strong ultraviolet radiation, release poison gas is reduced, the environmental-protecting performance of vulcanizate is helped to improve, in addition using has
Both machine accelerating agent and inorganic accelerator generate synergistic effect, help speed up the curing rate of vulcanized rubber, meanwhile, accelerating agent
With vulcanizing agent collective effect, the facilitation of accelerating agent is further enhanced.
Technical solution described in the invention is described further with reference to embodiment and comparative example.
Embodiment 1
A kind of environment-friendly type ethylene propylene diene rubber particle is present embodiments provided, mainly by the following raw material according to the mass fraction
It is prepared：100 parts of EPT rubber composition, 50 parts of calcium carbonate, 1 part of odium stearate, 2 parts of zinc oxide, N- cyclohexyl -2-
1 part of benzene thiazolyl sulfenamide, 5 parts of cumyl peroxide, 5 parts of graphene, 1 part of common color color masterbatch, wherein EPDM
Rubber composition is the mixing of ethylene propylene diene rubber, acrylonitrile modified ethylene propylene diene rubber and acrylic acid modified ethylene propylene diene rubber
Object, and the mass ratio of three is 3：1：1, acrylonitrile modified ethylene propylene diene rubber prepared by acrylonitrile and ethylene propylene diene rubber and
At, and the mass ratio of the two is 1:1；Acrylic acid modified ethylene propylene diene rubber is prepared by acrylic acid and ethylene propylene diene rubber,
And the mass ratio of the two is 1:12, the method for acrylonitrile modified ethylene propylene diene rubber and acrylic acid modified ethylene propylene diene rubber is as above
Described, details are not described herein.
Embodiment 2
A kind of environment-friendly type ethylene propylene diene rubber particle is present embodiments provided, mainly by the following raw material according to the mass fraction
It is prepared：100 parts of EPT rubber composition, 80 parts of talcum powder, 0.5 part of potassium stearate, 0.5 part of magnesia, dibenzyl
3 parts of zinc dithiocarbamate, 1 part of dual-tert-butyl peroxide propylbenzene, 10 parts of carbon fiber, 3 parts of common color color masterbatch, wherein three
First EP rubbers composition is ethylene propylene diene rubber, acrylonitrile modified ethylene propylene diene rubber and acrylic acid modified ethylene propylene diene rubber
Mixture, and the mass ratio of three be 3：1：1, acrylonitrile modified ethylene propylene diene rubber is by acrylonitrile and ethylene propylene diene rubber system
It is standby to form, and the mass ratio of the two is 3:4；Acrylic acid modified ethylene propylene diene rubber prepared by acrylic acid and ethylene propylene diene rubber and
At, and the mass ratio of the two is 1:18.
Embodiment 3
A kind of environment-friendly type ethylene propylene diene rubber particle is present embodiments provided, mainly by the following raw material according to the mass fraction
It is prepared：100 parts of EPT rubber composition, 60 parts of white carbon, 1 part of odium stearate, 1 part of zinc oxide, four benzyl of curing
2 parts of base thiuram, 1,1- di-t-butyl peroxy -3,3,2 parts of 5- trimethyl-cyclohexanes, 7 parts of carbon nanotube, common color color masterbatch
2 parts, wherein EPT rubber composition is ethylene propylene diene rubber, acrylonitrile modified ethylene propylene diene rubber and acrylic acid modified
The mixture of ethylene propylene diene rubber, and the mass ratio of three is 1：2：2, acrylonitrile modified ethylene propylene diene rubber is by acrylonitrile and three
First EP rubbers is prepared, and the mass ratio of the two is 3:4；Acrylic acid modified ethylene propylene diene rubber is by acrylic acid and ternary second
Third rubber is prepared, and the mass ratio of the two is 1:15.
Embodiment 4
The present embodiment and embodiment 3 the difference is that, use the Color master batch of hydrogen-containing compound to substitute common color
Color masterbatch, the hydrogen-containing compound are polyether polyol, and details are not described herein.
Embodiment 5
The present embodiment and embodiment 4 the difference is that, replaced using the mixture of graphene, carbon fiber and carbon nanotube
For carbon nanotube, and the mass ratio 6 of three:2:3.
Embodiment 6
The present embodiment and embodiment 4 the difference is that, replaced using the mixture of graphene, carbon fiber and carbon nanotube
For carbon nanotube, and the mass ratio 3 of three:2:3.
Embodiment 7
The present embodiment and embodiment 4 the difference is that, replaced using the mixture of graphene, carbon fiber and carbon nanotube
For carbon nanotube, and the mass ratio 1 of three:1:1.
Embodiment 8
The present embodiment and embodiment 7 the difference is that, acrylonitrile modified ethylene propylene diene rubber is by acrylonitrile and ternary
EP rubbers is prepared, and the mass ratio of the two is 5:3.
Embodiment 9
The present embodiment and embodiment 7 the difference is that, acrylonitrile modified ethylene propylene diene rubber is by acrylonitrile and ternary
EP rubbers is prepared, and the mass ratio of the two is 1:2.
Embodiment 10
The present embodiment and embodiment 7 the difference is that, acrylic acid modified ethylene propylene diene rubber is by acrylic acid and ternary
EP rubbers is prepared, and the mass ratio of the two is 1:20.
Embodiment 11
The present embodiment and embodiment 7 the difference is that, acrylic acid modified ethylene propylene diene rubber is by acrylic acid and ternary
EP rubbers is prepared, and the mass ratio of the two is 1:8.
The preparation method for the environment-friendly type ethylene propylene diene rubber particle that above-described embodiment 1-11 is provided, includes the following steps：
(a) by EPT rubber composition, filler, activator, environmentally friendly accelerating agent, vulcanizing agent, reinforcing agent and pigment
Be uniformly mixed, put into mixer in be kneaded, melting temperature be 125 DEG C, time 60min, put into again after mixing in open mill into
Row refining, refining temperature are 65 DEG C, and time 30min obtains refining mixture；
(b) refining mixture is put into into extruder extrusion sheet, extruder temperature is 120 DEG C, then input vulcanization
Vulcanized in tank, vulcanization time 30min, temperature is 160 DEG C, pressure 7MPa, and tank is gone out after vulcanization, and room temperature cools down 12 hours
It is granulated classification afterwards, obtains environment-friendly type ethylene propylene diene rubber particle.
Comparative example 1
This comparative example provides a kind of environment-friendly type ethylene propylene diene rubber particle, the difference of this comparative example and embodiment 7
It is, white carbon is 20 parts, 5 parts of odium stearate, 5 parts of zinc oxide.
Comparative example 2
This comparative example provides a kind of environment-friendly type ethylene propylene diene rubber particle, the difference of this comparative example and embodiment 7
It is, white carbon is 100 parts, 0.1 part of odium stearate, 0.1 part of zinc oxide.
Comparative example 3
This comparative example provides a kind of environment-friendly type ethylene propylene diene rubber particle, the difference of this comparative example and embodiment 7
It is, reinforcing agent is not added.
Comparative example 4
This comparative example and embodiment 7 the difference is that, EPT rubber composition is ethylene propylene diene rubber, propylene
The mixture of nitrile modified EPT rubber and acrylic acid modified ethylene propylene diene rubber, and the mass ratio of three is 5:2:1.
Comparative example 5
This comparative example and embodiment 7 the difference is that, EPT rubber composition is ethylene propylene diene rubber and third
The mixture of alkene nitrile modified EPT rubber, and the mass ratio of the two is 1:2.
Comparative example 6
This comparative example and embodiment 7 the difference is that, EPT rubber composition is ethylene propylene diene rubber and third
The mixture of olefin(e) acid modified EPT rubber, and the mass ratio of the two is 1:2.
Comparative example 7
This comparative example and embodiment 7 the difference is that, EPT rubber composition is ethylene propylene diene rubber.
Comparative example 8
This comparative example and embodiment 7 the difference is that, EPT rubber composition is acrylonitrile modified ternary second
Third rubber.
Comparative example 9
This comparative example and embodiment 7 the difference is that, EPT rubber composition is acrylic acid modified ternary second
Third rubber.
The preparation method for the environment-friendly type ethylene propylene diene rubber particle that above-mentioned comparative example 1-9 is provided is same as Example 7,
This is repeated no more.
It is that test specimens to be checked are tested for the property by the sheet material that embodiment 1-11 and comparative example 1-9 are squeezed out by extruder,
As a result as shown in Table 1 and Table 2：
1 environment-friendly type ethylene propylene diene rubber particulates' properties test data table (one) of table
| Tensile strength (MPa) | Elongation at break (%) | Hardness (shore A) | Density (g/cm3) | |
| Embodiment 1 | 5.72 | 715 | 61 | 1.30 |
| Embodiment 2 | 5.71 | 717 | 62 | 1.26 |
| Embodiment 3 | 5.85 | 721 | 61 | 1.32 |
| Embodiment 4 | 5.96 | 724 | 60 | 1.32 |
| Embodiment 5 | 6.07 | 728 | 62 | 1.33 |
| Embodiment 6 | 6.12 | 731 | 62 | 1.34 |
| Embodiment 7 | 6.25 | 735 | 63 | 1.35 |
| Embodiment 8 | 5.23 | 682 | 62 | 1.36 |
| Embodiment 9 | 5.16 | 679 | 61 | 1.35 |
| Embodiment 10 | 5.24 | 686 | 62 | 1.34 |
| Embodiment 11 | 5.21 | 683 | 60 | 1.34 |
| Comparative example 1 | 4.86 | 482 | 75 | 1.42 |
| Comparative example 2 | 4.47 | 473 | 53 | 1.24 |
| Comparative example 3 | 4.72 | 574 | 52 | 1.33 |
| Comparative example 4 | 4.84 | 567 | 55 | 1.34 |
| Comparative example 5 | 4.67 | 542 | 56 | 1.36 |
| Comparative example 6 | 4.58 | 538 | 57 | 1.35 |
| Comparative example 7 | 4.28 | 521 | 56 | 1.32 |
| Comparative example 8 | 5.06 | 519 | 56 | 1.34 |
| Comparative example 9 | 4.92 | 520 | 55 | 1.33 |
2 environment-friendly type ethylene propylene diene rubber particulates' properties test data table (two) of table
As can be seen from Table 1 and Table 2, the tensile strength for the environment-friendly type ethylene propylene diene rubber particle that embodiment 1-11 is provided is equal
Higher than 5MPa, elongation at break is higher than 680%, and hardness is between 60-65, and density is between 1.3-1.35, and by aging
After heat resistant test, tensile strength, elongation at break and hardness have no significant change, this illustrates environment-friendly type three provided by the invention
Not only tensile strength, wear-resistant strength, consistency and elasticity are very excellent for first EP rubbers particle, but also ageing-resistant and heat resistance is good
It is good, it can significantly prolong the service life, reduce the maintenance cost of plastic cement race track.
Environment-friendly type ethylene-propylene-diene monomer provided by the invention is can be seen that by the comparison of embodiment 1-11 and comparative example 1-9
Glue particle passes through EPT rubber composition, filler, activator, environmentally friendly accelerating agent, vulcanizing agent and reinforcing agent and pigment phase
Mutually collaboration, the tensile strength of environment-friendly type ethylene propylene diene rubber particle obtained, wear-resistant strength, consistency and elasticity significantly improve,
Service life significantly extends, and can be up to 5 years or more, effectively reduce the maintenance cost of plastic cement race track, save a large amount of people
Power and material resources.
Environment-friendly type ethylene-propylene-diene monomer provided by the invention is can be seen that by the comparison of embodiment 1-11 and comparative example 1-2
Glue particle, by by EPT rubber composition, filler, activator, environmentally friendly accelerating agent, vulcanizing agent and reinforcing agent and pigment
Quality proportioning limit in a certain range so that said components during preparing rubber to the greatest extent play collaboration make
With so that tensile strength, wear-resistant strength, hardness, elasticity, heat resistance and ageing properties significantly improve, and significantly extend and use
Service life reduces the maintenance cost of runway.
It can be seen that by the comparison of embodiment 1-11 and comparative example 3 by the way that reinforcing agent is added, environmental protection can be significantly improved
Tensile strength, wear-resistant strength, hardness, elasticity, heat resistance and the ageing properties of type ethylene propylene diene rubber particle.
It can be seen that by the comparison of embodiment 1-11 and comparative example 4-9 by selecting ethylene propylene diene rubber, acrylonitrile to change
Property ethylene propylene diene rubber and acrylic acid modified ethylene propylene diene rubber the EPT rubber composition that is formed of mixture as former
Material so that the tensile strength of prepared environment-friendly type ethylene propylene diene rubber particle, wear-resistant strength, hardness, elasticity, heat resistance and
Ageing properties significantly improve.
By the comparison of embodiment 4 and embodiment 3 as can be seen that selecting the colored color masterbatch replacement of hydrogen-containing compound common color
Color color masterbatch, can significantly improve the tensile strength of the environment-friendly type ethylene propylene diene rubber particle of preparation, wear-resistant strength, hardness, elasticity,
Heat resistance and ageing properties.
It can be seen that by the comparison of embodiment 5-7 and embodiment 4 when reinforcing agent is graphene, carbon fiber and carbon nanometer
When the mixture of pipe, the tensile strength of the environment-friendly type ethylene propylene diene rubber particle of preparation, wear-resistant strength, hard can be significantly improved
Degree, elasticity, heat resistance and ageing properties.
Can be seen that reinforcing agent by the comparison of embodiment 6-7 and embodiment 5 is graphene, carbon fiber and carbon nanotube
Mixture, and the mass ratio of three be (1-2)：(1-2)：When (1-2), the drawing of the environment-friendly type ethylene propylene diene rubber particle of preparation
Stretch that intensity, wear-resistant strength, hardness, elasticity, heat resistance and ageing properties are more excellent, especially when the mass ratio of three is 1：
1：When 1, comprehensive performance is more preferably.
It can be seen that by the comparison of embodiment 7 and embodiment 8-9 when preparing acrylonitrile modified ethylene propylene diene rubber,
The mass ratio of acrylonitrile and ethylene propylene diene rubber is 3:(3-4), the tensile strength of the environment-friendly type ethylene propylene diene rubber particle of preparation,
Wear-resistant strength, hardness, elasticity, heat resistance and ageing properties are more excellent.
It can be seen that work as by the comparison of embodiment 7 and embodiment 10-11 and prepare acrylic acid modified ethylene propylene diene rubber
When, the mass ratio of acrylic acid and ethylene propylene diene rubber is 1：(12-18), the stretching of the environment-friendly type ethylene propylene diene rubber particle of preparation
Intensity, wear-resistant strength, hardness, elasticity, heat resistance and ageing properties are more excellent.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of environment-friendly type ethylene propylene diene rubber particle, which is characterized in that mainly prepared by the following raw material according to the mass fraction
It forms：100 parts of EPT rubber composition, 50-80 parts of filler, 1-3 parts of activator, environmentally friendly accelerating agent 1-3 parts, vulcanizing agent
1-5 parts, 5-10 parts of reinforcing agent, 1-3 parts of pigment, wherein EPT rubber composition is ethylene propylene diene rubber, acrylonitrile modified
The mixture of ethylene propylene diene rubber and acrylic acid modified ethylene propylene diene rubber, and the mass ratio of three is (1-3)：(1-3)：(1-
3), preferably 1:2:2.
2. environment-friendly type ethylene propylene diene rubber particle according to claim 1, which is characterized in that mainly by according to the mass fraction
The following raw material be prepared：100 parts of EPT rubber composition, 55-65 parts of filler, 1-3 parts of activator, environmental protection promote
1-3 parts of agent, 2-4 parts of vulcanizing agent, 5-10 parts of reinforcing agent, 1-3 parts of pigment, wherein EPT rubber composition is EPDM
The mixture of rubber, acrylonitrile modified ethylene propylene diene rubber and acrylic acid modified ethylene propylene diene rubber, and the mass ratio of three is
(1-3)：(1-3)：(1-3), preferably 1:2:2.
3. environment-friendly type ethylene propylene diene rubber particle according to claim 1 or 2, which is characterized in that the reinforcing agent is selected from
At least one of graphene, carbon fiber and carbon nanotube；Preferably, the reinforcing agent is graphene, carbon fiber and carbon nanometer
The mixture of pipe, and the mass ratio of three is (1-2)：(1-2)：(1-2), more preferably 1:1:1.
4. environment-friendly type ethylene propylene diene rubber particle according to claim 1 or 2, which is characterized in that the pigment is containing work
The Color master batch of property hydrogen compound, the preparation method of the Color master batch of the active hydrogen-contg compound include the following steps：It will contain
Active dydrogen compounds is added in pigment, adds Color master batch carrier, then extruding pelletization, obtains active hydrogen-contg compound
Color master batch, wherein the active hydrogen-contg compound is polyether polyol or polyester polyol.
5. environment-friendly type ethylene propylene diene rubber particle according to claim 1 or 2, which is characterized in that described acrylonitrile modified
The preparation method of ethylene propylene diene rubber, includes the following steps：First ethylene propylene diene rubber is dissolved in toluene solution, adds third
Alkene nitrile and initiator generate acrylonitrile modified ethylene propylene diene rubber under heating conditions, wherein acrylonitrile and EPDM
The mass ratio of rubber is 3:(3-4).
6. environment-friendly type ethylene propylene diene rubber particle according to claim 1 or 2, which is characterized in that described acrylic acid modified
The preparation method of ethylene propylene diene rubber, includes the following steps：Acrylic acid, ethylene propylene diene rubber and initiator are uniformly mixed, passed through
Double screw extruder extruding pelletization obtains acrylic acid modified ethylene propylene diene rubber, wherein acrylic acid and ethylene propylene diene rubber
Mass ratio is 1：(12-18).
7. environment-friendly type ethylene propylene diene rubber particle according to claim 1 or 2, which is characterized in that the filler is selected from
At least one of calcium carbonate, white carbon, talcum powder, clay and zinc oxide；The activator is organic activator and inorganic work
The mixture of agent, the organic activator be odium stearate and/or potassium stearate, the inorganic activator be zinc oxide and/
Or magnesia.
8. environment-friendly type ethylene propylene diene rubber particle according to claim 1 or 2, which is characterized in that the environmental protection accelerating agent
Selected from N- cyclohexyl -2- benzene thiazolyls sulfenamide, zinc dibenzyl dithiocarbamate, tetra-benzyl thiram disulfide, two
Vulcanize at least one of dicaprolactam；The vulcanizing agent is selected from sulphur, cumyl peroxide, dual-tert-butyl and crosses oxygen propyl group
At least one of benzene, 1,1 di tert butylperoxy 3,3,5 trimethylcyclohexane.
9. according to the preparation method of claim 1-8 any one of them environment-friendly type ethylene propylene diene rubber particles, which is characterized in that
Include the following steps：
(a) EPT rubber composition, filler, activator, environmentally friendly accelerating agent, vulcanizing agent, reinforcing agent and pigment are mixed
Uniformly, it is kneaded and is refined successively, obtain refining mixture；
(b) refining mixture is extruded into sheet material, is granulated after sheet material is vulcanized, obtains environment-friendly type ethylene-propylene-diene monomer
Glue particle.
10. the preparation method of environment-friendly type ethylene propylene diene rubber particle according to claim 9, which is characterized in that in step
(a) in, mixing carries out in mixer, and refining carries out in mill.
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