CN104725729B - A kind of EPT rubber composite material and its preparation - Google Patents
A kind of EPT rubber composite material and its preparation Download PDFInfo
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- CN104725729B CN104725729B CN201310724151.7A CN201310724151A CN104725729B CN 104725729 B CN104725729 B CN 104725729B CN 201310724151 A CN201310724151 A CN 201310724151A CN 104725729 B CN104725729 B CN 104725729B
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- 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
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Abstract
The present invention provides a kind of high reinforcing EPT rubber composite material and preparation methods, and specifically, composite material of the present invention has the component of following parts by weight：30 70 parts of ethylene propylene diene rubber；70 30 parts of polypropylene；Through 1 10 parts of montmorillonite for holding alkenyl modification；0.1 1 parts of modified graphene oxide；16 parts of vulcanizing agent；1 10 parts of auxiliary agent.The excellent in mechanical performance such as the reinforcing EPT rubber composite rubber-plastic material tensile strength of height prepared using the present invention, are particularly suitable for belonging to the specific demand in the fields such as automobile, building.
Description
Technical field
Invention belongs to the preparation of composite rubber-plastic material, and it is multiple to be related to a kind of high reinforcing EPT rubber rubber and plastic
The preparation method of condensation material.
Background technology
Thermoplastic elastic material (TPE) is the material developed in recent years, is structurally characterized in that and is made of rubber and plastics.
Toughness deficiency after polypropylene, notch punching can be solved by preparing composite rubber-plastic material not only using ethylene propylene diene rubber and polypropylene
It is low can also to solve ethylene propylene diene rubber tearing toughness for the shortcomings of hit intensity is low, and heat distortion temperature is relatively low, and creep-resistant property is poor
Disadvantage.EPT rubber composite rubber-plastic material can be used as the composite material of function admirable, in necks such as automobile, buildings
Domain has broad application prospects.
In existing patent of invention, the Chinese patent of 1546561 A of Publication No. CN proposes a kind of use dynamic vulcanization skill
The method that art prepares halogen-free flame-retardant EPT rubber/thermoplastic elastomer.In Publication No. CN1687218 A
State's patent proposes that a kind of vulcanizing system using compositions such as bis- (3- triethoxysilylpropyltetrasulfides) tetrasulfides prepares ternary
The method of ethylene propylene rubber polypropylene thermoplastic elastomer.Any of the above thermoplastic elastomer (TPE) preparation formula is different with technique, but property
It can be with their own characteristics.But these thermoplastic elastomer (TPE) formulas and technique are relatively complicated, easily pollute the environment and mechanical property
Generally need to be further increased, as tensile strength is less than 15MPa.
Therefore, there is an urgent need in the art to select suitably formula and technique, more effective reinforcement system to improve rubber-plastics material
Mechanical property, to there is industrialized production to have great significance.
Invention content
The present invention provides a kind of EPT rubber composite rubber-plastic material of high reinforcing property and its preparation sides
Method.
First aspect present invention, provides a kind of EPT rubber composite material, and the composite material has
The component of following parts by weight：
Wherein, the end alkenyl is the C2-C6 linear chain or branched chain alkyl that double bond is located at end position.
In another preferred example, the parts by weight of the montmorillonite of the alkenyl containing end are 1-10 parts, are 3-7 parts more preferably.
In another preferred example, the graphene oxide parts by weight are 0.1-1 parts, preferably 0.2-0.3 parts.
In another preferred example, the end alkenyl includes vinyl, acrylic, cyclobutenyl.
In another preferred example, the end alkenyl is provided by the silane coupling agent of the alkenyl-functional groups containing end.
In another preferred example, the vinyl is provided by the silane coupling agent containing vinyl-functional.
In another preferred example, the silane coupling agent containing vinyl-functional includes vinyltriethoxysilane
Or vinyltrimethoxysilane or combinations thereof.
In another preferred example, the graphene oxide includes modified or non-modified graphene oxide.
In another preferred example, the modified graphene oxide be utilize graphene oxide modifying agent, such as cetylamine,
Octadecylamine modification graphene oxide is prepared.
In another preferred example, described through holding the montmorillonite of alkenyl modification to be prepared by montmorillonite and imvite modified dose
It arrives.
In another preferred example, described imvite modified dose includes silane coupling agent and quaternary ammonium containing vinyl-functional
Salt；
Preferably, the silane coupling agent containing vinyl-functional includes vinyltriethoxysilane, vinyl
Trimethoxy silane or combinations thereof；And/or
In another preferred example, the quaternary ammonium salt includes cetyl trimethylammonium bromide, octadecyl trimethyl bromine
Change ammonium, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride or combinations thereof.
In another preferred example, the montmorillonite and silane coupling agent (the especially vinyl containing vinyl-functional
Triethoxysilane) mass ratio be 5-50:0.5-3；Preferably, being 8-20：0.8-2.5；More preferably, it is 10-15：1-2.
In another preferred example, the weight ratio of the montmorillonite and quaternary ammonium salt is 4-25:4-10, preferably 8-20:4-
8；More preferably, it is 8-16:5-8.
In another preferred example, the montmorillonite of the alkenyl containing end is prepared by montmorillonite, imvite modified dose and water
It arrives.
In another preferred example, it is more preferably deionized water that the water, which includes deionized water, reverse osmosis water, distilled water,.
In another preferred example, the deionized water and the mass ratio of the montmorillonite are 2-20:1, preferably 4-8:
1。
In another preferred example, the vulcanizing agent includes cumyl peroxide or benzoyl peroxide；And/or
The auxiliary agent includes antioxidant, compatilizer.
In another preferred example, the antioxidant included four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] seasons
Doutrate (antioxidant 1010).
In another preferred example, the compatilizer includes paraffin oil, hydroxy silicon oil.
In another preferred example, the parts by weight of the antioxidant 1010 are 1-5 parts.
In another preferred example, the parts by weight of the paraffin oil are 1-5 parts.
In another preferred example, described through holding the montmorillonite of alkenyl modification to be prepared by following steps：
(a1) montmorillonite, the reaction mixture containing the silane coupling agent and water for holding alkenyl-functional groups are provided；
Wherein, the mass ratio of the montmorillonite and the silane coupling agent of the alkenyl-functional groups containing end is 5-50：0.5-3, compared with
Goodly, 10-15：1-2；And/or
The mass ratio of the montmorillonite and water is 1：2-20, preferably, being 3:4-20 is more preferably 1:4-8.
(b1) reaction mixture in (a1) is heated, to obtain the montmorillonite through holding alkenyl modification.
In another preferred example, the reaction mixture in step (a1) further includes quaternary ammonium salt.
In another preferred example, the mass ratio of the montmorillonite and quaternary ammonium salt is 8-16:5-8.
In another preferred example, further include that the reaction mixture is dissolved in alcoholic solution in step (a1), preferably, being
Absolute ethyl alcohol.
In another preferred example, the absolute ethyl alcohol and the mass ratio of the montmorillonite are 2-10:1, preferably 3-5:
1。
In another preferred example, the temperature heated described in step (b) is 30-100 DEG C, preferably 50-80 DEG C.
In another preferred example, the heating time is 2-10h, preferably 3-6h.
Second aspect of the present invention, provides that a kind of to prepare EPT rubber described in first aspect present invention multiple
The method of condensation material utilizes the montmorillonite through holding alkenyl modification, graphene oxide, ethylene propylene diene rubber, polypropylene, vulcanizing agent system
The standby EPT rubber composite material, wherein described through holding the montmorillonite of alkenyl modification by montmorillonite and Meng Tuo
Native modifying agent is prepared, and modified graphene oxide is prepared by graphene oxide and graphene oxide modifying agent.
In another preferred example, described imvite modified dose includes containing the silane coupling agent and quaternary ammonium for holding alkenyl-functional groups
Salt.
In another preferred example, the modified graphene oxide is modified system by graphene oxide through cetylamine or octadecylamine
.
In another preferred example, including step：
(i) montmorillonite once end alkenyl modification and modified graphene oxide are provided, wherein described through holding alkenyl modification
Montmorillonite by montmorillonite, vinyltriethoxysilane, cetyl trimethylammonium bromide and water react be made；And it is described
Modified graphene oxide is that graphene oxide is made through cetylamine modification；
Wherein, the mass ratio of the montmorillonite and the vinyltriethoxysilane of the alkenyl containing end is 10-15：1-2；With/
Or the mass ratio of montmorillonite and cetyl trimethylammonium bromide is 8-16:5-8；And/or the montmorillonite and deionized water
Amount is than being 1：2-20, preferably, being 3:4-20 is more preferably 1:4-8.
(ii) montmorillonite by described through holding alkenyl modification, modified graphene oxide, ethylene propylene diene rubber, polypropylene mix
Reaction is to obtain modified EPT rubber/polypropylene crude mixture；
(iii) vulcanizing agent is added into modified EPT rubber/polypropylene crude mixture and reacts, to be made as weighed
Profit requires any EPT rubber composite materials of 1-6.
In another preferred example, the vulcanizing agent is cumyl peroxide.
In another preferred example, the reaction in step (i), (ii), (iii) is that heating is reacted.
In another preferred example, step (ii) further includes that antioxidant 1010 is added before the reaction.
In another preferred example, step (ii) further includes that paraffin oil is further added in the crude mixture.
It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the invention and have in below (eg embodiment)
It can be combined with each other between each technical characteristic of body description, to form a new or preferred technical solution.As space is limited, exist
This no longer tires out one by one states.
Description of the drawings
Fig. 1 is the brittle failure face SEM of EPT rubber composite rubber-plastic material prepared by the embodiment of the present invention three
Figure.
Specific implementation mode
The present inventor after extensive and in-depth study, for the first time it was unexpectedly observed that in EPT rubber rubber and plastic
Modified montmorillonoid and modified graphene oxide containing unsaturated group are added in composite material, it is multiple that rubber and plastic can be effectively improved
The tensile strength and hardness of condensation material, to form high reinforcing composite rubber-plastic material, mechanical property is better than existing rubber
Moulding material.In addition, by adjusting different component ratios, the composite rubber-plastic material that different industrial mechanics need can be prepared.Herein
On the basis of, complete the present invention.
EPT rubber (EPDM/PP)
Thermoplastic elastic material (TPE) is the material developed in recent years, is structurally characterized in that and is made of rubber and plastics.
The rubber and plastic that EPDM refers to (EPDM) and polypropylene (PP) is compound, and toughness is insufficient after can not only solving PP moldings, notch shock
The shortcomings of intensity is low, and heat distortion temperature is relatively low, and creep-resistant property is poor can also solve the low disadvantage of EPDM tearing toughness.PP/
EPDM composite rubber-plastic materials can be used as the composite material of function admirable, be applied to the fields such as automobile, building.
Montmorillonite and modified montmorillonoid
Montmorillonite is a kind of viscous mineral with lamellar structure, can be widely used in the reinforcement of polymer material, can be had
Effect improves the mechanical properties such as tensile strength, Young's modulus, the impact strength of polymer, meanwhile, polymer can also be improved
Processing performance.However, lead to the poor compatibility of itself and rubber and plastic matrix of common montmorillonite, and interface binding power is not high, leads to rubber
The mechanical property of plastic composite materials is poor, therefore is difficult often the preparation for directly applying to composite rubber-plastic material.
As used herein, term " modified montmorillonoid ", " through the montmorillonite for holding alkenyl modification ", " changing containing unsaturated group
Property montmorillonite " be used interchangeably, refer both to by the imvite modified dose of modified montmorillonite containing end alkenyl.In order to make montmorillonite
Structural property be more suitable for composite rubber-plastic material, the silane idol agent containing end alkenyl is hydrolyzed the present inventor in water,
The hydroxyl reaction of hydrolysate and montmorillonite plate layer, to obtain unsaturated double-bond modification montmorillonite, can enhance montmorillonite with
The interface cohesion of rubber and plastic matrix acts on.In addition, the present invention can also be using quaternary ammonium salt as imvite modified dose of supplement, to more have
Effect ground expands montmorillonite layer interval, is conducive to the insertion of polymer molecule.
As used herein, described imvite modified dose refer to it is any can with illiteracy after the reacting of montmorillonite, can be made de-
Modifying agent of the soil containing unsaturated group.In general, imvite modified dose can make montmorillonite contain end position alkenyl, to keep illiteracy de-
Soil enhances in sulfidation to be acted on the interface cohesion of composite material.
In general, the modifying agent that montmorillonite contains end position alkenyl can be made to include containing the silane coupled of end position alkenyl-functional groups
Agent.A kind of silane coupling agent preferably containing end position alkenyl-functional groups is the silane coupling agent containing vinyl, preferably second
Alkenyl triethoxysilane, vinyltrimethoxysilane.
In addition, a kind of preferred imvite modified dose includes silane coupling agent and quaternary ammonium salt containing end position alkenyl-functional groups
Combination.
Preferred quaternary ammonium salt for use in the present invention includes cetyl trimethylammonium bromide, octadecyl trimethyl bromination
Quaternary ammonium salts such as ammonium, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride or combinations thereof.
In the present invention, be not particularly limited with the weight ratio of montmorillonite for imvite modified dose, can be it is any can be at
Work(modified montmorillonite, to the ratio for making montmorillonite contain unsaturated group.Preferably, when selection vinyltriethoxysilane
When with cetyl trimethylammonium bromide as imvite modified dose, montmorillonite：The mass ratio of vinyltriethoxysilane is
10-15：1-2；Montmorillonite：Cetyl trimethylammonium bromide 8-16:5-8.
In general, can will be well-dispersed in dicyandiamide solution after montmorillonite and imvite modified dose of mixing, or by montmorillonite
And imvite modified dose be scattered in dicyandiamide solution and mix respectively, in order to accelerate reaction speed and keep montmorillonite fully modified,
It is preferred that after dispersion montmorillonite and imvite modified dose heat.
In a preferred embodiment, through holding the montmorillonite preparation method of alkenyl modification as follows：
Montmorillonite is uniformly mixed with deionized water and absolute ethyl alcohol, under magnetic stirring, hydrochloric acid is added by pH of mixed
Value is adjusted to 3~4, and vinyltriethoxysilane is added afterwards, is heated at 50~100 DEG C modified a few hours, and hexadecane is added
Base trimethylammonium bromide is stirred at 50~80 DEG C, is filtered, washing, is dry, is finally obtained being modified containing unsaturated group and is covered
De- soil.Wherein, the montmorillonite：The mass ratio of vinyltriethoxysilane is 10-15：1-2；Montmorillonite：Cetyl three
The mass ratio of methyl bromide ammonium is 8-16:5-8.The absolute ethyl alcohol and the mass ratio of the montmorillonite are 1-10:1, preferably
For 3-5:1；The deionized water and the mass ratio of the montmorillonite are 2-20:1, preferably 4-8:1.
Graphene oxide
Graphene oxide is generally aoxidized through strong acid by graphite and is obtained.It, can be with since graphene oxide is single atomic layer
Some tens of pm is expanded on lateral dimension at any time, as excellent flexible material, with higher Young's modulus, is stretched by force
The advantages performance such as degree, fracture strength.The present invention further preferably uses modified graphene oxide, the oxidation stone that surface modification is crossed
The compatibility raising of black alkene itself and polymeric matrix, can effectively improve reinforcing effect.
Modified graphene oxide for use in the present invention is not particularly limited.In general, selecting suitable modifying agent to oxidation
Graphene carries out surface modification and various modified modified graphene oxides can be obtained.
A kind of preferred graphene oxide for use in the present invention be the graphene oxide by being further modified.Wherein,
Include cetylamine, octadecylamine etc. for further modified modifying agent.
In general, modified graphene oxide can be prepared according to method conventional in the prior art, also can as follows into
It is prepared by row：
Graphene oxide is scattered in the dicyandiamide solution of deionized water and absolute ethyl alcohol composition, 16 are added after evenly mixing
Amine heats and carries out 12~28h of back flow reaction, is more preferably 18-24h.By suction filtration, washing, drying, finally obtain modified
Modified graphene oxide.
Vulcanizing agent
Vulcanizing agent for use in the present invention is not particularly limited, and common peroxide in composite rubber-plastic material is prepared for this field
Change vulcanizing agent.Preferred vulcanizing agent includes cumyl peroxide, benzoyl peroxide.
In the present invention, it is preferred to which vulcanizing agent is added in dynamic vulcanization initial period.
Auxiliary agent
Auxiliary agent for use in the present invention is not particularly limited, and being prepared for this field improves material performance in composite rubber-plastic material
Any auxiliary agent.In general, auxiliary agent includes antioxidant, compatilizer.
Wherein, the antioxidant includes four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters
(1010)；The compatilizer includes paraffin oil, hydroxy silicon oil.
In a preferred example, the antioxidant is added in the initial heating mix stage for preparing composite rubber-plastic material,
The antioxygenic property of raw material is prepared with enhancing.
The number of auxiliary agent and addition time are not particularly limited, and are prepared for the conventional composite rubber-plastic material that can be used in this field
Dispersion and be added the time.
Preparation method
The present invention also provides in a kind of method of EPT rubber composite material, be using through holding alkene
The montmorillonite of base modification, modified graphene oxide, ethylene propylene diene rubber, polypropylene, vulcanizing agent prepare the ethylene propylene diene rubber/
PP composite material, wherein described through holding the montmorillonite of alkenyl modification to be prepared by montmorillonite and imvite modified dose.
A kind of preferred imvite modified dose includes vinyltriethoxysilane and cetyl trimethylammonium bromide.This
Outside, made from modified graphene oxide is modified by graphene oxide warp is further.
In a preferred embodiment, the method for the present invention includes：
(i) montmorillonite once end alkenyl modification and modified graphene oxide are provided, wherein unsaturated cover takes off
Soil is pressed by montmorillonite, vinyltriethoxysilane, cetyl trimethylammonium bromide reaction is made；And it is described modified oxidized
Graphene is that graphene oxide is made through cetylamine modification；
(ii) montmorillonite by described through holding alkenyl modification, modified graphene oxide, ethylene propylene diene rubber, polypropylene mix
Reaction is to obtain modified EPT rubber/polypropylene crude mixture；
(iii) vulcanizing agent is added into modified EPT rubber/polypropylene crude mixture and reacts, it is described to be made
EPT rubber composite material.
In another preferred example, the vulcanizing agent is cumyl peroxide.
In another preferred example, the reaction in step (i), (ii), (iii) is that heating is reacted.
In another preferred example, step (ii) further includes that antioxidant is added before the reaction.
In another preferred example, step (ii) further includes that compatilizer is further added in the crude mixture.
Beneficial effects of the present invention
It,, can be with ethylene-propylene-diene monomer xanthan molecule in sulfidation containing unsaturated group 1. montmorillonite is through more modification
Chain forms chemical bond, and the interface cohesion for enhancing it with composite rubber-plastic material acts on, and improves the mechanical property of composite material.
2. filling EPDM as reinforcement system using the montmorillonite and modified graphene oxide for containing unsaturated group
It is strong can to prepare different stretch while keeping thermoplastics processing type and caoutchouc elasticity as needed for rubber/polypropylene
The EPT rubber composite rubber-plastic material of degree, elongation at break, hardness.
3. with existing EPT rubber composite rubber-plastic material, (such as China Patent Publication No. is
CN1687218A it) compares, composite rubber-plastic material of the present invention has clear advantage in terms of mechanical property.
4. environmental pollution of the present invention is small, with strong points, promoted and applied conducive in industrial production.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip
Part, or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise percentage and number are weight percent and weight
Number.
The preparation of 1 EPT rubber composite material in the prior art of embodiment
The composite material of the present embodiment can be used this field conventional method and be made, specific as follows：
170 DEG C on mixer, under 80r/min, ethylene propylene diene rubber, polypropylene, antioxidant mixing 5min were added
Diisopropylbenzene (DIPB) dynamic vulcanization 3min is aoxidized, after mixture is granulated, compression molding 40min is to get high reinforcing ternary at 180 DEG C
Ethylene-propylene rubber/polypropylene composite material.
The preparation of the only composite material containing modified montmorillonoid of embodiment 2
The preparation of 2.1 modified montmorillonoids：
By montmorillonite：Deionized water：Absolute ethyl alcohol is 1：4：3 mass ratio, by montmorillonite, deionized water, absolute ethyl alcohol
It is uniformly mixed, under magnetic stirring, pH of mixed is adjusted to 3.5 by the hydrochloric acid that 0.1mol/L is added；
By montmorillonite：Vinyltriethoxysilane is 10：1 mass ratio, addition vinyltriethoxysilane, 60 DEG C
Lower modified 4h；
By montmorillonite：Cetyl trimethylammonium bromide is 5：Cetyl trimethylammonium bromide is added in 2 mass ratio,
45h is stirred at 60 DEG C, through filtering, 4 washings are dry, finally obtain modified montmorillonoid.
The preparation of 2.2 EPT rubber composite rubber-plastic materials：It, will under 80r/min 170 DEG C on mixer
Paraffin oil, modified montmorillonoid mixing 7min is added in ethylene propylene diene rubber, polypropylene, antioxidant mixing 5min, and peroxidating is added
Diisopropylbenzene (DIPB) dynamic vulcanization 3min, after mixture is granulated, compression molding 40min is to get high reinforcing EPDM at 170 DEG C
Rubber/polypropylene composite material.
The preparation of the only composite material containing modified graphene oxide of embodiment 3
The preparation of 3.1 modified graphene oxides：By graphene oxide：Deionized water：Absolute ethyl alcohol is 1：100：100 matter
Ratio is measured, graphene oxide, deionized water, absolute ethyl alcohol is added and uniformly mixes, under magnetic stirring, by graphene oxide：16
Amine is 1：1 mass ratio is added cetylamine, and at 100 DEG C, back flow reaction 20h, through filtering, 4 washings are dry, finally obtain and change
Property graphene oxide.
The preparation of 3.2 EPT rubber composite rubber-plastic materials：It, will under 80r/min 170 DEG C on mixer
Paraffin oil, modified graphene mixing 7min is added in ethylene propylene diene rubber, polypropylene, antioxidant mixing 5min, and peroxidating is added
Diisopropylbenzene (DIPB) dynamic vulcanization 3min, after mixture is granulated, compression molding 40min is to get high reinforcing EPDM at 170 DEG C
Rubber/polypropylene composite material.
4 EPT rubber composite rubber-plastic material of the present invention of embodiment prepares 1
The preparation of 4.1 modified montmorillonoids：By montmorillonite：Deionized water：Absolute ethyl alcohol is 1：5：3 mass ratio, it is de- by covering
Soil, deionized water, absolute ethyl alcohol are uniformly mixed, and under magnetic stirring, pH of mixed is adjusted to 3 by the hydrochloric acid that 0.1mol/L is added,
By montmorillonite：Vinyltriethoxysilane is 10：1 mass ratio is added vinyltriethoxysilane, is modified at 60 DEG C
3h, by montmorillonite：Cetyl trimethylammonium bromide is 5：Cetyl trimethylammonium bromide is added, at 60 DEG C in 2 mass ratio
3h is stirred, through filtering, washs for 3 times, is dry, finally obtaining modified montmorillonoid.
The preparation of 4.2 modified graphenes：By graphene oxide：Deionized water：Absolute ethyl alcohol is 1：100：100 quality
Than graphene oxide, deionized water, absolute ethyl alcohol is added and uniformly mixes, under magnetic stirring, by graphene oxide：Cetylamine
It is 1：1 mass ratio is added cetylamine, and at 90 DEG C, back flow reaction 18h is dry through filtering, 3 washings, finally obtains modified oxygen
Graphite alkene.
The preparation of 4.3 EPT rubber composite rubber-plastic materials：It, will under 80r/min 170 DEG C on mixer
Paraffin oil, reinforcement system mixing 7min is added in ethylene propylene diene rubber, polypropylene, antioxidant mixing 5min, and peroxidating two is added
Isopropylbenzene dynamic vulcanization 3min, after mixture is granulated, compression molding 40min is to get high reinforcing ethylene-propylene-diene monomer at 170 DEG C
Glue/PP composite material.
5 EPT rubber composite rubber-plastic material of the present invention of embodiment prepares 2
The preparation of 5.1 modified montmorillonoids：By montmorillonite：Deionized water：Absolute ethyl alcohol is 1：6：4 mass ratio, it is de- by covering
Soil, deionized water, absolute ethyl alcohol are uniformly mixed, and under magnetic stirring, pH of mixed is adjusted to by the hydrochloric acid that 0.2mol/L is added
3.5, by montmorillonite：Vinyltrimethoxysilane is 10：1 mass ratio is added vinyltrimethoxysilane, changes at 70 DEG C
Property 4h, by montmorillonite：Cetyltrimethylammonium bromide is 5：2 mass ratio, addition Cetyltrimethylammonium bromide, 70 DEG C
Lower stirring 4h through filtering, washs for 4 times, is dry, finally obtaining modified montmorillonoid.
The preparation of 5.2 modified graphenes：By graphene oxide：Deionized water：Absolute ethyl alcohol is 1：100：100 quality
Than graphene oxide, deionized water, absolute ethyl alcohol is added and uniformly mixes, under magnetic stirring, by graphene oxide：Cetylamine
It is 1：1 mass ratio is added cetylamine, and at 100 DEG C, back flow reaction 20h finally obtains modification through filtering, 4 washings, dry
Graphene oxide.
The preparation of 5.3 EPT rubber composite rubber-plastic materials：It, will under 85r/min 175 DEG C on mixer
Paraffin oil, reinforcement system mixing 9min is added in ethylene propylene diene rubber, polypropylene, antioxidant mixing 7min, and peroxidating two is added
Isopropylbenzene dynamic vulcanization 3.5min, after mixture is granulated, compression molding 50min is to get high reinforcing EPDM at 175 DEG C
Rubber/polypropylene composite material.
6 EPT rubber composite rubber-plastic material of the present invention of embodiment prepares 3
The preparation of 6.1 modified montmorillonoids：By montmorillonite：Deionized water：Absolute ethyl alcohol is 1：6：5 mass ratio, it is de- by covering
Soil, deionized water, absolute ethyl alcohol are uniformly mixed, and under magnetic stirring, pH of mixed is adjusted to 4 by the hydrochloric acid that 0.3mol/L is added,
By montmorillonite：Vinyltriethoxysilane is 10：1 mass ratio is added vinyltriethoxysilane, is modified at 80 DEG C
5h, by montmorillonite：Hexadecyltrimethylammonium chloride is 3：1 mass ratio adds hexadecyltrimethylammonium chloride, is stirred at 80 DEG C
5h is mixed, through filtering, washs for 5 times, is dry, finally obtaining modified montmorillonoid.
The preparation of 6.2 modified graphenes：By graphene oxide：Deionized water：Absolute ethyl alcohol is 1：100：100 quality
Than graphene oxide, deionized water, absolute ethyl alcohol is added and uniformly mixes, under magnetic stirring, by graphene oxide：Octadecylamine
It is 1：1 mass ratio is added octadecylamine, and at 110 DEG C, back flow reaction 22h finally obtains modification through filtering, 4 washings, dry
Graphene oxide.
The preparation of 6.3 EPT rubber composite rubber-plastic materials：It, will under 90r/min 180 DEG C on mixer
Paraffin oil, reinforcement system mixing 10min is added in ethylene propylene diene rubber, polypropylene, antioxidant mixing 9min, and peroxidating is added
Diisopropylbenzene (DIPB) dynamic vulcanization 4min, after mixture is granulated, compression molding 30min is to get high reinforcing EPDM at 180 DEG C
Rubber/polypropylene composite material.
Each Example formulations are shown in Table 1.
Table 1
In above-described embodiment, all raw materials are commercial product.
In above-described embodiment, all raw material dosages are parts by weight dosage, and ethylene propylene diene rubber+polypropylene=100.
In above-described embodiment, each step raw material dosage and technological parameter (temperature, rotating speed, time etc.) are value range, any
Point can use.
The performance measurement of composite material in 7 embodiment 1-6 of embodiment
Show that the brittle failure face SEM of EPT rubber composite rubber-plastic material schemes using embodiment 3, such as Fig. 1 institutes
Show.In figure, modified montmorillonoid is evenly dispersed in the matrix that ethylene propylene diene rubber is formed with polypropylene with modified graphene oxide.
Results of property is obtained using embodiment 1-6, is shown in Table 2.
Table 2
| Tensile strength, MPa | Elongation at break, % | Hardness, D | |
| Embodiment 1 | 8.6 | 326 | 47 |
| Embodiment 2 | 15.1 | 410 | 49 |
| Embodiment 3 | 10.7 | 380 | 48 |
| Embodiment 4 | 17.6 | 440 | 50 |
| Embodiment 5 | 18.1 | 451 | 50 |
| Embodiment 6 | 18.8 | 445 | 50 |
As can be seen from Table 2, according to the EPT rubber composite material (embodiment 1) prepared in the prior art
Performance is worst, and has been separately added into composite material (embodiment 2 and 3) property of modified montmorillonoid and modified graphene oxide of the present invention
It can slightly improve, but can not show a candle to add the composite material of the present invention (implementation of modified montmorillonoid and modified graphene oxide simultaneously
Example 4-6).
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can
To be made various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims
It encloses.
Claims (13)
1. a kind of EPT rubber composite material, which is characterized in that the composite material has following parts by weight
Component：
Wherein, the end alkenyl is the C2-C6 linear chain or branched chain alkyl that double bond is located at end position, and described through holding alkenyl modification
Montmorillonite prepared by following steps：
(a1) montmorillonite, the reaction mixture containing the silane coupling agent and water for holding alkenyl-functional groups are provided；
Wherein, the mass ratio of the montmorillonite and the silane coupling agent of the alkenyl-functional groups containing end is 5-50：3 and/or the illiteracy
The mass ratio of de- soil and water is 1：2-20；
(b1) reaction mixture in (a1) is heated, to obtain the montmorillonite through holding alkenyl modification；
Wherein, the modified graphene oxide is prepared by graphene oxide and cetylamine.
2. composite material as described in claim 1, which is characterized in that the end alkenyl includes vinyl, acrylic, butylene
Base.
3. composite material as described in claim 1, which is characterized in that the modified graphene oxide preparation method is as follows：It will
Graphene oxide is scattered in the dicyandiamide solution of deionized water and absolute ethyl alcohol composition, cetylamine is added after evenly mixing, heating is simultaneously
It carries out 12~28h of back flow reaction and finally obtains modified graphene oxide by suction filtration, washing, drying.
4. composite material as described in claim 1, which is characterized in that described through holding the montmorillonite of alkenyl modification by montmorillonite
It is prepared with imvite modified dose.
5. composite material as claimed in claim 4, which is characterized in that described imvite modified dose includes the alkenyl-functional groups containing end
Silane coupling agent and quaternary ammonium salt.
6. composite material as described in claim 1, which is characterized in that the vulcanizing agent includes cumyl peroxide or mistake
Benzoyl Oxide；And/or
The auxiliary agent includes antioxidant or compatilizer.
7. composite material as claimed in claim 1 or 2, which is characterized in that the montmorillonite and the alkenyl-functional groups containing end
The mass ratio of silane coupling agent is 8-20：2.5；And/or
The mass ratio of the montmorillonite and water is 1:4-8.
8. composite material as claimed in claim 1 or 2, which is characterized in that the mass ratio of the montmorillonite and water is 1:4-8.
9. composite material as claimed in claim 6, which is characterized in that the antioxidant includes four [β-(3,5- bis- tertiary fourths
Base -4- hydroxy phenyls) propionic acid] pentaerythritol ester.
10. the method for preparing EPT rubber composite material as described in claim 1, which is characterized in that utilize warp
The montmorillonite of end alkenyl modification, graphene oxide, ethylene propylene diene rubber, polypropylene, vulcanizing agent prepare the ethylene propylene diene rubber/
PP composite material, wherein described through holding the montmorillonite of alkenyl modification to be prepared by montmorillonite and imvite modified dose, institute
It includes modified graphene oxide to state graphene oxide, and the modified graphene oxide is prepared by graphene oxide and cetylamine
It arrives, and described through holding the montmorillonite of alkenyl modification to be prepared by following steps：
(a1) montmorillonite, the reaction mixture containing the silane coupling agent and water for holding alkenyl-functional groups are provided；
Wherein, the mass ratio of the montmorillonite and the silane coupling agent of the alkenyl-functional groups containing end is 5-50：3 and/or the illiteracy
The mass ratio of de- soil and water is 1：2-20；
(b1) reaction mixture in (a1) is heated, to obtain the montmorillonite through holding alkenyl modification.
11. method as claimed in claim 10, which is characterized in that the modified graphene oxide preparation method is as follows：By oxygen
Graphite alkene is scattered in the dicyandiamide solution of deionized water and absolute ethyl alcohol composition, cetylamine is added after evenly mixing, heating is gone forward side by side
Row 12~28h of back flow reaction finally obtains modified modified graphene oxide by suction filtration, washing, drying.
12. method as claimed in claim 10, which is characterized in that including step：
(i) montmorillonite once end alkenyl modification and modified graphene oxide are provided, wherein the illiteracy through holding alkenyl modification
De- soil is reacted by montmorillonite, vinyltriethoxysilane, cetyl trimethylammonium bromide and water to be made；And the modification
Graphene oxide is that graphene oxide is made through cetylamine modification；
Wherein, the mass ratio of the montmorillonite and the vinyltriethoxysilane of the alkenyl containing end is 10-15：1-2；And/or it covers
The mass ratio of de- soil and cetyl trimethylammonium bromide is 16:5-8；And/or the montmorillonite is with deionized water quality ratio
1：2-20；
(ii) montmorillonite by described through holding alkenyl modification, modified graphene oxide, ethylene propylene diene rubber, polypropylene hybrid reaction
To obtain modified EPT rubber/polypropylene crude mixture；
(iii) vulcanizing agent is added into modified EPT rubber/polypropylene crude mixture and reacts, to be made as right is wanted
Seek the 1 EPT rubber composite material.
13. composite material as claimed in claim 6, which is characterized in that the compatilizer includes paraffin oil or hydroxy silicon oil.
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| CN105295193B (en) * | 2015-10-22 | 2017-09-01 | 安徽大学 | Polypropylene-ethylene propylene diene monomer conductive composite material and preparation method thereof |
| CN105670079A (en) * | 2016-02-25 | 2016-06-15 | 联塑科技发展(贵阳)有限公司 | HDPE pipe material and preparing method thereof |
| CN105670117A (en) * | 2016-03-02 | 2016-06-15 | 安徽蓝通科技股份有限公司 | Graphene-oxide-modified polypropylene composite material |
| CN105694224A (en) * | 2016-03-30 | 2016-06-22 | 贵州省材料产业技术研究院 | Heat-resistant thermoplastic elastomer and preparation method thereof |
| CN106167262A (en) * | 2016-07-08 | 2016-11-30 | 上海应用技术学院 | A kind of utilize graphene oxide to the method increasing oil lubrication and heat conductivity |
| CN106700976A (en) * | 2016-11-09 | 2017-05-24 | 安徽中翰高分子科技有限公司 | Thermoplastic vulcanized rubber material serving as bonding base material |
| CN108034141B (en) * | 2018-01-15 | 2020-10-09 | 上海金发科技发展有限公司 | Graphene montmorillonite-filled general plastic nano material and preparation method thereof |
| CN109608776B (en) * | 2018-11-23 | 2021-05-18 | 安徽雄亚塑胶科技有限公司 | TPV (thermoplastic vulcanizate) material building sealing strip and preparation method thereof |
| CN109880349A (en) * | 2019-01-14 | 2019-06-14 | 脉通医疗科技(嘉兴)有限公司 | A kind of medical material and preparation method thereof |
| CN113248839B (en) * | 2021-06-22 | 2022-03-18 | 会通新材料股份有限公司 | Reinforced TPV (thermoplastic vulcanizate) material for MDI (diphenylmethane diisocyanate) foaming bonding and preparation method thereof |
| CN116285357A (en) * | 2021-12-13 | 2023-06-23 | 国网湖南省电力有限公司 | Montmorillonite/silicone rubber composite material based on electron beam radiation crosslinking, and preparation method and application thereof |
| CN118344671B (en) * | 2024-05-16 | 2024-10-29 | 山东瑞驰蔓环保科技有限公司 | Waterproof flame-retardant polypropylene plastic fresh-keeping box containing graphene and sand and preparation process thereof |
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