CN107254076B - A kind of composite material reinforced rubber and preparation method thereof - Google Patents
A kind of composite material reinforced rubber and preparation method thereof Download PDFInfo
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- CN107254076B CN107254076B CN201710499516.9A CN201710499516A CN107254076B CN 107254076 B CN107254076 B CN 107254076B CN 201710499516 A CN201710499516 A CN 201710499516A CN 107254076 B CN107254076 B CN 107254076B
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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
- C08L7/00—Compositions of natural rubber
- C08L7/02—Latex
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
Abstract
The present invention relates to a kind of composite material reinforced rubbers and preparation method thereof, the method comprise the steps that 1) by hydroxyapatite and TiO2It is distributed in water, forms dispersion liquid, hydro-thermal reaction, the mixed liquor for then obtaining hydro-thermal is mixed with graphene oxide suspension, is condensed back, is obtained hydroxyapatite/TiO2/ graphene oxide composite material；2) plasticizer, operation oil are added in latex, stir evenly to form latex mixed liquor, the composite material of step 1) is then added, 6-10h is stirred, coagulator is added, is occurred coprecipitated, then sediment washed, be dehydrated, being dried to get hydroxyapatite/TiO is arrived2/ graphene oxide composite material reinforced rubber.Reinforced rubber excellent in mechanical performance of the invention, breaking strength is in 27.0MPa or more, and tearing strength is in 118.7MPa or more, and hardness (shore A) is 83.0 or more.
Description
Technical field
The present invention relates to a kind of hydroxyapatite/TiO2/ graphene oxide composite material reinforced rubber and preparation method thereof.
Belong to chemical materials and its preparation technical field.
Background technique
Traditionally, production rubber product needs to utilize the dress such as rubber internal mixer, open mill, continuous screw kneading machine
It is standby, raw rubber and reinforcing agent, filler, vulcanization accelerator, anti-aging agent, operation oil, function additive etc. are kneaded, rubber is assigned
For rubber compound with specific processing performance and the specific physical and chemical performance of vulcanizate, this mixing method is also referred to as dry method mixing.This
Mixing process needs to expend a large amount of power.Reinforcing agent, operation oil are the maximum auxiliary agents of rubber industry dosage, kneading reinforcing agent,
The consumed power of operation oil accounts for about 40% or more of compounding rubber power.For many years, people are seeking to prepare always rubber mixed
When the reinforcing agent that additive amount is larger, dispersion is more difficult, the most rational method of operation oil are added into rubber.
Application No. is 02152077.1 patent of invention " preparation methods of carbon black filled powder rubber ", provide a kind of charcoal
The preparation method of black filled powder rubber includes the following steps: to measure contained dry glue: carbon black: carbon black emulsifier: behaviour by latex
Make oil: anti-aging agent: fatty acid alkali metal salt emulsifier: flocculating agent: the weight ratio of deionized water be 100: 10~100: 0.5~
6.0: 0~70: 0.5~3.0: 1.0~6.0: 2.0~5.0: 300~2000 proportion ingredient；The emulsification of carbon black；The heat of latex
Processing；The agglomeration process of latex；The post-processing of condensation product.Using the present invention prepare powdered rubber with covering additional amount compared with
Few, covered effect is good, and the powder formation rate of the advantage that pulverisation process is reliable and stable, easy, carbon black filled powder rubber reaches
99% or more, the particle diameter distribution of prepared carbon black filled powder rubber can be controlled by adjusting coherence condition, be made
Product physical mechanical property it is good, contactless pollution, good fluidity, stable storing.
Application No. is 200710029871.6 patent of invention " rare earth or transition metal doping carbon black filled powder rubbers
Preparation method ", the preparation method of a kind of rare earth or transition metal doping carbon black filled powder rubber, including following steps are provided
It is rapid: to measure contained dry glue: carbon black: rare earth or transition metal oxide: carbon black emulsifier: operation oil: anti-aging agent: fat by latex
Acid alkali metal salt emulsifier: flocculating agent: the weight ratio of deionized water is 100: 10~150: 0.01~15.0: 0.25~15.0: 0
~70: 0.5~3.0: 1.0~6.0: 1.5~5.0: 300~2500 proportion ingredient；The emulsification of carbon black；Rare earth compound or mistake
Cross the preparation of metallic compound doping carbon black；The heat treatment of latex；The agglomeration process of latex；The post-processing of condensation product.With biography
System is compared using undoped carbon black filled powder rubber prepared by moditying polybrene test, prepares rare earth or transition using the present invention
The powder formation rate of metal-doped carbon black filled powder rubber is high, contactless pollution, good fluidity, stable storing；It is made
Vulcanized mechanical especially stress at definite elongation and tensile strength be significantly improved.
Application No. is 97110667.3 patent of invention " preparation methods of butadienestyrene rubber with superfine calcium caronate powder filling ", mention
It is total using styrene-maleic anhydride alternating for a kind of preparation method of butadienestyrene rubber with superfine calcium caronate powder filling
The saponified of polymers is covering, is filling interleaving agent with the calcium carbonate superfine powder with reinforcing effect, with univalent metal salt and two
Valence metal salt makees flocculating agent, and partial size is made and is 0.45~0.9mm, stores and stablize, the calcium carbonate superfine powder powder filler of good fluidity
Butadiene-styrene rubber.Powdered of the present invention is stable, reliable, dehydration is easy, and equipment is simple.
Application No. is the patent of invention of 02152078.X " preparation methods of powdered rubber in stuffing type with extra fine calcium carbonate ", provide
A kind of preparation method of powdered rubber in stuffing type with extra fine calcium carbonate includes the following steps: to measure contained dry glue: ultra-fine carbon by latex
Sour calcium: surfactant: operation is oily: anti-aging agent: fatty acid alkali metal salt emulsifier: flocculating agent: the weight ratio of deionized water is
100: 0~250: 0.2~8.0: 0~70: 0.5~3.0: 2.5~6.0: 2.0~5.0: 300~2000 proportion ingredient；It is ultra-fine
The emulsification of calcium carbonate；The heat treatment of latex；The agglomeration process of latex；The post-processing of condensation product.Powder rubber is prepared using the present invention
Glue has covering additional amount less, and covered effect is good, the advantage that pulverisation process is reliable and stable, easy, calcium carbonate superfine powder
For the powder formation rate of filled powder rubber up to 99% or more, the particle diameter distribution of prepared powdered rubber in stuffing type with extra fine calcium carbonate can
To be controlled by adjusting coherence condition, manufactured product physical mechanical property is excellent, non-dusting, good fluidity, storage
Deposit stabilization.
The patent of invention " using lignin as the method for rubber reinforcing filler " of Patent No. 89109494.6 discloses one
Kind uses lignin formaldehyde resin as the method for nitrile rubber reinforcing agent, and addition formaldehyde is made wooden in the papermaking wastewater of concentration
Plain formaldehyde resin, then it is proportionally added into Sulfur, zinc oxide, stearic acid, vulcanizing agent, vulcanization accelerator, vulcanizing activator and rubber
Vulcanized at a certain temperature, can get and fill a large amount of lignin in rubber and be not required to add softening agent, save a large amount of rubber
And the vulcanizate of good properties.But the shortcomings that this method, is that three sections of whole manufacturing processes point carry out respectively, i.e. lignin first
The preparation of urea formaldehyde mixes, the phase boundary surface treatment of lignin and nitrile rubber with nitrile rubber, increases process complexity, and
And the higher cost of this method, need to be added various auxiliary agents；In addition, this method is only applicable to nitrile rubber, in elastomer
In application range it is also narrow.
Chinese patent disclosed above, or utilizing carbon black as the reinforcing agent of rubber (further includes being with silica
The white carbon black of main component), or using lignin as the reinforcing agent of rubber.
Carbon black dispersion, operation fat liquor are added then coprecipitated solidification in latex, are to traditional rubber by latex coprecipitation
A kind of supplement of dry method mixing method.Using this method, the SBR 1100 series of high temperature cream of commercialization has been produced at present
It is poly- fill carbon black butylbenzene masterbatch, 1200 series of high temperature cream of SBR gathers oil-filled butylbenzene masterbatch, 1300 series of high temperature cream of SBR is poly- fills
The serial low temperature cream of oil black carbon butylbenzene masterbatch, SBR 1600 is poly-, and to fill carbon black butylbenzene masterbatch, SBR Series 1700 low temperature cream poly-
The poly- gross butylbenzene masterbatch of the serial low temperature cream of oil-filled butylbenzene masterbatch, SBR 1800.
But it prepares carbon black dispersion to need using ball mill, liquid stream grinder or magnetic oscillator, and it is living that surface is added
Property agent and water, then with the intermediate during production emulsion polymerized styrene butadiene rubber --- styrene-butadiene latex, fat liquor according to certain plus
Material sequence mixes, and since above-mentioned mixed liquor is thermodynamically and unstable, gained mixed liquor needs
In minute, coagulator appropriate (such as sodium chloride solution, acetum, dilute sulfuric acid) is added, is solidified, be then dehydrated, wash,
It is dry, the butadiene-styrene rubber of the various trades mark is made.
Therefore, utilize carbon black as the reinforcing agent of rubber, although in technique and economically with traditional method for mixing rubber
It compares, there is certain superiority, but there is also following disadvantages: (1) since carbon black is hydrophobic material, preparing carbon black dispersion
When, the effect for the shearing force being subject to when the shearing force that carbon black pellet is subject in the ball mill is much smaller than mixing, therefore carbon black is in life
Traditional attainable dispersion scale of mixing method institute cannot be reached in glue, cause certain performances of rubber to weaken, for example pull apart
Intensity can reduce, and permanent deformation will increase.(2) in latex the amount of added carbon black also by larger limitation, mainly because
For the property that carbon black has density big, hydrophobic, dispersion stability is poor, is unable to reach desired by rubber product institute
The purpose in raw rubber is added by the method for latex coprecipitation for the most of carbon black needed.
102718995 B of CN discloses a kind of industrial lignin reinforced rubber and preparation method thereof comprising lignin point
Granular media, latex and a small amount of plasticizer, operation oil can merge while not reducing rubber mixed physical mechanical property
The drying process of lignin and rubber production process reduces the power consumption of compounding rubber, still, intensity and breaking strength etc.
Mechanical property is relatively poor, needs to be further increased.
Summary of the invention
For the above-mentioned problems in the prior art, the purpose of the present invention is to provide a kind of composite material reinforced rubbers
Preparation method, hydroxyapatite/TiO of the invention2/ graphene oxide composite material reinforced rubber, which not only overcomes, utilizes charcoal
Black dispersion conventional dry compared with the coprecipitated reinforced rubber of rubber latex emulsion is there are rubber compound physical mechanical property is kneaded and reduces
The shortcomings that and the existing disadvantage that energy consumption is high, dust pollution is big of the rubber mixed process of prior art preparation, and the rubber
Excellent in mechanical performance, have broad application prospects.
In order to achieve the above object, the invention adopts the following technical scheme:
A kind of preparation method of composite material reinforced rubber, it is characterized in that: the described method comprises the following steps:
(1) by hydroxyapatite and TiO2It is distributed in water, forms dispersion liquid, be added in reaction kettle, it is anti-in 160 DEG C of hydro-thermals
12-24h is answered, the mixed liquor for then obtaining hydro-thermal is mixed with graphene oxide suspension, in 80-100 DEG C of condensing reflux 12-
For 24 hours, hydroxyapatite/TiO is obtained2/ graphene oxide composite material；
(2) plasticizer, operation oil are added in latex, stir evenly, hydroxyapatite/TiO is then added2/ graphene oxide
Composite material stirs 6-10h, adds coagulator, and generation is coprecipitated, forms sediment, is then washed, taken off to sediment
Water is dried to get hydroxyapatite/TiO is arrived2/ graphene oxide composite material reinforced rubber.
Preferably, in step (1), the hydroxyapatite and TiO2Mass ratio be (20-30): (1-5), for example,
20:1,20:2,20:3,25:1,25:2,25:3,25:4,25:5,27:1,27:2,27:3,27:4,30:1,30:2,30:3 or
30:4.5 waiting, preferably 25:3.
Preferably, in step (1), in the dispersion liquid, hydroxyapatite and TiO2Total molar concentration be 1-5mol/
L, for example, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L or 5mol/L etc..
Preferably, in step (1), the molar concentration of the graphene oxide suspension is 1mg/mL.
Preferably, in step (1), the volume ratio of mixed liquor and graphene oxide suspension that hydro-thermal obtains is 1:(10-
15)。
Preferably, in step (2), plasticizer, operation oil, latex and hydroxyapatite/TiO2/ graphene oxide composite wood
Material, mass ratio 1:1:100:(5-10), for example, 1:1:100:5,1:1:100:6,1:1:100:7,1:1:100:7.5,
1:1:100:8,1:1:100:9 or 1:1:100:10 etc., preferably 1:1:100:8.
Preferably, in step (2), the latex is Heveatex or synthetic rubber latex.
Preferably, in step (2), in step (2), the latex is Heveatex, styrene-butadiene latex, NBR latex, isoamyl
Rubber latex, butyl rubber latex, Neoprene latex or other unlisted all synthesis produced with emulsion polymerisation process
The latex of rubber.
In the present invention, the mode that plasticizer and operation oil formation latex mixed liquor are added into latex can be following feelings
Condition: by fat liquor made of rubber industry common plasticizers, operation oil, such as aromatic naphtha, epoxidized soybean oil, machine oil, castor oil, three
One of line oil, high sulfone oil, dibutyl phthalate or dioctyl phthalate fat liquor or two kinds of combination of the above, add
Enter in latex, forms latex mixed liquor；Or rubber industry common plasticizers, operation oil, such as aromatic hydrocarbons are directly added into latex
Oil, epoxidized soybean oil, machine oil, castor oil, third fractional oil, high sulfone oil, dibutyl phthalate or dioctyl phthalate
One or two or more kinds combination, forms latex mixed liquor.
The invention has the advantages that and the utility model has the advantages that
(1) present invention uses hydroxyapatite, TiO2Composite wood is prepared with graphene oxide in hydro-thermal+water-bath method
Material, and the composite material is used to prepare reinforced rubber, the mating reaction between this three generates synergistic effect, can reply promotion
The mechanical property of obtained rubber, hydroxyapatite/TiO of the invention2/ graphene oxide composite material reinforced rubber is pulled apart
Intensity is in 27.0MPa or more, and tearing strength is in 118.7MPa or more, and hardness (shore A) is 83.0 or more.
(2) method of the invention is simple, at low cost, energy consumption is small, and the dust pollution for reducing rubber mixing process is suitble to work
Industry metaplasia produces.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, of the invention is typical but non-limiting
Embodiment it is as follows:
Embodiment 1
Hydroxyapatite/TiO2/ graphene oxide composite material with Heveatex is coprecipitated is blended, for tire tread glue
Production.
(1) hydroxyapatite/TiO is prepared2/ graphene oxide composite material:
By hydroxyapatite and TiO2It is distributed in water, forms dispersion liquid (wherein, hydroxyapatite and TiO2Total rub
Your concentration is 5mol/L, and hydroxyapatite and TiO2Mass ratio be 25:2), be added reaction kettle in, in 160 DEG C of hydro-thermal reactions
For 24 hours, then the mixed liquor that hydro-thermal obtains is mixed with graphene oxide suspension according to the volume ratio of 1:10, is condensed back in 80 DEG C
Stream for 24 hours, obtains hydroxyapatite/TiO2/ graphene oxide composite material.
(2) hydroxyapatite/TiO is prepared2/ graphene oxide composite material reinforced rubber:
Plasticizer, operation oil are added in latex, stirs evenly to form latex mixed liquor, hydroxyapatite/TiO is then added2/
Graphene oxide composite material stirs 6-10h, adds appropriate dilute sulfuric acid, makes latex coagulation, and coprecipitated, formation sediment occurs,
Then sediment washed, be dehydrated, being dried to get hydroxyapatite/TiO is arrived2/ graphene oxide composite material reinforcement rubber
Glue.
Hydroxyapatite/the TiO of the present embodiment2In/graphene oxide composite material reinforced rubber, plasticizer, operation oil,
Latex and hydroxyapatite/TiO2The mass ratio of/graphene oxide composite material is 1:1:100:5.
Through detecting, the hydroxyapatite/TiO of the present embodiment2The breaking strength of/graphene oxide composite material reinforced rubber
For 26.8MPa, tearing strength 123.5KN/m, hardness (shore A) is 82.6.
Embodiment 2
Hydroxyapatite/TiO2/ graphene oxide composite material with Heveatex is coprecipitated is blended, for tire tread glue
Production.
(1) hydroxyapatite/TiO is prepared2/ graphene oxide composite material:
By hydroxyapatite and TiO2It is distributed in water, forms dispersion liquid (wherein, hydroxyapatite and TiO2Total rub
Your concentration is 3mol/L, and hydroxyapatite and TiO2Mass ratio be 20:1), be added reaction kettle in, in 180 DEG C of hydro-thermal reactions
Then the mixed liquor that hydro-thermal obtains is mixed with graphene oxide suspension according to volume ratio for 1:12, is condensed in 100 DEG C by 12h
Flow back 12h, obtains hydroxyapatite/TiO2/ graphene oxide composite material.
(2) hydroxyapatite/TiO is prepared2/ graphene oxide composite material reinforced rubber:
Plasticizer, operation oil are added in latex, stirs evenly to form latex mixed liquor, hydroxyapatite/TiO is then added2/
Graphene oxide composite material stirs 6-10h, adds appropriate dilute sulfuric acid, makes latex coagulation, and coprecipitated, formation sediment occurs,
Then sediment washed, be dehydrated, being dried to get hydroxyapatite/TiO is arrived2/ graphene oxide composite material reinforcement rubber
Glue.
Hydroxyapatite/the TiO of the present embodiment2In/graphene oxide composite material reinforced rubber, plasticizer, operation oil,
Latex and hydroxyapatite/TiO2The mass ratio of/graphene oxide composite material is 1:1:100:7.
Through detecting, the hydroxyapatite/TiO of the present embodiment2The breaking strength of/graphene oxide composite material reinforced rubber
For 27.5MPa, tearing strength 118.7KN/m, hardness (shore A) is 83.1.
Embodiment 3
Hydroxyapatite/TiO2/ graphene oxide composite material with Heveatex is coprecipitated is blended, for tire tread glue
Production.
(1) hydroxyapatite/TiO is prepared2/ graphene oxide composite material:
By hydroxyapatite and TiO2It is distributed in water, forms dispersion liquid (wherein, hydroxyapatite and TiO2Total rub
Your concentration is 2.5mol/L, and hydroxyapatite and TiO2Mass ratio be 20:4), be added reaction kettle in, it is anti-in 170 DEG C of hydro-thermals
18h is answered, then the mixed liquor that hydro-thermal obtains is mixed with graphene oxide suspension according to volume ratio for 1:14, is condensed in 90 DEG C
Flow back 15h, obtains hydroxyapatite/TiO2/ graphene oxide composite material.
(2) hydroxyapatite/TiO is prepared2/ graphene oxide composite material reinforced rubber:
Plasticizer, operation oil are added in latex, stirs evenly to form latex mixed liquor, hydroxyapatite/TiO is then added2/
Graphene oxide composite material stirs 6-10h, adds appropriate dilute sulfuric acid, makes latex coagulation, and coprecipitated, formation sediment occurs,
Then sediment washed, be dehydrated, being dried to get hydroxyapatite/TiO is arrived2/ graphene oxide composite material reinforcement rubber
Glue.
Hydroxyapatite/the TiO of the present embodiment2In/graphene oxide composite material reinforced rubber, plasticizer, operation oil,
Latex and hydroxyapatite/TiO2The mass ratio of/graphene oxide composite material is 1:1:100:8.
Through detecting, the hydroxyapatite/TiO of the present embodiment2The breaking strength of/graphene oxide composite material reinforced rubber
For 28.0MPa, tearing strength 123.5KN/m, hardness (shore A) is 83.8.
Embodiment 4
Hydroxyapatite/TiO2/ graphene oxide composite material with Heveatex is coprecipitated is blended, for tire tread glue
Production.
(1) hydroxyapatite/TiO is prepared2/ graphene oxide composite material:
By hydroxyapatite and TiO2It is distributed in water, forms dispersion liquid (wherein, hydroxyapatite and TiO2Total rub
Your concentration is 1mol/L, and hydroxyapatite and TiO2Mass ratio be 30:3), be added reaction kettle in, in 165 DEG C of hydro-thermal reactions
Then the mixed liquor that hydro-thermal obtains is mixed with graphene oxide suspension according to volume ratio for 1:13, is condensed back in 85 DEG C by 20h
18h is flowed, hydroxyapatite/TiO is obtained2/ graphene oxide composite material.
(2) hydroxyapatite/TiO is prepared2/ graphene oxide composite material reinforced rubber:
Plasticizer, operation oil are added in latex, stirs evenly to form latex mixed liquor, hydroxyapatite/TiO is then added2/
Graphene oxide composite material stirs 6-10h, adds appropriate dilute sulfuric acid, makes latex coagulation, and coprecipitated, formation sediment occurs,
Then sediment washed, be dehydrated, being dried to get hydroxyapatite/TiO is arrived2/ graphene oxide composite material reinforcement rubber
Glue.
Hydroxyapatite/the TiO of the present embodiment2In/graphene oxide composite material reinforced rubber, plasticizer, operation oil,
Latex and hydroxyapatite/TiO2The mass ratio of/graphene oxide composite material is 1:1:100:9.
Through detecting, the hydroxyapatite/TiO of the present embodiment2The breaking strength of/graphene oxide composite material reinforced rubber
For 27.0MPa, tearing strength 120.2KN/m, hardness (shore A) is 83.3.
Embodiment 5
Hydroxyapatite/TiO2/ graphene oxide composite material with Heveatex is coprecipitated is blended, for tire tread glue
Production.
(1) hydroxyapatite/TiO is prepared2/ graphene oxide composite material:
By hydroxyapatite and TiO2It is distributed in water, forms dispersion liquid (wherein, hydroxyapatite and TiO2Total rub
Your concentration is 3.5mol/L, and hydroxyapatite and TiO2Mass ratio be 25:3), be added reaction kettle in, it is anti-in 175 DEG C of hydro-thermals
22h is answered, then mixes the mixed liquor that hydro-thermal obtains for 1:15 according to volume ratio with graphene oxide suspension, it is cold in 100 DEG C
Solidifying reflux 14h, obtains hydroxyapatite/TiO2/ graphene oxide composite material.
(2) hydroxyapatite/TiO is prepared2/ graphene oxide composite material reinforced rubber:
Plasticizer, operation oil are added in latex, stirs evenly to form latex mixed liquor, hydroxyapatite/TiO is then added2/
Graphene oxide composite material stirs 6-10h, adds appropriate dilute sulfuric acid, makes latex coagulation, and coprecipitated, formation sediment occurs,
Then sediment washed, be dehydrated, being dried to get hydroxyapatite/TiO is arrived2/ graphene oxide composite material reinforcement rubber
Glue.
Hydroxyapatite/the TiO of the present embodiment2In/graphene oxide composite material reinforced rubber, plasticizer, operation oil,
Latex and hydroxyapatite/TiO2The mass ratio of/graphene oxide composite material is 1:1:100:10.
Through detecting, the hydroxyapatite/TiO of the present embodiment2The breaking strength of/graphene oxide composite material reinforced rubber
For 29.0MPa, tearing strength 132.5KN/m, hardness (shore A) is 84.8.
Comparative example 1
Except by hydroxyapatite/TiO2/ graphene oxide composite material replaces with TiO2Outside, other preparation methods and condition
It is same as Example 1.
Through detecting, the breaking strength of the rubber of this comparative example is 19.9MPa, tearing strength 92.4KN/m, hardness (shore
It A) is 66.4.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office
Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of preparation method of composite material reinforced rubber, it is characterized in that: the described method comprises the following steps:
(1) by hydroxyapatite and TiO2It is distributed in water, forms dispersion liquid, be added in reaction kettle, it is anti-in 160-180 DEG C of hydro-thermal
12-24h is answered, the mixed liquor for then obtaining hydro-thermal is mixed with graphene oxide suspension, in 80-100 DEG C of condensing reflux 12-
For 24 hours, hydroxyapatite/TiO is obtained2/ graphene oxide composite material；
(2) plasticizer, operation oil are added in latex, stir evenly to form latex mixed liquor, hydroxyapatite/TiO is then added2/ oxygen
Graphite alkene composite material stirs 6-10h, adds coagulator, coprecipitated, formation sediment occurs, then to sediment progress
Washing, dehydration are dried to get hydroxyapatite/TiO is arrived2/ graphene oxide composite material reinforced rubber.
2. the method as described in claim 1, it is characterized in that: in step (1), the hydroxyapatite and TiO2Mass ratio be
(20-30): (1-5).
3. the method as described in claim 1, it is characterized in that: in step (1), the hydroxyapatite and TiO2Mass ratio be
25:3。
4. the method as described in claim 1, it is characterized in that: in step (1), in the dispersion liquid, hydroxyapatite and TiO2's
Total molar concentration is 1-5mol/L.
5. the method as described in claim 1, it is characterised in that: in step (1), the concentration of the graphene oxide suspension is
1mg/mL。
6. the method as described in claim 1, it is characterised in that: in step (1), mixed liquor and graphene oxide that hydro-thermal obtains
The volume ratio of suspension is 1:(10-15).
7. the method as described in claim 1, it is characterised in that: in step (2), plasticizer, operation oil, latex and hydroxy-apatite
Stone/TiO2The mass ratio of/graphene oxide composite material is 1:1:100:(5-10).
8. the method as described in claim 1, it is characterised in that: in step (2), plasticizer, operation oil, latex and hydroxy-apatite
Stone/TiO2The mass ratio of/graphene oxide composite material is 1:1:100:8.
9. the method as described in claim 1, it is characterised in that: in step (2), the latex is Heveatex or synthetic rubber
Latex.
10. such as the described in any item methods of claim 1-9, it is characterised in that: in step (2), the latex is Heveatex,
Styrene-butadiene latex, NBR latex, isoprene rubber latex, butyl rubber latex, Neoprene latex or other are unlisted with lotion
The latex of all synthetic rubber of polymerization production.
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|---|---|---|---|---|
| CN102437321B (en) * | 2011-12-20 | 2013-10-16 | 中国科学院新疆理化技术研究所 | Graphene-TiO2(B) nanotube composite material and preparation method thereof |
| CN102569749B (en) * | 2012-03-06 | 2014-10-29 | 江苏大学 | Graphene/hydroxyapatite nano composite and preparation method thereof |
| BR112018007052B1 (en) * | 2015-10-09 | 2023-01-17 | Ossiform Aps | PROCESS FOR 3D PRINTING A THREE-DIMENSIONAL OBJECT |
| CN105497986A (en) * | 2015-12-10 | 2016-04-20 | 青岛大学 | Synthesis method of graphene-hydroxyapatite composite material |
| CN106751163A (en) * | 2016-12-06 | 2017-05-31 | 安徽圣源橡塑科技有限公司 | A kind of heat-resistant PVC composite foamed plate high of graphene oxide hydroxyapatite reinforcement and preparation method thereof |
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