CN108929470A - A kind of anti-aging rubber composition and preparation method thereof - Google Patents
A kind of anti-aging rubber composition and preparation method thereof Download PDFInfo
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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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
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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
- C08K3/18—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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a kind of anti-aging rubber compositions, include 55-60% matrix, 2-3% epoxy resin, 4-5% zinc oxide, 2-4% stearic acid, 4-6% anti-aging agent and 25-35% filler by mass percentage；Described matrix includes natural rubber, nitrile rubber, butadiene-styrene rubber and the polyester polyol that mass ratio is 1-2:1.2-3:2-4:0.2-1；The filler includes the calcium carbonate and barium sulfate that mass ratio is 1-3:2-5；The anti-aging agent includes antioxidant D NP, antioxidant MB, antioxidant DOD and the antioxidant A that mass ratio is 3-5:1-2.3:1-2:2-5.Anti-aging rubber of the invention can continue to use at high temperature, can the oxidation of heat resistanceheat resistant oxygen and ozone oxidation.
Description
Technical field
The present invention relates to field of rubber technology, in particular to a kind of anti-aging rubber composition and preparation method thereof.
Background technique
Rubber or rubber product are during processing, storage and use, (such as due to the comprehensive function by inside and outside factor
Heat, oxygen, ozone, metal ion, ionising radiation, light, mechanical force etc.) it is gradually reduced performance, so that last lose the valence of using
Value, this phenomenon are known as the aging of rubber.
The most important factor of ageing of rubber is oxidation, it makes rubber molecule structure that cracking or structuring occur, and is caused
Rubber material performance depreciation, temperature have a significant impact to oxidation, and rubber oxidation reaction, especially rubber system can be accelerated by improving temperature
Product are at high temperature or dynamic is lower in use, significant thermal oxidation can occur for heat raising.
Prevent the measure of ageing of rubber from having at present: the raw rubber kind for selecting ageing-resistant performance good such as selects nitrile rubber；Choosing
With the good vulcanizing system of ageing-resistant performance, zinc dimethyl dithiocarbamate is such as selected；Aging aids are added, as phenols is anti-old
Agent.
Summary of the invention
Goal of the invention: the present invention provides a kind of anti-aging rubber composition, the rubber of the composition preparation has high temperature
Lower anti ageing property is excellent.It is a further object of the present invention to provide the preparation methods of the anti-aging rubber.
Technical solution: a kind of anti-aging rubber composition of the present invention includes by mass percentage 55-60%
Matrix, 2-3% epoxy resin, 4-5% zinc oxide, 2-4% stearic acid, 4-6% anti-aging agent and 25-35% filler；It is described
Matrix includes natural rubber, nitrile rubber, butadiene-styrene rubber and the polyester polyols that mass ratio is 1-2:1.2-3:2-4:0.2-1
Alcohol；The filler includes the calcium carbonate and barium sulfate that mass ratio is 1-3:2-5；The anti-aging agent includes that mass ratio is 3-5:1-
2.3:1-2:2-5 antioxidant D NP, antioxidant MB, antioxidant DOD and antioxidant A.
Further, the epoxy resin is the bisphenol A type epoxy resin and phenol novolak type epoxy that mass ratio is 1-2:3
The mixture of resin.
Further, the partial size of the calcium carbonate is 30-100nm, and the partial size of the barium sulfate is 50-200nm.
Further, the anti-aging agent includes antioxidant D NP, antioxidant MB, the anti-aging agent that mass ratio is 4.3:2:1.5:3
DOD and antioxidant A.
Further, described matrix include mass ratio be comprising mass ratio be 1.5:3:3:0.7 natural rubber, butyronitrile rubber
Glue, butadiene-styrene rubber and polyester polyol.
It further, include the polyurethane of 0.5-1.2% in the composition.
Further, the filler includes calcium carbonate, barium sulfate and the titanium dioxide that mass ratio is 1-3:2-5:0.2-0.5
Titanium.
The preparation method of the anti-aging rubber of above-mentioned anti-aging rubber composition preparation, specific as follows:
(1) mixing: will, by mass percentage, comprising 55-60% matrix, 2-3% epoxy resin, 4-5% zinc oxide,
The raw material of 2-4% stearic acid, 4-6% anti-aging agent and 25-35% filler pours into mixer, in the case where not being pressed into weight
After mixing evenly, it then is kneaded, the water temperature of mixer is controlled at 70 DEG C hereinafter, compressed air pressure 0.7-0.9MPa, material temperature
Material is discharged when being 115-120 DEG C；Described matrix includes natural rubber, the butyronitrile that mass ratio is 1-2:1.2-3:2-4:0.2-1
Rubber, butadiene-styrene rubber and polyester polyol；The filler includes the calcium carbonate and barium sulfate that mass ratio is 1-3:2-5；Institute
Stating anti-aging agent includes antioxidant D NP, antioxidant MB, antioxidant DOD and the antioxidant A that mass ratio is 3-5:1-2.3:1-2:2-5；
(2) mixer discharge material mill: is sent into open mill mill, 85-90 DEG C of preceding roll temperature, rear roll temperature 75-80
DEG C, roll spacing 0.3-0.7mm mends refining 3-5 times；
(3) slice: sending the material after mill into slice machining, obtains cooling, coolant water temperature≤35 DEG C after tablet；
(4) vulcanize: tablet being sent into vulcanizing press and carries out vulcanizing treatment, steam pressure 0.6-0.7MPa, vulcanization time
For 20-30min；
(5) it processes: the sheet material vulcanizated being placed and is cooled down, be sliced deburring, then be punched into rubber sole.
A kind of another preparation process of heretofore described anti-aging rubber is as follows:
(1) mixing: will, by mass percentage, comprising 55-60% matrix, 2-3% epoxy resin, 4-5% zinc oxide,
2-4% stearic acid, the polyurethane of 0.5-1.2%, 4-6% anti-aging agent and 25-35% filler raw material pour into mixer,
It is not pressed into the case where weight after mixing evenly, then is kneaded, the water temperature of mixer is controlled at 70 DEG C hereinafter, compressed air pressure
Material is discharged when being 115-120 DEG C in power 0.7-0.9MPa, material temperature；Described matrix includes that mass ratio is 1-2:1.2-3:2-4:0.2-
1 natural rubber, nitrile rubber, butadiene-styrene rubber and polyester polyol；Filler includes that mass ratio is 1-3:2-5:0.2-0.5
Calcium carbonate, barium sulfate and titanium dioxide；The anti-aging agent include mass ratio be 3-5:1-2.3:1-2:2-5 antioxidant D NP,
Antioxidant MB, antioxidant DOD and antioxidant A；
(2) mixer discharge material mill: is sent into open mill mill, 85-90 DEG C of preceding roll temperature, rear roll temperature 75-80
DEG C, roll spacing 0.3-0.7mm mends refining 3-5 times；
(3) slice: sending the material after mill into slice machining, obtains cooling, coolant water temperature≤35 DEG C after tablet；
(4) vulcanize: tablet being sent into vulcanizing press and carries out vulcanizing treatment, steam pressure 0.6-0.7MPa, vulcanization time
For 30-35min；
(5) it processes: the sheet material vulcanizated being placed and is cooled down, be sliced deburring, then be punched into rubber sole.
The utility model has the advantages that (1) present invention utilizes antioxidant A and the excellent thermo oxidative aging performance of antioxidant DOD, anti-aging agent
DNP has the function of excellent heat-proof aging, the preventing ultraviolet of resistance to natural weathering, and antioxidant MB is added and improves between different anti-aging agents
Synergy, so that the rubber in the present invention has excellent anti ageing property；(2) it joined the polynary alcoholysis of ester type in the present invention
Certainly the problem of complex antiager bloom, it is that antioxidant MB the problem of bloom occurs by it, can further improve the comprehensive of rubber
Energy；(3) it joined titanium dioxide as reinforcing agent and ozone-resistant oxidant in the present invention, and solve system phase using polyurethane
The problem of capacitive, the case where avoiding stress raisers.
Specific embodiment
One, raw material sources
The average grain diameter for the calcium carbonate selected in embodiment is 30-100nm, and the average grain diameter of barium sulfate is 50-200nm；
The commercially available gained of remaining material.
Two, experimental method
2.1 referring to GBT 3512-2001 " vulcanized rubber or thermoplastic elastomer heat ageing and heat resistant test "
Temperature: 120 DEG C；
Time: 72h；
After temperature is stablized, sample is carried out degradation in free state suspension, the distance between every two sample is not small
In 5mm, the distance between sample and tank wall are not less than 70mm；
Sample is put into the aging of constant temperature backward, that is, starts to calculate ageing time；
The sample of taking-up is parked for 24 hours at 23 ± 2 DEG C of temperature；
Detect performance change rate of the rubber after artificial ageing: tensile strength, elongation at break and hardness, ratio are exactly old
Change coefficient.
Laboratory apparatus: air oven aging test case.
2.2 referring to GB/T 12831 vulcanized rubber artificial climate (xenon lamp) aging testing method, and the weather for measuring sample is old
Change performance；
2.3, referring to GB/T 13642-1992 vulcanized rubber ozone and aging resistance test (dynamic tensile test method(s)), measure sample
Ozone-resistant oxidation susceptibility.
Three, sample preparation
Embodiment 1:
Step 1: natural rubber, nitrile rubber, butadiene-styrene rubber and the polyester polyols for being 1:1.2:2:0.2 by mass ratio
Alcohol is mixed into matrix；
Calcium carbonate and barium sulfate that mass ratio is 1:2 are mixed into filler；
Bisphenol A type epoxy resin and phenol novolak type epoxy that mass ratio is 1:3 are mixed into epoxy resin；
Antioxidant D NP, antioxidant MB, antioxidant DOD and antioxidant A that mass ratio is 3:1:1:2 are mixed into anti-aging agent；
By mass percentage, by 55% matrix, 2% epoxy resin, 4% zinc oxide, 2% stearic acid, 4% anti-aging agent with
And 33% the raw material of filler pour into mixer, be not pressed into the case where weight after mixing evenly, then be kneaded, mixer
Water temperature control at 70 DEG C hereinafter, compressed air pressure 0.7-0.9MPa, material is discharged when being 115-120 DEG C in material temperature；
Step 2: mixer discharge material is sent into open mill mill, 85-90 DEG C of preceding roll temperature, rear roll temperature 75-80
DEG C, roll spacing 0.3-0.7mm mends refining 3-5 times；
Step 3: sending the material after mill into slice machining, obtains cooling, coolant water temperature≤35 DEG C after tablet；
Step 4: tablet is sent into vulcanizing press and carries out vulcanizing treatment, steam pressure 0.6-0.7MPa, vulcanization time is
20min；
Step 5: the sheet material vulcanizated being placed and is cooled down, and is sliced deburring, then be punched into rubber sole.
Embodiment 2:
Step 1: natural rubber, nitrile rubber, butadiene-styrene rubber and polyester polyol that mass ratio is 2:3:4:1 are mixed
Synthesize matrix；
Calcium carbonate and barium sulfate that mass ratio is 3:5 are mixed into filler；
Bisphenol A type epoxy resin and phenol novolak type epoxy that mass ratio is 2:3 are mixed into epoxy resin；
Antioxidant D NP, antioxidant MB, antioxidant DOD and antioxidant A that mass ratio is 5:2.3:2:5 are mixed into anti-old
Agent；
By mass percentage, by 60% matrix, 3% epoxy resin, 5% zinc oxide, 4% stearic acid, 6% anti-aging agent with
And 22% the raw material of filler pour into mixer, be not pressed into the case where weight after mixing evenly, then be kneaded, mixer
Water temperature control at 70 DEG C hereinafter, compressed air pressure 0.7-0.9MPa, material is discharged when being 115-120 DEG C in material temperature；
Step 2: mixer discharge material is sent into open mill mill, 85-90 DEG C of preceding roll temperature, rear roll temperature 75-80
DEG C, roll spacing 0.3-0.7mm mends refining 3-5 times；
Step 3: sending the material after mill into slice machining, obtains cooling, coolant water temperature≤35 DEG C after tablet；
Step 4: tablet is sent into vulcanizing press and carries out vulcanizing treatment, steam pressure 0.6-0.7MPa, vulcanization time is
25min；
Step 5: the sheet material vulcanizated being placed and is cooled down, and is sliced deburring, then be punched into rubber sole.
Embodiment 3:
Step 1: natural rubber, nitrile rubber, butadiene-styrene rubber and the polyester polyols for being 1.5:3:3:0.7 by mass ratio
Alcohol is mixed into matrix；
Calcium carbonate and barium sulfate that mass ratio is 2:5 are mixed into filler；
Bisphenol A type epoxy resin and phenol novolak type epoxy that mass ratio is 2:3 are mixed into epoxy resin；
Antioxidant D NP, antioxidant MB, antioxidant DOD and antioxidant A that mass ratio is 4.3:2:1.5:3 are mixed into anti-
Old agent；
By mass percentage, by 57% matrix, 3% epoxy resin, 5% zinc oxide, 3% stearic acid, 5% anti-aging agent with
And 27% the raw material of filler pour into mixer, be not pressed into the case where weight after mixing evenly, then be kneaded, mixer
Water temperature control at 70 DEG C hereinafter, compressed air pressure 0.7-0.9MPa, material is discharged when being 115-120 DEG C in material temperature；
Step 2: mixer discharge material is sent into open mill mill, 85-90 DEG C of preceding roll temperature, rear roll temperature 75-80
DEG C, roll spacing 0.3-0.7mm mends refining 3-5 times；
Step 3: sending the material after mill into slice machining, obtains cooling, coolant water temperature≤35 DEG C after tablet；
Step 4: tablet is sent into vulcanizing press and carries out vulcanizing treatment, steam pressure 0.6-0.7MPa, vulcanization time is
25min；
Step 5: the sheet material vulcanizated being placed and is cooled down, and is sliced deburring, then be punched into rubber sole.
Embodiment 4:
Step 1: natural rubber, nitrile rubber, butadiene-styrene rubber and the polyester polyols for being 1.5:3:3:0.7 by mass ratio
Alcohol is mixed into matrix；
Calcium carbonate, barium sulfate and titanium dioxide that mass ratio is 2:5:0.5 are mixed into filler；
Bisphenol A type epoxy resin and phenol novolak type epoxy that mass ratio is 2:3 are mixed into epoxy resin；
Antioxidant D NP, antioxidant MB, antioxidant DOD and antioxidant A that mass ratio is 4.3:2:1.5:3 are mixed into anti-
Old agent；
By mass percentage, by 56% matrix, 3% epoxy resin, 5% zinc oxide, 3% stearic acid, 1% polyurethane,
The raw material of 5% anti-aging agent and 27% filler pours into mixer, is not pressed into the case where weight after mixing evenly, then carry out
It is kneaded, the water temperature of mixer is controlled at 70 DEG C hereinafter, compressed air pressure 0.7-0.9MPa, material temperature are discharged when being 115-120 DEG C
Material；
Step 2: mixer discharge material is sent into open mill mill, 85-90 DEG C of preceding roll temperature, rear roll temperature 75-80
DEG C, roll spacing 0.3-0.7mm mends refining 3-5 times；
Step 3: sending the material after mill into slice machining, obtains cooling, coolant water temperature≤35 DEG C after tablet；
Step 4: tablet is sent into vulcanizing press and carries out vulcanizing treatment, steam pressure 0.6-0.7MPa, vulcanization time is
25min；
Step 5: the sheet material vulcanizated being placed and is cooled down, and is sliced deburring, then be punched into rubber sole.
Embodiment 5:
Step 1: natural rubber, nitrile rubber, butadiene-styrene rubber and the polyester polyols for being 1.5:3:3:0.7 by mass ratio
Alcohol is mixed into matrix；
Calcium carbonate, barium sulfate and titanium dioxide that mass ratio is 2:5:0.5 are mixed into filler；
Bisphenol A type epoxy resin and phenol novolak type epoxy that mass ratio is 2:3 are mixed into epoxy resin；
Antioxidant D NP, antioxidant MB, antioxidant DOD and antioxidant A that mass ratio is 4.3:2:1.5:3 are mixed into anti-
Old agent；
By mass percentage, by 55.8% matrix, 3% epoxy resin, 5% zinc oxide, 3% stearic acid, 1.2% poly- ammonia
The raw material of ester, 5% anti-aging agent and 27% filler pours into mixer, is not pressed into the case where weight after mixing evenly, then
It is kneaded, the water temperature of mixer is controlled at 70 DEG C hereinafter, compressed air pressure 0.7-0.9MPa, when material temperature is 115-120 DEG C
Material is discharged；
Step 2: mixer discharge material is sent into open mill mill, 85-90 DEG C of preceding roll temperature, rear roll temperature 75-80
DEG C, roll spacing 0.3-0.7mm mends refining 3-5 times；
Step 3: sending the material after mill into slice machining, obtains cooling, coolant water temperature≤35 DEG C after tablet；
Step 4: tablet is sent into vulcanizing press and carries out vulcanizing treatment, steam pressure 0.6-0.7MPa, vulcanization time is
25min；
Step 5: the sheet material vulcanizated being placed and is cooled down, and is sliced deburring, then be punched into rubber sole.
Comparative example 1: without antioxidant A, remaining is the same as embodiment 5.
Comparative example 2: without antioxidant DOD, remaining is the same as embodiment 5.
Comparative example 3: without antioxidant MB, remaining is the same as embodiment 5.
Comparative example 4: without antioxidant D NP, remaining is the same as embodiment 5.
Comparative example 5: without polyester polyol, remaining is the same as embodiment 5.
Four, sample tests
4.1 thermo oxidative aging performances
Before (tensile strength × elongation at break)/aging after aging coefficient=aging (tensile strength × elongation at break)
× 100%
The different sample thermo oxidative aging performance measurement results of table 1
4.2 ozone-resistant ageing properties
Before (tensile strength × elongation at break)/aging after aging coefficient=aging (tensile strength × elongation at break)
× 100%
The different sample ozone-resistant ageing properties measurement results of table 2
4.3 Weather performances
Before (tensile strength × elongation at break)/aging after aging coefficient=aging (tensile strength × elongation at break)
× 100%
The anti-Weather performance measurement result of the different samples of table 3
As can be seen from the above results, antioxidant A ozone-resistant ageing properties are poor, individual antioxidant A be unable to satisfy resist it is smelly
The ability of oxygen aging；From comparative example 2 and the comparison of embodiment 5 as can be seen that antioxidant DOD has protective action to air aging, from
Comparative example 3 and the comparison of embodiment 5 can be seen that antioxidant MB and other anti-aging agents are used in conjunction with apparent synergy, still
Antioxidant MB is easy to appear bloom, therefore polyester polyol is added in the present invention and solves the problems, such as complex antiager bloom.From right
Ratio 4 and the comparison of embodiment 5 can be seen that antioxidant D NP has the function of excellent heat-proof aging, the preventing ultraviolet of resistance to natural weathering,
Improve the ozone-resistant ageing properties of rubber sample.
Furthermore in the present invention, the addition of filler and the addition of polyurethane improve the whole anti-aging property of rubber, and two
Titanium oxide in anti-aging rubber of the invention, can prevent the ozone-resistant of rubber other than reinforcing agent that can be excellent as rubber
Aging, but the addition of different inorganic particulates will cause inorganic system and mutually separate with organic system appearance, therefore into one in the present invention
Step joined polyurethane, and polyurethane can increase the compatibility of filler and rubbery system, improve the overall performance of rubber, therefore
It is not in that filler is unevenly distributed, the case where influencing the mechanical property of material, particular avoid stress raisers, therefore
When anti-aging, the phenomenon that being not in answer local damage, substantially reduce its anti-aging property.
Claims (9)
1. a kind of anti-aging rubber composition, which is characterized in that the rubber composition includes by mass percentage 55-
60% matrix, 2-3% epoxy resin, 4-5% zinc oxide, 2-4% stearic acid, 4-6% anti-aging agent and 25-35% filler；
Described matrix includes that the natural rubber that mass ratio is 1-2:1.2-3:2-4:0.2-1, nitrile rubber, butadiene-styrene rubber and polyester-type are more
First alcohol；The filler includes the calcium carbonate and barium sulfate that mass ratio is 1-3:2-5；The anti-aging agent includes that mass ratio is 3-5:
1-2.3:1-2:2-5 antioxidant D NP, antioxidant MB, antioxidant DOD and antioxidant A.
2. anti-aging rubber composition according to claim 1, which is characterized in that the epoxy resin is that mass ratio is 1-
The bisphenol A type epoxy resin of 2:3 and the mixture of phenol novolak type epoxy.
3. anti-aging rubber composition according to claim 1, which is characterized in that the partial size of the calcium carbonate is 30-
100nm, the partial size of the barium sulfate are 50-200nm.
4. anti-aging rubber composition according to claim 1, which is characterized in that the anti-aging agent includes that mass ratio is
4.3:2:1.5:3 antioxidant D NP, antioxidant MB, antioxidant DOD and antioxidant A.
5. anti-aging rubber composition according to claim 1, which is characterized in that described matrix include mass ratio be comprising
Mass ratio is natural rubber, nitrile rubber, butadiene-styrene rubber and the polyester polyol of 1.5:3:3:0.7.
6. anti-aging rubber composition according to claim 1, which is characterized in that include 0.5- in the rubber composition
1.2% polyurethane.
7. anti-aging rubber composition according to claim 6, which is characterized in that the filler includes that mass ratio is 1-
Calcium carbonate, barium sulfate and the titanium dioxide of 3:2-5:0.2-0.5.
8. a kind of preparation method of anti-aging rubber, which is characterized in that comprise the steps of:
(1) mixing: will, it include 55-60% matrix, 2-3% epoxy resin, 4-5% zinc oxide, 2-4% by mass percentage
The raw material of stearic acid, 4-6% anti-aging agent and 25-35% filler pours into mixer, stirs in the case where not being pressed into weight
It after uniformly, then is kneaded, the water temperature of mixer is controlled at 70 DEG C hereinafter, compressed air pressure 0.7-0.9MPa, material temperature are
Material is discharged at 115-120 DEG C；Described matrix includes that mass ratio is the natural rubber of 1-2:1.2-3:2-4:0.2-1, butyronitrile rubber
Glue, butadiene-styrene rubber and polyester polyol；The filler includes the calcium carbonate and barium sulfate that mass ratio is 1-3:2-5；It is described
Anti-aging agent includes antioxidant D NP, antioxidant MB, antioxidant DOD and the antioxidant A that mass ratio is 3-5:1-2.3:1-2:2-5；
(2) mixer discharge material mill: is sent into open mill mill, 85-90 DEG C of preceding roll temperature, 75-80 DEG C of rear roll temperature, roller
Away from 0.3-0.7mm, refining 3-5 times is mended；
(3) slice: sending the material after mill into slice machining, obtains cooling, coolant water temperature≤35 DEG C after tablet；
(4) vulcanize: tablet being sent into vulcanizing press and carries out vulcanizing treatment, steam pressure 0.6-0.7MPa, vulcanization time 20-
30min；
(5) it processes: the sheet material vulcanizated being placed and is cooled down, be sliced deburring, then be punched into rubber sole.
9. a kind of preparation method of anti-aging rubber, which is characterized in that comprise the steps of:
(1) mixing: will, it include 55-60% matrix, 2-3% epoxy resin, 4-5% zinc oxide, 2-4% by mass percentage
Stearic acid, the polyurethane of 0.5-1.2%, 4-6% anti-aging agent and 25-35% filler raw material pour into mixer, do not press
Enter in the case where weight after mixing evenly, then be kneaded, the water temperature of mixer is controlled at 70 DEG C hereinafter, compressed air pressure
Material is discharged when being 115-120 DEG C in 0.7-0.9MPa, material temperature；Described matrix includes that mass ratio is 1-2:1.2-3:2-4:0.2-1
Natural rubber, nitrile rubber, butadiene-styrene rubber and polyester polyol；Filler includes that mass ratio is 1-3:2-5:0.2-0.5
Calcium carbonate, barium sulfate and titanium dioxide；The anti-aging agent include mass ratio be 3-5:1-2.3:1-2:2-5 antioxidant D NP,
Antioxidant MB, antioxidant DOD and antioxidant A；
(2) mixer discharge material mill: is sent into open mill mill, 85-90 DEG C of preceding roll temperature, 75-80 DEG C of rear roll temperature, roller
Away from 0.3-0.7mm, refining 3-5 times is mended；
(3) slice: sending the material after mill into slice machining, obtains cooling, coolant water temperature≤35 DEG C after tablet；
(4) vulcanize: tablet being sent into vulcanizing press and carries out vulcanizing treatment, steam pressure 0.6-0.7MPa, vulcanization time 30-
35min；
(5) it processes: the sheet material vulcanizated being placed and is cooled down, be sliced deburring, then be punched into rubber sole.
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