CN108586945A - A kind of preparation method and applications of corrosion resistance rubber composite material - Google Patents
A kind of preparation method and applications of corrosion resistance rubber composite material 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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/12—Aldehydes; Ketones
- D06M13/123—Polyaldehydes; Polyketones
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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
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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
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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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
Abstract
The invention discloses a kind of preparation method and applications of corrosion resistance rubber composite material, this method is used diatomite, aluminium hydroxide, polyester fiber ball milling；Polyamide staple fibre, methyl ethyl ketone peroxide are immersed in supersound process, isolated centrifugal deposition object in acid solution, are transferred to after washing in high-pressure stirring reaction kettle, naphthenic oil is added and is stirred to react to obtain high-pressure stirring reactant；Methylbenzoic acid ethyl ester, acetoacetic acid allyl ester are added in distilled water to stir evenly to form mixed liquor, then heat up and cyclohexylthiophthalimide is added obtains isothermal holding mixed liquor through standing isothermal holding；Internal mixing and plasticizing after finally above-mentioned product is mixed, then obtained mixing mixing glue and ethylene propylene diene rubber, methyl phenyl vinyl silicone rubber be kneaded jointly, sulfidization molding, drying, obtain finished product rubber composite material.The rubber composite material being prepared, corrosion resistance is good, has a good application prospect on oil gas production equipment inner piece.
Description
Technical field
The present invention relates to technical field of rubber material, and in particular to a kind of preparation method of corrosion resistance rubber composite material
And its application.
Background technology
Rubber is a kind of flexible polymer, as a kind of important strategic goods and materials, be widely used in new and high technology,
The fields such as national economy and defence and military.Rubber can be divided into general purpose rubber and specific rubber again by performance and purposes.Universal rubber
The comprehensive performance of glue is preferable, is widely used.Mainly have：Natural rubber：It is made from the latex of para ruber, basic chemical composition
For cis- polyisoprene, elasticity is good, and intensity is high, good combination property.Isoprene rubber：The high-cis made from isoprene synthesizes
Rubber, because its structure and performance are approximate with natural rubber, therefore also known as natural man-made rubber.Butadiene-styrene rubber：By butadiene and benzene second
Alkene copolymerization is made, and comprehensive performance and chemical stability are good.Butadiene rubber is made by polymerizing butadiene, with other universal rubbers
Glue ratio, the cold resistance of the butadiene rubber after vulcanization, wearability and elasticity are especially excellent, generate heat under dynamic load few, ageing-resistant performance
It is good, easily it is used in combination with natural rubber, neoprene, nitrile rubber etc..Neoprene：It is made, is had good by chlorobutadiene polymerization
Comprehensive performance, oil resistant, resistance to combustion, resistance to oxidation and resistance to ozone, but its density is larger, easily crystallization is hardened under room temperature, depot bad,
Cold resistance is poor.Special type rubber refers to the rubber with certain properties.Mainly have：Nitrile rubber：Butadiene and acrylonitrile are total
Poly- to be made, oil resistant, ageing-resistant performance are good, can for a long time be used in 120 DEG C of air or in 150 DEG C of oil.In addition, also having
Water resistance, air-tightness and excellent adhesive property.Silicon rubber：Main chain is alternately made of silicone atom, is had on the silicon atoms
Machine group, high-low temperature resistant, resistance to ozone, electrical insulating property are good.Fluorubber：Synthetic rubber containing fluorine atom in molecular structure, resistance to height
It is temperature, oil resistant, resistant to chemical etching.Polysulfide rubber：It is formed, is had by the polysulfide polycondensation of saturated dihalide and alkali or alkaline earth metal
Excellent oil resistant and solvent resistance, but intensity is not high, and resistance to ag(e)ing, processability are bad, have stink, are mostly used in combination with nitrile rubber.
In addition, also polyurethane rubber, chlorohydrin rubber, acrylic rubber etc..
Rubber in processing, use or storage process by the catalytic action of heat, light, ozone oxidation or metal ion when,
Be easy carry out autocatalytic reaction, molecule chain rupture or excessively crosslinking, to surface can gradually occur discoloration, bloom, it is tacky, be hardened
Phenomena such as embrittlement, crackle, while its mechanical property also will appear and be decreased obviously, or even use value is lost, to limit rubber
The application of glue material.
Invention content
In order to solve the above technical problems, the present invention provides a kind of preparation method of corrosion resistance rubber composite material and its answers
With this method is used diatomite, aluminium hydroxide, polyester fiber ball milling；Polyamide staple fibre, methyl ethyl ketone peroxide are immersed in acid
It is ultrasonically treated in liquid, isolated centrifugal deposition object, is transferred in high-pressure stirring reaction kettle after centrifugal deposition object is washed, is added
Naphthenic oil is stirred to react to obtain high-pressure stirring reactant；Methylbenzoic acid ethyl ester, acetoacetic acid allyl ester are added to distilled water
In stir evenly to form mixed liquor, then heat up and be added cyclohexylthiophthalimide through stand isothermal holding obtain
Isothermal holding mixed liquor；Internal mixing and plasticizing after finally above-mentioned product is mixed, then the mixing mixing glue and ethylene-propylene-diene monomer that will obtain
Glue, methyl phenyl vinyl silicone rubber be kneaded jointly, sulfidization molding, drying, obtain finished product rubber composite material.The rubber being prepared
Glue composite material, corrosion resistance is good, has a good application prospect on oil gas production equipment inner piece.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of preparation method of corrosion resistance rubber composite material, includes the following steps：
（1）It will be carried out at ball milling in 3-5 parts of 6-8 parts of diatomite, 3-5 parts of aluminium hydroxide, polyester fiber input planetary ball mills
Reason, obtains ball-milled powder；
（2）22-24 parts of polyamide staple fibre, 16-20 parts of methyl ethyl ketone peroxide are immersed in the HCl solution of a concentration of 0.1 mol/L
In be ultrasonically treated, will then be ultrasonically treated mixed liquor and be neutralized to neutrality with sodium hydroxide solution, then through being centrifuged at a high speed
Go out centrifugal deposition object, centrifugal deposition object is washed with distilled water 2-4 times and is transferred in high-pressure stirring reaction kettle, naphthenic oil is added
5-9 parts, it is 150 DEG C to set the pressure of high-pressure stirring reaction kettle as 15 MPa, temperature, is stirred under 250-260 revs/min of rate
Reaction 30 minutes is mixed, high-pressure stirring reactant is obtained；
（3）By 16-18 parts of 15-25 parts of methylbenzoic acid ethyl ester, acetoacetic acid allyl ester distilled water for being added to 60-80 times of quality
In stir evenly to form mixed liquor according to 80-100 revs/min of rate, mixeding liquid temperature is slowly raised to 80-90 DEG C, is added
Enter 6-8 parts of cyclohexylthiophthalimide, stands isothermal holding 30 minutes, obtain isothermal holding mixed liquor；
（4）By step（1）-（3）Obtained ball-milled powder, high-pressure stirring reactant and isothermal holding mixed liquor is transferred to adding pressure type
In mixer, the temperature of adding pressure type mixer is set as 80-90 DEG C, anti-aging agent 1-3 is then added in internal mixing and plasticizing 10-15 minutes
Part, 1-3 parts of vulcanizing agent continue internal mixing and plasticizing 6-8 minutes, and mixing mixing glue is obtained after plastic emitting；
（5）By step（4）Obtained mixing mixing glue and 55-65 parts of ethylene propylene diene rubber, methyl phenyl vinyl silicone rubber 50-
In 60 parts of common input open mills, the roll spacing of open mill is set as 3 mm, open mill temperature is 50-60 DEG C, mixing time 18-
20 minutes, thin logical 2-3 postcooling obtained whole epoxy glue；
（6）By step（5）Obtained whole epoxy glue is placed in sulfidization molding on vulcanizing press, then by sulfur product at 120 DEG C
Lower forced air drying 80-100 minutes after being cooled to room temperature, obtains finished product rubber composite material.
Further, the step（1）The ratio of grinding media to material of middle ball mill is 15:1, drum's speed of rotation is 200-220 revs/min
Clock, Ball-milling Time are 8-10 hours.
Further, the step（2）The frequency of middle supersound process is 12-16 kHz, and the power of supersound process is 180-
The time of 200 W, supersound process are 50-60 minutes.
Further, the step（4）In anti-aging agent be selected from N- (1,3- dimethylbutyls)-N '-diphenyl-para-phenylene diamines,
4,4 '-thiobis（6- tertiary butyl -3- methylphenols）, N, any one in N- nickel dibutyl dithiocarbamates.
Further, the step（4）In vulcanizing agent be selected from toluene diisocyanate dimer, four vulcanization two morphines
Any one in quinoline, dual-tert-butyl peroxy isopropyl base benzene.
Further, the step（6）The curing temperature of middle plateform vulcanizer is 135-145 DEG C, sulfide stress 7-9
MPa, vulcanization time are 35-45 minutes.
At the same time, the invention also discloses corrosion resistance rubber composite materials made from above-mentioned preparation method to be opened in oil gas
Adopt the application on equipment inner piece.
Compared with prior art, the present invention advantage is：
（1）The preparation method of the corrosion resistance rubber composite material of the present invention is used diatomite, aluminium hydroxide, polyester fiber ball
Mill；Polyamide staple fibre, methyl ethyl ketone peroxide are immersed in supersound process, isolated centrifugal deposition object in acid solution, centrifugation is heavy
It is transferred in high-pressure stirring reaction kettle after product object washing, naphthenic oil is added and is stirred to react to obtain high-pressure stirring reactant；By methyl
Ethyl benzoate, acetoacetic acid allyl ester, which are added in distilled water, to stir evenly to form mixed liquor, then heats up and hexamethylene is added
Base thiophthalimide obtains isothermal holding mixed liquor through standing isothermal holding；Mixing after finally above-mentioned product is mixed
It is plasticized, then obtained mixing mixing glue is kneaded jointly with ethylene propylene diene rubber, methyl phenyl vinyl silicone rubber, is sulfided into
Type, drying obtain finished product rubber composite material.The rubber composite material being prepared, corrosion resistance is good, in oil-gas mining
It has a good application prospect on equipment inner piece.
（2）Present invention employs polyamide staple fibre, methyl ethyl ketone peroxide, methylbenzoic acid ethyl ester, acetoacetic acid allyl esters
Equal raw materials participate in preparing corrosion resistance rubber composite material, and effective performance boost has been carried out to rubber composite material, although this
A little materials are not first Application in rubber composite material, but are aided with corresponding processing mode after amount combination according to a certain ratio,
Increasing substantially in performance is brought to the rubber composite material being finally prepared, this is not in previous research
Once it reported, for realizing that it is conclusive that the technique effect of the present invention plays the role of.
Specific implementation mode
The technical solution of invention is described in detail with reference to specific embodiment.
Embodiment 1
（1）Ball-milling treatment, ball milling will be carried out in 3 parts of 6 parts of diatomite, 3 parts of aluminium hydroxide, polyester fiber input planetary ball mills
The ratio of grinding media to material of machine is 15:1, drum's speed of rotation is 200 revs/min, and Ball-milling Time is 8 hours, obtains ball-milled powder；
（2）22 parts of polyamide staple fibre, 16 parts of methyl ethyl ketone peroxide are immersed in the HCl solution of a concentration of 0.1 mol/L and are carried out
It being ultrasonically treated, the frequency of supersound process is 12 kHz, and the power of supersound process is 180 W, and the time of supersound process is 50 minutes,
Mixed liquor will be then ultrasonically treated and be neutralized to neutrality with sodium hydroxide solution, then through the centrifugal deposition object that is centrifuged at a high speed out, it will
Centrifugal deposition object is washed with distilled water 2 times and is transferred in high-pressure stirring reaction kettle, and 5 parts of naphthenic oil is added, and sets high-pressure stirring
The pressure of reaction kettle is 15 MPa, temperature is 150 DEG C, is stirred to react under 250 revs/min of rate 30 minutes, obtains high pressure
Reaction stirred；
（3）15 parts of methylbenzoic acid ethyl ester, 16 parts of acetoacetic acid allyl ester are added in the distilled water of 60 times of quality according to 80
Rev/min rate stir evenly to form mixed liquor, mixeding liquid temperature is slowly raised to 80 DEG C, cyclohexyl thio neighbour's benzene is added
6 parts of dicarboximide stands isothermal holding 30 minutes, obtains isothermal holding mixed liquor；
（4）By step（1）-（3）Obtained ball-milled powder, high-pressure stirring reactant and isothermal holding mixed liquor is transferred to adding pressure type
In mixer, the temperature of adding pressure type mixer is set as 80 DEG C, N- (1,3- dimethyl butyrates are then added in internal mixing and plasticizing 10 minutes
Base) 1 part of-N '-diphenyl-para-phenylene diamines, 1 part of toluene diisocyanate dimer continue internal mixing and plasticizing 6 minutes, it is mixed after plastic emitting
Close mixing glue；
（5）By step（4）Obtained mixing mixing glue and 55 parts of ethylene propylene diene rubber, 50 parts of methyl phenyl vinyl silicone rubber are total
With in input open mill, the roll spacing of open mill is set as 3 mm, open mill temperature is 50 DEG C, and mixing time is 18 minutes, Bao Tong
2-3 postcooling obtains whole epoxy glue；
（6）By step（5）Obtained whole epoxy glue is placed in sulfidization molding on vulcanizing press, and the curing temperature of vulcanizing press is
135 DEG C, sulfide stress 7MPa, vulcanization time be 35 minutes, then by sulfur product at 120 DEG C forced air drying 80 minutes,
After being cooled to room temperature, finished product rubber composite material is obtained.
The performance test results of rubber composite material obtained are as shown in table 1.
Embodiment 2
（1）Ball-milling treatment, ball milling will be carried out in 4 parts of 7 parts of diatomite, 4 parts of aluminium hydroxide, polyester fiber input planetary ball mills
The ratio of grinding media to material of machine is 15:1, drum's speed of rotation is 210 revs/min, and Ball-milling Time is 9 hours, obtains ball-milled powder；
（2）23 parts of polyamide staple fibre, 18 parts of methyl ethyl ketone peroxide are immersed in the HCl solution of a concentration of 0.1 mol/L and are carried out
It being ultrasonically treated, the frequency of supersound process is 14 kHz, and the power of supersound process is 190 W, and the time of supersound process is 55 minutes,
Mixed liquor will be then ultrasonically treated and be neutralized to neutrality with sodium hydroxide solution, then through the centrifugal deposition object that is centrifuged at a high speed out, it will
Centrifugal deposition object is washed with distilled water 3 times and is transferred in high-pressure stirring reaction kettle, and 7 parts of naphthenic oil is added, and sets high-pressure stirring
The pressure of reaction kettle is 15 MPa, temperature is 150 DEG C, is stirred to react under 255 revs/min of rate 30 minutes, obtains high pressure
Reaction stirred；
（3）20 parts of methylbenzoic acid ethyl ester, 17 parts of acetoacetic acid allyl ester are added in the distilled water of 70 times of quality according to 90
Rev/min rate stir evenly to form mixed liquor, mixeding liquid temperature is slowly raised to 85 DEG C, cyclohexyl thio neighbour's benzene is added
7 parts of dicarboximide stands isothermal holding 30 minutes, obtains isothermal holding mixed liquor；
（4）By step（1）-（3）Obtained ball-milled powder, high-pressure stirring reactant and isothermal holding mixed liquor is transferred to adding pressure type
In mixer, the temperature of adding pressure type mixer is set as 85 DEG C, 4,4 '-thiobis are then added in internal mixing and plasticizing 12 minutes（Uncle 6-
Butyl -3- methylphenols）2 parts, 2 parts of four two morpholines of vulcanization continuation internal mixing and plasticizing 7 minutes, obtain mixing mixing glue after plastic emitting；
（5）By step（4）Obtained mixing mixing glue and 60 parts of ethylene propylene diene rubber, 55 parts of methyl phenyl vinyl silicone rubber are total
With in input open mill, the roll spacing of open mill is set as 3 mm, open mill temperature is 55 DEG C, and mixing time is 19 minutes, Bao Tong
2-3 postcooling obtains whole epoxy glue；
（6）By step（5）Obtained whole epoxy glue is placed in sulfidization molding on vulcanizing press, and the curing temperature of vulcanizing press is
140 DEG C, sulfide stress be 8 MPa, vulcanization time be 40 minutes, then by sulfur product at 120 DEG C forced air drying 90 minutes,
After being cooled to room temperature, finished product rubber composite material is obtained.
The performance test results of rubber composite material obtained are as shown in table 1.
Embodiment 3
（1）Ball-milling treatment, ball milling will be carried out in 5 parts of 8 parts of diatomite, 5 parts of aluminium hydroxide, polyester fiber input planetary ball mills
The ratio of grinding media to material of machine is 15:1, drum's speed of rotation is 220 revs/min, and Ball-milling Time is 10 hours, obtains ball-milled powder；
（2）24 parts of polyamide staple fibre, 20 parts of methyl ethyl ketone peroxide are immersed in the HCl solution of a concentration of 0.1 mol/L and are carried out
It being ultrasonically treated, the frequency of supersound process is 16 kHz, and the power of supersound process is 200 W, and the time of supersound process is 60 minutes,
Mixed liquor will be then ultrasonically treated and be neutralized to neutrality with sodium hydroxide solution, then through the centrifugal deposition object that is centrifuged at a high speed out, it will
Centrifugal deposition object is washed with distilled water 4 times and is transferred in high-pressure stirring reaction kettle, and 9 parts of naphthenic oil is added, and sets high-pressure stirring
The pressure of reaction kettle is 15 MPa, temperature is 150 DEG C, is stirred to react under 260 revs/min of rate 30 minutes, obtains high pressure
Reaction stirred；
（3）25 parts of methylbenzoic acid ethyl ester, 18 parts of acetoacetic acid allyl ester are added in the distilled water of 80 times of quality according to 100
Rev/min rate stir evenly to form mixed liquor, mixeding liquid temperature is slowly raised to 90 DEG C, cyclohexyl thio neighbour's benzene is added
8 parts of dicarboximide stands isothermal holding 30 minutes, obtains isothermal holding mixed liquor；
（4）By step（1）-（3）Obtained ball-milled powder, high-pressure stirring reactant and isothermal holding mixed liquor is transferred to adding pressure type
In mixer, the temperature of adding pressure type mixer is set as 90 DEG C, N, N- dibutyl dithios is then added in internal mixing and plasticizing 15 minutes
3 parts of carbamic acid nickel, 3 parts of dual-tert-butyl peroxy isopropyl base benzene continue internal mixing and plasticizing 8 minutes, and mixing mixing glue is obtained after plastic emitting；
（5）By step（4）Obtained mixing mixing glue and 65 parts of ethylene propylene diene rubber, 60 parts of methyl phenyl vinyl silicone rubber are total
With in input open mill, the roll spacing of open mill is set as 3 mm, open mill temperature is 60 DEG C, and mixing time is 20 minutes, thin by logical 3
Secondary postcooling obtains whole epoxy glue；
（6）By step（5）Obtained whole epoxy glue is placed in sulfidization molding on vulcanizing press, and the curing temperature of vulcanizing press is
145 DEG C, sulfide stress is 9 MPa, and vulcanization time is 45 minutes, and then by sulfur product, forced air drying 100 divides at 120 DEG C
Clock after being cooled to room temperature, obtains finished product rubber composite material.
The performance test results of rubber composite material obtained are as shown in table 1.
Comparative example 1
（1）Ball-milling treatment, ball milling will be carried out in 4 parts of 7 parts of diatomite, 4 parts of aluminium hydroxide, polyester fiber input planetary ball mills
The ratio of grinding media to material of machine is 15:1, drum's speed of rotation is 210 revs/min, and Ball-milling Time is 9 hours, obtains ball-milled powder；
（2）18 parts of methyl ethyl ketone peroxide is immersed in the HCl solution of a concentration of 0.1 mol/L and is ultrasonically treated, at ultrasound
The frequency of reason is 14 kHz, and the power of supersound process is 190 W, and the time of supersound process is 55 minutes, will be then ultrasonically treated
Mixed liquor is neutralized to neutrality with sodium hydroxide solution, then through the centrifugal deposition object that is centrifuged at a high speed out, centrifugal deposition object is steamed
Distilled water is washed and 3 times and is transferred in high-pressure stirring reaction kettle, and 7 parts of naphthenic oil is added, set the pressure of high-pressure stirring reaction kettle as
15 MPa, temperature are 150 DEG C, are stirred to react under 255 revs/min of rate 30 minutes, obtain high-pressure stirring reactant；
（3）20 parts of methylbenzoic acid ethyl ester, 17 parts of acetoacetic acid allyl ester are added in the distilled water of 70 times of quality according to 90
Rev/min rate stir evenly to form mixed liquor, mixeding liquid temperature is slowly raised to 85 DEG C, cyclohexyl thio neighbour's benzene is added
7 parts of dicarboximide stands isothermal holding 30 minutes, obtains isothermal holding mixed liquor；
（4）By step（1）-（3）Obtained ball-milled powder, high-pressure stirring reactant and isothermal holding mixed liquor is transferred to adding pressure type
In mixer, the temperature of adding pressure type mixer is set as 85 DEG C, 4,4 '-thiobis are then added in internal mixing and plasticizing 12 minutes（Uncle 6-
Butyl -3- methylphenols）2 parts, 2 parts of four two morpholines of vulcanization continuation internal mixing and plasticizing 7 minutes, obtain mixing mixing glue after plastic emitting；
（5）By step（4）Obtained mixing mixing glue and 60 parts of ethylene propylene diene rubber, 55 parts of methyl phenyl vinyl silicone rubber are total
With in input open mill, the roll spacing of open mill is set as 3 mm, open mill temperature is 55 DEG C, and mixing time is 19 minutes, Bao Tong
2-3 postcooling obtains whole epoxy glue；
（6）By step（5）Obtained whole epoxy glue is placed in sulfidization molding on vulcanizing press, and the curing temperature of vulcanizing press is
140 DEG C, sulfide stress be 8 MPa, vulcanization time be 40 minutes, then by sulfur product at 120 DEG C forced air drying 90 minutes,
After being cooled to room temperature, finished product rubber composite material is obtained.
The performance test results of rubber composite material obtained are as shown in table 1.
Comparative example 2
（1）Ball-milling treatment, ball milling will be carried out in 4 parts of 7 parts of diatomite, 4 parts of aluminium hydroxide, polyester fiber input planetary ball mills
The ratio of grinding media to material of machine is 15:1, drum's speed of rotation is 210 revs/min, and Ball-milling Time is 9 hours, obtains ball-milled powder；
（2）23 parts of polyamide staple fibre is immersed in the HCl solution of a concentration of 0.1 mol/L and is ultrasonically treated, is ultrasonically treated
Frequency be 14 kHz, the power of supersound process is 190 W, and the time of supersound process is 55 minutes, will be then ultrasonically treated mixed
It closes liquid and is neutralized to neutrality with sodium hydroxide solution, then through the centrifugal deposition object that is centrifuged at a high speed out, centrifugal deposition object is distilled
Water washing 3 times is simultaneously transferred in high-pressure stirring reaction kettle, and 7 parts of naphthenic oil is added, and sets the pressure of high-pressure stirring reaction kettle as 15
MPa, temperature are 150 DEG C, are stirred to react under 255 revs/min of rate 30 minutes, obtain high-pressure stirring reactant；
（3）20 parts of methylbenzoic acid ethyl ester, 17 parts of acetoacetic acid allyl ester are added in the distilled water of 70 times of quality according to 90
Rev/min rate stir evenly to form mixed liquor, mixeding liquid temperature is slowly raised to 85 DEG C, cyclohexyl thio neighbour's benzene is added
7 parts of dicarboximide stands isothermal holding 30 minutes, obtains isothermal holding mixed liquor；
（4）By step（1）-（3）Obtained ball-milled powder, high-pressure stirring reactant and isothermal holding mixed liquor is transferred to adding pressure type
In mixer, the temperature of adding pressure type mixer is set as 85 DEG C, 4,4 '-thiobis are then added in internal mixing and plasticizing 12 minutes（Uncle 6-
Butyl -3- methylphenols）2 parts, 2 parts of four two morpholines of vulcanization continuation internal mixing and plasticizing 7 minutes, obtain mixing mixing glue after plastic emitting；
（5）By step（4）Obtained mixing mixing glue and 60 parts of ethylene propylene diene rubber, 55 parts of methyl phenyl vinyl silicone rubber are total
With in input open mill, the roll spacing of open mill is set as 3 mm, open mill temperature is 55 DEG C, and mixing time is 19 minutes, Bao Tong
2-3 postcooling obtains whole epoxy glue；
（6）By step（5）Obtained whole epoxy glue is placed in sulfidization molding on vulcanizing press, and the curing temperature of vulcanizing press is
140 DEG C, sulfide stress be 8 MPa, vulcanization time be 40 minutes, then by sulfur product at 120 DEG C forced air drying 90 minutes,
After being cooled to room temperature, finished product rubber composite material is obtained.
The performance test results of rubber composite material obtained are as shown in table 1.
Comparative example 3
（1）Ball-milling treatment, ball milling will be carried out in 4 parts of 7 parts of diatomite, 4 parts of aluminium hydroxide, polyester fiber input planetary ball mills
The ratio of grinding media to material of machine is 15:1, drum's speed of rotation is 210 revs/min, and Ball-milling Time is 9 hours, obtains ball-milled powder；
（2）23 parts of polyamide staple fibre, 18 parts of methyl ethyl ketone peroxide are immersed in the HCl solution of a concentration of 0.1 mol/L and are carried out
It being ultrasonically treated, the frequency of supersound process is 14 kHz, and the power of supersound process is 190 W, and the time of supersound process is 55 minutes,
Mixed liquor will be then ultrasonically treated and be neutralized to neutrality with sodium hydroxide solution, then through the centrifugal deposition object that is centrifuged at a high speed out, it will
Centrifugal deposition object is washed with distilled water 3 times and is transferred in high-pressure stirring reaction kettle, and 7 parts of naphthenic oil is added, and sets high-pressure stirring
The pressure of reaction kettle is 15 MPa, temperature is 150 DEG C, is stirred to react under 255 revs/min of rate 30 minutes, obtains high pressure
Reaction stirred；
（3）17 parts of acetoacetic acid allyl ester is added in the distilled water of 70 times of quality stirred according to 90 revs/min of rate it is equal
Mixeding liquid temperature is slowly raised to 85 DEG C, 7 parts of cyclohexylthiophthalimide is added, stood by even formation mixed liquor
Isothermal holding 30 minutes, obtains isothermal holding mixed liquor；
（4）By step（1）-（3）Obtained ball-milled powder, high-pressure stirring reactant and isothermal holding mixed liquor is transferred to adding pressure type
In mixer, the temperature of adding pressure type mixer is set as 85 DEG C, 4,4 '-thiobis are then added in internal mixing and plasticizing 12 minutes（Uncle 6-
Butyl -3- methylphenols）2 parts, 2 parts of four two morpholines of vulcanization continuation internal mixing and plasticizing 7 minutes, obtain mixing mixing glue after plastic emitting；
（5）By step（4）Obtained mixing mixing glue and 60 parts of ethylene propylene diene rubber, 55 parts of methyl phenyl vinyl silicone rubber are total
With in input open mill, the roll spacing of open mill is set as 3 mm, open mill temperature is 55 DEG C, and mixing time is 19 minutes, Bao Tong
2-3 postcooling obtains whole epoxy glue；
（6）By step（5）Obtained whole epoxy glue is placed in sulfidization molding on vulcanizing press, and the curing temperature of vulcanizing press is
140 DEG C, sulfide stress be 8 MPa, vulcanization time be 40 minutes, then by sulfur product at 120 DEG C forced air drying 90 minutes,
After being cooled to room temperature, finished product rubber composite material is obtained.
The performance test results of rubber composite material obtained are as shown in table 1.
Comparative example 4
（1）Ball-milling treatment, ball milling will be carried out in 4 parts of 7 parts of diatomite, 4 parts of aluminium hydroxide, polyester fiber input planetary ball mills
The ratio of grinding media to material of machine is 15:1, drum's speed of rotation is 210 revs/min, and Ball-milling Time is 9 hours, obtains ball-milled powder；
（2）23 parts of polyamide staple fibre, 18 parts of methyl ethyl ketone peroxide are immersed in the HCl solution of a concentration of 0.1 mol/L and are carried out
It being ultrasonically treated, the frequency of supersound process is 14 kHz, and the power of supersound process is 190 W, and the time of supersound process is 55 minutes,
Mixed liquor will be then ultrasonically treated and be neutralized to neutrality with sodium hydroxide solution, then through the centrifugal deposition object that is centrifuged at a high speed out, it will
Centrifugal deposition object is washed with distilled water 3 times and is transferred in high-pressure stirring reaction kettle, and 7 parts of naphthenic oil is added, and sets high-pressure stirring
The pressure of reaction kettle is 15 MPa, temperature is 150 DEG C, is stirred to react under 255 revs/min of rate 30 minutes, obtains high pressure
Reaction stirred；
（3）20 parts of methylbenzoic acid ethyl ester is added in the distilled water of 70 times of quality stirred according to 90 revs/min of rate it is equal
Mixeding liquid temperature is slowly raised to 85 DEG C, 7 parts of cyclohexylthiophthalimide is added, stood by even formation mixed liquor
Isothermal holding 30 minutes, obtains isothermal holding mixed liquor；
（4）By step（1）-（3）Obtained ball-milled powder, high-pressure stirring reactant and isothermal holding mixed liquor is transferred to adding pressure type
In mixer, the temperature of adding pressure type mixer is set as 85 DEG C, 4,4 '-thiobis are then added in internal mixing and plasticizing 12 minutes（Uncle 6-
Butyl -3- methylphenols）2 parts, 2 parts of four two morpholines of vulcanization continuation internal mixing and plasticizing 7 minutes, obtain mixing mixing glue after plastic emitting；
（5）By step（4）Obtained mixing mixing glue and 60 parts of ethylene propylene diene rubber, 55 parts of methyl phenyl vinyl silicone rubber are total
With in input open mill, the roll spacing of open mill is set as 3 mm, open mill temperature is 55 DEG C, and mixing time is 19 minutes, Bao Tong
2-3 postcooling obtains whole epoxy glue；
（6）By step（5）Obtained whole epoxy glue is placed in sulfidization molding on vulcanizing press, and the curing temperature of vulcanizing press is
140 DEG C, sulfide stress be 8 MPa, vulcanization time be 40 minutes, then by sulfur product at 120 DEG C forced air drying 90 minutes,
After being cooled to room temperature, finished product rubber composite material is obtained.
The performance test results of rubber composite material obtained are as shown in table 1.
By the rubber composite material obtained of embodiment 1-3 and comparative example 1-4 respectively according to the method for GB/T 528-2009
Its tensile property is tested, is then being tested for the property above-mentioned material again after hydrogen sulfide gaseous corrosion, and quality measurement
Change rate.Hydrogen sulfide gas phase etching condition is as follows：90 DEG C of temperature, 7.5 MPa of pressure, gas form H2S：25%, CO2：5%,
CH4：70%, liquid phase tests into n- hexanes：25%, n- octane：20%, n- decane：50%, n- toluene：5%, 120 hours time,
Other conditions are with reference to NACE TM0187-2003.
Table 1
| Tensile strength before corrosion（MPa） | Corrode post-tensioning intensity（MPa） | Mass change（%） | |
| Embodiment 1 | 24.9 | 20.5 | 4.02 |
| Embodiment 2 | 25.6 | 21.2 | 3.95 |
| Embodiment 3 | 25.3 | 20.8 | 3.96 |
| Comparative example 1 | 20.4 | 13.7 | 7.25 |
| Comparative example 2 | 18.5 | 11.2 | 7.51 |
| Comparative example 3 | 21.2 | 14.0 | 6.99 |
| Comparative example 4 | 19.7 | 12.1 | 7.08 |
The preparation method of the corrosion resistance rubber composite material of the present invention is used diatomite, aluminium hydroxide, polyester fiber ball milling；
Polyamide staple fibre, methyl ethyl ketone peroxide are immersed in supersound process, isolated centrifugal deposition object in acid solution, by centrifugal deposition object
It is transferred to after washing in high-pressure stirring reaction kettle, naphthenic oil is added and is stirred to react to obtain high-pressure stirring reactant；By methylbenzene first
Acetoacetic ester, acetoacetic acid allyl ester, which are added in distilled water, to stir evenly to form mixed liquor, then heats up and cyclohexyl sulphur is added
For phthalimide isothermal holding mixed liquor is obtained through standing isothermal holding；Mixing is moulded after finally above-mentioned product is mixed
Change, then obtained mixing mixing glue and ethylene propylene diene rubber, methyl phenyl vinyl silicone rubber are kneaded jointly, sulfidization molding,
It is dry, obtain finished product rubber composite material.The rubber composite material being prepared, corrosion resistance is good, is set in oil-gas mining
It has a good application prospect on standby inner piece.Also, present invention employs polyamide staple fibre, methyl ethyl ketone peroxide, methylbenzenes
The raw materials such as Ethyl formate, acetoacetic acid allyl ester participate in preparing corrosion resistance rubber composite material, are carried out to rubber composite material
Effective performance boost, although these materials are not first Application in rubber composite material, amount group according to a certain ratio
After conjunction, it is aided with corresponding processing mode, is brought in performance significantly to the rubber composite material being finally prepared
It improves, this is never to report in previous research, for realizing that the technique effect of the present invention plays conclusive work
With.
Example the above is only the implementation of the present invention is not intended to limit the scope of the invention, every to utilize this hair
Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks
Domain is included within the scope of the present invention.
Claims (7)
1. a kind of preparation method of corrosion resistance rubber composite material, which is characterized in that include the following steps：
（1）It will be carried out at ball milling in 3-5 parts of 6-8 parts of diatomite, 3-5 parts of aluminium hydroxide, polyester fiber input planetary ball mills
Reason, obtains ball-milled powder；
（2）22-24 parts of polyamide staple fibre, 16-20 parts of methyl ethyl ketone peroxide are immersed in the HCl solution of a concentration of 0.1 mol/L
In be ultrasonically treated, will then be ultrasonically treated mixed liquor and be neutralized to neutrality with sodium hydroxide solution, then through being centrifuged at a high speed
Go out centrifugal deposition object, centrifugal deposition object is washed with distilled water 2-4 times and is transferred in high-pressure stirring reaction kettle, naphthenic oil is added
5-9 parts, it is 150 DEG C to set the pressure of high-pressure stirring reaction kettle as 15 MPa, temperature, is stirred under 250-260 revs/min of rate
Reaction 30 minutes is mixed, high-pressure stirring reactant is obtained；
（3）By 16-18 parts of 15-25 parts of methylbenzoic acid ethyl ester, acetoacetic acid allyl ester distilled water for being added to 60-80 times of quality
In stir evenly to form mixed liquor according to 80-100 revs/min of rate, mixeding liquid temperature is slowly raised to 80-90 DEG C, is added
Enter 6-8 parts of cyclohexylthiophthalimide, stands isothermal holding 30 minutes, obtain isothermal holding mixed liquor；
（4）By step（1）-（3）Obtained ball-milled powder, high-pressure stirring reactant and isothermal holding mixed liquor is transferred to adding pressure type
In mixer, the temperature of adding pressure type mixer is set as 80-90 DEG C, anti-aging agent 1-3 is then added in internal mixing and plasticizing 10-15 minutes
Part, 1-3 parts of vulcanizing agent continue internal mixing and plasticizing 6-8 minutes, and mixing mixing glue is obtained after plastic emitting；
（5）By step（4）Obtained mixing mixing glue and 55-65 parts of ethylene propylene diene rubber, methyl phenyl vinyl silicone rubber 50-
In 60 parts of common input open mills, the roll spacing of open mill is set as 3 mm, open mill temperature is 50-60 DEG C, mixing time 18-
20 minutes, thin logical 2-3 postcooling obtained whole epoxy glue；
（6）By step（5）Obtained whole epoxy glue is placed in sulfidization molding on vulcanizing press, then by sulfur product at 120 DEG C
Lower forced air drying 80-100 minutes after being cooled to room temperature, obtains finished product rubber composite material.
2. the preparation method of corrosion resistance rubber composite material according to claim 1, which is characterized in that the step
（1）The ratio of grinding media to material of middle ball mill is 15:1, drum's speed of rotation is 200-220 revs/min, and Ball-milling Time is 8-10 hours.
3. the preparation method of corrosion resistance rubber composite material according to claim 1, which is characterized in that the step
（2）The frequency of middle supersound process is 12-16 kHz, and the power of supersound process is 180-200 W, and the time of supersound process is 50-
60 minutes.
4. the preparation method of corrosion resistance rubber composite material according to claim 1, which is characterized in that the step
（4）In anti-aging agent be selected from N- (1,3- dimethylbutyls)-N '-diphenyl-para-phenylene diamines, 4,4 '-thiobis（6- tertiary butyl -3- first
Base phenol）, N, any one in N- nickel dibutyl dithiocarbamates.
5. the preparation method of corrosion resistance rubber composite material according to claim 1, which is characterized in that the step
（4）In vulcanizing agent selected from toluene diisocyanate dimer, four two morpholines of vulcanization, in dual-tert-butyl peroxy isopropyl base benzene
Any one.
6. the preparation method of corrosion resistance rubber composite material according to claim 1, which is characterized in that the step
（6）The curing temperature of middle plateform vulcanizer is 135-145 DEG C, and sulfide stress is 7-9 MPa, and vulcanization time is 35-45 minutes.
7. being set in oil-gas mining according to corrosion resistance rubber composite material made from any one of the claim 1-6 preparation methods
Application on standby inner piece.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1225931A (en) * | 1998-12-17 | 1999-08-18 | 湖北大学化学与材料科学学院 | Ethylene propylene/polypropene blended thermoplastic elastic body and preparation method |
| CN1629216A (en) * | 2003-12-16 | 2005-06-22 | 深圳市沃尔热缩材料有限公司 | Halogen-free flame-retardant thermal-shrinkage sleeve materials and sleeve prepared thereby |
| CN104072995A (en) * | 2014-07-02 | 2014-10-01 | 深圳市沃尔核材股份有限公司 | Ceramic contracted cable accessory and preparation method thereof |
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2018
- 2018-03-29 CN CN201810273587.1A patent/CN108586945A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1225931A (en) * | 1998-12-17 | 1999-08-18 | 湖北大学化学与材料科学学院 | Ethylene propylene/polypropene blended thermoplastic elastic body and preparation method |
| CN1629216A (en) * | 2003-12-16 | 2005-06-22 | 深圳市沃尔热缩材料有限公司 | Halogen-free flame-retardant thermal-shrinkage sleeve materials and sleeve prepared thereby |
| CN104072995A (en) * | 2014-07-02 | 2014-10-01 | 深圳市沃尔核材股份有限公司 | Ceramic contracted cable accessory and preparation method thereof |
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