CN109180938A - A kind of preparation method of shock resistance high-adhesion polysulfide rubber - Google Patents
A kind of preparation method of shock resistance high-adhesion polysulfide rubber Download PDFInfo
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- CN109180938A CN109180938A CN201811011466.6A CN201811011466A CN109180938A CN 109180938 A CN109180938 A CN 109180938A CN 201811011466 A CN201811011466 A CN 201811011466A CN 109180938 A CN109180938 A CN 109180938A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/14—Polysulfides
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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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Abstract
The present invention relates to a kind of preparation methods of shock resistance high-adhesion polysulfide rubber, belong to technical field of rubber preparation.Flaky graphite is carried out oxidation reaction by the present invention in sulfuric acid solution, by hydrazine hydrate reduction after oxidation, nano-graphene material is made after reduction, nano-graphene material possesses biggish specific surface area, the chemical structure for recycling nano-graphene itself stable, to reinforce the toughness and impact resistance of polysulfide rubber material；The present invention introduces bromine among graphene, make that coupling reaction occurs to propyl phenyl boric acid and the graphene molecules with bromo using the catalytic action of tetra-triphenylphosphine palladium, make to introduce among graphene propyl phenyl, the introducing of phenyl enhances graphene molecules to the caking property of polymer material, phenyl is located on the branch of graphene molecules chain simultaneously, and there is more branch on main chain, graphene is set to bond multiple molecules, making the molecular structure for the caking property and inside that polysulfide rubber is external is all enhanced, and is had broad application prospects.
Description
Technical field
The present invention relates to a kind of preparation methods of shock resistance high-adhesion polysulfide rubber, belong to technical field of rubber preparation.
Background technique
Polysulfide rubber is a kind of synthetic rubber, the general name of the special synthetic rubber containing sulphur atom.It is aliphatic hydrocarbon, ethers etc.
Dihalogen derivatives or their mixture and alkali metal, alkaline-earth metal polysulfide condensation polymer.Each repetitive unit tool
There are two the straight chains to four sulphur atoms.
According to the raw materials used difference with their ratio, available various tough and tensile bulks, powdery or thick liquid
Body substance.Yellow green, light brown or dark brown.Insoluble in oils and various solvents, slightly it is swollen in carbon disulfide.Not because oxygen,
The effects of ozone and daylight and change.Gas permeability is small.Tensile strength and elongation are lower, and black-reinforced need to be added.Due to
Its oil resistivity is strong, need to make softening agent with promotors such as guanidine, thiazoles, thiurams, make vulcanizing agent with lead oxide, zinc oxide.
It can be with other rubber blendings.Its major defect is that cold resistance, heat resistance, adherence are poor, there is stink.Mainly for the manufacture of various
Oil resistant rubber product.It can be deposited in inert media with dispersing agent by the polysulfide of dihalogen derivatives and alkali and alkaline earth metal ions
It is made under in 60 DEG C or so agitated polycondensations.
There are mainly three types of solid-state polysulfide rubber products: A type polysulfide rubber, is dichloroethanes and alkali metal tetrasulfides
Condensation polymer.FA type polysulfide rubber is the condensation polymer of dichloroethanes, double -2- chloroethyl formals and alkali metal disulfides.ST type
Polysulfide rubber is the condensation polymer of double dichloroethylene formals, trichloropropane and alkali metals polysulfide.Also exploitation in succession simultaneously
The polysulfide rubber vulcanizing system of five big types out has metal oxide-type, metal peroxides class, inorganic oxidizer class, organic
Peroxide, organic oxidizing agent class.
It can be seen that the sealing being prepared as a raw material with polysulfide rubber from the curing mechanism of the existing curing agent of polysulfide rubber
Attached dose of two components of polysulfide rubber host agent and curing agent are usually temporarily uniformly mixed by glue using preceding by proper proportion, this gives
It is made troubles using operation.And polysulfide rubber sealant is to the cementability of most of pore-free materials such as metal, glass, plastics
It is not good enough.Water-proofing treatment in the field of construction is an importance of construction, water-proofing treatment, be such as widely used in building,
Waterproof sealing of deformation joints such as flexible, sedimentation of concrete etc. in municipal administration, subway, tunnel and hydraulic engineering.And it is used for waterproof
Processing aspect commonly use polysulfide rubber the disadvantage is that: elongation percentage declines to a great extent under daylight long-term irradiation, and corrugation, cracking, de- easily occurs
It is viscous, phenomena such as, bad, and impact resistance, poor toughness are bonded with cement surface.Therefore, invent that a kind of intensity is high and adhesive property is good
Shock resistance high-adhesion polysulfide rubber to technical field of rubber preparation have positive effect.
Summary of the invention
The technical problems to be solved by the invention: it is poor for current polysulfide rubber bond effect, cause polysulfide rubber easily de-
It falls, while being directed to polysulfide rubber impact resistance, the defect of poor toughness, provide a kind of system of shock resistance high-adhesion polysulfide rubber
Preparation Method.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A kind of preparation method of shock resistance high-adhesion polysulfide rubber, it is characterised in that specific preparation step are as follows:
(1) according to parts by weight, 50~55 parts of sulfuric acid solutions, 5~7 parts of flaky graphites and 2~4 parts of sodium nitrate investments are weighed to burn
Obtained mixing suspension is uniformly mixed in cup, the potassium permanganate powder of mixing suspension quality 2~4% is added into beaker by every 5min
End adds 3 times altogether, adds the distilled water with quality such as mixing suspensions after addition, and by heated at constant temperature in beaker water-bath,
Filter residue is obtained by filtration after heating, and is successively cleaned filter residue 3~5 times with hydrochloric acid and distilled water；
(2) by above-mentioned filter residue and distilled water 1:100 in mass ratio investment round-bottomed flask, round bottom flask is entered into sonic oscillation instrument
Dispersion liquid is made in middle oscillation, and the hydrazine hydrate of dispersion liquid quality 1.5~2.0% is added dropwise into round-bottomed flask, flask is heated to 98
~100 DEG C, carry out 24~25h of condensing reflux, after filter cake is obtained by filtration, successively clean 3~5 with distilled water and dehydrated alcohol
It is put into drying in baking oven after secondary and obtains reaction solid product；
(3) it by above-mentioned reaction solid product and bromine 1:20 in mass ratio investment beaker, places the beaker in sonic oscillation instrument,
It is vibrated under conditions of nitrogen environment, filtrate is obtained by filtration after oscillation, with acetone wash filtrate 4~8 times, put filtrate after cleaning
Enter dry obtained brominated product in baking oven；
(4) according to parts by weight, 4~6 parts are weighed to propyl phenyl boric acid, 18~20 parts of n,N-Dimethylformamide, 0.6~0.8
Part tetra-triphenylphosphine palladium, 0.3~0.5 part of tetrabutylammonium bromide, 2~4 parts of saturated sodium carbonate solutions, 1.5~1.8 parts of above-mentioned brominations
It is reacted in product and 7~8 parts of distilled water investment reaction kettles and mixed emulsion is made；
(5) according to parts by weight, 7~9 parts of above-mentioned mixed emulsions, 1.5~1.8 parts of hydrochloric acid and 10~13 parts of dehydrated alcohols are weighed to throw
Enter in three-necked flask and be uniformly mixed, precipitation solid is obtained by filtration after mixing, wash with distilled water after precipitation solid 3~5 times, is put into
It is dry in baking oven, desciccate is made；
(6) according to parts by weight, weigh 3~5 parts of above-mentioned desciccates, 1~2 part of vulcanized sodium, 13~15 parts of 1,2- Difluoroethanes,
7~9 part 2,2 '-dichloro-o-xylenes and 25~28 parts of propylene glycol are put into ground and mixed in reaction kettle and obtain mix products, increase
Temperature of reaction kettle, and the vinyl triamine of mix products quality 5~8% is added, cooling obtained shock resistance high bonding after being stirred
Property polysulfide rubber.
The mass fraction of sulfuric acid solution as described in step (1) is 75~80%, and the bath temperature in water-bath is 30~35
DEG C, the heated at constant temperature time is 30~40min, and the mass fraction of hydrochloric acid is 5~8%.
Frequency in sonic oscillation instrument described in step (2) is 35~40kHz, and duration of oscillation is 3~4h, flask heating
For temperature to 98~100 DEG C, the condensing reflux time is 24~25h.
Frequency in sonic oscillation instrument described in step (3) is 35~40kHz, and duration of oscillation is 2~3h, in baking oven
Temperature is 110~120 DEG C, and drying time is 12~14h.
Speed of agitator in reaction kettle described in step (4) is 200~250r/min, temperature is 80~90 DEG C, reaction
Time is 72~74h.
The mass fraction of hydrochloric acid described in step (5) is 5~8%, and temperature is 105~110 DEG C in baking oven, drying time
For 12~13h.
Temperature is increased to 120~130 DEG C in reaction kettle described in step (6), and being stirred the time is 60~70min.
The method have the benefit that:
(1) graphite is placed in sulfuric acid solution by the present invention first reacts with potassium permanganate, and hydrazine hydrate is added after reaction and is restored
Reaction solid product is generated, then reaction solid product is mixed with bromine, brominated product is made in sonic oscillation, then produces bromination
Object reacts generation mixed emulsion under conditions of tetra-triphenylphosphine palladium catalysis and other promoter effects with to propyl phenyl boric acid, with
Desciccate is made in mixed emulsion and mixed in hydrochloric acid reaction and drying afterwards, finally by desciccate, vulcanized sodium, 1,2- difluoro second
Alkane, 2,2 '-dichloro-o-xylenes and mixed with propylene glycol heating, and vinyl triamine is added and is solidified, it is high that shock resistance is made
Flaky graphite is carried out oxidation reaction by adhesion polysulfide rubber, the present invention in sulfuric acid solution, by hydrazine hydrate reduction after oxidation,
Nano-graphene material is made after reduction, nano-graphene material possesses biggish specific surface area, to reinforce to polymeric material
The dispersion effect of the suction-operated of material and nano-graphene in rubber material, the chemistry for recycling nano-graphene itself stable
Structure, to reinforce the toughness and impact resistance of polysulfide rubber material；
(2) present invention introduces bromine among graphene, is made using the catalytic action of tetra-triphenylphosphine palladium to propyl phenyl boric acid and band
Coupling reaction occurs for the graphene molecules of bromo, makes to introduce among graphene propyl phenyl, the introducing of phenyl makes graphene point
Son enhances the caking property of polymer material, while phenyl is located on the branch of graphene molecules chain, and has on main chain more
Branch, so that graphene is bonded multiple molecules, obtain caking property that polysulfide rubber is external and the molecular structure of inside all
Enhancing, has broad application prospects.
Specific embodiment
According to parts by weight, sulfuric acid solution, 5~7 parts of flaky graphites that 50~55 parts of mass fractions are 75~80% are weighed
It is uniformly mixed obtained mixing suspension in 2~4 parts of sodium nitrate investment beakers, mixing suspension matter is added into beaker by every 5min
The potassium permanganate powder of amount 2~4% is added 3 times altogether, the distilled water with quality such as mixing suspensions is added after addition, and will burn
It is 30~40min of heated at constant temperature in 30~35 DEG C of water-bath that cup, which is placed in bath temperature, is obtained by filtration filter residue after heating, and according to
The secondary hydrochloric acid and distilled water for being 5~8% with mass fraction cleans filter residue 3~5 times；By above-mentioned filter residue and distilled water in mass ratio 1:
In 100 investment round-bottomed flasks, round bottom flask is entered into 3~4h of hunting of frequency in sonic oscillation instrument with 35~40kHz, is made and divides
The hydrazine hydrate of dispersion liquid quality 1.5~2.0% is added dropwise into round-bottomed flask for dispersion liquid, and flask is heated to 98~100 DEG C, is carried out cold
24~25h of solidifying reflux, after filter cake is obtained by filtration, be put into baking oven after successively cleaning 3~5 times with distilled water and dehydrated alcohol
Drying obtains reaction solid product；By in above-mentioned reaction solid product and bromine 1:20 in mass ratio investment beaker, beaker is set
In sonic oscillation instrument, 2~3h is vibrated under conditions of frequency is 35~40kHz and nitrogen environment, filter is obtained by filtration after oscillation
Liquid is put the filtrate into baking oven with the dry 12~14h system of 110~120 DEG C of temperature with acetone wash filtrate 4~8 times after cleaning
Obtain brominated product；According to parts by weight, weigh 4~6 parts to propyl phenyl boric acid, 18~20 parts of n,N-Dimethylformamide, 0.6~
0.8 part of tetra-triphenylphosphine palladium, 0.3~0.5 part of tetrabutylammonium bromide, 2~4 parts of saturated sodium carbonate solutions, 1.5~1.8 parts it is above-mentioned
In brominated product and 7~8 parts of distilled water investment reaction kettles, speed of agitator is 200~250r/min, temperature is 80~90 DEG C
Under the conditions of react 72~74h, be made mixed emulsion weigh 7~9 parts of above-mentioned mixed emulsions, 1.5~1.8 parts according to parts by weight
The hydrochloric acid and 10~13 parts of dehydrated alcohols that mass fraction is 5~8% put into three-necked flask and are uniformly mixed, and are obtained by filtration after mixing
Precipitation solid, wash with distilled water after precipitation solid 3~5 times, be put into baking oven with 105~110 DEG C of temperature dry 12~
Desciccate is made in 13h；According to parts by weight, 3~5 parts of above-mentioned desciccates, 1~2 part of vulcanized sodium, 13~15 part 1 are weighed,
2- Difluoroethane, 7~9 part of 2,2 '-dichloro-o-xylene and 25~28 parts of propylene glycol are put into ground and mixed in reaction kettle and are mixed
Product is closed, increases temperature of reaction kettle to 120~130 DEG C, and the vinyl triamine of mix products quality 5~8% is added, stirring is mixed
Shock resistance high-adhesion polysulfide rubber is made in cooling after closing 60~70min.
According to parts by weight, sulfuric acid solution, 5 parts of flaky graphites and 2 parts of sodium nitrate that 50 parts of mass fractions are 75% are weighed
It puts into beaker and is uniformly mixed obtained mixing suspension, the potassium permanganate of mixing suspension quality 2% is added into beaker by every 5min
Powder adds 3 times altogether, the distilled water with quality such as mixing suspensions is added after addition, and place the beaker bath temperature and be
In 30 DEG C of water-bath, filter residue is obtained by filtration in heated at constant temperature 30min after heating, and successively with mass fraction be 5% hydrochloric acid and
Distilled water cleans filter residue 3 times；Above-mentioned filter residue and distilled water 1:100 in mass ratio are put into round-bottomed flask, by round bottom flask
Enter the hunting of frequency 3h in sonic oscillation instrument with 35kHz, dispersion liquid is made, dispersion liquid quality 1.5% is added dropwise into round-bottomed flask
Flask is heated to 98 DEG C, is condensed back for 24 hours by hydrazine hydrate, after filter cake is obtained by filtration, with distilled water and dehydrated alcohol
It is put into drying in baking oven after successively cleaning 3 times and obtains reaction solid product；In mass ratio by above-mentioned reaction solid product and bromine
1:20 is put into beaker, is placed the beaker in sonic oscillation instrument, vibrates 2h under conditions of frequency is 35kHz and nitrogen environment,
Filtrate is obtained by filtration after oscillation, with acetone wash filtrate 4 times, is put the filtrate into after cleaning dry with 110 DEG C of temperature in baking oven
Brominated product is made in 12h；According to parts by weight, 4 parts are weighed to propyl phenyl boric acid, 18 parts of n,N-Dimethylformamide, 0.6 part four
Triphenylphosphine palladium, 0.3 part of tetrabutylammonium bromide, 2 parts of saturated sodium carbonate solutions, 1.5 parts of above-mentioned brominated products and 7 parts of distilled water are thrown
Enter in reaction kettle, react 72h under conditions of speed of agitator is 200r/min, temperature is 80 DEG C, mixed emulsion is made, by weight
Number meter weighs 7 parts of above-mentioned mixed emulsions, the hydrochloric acid that 1.5 parts of mass fractions are 5% and 10 parts of dehydrated alcohols and puts into three-necked flask
In be uniformly mixed, precipitation solid is obtained by filtration after mixing, wash with distilled water after precipitation solid 3 times, is put into baking oven with 105 DEG C
The dry 12h of temperature, desciccate is made；According to parts by weight, 3 parts of above-mentioned desciccates, 1 part of vulcanized sodium, 13 part 1 are weighed,
2- Difluoroethane, 7 part 2,2 '-dichloro-o-xylenes and 25 parts of propylene glycol are put into ground and mixed in reaction kettle and obtain mix products,
Temperature of reaction kettle is increased to 120 DEG C, and the vinyl triamine of mix products quality 5% is added, is stirred cooling system after 60min
Obtain shock resistance high-adhesion polysulfide rubber.
According to parts by weight, sulfuric acid solution, 6 parts of flaky graphites and 3 parts of sodium nitrate that 52 parts of mass fractions are 77% are weighed
It puts into beaker and is uniformly mixed obtained mixing suspension, the potassium permanganate of mixing suspension quality 3% is added into beaker by every 5min
Powder adds 3 times altogether, the distilled water with quality such as mixing suspensions is added after addition, and place the beaker bath temperature and be
In 32 DEG C of water-bath, filter residue is obtained by filtration in heated at constant temperature 35min after heating, and successively with mass fraction be 7% hydrochloric acid and
Distilled water cleans filter residue 4 times；Above-mentioned filter residue and distilled water 1:100 in mass ratio are put into round-bottomed flask, by round bottom flask
Enter the hunting of frequency 3.5h in sonic oscillation instrument with 37kHz, dispersion liquid is made, dispersion liquid quality 1.7% is added dropwise into round-bottomed flask
Hydrazine hydrate, flask is heated to 99 DEG C, carries out condensing reflux 24.5h, after filter cake is obtained by filtration, with distilled water and anhydrous
Ethyl alcohol is put into drying in baking oven and obtains reaction solid product after successively cleaning 4 times；Above-mentioned reaction solid product and bromine are pressed into matter
Amount is than placing the beaker in sonic oscillation instrument, vibrating under conditions of frequency is 37kHz and nitrogen environment in 1:20 investment beaker
Filtrate is obtained by filtration after oscillation in 2.5h, with acetone wash filtrate 6 times, is put the filtrate into baking oven after cleaning with 115 DEG C of temperature
Brominated product is made in dry 13h；According to parts by weight, 5 parts are weighed to propyl phenyl boric acid, 19 parts of n,N-Dimethylformamide, 0.7
Part tetra-triphenylphosphine palladium, 0.4 part of tetrabutylammonium bromide, 3 parts of saturated sodium carbonate solutions, 1.6 parts of above-mentioned brominated products and 7 parts of distillations
Water is put into reaction kettle, reacts 73h under conditions of speed of agitator is 220r/min, temperature is 85 DEG C, and mixed emulsion is made, presses
Parts by weight meter weighs 8 parts of above-mentioned mixed emulsions, the hydrochloric acid that 1.7 parts of mass fractions are 7% and 12 parts of dehydrated alcohols and puts into three mouthfuls
Be uniformly mixed in flask, precipitation solid be obtained by filtration after mixing, wash with distilled water after precipitation solid 4 times, be put into baking oven with
The dry 12.5h of 107 DEG C of temperature, is made desciccate；According to parts by weight, weigh 4 parts of above-mentioned desciccates, 1 part of vulcanized sodium,
14 parts of 1,2- Difluoroethanes, 8 part of 2,2 '-dichloro-o-xylene and 27 parts of propylene glycol are put into ground and mixed in reaction kettle and are mixed
Product is closed, temperature of reaction kettle is increased to 125 DEG C, and the vinyl triamine of mix products quality 7% is added, after being stirred 65min
Cooling obtained shock resistance high-adhesion polysulfide rubber.
According to parts by weight, sulfuric acid solution, 7 parts of flaky graphites and 4 parts of sodium nitrate that 55 parts of mass fractions are 80% are weighed
It puts into beaker and is uniformly mixed obtained mixing suspension, the potassium permanganate of mixing suspension quality 4% is added into beaker by every 5min
Powder adds 3 times altogether, the distilled water with quality such as mixing suspensions is added after addition, and place the beaker bath temperature and be
In 35 DEG C of water-bath, filter residue is obtained by filtration in heated at constant temperature 40min after heating, and successively with mass fraction be 8% hydrochloric acid and
Distilled water cleans filter residue 5 times；Above-mentioned filter residue and distilled water 1:100 in mass ratio are put into round-bottomed flask, by round bottom flask
Enter the hunting of frequency 4h in sonic oscillation instrument with 40kHz, dispersion liquid is made, dispersion liquid quality 2.0% is added dropwise into round-bottomed flask
Flask is heated to 100 DEG C, carries out condensing reflux 25h by hydrazine hydrate, after filter cake is obtained by filtration, with distilled water and anhydrous second
Alcohol is put into drying in baking oven and obtains reaction solid product after successively cleaning 5 times；Above-mentioned reaction solid product and bromine are pressed into quality
Than placing the beaker in sonic oscillation instrument, being vibrated under conditions of frequency is 40kHz and nitrogen environment in 1:20 investment beaker
Filtrate is obtained by filtration after oscillation in 3h, with acetone wash filtrate 8 times, puts the filtrate into after cleaning dry with 120 DEG C of temperature in baking oven
Brominated product is made in dry 14h；According to parts by weight, 6 parts are weighed to propyl phenyl boric acid, 20 parts of n,N-Dimethylformamide, 0.8 part
Tetra-triphenylphosphine palladium, 0.5 part of tetrabutylammonium bromide, 4 parts of saturated sodium carbonate solutions, 1.8 parts of above-mentioned brominated products and 8 parts of distilled water
Put into reaction kettle in, speed of agitator be 250r/min, it is at a temperature of 90 °C under the conditions of react 74h, be made mixed emulsion, by weight
Number meter is measured, 9 parts of above-mentioned mixed emulsions, the hydrochloric acid that 1.8 parts of mass fractions are 8% and 13 parts of dehydrated alcohols is weighed and puts into three mouthfuls of burnings
It is uniformly mixed in bottle, precipitation solid is obtained by filtration after mixing, wash with distilled water after precipitation solid 5 times, be put into baking oven with 110
DEG C the dry 13h of temperature, desciccate is made；According to parts by weight, 5 parts of above-mentioned desciccates, 2 parts of vulcanized sodium, 15 parts are weighed
1,2- Difluoroethane, 9 part of 2,2 '-dichloro-o-xylene and 28 parts of propylene glycol are put into ground and mixed in reaction kettle and obtain mixing production
Object increases temperature of reaction kettle to 130 DEG C, and the vinyl triamine of mix products quality 8% is added, and is stirred cooling after 70min
Shock resistance high-adhesion polysulfide rubber is made.
Comparative example is as a comparison case made the present invention with the shock resistance high-adhesion polysulfide rubber that Shanghai company produces
Shock resistance high-adhesion polysulfide rubber and comparative example in shock resistance high-adhesion polysulfide rubber carry out performance detection, detection knot
Fruit is as shown in table 1:
Test method:
Elastic restoration ratio test is detected referring to ASTM D3107.
Test of elongation rate is detected using elongation at break analyzer.
Tensile strength test is detected using tensile strength test digital display HTS-BLY2500 Series Measurement instrument.
Peel strength test is detected by ASTM_D429-81 standard.
Press with φ 50mm cylinder bond strength test: GB/T6329 standard is detected.
1 polysulfide rubber performance measurement result of table
| Test item | Example 1 | Example 2 | Example 3 | Comparative example |
| Elastic restoration ratio (%) | 92 | 93 | 94 | 55 |
| Elongation (%) | 425 | 430 | 440 | 300 |
| Tensile strength (MPa) | 21 | 22 | 23 | 12 |
| Peel strength (N) | 730 | 740 | 750 | 400 |
| φ 50mm cylinder adhesive strength (kg) | 380 | 390 | 400 | 160 |
Good, the elongation according to the shock resistance high-adhesion polysulfide caoutchouc elasticity recovery rate produced by the present invention of data among the above
Height, tensile strength is high, good toughness, good impact resistance, and peel strength is high, and adhesive strength is high, and adhesive property is good, has wide answer
Use prospect.
Claims (7)
1. a kind of preparation method of shock resistance high-adhesion polysulfide rubber, it is characterised in that specific preparation step are as follows:
(1) according to parts by weight, 50~55 parts of sulfuric acid solutions, 5~7 parts of flaky graphites and 2~4 parts of sodium nitrate investments are weighed to burn
Obtained mixing suspension is uniformly mixed in cup, the potassium permanganate powder of mixing suspension quality 2~4% is added into beaker by every 5min
End adds 3 times altogether, adds the distilled water with quality such as mixing suspensions after addition, and by heated at constant temperature in beaker water-bath,
Filter residue is obtained by filtration after heating, and is successively cleaned filter residue 3~5 times with hydrochloric acid and distilled water；
(2) by above-mentioned filter residue and distilled water 1:100 in mass ratio investment round-bottomed flask, round bottom flask is entered into sonic oscillation instrument
Dispersion liquid is made in middle oscillation, and the hydrazine hydrate of dispersion liquid quality 1.5~2.0% is added dropwise into round-bottomed flask, flask is heated to 98
~100 DEG C, carry out 24~25h of condensing reflux, after filter cake is obtained by filtration, successively clean 3~5 with distilled water and dehydrated alcohol
It is put into drying in baking oven after secondary and obtains reaction solid product；
(3) it by above-mentioned reaction solid product and bromine 1:20 in mass ratio investment beaker, places the beaker in sonic oscillation instrument,
It is vibrated under conditions of nitrogen environment, filtrate is obtained by filtration after oscillation, with acetone wash filtrate 4~8 times, put filtrate after cleaning
Enter dry obtained brominated product in baking oven；
(4) according to parts by weight, 4~6 parts are weighed to propyl phenyl boric acid, 18~20 parts of n,N-Dimethylformamide, 0.6~0.8
Part tetra-triphenylphosphine palladium, 0.3~0.5 part of tetrabutylammonium bromide, 2~4 parts of saturated sodium carbonate solutions, 1.5~1.8 parts of above-mentioned brominations
It is reacted in product and 7~8 parts of distilled water investment reaction kettles and mixed emulsion is made；
(5) according to parts by weight, 7~9 parts of above-mentioned mixed emulsions, 1.5~1.8 parts of hydrochloric acid and 10~13 parts of dehydrated alcohols are weighed to throw
Enter in three-necked flask and be uniformly mixed, precipitation solid is obtained by filtration after mixing, wash with distilled water after precipitation solid 3~5 times, is put into
It is dry in baking oven, desciccate is made；
(6) according to parts by weight, weigh 3~5 parts of above-mentioned desciccates, 1~2 part of vulcanized sodium, 13~15 parts of 1,2- Difluoroethanes,
7~9 part 2,2 '-dichloro-o-xylenes and 25~28 parts of propylene glycol are put into ground and mixed in reaction kettle and obtain mix products, increase
Temperature of reaction kettle, and the vinyl triamine of mix products quality 5~8% is added, cooling obtained shock resistance high bonding after being stirred
Property polysulfide rubber.
2. a kind of preparation method of shock resistance high-adhesion polysulfide rubber according to claim 1, it is characterised in that: step
(1) mass fraction of the sulfuric acid solution described in is 75~80%, and the bath temperature in water-bath is 30~35 DEG C, heated at constant temperature
Time is 30~40min, and the mass fraction of hydrochloric acid is 5~8%.
3. a kind of preparation method of shock resistance high-adhesion polysulfide rubber according to claim 1, it is characterised in that: step
(2) frequency in sonic oscillation instrument described in is 35~40kHz, and duration of oscillation is 3~4h, flask heating temperatures to 98~
100 DEG C, the condensing reflux time is 24~25h.
4. a kind of preparation method of shock resistance high-adhesion polysulfide rubber according to claim 1, it is characterised in that: step
(3) frequency in sonic oscillation instrument described in is 35~40kHz, and duration of oscillation is 2~3h, the temperature in baking oven is 110~
120 DEG C, drying time is 12~14h.
5. a kind of preparation method of shock resistance high-adhesion polysulfide rubber according to claim 1, it is characterised in that: step
(4) speed of agitator in reaction kettle described in is 200~250r/min, temperature is 80~90 DEG C, the reaction time be 72~
74h。
6. a kind of preparation method of shock resistance high-adhesion polysulfide rubber according to claim 1, it is characterised in that: step
(5) mass fraction of the hydrochloric acid described in is 5~8%, and temperature is 105~110 DEG C in baking oven, and drying time is 12~13h.
7. a kind of preparation method of shock resistance high-adhesion polysulfide rubber according to claim 1, it is characterised in that: step
(6) temperature is increased to 120~130 DEG C in the reaction kettle described in, and being stirred the time is 60~70min.
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