CN101649026A - Preparation method of butyronitrile latex with high nitrile group content - Google Patents
Preparation method of butyronitrile latex with high nitrile group content Download PDFInfo
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Abstract
The invention provides butyronitrile latex with high nitrile group content for manufacturing asbestos or a non-asbestus sheet. The butyronitrile latex is prepared by taking butadiene and acrylonitrileas monomers and adopting a compound emulsifying system formed by an anionic emulsifier and a non-ionic emulsifier and a redox initiation system formed by persulfate and mercaptan. An intermediate-temperate emulsion polymerization technology of a three-stage stepped temperature control process that the monomers, an emulsifying agent, an initiating agent, a reducing agent, an auxiliary reducing agent, and the like are added in batches is adopted so as to ensure that the polymerization stability of the latex is greatly improved, prevent the generation of gel and improve the mechanical stabilityof the latex. The content of the acrylonitrile combined by the latex is 28-33 percent, and the strength in each aspect of the nitrile latex exceeds the strength of the prior nitrile latex product. Particularly, the butyronitrile latex has good oil resistivity and low loss ratio in a solvent, thus the nitrile latex has excellent performance when used for manufacturing the asbestos or the non-asbestes sheet.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of preparation method of nitrile rubber, relate in particular to a kind of preparation method of butyronitrile latex with high nitrile group content, be mainly used in and make asbestos or non-asbestos collecting plate.
Background technology
Asbestos or non-asbestos latex sheet are with asbestos-free various inorganic or organic synthetic fibers, the latex Synergist S-421 95 is a main raw material, through making beating, copies and gets, the sealing material that sulfuration forms mainly is used to the base material of cylinder of internal-combustion engine gasket seal and the static seal pad of other mechanism.Be used to make asbestos or the related latex of non-asbestos collecting plate mainly contains nitrile rubber, styrene-butadiene emulsion, acrylic ester emulsion etc., wherein nitrile rubber is most widely used with its excellent elasticity and oil resistance and enjoy favor.
Along with improving constantly of automotive performance, to the also raising gradually of requirement of friction materials.For example compression resilience, oil resistance, solvent resistance, resistance to elevated temperatures.But at present, the used nitrile rubber of non-asbestos collecting plate industry exists bound acrylonitrile content lower.With butyronitrile 26 latex commonly used is example, and its bound acrylonitrile content has only about 20%, resistance to low temperature-30 ℃, and 180 ℃ of resistances to elevated temperatures can not satisfy these requirements.In addition, nitrile rubber is because surface tension is lower, and is not good with the wetting property of fibrous magnesium silicate, the phenomenon of partly flocculating can occur in pulping process, it is unclear to copy the back residual water, resident more, polluted-water causes environmental hazard easily, particularly for the absorption of no fibrous magnesium silicate, nitrile rubber and styrene-butadiene latex are difficult to absorption more, cause parking, can't continuous production.Therefore, the nitrile rubber of necessary exploitation high-nitrile substitutes above-mentioned emulsion and has crucial meaning.
Summary of the invention
The objective of the invention is in order to overcome the deficiencies in the prior art, provide a kind of preparation method who is used to make the high-nitrile nitrile rubber of asbestos or non-asbestos collecting plate, to satisfy the high request of growing automotive performance to friction materials.
The preparation method of high-nitrile nitrile rubber of the present invention, finished by the raw material and the technology of following prescription:
Composition of raw materials: in mass parts
Monomer: 40～85 parts of divinyl, 15～60 parts of vinyl cyanide.
Emulsifying agent: anionic emulsifier and nonionic emulsifying agent are composite with 3: 1～1: 1 volume ratio; 1.5～3.0 parts.
Wherein, anionic emulsifier is at least a in the sodium salt of mixed fatty acid or sylvite, oleic sodium salt or sylvite, stearic sodium salt or sylvite, alkylbenzene sulfonate, alkyl-sulphate, the alkylsulfonate; Nonionic emulsifying agent is alkyl phenylate type or alkyl ether type.
Initiator: water-soluble thermolysis type superoxide, as ammonium persulphate, Potassium Persulphate or Sodium Persulfate; 0.4～1.3 parts.
Molecular weight regulator: sulfur alcohol compound or sulfur alcohol compound and low molecule Organohalogen compounds are with the composite compound conditioning agent that forms of 3: 1～4: 1 volume ratio, and it is simultaneously as reductive agent; 0.8～1.5 parts.
Wherein, sulfur alcohol compound is t-lauryl mercaptan (tert-dodecyl mercaptan) or n-lauryl mercaptan (dodecyl mercaptan carbon); Low molecule Organohalogen compounds are tetracol phenixin.
Auxiliary agent: basic metal sodium salt (as sodium hydroxide or potassium hydroxide) or alkaline-earth metal sodium salt (as calcium hydroxide, magnesium hydroxide); 0.01～0.1 part.
The pH buffer reagent: alkaline carbonate or alkali metal hydrocarbonate, as yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus etc.; 0.01～0.5 part.
Ionogen: Repone K or potassiumphosphate; 0.01～0.5 part.
Sequestrant: disodium ethylene diamine tetraacetate or tetrasodium ethylenediamine tetraacetate; 0.01～0.5 part.
Help reductive agent: sodium bisulfite, 0.1～0.3 part.
Soft water: 100～150 parts.
Technology:
(1) one section feeds intake: after polymeric kettle is vacuumized, to the soft water, emulsifying agent, molecular weight regulator, initiator and the monomer that wherein drop into prescription total amount 40% and whole auxiliary agent, pH buffer reagent, ionogen, sequestrants;
(2) reaction control and adding: one section back that feeds intake was in normal-temperature reaction 7～8 hours; Improve 5～10 ℃ of temperature of reaction, react to polymerisation conversion and reach at 60%～80% o'clock in the monomer total amount, add two sections materials: soft water, emulsifying agent and the molecular weight regulator of prescription total amount 55%, the initiator and the monomer of prescription total amount 60% continue reaction 4～5 hours; When polymerisation conversion reach the monomer total amount 90%～94% the time, add remaining soft water, emulsifying agent, molecular weight regulator and whole reductive agent that helps, improve 5～10 ℃ of temperature of reaction, keep to react to polymerisation conversion and reach more than 97.0% of monomer total amount;
(3) remove residual monomer and aftertreatment: polymerisation conversion reaches 97.0% when above of monomer total amount, stopped reaction, and the discharging processing that outgases reaches between 9～10 with alkali lye impregnation breast pH value then, cools to below 30 ℃, filters the back and packs.
Degassing treatment process is: in degassing still, and 40～80 ℃ of temperature, vacuum tightness-0.06～0.09MPa outgased 1.5～3.0 hours down.
Nitrile rubber bound acrylonitrile amount height (bound acrylonitrile amount 25～33%) residual acrylonitrile content＜500ppm of the present invention's preparation, have good compression rebound resilience, oil resistance, solvent resistance and resistance to elevated temperatures (below the resistance to low temperature-45 ℃, resistance to elevated temperatures is more than 220 ℃), be the preferred material of making asbestos or non-asbestos collecting plate.
The present invention compared with prior art has following substantive distinguishing features and obvious improvement:
1, increased substantially the add-on of vinyl cyanide, the highlyest can reach 60%, improved polymkeric substance in conjunction with acrylonitrile content, finished product oil resistant, crocking resistance, solvent resistance improves, resistance toheat improves, and the scope of application is wider.
2, the way that adopt monomer, emulsifying agent, initiator, reductive agent, helps reductive agent, conditioning agent gradation to add had both guaranteed high transformation efficiency, had guaranteed quality product again, and what also guaranteed vinyl cyanide simultaneously evenly increases chain.Improve polymerization conversion, reduce and reclaim amount of monomer.Transformation efficiency rises to 97% from 95%, reclaims amount of monomer and can reduce more than three times, and this not only reduces energy expenditure, and significantly reduces the chance that pollutes.
3, adopt in temperature (the temperature control scope is at 20 ℃～50 ℃) emulsion polymerization technology, produce nitrile rubber technology with cold process and compare the energy expenditure that has reduced.Low temperature polymerization needs cooling (polymkeric substance per ton to be needed 6.54 * 10 approximately except that the initial reaction stage material drops to polymeric reaction temperature by normal temperature
4Kcal) outside, keeping of later temperature of reaction need be removed a large amount of polymerization reaction heats, and these two promptly reach 37 * 10
4Kcal, save energy.
4, the composite emulsifying system that adopts anionic emulsifier and nonionic emulsifying agent to constitute, the fibrous magnesium silicate blending performance that has improved in speed of response and polymerization stability, the product use improves.
5, adopt persulphate-mercaptan oxidation reduction initiating system, its resolvent remains in the pollution that causes in the glue when having avoided using organo-peroxide to make initiator, and the efficiency of initiation height shortened the reaction times more than 5 hours;
6, adopt three sections ladder temperature control technologies, make the polymerization stability of latex that bigger improvement be arranged, can prevent that gel from producing, and improved the mechanical stability of latex.
7, adopt interpolation special auxiliary agent (basic metal sodium salt or alkaline-earth metal sodium salt), effectively improved the multipolymer bound acrylonitrile content, can reach more than 33%.
8, it is good that Zhi Bei latex bound acrylonitrile amount 28～33%, every intensity of goods surpass existing nitrile rubber product, particularly oil resistance, and rate of loss is low in solvent, is used to make asbestos or non-asbestos collecting plate, excellent performance.
Embodiment
Be described further below by preparation, performance and the asbestos in making asbestos or non-asbestos collecting plate or the application of non-asbestos collecting plate of specific embodiment nitrile rubber of the present invention.
Embodiment one: the production of nitrile rubber
1, prescription: in mass parts
Monomer: 70 parts of divinyl, 30 parts of vinyl cyanide;
Oxygenant: 1.2 parts of Potassium Persulphates;
Emulsifying agent: sodium lauryl sulphate: 1.8 parts, the ninth of the ten Heavenly Stems phenolic group Soxylat A 25-7 TX-12:0.8 part, the sodium formaldehyde condensation products is 0.3 part;
Reductive agent (molecular weight regulator): n-dodecyl mercaptan, 1.4 parts;
Auxiliary agent: potassium hydroxide: 0.05 part;
PH buffer reagent: sodium bicarbonate; 0.43 part;
Ionogen: 0.4 part of potassiumphosphate;
Sequestrant: 0.3 part of tetrasodium ethylenediamine tetraacetate (hereinafter to be referred as EDTA four sodium);
Help reductive agent: sodium bisulfite, 0.1 part;
Soft water: 120 parts.
2, technology:
(1) one section feeds intake: (polymeric kettle at first vacuumizes in the 10L polymeric kettle of a band stirring, import and export of nitrogen, material import and export, thermometric pressure tap and chuck, use nitrogen replacement again, vacuum tightness reaches-during 0.10MPa) drop into 35 parts of soft water in mass successively, (wherein soft water is 10 parts for emulsifier solution, 1.0 parts of sodium lauryl sulphate, the ninth of the ten Heavenly Stems, phenolic group Soxylat A 25-7 TX-12 was that 0.4 part, sodium formaldehyde condensation products are 0.1 part).0.4 part of potassiumphosphate, 0.43 part of sodium bicarbonate, 0.3 part in EDTA four sodium, 0.05 part in potassium hydroxide add polymeric kettle with 10 parts of soft water dissolving backs.1.1 parts of n-dodecyl mercaptans, 12 parts of vinyl cyanide, divinyl adds polymeric kettle for 28 parts; After stirring 30 minutes at normal temperatures, add persulfate aqueous solution (1 part of Potassium Persulphate dissolves with 17 parts of soft water).Under normal temperature (25 ± 2 ℃), begin reaction.
(2) reaction is controlled and is added: reacted about 7～8 hours, when polymerisation conversion reaches 75%～80% to add for the first time the monomer total amount, add and add liquid for the second time: 35 parts of soft water, 0.5 part of sodium lauryl sulphate, the ninth of the ten Heavenly Stems phenolic group Soxylat A 25-7 TX-120.3 part, the sodium formaldehyde condensation products is 0.1 part, 0.2 part of n-dodecyl mercaptan, 0.2 part of Potassium Persulphate, 18 parts of vinyl cyanide, 42 parts of divinyl; Be warming up to 35 ± 2 ℃ keep reaction until polymerisation conversion in the monomer total amount greater than 95%; Add remaining emulsifying agent (0.1 part of sodium lauryl sulphate, the ninth of the ten Heavenly Stems, phenolic group Soxylat A 25-7 TX-120.1 part, sodium formaldehyde condensation products were 0.1 part), 0.1 part of reductive agent (n-dodecyl mercaptan), help 0.1 part of reductive agent sodium bisulfite, improve temperature of reaction and be warming up to 45 ± 2 ℃, keep reaction and reach more than 97% in the monomer total amount until polymerisation conversion.
(3) remove residual monomer and aftertreatment: transformation efficiency reaches 97% when above in the monomer total amount, stopped reaction, changing latex over to degassing still and remove residual monomer: degassing still vacuum tightness be-0.06～-0.09MPa, 60 ℃ of the still temperature that outgases, the degassing time is 1.5～3.0 hours.Slowly add 20% alkali lye (potassium hydroxide aqueous solution) then and regulate pH value, make them between 9～10, be cooled to below 30 ℃, filter the back and pack.
3, the physical index of Zhi Bei nitrile rubber
Total solid substance 45.8% pH value 8.95 viscosity 65mPas surface tension 47mN/m
Particle diameter 192.0nm mechanical stability 1.5% chemical stability 0.4%
Second-order transition temperature-18.2 ℃ structural gel 77.5% macroscopical gel 0.005%
Bound acrylonitrile amount 28% residual acrylonitrile content＜500ppm.
The production of embodiment two, nitrile rubber
1, prescription: in mass parts;
Monomer: 65 parts of divinyl, 35 parts of vinyl cyanide;
Initiator: 1.3 parts of Potassium Persulphates;
Emulsifying agent: sodium lauryl sulphate: 1.6 parts, the ninth of the ten Heavenly Stems phenolic group Soxylat A 25-7 TX-12:1.0 part, the sodium formaldehyde condensation products is 0.3 part;
Molecular weight regulator: 1.5 parts of uncle's lauryl mercaptans;
Auxiliary agent: 0.08 part in sodium hydroxide;
PH buffer reagent: 0.45 part in yellow soda ash;
Ionogen: Repone K, 0.35 part;
Sequestrant: disodium ethylene diamine tetraacetate (hereinafter to be referred as the EDTA disodium), 0.32 part;
Help reductive agent: sodium bisulfite, 0.2 part
Soft water: 125 parts
2, technology:
(1) one section feeds intake: (polymeric kettle at first vacuumizes in the 10L polymeric kettle of a band stirring, import and export of nitrogen, material import and export, thermometric pressure tap and chuck, use nitrogen replacement again, vacuum tightness reaches-during 0.10MPa) drop into 40 parts of soft water in mass successively, (wherein soft water is 10 parts for emulsifier solution, 1.0 parts of sodium lauryl sulphate, the ninth of the ten Heavenly Stems, phenolic group Soxylat A 25-7 TX-12 was that 0.6 part, sodium formaldehyde condensation products are 0.1 part).0.35 part in Repone K, 0.45 part in yellow soda ash, 0.32 part of EDTA disodium, 0.08 part in potassium hydroxide add polymeric kettle with 10 parts of soft water dissolving backs.1.2 parts of uncle's lauryl mercaptans, 14 parts of vinyl cyanide, divinyl adds polymeric kettle for 26 parts; After stirring 30 minutes at normal temperatures, add persulfate aqueous solution (1 part of Potassium Persulphate dissolves with 17 parts of soft water).Begin reaction in normal temperature (25 ± 2 ℃).
(2) reaction is controlled and is added: reacted about 7～8 hours, when polymerisation conversion reaches 75%～80% to add for the first time the monomer total amount, add and add liquid for the second time: 35 parts of soft water, 0.5 part of sodium lauryl sulphate, the ninth of the ten Heavenly Stems phenolic group Soxylat A 25-7 TX-120.3 part, the sodium formaldehyde condensation products is 0.1 part, 0.2 part of uncle's lauryl mercaptan, 0.3 part of Potassium Persulphate, 21 parts of vinyl cyanide, 39 parts of divinyl; Be warming up to 35 ± 2 ℃ keep reaction until polymerisation conversion in the monomer total amount greater than 95%; Add remaining emulsifying agent (0.1 part of sodium lauryl sulphate, the ninth of the ten Heavenly Stems, phenolic group Soxylat A 25-7 TX-120.1 part, sodium formaldehyde condensation products were 0.1 part), 0.1 part of reductive agent (uncle's lauryl mercaptan), help 0.1 part of reductive agent (sodium bisulfite), improve temperature of reaction and be warming up to 45 ± 2 ℃, keep reaction and reach more than 97% in the monomer total amount until polymerisation conversion.
(3) remove residual monomer and aftertreatment: transformation efficiency reaches 97% when above in the monomer total amount, stopped reaction, changing latex over to degassing still and remove residual monomer: degassing still vacuum tightness be-0.06～-0.09MPa, 60 ℃ of the still temperature that outgases, the degassing time is 1.5～3.0 hours.Slowly add 20% alkali lye (potassium hydroxide aqueous solution) then and regulate pH value, make them between 9～10, be cooled to below 30 ℃, filter the back and pack.
3, the physical index of Zhi Bei nitrile rubber
Total solid substance 45.3% pH value 9.24 viscosity 72mPas surface tension 43mN/m
Particle diameter 200.2nm mechanical stability 2.1% chemical stability 0.7%
Second-order transition temperature-12.3 ℃ structural gel 83.4% macroscopical gel 0.008%
Bound acrylonitrile amount 32% residual acrylonitrile content＜500ppm
The production of embodiment three, nitrile rubber
1, prescription: in mass parts;
Monomer: 60 parts of divinyl, 40 parts of vinyl cyanide;
Initiator: 1.3 parts of Potassium Persulphates;
Emulsifying agent: 1.6 parts of sodium lauryl sulphate, the ninth of the ten Heavenly Stems phenolic group Soxylat A 25-7 TX-121.0 part, the sodium formaldehyde condensation products is 0.3 part;
Molecular weight regulator: uncle's lauryl mercaptan, 1.5 parts;
Auxiliary agent: 0.09 part in sodium hydroxide;
PH buffer reagent: 0.47 part of sodium bicarbonate;
Ionogen: 0.40 part in Repone K;
Sequestrant: disodium ethylene diamine tetraacetate (hereinafter to be referred as the EDTA disodium), 0.38 part;
Help reductive agent: sodium bisulfite, 0.22 part
Soft water: 130 parts
2, technology:
(1) one section feeds intake: (polymeric kettle at first vacuumizes in the 10L polymeric kettle of a band stirring, import and export of nitrogen, material import and export, thermometric pressure tap and chuck, use nitrogen replacement again, vacuum tightness reaches-during 0.10MPa) drop into 45 parts of soft water in mass successively, (wherein soft water is 10 parts for emulsifier solution, 1.0 parts of sodium lauryl sulphate, the ninth of the ten Heavenly Stems, phenolic group Soxylat A 25-7 TX-12 was that 0.6 part, sodium formaldehyde condensation products are 0.1 part).0.40 part in Repone K, 0.47 part of sodium bicarbonate, 0.38 part of EDTA disodium, 0.09 part in potassium hydroxide add polymeric kettle with 10 parts of soft water dissolving backs.1.2 parts of uncle's lauryl mercaptans, 16 parts of vinyl cyanide, divinyl adds polymeric kettle for 24 parts; After stirring 30 minutes at normal temperatures, add persulfate aqueous solution (1 part of Potassium Persulphate dissolves with 17 parts of soft water).Begin reaction.Temperature of reaction: 25 ± 2 ℃
(2) reaction is controlled and is added: reacted about 7～8 hours, when polymerisation conversion reaches 75%～80% to add for the first time the monomer total amount, add and add liquid for the second time: 35 parts of soft water, 0.5 part of sodium lauryl sulphate, the ninth of the ten Heavenly Stems phenolic group Soxylat A 25-7 TX-120.3 part, the sodium formaldehyde condensation products is 0.1 part, 0.2 part of uncle's lauryl mercaptan, 0.3 part of Potassium Persulphate, 24 parts of vinyl cyanide, 36 parts of divinyl; Be warming up to 35 ± 2 ℃ keep reaction until polymerisation conversion in the monomer total amount greater than 95%; Add remaining emulsifying agent (0.1 part of sodium lauryl sulphate, the ninth of the ten Heavenly Stems, phenolic group Soxylat A 25-7 TX-120.1 part, sodium formaldehyde condensation products were 0.1 part), 0.1 part of reductive agent (uncle's lauryl mercaptan), help 0.1 part of reductive agent (sodium bisulfite), improve temperature of reaction and be warming up to 45 ± 2 ℃, keep reaction and reach more than 97% in the monomer total amount until polymerisation conversion.
(3) remove residual monomer and aftertreatment: transformation efficiency reaches 97% when above in the monomer total amount, stopped reaction, changing latex over to degassing still and remove residual monomer: degassing still vacuum tightness be-0.06～-0.09MPa, 60 ℃ of the still temperature that outgases, the degassing time is 1.5～3.0 hours.Slowly add 20% alkali lye (potassium hydroxide aqueous solution) then and regulate pH value, make them between 9～10, be cooled to below 30 ℃, filter the back and pack.
3, the physical index of Zhi Bei nitrile rubber
Total solid substance 45.6% pH value 9.32 viscosity 68mPas surface tension 39.5mN/m
Particle diameter 190.7nm mechanical stability 1.6% chemical stability 0.9%
Second-order transition temperature-7.8 ℃ structural gel 91.7% macroscopical gel 0.01%
Bound acrylonitrile amount 33% residual acrylonitrile content＜500ppm
Embodiment four, fibrous magnesium silicate strengthen the preparation of plates of latex gasket seal
Prescription A (in dry mass per-cent)
Fibrous magnesium silicate 25%
Fibrous sepiolite 25%
Nitrile rubber of the present invention (bound acrylonitrile content 28%) 20%
Zinc oxide 0.18%
Antioxidant D 0.21%
Casein 0.15%
Potassium hydroxide 0.04%
Lanolin 0.03%
Promotor 0.20%
Water dispersible dead front type carbimide emulsion 2.02%
Nanoclay 5.00%
Crystal whisker of gypsum 5.00%
Lime carbonate 7.00%
Talcum powder 5.00%
Diatomite 5.00%
Technology: with above-mentioned each component totally 50 kilograms (dry mass) routinely wet method copy and get moulding process and vulcanize (referring to the vulcanization of rubber), promptly get non-asbestos fiber and strengthen emulsion gasket seal sheet material.Cure conditions: 135 ℃ of curing temperatures, sulfide stress 6.35MPa, curing time 20 minutes.
According to relevant criterion and experimental technique its salient features is detected, and with the contrast of the technical parameter of butyronitrile 26 latex formulations, the result is shown in table 1, table 2.
The test result of the main mechanical performance index of table 1 prescription A development sheet material
| Test parameter | Testing standard | The present invention A that fills a prescription | Butyronitrile 26 latex formulations |
| Cross direction tensile strength, MPa | ??ASTM??F152 | ??13.5 | ??6.20 |
| Rate of compression, % | ??ASTM?F36 | ??17.8 | ??34.6 |
| Rebound degree, % | ??ASTM?F36 | ??54.0 | ??23.8 |
| The creep relaxation rate, % | ??ASTM?F38 | ??20.4 | ??60.8 |
| Flexibility | ??ASTM??F147 | Flawless | ??- |
The rate of weight loss (%) of the anti-common chemical corrosion medium (room temperature was flooded 24 hours) of table 2 prescription A development sheet material
| Chemical mediator | The present invention A that fills a prescription | Butyronitrile 26 latex formulations |
| 30%HCl solution | ??1.5 | ??5.5 |
| ??30％H 2SO4 solution | ??5.1 | ??41.9 |
| 5%NaOH solution | ??1.5 | ??9.8 |
Embodiment five, non-asbestos fiber strengthen the Latex Gasket Sheet Crosslinked preparation of plates
Prescription B (in dry mass per-cent)
Kevlar pulp 10.00%
Glass fibre (L/D=200) 12.00%
Carbon fiber (L/D=200) 5.00%
Fibrous sepiolite 25.00%
Nitrile rubber of the present invention (bound acrylonitrile content 28%) 20.00%
Zinc oxide 0.30%
Antioxidant D 0.20%
Casein 0.02%
Lanolin 0.10%
Promotor 0.20%
Sulphur 0.30%
Water dispersible dead front type is with clearance fat liquor 2.52%
Nanoclay 5.00%
Crystal whisker of gypsum 4.36%
Lime carbonate 7.00%
Talcum powder 4.00%
Diatomite 4.00%
Technology: with above-mentioned each component altogether 50KG (dry mass) routinely wet method copy and get moulding process, vulcanize, non-asbestos fiber strengthens emulsion gasket seal sheet material.Cure conditions: 137 ℃ of curing temperatures, sulfide stress 6.25MPa, curing time 23 minutes.
According to relevant criterion and experimental technique its salient features is detected, and contrast with butyronitrile 26 latex formulations 8 technical parameters, the result is shown in table 3, table 4.
The test result of the main mechanical performance index of table 3 prescription B development sheet material
| Test parameter | Testing standard | The present invention B that fills a prescription | Butyronitrile 26 latex formulations |
| Cross direction tensile strength, MPa | ??ASTM?F152 | ??12.7 | ??6.20 |
| Rate of compression, % | ??ASTM?F36 | ??16.3 | ??34.6 |
| Rebound degree, % | ??ASTM?F36 | ??51.0 | ??23.8 |
| The creep relaxation rate, % | ??ASTM?F38 | ??16.8 | ??60.8 |
| Flexibility | ??ASTM??F147 | Flawless | ??- |
The rate of weight loss of the anti-common chemical corrosion medium (room temperature was flooded 24 hours) of table 4 prescription B development sheet material, %
| Chemical mediator | The present invention A that fills a prescription | Butyronitrile 26 latex formulations |
| 30%HCl solution | ??0.6 | ??5.5 |
| 30%H2SO4 solution | ??1.2 | ??41.9 |
| 5%NaOH solution | ??0.8 | ??9.8 |
From the foregoing description four, five as seen, the enhancing that mixes at nanoclay, organic and fibrous magnesium silicate, inorganic non-asbestos fiber (or pulp), and isocyanate groups crosslinked down, the salient features that the asbestos of nitrile rubber manufacturing of the present invention of the present invention or non-asbestos fiber strengthen emulsion gasket seal sheet material has surmounted the nitrile rubber in usefulness comprehensively.
Claims (10)
1, a kind of preparation method of high-nitrile nitrile rubber, finished by the raw material and the technology of following prescription:
Composition of raw materials: in mass parts
Monomer: 40～85 parts of divinyl, 15～60 parts of vinyl cyanide;
Emulsifying agent: anionic emulsifier and nonionic emulsifying agent are composite with 3: 1～1: 1 volume ratio; 1.5～3.0 parts;
Initiator: water-soluble thermolysis type superoxide, 0.4～1.3 part;
Molecular weight regulator: the compound conditioning agent that sulfur alcohol compound or sulfur alcohol compound and low molecule Organohalogen compounds are formed; 0.8～1.5 parts
Auxiliary agent: basic metal sodium salt or alkaline-earth metal sodium salt; 0.01～0.1 part:
PH buffer reagent: alkaline carbonate or alkali metal hydrocarbonate; 0.01～0.5 part;
Ionogen: Repone K or potassiumphosphate; 0.01～0.5 part;
Sequestrant: disodium ethylene diamine tetraacetate or tetrasodium ethylenediamine tetraacetate; 0.01～0.5 part;
Help reductive agent: sodium bisulfite, 0.1～0.3 part;
Soft water: 100～150 parts
Technology:
(1) one section feeds intake: after polymeric kettle is vacuumized, to the soft water, emulsifying agent, molecular weight regulator, initiator and the monomer that wherein drop into prescription total amount 40% and whole auxiliary agent, pH buffer reagent, ionogen, sequestrants;
(2) reaction control and adding: one section back that feeds intake was in normal-temperature reaction 7～8 hours; Improve 5～10 ℃ of temperature of reaction, react to polymerisation conversion and reach at 60%～80% o'clock in the monomer total amount, add two sections materials: soft water, emulsifying agent and the molecular weight regulator of prescription total amount 55%, the initiator and the monomer of prescription total amount 60% continue reaction 4～5 hours; When polymerisation conversion reach the monomer total amount 90%～94% the time, add remaining soft water, emulsifying agent, molecular weight regulator and whole reductive agent that helps, improve 5～10 ℃ of temperature of reaction, keep to react to polymerisation conversion and reach more than 97.0% of monomer total amount;
(3) remove residual monomer and aftertreatment: polymerisation conversion reaches 96.0% when above of monomer total amount, stopped reaction, and the discharging processing that outgases reaches between 9～10 with alkali lye impregnation breast pH value then, cools to below 30 ℃, filters the back and packs.
2, the preparation method of high-nitrile nitrile rubber according to claim 1 is characterized in that: described anionic emulsifier is at least a in the sodium salt of mixed fatty acid or sylvite, oleic sodium salt or sylvite, stearic sodium salt or sylvite, alkylbenzene sulfonate, alkyl-sulphate, the alkylsulfonate.
3, the preparation method of high-nitrile nitrile rubber according to claim 1, it is characterized in that: described nonionic emulsifying agent is alkyl phenylate type or alkyl ether type.
4, the preparation method of high-nitrile nitrile rubber according to claim 1, it is characterized in that: described water-soluble thermolysis type superoxide is ammonium persulphate, Potassium Persulphate or Sodium Persulfate.
5, the preparation method of high-nitrile nitrile rubber according to claim 1, it is characterized in that: described sulfur alcohol compound is tert-dodecyl mercaptan or dodecyl mercaptan carbon.
6, the preparation method of high-nitrile nitrile rubber according to claim 1, it is characterized in that: described low molecule Organohalogen compounds are tetracol phenixin.
7, the preparation method of high-nitrile nitrile rubber according to claim 1, it is characterized in that: described sulfur alcohol compound and low molecule Organohalogen compounds are composite with 3: 1～4: 1 volume ratio.
8, the preparation method of high-nitrile nitrile rubber according to claim 1, it is characterized in that: described basic metal sodium salt is sodium hydroxide or potassium hydroxide.
9, the preparation method of high-nitrile nitrile rubber according to claim 1 is characterized in that:; Described alkaline-earth metal sodium salt is calcium hydroxide, magnesium hydroxide.
10, the preparation method of high-nitrile nitrile rubber according to claim 1 is characterized in that: the treatment process of the degassing described in the technology is: in degassing still, and 40～80 ℃ of temperature, vacuum tightness-0.06～-the 0.09MPa degassing 1.5～3.0 hours down.
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| CN103421146A (en) * | 2012-05-15 | 2013-12-04 | 中国石油天然气股份有限公司 | Preparation method of nitrile rubber with high acrylonitrile content |
| CN103665265A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Preparation method of acrylonitrile-butadiene rubber |
| CN103665264A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | High-performance oil-resistant acrylonitrile-butadiene rubber |
| CN109320655A (en) * | 2018-10-24 | 2019-02-12 | 安庆华兰科技有限公司 | A kind of high nitrile cross-linked powdery acrylonitrile butadiene and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS54107995A (en) * | 1978-02-14 | 1979-08-24 | Nippon Zeon Co Ltd | Preparation of nbr |
| CN1978476A (en) * | 2005-12-05 | 2007-06-13 | 中国石油天然气集团公司 | Method for preparing liquid nitrile butadiene rubber |
| CN101423586B (en) * | 2007-11-01 | 2011-09-07 | 中国石油天然气股份有限公司 | Method for producing high conversion rate butadiene-acrylonitrile copolymer rubber |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103421146A (en) * | 2012-05-15 | 2013-12-04 | 中国石油天然气股份有限公司 | Preparation method of nitrile rubber with high acrylonitrile content |
| CN103421146B (en) * | 2012-05-15 | 2016-03-09 | 中国石油天然气股份有限公司 | A kind of preparation method of nitrile rubber with high acrylonitrile content |
| CN103665265A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Preparation method of acrylonitrile-butadiene rubber |
| CN103665264A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | High-performance oil-resistant acrylonitrile-butadiene rubber |
| CN109320655A (en) * | 2018-10-24 | 2019-02-12 | 安庆华兰科技有限公司 | A kind of high nitrile cross-linked powdery acrylonitrile butadiene and preparation method thereof |
| CN109320655B (en) * | 2018-10-24 | 2021-05-11 | 安庆华兰科技有限公司 | Super-high nitrile cross-linking type powdery nitrile rubber and preparation method thereof |
| CN113993919A (en) * | 2020-05-26 | 2022-01-28 | 株式会社Lg化学 | Method for preparing carboxylic acid modified nitrile copolymer latex |
| CN113993919B (en) * | 2020-05-26 | 2024-04-05 | 株式会社Lg化学 | Process for preparing carboxylic acid modified nitrile copolymer latex |
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