CN101649025A - Preparation method of carboxylic styrene butadiene latex - Google Patents
Preparation method of carboxylic styrene butadiene latex Download PDFInfo
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Abstract
The invention provides a preparation method of carboxylic styrene-butadiene latex. In the method, butadiene and styrene are adopted as main monomers, and unsaturated carboxylic acid or unsaturated carboxylic ester functional monomers are additionally adopted; a compound emulsifying system formed by a reacting type emulsifier, an anion emulsifier and a non-ionic emulsifier is adopted, and a persulfate thermal decomposition initiating agent is also adopted. Low-temperature polymerization is replaced by high-temperature polymerization, and a two-stage stepped temperature control process is adopted so as to ensure that the stability of the polymerization of the latex is greatly improved, prevent the generation of gel, improve the mechanical stability of the latex and reduce the energy consumption. The carboxylic styrene-butadiene latex prepared by the method has excellent oil resistance, solvent resistance, high and low temperature resistance (resistance of high temperature of -45 DEG C and high temperature of 220 DEG C) and good strength and is quite suitable for manufacturing asbestos or the non-asbestes sheet for a sealing gasket of a vehicle.
Description
Technical field
The invention belongs to technical field of organic synthesis, relate to a kind of preparation method of styrene-butadiene latex, relate in particular to a kind of preparation method of carboxylic styrene butadiene latex, be mainly used in the manufacturing of 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 blending performance and adhesive property and enjoy favor.
At present, the styrene-butadiene latex that asbestos collecting plate industry is used 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, and it is unclear, resident more to copy the back residual water, and polluted-water causes environmental hazard easily.Particularly for the absorption of no fibrous magnesium silicate, existing styrene-butadiene latex is difficult to absorption more, causes parking, can't continuous production.
The asbestos collecting plate also explicitly calls for scope with styrene-butadiene latex to styrene content.Be higher than 35% as the combined styrene amount, then film-forming is slower at normal temperatures for latex, and forms the film of hardened resin character.Too high as styrene content, though can improve resistance to compression and tensile strength, reduced cementability and bending property.When being used for the asbestos collecting plate, styrene content is that 25～35% latex over-all properties is good.
Domestic production asbestos collecting plate is with the method for styrene-butadiene latex, is to be monomer with divinyl, vinylbenzene, and synthetic under multiple promoter effect, auxiliary agent is of a great variety, costs an arm and a leg, and is unfavorable for applying.The external asbestos collecting plate styrene-butadiene latex of producing is to be the polymerization main monomer with divinyl, vinylbenzene, and unsaturated carboxylic acid or esters of unsaturated carboxylic acids are the 3rd function monomer, feeding manner of most employings.Synthetic technology mainly contains 1. pyroprocess: under the low soap composite emulsifying system, 78 ℃～85 ℃ of polymeric reaction temperatures; Emulsification system generally adopts anionic emulsifier, and consumption is higher, is 2.0%～7.0% of monomer total amount substantially, is trending towards adopting macromolecule emulsifier and reactable emulsifying agent at present; 2. middle warm therapy: under high soap composite emulsifying system, 40 ℃～65 ℃ of polymeric reaction temperatures.
Below be the external asbestos collecting plate styrene-butadiene latex main manufacturer of part, the trade mark, basic physical properties index.
The external asbestos collecting plate styrene-butadiene latex main manufacturer of table 1, the trade mark, basic physical properties index
| Main manufacturer | Trade names | Solid content/% | Viscosity/mPa.s | Machine is steady/% | The pH value |
| U.S. Dow | ??LATEX?646 | ??＞48.0 | ??35～60 | ??＜0.2 | ??9～10 |
| U.S. Reichhold | ??Tylac743 | ??＞48.0 | ??＞35 | ??＜0.3 | ??9～10 |
| Germany BASF | ??B4603 | ??＞48.5 | ??＞40 | ??＜0.25 | ??9～10 |
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who is used to make the carboxylic styrene butadiene latex of asbestos or non-asbestos collecting plate.
The preparation method of carboxylic styrene butadiene latex of the present invention, finished by the raw material and the technology of following prescription:
Composition of raw materials: in mass parts
Monomer: 50～70 parts of divinyl, 20～50 parts of vinylbenzene, 1～5 part of unsaturated carboxylic acid, 0～8 part of esters of unsaturated carboxylic acids.
Wherein unsaturated carboxylic acid is in vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, toxilic acid, butyl acrylate, the ethyl propenoate, at least a in the Propylene glycol monoacrylate.Preferable methyl vinylformic acid of the present invention and methylene-succinic acid are composite with 1: 1～2: 1 volume ratio.
Esters of unsaturated carboxylic acids adopts alkyl acrylate.
Emulsifying agent: reactable emulsifying agent and anionic emulsifier, nonionic emulsifying agent are composited with the volume ratio of (1: 1: 1)～(1: 2: 2), and its formula ratio is 1.5～3 parts.
Wherein the reactable emulsifying agent is oleic sodium salt or sylvite; Described anionic emulsifier is sodium salt or sylvite, alkylbenzene sulfonate, alkyl-sulphate or the alkylsulfonate of stearic sodium salt or sylvite, mixed fatty acid; Described nonionic emulsifying agent is alkyl phenylate type or alkyl ether type.
Initiator: water-soluble thermolysis type superoxide, formula ratio is 0.4～1 part.
Water-soluble thermolysis type superoxide mainly adopts ammonium persulphate or Potassium Persulphate.
Molecular weight regulator: sulfur alcohol compound or sulfur alcohol compound and the organic halogen of low molecule are with the composite compound conditioning agent that forms of 1: 3～1: 4 volume ratio, and formula ratio is 0.1～0.8 part.
Wherein sulfur alcohol compound is (t-lauryl mercaptan (tert-dodecyl mercaptan), n-lauryl mercaptan (dodecyl mercaptan carbon); Low molecule Organohalogen compounds are tetracol phenixin.
The pH buffer reagent: subcarbonate, as sodium bicarbonate, yellow soda ash etc., formula ratio is 0.01～0.5 part.
Ionogen: sodium-chlor, Repone K or potassiumphosphate, formula ratio are 0.01～5 part.
Sequestrant: ethylenediamine-N,N'-diacetic acid(EDDA) disodium or tetrasodium ethylenediamine tetraacetate, formula ratio are 0.01～5 part.
Soft water: formula ratio is 100～150 parts.
Technology: drop into part soft water, emulsifying agent, molecular weight regulator and monomer after polymeric kettle vacuumizes respectively, all pH buffer reagents, ionogen and sequestrant, be warmed up to 50～55 ℃ after, add the part initiator, reacted 0.5～2.5 hour; Improve 5～10 ℃ of temperature of reaction, react to transformation efficiency and reach 60 of monomer total amount～90% o'clock, add leftover materials; When transformation efficiency reaches more than 97.0% of monomer total amount, the processing that outgases reaches between 7～9 with alkali lye impregnation breast pH value, cool to 30～50 ℃ after discharging pack.Wherein one section charging capacity is 20～80%.
Described degassing treatment process is: in degassing still, and 40～80 ℃ of temperature, vacuum tightness-0.06～-0.09MPa is following to outgas 1.5～3.0 hours.
The present invention compared with prior art has following substantive distinguishing features and obvious improvement:
1, it is main adopting divinyl, vinylbenzene, and unsaturated carboxylic acid, esters of unsaturated carboxylic acids are the monomer system of assisting, and have improved surface charge intensity, and the consistency of latex and other auxiliary agents is good, and is good to the absorption property of fiber; When preparation asbestos or non-asbestos collecting plate, flowability, water-retentivity, the mechanical stability excellence of the making beating liquid of preparation under shear conditions; Unsaturated carboxylic acid selects for use methacrylic acid to cooperate with methylene-succinic acid, has improved the polymerization stability of latex; Still cheap owing to its price simultaneously, and consumption is little, to the bigger effect that reduced cost.
2, but the composite emulsifying system of employing reactive emulsifier, anionic emulsifier and nonionic emulsifying agent has improved speed of response, greatly reduces the consumption of emulsifying agent, has reduced the consumption of emulsifying agent, has saved cost;
3, be initiator with water-soluble thermolysis type superoxide, its resolvent is water-soluble, need not reductive agent, and avoided the use organo-peroxide to make initiator, its resolvent remains in the glue, the pollution that causes;
4, the way that adopts gradation such as monomer, emulsifying agent, conditioning agent to add had both guaranteed high transformation efficiency, had guaranteed quality product again, had also guaranteed the cinnamic chain that evenly increases simultaneously.
5, adopt potassiumphosphate etc. as special ionogen, be different from prior art Repone K commonly used, satisfy the particular requirement of asbestos collecting plate manufacturing making beating.
6, the compound conditioning agent that adopts the organic halogen of sulfur alcohol compound or sulfur alcohol compound and low molecule to form, chainpropagation is controlled, and the molecular-weight adjusting effect is obvious.
7, replace low temperature polymerization with high temperature polymerization, reduce energy consumption.High temperature polymerization needs heating (polymkeric substance per ton to be needed 6.54 * 10 approximately except that the initial reaction stage material is raised to polymeric reaction temperature by normal temperature
4Kcal) outside, keeping and improving of later temperature of reaction then can be replenished by polymerization reaction heat; Require the expenditure of energy and low temperature polymerization not only drops to polymeric reaction temperature (as 5 ℃) with material by normal temperature, and need remove a large amount of polymerization reaction heats, these two promptly reach 37 * 10
4Kcal;
8, adopt two 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;
9, improve the transformation efficiency of polyreaction, reduced MONOMER RECOVERY and energy expenditure: 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;
10, the carboxy styrene-butadiene rubber emulsion of the present invention's preparation has excellent oil resistant, solvent resistance, and high and low temperature resistance (low temperature can be anti--45 ℃, 220 ℃ of high temperature) and good intensity are fit to automobile sealed pad and use with no asbestos collecting plate manufacturing very much.
Embodiment
Be described further below by preparation, performance and the application in making asbestos or non-asbestos collecting plate thereof of specific embodiment carboxylic styrene butadiene latex of the present invention.
Embodiment one: the production of carboxylic styrene butadiene latex
1, composition of raw materials: in mass parts
Monomer: 62 parts of divinyl, 28 parts of vinylbenzene, 6 parts of methacrylic acids, 3 parts of methylene-succinic acids.
Emulsifying agent: 0.8 part of potassium oleate, 0.8 part of Sodium dodecylbenzene sulfonate, 0.6 part in polyoxyethylene nonylphenol ether, 0.3 part of sodium formaldehyde condensation products.
Initiator: 1.2 parts of Potassium Persulphates.
Molecular weight regulator: 0.4 part of n-dodecyl mercaptan.
The pH buffer reagent: sodium bicarbonate, formula ratio are 0.3 part.
Ionogen: potassiumphosphate, formula ratio are 0.2 part.
Sequestrant: tetrasodium ethylenediamine tetraacetate, formula ratio are 0.4 part.
Soft water: 120 parts.
2, technology:
(1) process that feeds intake: stir at a band, import and export of nitrogen, material import and export, (polymeric kettle at first vacuumizes in the 10L polymeric kettle of thermometric pressure tap and chuck, use nitrogen replacement again, vacuum tightness reaches-during 0.10MPa) drop into 63 parts of soft water in mass successively, (wherein soft water is 10 parts for emulsifier solution, potassium oleate is 0.6 part, 0.6 part of Sodium dodecylbenzene sulfonate, 0.3 part in polyoxyethylene nonylphenol ether, the sodium formaldehyde condensation products is 0.2 part), 0.2 part of potassiumphosphate, 0.3 part of sodium bicarbonate, 0.4 part in EDTA four sodium, totally 0.9 part, 0.2 part of n-dodecyl mercaptan, 12 parts of vinylbenzene, 34 parts of divinyl, 4 parts of methacrylic acids, 2 parts of methylene-succinic acids begin to heat up then; When temperature of reaction reaches 50 ℃, add initiator solution (1 part of Potassium Persulphate, 12 parts of soft water).
(2) reaction is controlled and is added: keep about 2 hours of reaction, improve temperature of reaction to 60 ± 2 ℃, react to polymerisation conversion and reach at 75%～90% o'clock in the monomer total amount, add and add liquid for the second time: 35 parts of soft water, potassium oleate is 0.2 part, 0.2 part of sodium lauryl sulphate, 0.3 part 0.1 part in polyoxyethylene nonylphenol ether, sodium formaldehyde condensation products are 0.1 part, 0.2 part of n-dodecyl mercaptan, 0.2 part of Potassium Persulphate, 16 parts of vinylbenzene, 28 parts of divinyl, 2 parts of methacrylic acids, 1 part of methylene-succinic acid; Be warming up to 65 ± 2 ℃ keep reaction until polymerisation conversion in the monomer total amount greater than 97%.
(3) remove residual monomer and aftertreatment: polymerisation conversion reaches 97% when above in the monomer total amount, stopped reaction, latex is changed in the degassing still, be-0.06 in vacuum tightness～-removing residual monomer under the condition of 60 ℃ of 0.09MPa, still temperature, the degassing time is 1.5～3.0 hours; Slowly add 20% alkali lye (aqueous sodium hydroxide solution) then and regulate pH value to 7～9 for 50 kilograms; Cooling, filtration back packing.
3, the physical index of latex
Total solid substance 49.2% pH value 7.83 viscosity 125mPas surface tension 40mN/m
Particle diameter 189.3nm mechanical stability 0.03% chemical stability 0.04%
Second-order transition temperature-17.2 ℃ structural gel 78.5% macroscopical gel 0.005%
The production of embodiment two, carboxylic styrene butadiene latex
1, composition of raw materials: in mass parts
Monomer: 60 parts of divinyl, 28 parts of vinylbenzene, 6 parts of methacrylic acids, 6 parts of methylene-succinic acids.
Emulsifying agent: 0.8 part of potassium oleate, 0.8 part of Sodium dodecylbenzene sulfonate, 0.6 part in polyoxyethylene nonylphenol ether, 0.3 part of sodium formaldehyde condensation products.
Initiator: 1.2 parts of Potassium Persulphates.
Molecular weight regulator: 0.3 part of uncle's lauryl mercaptan.
The pH buffer reagent: sodium bicarbonate, formula ratio are 0.4 part.
Ionogen: potassiumphosphate, formula ratio are 0.3 part.
Sequestrant: disodium ethylene diamine tetraacetate, formula ratio are 0.3 part.
Soft water: 110 parts.
2, technology:
(1) process that feeds intake: stir at a band, import and export of nitrogen, material import and export, (polymeric kettle at first vacuumizes in the 10L polymeric kettle of thermometric pressure tap and chuck, use nitrogen replacement again, vacuum tightness reaches-during 0.08MPa) drop into 70 parts of soft water in mass successively, (wherein soft water is 10 parts for emulsifier solution, potassium oleate is 0.6 part, 0.6 part of Sodium dodecylbenzene sulfonate, 0.3 part in polyoxyethylene nonylphenol ether, the sodium formaldehyde condensation products is 0.2 part), 0.3 part of potassiumphosphate, 0.4 part of sodium bicarbonate, 0.3 part of EDTA disodium, totally 1.0 parts, 0.2 part of uncle's lauryl mercaptan, 12 parts of vinylbenzene, 30 parts of divinyl, 3 parts of methacrylic acids, 3 parts of methylene-succinic acids begin to heat up then; When temperature of reaction reaches 50 ℃, add initiator solution (1 part of Potassium Persulphate, 12 parts of soft water).
(2) reaction is controlled and is added: keep about 2 hours of reaction, improve temperature of reaction to 60 ± 2 ℃, react to polymerisation conversion and reach at 75%～90% o'clock in the monomer total amount, add and add liquid for the second time: 28 parts of soft water, potassium oleate is 0.2 part, 0.2 part of sodium lauryl sulphate, 0.3 part 0.1 part in polyoxyethylene nonylphenol ether, sodium formaldehyde condensation products are 0.1 part, 0.2 part of n-dodecyl mercaptan, 0.2 part of Potassium Persulphate, 16 parts of vinylbenzene, 22 parts of divinyl, 3 parts of methacrylic acids, 3 parts of methylene-succinic acids; Be warming up to 65 ± 2 ℃ keep reaction until polymerisation conversion in the monomer total amount greater than 97%.
(3) remove residual monomer and aftertreatment: polymerisation conversion reaches 97% when above in the monomer total amount, stopped reaction, latex is changed in the degassing still, remove residual monomer under the condition of vacuum tightness for 60 ℃ of-0.06-0.09MPa, still temperature, the degassing time is 1.5～3.0 hours; Slowly add 20% alkali lye (aqueous sodium hydroxide solution) then and regulate pH value to 7～9 for 50 kilograms; Cooling, filtration back packing.
3, the physical index of latex
Total solid substance 49.4% pH value 8.23 viscosity 154mPas surface tension 47mN/m
Particle diameter 190.6nm mechanical stability 0.01% chemical stability 0.08%
Second-order transition temperature-14.3 ℃ structural gel 86.5% macroscopical gel 0.002%
The production of embodiment three, carboxylic styrene butadiene latex
1, composition of raw materials: in mass parts
Monomer: 64 parts of divinyl, 30 parts of vinylbenzene, 3 parts of methacrylic acids, 3 parts of methylene-succinic acids.
Emulsifying agent: 0.8 part of potassium oleate, 0.8 part of Sodium dodecylbenzene sulfonate, 0.6 part in polyoxyethylene nonylphenol ether, 0.3 part of sodium formaldehyde condensation products.
Initiator: 1.2 parts of Potassium Persulphates.
Molecular weight regulator: 0.38 part of uncle's lauryl mercaptan.
The pH buffer reagent: sodium bicarbonate, formula ratio are 0.37 part.
Ionogen: potassiumphosphate, formula ratio are 0.40 part.
Sequestrant: tetrasodium ethylenediamine tetraacetate, formula ratio are 0.42 part.
Soft water: 115 parts.
2, technology:
(1) process that feeds intake: stir at a band, import and export of nitrogen, material import and export, (polymeric kettle at first vacuumizes in the 10L polymeric kettle of thermometric pressure tap and chuck, use nitrogen replacement again, vacuum tightness reaches-during 0.08MPa) drop into 65 parts of soft water in mass successively, (wherein soft water is 10 parts for emulsifier solution, potassium oleate is 0.6 part, 0.6 part of Sodium dodecylbenzene sulfonate, 0.3 part in polyoxyethylene nonylphenol ether, the sodium formaldehyde condensation products is 0.2 part), 0.40 part of potassiumphosphate, 0.37 part of sodium bicarbonate, 0.42 part in EDTA four sodium, totally 1.19 parts, 0.38 part of uncle's lauryl mercaptan, 18 parts of vinylbenzene, 34 parts of divinyl, 1.5 parts of methacrylic acids, 1.5 parts of methylene-succinic acids begin to heat up then; When temperature of reaction reaches 50 ℃, add initiator solution (1 part of Potassium Persulphate, 12 parts of soft water).
(2) reaction is controlled and is added: keep about 2 hours of reaction, improve temperature of reaction to 60 ± 2 ℃, react to polymerisation conversion and reach at 75%～90% o'clock in the monomer total amount, add and add liquid for the second time: 28 parts of soft water, potassium oleate is 0.2 part, 0.2 part of sodium lauryl sulphate, 0.3 part 0.1 part in polyoxyethylene nonylphenol ether, sodium formaldehyde condensation products are 0.1 part, 0.2 part of n-dodecyl mercaptan, 0.2 part of Potassium Persulphate, 16 parts of vinylbenzene, 22 parts of divinyl, 1.5 parts of methacrylic acids, 1.5 parts of methylene-succinic acids; Be warming up to 65 ± 2 ℃ keep reaction until polymerisation conversion in the monomer total amount greater than 97%.
(3) remove residual monomer and aftertreatment: polymerisation conversion reaches 97% when above in the monomer total amount, stopped reaction, latex is changed in the degassing still, be-0.06 in vacuum tightness～-removing residual monomer under the condition of 60 ℃ of 0.09MPa, still temperature, the degassing time is 1.5～3.0 hours; Slowly add 20% alkali lye (aqueous sodium hydroxide solution) then and regulate pH value to 7～9 for 50 kilograms; Cooling, filtration back packing.
3, the physical index of latex
Total solid substance 48.7% pH value 8.42 viscosity 135mPas surface tension 50mN/m
Particle diameter 180.6nm mechanical stability 0.02% chemical stability 0.06%
Second-order transition temperature-16.7 ℃ structural gel 76.8% macroscopical gel 0.003%
Embodiment four, the carboxylic styrene butadiene latex that adopts present embodiment 1 to produce are made fibrous magnesium silicate and are strengthened latex gasket seal sheet material
Prescription A: in dry mass per-cent
Fibrous magnesium silicate 25.00%
Fibrous sea bubble 20%
Styrene-butadiene latex 25% of the present invention
Zinc oxide 0.20%
Antioxidant D 0.19%
Casein 0.15%
Potassium hydroxide 0.05%
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, promptly get fibrous magnesium silicate and strengthen emulsion gasket seal sheet material.Cure conditions: 125 ℃ of curing temperatures, sulfide stress 6.30MPa, curing time 15 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 | ??8.5 | ??6.20 |
| Rate of compression, % | ??ASTM?F36 | ??22.7 | ??34.6 |
| Rebound degree, % | ??ASTM?F36 | ??49.0 | ??23.8 |
| The creep relaxation rate, % | ??ASTM?F38 | ??26.7 | ??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 | ??2.5 | ??5.5 |
| 30%H2SO4 solution | ??8.2 | ??41.9 |
| 5%NaOH solution | ??3.6 | ??9.8 |
Embodiment five, the carboxylic styrene butadiene latex that adopts present embodiment 1 to produce are made non-asbestos fiber and are strengthened Latex Gasket Sheet Crosslinked sheet material
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 20.00%
Styrene-butadiene latex 25.00% of the present invention
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 and vulcanize, promptly getting does not have fibrous magnesium silicate and strengthens emulsion gasket seal sheet material.Cure conditions: 127 ℃ of curing temperatures, sulfide stress 6.30MPa, curing time 15 minutes.
According to relevant criterion and experimental technique its salient features is detected, and with U.S. Pat P4,387,178 technical parameters contrasts, 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 | ??11.8 | ??6.20 |
| Rate of compression, % | ??ASTM?F36 | ??18.5 | ??34.6 |
| Rebound degree, % | ??ASTM?F36 | ??48.0 | ??23.8 |
| The creep relaxation rate, % | ??ASTM?F38 | ??17.0 | ??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 | ??1.6 | ??5.5 |
| 30%H2SO4 solution | ??5.2 | ??41.9 |
| 5%NaOH solution | ??7.8 | ??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 is crosslinked following, asbestos or the non-asbestos fiber made with the styrene-butadiene latex of the present invention's preparation strengthen emulsion gasket seal sheet material, and its salient features has surmounted the like product of foreign literature report comprehensively.
Claims (10)
1, a kind of preparation method of carboxylic styrene butadiene latex, finished by the raw material and the technology of following prescription:
Composition of raw materials: in mass parts
Monomer: 50～70 parts of divinyl, 20～50 parts of vinylbenzene, 1～5 part of unsaturated carboxylic acid, 0～8 part of esters of unsaturated carboxylic acids;
Emulsifying agent: reactable emulsifying agent and anionic emulsifier, nonionic emulsifying agent are composited with the volume ratio of (1: 1: 1)～(1: 2: 2), and its formula ratio is 1.5～3 parts;
Initiator: water-soluble thermolysis type superoxide, formula ratio is 0.4～1 part;
Molecular weight regulator: the compound conditioning agent that sulfur alcohol compound or sulfur alcohol compound and low molecule Organohalogen compounds are formed, formula ratio is 0.1～0.8 part;
The pH buffer reagent: subcarbonate, formula ratio are 0.01～0.5 part;
Ionogen: sodium-chlor, Repone K or potassiumphosphate, formula ratio are 0.01～5 part;
Sequestrant: ethylenediamine-N,N'-diacetic acid(EDDA) disodium or tetrasodium ethylenediamine tetraacetate, formula ratio are 0.01～5 part;
Soft water: formula ratio is 100～150 parts;
Technology: drop into 20～80% soft water, emulsifying agent, molecular weight regulator and monomer after polymeric kettle vacuumizes respectively, whole pH buffer reagent, ionogen and sequestrant; After being warmed up to 50～55 ℃, add 20～80% initiator, reacted 0.5～2.5 hour; Improve 5～10 ℃ of temperature of reaction, react to transformation efficiency and reach 60 of monomer total amount～90% o'clock, add leftover materials; When transformation efficiency reaches more than 97.0% of monomer total amount, the processing that outgases reaches between 7～9 with alkali lye impregnation breast pH value, cool to 30～50 ℃ after discharging pack.
2, the preparation method of carboxylic styrene butadiene latex according to claim 1, it is characterized in that: described unsaturated carboxylic acid is in vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, toxilic acid, butyl acrylate, the ethyl propenoate, at least a in the Propylene glycol monoacrylate.
3, the preparation method of carboxylic styrene butadiene latex according to claim 1, it is characterized in that: described unsaturated carboxylic acid is that methacrylic acid and methylene-succinic acid are composite with 1: 1～2: 1 volume ratio.
4, the preparation method of carboxylic styrene butadiene latex according to claim 1, it is characterized in that: described esters of unsaturated carboxylic acids is an alkyl acrylate.
5, the preparation method of carboxylic styrene butadiene latex according to claim 1, it is characterized in that: described reactable emulsifying agent is oleic sodium salt or sylvite; Described anionic emulsifier is sodium salt or sylvite, alkylbenzene sulfonate, alkyl-sulphate or the alkylsulfonate of stearic sodium salt or sylvite, mixed fatty acid; Described nonionic emulsifying agent is alkyl phenylate type or alkyl ether type.
6, the preparation method of carboxylic styrene butadiene latex according to claim 1, it is characterized in that: described water-soluble thermolysis type superoxide is ammonium persulphate or Potassium Persulphate.
7, the preparation method of carboxylic styrene butadiene latex according to claim 1, it is characterized in that: described sulfur alcohol compound is tert-dodecyl mercaptan or dodecyl mercaptan carbon.
8, the preparation method of carboxylic styrene butadiene latex according to claim 1, it is characterized in that: described low molecule Organohalogen compounds are tetracol phenixin.
9, the preparation method of carboxylic styrene butadiene latex according to claim 1, it is characterized in that: described sulfur alcohol compound and low molecule Organohalogen compounds are composite with 1: 3～1: 4 volume ratio.
10, the preparation method of carboxylic styrene butadiene latex according to claim 1, it is characterized in that: described 9, the preparation method of carboxylic styrene butadiene latex according to claim 1, it is characterized in that: the treatment process of the degassing described in the technology is: in degassing still, 40～80 ℃ of temperature, vacuum tightness-0.06～-0.09MPa is following to outgas 1.5～3.0 hours.
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