CN103497372A - Production method of PVC (polyvinyl chloride) and NBR (nitrile-butadiene rubber) co-precipitate rubber - Google Patents
Production method of PVC (polyvinyl chloride) and NBR (nitrile-butadiene rubber) co-precipitate rubber Download PDFInfo
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Abstract
The invention relates to a production method of PVC (polyvinyl chloride) and NBR (nitrile-butadiene rubber) co-precipitate rubber, which comprises the steps of sequentially adding soft water, an emulsifier, a dispersing agent, a buffer agent, a molecular weight regulator, a crosslinking agent, acrylonitrile, methacrylic acid, an initiator, a deoxidant, butadiene and an activation phase to perform a polymerization reaction, and supplementing a regulator during the polymerization reaction; finally, adding a composite terminator to terminate the reaction to obtain NBR slurry; adding the NBR slurry, an anti-aging agent, a low-hardness trialkyl ammonium chloride solution with concentration of 1-2%, PVC emulsion, a high-hardness trialkyl ammonium chloride solution with concentration of 0.2-0.4% and a magnesium sulfate or calcium chloride solution into a condensation kettle for sufficient condensation, and then adding a composite separant for cooling to obtain powdery NBR slurry; finally, dehydrating and drying the NBR slurry. The production method provided by the invention has the advantages of simple technology, low cost, low energy consumption and high conversion rate; moreover, the PVC and NBR co-precipitate rubber provided by the invention has good toughness and cold resistance.
Description
Technical field
The present invention relates to the production method of a kind of coprecipitated gel, particularly a kind of PVC and the coprecipitated glue of NBR.
Background technology
In multiple rubble thermoplastics blend, paracril (NBR)/polyvinyl chloride (PVC) blend glue industry (1958) production technology is the most ripe, and manufacturing enterprise is many, and wide application still is widely used so far.Abroad just NBR/PVC has been carried out to a large amount of research since nineteen forty-six, rapidly, range of application progressively enlarges in the Industrialized processing technique development.Domestic NBR/PVC has also been carried out to a large amount of research, in the majority with laboratory study, although also there is more producer to carry out suitability for industrialized production, mainly take NBR glue and PVC powder carries out the method for physical blending as main.The manufacture method of NBR/PVC blend has 3 kinds of latex coprecipitation method, mechanical blending method and solution blended processes.At present, solution blended process does not adopt industrial, commercial NBR/PVC blend is the latex coprecipitation blend basically in the world, due to limited conditions, domestic rubber enterprise is except being used the external latex coprecipitation NBR/PVC blend glue of producing, also utilize Banbury mixer and mill to carry out mechanical blending, and in the majority with the latter.Paracril (NBR) has been the main glue kind of current rubber and plastic with the blend glue of polyvinyl chloride (PVC), be widely used, its major advantage is the ozone resistance of the oil-proofness, crosslinkable and the polyvinyl chloride that have paracril concurrently, has good physical and mechanical properties.Its material of main part PVC source is abundant, cheap, therefore purposes is quite extensive, at the bottom of can be used for fuel hose, electric wire and cable jacket, weather strip for automobile, printing and textile rubber roll and cushion rubber, microporous sponge and frothing heat-insulating layer, boots, the numerous areas such as brake system of car accessory, conveying belt, valve member and pad, synthetic paper, floor tile and floor, separated from petroleum refining original paper, ion-exchange membrane, wooden moulded parts.
Contrast is total to the performance of the NBR/PVC blend glue of cohesion and the production of mechanical blending method, finds that the former has 300% higher stress at definite elongation, tensile strength, tear strength, heat-resistant aging, anti-ozone ageing.Therefore, using latex blend coacervation to produce NBR/PVC blend glue is to select preferably.With the mechanical blending method, compare, it has following advantage: polyvinyl chloride mixes with latex form with paracril, and the mixing of each component is more even, can guarantee the homogeneous of product physicals; Under the prerequisite fix in component, proportioning is identical, co-agglomeration blend glue Mooney viscosity is on the low side, is generally 60～80, is convenient to processing; The molding, granulating of co-agglomeration blend glue, without high-temperature mixing, be conducive to reduce the incipient scorch of sizing material energy-conservation; But serialization is produced in enormous quantities; Held concurrently and produced co-agglomeration blend glue by paracril or Production of PVC producer, be conducive to bring into play the overall efficiency of its production equipment, and greatly facilitate the user, utilize the method to produce the coprecipitated glue of NBR/PVC, step is as follows:
The latex coprecipitation method is one of main method of production Powdered acrylonitrile-butadiene rubber, and its operation comprises: the cohesion synthetic, the coprecipitated glue of NBR/PVC of butadiene-acrylonitrile cement is isolated into dehydrating of powder, the coprecipitated glue slurry of NBR/PVC.
1. butadiene-acrylonitrile cement is synthetic: the powdered nitrile rubber rubber cement for preparing cross-linking type adopts emulsion polymerization technology.Take lipid acid potassium/potassium oleate or synthetic anionic soap (as alkyl-sulphate, alkylaryl sulphonate etc.) as Lanzhou Chemical Industry Company is emulsifying agent, take persulphate as initiator, synthetic mooney viscosity (ML under middle hot conditions
1+4 100 ℃) 90-140, structural gel content 70-85%, the high nitrile rubber in conjunction with nitrile content.The Powdered acrylonitrile-butadiene rubber production process generally all adds buffer reagent, its existence can reduce the surface tension of system, increase the latex particle granularity, improve mobility and the stability of latex, as Lanzhou, chemistry company limited adopts Repone K as buffer reagent, but the industrial potassium chloride quality is unstable, easily can cause rubber powder partially thick, directly affect the grade of product.In addition, the terminator used in prior art only comprises single component, easily causes the product Mooney that makes stable not.
2. the cohesion of the coprecipitated glue of NBR/PVC is isolated into powder: at first, with the aqueous solution of inorganic salt (as sodium-chlor, sal epsom) as flocculation agent, adopt the method for one section cohesion or segmentation cohesion to carry out common cohesion to butadiene-acrylonitrile cement and PVC emulsion, afterwards, with inorganics (light calcium carbonate, talcum powder etc.), organism (stearate, silicone oil etc.) etc. as separant, be isolated into powder, obtain the slurry of Powdered acrylonitrile-butadiene rubber, as be interrupted pre crossbridged nitrile butadiene rubber (NBR-26) latex of low temperature polymerization method production and the RH-II type polyvinyl chloride emulsion that Ge Dian chemical plant, Wuhan produces in the employing Lanzhou Petrochemical Company synthetic rubber plants such as Yang little Yan, use common cohesion process, made NBR/PVC blend glue.The Chen Yao of Beijing University of Chemical Technology front yards etc. are same adopts co-agglomeration to develop to take the polyvinylchloride modifier of paracril as core, the polyvinyl chloride nucleocapsid structure that is shell.Traditional Powdered acrylonitrile-butadiene rubber anti-aging agent is generally 1076,2246, resulting product can be used by longer-term in the air dielectric below 120 ℃, as Lanzhou, chemistry company limited adopts 1076 anti-aging agent as Powdered acrylonitrile-butadiene rubber, but can't guarantee that with this kind of anti-aging agent product is effectively high temperature resistant, can not meet the high request of high temperature resistant brake-shoe for train.
3. dehydrating of the coprecipitated glue slurry of NBR/PVC: adopt centrifuge dehydration, dynamically drying makes Powdered acrylonitrile-butadiene rubber.Be combined to rubber plant as orchid and adopt the fluidizing drying bed drying of carrying out.
Summary of the invention
The object of the present invention is to provide the production method of a kind of PVC and the coprecipitated glue of NBR, production technique of the present invention is simple, and production cost is low, and energy consumption is little, and transformation efficiency is high, and the PVC that utilizes the present invention to produce and the coprecipitated glue of NBR have good toughness and winter hardiness.
Purpose of the present invention is achieved through the following technical solutions, the production method of a kind of PVC and the coprecipitated glue of NBR, and concrete steps are as follows:
(1), with divinyl, vinyl cyanide is the polymerization that monomer carries out butadiene-acrylonitrile cement
Drop into successively soft water, emulsifying agent, diffusant, buffer reagent, molecular weight regulator, linking agent, vinyl cyanide, methacrylic acid, initiator, oxygen scavenger, divinyl and activation phase, be warming up to 25～35 ℃, start to carry out polyreaction; When transformation efficiency reaches 35% and 60%, add respectively conditioning agent; When reaction conversion ratio reaches more than 97%, latex is gone to degassed still, first add compound terminator termination reaction, then add defoamer, continue to be warming up to 68～70 ℃ of boilings to slough unreacted free monomer, obtain butadiene-acrylonitrile cement, the mixing solutions that described compound terminator is diethyl hydroxylamine, oxammonium sulfate, potassium hydroxide and soft water, wherein the mass ratio of diethyl hydroxylamine, oxammonium sulfate, potassium hydroxide and soft water is 4:1:2:70 or 3:2:2:70;
(2) butadiene-acrylonitrile cement and PVC emulsion are jointly condensed and are isolated into powder
Add described butadiene-acrylonitrile cement, anti-aging agent in the cohesion still, be warming up to 50 ℃, add successively again the high rigidity tri alkyl ammomium chloride solution that soft tri alkyl ammomium chloride solution, PVC emulsion, concentration that concentration is 1～2% are 0.2～0.4%, be warming up to 55～65 ℃, then add sal epsom or calcium chloride solution, after rubber cement fully condenses, be warming up to 75 ℃, add compound separant, be cooled to 30～40 ℃, obtain the Powdered acrylonitrile-butadiene rubber slurry; The component proportioning of described anti-aging agent is: the WSL(p-cresol of 80～100 weight parts and the butylation reaction product of double focusing cyclopentadiene), the DLTP(Tyox B of 80～100 weight parts), the stearic acid of 10～15 weight parts, the potassium hydroxide solution that 10～15 weight part concentration are 20%, the soft water of 200～250 weight parts, wherein said stearic acid and the reaction of described potassium hydroxide generate potassium stearate as emulsifying agent, be mixed into the anti-aging agent emulsion with described WSL, DLTP, and use with the form of emulsion;
(3) the Powdered acrylonitrile-butadiene rubber slurry dehydrates
Described Powdered acrylonitrile-butadiene rubber slurry is sent into to the whizzer centrifuge dehydration to water content<40%, when centrifugal, temperature is controlled at below 40 ℃, then with feeding screw, wet feed is sent into to the cyclone drying bed, the drying tower temperature in is 90～120 ℃, material is 3～10 seconds at dwell time in the tower, obtains the Powdered acrylonitrile-butadiene rubber of water content<1.0% through 16 orders and 30 mesh standard sieve separation of material.
Preferably, in step (1), the pressure of described polyreaction is 0.2～0.52MPa.
Preferably, in step (1), the consumption proportion of each raw material is: soft water 180～220 weight parts, emulsifying agent 2-～3 weight parts, diffusant 0.5～1.0 weight part, buffer reagent 0.2～0.5 weight part, molecular weight regulator 1.0～1.5 weight parts, linking agent 0.5～1 weight part, vinyl cyanide is 31.5～37.5 weight parts, methacrylic acid 5～10 weight parts, initiator 0.2～0.3 weight part, oxygen scavenger 0.04 weight part, divinyl is 52～57.5 weight parts, activation is 0.1～0.15 weight part mutually, compound terminator 0.1～0.4 weight part, defoamer 0.05 weight part.
Preferably, described emulsifying agent is Sodium dodecylbenzene sulfonate; Described diffusant is NF; Described buffer reagent is sodium carbonate; Described linking agent is trimethylolpropane tris first acrylate; Described initiator is Potassium Persulphate; Described activation is trolamine mutually; Described defoamer is silicone oil emulsion type defoamer.
Preferably, described molecular weight regulator is tert-dodecyl mercaptan; In step (1), while starting to carry out polyreaction, during transformation efficiency 35%, during transformation efficiency 60%, add respectively 0.35～0.55 weight part, 0.35～0.55 weight part, the described molecular weight regulator of 0.3～0.4 weight part.
Preferably, in step (2), the consumption proportion of each raw material is: butadiene-acrylonitrile cement 100 weight parts, high rigidity tri alkyl ammomium chloride solution 40～65 weight parts, sal epsom or calcium chloride solution 5～6 weight parts, compound separant 3～6 weight parts that soft tri alkyl ammomium chloride solution 50～70 weight parts, PVC emulsion 10～30 weight parts, the concentration that soft water 35～45 weight parts, anti-aging agent 1.0～1.5 weight parts, concentration are 1～2% is 0.2～0.4%.
Preferably, described compound separant is comprised of Zinic stearas emulsion, calcium stearate emulsion and silicone oil, preferred, and the weight ratio of described Zinic stearas emulsion, calcium stearate emulsion, silicone oil is: (20～25): (20～25): (0.5～1).
Preferably, in step (3), described whizzer is horizontal centrifuge.
Compared with prior art, the present invention has following beneficial effect: production technique of the present invention is simple, easy handling, and production cost is low, and energy consumption is little, and transformation efficiency is high, can reach more than 95%; Adopt TriMethylolPropane(TMP) as linking agent, form structural gel, improved the elasticity of product; Adopt the new type compound terminator, Mooney is stable, stops effective; The present invention adds the 3rd monomer methacrylic acid, has introduced carboxyl, improves significantly the processing characteristics of paracril; Improve tear strength, the anti-ozone ageing of paracril; Improve the polarity of butyronitrile molecule, increase the consistency of itself and polyvinyl chloride, resol.The present invention adopts PVC emulsion and NBR rubber cement to condense altogether, and rubber powder is thinner, and has avoided the reunion of rubber powder, has improved the dispersiveness that adds man-hour, has improved ozone resistance, weathering resistance, heat-resistant aging, flame retardant resistance, tensile strength of PNBR etc.; Adopt the polymeric flocculant tri alkyl ammomium chloride to substitute traditional sodium-chlor as flocculation agent, both saved cost, improved again quality product, more improved the feature of environmental protection of production process; Novel anti-aging agent WSL has high reactivity and volatility is very low, adopt WSL and DLTP to be used in conjunction with, stability and the thermotolerance of product have been improved, can be under 130 ℃ life-time service under higher temperature even, there is good toughness and winter hardiness simultaneously, for the PVC modification, can meet the application requiring in weather strip for automobile and door and window sealing strip.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art further to understand the present invention, but not limit in any form the present invention.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make certain adjustments and improvements.These all belong to protection scope of the present invention.
The WSL used in the present invention is produced by europeanized of Yi Li company, and buying is from Guangzhou Shen Yue trade Co., Ltd; The polymerization degree of PVC emulsion is 1000, feature viscosity 1.8, and particle diameter is 0.1～2 μ m, pH=7～9, buying is from Hangzhou Guang He company limited.
embodiment 1
(1) butadiene-acrylonitrile cement is synthetic
At first polymeric kettle is evacuated, drop into successively soft water 205 weight parts, Sodium dodecylbenzene sulfonate 3 weight parts, diffusant methylene radical two is sodium sulfonate 1 weight part how, buffer reagent sodium carbonate 0.2 weight part, molecular weight regulator tert-dodecyl mercaptan 0.55 weight part and trimethylolpropane tris first acrylate 0.5 weight part, stir after 10 minutes, add vinyl cyanide 34 weight parts, initiator potassium persulfate 0.2 weight part and oxygen scavenger 0.04 weight part, inflated with nitrogen vacuumizes and three times repeatedly, add again divinyl 60.5 weight parts, methacrylic acid 5 weight parts and activation be 0.12 weight part mutually, under the reaction pressure of the temperature of reaction of 25～35 ℃ and 0.2～0.52MPa, 17～20 hours reaction times, when transformation efficiency reaches 35%, add molecular weight regulator tert-dodecyl mercaptan 0.55 weight part, when transformation efficiency reaches 60%, add molecular weight regulator tert-dodecyl mercaptan 0.40 weight part, when transformation efficiency reaches 96% when above, add compound terminator 0.4 weight part termination reaction, by the butadiene-acrylonitrile cement of gained 70 ± 2 ℃ of temperature in the kettle and-0.06MPa still internal pressure under, carry out flash liberation 2～3 hours, obtain qualified butadiene-acrylonitrile cement,
Sampling analysis, the performance index of gained butadiene-acrylonitrile cement are: pH value 9.8, mooney viscosity (ML
1+4 100 ℃) 49, total solid substance concentration 31.4%, gel content 13%, bound acrylonitrile content 32.3%;
(2) cohesion of Powdered acrylonitrile-butadiene rubber is isolated into powder
Drop into butadiene-acrylonitrile cement 100 weight parts in the cohesion still, soft water 37.5 weight parts, each 1.44 weight parts of anti-aging agent WSL and DLTP, be warming up to 50 ℃, add successively soft tri alkyl ammomium chloride solution 56 weight parts that concentration is 1～2%, high rigidity tri alkyl ammomium chloride solution 44 weight parts that PVC emulsion 20 weight parts and concentration are 0.2～0.4%, be warming up to 55～65 ℃ after dropwising, add again Adlerika 5 weight parts that concentration is 20%, after treating that rubber cement fully condenses, be warming up to 75 ℃, add compound separant potassium stearate and silicone oil 4 weight parts, stir, finally, be cooled to 30～40 ℃, make the Powdered acrylonitrile-butadiene rubber slurry,
(3) dehydrating of Powdered acrylonitrile-butadiene rubber what slurry:
The Powdered acrylonitrile-butadiene rubber slurry is sent into to the horizontal centrifuge centrifuge dehydration, when centrifugal, temperature will be controlled at below 40 ℃, to water content<40%, then with feeding screw, wet feed is sent into to the cyclone drying bed, the drying tower temperature in is 90-120 ℃, material is 3-10 second at dwell time in the tower, obtains the Powdered acrylonitrile-butadiene rubber of water content<1.0% through 16 orders, 30 mesh standard sieve separation of material;
Sampling analysis, the indices of gained Powdered acrylonitrile-butadiene rubber is: white powder, tasteless, particle diameter in the 0.6-1.25mm scope account for 5.7%, Li Jing<=0.6mm account for 94.3%, water content is 0.84%.
embodiment 2
By in the synthesis step of butadiene-acrylonitrile cement in embodiment 1, add soft water 210 weight parts, emulsifying agent Sodium dodecylbenzene sulfonate 3 weight parts, vinyl cyanide 33 weight parts, divinyl 61.5 weight parts, trimethylolpropane tris first acrylate 0.5 weight part and methacrylic acid 5 weight parts, other technical recipes are same as embodiment 1;
The performance index of gained butadiene-acrylonitrile cement are: pH value 6.6, mooney viscosity (ML
1+4 100 ℃) 50, total solid substance concentration 30.8%, gel content 15%, bound acrylonitrile content 31.8%;
After being isolated into powder and dehydrating, the products obtained therefrom index is in the span of control shown in table 2.
embodiment 3
By in the synthesis step of butadiene-acrylonitrile cement in embodiment 1, add soft water 210 weight parts, emulsifying agent Sodium dodecylbenzene sulfonate 3 weight parts, vinyl cyanide 33 weight parts, divinyl 56.5 weight parts, trimethylolpropane tris first acrylate 0.5 weight part, methacrylic acid 10 weight parts, other technical recipes are same as embodiment 1;
The performance index of gained butadiene-acrylonitrile cement are: pH value 5.5, mooney viscosity (ML
1+4 100 ℃) 41, total solid substance concentration 30.9%, gel content 10.2%, bound acrylonitrile content 31.3%;
After being isolated into powder and dehydrating, the products obtained therefrom index is in the span of control shown in table 2.
embodiment 4
By in the synthesis step of butadiene-acrylonitrile cement in embodiment 1, add the compound terminator of 0.3 weight part (mixing solutions of diethyl hydroxylamine, oxammonium sulfate, potassium hydroxide and soft water, its mass ratio is 3:2:2:70), other technical recipes are with embodiment 1;
The performance index of gained butadiene-acrylonitrile cement are: pH value 6.2, mooney viscosity (ML
1+4 100 ℃) 54, total solid substance concentration 30.7%, gel content 17%, bound acrylonitrile content 32.6%;
After being isolated into powder and dehydrating, the products obtained therefrom index is in the span of control shown in table 2.
embodiment 5
By in the synthesis step of butadiene-acrylonitrile cement in embodiment 1, add diffusion dosage 0.5 weight part, buffer reagent 0.5 weight part, molecular weight regulator 1.2 weight parts (to react and initially add 0.45 weight part, transformation efficiency 35% adds 0.45 weight part, transformation efficiency 60% adds 0.3 weight part), initiator 0.3 weight part, other technical recipes are with embodiment 1;
The performance index of gained butadiene-acrylonitrile cement are: pH value 5.7, mooney viscosity (ML
1+4 100 ℃) 57, total solid substance concentration 30.7%, gel content 19%, bound acrylonitrile content 32.9%;
After being isolated into powder and dehydrating, the products obtained therefrom index is in the span of control shown in table 2.
embodiment 6
Powdered rubber cohesion in embodiment 1 is isolated in the powder step, and the divalent metal salt of flocculation agent changes 6 weight part calcium chloride into, and other technical recipes are with embodiment 1;
After dehydrating, the indices of gained Powdered acrylonitrile-butadiene rubber is: white powder, tasteless, particle diameter in the 0.6-1.25mm scope account for 7.4%, Li Jing<=0.6mm account for 92.6%, water content is 0.86%, in the span of control shown in table 2.
embodiment 7
Powdered rubber cohesion in embodiment 1 is isolated in the powder step, adds PVC emulsion 30 weight parts, other technical recipes are with embodiment 1;
After dehydrating, the indices of gained Powdered acrylonitrile-butadiene rubber is: white powder, tasteless, particle diameter in the 0.6-1.25mm scope account for 9.4%, Li Jing<=0.6mm account for 97.6%, water content is 0.97%, in the span of control shown in table 2.
embodiment 8
Powdered rubber cohesion in embodiment 1 is isolated in the powder step, and adding the soft tri alkyl ammomium chloride solution that concentration is 1-2% is 50 weight parts, and other technical recipes are with embodiment 1;
After dehydrating, the indices of gained Powdered acrylonitrile-butadiene rubber is: white powder, and tasteless, particle diameter in the 0.6-1.25mm scope account for 9.4%, Li Jing<=0.6mm account for 93.6%, water content is 0.97%, isolation effect is better, in the span of control shown in table 2.
embodiment 9
Powdered rubber cohesion in embodiment 1 is isolated in the powder step, and compound separant increases to 4 weight parts by 3 weight parts, and other technical recipes are with embodiment 1;
After dehydrating, the indices of gained Powdered acrylonitrile-butadiene rubber is: white powder, tasteless, particle diameter in the 0.6-1.25mm scope account for 3.2%, Li Jing<=0.6mm account for 96.2%, water content is 0.92%, in the span of control shown in table 2.
the evaluation of implementation result
The butadiene-acrylonitrile cement performance index that above-described embodiment obtains are as shown in table 1 below, and the indices of the resulting Powdered acrylonitrile-butadiene rubber of above-described embodiment is as shown in table 2.
Table 1
| PH value 5-7 | Mooney viscosity (ML 1+4 100℃）40-60 | Total solid substance concentration 30-32% |
| Gel content 10-20% | Bound acrylonitrile content 30-33% | ? |
Table 2
| Carefully | Particle diameter 0.6-1.25mm | 5-10％? | Outward appearance and smell: | White powder, tasteless |
| Degree | Li Jing<=0.6mm | ≧90％ | Water content: | <1.0% |
Above specific embodiments of the invention are described.It will be appreciated that, the present invention is not limited to above-mentioned specific implementations, and those skilled in the art can make various distortion or modification within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (9)
1. the production method of a PVC and the coprecipitated glue of NBR is characterized in that: comprise following concrete steps:
(1), with divinyl, vinyl cyanide is the polymerization that monomer carries out butadiene-acrylonitrile cement
Drop into successively soft water, emulsifying agent, diffusant, buffer reagent, molecular weight regulator, linking agent, vinyl cyanide, methacrylic acid, initiator, oxygen scavenger, divinyl and activation phase, be warming up to 25～35 ℃, start to carry out polyreaction; When transformation efficiency reaches 35% and 60%, add respectively conditioning agent; When reaction conversion ratio reaches more than 97%, latex is gone to degassed still, first add compound terminator termination reaction, then add defoamer, continue to be warming up to 68～70 ℃ of boilings to slough unreacted free monomer, obtain butadiene-acrylonitrile cement, the mixing solutions that described compound terminator is diethyl hydroxylamine, oxammonium sulfate, potassium hydroxide and soft water, wherein the mass ratio of diethyl hydroxylamine, oxammonium sulfate, potassium hydroxide and soft water is 4:1:2:70 or 3:2:2:70;
(2) butadiene-acrylonitrile cement and PVC emulsion are jointly condensed and are isolated into powder
Add described butadiene-acrylonitrile cement, anti-aging agent in the cohesion still, be warming up to 50 ℃, add successively again the high rigidity tri alkyl ammomium chloride solution that soft tri alkyl ammomium chloride solution, PVC emulsion, concentration that concentration is 1～2% are 0.2～0.4%, be warming up to 55～65 ℃, then add sal epsom or calcium chloride solution, after rubber cement fully condenses, be warming up to 75 ℃, add compound separant, be cooled to 30～40 ℃, obtain the Powdered acrylonitrile-butadiene rubber slurry; The component proportioning of described anti-aging agent is: the potassium hydroxide solution that the DLTP of the WSL of 80～100 weight parts, 80～100 weight parts, the stearic acid of 10～15 weight parts, 10～15 weight part mass body volume concentrations are 20%, the soft water of 200～250 weight parts, wherein said stearic acid and the reaction of described potassium hydroxide generate potassium stearate as emulsifying agent, be mixed into the anti-aging agent emulsion with described WSL, DLTP, and use with the form of emulsion;
(3) the Powdered acrylonitrile-butadiene rubber slurry dehydrates
Described Powdered acrylonitrile-butadiene rubber slurry is sent into to the whizzer centrifuge dehydration to water content<40%, when centrifugal, temperature is controlled at below 40 ℃, then with feeding screw, wet feed is sent into to the cyclone drying bed, the drying tower temperature in is 90～120 ℃, material is 3～10 seconds at dwell time in the tower, obtains the Powdered acrylonitrile-butadiene rubber of water content<1.0% through 16 orders and 30 mesh standard sieve separation of material.
2. the production method of PVC according to claim 1 and the coprecipitated glue of NBR, is characterized in that, in step (1), the pressure of described polyreaction is 0.2～0.52MPa.
3. the production method of PVC according to claim 1 and the coprecipitated glue of NBR, it is characterized in that, in step (1), the consumption proportion of each raw material is: soft water 180～220 weight parts, emulsifying agent 2-～3 weight parts, diffusant 0.5～1.0 weight part, buffer reagent 0.2～0.5 weight part, molecular weight regulator 1.0～1.5 weight parts, linking agent 0.5～1 weight part, vinyl cyanide is 31.5～37.5 weight parts, methacrylic acid 5～10 weight parts, initiator 0.2～0.3 weight part, oxygen scavenger 0.04 weight part, divinyl is 52～57.5 weight parts, activation is 0.1～0.15 weight part mutually, compound terminator 0.1～0.4 weight part, defoamer 0.05 weight part.
4. according to the production method of the described PVC of claim 1 or 3 and the coprecipitated glue of NBR, it is characterized in that, described emulsifying agent is Sodium dodecylbenzene sulfonate; Described diffusant is NF; Described buffer reagent is sodium carbonate; Described linking agent is trimethylolpropane tris first acrylate; Described initiator is Potassium Persulphate; Described activation is trolamine mutually; Described defoamer is silicone oil emulsion type defoamer.
5. according to the production method of the described PVC of claim 1 or 3 and the coprecipitated glue of NBR, it is characterized in that, described molecular weight regulator is tert-dodecyl mercaptan; In step (1), while starting to carry out polyreaction, during transformation efficiency 35%, during transformation efficiency 60%, add respectively 0.35～0.55 weight part, 0.35～0.55 weight part, the described molecular weight regulator of 0.3～0.4 weight part.
6. the production method of PVC according to claim 1 and the coprecipitated glue of NBR, it is characterized in that, in step (2), the consumption proportion of each raw material is: high rigidity tri alkyl ammomium chloride solution 40～65 weight parts, sal epsom or calcium chloride solution 5～6 weight parts, compound separant 3～6 weight parts that soft tri alkyl ammomium chloride solution 50～70 weight parts, PVC emulsion 10～30 weight parts, the concentration that butadiene-acrylonitrile cement 100 weight parts, soft water 35～45 weight parts, anti-aging agent 1.0～1.5 weight parts, concentration are 1～2% is 0.2～0.4%.
7. according to the production method of the described PVC of claim 1 or 6 and the coprecipitated glue of NBR, it is characterized in that, described compound separant is comprised of Zinic stearas emulsion, calcium stearate emulsion and silicone oil.
8. the production method of PVC according to claim 7 and the coprecipitated glue of NBR, is characterized in that, the weight ratio of described Zinic stearas emulsion, calcium stearate emulsion, silicone oil is: (20～25): (20～25): (0.5～1).
9. the production method of PVC according to claim 1 and the coprecipitated glue of NBR, it is characterized in that: in step (3), described whizzer is horizontal centrifuge.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105038074A (en) * | 2015-05-28 | 2015-11-11 | 安徽同丰橡塑工业有限公司 | Agglomeration graft modified powder nitrile butadiene rubber preparation method |
| CN107189133A (en) * | 2017-07-12 | 2017-09-22 | 宁国市天瑞橡塑零部件有限公司 | A kind of y-type seal ring and its production technology |
| CN107880444A (en) * | 2017-11-24 | 2018-04-06 | 孙荣华 | NBR, PVC blending formula |
| CN113861325A (en) * | 2021-10-25 | 2021-12-31 | 安徽华塑股份有限公司 | Preparation process of polyvinyl chloride resin for PVC soft product production |
| CN114380949A (en) * | 2020-10-21 | 2022-04-22 | 中国石油天然气股份有限公司 | Nitrile rubber and preparation method and application thereof |
| CN114380948A (en) * | 2020-10-21 | 2022-04-22 | 中国石油天然气股份有限公司 | Nitrile rubber and preparation method and application thereof |
| CN114773500A (en) * | 2022-03-23 | 2022-07-22 | 广东金发科技有限公司 | Butyronitrile glove coagulant, and preparation method and application thereof |
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| US4065426A (en) * | 1975-07-16 | 1977-12-27 | Mitsubishi Chemical Industries, Ltd. | Method for the preparation of powdered rubber |
| CN103254359A (en) * | 2013-01-28 | 2013-08-21 | 安庆华兰科技有限公司 | Production method of powder acrylonitrile butadiene rubber for oil resistance product and soft friction material modification |
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| US4065426A (en) * | 1975-07-16 | 1977-12-27 | Mitsubishi Chemical Industries, Ltd. | Method for the preparation of powdered rubber |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105038074A (en) * | 2015-05-28 | 2015-11-11 | 安徽同丰橡塑工业有限公司 | Agglomeration graft modified powder nitrile butadiene rubber preparation method |
| CN107189133A (en) * | 2017-07-12 | 2017-09-22 | 宁国市天瑞橡塑零部件有限公司 | A kind of y-type seal ring and its production technology |
| CN107880444A (en) * | 2017-11-24 | 2018-04-06 | 孙荣华 | NBR, PVC blending formula |
| CN114380949A (en) * | 2020-10-21 | 2022-04-22 | 中国石油天然气股份有限公司 | Nitrile rubber and preparation method and application thereof |
| CN114380948A (en) * | 2020-10-21 | 2022-04-22 | 中国石油天然气股份有限公司 | Nitrile rubber and preparation method and application thereof |
| CN114380948B (en) * | 2020-10-21 | 2024-03-01 | 中国石油天然气股份有限公司 | Nitrile rubber and preparation method and application thereof |
| CN114380949B (en) * | 2020-10-21 | 2024-03-01 | 中国石油天然气股份有限公司 | Nitrile rubber and preparation method and application thereof |
| CN113861325A (en) * | 2021-10-25 | 2021-12-31 | 安徽华塑股份有限公司 | Preparation process of polyvinyl chloride resin for PVC soft product production |
| CN114773500A (en) * | 2022-03-23 | 2022-07-22 | 广东金发科技有限公司 | Butyronitrile glove coagulant, and preparation method and application thereof |
| CN114773500B (en) * | 2022-03-23 | 2023-10-31 | 广东金发科技有限公司 | Butyronitrile glove coagulant and preparation method and application thereof |
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