CN100475870C - Low content nitrile cross-linked powdery acrylonitrile butadiene preparation method - Google Patents
Low content nitrile cross-linked powdery acrylonitrile butadiene preparation method Download PDFInfo
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- CN100475870C CN100475870C CNB2005100711061A CN200510071106A CN100475870C CN 100475870 C CN100475870 C CN 100475870C CN B2005100711061 A CNB2005100711061 A CN B2005100711061A CN 200510071106 A CN200510071106 A CN 200510071106A CN 100475870 C CN100475870 C CN 100475870C
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Abstract
The invention discloses a manufacturing method of cross linking powder butadiene acrylonitrile rubber with low acrylonitrile content, which is characterized by the following: adopting aliphatic potassium or sodium and potassium or sodium oleate as compound emulsifier to produce butadiene acrylonitrile rubber slurry through polymerization emulsion with 20-20 percent combination acrylic nitrile content; using 8-10 pH value saturated NaCl solution as coagulant, polymer resin emulsion-inorganic separant (lightweight CaCO3)-organic separant(potassium oleate)as composite separant to proceed agglomeration separation powdered reaction for butadiene acrylonitrile rubber slurry at 30-65 deg.c. The invention is easy to operate to produce stable index product, which satisfies the appliance need of resin and abrasion material.
Description
Technical field
The present invention relates to the production method of a kind of production method of Powdered acrylonitrile-butadiene rubber, particularly a kind of low content nitrile cross-linked powdery acrylonitrile butadiene
Background technology
Powdered acrylonitrile-butadiene rubber not only has the superiority of processing aspect, also is widely used in the modification aspect of plastics, resin and abrasives.Aspect resin modified, it can improve performances such as the oil resistant of goods, wear-resisting, resistance to impact shock greatly.
At present, the production method of Powdered acrylonitrile-butadiene rubber mainly contains two big classes: the first kind is to be the mechanical crushing method and the low temperature mechanical crushing method method of raw material with block paracril.This method energy consumption is big, and particle is thick, is used for giving up, old rubber utilizes again more.Second class is to be four kinds of the desiccating method, co-agglomeration, polymerization of raw material and cohesion desiccating methods with latex.Polymerization is still immature.Its excess-three kind method all needs to be converted into rubber grain to rubber cement, with separant isolate, drying.Using now is the cohesion desiccating method more widely.This method technological process roughly is:
The cohesion desiccating method is one of main method of production Powdered acrylonitrile-butadiene rubber, and its operation comprises: the cohesion synthetic, butadiene-acrylonitrile cement of butadiene-acrylonitrile cement is isolated into dehydrating of powder, Powdered acrylonitrile-butadiene rubber slurry.1. butadiene-acrylonitrile cement is synthetic: the powdered nitrile rubber rubber cement of preparation cross-linking type adopts emulsion polymerization technology.Is emulsifying agent as Lanzhou chemical industrial company with lipid acid potassium and potassium oleate, is initiator with the persulphate, under middle hot conditions, and synthetic mooney viscosity ML
1+4 100 ℃90～140, structural gel content 70～85%, the nitrile rubber that bound acrylonitrile content is high.2. the cohesion of butadiene-acrylonitrile cement is isolated into powder: at first, the aqueous solution of using inorganic salt is (as NaCl, CaCl
2, MgSO
4) as flocculation agent, adopt the method for one section cohesion or segmentation cohesion that rubber cement is condensed, adopt the method for carrying out two sections cohesions that the rubber cement of high-nitrile cross-linking type is condensed with monovalence and divalent metal salt as Synthetic Rubber Factory, Lanzhou Chemical Industry Corp; The MgSO of U.S. B.F.Goodrich company
4And Al
2(SO
4)
3Mixing solutions at 60 ℃ butadiene-acrylonitrile cement is condensed; Japan Japan Cao Da industrial adds 1～25 part of sodium dodecyl sulfate solution in latex, add CaCl then
2Solution casting makes Powdered acrylonitrile-butadiene rubber.Afterwards, as separant, be isolated into powder, obtain the slurry of Powdered acrylonitrile-butadiene rubber with inorganics (as light calcium carbonate, talcum powder etc.), organism (as stearate, silicone oil etc.) or superpolymer (as polyvinyl chloride, polystyrene etc.).The Zinic stearas that adds 1～10 part of wet pasty state as U.S. B.F.Goodrich company is isolated into powder; Synthetic Rubber Factory, Lanzhou Chemical Industry Corp adopts stearate to be isolated into powder, obtains the slurry of Powdered acrylonitrile-butadiene rubber; South China Science ﹠ Engineering University adopts organic coating to be isolated into powder.3. dehydrating of Powdered acrylonitrile-butadiene rubber slurry: adopt centrifuge dehydration, dynamically drying makes Powdered acrylonitrile-butadiene rubber.Adopt the fluidizing drying bed drying of carrying out as Lan Hua company synthetic rubber plant.
Technology of preparing from low content nitrile powder process end paracril at first will adopt emulsion polymerization technology to synthesize the butadiene-acrylonitrile cement of low content nitrile, high-crosslinking-degree; Next is with inorganic flocculant this butadiene-acrylonitrile cement to be condensed, and with inorganic, organic or superpolymer separant powder particle is isolated antiseizedly again, adopts dynamic drying plant to carry out drying at last.
Summary of the invention
The object of the present invention is to provide a kind of production method that satisfies plastics, resin and friction materials modification with low content nitrile, cross-linked powdery shape paracril.
The invention provides a kind of production method of low content nitrile cross-linked powdery acrylonitrile butadiene, at first carry out the synthetic of butadiene-acrylonitrile cement, then butadiene-acrylonitrile cement is condensed and be isolated into powder, dehydrate at last and obtain, it is characterized in that with divinyl, vinyl cyanide be monomer, in total monomer weight is 100 parts, and wherein 22～35 parts of vinyl cyanide, 65～78 parts of divinyl are that compound emulsifying agent obtains butadiene-acrylonitrile cement through letex polymerization with fatty acids potassium or sodium and potassium oleate or sodium; With pH value 8～10 saturated NaCl solution is flocculation agent, with fluoropolymer resin emulsion-inorganic separant (as lightweight CaCO
3)-organic separant (as potassium oleate) is isolated into powder for compound separant condenses butadiene-acrylonitrile cement under 30～65 ℃; Dehydrating the Powdered acrylonitrile-butadiene rubber slurry at last.Wherein the fluoropolymer resin emulsion can be high-phenylethylene content styrene-butadiene polymer emulsion, polystyrene emulsion, polyvinyl chloride (PVC) RESINS emulsion etc., mainly be have coating, buffer action gets final product, what effect was best is that styrene content is the high-phenylethylene content styrene-butadiene polymer emulsion more than 70%.Inorganic separant can use inorganic separant such as lightweight CaCO commonly used in the powdered rubber technology
3, talcum powder etc., preferred lightweight CaCO
3, organic separant is meant fatty acid soaps, and is concrete as potassium oleate, potassium stearate etc. as lipid acid potassium, preferred potassium oleate.Triplicity makes the butadiene-acrylonitrile cement after the cohesion better be isolated into powder.
Concretely, the technology of the present invention's employing is divided into and is three parts: at first carry out the synthetic of butadiene-acrylonitrile cement; Then butadiene-acrylonitrile cement is condensed and be isolated into powder; Dehydrate at last.Concrete steps are as follows:
1) butadiene-acrylonitrile cement is synthetic
The present invention is a monomer with divinyl, vinyl cyanide, is 100 parts (as follows) in total monomer weight, and wherein 22～35 parts of vinyl cyanide, 65～78 parts of divinyl are that compound emulsifying agent obtains through letex polymerization with fatty acids potassium or sodium, potassium oleate or sodium.
In letex polymerization, preferably add diffusant such as diffusion agent N F (sodium metnylene bis-naphthalene sulfonate), preferably 0.3～1.0 part of add-on, other condition in the letex polymerization is not limited, as can being that successive polymerization also can be a batchwise polymerization, it can be general peroxide initiator such as Potassium Persulphate that molecular weight regulator can adopt general molecular weight regulator such as tert-dodecyl mercaptan, initiator, it also can be di-isopropylbenzene hydroperoxide-ferrous sulfate etc., terminator can be general terminator, as Sodium Dimethyldithiocarbamate etc.The adding mode of monomer and auxiliary agent thereof is not limited yet, and can adopt disposable input, under 25～50 ℃ (initiator is a Potassium Persulphate) or 5～8 ℃ of (initiator is di-isopropylbenzene hydroperoxide-ferrous sulfate) conditions, and synthetic butadiene-acrylonitrile cement.Outside the demonomerization proportioning of the present invention, mainly limiting butadiene-acrylonitrile cement is to adopt the mode of letex polymerization to obtain, and employed emulsifying agent is the compound emulsifying agent of fatty acids potassium or sodium and potassium oleate or sodium.Preferably 3～6 parts of the add-ons of compound emulsifying agent, the mass ratio of lipid acid potassium or sodium and potassium oleate or sodium is preferably 0.2～1: 0.3～1.
The physical index of the butadiene-acrylonitrile cement the best that is obtained is: pH value 9～11, mooney viscosity (ML
1+4 100 ℃) 90～140, structural gel 70～85% (quality), bound acrylonitrile content 20～33% (quality).
The present invention also provides best synthetic set of dispense ratio: 3～6 parts in 160～200 parts in water, lipid acid potassium or sodium-potassium oleate or sodium, 0～1.0 part of diffusion agent N F, 0.4～0.7 part of molecular weight regulator, 22～35 parts of vinyl cyanide, 65～78 parts of divinyl, 0.3～0.5 part of initiator, 0.1～0.3 part of terminator.
The present invention also provides best synthesis process: the composite solution, molecular weight regulator, vinyl cyanide, the divinyl that drop into soft water, lipid acid potassium or sodium, potassium oleate or sodium and diffusion agent N F in proportion successively.When initiator is Potassium Persulphate, add initiator when being warming up to 25～30 ℃, begin reaction, when reaching 60%, improves transformation efficiency temperature of reaction to 45～50 ℃; When initiator is di-isopropylbenzene hydroperoxide-ferrous sulfate, under 5～8 ℃ of conditions, add initiator, carry out polyreaction.Reaction conversion ratio reaches more than 95%, adds terminator Sodium Dimethyldithiocarbamate termination reaction.Butadiene-acrylonitrile cement is sent into degassing still and is removed unreacted monomer.Sampling analysis pH value, mooney viscosity, bound acrylonitrile content, structural gel content.
2) cohesion of butadiene-acrylonitrile cement is isolated into powder
With pH value 8～10 saturated NaCl solution is flocculation agent, with fluoropolymer resin emulsion (as high-phenylethylene content styrene-butadiene polymer emulsion, polystyrene emulsion)-inorganic separant (lightweight CaCO
3, talcum powder)-organic separant (potassium oleate, potassium stearate) is compound separant, under 30～65 ℃, butadiene-acrylonitrile cement condensed to be isolated into powder.
Condense when being isolated into powder at butadiene-acrylonitrile cement, can in butadiene-acrylonitrile cement, add general anti-aging agent as 1076 (β-3,5-di-t-butyl-4-hydroxy-propionic acid 18 sulphonates), 2264 (2,2 '-methylene bis (4-methyl-6 tertiary butyl-4 cresols) etc., anti-aging agent also can add in the butadiene-acrylonitrile cement that the degassing is handled.After flocculation agent adds, add divalent metal salt such as sal epsom, calcium chloride etc. again.
In 100 parts of butadiene-acrylonitrile cement (amounting to dried glue) quality, best butadiene-acrylonitrile cement cohesion provided by the invention is isolated the set of dispense ratio and is: 11～28 parts of the solution of 100 parts of rubber cements, 0.5～1.5 part in anti-aging agent, 250～400 parts in flocculation agent, divalent salts 0～9 part (preferably 3～9 parts), compound separants.
The present invention is a flocculation agent with pH value 8～10 saturated NaCl solution, the pH value that can transfer saturated NaCl solution with alkaline matters such as sodium hydroxide, potassium hydroxide, yellow soda ash; Fluoropolymer resin emulsion (as high-phenylethylene content styrene-butadiene polymer emulsion, polystyrene emulsion)-inorganic separant (lightweight CaCO
3, talcum powder)-mixture of organic separant (as potassium oleate, potassium stearate) is a separant.Its weight proportion is preferably the fluoropolymer resin emulsion: inorganic separant: organic separant=2～5: 2～5: 1～3.Divalent salt solutions is Adlerika preferably, butadiene-acrylonitrile cement is condensed be isolated into powder.
The technological process that the present invention recommends is: add butadiene-acrylonitrile cement, anti-aging agent in the cohesion still, be warming up to 35～45 ℃, add flocculation agent, be warming up to 55～65 ℃ afterwards, add the divalent metal salts solution, rubber cement is fully condensed after, add compound separant again, stir; At last, be cooled to 20～25 ℃, prepare the slurry of Powdered acrylonitrile-butadiene rubber.
3) the Powdered acrylonitrile-butadiene rubber slurry dehydrates
The drying of Powdered acrylonitrile-butadiene rubber is preferably selected dynamic exsiccant mode for use, and dynamically drying can adopt expansion drying, fluidized drying etc.The technological process that the present invention recommends: the Powdered acrylonitrile-butadiene rubber slurry is sent into horizontal centrifuge carry out the first-stage centrifugal dehydration, Powdered acrylonitrile-butadiene rubber wet-milling (water content＜40%) is sent into rinse bath washing and is sent into horizontal centrifuge after 60～90 minutes and carry out secondary centrifuge dehydration (water content＜40%), the paracril wet-milling is sent into spiral flash distillation dryer (the drying tower temperature in is 120～150 ℃) with feeding screw and is carried out drying, material is 3～10s at dwell time in the tower, obtains the Powdered acrylonitrile-butadiene rubber of water content＜1.0% through 16 orders, 40 mesh standard sieve separation of material.The paracril wet-milling also can be with the fluidizing drying bed drying of carrying out, and drying temperature is 80-90 ℃.
Use the preparation method of low content nitrile cross-linked powdery acrylonitrile butadiene of the present invention, technology is simple, easy handling, and the butadiene-acrylonitrile cement performance index that make are stable, the aggregation efficiency height, isolation effect is good, the drying efficiency height, the Powdered acrylonitrile-butadiene rubber powder formation rate can reach more than 95%.Powdered acrylonitrile-butadiene rubber can satisfy the application requiring of resin and abrasives.Used butadiene-acrylonitrile cement performance index and use the every index of Powdered acrylonitrile-butadiene rubber that method of the present invention obtains and see the following form.
Table 1 butadiene-acrylonitrile cement performance index
The every index of table 2 Powdered acrylonitrile-butadiene rubber
Embodiment
Analysis, testing method and raw material sources:
1. mooney viscosity: referring to GB1232-92
2. structural gel content: referring to SH/T1050-91
3. bound acrylonitrile content: rower SH/T1503-92
4. trade(brand)name: high benzene styrene-butadiene resin emulsion: index: styrene content＞70%, total solid substance concentration 34%～36% provides producer: Lan Hua company
5. lightweight CaCO
3: (its leading indicator: CaCO
3Content 98%; PH is 9.0～10.5; Fugitive constituent＜0.7%; Insolubles＜0.2%; Settling volume 〉=2.6L/g provides producer: sky, Ningxia power company limited
6. anti-aging agent 1076,2264: producer is provided: Nanjing steps and reaches chemical Industrial Co., Ltd.
Embodiment 1
A: butadiene-acrylonitrile cement preparation: at first polymeric kettle is vacuumized, drop into 180 parts of soft water successively, lipid acid potassium-5 parts of its proportionings of potassium oleate compound emulsifying agent 1: 0.5,0.6 part of diffusion agent N F, 0.5 part of tert-dodecyl mercaptan, 28 parts of vinyl cyanide, 0.4 part of initiator (Potassium Persulphate), stop to vacuumize, add 72 parts of divinyl; Be warming up to 29 ± 1 ℃, when transformation efficiency reaches 60%, be warming up to 47 ± 1 ℃, when transformation efficiency reaches more than 95%, add 0.2 part of termination reaction of Sodium Dimethyldithiocarbamate, rubber cement is sent into degassing still flash distillation and is removed unreacted divinyl, vinyl cyanide, and its flash liberation condition is: 60～70 ℃ of temperature, vacuum tightness-0.04～-0.06MPa, degassing time are 2～3hr.
The every index of gained rubber cement is as follows:
Solid content: 35.6%; PH value: 10.7 structural gel content: 78%;
Mooney viscosity (ML
1+4 100 ℃): 125; Bound acrylonitrile: 26.2%
B: the butadiene-acrylonitrile cement cohesion is isolated into powder: drop into 100 parts of rubber cements, (1076) 0.6 parts in anti-aging agent in the cohesion still; Fully mix, be warming up to 40～45 ℃, 340 parts of the saturated NaCl solution of adding flocculation agent pH=9; Be warming up to 60 ± 1 ℃, add 30%MgSO
46 parts of solution; (it consists of: high-phenylethylene content styrene-butadiene polymer emulsion: lightweight CaCO to add 11 portions of compound separants
3: potassium oleate: water=5: 5: 3: 30), dispersed with stirring is even.
C: the dehydrating of Powdered acrylonitrile-butadiene rubber slurry: slurry dewaters through first-stage centrifugal, the humidity of Powdered acrylonitrile-butadiene rubber＜40%, the water agitator treating that adds 3 times of its quality 80 minutes, again its mixture is squeezed into the secondary centrifuge dewatering with pump, Powdered acrylonitrile-butadiene rubber humidity＜40% after the dehydration, wet-milling enters the spiral flash distillation dryer and carries out drying, sub-sieve, packing.Gained Powdered acrylonitrile-butadiene rubber index is as follows:
Embodiment 2
With the potassium of the lipid acid in the butadiene-acrylonitrile cement preparation section among the embodiment 1-when potassium oleate compound consumption is adjusted to 6 parts, without diffusion agent N F, vinyl cyanide is adjusted to 35 parts by 28 parts, initiator (Potassium Persulphate) is transferred 0.3 part by 0.4 part, add divinyl and be adjusted to 65 parts by 72 parts, other technical recipe is with embodiment 1, and the products obtained therefrom index is still in the span of control shown in the table 2.Its index is as follows:
Solid content: 35.4%; PH value: 10.6 structural gel content: 82%; Mooney viscosity (ML
1+4 100 ℃): 130; Bound acrylonitrile: 32.7%
Embodiment 3
The consumption of the divinyl in the butadiene-acrylonitrile cement preparation section among the embodiment 1 is adjusted to 70 parts by 72 parts, vinyl cyanide is adjusted to 30 parts by 28 parts, initiator potassium persulfate changes di-isopropylbenzene hydroperoxide-ferrous sulfate into and reacts under 5～8 ℃ of conditions as initiator, other technical recipe is with embodiment 1, and the products obtained therefrom index is still in the span of control shown in the table 2.Its index is as follows:
Solid content: 35.9%; PH value: 10.6 structural gel content: 76%; Mooney viscosity (ML
1+4 100 ℃): 110; Bound acrylonitrile: 26.2%
Embodiment 4
Flocculation agent pH in the cohesion isolation operation among the embodiment 1 is transferred to 10 by 9, consumption is adjusted to 250 parts, and the potassium oleate in the compound spacer components changes stearic acid into, and the proportioning consumption is constant, other technical recipe is with embodiment 1, and the products obtained therefrom index is still in the span of control shown in the table 2.Its index is as follows:
Particle diameter 0.4～1.0mm 8.0%; Outward appearance and smell: white powder, tasteless
Fineness
Particle diameter≤0.4mm 92.0%; Moisture content: 0.9%
Embodiment 5
Flocculation agent pH in the cohesion isolation operation among the embodiment 1 is transferred to 10 by 9, consumption is adjusted to 290 parts by 340 parts, and the potassium oleate in the compound spacer components changes stearic acid into, and the proportioning consumption is constant, other technical recipe is with embodiment 1, and the products obtained therefrom index is still in the span of control shown in the table 2.Its index is as follows:
Particle diameter 0.4～1.0mm 8.2%; Outward appearance and smell: white powder, tasteless
Fineness
Particle diameter≤0.4mm 91.8%; Moisture content: 0.9%
Embodiment 6
Flocculation agent pH in the cohesion isolation operation among the embodiment 1 is transferred to 8 by 9, add-on is adjusted to 370 parts by 340 parts, high-phenylethylene content styrene-butadiene polymer emulsion in the compound spacer components changes polystyrene emulsion into, its proportioning consumption is constant, other technical recipe is with embodiment 1, and the products obtained therefrom index is still in the span of control shown in the table 2.Its index is as follows:
Particle diameter 0.4～1.0mm 9.5%; Outward appearance and smell: white powder, tasteless
Fineness
Particle diameter≤0.4mm 90.5%; Moisture content: 0.5%
Embodiment 7
The inorganic separant lightweight CaCO in the compound spacer components in the operation is isolated in cohesion among the embodiment 1
3Change talcum powder into, its proportioning consumption is constant, and other technical recipe is with embodiment 1, and the products obtained therefrom index is still in the span of control shown in the table 2.Its index is as follows:
Particle diameter 0.4～1.0mm 7.2%; Outward appearance and smell: white powder, tasteless
Fineness
Particle diameter≤0.4mm 92.8%; Moisture content: 0.5%
Embodiment 8
Change divalent metal salt sal epsom in the cohesion isolation operation among the embodiment 1 into calcium chloride, other technical recipe is with embodiment 1, and the products obtained therefrom index is still in the span of control shown in the table 2.Its index is as follows:
Particle diameter 0.4～1.0mm 8.1%; Outward appearance and smell: white powder, tasteless
Fineness
Particle diameter≤0.4mm 91.9%; Moisture content: 0.6%
Embodiment 9
Change flocculation agent consumption in the cohesion isolation operation among the embodiment 1 into 370 parts by 340 parts, the temperature of condensing is adjusted into 35～39 ℃ by 40～45 ℃, other technical recipe is with embodiment 1, and the products obtained therefrom index is still in the span of control shown in the table 2.
Embodiment 10
Flocculation agent add-on in the cohesion isolation operation among the embodiment 1 is adjusted to 400 parts by 340 parts, does not use divalent metal salt sal epsom, other technical recipe is with embodiment 1, and the products obtained therefrom index is still in the span of control shown in the table 2.
Embodiment 11
With the proportioning of separant in the cohesion isolation operation among the embodiment 1, be transferred to 3 parts, lightweight CaCO by 5 parts by the high-phenylethylene content styrene-butadiene polymer emulsion among the embodiment 1
3By 5 parts be transferred to 3 parts, when potassium oleate is transferred to 1.5 parts by 3 parts, when water was adjusted to 24 parts by 30 parts, the add-on of compound separant was adjusted to 23 parts by 11 parts, other technical recipe is with embodiment 1, the products obtained therefrom index is still in the span of control shown in the table 2.
Embodiment 12
Change the spiral expansion drying of wet-milling after the centrifuge dehydration in the drying process among the embodiment 1 into fluidizing drying bed drying, drying temperature is 80-90 ℃, and other technical recipe is with embodiment 1, and the products obtained therefrom index is still in the span of control shown in the table 2.
Comparative Examples 1
The proportioning of the potassium of the lipid acid in the butadiene-acrylonitrile cement preparation section among the embodiment 1-potassium oleate compound soap is adjusted to 1: 0, and when its consumption was 5 parts, other technical recipe was with embodiment 1, and the polymerization process instability produces macroscopical condensation product, can not ordinary production.
Comparative Examples 2
The proportioning of the potassium of the lipid acid in the butadiene-acrylonitrile cement preparation section among the embodiment 1-potassium oleate compound soap is adjusted to 0: 1, and when its consumption was 5 parts, other technical recipe was with embodiment 1, and the polymerization process instability produces macroscopical condensation product, can not ordinary production.
Comparative Examples 3
Lipid acid in the butadiene-acrylonitrile cement preparation section among the embodiment 1 potassium-potassium oleate compound soap is become sodium lauryl sulphate, and other technical recipe can not get powdered rubber with embodiment 1 during cohesion.
Comparative Examples 4
Butadiene-acrylonitrile cement cohesion among the embodiment 1 is isolated into potassium oleate becomes sodium lauryl sulphate in the compound soap of powder operation, other technical recipe is with embodiment 1, still can not condense powdered rubber after adding flocculation agent.
Comparative Examples 5
Butadiene-acrylonitrile cement cohesion among the embodiment 1 is isolated in the compound separant in the powder operation fluoropolymer resin emulsion (as high-phenylethylene content styrene-butadiene polymer emulsion, polystyrene emulsion) component to be removed, other technical recipe is with embodiment 1, and the powdered rubber of particle diameter 〉=1mm only accounts for 40%.Do not reach the index request of table 2.
Comparative Examples 6
Butadiene-acrylonitrile cement among the embodiment 1 is condensed inorganic separant (lightweight CaCO in the compound separant that is isolated into the powder operation
3Or talcum powder) component is removed, and other technical recipe is with embodiment 1, and the powdered rubber of particle diameter 〉=1mm accounts for 23%.Do not reach the index request of table 2.
Claims (14)
1, a kind of production method of low content nitrile cross-linked powdery acrylonitrile butadiene, at first carry out the synthetic of butadiene-acrylonitrile cement, then butadiene-acrylonitrile cement is condensed and be isolated into powder, dehydrate at last and obtain, it is characterized in that with divinyl, vinyl cyanide be monomer, is 100 parts in total monomer weight, wherein 22～35 parts of vinyl cyanide, 65～78 parts of divinyl, with fatty acids potassium or sodium and potassium oleate or sodium is that compound emulsifying agent obtains butadiene-acrylonitrile cement through letex polymerization, and the add-on of compound emulsifying agent is 3～6 parts; With pH value 8～10 saturated NaCl solution is flocculation agent, is that compound separant condenses butadiene-acrylonitrile cement under 30～65 ℃ and is isolated into powder with fluoropolymer resin emulsion-inorganic separant-organic separant, at last with Powdered acrylonitrile-butadiene rubber slurry dewatering drying; In the dried glue weight of butadiene-acrylonitrile cement is 100 parts, and the set of dispense ratio was when butadiene-acrylonitrile cement cohesion was isolated into powder: 11～28 parts of 100 parts of rubber cements, 0.5～1.5 part in anti-aging agent, 250～400 parts in flocculation agent, 0～9 part of the solution of divalent salts, compound separant; Fluoropolymer resin emulsion in the compound separant is that styrene content is high-phenylethylene content styrene-butadiene polymer emulsion, polystyrene emulsion or the polyvinyl chloride (PVC) RESINS emulsion more than 70%, and inorganic separant is lightweight CaCO
3Or talcum powder, organic separant is a lipid acid potassium.
2, production method according to claim 1 is characterized in that the mass ratio of lipid acid potassium in the compound emulsifying agent or sodium and potassium oleate or sodium is 0.2～1: 0.3～1.
3, the described production method of claim 1 is characterized in that the physical index of butadiene-acrylonitrile cement is: pH value 9～11, mooney viscosity 90～140, structural gel 70～85 quality %, bound acrylonitrile content 20～33%.
4, production method according to claim 1, it is characterized in that the synthetic set of dispense ratio of butadiene-acrylonitrile cement: 3～6 parts in 160～200 parts of soft water, lipid acid potassium or sodium-potassium oleate or sodium, 0～1.0 part of diffusant, 0.4～0.7 part of molecular weight regulator, 22～35 parts of vinyl cyanide, 65～78 parts of divinyl, 0.3～0.5 part of initiator, 0.1～0.3 part of terminator.
5, production method according to claim 4, it is characterized in that the butadiene-acrylonitrile cement synthesis process is for dropping into complex liquid, molecular weight regulator, vinyl cyanide, divinyl, the initiator of soft water, lipid acid potassium or sodium, potassium oleate or sodium and diffusant successively, begin reaction, when reaching 60%, transformation efficiency improves temperature of reaction to 45～50 ℃, reaction conversion ratio reaches more than 95%, add the terminator termination reaction, product is sent into degassing still remove unreacted monomer and obtain butadiene-acrylonitrile cement.
6, production method according to claim 4, the add-on that it is characterized in that diffusant is 0.3～1.0 part.
7,, it is characterized in that diffusant is a sodium metnylene bis-naphthalene sulfonate according to claim 4 or 5 described production methods.
8, production method according to claim 1 is characterized in that adding when butadiene-acrylonitrile cement cohesion is isolated into powder 3～9 parts of the solution of divalent salts.
9, production method according to claim 1, it is characterized in that the butadiene-acrylonitrile cement cohesion is isolated into the powder craft process and is: add butadiene-acrylonitrile cement, anti-aging agent in the cohesion still, be warming up to 35～45 ℃, add flocculation agent, be warming up to 55～65 ℃ afterwards, add divalent salt solutions, rubber cement is fully condensed after, add compound separant again, stir; At last, be cooled to 20～25 ℃, prepare the slurry of Powdered acrylonitrile-butadiene rubber.
10, production method according to claim 1 is characterized in that the fluoropolymer resin emulsion in the compound separant is that styrene content is the high-phenylethylene content styrene-butadiene polymer emulsion more than 70%.
11, production method according to claim 1 is characterized in that the inorganic separant in the compound separant is lightweight CaCO
3
12, production method according to claim 1 is characterized in that the organic separant in the compound separant is potassium oleate or potassium stearate.
13, production method according to claim 1 is characterized in that the drying mode of Powdered acrylonitrile-butadiene rubber slurry adopts dynamically dry.
14, production method according to claim 13 is characterized in that the drying mode of Powdered acrylonitrile-butadiene rubber slurry adopts expansion drying or the fluidizing drying bed drying of carrying out.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007024008A1 (en) * | 2007-05-22 | 2008-11-27 | Lanxess Deutschland Gmbh | nitrile rubbers |
| RU2010135773A (en) * | 2008-01-29 | 2012-03-10 | ЛЕНКСЕСС Дойчланд ГмбХ (DE) | IF NECESSARY, HYDROGEN NITRILE RUBBERS CONTAINING END ALKYLTHIOGROUPS WHEN NECESSARY |
| CN101643528B (en) * | 2009-08-28 | 2012-03-28 | 黄山华兰科技有限公司 | Method for producing cross-linking powder nitrile-butadiene rubber with medium and high nitrile content |
| CN102070789B (en) * | 2009-11-25 | 2012-10-17 | 中国石油天然气股份有限公司 | Preparation method of powder rubber |
| CN102070729B (en) * | 2009-11-25 | 2013-11-06 | 中国石油天然气股份有限公司 | Method for preparing powder rubber at low temperature |
| CN102464768B (en) * | 2010-11-18 | 2013-07-03 | 中国石油天然气股份有限公司 | Preparation of high-strength nitrile butadiene rubber |
| CN102464769B (en) * | 2010-11-18 | 2013-07-03 | 中国石油天然气股份有限公司 | Preparation method of microgel acrylonitrile-butadiene rubber |
| CN102199354B (en) * | 2011-04-22 | 2013-01-09 | 广东华声电器股份有限公司 | Cable insulator |
| ITMI20111170A1 (en) * | 2011-06-27 | 2012-12-28 | Polimeri Europa Spa | "PROCEDURE FOR THE PREPARATION OF NITRILE TIRES" |
| CN103159963B (en) * | 2011-12-15 | 2015-05-20 | 中国石油天然气股份有限公司 | Preparation method of powdered acrylonitrile-butadiene rubber with high performance |
| CN103554569B (en) * | 2013-09-29 | 2016-04-13 | 安徽同丰橡塑工业有限公司 | A kind of Powdered acrylonitrile-butadiene rubber production technique |
| CN104628955A (en) * | 2013-11-13 | 2015-05-20 | 中国石油天然气股份有限公司 | Chemically modified butyronitrile rubber and production method thereof |
| CN109206709B (en) * | 2018-08-22 | 2021-05-28 | 四川之江高新材料股份有限公司 | Preparation method of powdered rubber polyethylene mixture containing modified graphene fluoride for 3D printing |
| CN108948500B (en) * | 2018-08-23 | 2020-12-29 | 之江（四川）高新材料应用技术研究院有限公司 | Preparation method of polyethylene mixture containing polyurethane modified powder rubber for 3D printing |
| CN109294153A (en) * | 2018-09-10 | 2019-02-01 | 浙江畅通科技有限公司 | A kind of anti-oxidant plastic housing of lead-acid accumulator and preparation method thereof |
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