CN104193899A - Salt-free powdery nitrile rubber - Google Patents
Salt-free powdery nitrile rubber Download PDFInfo
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- CN104193899A CN104193899A CN201410390496.8A CN201410390496A CN104193899A CN 104193899 A CN104193899 A CN 104193899A CN 201410390496 A CN201410390496 A CN 201410390496A CN 104193899 A CN104193899 A CN 104193899A
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- salt
- butadiene rubber
- powdered acrylonitrile
- emulsion splitter
- polyacrylamide
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Abstract
The invention discloses a salt-free powdery nitrile rubber which comprises the following raw materials in percentage by mass: 52-60% of butadiene, 35-42% of acrylonitrile, 2-3% of emulsifier, 0.5-2% of age resister and 2-4% of polyacrylamide demulsifier. According to the proportioning of the raw materials, the high-temperature-resisting powdery nitrile rubber is prepared by the following steps: in a polymerization step, polymerizing butadiene, acrylonitrile and the emulsifier, wherein the polymerization temperature is 40-60 DEG C; in a condensation step, sequentially adding the age resister and the polyacrylamide demulsifier into the material obtained in the polymerization step to carry out condensation for 4-5h until complete demulsification, wherein the condensation temperature is 40-45 DEG C and the concentration of the polyacrylamide demulsifier is 9-10%; and carrying out centrifugal washing on the material obtained in the polymerization and carrying out drying and grinding to obtain the salt-free powdery nitrile rubber. According to the salt-free powdery nitrile rubber, salt-free polyermization is carried out in the process, so that the environment is protected, the corrosion resistance is provided and the resources are saved.
Description
Technical field
The present invention relates to Powdered acrylonitrile-butadiene rubber technical field, relate in particular to a kind of salt-free Powdered acrylonitrile-butadiene rubber.
Background technology
Powdered acrylonitrile-butadiene rubber belongs to the class in paracril, a kind of toughner, main as modifier, occupy critical role in rubber blending goods field, compared with block glue, because its particle diameter is little, good dispersity, be convenient to processing aid or resin-oatmeal blending after directly extrude or injection moulding, for condition has been created in the serialization, the automatization that shape, the existing main application of Powdered acrylonitrile-butadiene rubber has 2 points: making friction materials increases toughness and crocking resistance with modified phenolic resins; Add in the macromolecular material such as PVC, PV, to improve stretch-proof ability and the toughness of product.
What at present external producer taked is the manufacture of cryospray drying means, and its advantage is environmental protection, and shortcoming is that equipment requirements is high, product cost is high; The domestic condensation powdering method manufacture of taking, advantage is that production efficiency is high, equipment requirements is low, and product cost is little, and the most obvious shortcoming is that agglomeration process need to use salt (NaCl) to do emulsion splitter, the finished product chloride ion-containing, have corrosive nature, environmental protection treatment is wasted a large amount of water, and because the existence of salinity cannot be taked biochemical method reduction COD, scale operation need to adopt reverse osmosis to dispose of sewage, and environmental protection cost is high.
In the prior art, documents 1: Huang Liben, He Shixin etc. disclose a kind of production technique of Powdered acrylonitrile-butadiene rubber, wherein Powdered acrylonitrile-butadiene rubber production method has mechanical crushing method, spray-drying process, expansion drying method, freeze-drying, carbon black coprecipitation method and latex coacervation, the most conventional with first two and carbon black coprecipitation method, with latex coacervation comparatively economy and technical difficulty low, separant used is the organic separant of bipolarity, plastic barrier agent and inorganic separant, make PNBR not be adhered caking in processing and storage and transport process, in literary composition, mention this technique and carry out segmentation condensation powdering with monovalence and divalent metal salt,
Documents 2: He Shixin, Qi Shengjie etc. disclose and have prepared Powdered acrylonitrile-butadiene rubber with coacervation, butadiene-40 glue taking non-crosslinked or cross-linking type is starched as raw material, that rubber becomes powder to obtain powdered rubber slurry with positive coacervation, adding separant anti-stick, wash after filtration,, sieve, dry and make particle diameter and be not more than 1.25mm, the Powdered acrylonitrile-butadiene rubber that rubber content is greater than 93%.Studied the impact on powder formation rate such as structure of cohesion mode, separant, flocculation agent, rubber cement stablizer, coherence condition, cohesion equipment, powder formation rate reaches more than 90%.The flocculation agent of mentioning this process using in literary composition is industrial goods, is one to add and the inorganic salt (China Synthetic Rubber Industry, 1997.6:331-334) of divalent metal.
The production technique of the disclosed a kind of paracril of documents 3::CN102532414A, for a kind of production technique of improved paracril, comprise polymerization, degassed, cohesion three large steps, by raw material propylene nitrile, divinyl, desalination deoxidation gas, concentrated water is conveyed into polymerization post together with molecular weight regulator, collector place in polymerization post is mixed, mixed mixture carries out pre-emulsification through in-line pump and line mixer successively, cooling through the heat exchange of ammonia cold heat exchanger, cooled mixture enters successively multiple reactor polyreactions and generates latex together with activator solution with initiator emulsion, polymerisation conversion reaches after 65-75%, reactor latex out enters ripe still together with stopping defoamer fully to be mixed, then enter degassing tower degassed, enter again the cohesion of cohesion still, the problem that this invention has avoided interchanger to stop up, simple for process, stable production process, economical, rubber Mooney is easy to control, the paracril quality better of producing, this technique cohesion adopts salt-free cohesion.
Above-mentioned relevant salt-free Powdered acrylonitrile-butadiene rubber aspect, from pertinent literature Reporting, similar Powdered acrylonitrile-butadiene rubber technique all adopts the inorganic salt of monovalence and divalence summary to make flocculation agent, and the production technique of disclosed a kind of paracril introduces its agglomeration step and adopt salt-free cohesion, but it not Powdered acrylonitrile-butadiene rubber product.
Summary of the invention
The present invention proposes a kind of salt-free Powdered acrylonitrile-butadiene rubber, adopt salt-free cohesion, environmental protection, corrosion-resistant and economize on resources, technique is simple, is convenient to scale operation.
The salt-free Powdered acrylonitrile-butadiene rubber of one that the present invention proposes, its raw materials by weight comprises: divinyl 52-60%, vinyl cyanide 35-42%, emulsifying agent 2-3%, anti-aging agent 0.5-2%, polyacrylamide emulsion splitter 2-4%;
According to above-mentioned raw materials proportioning, prepare described high temperature resistant Powdered acrylonitrile-butadiene rubber according to following steps:
In polymerization procedure, by proportioning, divinyl, vinyl cyanide and emulsifying agent are carried out to polymerization, polymerization temperature is 40-60 DEG C;
In agglomeration step, add polyacrylamide emulsion splitter to condense after adding anti-aging agent in the material obtaining to polyreaction, condensation temperature is 40-45 DEG C, the complete breakdown of emulsion of cohesion 4-5h, the concentration of polyacrylamide emulsion splitter is 9-10%; Then the centrifugal washing of material polyreaction being obtained, drying and crushing obtains described salt-free Powdered acrylonitrile-butadiene rubber.
Preferably, its raw materials by weight comprises: divinyl 55-59%, vinyl cyanide 35-37%, emulsifying agent 2.5-3%, anti-aging agent 1-1.5%, polyacrylamide emulsion splitter 2.5-3%.
Preferably, the add-on of polyacrylamide emulsion splitter is 2.6-3.4%, is preferably 2.8-3.2%, is more preferably 2.9-3.1%, is further preferably 3%.
Preferably, in polymerization procedure, by proportioning, divinyl, vinyl cyanide and emulsifying agent are carried out to polymerization, polymerization temperature is 45-48 DEG C.
Preferably, in agglomeration step, after adding anti-aging agent in the material obtaining to polyreaction, add polyacrylamide emulsion splitter to condense, condensation temperature is the complete breakdown of emulsion of 41-43h, the concentration of polyacrylamide emulsion splitter is the centrifugal washing of material that 9-9.5 polyreaction obtains, and drying and crushing obtains described salt-free Powdered acrylonitrile-butadiene rubber.
Preferably, described polyacrylamide emulsion splitter can be by anionic polyacrylamide class emulsion splitter, cationic polyacrylamide, one or both form.
Preferably, emulsifying agent is one or more combinations in tallow fatty acid, vegetable fatty acid, synthetic fatty acid; For example, emulsifying agent can be sodium lauryl sulphate, oleic acid etc.
Preferably, anti-aging agent is phenolic type antioxidant or amines antioxidants.
Preferably, after drying and crushing, cross 40 mesh sieves, obtain the particle diameter≤0.45mm of salt-free Powdered acrylonitrile-butadiene rubber.Preferably, above-mentioned salt-free Powdered acrylonitrile-butadiene rubber, its raw materials by weight comprises: divinyl 55%, vinyl cyanide 34.5%, emulsifying agent 2.5%, anti-aging agent 1%, polyacrylamide emulsion splitter 2.5%;
According to above-mentioned raw materials proportioning, prepare described high temperature resistant Powdered acrylonitrile-butadiene rubber according to following steps:
In polymerization procedure, by proportioning, divinyl, vinyl cyanide and emulsifying agent are carried out to polymerization, polymerization temperature is 45 DEG C;
In agglomeration step, add polyacrylamide emulsion splitter to condense after adding anti-aging agent in the material obtaining to polyreaction, condensation temperature is 43 DEG C, the complete breakdown of emulsion of cohesion 5h, the concentration of polyacrylamide emulsion splitter is 9.8%; Then the centrifugal washing of material polyreaction being obtained, drying and crushing, sieves and obtains described salt-free Powdered acrylonitrile-butadiene rubber.
In the present invention, in agglomeration process, first our alternative material screening that carried out to existing usual flocculation agent NaCl, considers that organic hydrophilic species is more, and the inorganic salt of other chloride ion-containings are not at the row of considering category, we start to utilize dilute sulphuric acid and dilute hydrochloric acid to test, find that breakdown of emulsion process is too fierce, wayward agglomeration process, product is difficult for into powder, and equipment is had to more intense corrodibility, then abandon this path.Then, we have adopted again the inorganic salt such as calcium carbonate to test, and by the whole bag of tricks, though breakdown of emulsion process relaxes a little, elution process is still complicated, and economy and the feature of environmental protection cannot meet.Finally, we still screen water-based organic polymer class emulsion splitter, polyacrylamide emulsion splitter has entered screening scope as good sewage sinking agent, by concentration select, the checking of the series of process such as temperature control, its elution process is simple, product yield is high, and over-all properties is better.
Polyacrylamide emulsion splitter adds and carries out the breakdown of emulsion time and be more or less the same with traditional flocculation agent joining day, adds too fast one-tenth powder thicker, can not conformance with standard (at least cross 40 mesh sieves, particle diameter≤0.45mm), the joining day is excessively slow, and production efficiency is not high, condensation temperature control should be at 40 DEG C-45 DEG C, higher than this temperature, along with whipping process, a large amount of foams will be produced, easily cause material to overflow, and become powder thick, wayward, production efficiency lowly easily causes waste; Lower than this temperature, latex is unstable, and breakdown of emulsion process is violent, and yield reduces.
Through our test, the concentration of polyacrylamide emulsion splitter is also the important factor that affects yield and product stability with adding total amount, and we have determined the concentration that adds of 9-10%, in process of the test, find, lower than this concentration, breakdown of emulsion process is slow, and charging capacity strengthens, cause production cost to strengthen, production efficiency step-down, as excessive concentration, breakdown of emulsion is violent, yield is lower, wayward.Add the total amount should be between 2-4%, lower than this region, breakdown of emulsion be not thorough, after add-on exceedes 4%, no longer affects yield, has increased cost input.
The present invention is by independent research, adopt the condensation powdering method production Powdered acrylonitrile-butadiene rubber of domestic main flow, in breakdown of emulsion process, utilize polyacrylamide emulsion splitter, in whole production process, avoid the use of salt, salt-free in production process, the finished product are realized without chlorion, product does not have corrodibility, save the consumption of water in cleaning process simultaneously, owing to not having existence salty, can adopt biochemical method to dispose of sewage, reduce processing cost, energy-conserving and environment-protective, in polymerization process, in the time that polymerisation conversion reaches 68-73%, control temperature at 55-57 DEG C, by our repetition test data statistics, agglomeration process can have 95% yield, higher than current colleague's level, when product performance significantly improve, production efficiency is high, requirement to equipment is general, possesses the prospect of suitability for industrialized production, economic benefit and environmental benefit are remarkable.
Embodiment
Embodiment 1
A kind of salt-free Powdered acrylonitrile-butadiene rubber, its raw materials by weight comprises: divinyl 52.6%, vinyl cyanide 41.1%, emulsifying agent 2.4%, anti-aging agent 1.7%, polyacrylamide emulsion splitter 2.2%;
According to above-mentioned raw materials proportioning, prepare described high temperature resistant Powdered acrylonitrile-butadiene rubber according to following steps:
In polymerization procedure, by proportioning, divinyl, vinyl cyanide and emulsifying agent are carried out to polymerization, polymerization temperature is 41 DEG C;
In agglomeration step, add polyacrylamide emulsion splitter to condense after adding anti-aging agent in the material obtaining to polyreaction, condensation temperature is 44, the complete breakdown of emulsion of cohesion 4h, the concentration of polyacrylamide emulsion splitter is 9.8%; Then the centrifugal washing of material polyreaction being obtained, can cross 40 mesh sieves after drying and crushing, obtains described salt-free Powdered acrylonitrile-butadiene rubber, its particle diameter≤0.45mm.
Embodiment 2
A kind of salt-free Powdered acrylonitrile-butadiene rubber, its raw materials by weight comprises: divinyl 58.9%, vinyl cyanide 35%, emulsifying agent 2.8%, anti-aging agent 0.8%, cationic polyacrylamide class emulsion splitter 2.5%;
According to above-mentioned raw materials proportioning, prepare described high temperature resistant Powdered acrylonitrile-butadiene rubber according to following steps:
In polymerization procedure, by proportioning, divinyl, vinyl cyanide and emulsifying agent are carried out to polymerization, polymerization temperature is 58 DEG C;
In agglomeration step, add cationic polyacrylamide class emulsion splitter to condense after adding anti-aging agent in the material obtaining to polyreaction, condensation temperature is 41 DEG C, breakdown of emulsion completely after cohesion 5h, the concentration of cationic polyacrylamide class emulsion splitter is 9.1%; Then the centrifugal washing of material polyreaction being obtained, drying and crushing obtains described salt-free Powdered acrylonitrile-butadiene rubber, and described salt-free Powdered acrylonitrile-butadiene rubber can be crossed 50 mesh sieves, particle diameter≤0.35mm.
Embodiment 3
A kind of salt-free Powdered acrylonitrile-butadiene rubber, its raw materials by weight comprises: divinyl 53.8%, vinyl cyanide 39.5%, emulsifying agent 2.5%, anti-aging agent 1.2%, anionic polyacrylamide class emulsion splitter 3%;
According to above-mentioned raw materials proportioning, prepare described high temperature resistant Powdered acrylonitrile-butadiene rubber according to following steps:
In polymerization procedure, by proportioning, divinyl, vinyl cyanide and emulsifying agent are carried out to polymerization, polymerization temperature is 55 DEG C;
In agglomeration step, add anionic polyacrylamide class emulsion splitter to condense after adding anti-aging agent in the material obtaining to polyreaction, condensation temperature is 43 DEG C, the complete breakdown of emulsion of cohesion 4.5h, the concentration of anionic polyacrylamide class emulsion splitter is 9.6%; Then the centrifugal washing of material polyreaction being obtained, drying and crushing obtains described salt-free Powdered acrylonitrile-butadiene rubber.
Embodiment 4
A kind of salt-free Powdered acrylonitrile-butadiene rubber, its raw materials by weight comprises: divinyl 54.7%, vinyl cyanide 38.5%, emulsifying agent 2.5%, anti-aging agent 1%, polyacrylamide emulsion splitter 3.3%;
According to above-mentioned raw materials proportioning, prepare described high temperature resistant Powdered acrylonitrile-butadiene rubber according to following steps:
In polymerization procedure, by proportioning, divinyl, vinyl cyanide and emulsifying agent are carried out to polymerization, polymerization temperature is 45 DEG C;
In agglomeration step, add polyacrylamide emulsion splitter to condense after adding anti-aging agent in the material obtaining to polyreaction, condensation temperature is 43 DEG C, the complete breakdown of emulsion of cohesion 5h, the concentration of polyacrylamide emulsion splitter is 9.4%; Then the centrifugal washing of material polyreaction being obtained, drying and crushing, sieves and obtains described salt-free Powdered acrylonitrile-butadiene rubber.
Wherein, polyacrylamide emulsion splitter is made up of the poly-propyl amides of negatively charged ion and the poly-propyl amides of nonionic.
In embodiment 1-4, in whole preparation process, avoid the use of salt, product does not have corrodibility, save the consumption of water in cleaning process simultaneously, owing to not having existence salty, can adopt biochemical method to dispose of sewage, reduce processing cost, energy-conserving and environment-protective, by our repetition test data statistics, agglomeration process can have 95% yield, higher than current colleague's level, when product performance significantly improve, production efficiency is high, requirement to equipment is general, possesses the prospect of suitability for industrialized production, and economic benefit and environmental benefit are remarkable.
The above; it is only preferably embodiment of the present invention; but protection scope of the present invention is not limited to this; any be familiar with those skilled in the art the present invention disclose technical scope in; be equal to replacement or changed according to technical scheme of the present invention and inventive concept thereof, within all should being encompassed in protection scope of the present invention.
Claims (10)
1. a salt-free Powdered acrylonitrile-butadiene rubber, is characterized in that, its raw materials by weight comprises: divinyl 52-60%, vinyl cyanide 35-42%, emulsifying agent 2-3%, anti-aging agent 0.5-2%, polyacrylamide emulsion splitter 2-4%;
According to above-mentioned raw materials proportioning, prepare described high temperature resistant Powdered acrylonitrile-butadiene rubber according to following steps:
In polymerization procedure, by proportioning, divinyl, vinyl cyanide and emulsifying agent are carried out to polymerization, polymerization temperature is 40-60 DEG C;
In agglomeration step, add polyacrylamide emulsion splitter to condense after adding anti-aging agent in the material obtaining to polyreaction, condensation temperature is 40-45 DEG C, the complete breakdown of emulsion of cohesion 4-5h, the concentration of polyacrylamide emulsion splitter is 9-10%; Then the centrifugal washing of material polyreaction being obtained, drying and crushing obtains described salt-free Powdered acrylonitrile-butadiene rubber.
2. salt-free Powdered acrylonitrile-butadiene rubber according to claim 1, is characterized in that, its raw materials by weight comprises: divinyl 55-59%, vinyl cyanide 35-37%, emulsifying agent 2.5-3%, anti-aging agent 1-1.5%, polyacrylamide emulsion splitter 2.5-3.5%.
3. salt-free Powdered acrylonitrile-butadiene rubber according to claim 1 and 2, is characterized in that, the add-on of polyacrylamide emulsion splitter is 2.6-3.4%, is preferably 2.8-3.2%, is more preferably 2.9-3.1%, is further preferably 3%.
4. according to the salt-free Powdered acrylonitrile-butadiene rubber described in claim 1-3 any one, it is characterized in that, in polymerization procedure, by proportioning, divinyl, vinyl cyanide and emulsifying agent are carried out to polymerization, polymerization temperature is 45-48 DEG C.
5. according to the salt-free Powdered acrylonitrile-butadiene rubber described in claim 1-4 any one, it is characterized in that, in agglomeration step, after adding anti-aging agent in the material obtaining to polyreaction, add polyacrylamide emulsion splitter to condense, condensation temperature is the complete breakdown of emulsion of 41-43h, the concentration of polyacrylamide emulsion splitter is the centrifugal washing of material that 9-9.5 polyreaction obtains, and drying and crushing obtains described salt-free Powdered acrylonitrile-butadiene rubber.
6. according to the salt-free Powdered acrylonitrile-butadiene rubber described in claim 1-5 any one, it is characterized in that, described polyacrylamide emulsion splitter can be one or both compositions in anionic polyacrylamide class emulsion splitter, cationic polyacrylamide class emulsion splitter.
7. according to the salt-free Powdered acrylonitrile-butadiene rubber described in claim 1-6 any one, it is characterized in that, emulsifying agent is one or more combinations in tallow fatty acid, vegetable fatty acid, synthetic fatty acid.
8. according to the high temperature resistant Powdered acrylonitrile-butadiene rubber described in claim 1-7 any one, it is characterized in that, anti-aging agent is phenolic type antioxidant or amines antioxidants.
9. according to the salt-free Powdered acrylonitrile-butadiene rubber described in claim 1-8 any one, it is characterized in that, after drying and crushing, cross 40 mesh sieves, obtain the particle diameter≤0.45mm of salt-free Powdered acrylonitrile-butadiene rubber.
10. according to the salt-free Powdered acrylonitrile-butadiene rubber described in claim 1-9 any one, it is characterized in that, its raw materials by weight comprises: divinyl 55%, vinyl cyanide 34.5%, emulsifying agent 2.5%, anti-aging agent 1%, polyacrylamide emulsion splitter 2.5%;
According to above-mentioned raw materials proportioning, prepare described high temperature resistant Powdered acrylonitrile-butadiene rubber according to following steps:
In polymerization procedure, by proportioning, divinyl, vinyl cyanide and emulsifying agent are carried out to polymerization, polymerization temperature is 45 DEG C;
In agglomeration step, add polyacrylamide emulsion splitter to condense after adding anti-aging agent in the material obtaining to polyreaction, condensation temperature is 43 DEG C, the complete breakdown of emulsion of cohesion 5h, the concentration of polyacrylamide emulsion splitter is 9.8%; Then the centrifugal washing of material polyreaction being obtained, drying and crushing, sieves and obtains described salt-free Powdered acrylonitrile-butadiene rubber.
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| CN201410390496.8A CN104193899A (en) | 2014-08-10 | 2014-08-10 | Salt-free powdery nitrile rubber |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4920176A (en) * | 1988-12-05 | 1990-04-24 | The B. F. Goodrich Company | Nitrile emulsion polymers having improved adhesion properties |
| CN102532414A (en) * | 2011-12-21 | 2012-07-04 | 宁波顺泽橡胶有限公司 | Nitrile rubber production process |
| CN103450397A (en) * | 2012-05-28 | 2013-12-18 | 中国石油天然气股份有限公司 | Preparation method of acrylonitrile butadiene rubber |
| CN103497373A (en) * | 2013-09-27 | 2014-01-08 | 安庆华兰科技有限公司 | Preparation method of powdered butyronitrile rubber |
-
2014
- 2014-08-10 CN CN201410390496.8A patent/CN104193899A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4920176A (en) * | 1988-12-05 | 1990-04-24 | The B. F. Goodrich Company | Nitrile emulsion polymers having improved adhesion properties |
| CN102532414A (en) * | 2011-12-21 | 2012-07-04 | 宁波顺泽橡胶有限公司 | Nitrile rubber production process |
| CN103450397A (en) * | 2012-05-28 | 2013-12-18 | 中国石油天然气股份有限公司 | Preparation method of acrylonitrile butadiene rubber |
| CN103497373A (en) * | 2013-09-27 | 2014-01-08 | 安庆华兰科技有限公司 | Preparation method of powdered butyronitrile rubber |
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