CN1300223C - Method for making powdered rubber - Google Patents
Method for making powdered rubber Download PDFInfo
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- CN1300223C CN1300223C CNB2004100460232A CN200410046023A CN1300223C CN 1300223 C CN1300223 C CN 1300223C CN B2004100460232 A CNB2004100460232 A CN B2004100460232A CN 200410046023 A CN200410046023 A CN 200410046023A CN 1300223 C CN1300223 C CN 1300223C
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- rubber
- preparation
- latex
- flocculation agent
- alkali metal
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Abstract
The present invention relates to a method for preparing powdered rubber, particularly to a method of using a flocculating agent to prepare powdered rubber. The present invention is characterized in that rubber latex is added in a water solution which comprises a flocculating agent and has the volume concentration of 2% to 25%; every 100 parts of latex (by the weight of solid glue) is added with 0.1 to 30 parts of carboxylic acid alkali metal soaps in the process of being agglomerated into powder to be stirred by a stirrer with the functions of shearing and pulverization in a turbine mode, and the rotary speed is more than 3000 circles/minute. The powdered rubber prepared by the method for preparing powdered rubber of the present invention has the advantages of no adhesion among particles, no agglomeration when stored and less impurity content, and the present invention has the advantages of short powder forming time and high productive efficiency, and can adapt to the power formation of rubber latex synthesized by strong-bonding anion or non-ion emulsifying agents with gel or no gel, high Mooney viscosity and low Mooney viscosity, and natural rubber latex.
Description
Technical field
The present invention relates to a kind of preparation method of powdered rubber, in more detail, is that a kind of use flocculation agent makes emulsion condensation powdering, adds separant then, the method for the rubber that makes powder.
Background technology
At present, the manufacture method of relevant powdered rubber is existing multiple, as being the mechanical crushing method of raw material with the solid rubber; With latex, glue is the direct drying method of raw material, coprecipitation method, coacervation etc.
Mechanical crushing method is to be raw material with the solid rubber, carries out normal temperature or freezing and pulverizing, adopts this method, and energy consumption is big, and yield is low, and powder is thick, and particle is irregular, the production cost height.
Direct drying method and coprecipitation methods such as spray-drying process, expansion drying method exist the release agent consumption big, and nonrubber composition such as emulsifying agent a large amount of shortcomings such as residual in drying influence product performance in the latex.
Directly coacervation is meant under agitation condition, segmentation adds flocculation agent in latex, or latex directly joined the method for preparing powdered rubber in the flocculation agent, though can obtain well behaved powdered rubber sometimes, but if use low gel, low mooney viscosity rubber and the strong rubber of cementability, as carboxy nitrile rubber, carboxylic styrene-butadiene rubber, chloroprene rubber etc., or need to add a large amount of weighting agents, otherwise stick together between particle.Be difficult to obtain the few powdered rubber of suitable particle diameter and foreign matter content with the finely particulate cohesion.
The preparation method of acrylonitrile-butadiene rubber powder among the patent ZL93101142.6, be that segmentation adds monovalence and divalent metal salt brine solution in nitrile rubber, through pre-coagulate, flocculation, micelle sclerosis equal segments cohesion complex process, and powder formation rate is relatively low, become the powder time long, production efficiency is also lower, shortcoming such as energy consumption, material consumption are big.And for low gel, low mooney viscosity rubber and the strong rubber of cementability, or need to add a large amount of weighting agents, otherwise adopt this method to be difficult to the finely particulate condensation powdering, obtain the few powdered rubber of suitable particle diameter and foreign matter content.
Also do not have a kind of condensing method at present, do not use a large amount of weighting agents, the direct condensation powdering of all kinds latex can be produced adhesion between rubber particles, do not lump during storage, foreign matter content is few, the preparation method of the powdered rubber that production efficiency is high.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing powdered rubber with coacervation.Make adhesion between the powdered rubber particle that makes in this way, do not lump during storage, foreign matter content is few, and the powder formation rate height, becomes the powder time short (becoming the powder time to shorten to original sixth), the production efficiency height.Can be adapted to contain gel, gel-free, high Mooney viscosity, low mooney viscosity and have cementabilities such as polar group strong by negatively charged ion or nonionic emulsifying agent synthetic rubber latex and natural rubber latex.
The present invention's trial directly joins latex and prepares powdered rubber in the flocculation agent, this process joins in the latex different with flocculation agent, it is mutation process, compole is short when becoming powder, original stable latex is destroyed in moment, do not have adequate time to form sealing coat, isolation effect is relatively poor, is not used usually.The present invention has done a series of conditions for this reason and has improved.
Powdered rubber preparation method of the present invention is a kind of under agitation condition, uses flocculation agent to prepare the method for powdered rubber, and it is characterized in that: it is 2～25% that rubber latex is joined the volumetric concentration that contains flocculation agent, in best 5～20% the aqueous solution; With per 100 parts of latex (weight by dry rubber, as follows), in the condensation powdering process, add 0.1～30 part of preferably organic carboxyl acid alkali metal soap of 0.5～25 part, 1～20 part of flocculation agent of 2～15 parts preferably; Agitator is the turbine type stirring that has shearing, pulverizes function, and rotating speed is more than 3000 rev/mins.
Best mode is to have added 0～10 part of calcium, magnesium ion salt (contain calcium in as flocculation agent, magnesium ion can not add) in this process again, and calcium, magnesium ion salt can be that calcium ion salts also can be that magnesium ion salt can also be calcium, two kinds of mixing salts of magnesium.The present invention does not get rid of other separant of use.
The method of special recommendation of the present invention is to add 0～15 part (particularly 0.5～10 part in rubber latex in advance,) the organic carboxyl acid alkali metal soap, mix, then it is joined and contain in knockouts flocculation agent (univalent metal salt and/or two, the trivalent metal salt) aqueous solution, that have high speed agitator, use rubber with Powdered separation with shearing and the stirring of pulverizing function turbine type; And then add 0.1～15 part corresponding organic carboxyl acid alkali metal soap and 0～10 part of calcium, magnesium ion salt (as contain calcium in the flocculation agent, magnesium ion can not add), finish its isolation.Through intensification slaking, separation, dehydration, drying, make powdered rubber.Inadhesion between the powdered rubber particle that makes with this method is not lumpd in the storage, and the powder formation rate height becomes the powder time short, the production efficiency height.
Rubber latex among the present invention can be a natural rubber latex, also can be negatively charged ion or nonionic emulsifying agent synthetic latex, the independent polymkeric substance of conjugated diolefine hydrocarbon compound that polymerization makes as conventional emulsion-poly-fourth two right rubber latexs, chloroprene rubber latex etc.; The binary of vinyl compounds such as conjugated diolefine hydrocarbon compound and vinylbenzene, vinyl cyanide, vinylformic acid, methacrylic acid or terpolymer-styrene butadiene rubber latex, paracril latex, carboxy nitrile rubber latex, carboxylic styrene-butadiene rubber latex etc.
The used organic carboxyl acid alkali metal soap of the present invention is preferably C
12～C
18Carboxy acid alkali's metallic soap is as lauric acid soap, fatty acid soaps, stearate soap etc.
For per 100 parts of latex (weight by dry rubber), these organic carboxyl acid alkali metal soap additions use in 0.1～30 part of scope, be preferably in 0.5～25 part of scope and use, according to the character that becomes the arogel breast, can once add, also can add in batches, promptly add a part in the latex before the cohesion, add a part after having condensed again.If the organic carboxyl acid alkali metal soap that need add is contained in the virgin rubber Ruzhong, or high Mooney viscosity, high gel rubber, then can not add or add less before the cohesion, otherwise before the cohesion 15 parts of essential addings with interior organic carboxyl acid alkali metal soap.If do not add corresponding organic carboxyl acid alkali metal soap, then do not become required microgranular powdered rubber with fixed attention, easily form macroparticle or block.If the corresponding organic carboxyl acid alkali metal soap that adds in the latex before the cohesion surpasses 15 parts, then the cohesion dosage of emulsion condensation consumption increases, and foam increases, and influence is produced; Add again after having condensed 0.1～15 part of corresponding organic carboxyl acid alkali metal soap and calcium, magnesium ion salt 0%～10% (as contain calcium in the flocculation agent, magnesium ion can not add), finish its isolation.The organic carboxyl acid alkali metal soap preferably adds in batches, otherwise influences into powder and isolation effect.The organic carboxyl acid alkali metal soap is necessary auxiliary agent in the present invention, and is different with the technology that adds flocculation agent in latex, and preferably adds in batches, and this is relevant with the specific feed way of this technology.
The used flocculation agent of the present invention is univalent metal salt, divalent metal salt, also can be trivalent metal salt, needs to select different flocculation agent for use according to different latex, can be NaCL, KCL, CaCL
2, MgSO
4, in the alum etc. one or more.
These univalent metal salts, divalence, trivalent metal salt use with aqueous solution form, and addition is 1～20 part, is preferably in 2～15 parts.Concentration is 2%～25%, is preferably in 5%～20%.The flocculation agent consumption or (with) the concentration deficiency, latex is difficult for breakdown of emulsion, or forms oversize particle and block; If consumption is excessive, though can form particle, can increase the flocculation agent consumption, increase product cost.
The present invention has changed in the past the salt that in latex segmentation sprays into high saturated different hardness, the practice of sal epsom, two kinds of main and auxiliary logistics directions of cohesion process are opposite, after technological improvement, shortened the one-tenth powder time, improved production efficiency, and on the basis of the consumption that has reduced flocculation agent widely, make that also rubber powder Cheng Fengeng is thin.
The present invention is unqualified to the pH value of rubber latex.
Used its stirring rake of high speed agitator of the present invention is that turbine type stirs modified version, has shearing, pulverizes function.Rotating speed generally between 3000～10000 rev/mins, is preferably regulated between 4000～8000 rev/mins more than 3000 rev/mins, can reach the powdered rubber of demand fully.Rotating speed too low (being lower than 3000 rev/mins) then is difficult to form granular powder rubber, is easy to form oversize particle or block; Rotating speed surpasses 10000 rev/mins, though can form minuteness particle, to the manufacturing and the safety performance requirement increase of equipment.As not adopting the used agitator of the present invention,, can not reach the condensation powdering effect of latex of the present invention even rotating speed reaches requirement.Its stirring rake of high speed agitator used in the embodiment of the invention is made up of two groups of opposite cutter blade profile stirring rakes of direction.
Powdered rubber separates, dry together existing manufacturing technology is identical.Centrifugal, separating and dehydrating obtain the wet powder rubber that can pulverize with slight strength, and be dry then, can freely select methods such as air seasoning, warm air drying, vacuum-drying, mobile drying.
Embodiment
Below illustrate that with embodiment but the present invention is not limited to these embodiment.Unless outside specializing among the embodiment, " part ", " % " all refer to weight percentage.The flocculation agent concentration of aqueous solution is 8～15% (volumes) in embodiment 1～9 and the Comparative Examples 1～4, and the flocculation agent concentration of aqueous solution is 25% (volume) in the Comparative Examples 5～8.
Rubber latex among the embodiment is as described below:
(A) paracril latex (to call NBR in the following text)
High nitrile, high Mooney viscosity NBR latex (trade(brand)name N21) that the CNPC Lanzhou Petrochemical is produced carry out the DN214 latex of higher gel of precrosslink and mooney viscosity, contain the DN631 latex of carboxyl functional group, the N32 latex of low gel and low mooney viscosity.
(B) styrene-butadiene latex (to call SBR in the following text)
Styrene butadiene rubber latex SBR-1500, XSBR, SBR-1712 that CNPC's Lanzhou Petrochemical is produced.
(C) content of polybutadiene rubber latex (to call BR in the following text)
The polybutadiene latex that CNPC Lanzhou Petrochemical synthetic rubber plant produces.
(D) chloroprene rubber latex (to call CR in the following text)
Homemade commodity latex.
Agitator 1: high speed agitator, its stirring rake is made up of two groups of opposite cutter blade profile stirring rakes of direction, and rotating speed is more than 3000 rev/mins, and is adjustable.Rotating speed is between 3000～10000 rev/mins.
Agitator 2: high speed agitator, its stirring rake are the oblique oars of three leaves, and rotating speed is more than 3000 rev/mins, and is adjustable.Rotating speed is between 3000～10000 rev/mins.
Embodiment 1-9
According to each the raw material consumption shown in the table 1, rubber makes powder.0～15 part of organic carboxyl acid alkali metal soap is joined in the latex that contains the dried glue rubber of 300g, stir, after stablizing, listed corresponding flocculation agent of table 1 and amount are joined in the knockouts of 3L, under the high-speed stirring, above-mentioned latex is added in the flocculation agent then, rubber is promptly with Powdered separation.And then add 0.1～15 part of corresponding organic acid alkali metal soap and calcium, magnesium ion (as contain calcium in the flocculation agent, magnesium ion can not add) salt isolates, finishes and isolate back intensification slaking.Separation, dehydration, drying make the finished product powdered rubber.
As shown in table 1, according to method of the present invention, can be made into inadhesion between particle, store non-caking powdered rubber.
Comparative Examples 1-4:
The same embodiment of experimental technique, anti-coagulating.
Comparative Examples 5-8:
According to each the raw material consumption shown in the table 1, rubber makes powder.0～15 part of organic carboxyl acid alkali metal soap is joined in the latex that contains the dried glue rubber of 300g, stir, after stablizing, under agitation condition, listed corresponding flocculation agent of table 1 and amount are joined in the latex then, condense, rubber is promptly with Powdered separation.And then add 0.1～15 part of corresponding organic acid alkali metal soap and calcium, magnesium ion (as contain calcium in the flocculation agent, magnesium ion can not add) salt isolates, finishes and isolate back intensification slaking.Separation, dehydration, drying make the finished product powdered rubber.(preparation method of this Comparative Examples is identical with the preparation method of acrylonitrile-butadiene rubber powder among the patent CN-ZL93101142.6, just coagulates)
The different condensation powdering modes of table 1 prepare the powdered rubber contrast
| Numbering | Rubber latex | The organic acid alkali metal soap | Flocculation agent/amount (part) | Condensed back calcium ions and magnesium ions salt/add-on (part) | Agitator 1 | Agitator 2 | The one-tenth powder time (minute) | Become the powder situation | |||
| Add soap/amount (part) in the latex before the cohesion | The cohesion back adds soap/amount (part) | Rotating speed (rev/min) | Rotating speed (rev/min) | ||||||||
| Embodiment | Anti-coagulating | 1 2 3 4 5 6 7 8 9 | N21 N32 DN214 DN631 SBR1500 SBR1712 XSBR BR CR | Potassium stearate/2 potassium stearates/3 potassium stearates/0 potassium stearate/4 aliphatic acid potassium/4 aliphatic acid potassium/2 potassium stearates/5 potassium stearates/4 sodium laurates/5 | Ditto/2 ditto/2 ditto/2 ditto/4 ditto/3 ditto/3 ditto/4 ditto/4 ditto/4 | NaCL/10 NaCL/8 and MgSO 4/1 CaCL 2/5 NaCL/10 KCL/10 NaCL/10 NaCL/10 NaCL/10 NaCL/10 | MgSO 4/ 2 and CaCL 2/1 CaCL 2/2 0 MgSO 4/3 CaCL 2/3 CaCL 2/3 MgSO 4/3 MgSO 4/2 MgSO 4/3 | 4000 5000 4000 5000 4000 4000 4000 5000 5000 | 15 15 15 15 15 15 15 15 15 | 0.45mm it is the same the same that following micro mist end accounts for more than 99% | |
| Comparative example | Anti-coagulating | 1 2 3 4 | CR CR CR CR | Sodium laurate/5 sodium laurates/5 sodium lauryl sulphate/5 Sodium dodecylbenzene sulfonatees/5 | Ditto/4 the same/4 ditto/4 ditto/2 | NaCL/10 NaCL/10 NaCL/10 NaCL/10 | MgSO 4/2 MgSO 4/2 MgSO 4/2 MgSO 4/2 | 2500 4000 4000 | 5000 | 15 15 15 15 | Particle diameter is the same the same greater than particle and the block of 4mm |
| Just coagulate | 5 6 7 8 | N21 N32 DN214 CR | Potassium stearate/2 potassium stearates/3 potassium stearates/0 sodium laurate/5 | Ditto/2 the same/2 ditto/2 ditto/2 | NaCL/10 NaCL/8 and CaCL 2/1 CaCL 2/5 NaCL/10 | MgSO 4/ 2 and CaCL 2/1 MgSO 4/2 0 MgSO 4/3 | 4000 5000 4000 5000 | 90 90 90 90 | 0.45mm following micro mist end is up to the following micro mist end of 92% 0.4mm and is up to the following micro mist end of 85% 0.4mm and is up to 92% particle diameter greater than particle and the block of 4mm |
Claims (13)
1. the preparation method of a powdered rubber under agitation condition, uses flocculation agent to prepare powdered rubber, it is characterized in that: with rubber latex join contain flocculation agent, its volumetric concentration is in 2～25% the aqueous solution; Weight by dry rubber, per 100 parts of latex add 0.1～30 part of organic carboxyl acid alkali metal soap in the condensation powdering process; 1～20 part flocculation agent; Agitator is the turbine type stirring that has shearing, pulverizes function, and rotating speed is more than 3000 rev/mins.
2. preparation method according to claim 1, the aqueous solution volumetric concentration that it is characterized in that flocculation agent is 5～20%.
3. preparation method according to claim 1, the add-on that it is characterized in that flocculation agent is 2～15 parts.
4. preparation method according to claim 1, the add-on that it is characterized in that the organic carboxyl acid alkali metal soap is 0.5～25 part.
5. preparation method according to claim 1 is characterized in that also being added with 0～10 part of calcium, magnesium ion salt in the condensation powdering process, form separant with the reaction of organic carboxyl acid alkali metal soap.
6. preparation method according to claim 1, it is characterized in that in rubber latex, adding in advance 0～15 part organic carboxyl acid alkali metal soap, mix, it is joined in the knockouts of the high speed agitator that contains the flocculation agent aqueous solution then, make rubber with Powdered separation; And then corresponding organic carboxyl acid alkali metal soap and 0～10 part of calcium, magnesium ion salt of adding 0.1～15 part are finished its isolation; Through intensification slaking, separation, dehydration, drying, make powdered rubber.
7. preparation method according to claim 4 is characterized in that adding in advance 0.5～15 part organic carboxyl acid alkali metal soap in rubber latex, it is joined contain in the flocculation agent aqueous solution then.
8. preparation method according to claim 1 is characterized in that rubber latex is a natural rubber latex, or uses negatively charged ion, nonionic emulsifying agent synthetic latex.
9. preparation method according to claim 1 is characterized in that the organic carboxyl acid alkali metal soap is C
12～C
18Carboxy acid alkali's metallic soap.
10. preparation method according to claim 9 is characterized in that the organic carboxyl acid alkali metal soap is lauric acid soap, fatty acid soaps or stearate soap.
11. preparation method according to claim 1, it is characterized in that flocculation agent be in univalent metal salt, divalent metal salt, the trivalent metal salt one or more.
12. preparation method according to claim 11 is characterized in that flocculation agent is NaCl, KCl, CaCl
2, MgSO
4, in the alum one or more.
13. preparation method according to claim 1 is characterized in that its stirring rake of agitator is made up of two groups of opposite cutter blade profile stirring rakes of direction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100460232A CN1300223C (en) | 2004-06-02 | 2004-06-02 | Method for making powdered rubber |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100460232A CN1300223C (en) | 2004-06-02 | 2004-06-02 | Method for making powdered rubber |
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|---|---|
| CN1704439A CN1704439A (en) | 2005-12-07 |
| CN1300223C true CN1300223C (en) | 2007-02-14 |
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|---|---|---|---|
| CNB2004100460232A Expired - Fee Related CN1300223C (en) | 2004-06-02 | 2004-06-02 | Method for making powdered rubber |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103159611B (en) * | 2011-12-15 | 2014-12-24 | 中国石油天然气股份有限公司 | Preparation method of flame retardant type separant |
| CN103319632B (en) * | 2013-06-27 | 2015-03-11 | 中昊晨光化工研究院有限公司 | Preparation method of powder rubber |
| CN114015123A (en) * | 2021-11-30 | 2022-02-08 | 深圳市汉唐世家服饰有限公司 | Daily-use clothes cutting-resistant material and preparation method thereof |
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|---|---|---|---|---|
| JPS51143082A (en) * | 1975-06-04 | 1976-12-09 | Mitsubishi Chem Ind | Process for producing rubber powder |
| JPS52104582A (en) * | 1976-03-01 | 1977-09-02 | Mitsubishi Chem Ind | Process for producing rubber powder |
| EP0071240A1 (en) * | 1981-07-29 | 1983-02-09 | The B.F. GOODRICH Company | Production of emulsion-polymerized butadiene rubber in powder form |
| JPH06122865A (en) * | 1992-07-17 | 1994-05-06 | Tohoku Kako Kk | Friction material |
| CN1415648A (en) * | 2002-11-29 | 2003-05-07 | 华南理工大学 | Method for preparing powdered rubber in stuffing type with extra fine calcium carbonate |
| CN1415653A (en) * | 2002-11-29 | 2003-05-07 | 华南理工大学 | Method for preparing powdered rubber with carbon black stuffing |
| CN1468872A (en) * | 2002-07-17 | 2004-01-21 | 中国石油天然气集团公司 | Production process of high-Mooney point crosslinked butadiene-acrylonitrile rubber powder for modifying plastics |
-
2004
- 2004-06-02 CN CNB2004100460232A patent/CN1300223C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51143082A (en) * | 1975-06-04 | 1976-12-09 | Mitsubishi Chem Ind | Process for producing rubber powder |
| JPS52104582A (en) * | 1976-03-01 | 1977-09-02 | Mitsubishi Chem Ind | Process for producing rubber powder |
| EP0071240A1 (en) * | 1981-07-29 | 1983-02-09 | The B.F. GOODRICH Company | Production of emulsion-polymerized butadiene rubber in powder form |
| JPH06122865A (en) * | 1992-07-17 | 1994-05-06 | Tohoku Kako Kk | Friction material |
| CN1468872A (en) * | 2002-07-17 | 2004-01-21 | 中国石油天然气集团公司 | Production process of high-Mooney point crosslinked butadiene-acrylonitrile rubber powder for modifying plastics |
| CN1415648A (en) * | 2002-11-29 | 2003-05-07 | 华南理工大学 | Method for preparing powdered rubber in stuffing type with extra fine calcium carbonate |
| CN1415653A (en) * | 2002-11-29 | 2003-05-07 | 华南理工大学 | Method for preparing powdered rubber with carbon black stuffing |
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