CN100443506C - Low acid value solvent process of preparing chlorinated rubber - Google Patents
Low acid value solvent process of preparing chlorinated rubber Download PDFInfo
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- CN100443506C CN100443506C CNB2006101353453A CN200610135345A CN100443506C CN 100443506 C CN100443506 C CN 100443506C CN B2006101353453 A CNB2006101353453 A CN B2006101353453A CN 200610135345 A CN200610135345 A CN 200610135345A CN 100443506 C CN100443506 C CN 100443506C
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Abstract
The low acid value solvent process of preparing chlorinated rubber includes the following steps: plasticating natural rubber; chemically degrading; chlorinating reaction; and dechlorinating. It has the dechlorinating step. After finishing chlorinating reaction, water solution of stearate and water solution of weak alkaline salt are added into the reactor and mixed homogeneously, and the organic chlorinated natural rubber solution is finally dried to form the product. The said preparation process can eliminate HCl and Cl2 dissolved in organic solvent completely top high quality low acid value chlorinated rubber.
Description
Technical field
The present invention relates to the improvement of solvent process of preparing chlorinated rubber.
Background technology
Chlorinated natural rubber (chlorinated natural rubber, CNR), be the derivative of a kind of chlorinity more than 60% that obtains after chlorination modified by natural rubber, dissolve in aromatic hydrocarbon, ester class, ketone, ethers, vegetable and animals oils equal solvent, but be insoluble to aliphatic hydrocarbon, alcohols and water.It since have excellent film forming, adhesion, weather-proof, wear-resisting, fast dried, anticorrosive, prevent performances such as permeable, fire-retardant and insulation, be widely used in industries such as coating, printing ink, tackiness agent.In recent years, the Application Areas of chlorinated natural rubber constantly enlarges, and its demand is also increasing.
Traditional solvent method chlorinated natural rubber production technique is: earlier the macromole natural rubber is plasticated in rubber mixing machine; Add the tetracol phenixin dissolving, heat up and carry out chemical degradation; Add catalyzer, feed Cl at 50～70 ℃
2Reacted 8～16 hours; After reaction finished, bubbling air was with HCl and unreacted Cl
2Blow out; The chlorinated natural rubber carbon tetrachloride solution that generates distills tetracol phenixin with water vapor in the elutriation tower; The chlorinated natural rubber pressed powder is dispersed in the water, through separate, drying obtains product (referring to US2504065, ES8703896, SU1235871).Produce in the process of chlorinated natural rubber in solution method, the molecular chain of natural rubber is in extended configuration, and reaction can evenly be carried out, be easy to control, products obtained therefrom cl content higher (64～68%), the structure of chlorinated natural rubber and consistency of performance are good, better heat stability; But this production technique exists tetracol phenixin to consume high (produce 1 ton of chlorinated natural rubber and need consume 1.0～1.2 tons of tetracol phenixin), and product color is dark, contains shortcomings such as the wastewater flow rate of tetracol phenixin is big.
Therefore, various countries improve solvent method chlorinated natural rubber production technique, for example: German Bayer company exchange of solvent technology.Its technical process: earlier the macromole natural rubber is plasticated in rubber mixing machine; Add the tetracol phenixin dissolving, heat up and carry out chemical degradation; Add catalyzer, feed Cl at 50～70 ℃
2Carried out chlorination reaction 8～16 hours; Reaction adds toluene after finishing in carbon tetrachloride solution, carry out rectifying separation and go out tetracol phenixin, HCl and unreacted Cl
2Tetracol phenixin is removed Cl through dehydration
2, recycle behind HCl and other impurity; The chlorinated natural rubber toluene solution is precipitated out chlorinated natural rubber through elutriation from toluene solution, obtain the chlorinated natural rubber product through separation, drying; Toluene through the dehydration after return distillation system reuse (referring to: DE2359461).This production technique is moved in totally-enclosed system, the consumption of tetracol phenixin extremely low (generate 1 ton of chlorinated natural rubber and only consume the 2.03Kg tetracol phenixin); And thoroughly remove tetracol phenixin, HCl and unreacted Cl in the chlorinated natural rubber by rectifying
2, the product acid number is low, the thermostability height.But this complex manufacturing, facility investment is big, the energy consumption height, generation contains toluene waste water, running cost height in a large number in the production process.
China has realized the anhydrous production technique of solvent method chlorinated natural rubber also to the improvement of solvent method chlorinated natural rubber production technique.Technical process: earlier the macromole natural rubber is plasticated in rubber mixing machine; Add the tetracol phenixin dissolving, heat up and carry out chemical degradation; Add catalyzer, fed chlorine reaction 8～16 hours at 50～70 ℃; After reaction finishes, bubbling air will be dissolved in HCl and the unreacted Cl in the tetracol phenixin
2Blow out; Then the chlorinated natural rubber drying is made finished product.This technological process is moved in totally-enclosed system, and tetracol phenixin consumes low, and facility investment is little, and energy consumption is low, and running cost is lower.But, in this production process, HCl in the carbon tetrachloride solution and unreacted Cl
2Be difficult to blow out fully with air fully; And residual HCl and Cl
2Be adsorbed in the chlorinated natural rubber micropore, in follow-up drying process, also be difficult to remove.So the acid number of chlorinated natural rubber finished product is higher, corrodibility is strong, and thermostability is relatively poor.
HCl that contains in the chlorinated natural rubber and Cl
2Had a strong impact on the quality of chlorinated natural rubber, restricted its application at high-end product; And with containing HCl and Cl
2The paint produced of chlorinated natural rubber can the heavy corrosion iron and steel, make iron and steel produce rust staining.Simultaneously, HCl takes off the HCl degraded to chlorinated natural rubber and has self-catalysis, has quickened chlorinated natural rubber decomposes speed, and the cl content of chlorinated natural rubber is reduced, and causes the chlorinated natural rubber performance to become bad.Therefore, be necessary solvent method chlorinated rubber production technique is improved, thoroughly remove HCl and Cl in the chlorinated natural rubber
2, prepare low acid number chlorinated natural rubber.
Summary of the invention
The objective of the invention is at the problems referred to above, a kind of low acid value solvent process of preparing chlorinated rubber is provided.
The present invention is low, and acid number solvent process of preparing chlorinated rubber comprises: (1) natural rubber step of plasticating; (2) chemical degradation step; (3) chlorination reaction step; (4) dechlorination treatment step; It is characterized in that: the dechlorination treatment step is improved, described preparation method is: after chlorination reaction finishes, add stearate and weakly alkaline salt brine solution in the reaction vessel, mix, will react chlorinated natural rubber organic solution drying after the end at last, make finished product.
Advantage of the present invention is: 1, select for use in the weakly alkaline salt such as S-WAT, sodium bisulfite, Sulfothiorine, sodium bicarbonate, yellow soda ash and HCl and Cl in the chlorinated natural rubber organic solution
2Thereby, solved HCl and Cl in drying process
2Be adsorbed on a difficult problem that is difficult to remove in the micropore of chlorinated natural rubber.2, since weakly alkaline salt brine solution and organic solution do not dissolve each other, this preparation method adds in organic solution and has the amphiphilic group and (promptly have oil loving long chain hydrocarbon groups, also have hydrophilic carboxyl simultaneously) stearate as dispersion agent, make the weakly alkaline salt brine solution at the organic solution homodisperse.
Embodiment
In the dechlorination treatment step, in reaction vessel, add stearate earlier, after stirring is dissolved stearate fully, again the weakly alkaline salt brine solution slowly is added drop-wise in the container and reacts, will react chlorinated natural rubber organic solution drying after finishing at last, make the powder finished product.
The weakly alkaline salt of selecting for use can be one or more in S-WAT, sodium bisulfite, Sulfothiorine, sodium bicarbonate, the yellow soda ash, preferentially selects Sulfothiorine, yellow soda ash for use; Selecting stearate for use can be in calcium stearate, barium stearate, Zinic stearas, cadmium stearate, the lead stearate one or more, preferentially selects calcium stearate, cadmium stearate for use.
The umber of stearate that adds in the preparation and the weakly alkaline salt organic solution that contains chlorinated natural rubber after with respect to 100 parts of steps (3) is (weight ratio):
0.1～2 part of stearate
0.01～0.4 part of weakly alkaline salt
The concentration of weakly alkaline salt brine solution is 0.5～3mol/L.
In the low acid value solvent process of preparing chlorinated rubber: (1) natural rubber step of plasticating; (2) chemical degradation step; (3) reaction in chlorination reaction step and (4) the dechlorination treatment step is all carried out in water bath with thermostatic control, and the temperature of described water bath with thermostatic control is 40～80 ℃.
The reaction times is 0～60 minute in the water bath with thermostatic control of step (4).
Embodiment 1
Measure chlorinated natural rubber organic solution after the 500ml chlorination reaction finishes in the 1000ml there-necked flask, add the 5g calcium stearate, open stirrer calcium stearate is dissolved fully; 6ml 1.5mol/L yellow soda ash slowly is added drop-wise to (about 1ml/min) in the there-necked flask, then there-necked flask is placed 60 ℃ of water bath with thermostatic control reactions 40 minutes.After question response finished, it was that 60 ℃, vacuum tightness are dry 6 hours of the vacuum drying oven of 0.075MPa that chlorinated natural rubber solution is placed temperature, makes the powder finished product.
Embodiment 2
Measure chlorinated natural rubber organic solution after the 500ml chlorination reaction finishes in the 1000ml there-necked flask, add the 5g calcium stearate, open stirrer calcium stearate is dissolved fully; 6ml 1.5mol/L sodium bicarbonate slowly is added drop-wise to (about 1ml/min) in the there-necked flask, then there-necked flask is placed 70 ℃ of water bath with thermostatic control reactions 40 minutes.After question response finished, it was that 60 ℃, vacuum tightness are dry 6 hours of the vacuum drying oven of 0.075MPa that chlorinated natural rubber solution is placed temperature, makes the powder finished product.
Embodiment 3
Measure chlorinated natural rubber organic solution after the 500ml chlorination reaction finishes in the 1000ml there-necked flask, add the 5g calcium stearate, open stirrer calcium stearate is dissolved fully; 3ml2.0mol/L Sulfothiorine slowly is added drop-wise to (about 1ml/min) in the there-necked flask, then there-necked flask is placed 50 ℃ of water bath with thermostatic control reactions 60 minutes.After question response finished, it was that 60 ℃, vacuum tightness are dry 6 hours of the vacuum drying oven of 0.075MPa that chlorinated natural rubber solution is placed temperature, makes the powder finished product.
Embodiment 4
Measure chlorinated natural rubber organic solution after the 500ml chlorination reaction finishes in the 1000ml there-necked flask, add the 5g calcium stearate, open stirrer calcium stearate is dissolved fully; 4ml 1.5mol/L S-WAT slowly is added drop-wise to (about 1ml/min) in the there-necked flask, then there-necked flask is placed 60 ℃ of water bath with thermostatic control reactions 40 minutes.After question response finished, it was that 60 ℃, vacuum tightness are dry 6 hours of the vacuum drying oven of 0.075MPa that chlorinated natural rubber solution is placed temperature, makes the powder finished product.
Embodiment 5
Measure chlorinated natural rubber organic solution after the 500ml chlorination reaction finishes in the 1000ml there-necked flask, add the 5g calcium stearate, open stirrer calcium stearate is dissolved fully; The 3ml2.0mol/L sodium bisulfite slowly is added drop-wise to (about 1ml/min) in the there-necked flask, then there-necked flask is placed 60 ℃ of water bath with thermostatic control reactions 40 minutes.After question response finished, it was that 60 ℃, vacuum tightness are dry 6 hours of the vacuum drying oven of 0.075MPa that chlorinated natural rubber solution is placed temperature, makes the powder finished product.
Embodiment 6
Measure chlorinated natural rubber organic solution after the 500ml chlorination reaction finishes in the 1000ml there-necked flask, add the 5g cadmium stearate, open stirrer cadmium stearate is dissolved fully; The 2.0mol/L Sulfothiorine of 3ml slowly is added drop-wise to (about 1ml/min) in the there-necked flask, then there-necked flask is placed 60 ℃ of water bath with thermostatic control reactions 40 minutes.After question response finished, it was that 60 ℃, vacuum tightness are dry 6 hours of the vacuum drying oven of 0.075MPa that chlorinated natural rubber solution is placed temperature, makes the powder finished product.
Embodiment 7
Measure chlorinated natural rubber organic solution after the 500ml chlorination reaction finishes in the 1000ml there-necked flask, add the 5g cadmium stearate, open stirrer cadmium stearate is dissolved fully; 6ml 1.5mol/L yellow soda ash slowly is added drop-wise to (about 1ml/min) in the there-necked flask, then there-necked flask is placed 70 ℃ of water bath with thermostatic control reactions 60 minutes.After question response finished, it was that 60 ℃, vacuum tightness are dry 6 hours of the vacuum drying oven of 0.075MPa that chlorinated natural rubber solution is placed temperature, makes the powder finished product.
Embodiment 8
Measure chlorinated natural rubber organic solution after the 500ml chlorination reaction finishes in the 1000ml there-necked flask, add the 5g Zinic stearas, open stirrer Zinic stearas is dissolved fully; 6ml 1.5mol/L yellow soda ash slowly is added drop-wise to (about 1ml/min) in the there-necked flask, then there-necked flask is placed 60 ℃ of water bath with thermostatic control reactions 60 minutes.After question response finished, it was that 60 ℃, vacuum tightness are dry 6 hours of the vacuum drying oven of 0.075MPa that chlorinated natural rubber solution is placed temperature, makes the powder finished product.
Embodiment 9
Measure chlorinated natural rubber organic solution after the 500ml chlorination reaction finishes in the 1000ml there-necked flask, add the 5g lead stearate, open stirrer lead stearate is dissolved fully; 6ml 1.5mol/L yellow soda ash slowly is added drop-wise to (about 1ml/min) in the there-necked flask, then there-necked flask is placed 70 ℃ of water bath with thermostatic control reactions 40 minutes.After question response finished, it was that 60 ℃, vacuum tightness are dry 6 hours of the vacuum drying oven of 0.075MPa that chlorinated natural rubber solution is placed temperature, makes the powder finished product.
Embodiment 10
Measure chlorinated natural rubber organic solution after the 500ml chlorination reaction finishes in the 1000ml there-necked flask, add the 5g lead stearate, open stirrer lead stearate is dissolved fully; 4ml 1.5mol/L sodium thiosulfate solution slowly is added drop-wise to (about 1ml/min) in the there-necked flask, then there-necked flask is placed 60 ℃ of water bath with thermostatic control reactions 40 minutes.After question response finished, it was that 60 ℃, vacuum tightness are dry 6 hours of the vacuum drying oven of 0.075MPa that chlorinated natural rubber solution is placed temperature, makes the powder finished product.
Embodiment 11
Measure chlorinated natural rubber organic solution after the 500ml chlorination reaction finishes in the 1000ml there-necked flask, add 3g calcium stearate and 3g Zinic stearas, open stirrer calcium stearate and Zinic stearas are dissolved fully; 4ml 1.5mol/L aqueous sodium carbonate slowly is added drop-wise to (about 1ml/min) in the there-necked flask, then there-necked flask is placed 50 ℃ of water bath with thermostatic control reactions 60 minutes.After question response finished, it was that 60 ℃, vacuum tightness are dry 6 hours of the vacuum drying oven of 0.075MPa that chlorinated natural rubber solution is placed temperature, makes the powder finished product.
Embodiment 12
Measure chlorinated natural rubber organic solution after the 500ml chlorination reaction finishes in the 1000ml there-necked flask, add 3g calcium stearate and 3g Zinic stearas, open stirrer calcium stearate and Zinic stearas are dissolved fully; 4ml 1.5mol/L aqueous sodium carbonate and 4ml 1.5mol/L sodium sulfite aqueous solution slowly are added drop-wise to (about 1ml/min) in the there-necked flask, then there-necked flask are placed 60 ℃ of water bath with thermostatic control reactions 40 minutes.After question response finished, it was that 60 ℃, vacuum tightness are dry 6 hours of the vacuum drying oven of 0.075MPa that chlorinated natural rubber solution is placed temperature, makes the powder finished product.
Embodiment 13
Measure chlorinated natural rubber organic solution after the 500ml chlorination reaction finishes in the 1000ml there-necked flask, add 3g barium stearate and 3g cadmium stearate, open stirrer barium stearate and cadmium stearate are dissolved fully; 4ml 1.5mol/L sodium thiosulfate solution slowly is added drop-wise to (about 1ml/min) in the there-necked flask, then there-necked flask is placed 60 ℃ of water bath with thermostatic control reactions 60 minutes.After question response finished, it was that 60 ℃, vacuum tightness are dry 6 hours of the vacuum drying oven of 0.075MPa that chlorinated natural rubber solution is placed temperature, makes the powder finished product.
Embodiment 14
Measure chlorinated natural rubber organic solution after the 500ml chlorination reaction finishes in the 1000ml there-necked flask, add 3g barium stearate and 3g cadmium stearate, open stirrer barium stearate and cadmium stearate are dissolved fully; 4ml 1.5mol/L aqueous sodium carbonate and 4ml 1.5mol/L sodium sulfite aqueous solution slowly are added drop-wise to (about 1ml/min) in the there-necked flask, then there-necked flask are placed 70 ℃ of water bath with thermostatic control reactions 40 minutes.After question response finished, it was that 60 ℃, vacuum tightness are dry 6 hours of the vacuum drying oven of 0.075MPa that chlorinated natural rubber solution is placed temperature, grinds and makes finished product.
Claims (8)
1. low acid value solvent process of preparing chlorinated rubber: comprising: (1) natural rubber step of plasticating; (2) chemical degradation step; (3) chlorination reaction step; (4) dechlorination treatment step; It is characterized in that: the dechlorination treatment step is improved: add stearate and weakly alkaline salt brine solution in the reaction vessel, mix, will react chlorinated natural rubber organic solution drying after the end at last, make finished product.
2. low acid value solvent process of preparing chlorinated rubber according to claim 1, it is characterized in that: in reaction vessel, add stearate earlier in the described dechlorination treatment step, after stirring is dissolved stearate fully, again the weakly alkaline salt brine solution slowly is added drop-wise in the container and reacts, will react chlorinated natural rubber organic solution drying after finishing at last, make the powder finished product.
3. low acid value solvent process of preparing chlorinated rubber according to claim 1 is characterized in that: the umber of described stearate and the weakly alkaline salt organic solution that contains chlorinated natural rubber after with respect to 100 parts of steps (3) is a weight ratio:
0.1～2 part of stearate
0.01～0.4 part of weakly alkaline salt.
4. according to claim 1,2 or 3 described low acid value solvent process of preparing chlorinated rubber, it is characterized in that:
The concentration of described weakly alkaline salt brine solution is 0.5～3mol/L.
5. low acid value solvent process of preparing chlorinated rubber according to claim 4 is characterized in that: described weakly alkaline salt is one or more in S-WAT, sodium bisulfite, Sulfothiorine, sodium bicarbonate or the yellow soda ash.
6. according to claim 1,2 or 3 described low acid value solvent process of preparing chlorinated rubber, it is characterized in that: described stearate is one or more in calcium stearate, barium stearate, Zinic stearas, cadmium stearate or the lead stearate.
7. low acid value solvent process of preparing chlorinated rubber according to claim 1 and 2 is characterized in that: in the described low acid value solvent process of preparing chlorinated rubber: (1) natural rubber step of plasticating; (2) chemical degradation step; (3) reaction in chlorination reaction step and (4) the dechlorination treatment step is all carried out in water bath with thermostatic control, and the temperature of described water bath with thermostatic control is 40～80 ℃.
8. low acid value solvent process of preparing chlorinated rubber according to claim 1 and 2 is characterized in that: the reaction times is 0～60 minute in the water bath with thermostatic control of described step (4).
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| CNB2006101353453A CN100443506C (en) | 2006-12-20 | 2006-12-20 | Low acid value solvent process of preparing chlorinated rubber |
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| CN100443506C true CN100443506C (en) | 2008-12-17 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280028B (en) * | 2008-05-23 | 2010-12-08 | 童柏林 | Non-carbon tetrachloride waterless type green production method of chlorinated rubber |
| CN102250262A (en) * | 2010-12-28 | 2011-11-23 | 广东海洋大学 | Method for preparing viscosity controllable chlorinated natural rubber |
| CN104530264A (en) * | 2014-12-30 | 2015-04-22 | 安徽微威胶件集团有限公司 | Preparation method for producing chlorinated rubber |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4144203A (en) * | 1973-11-29 | 1979-03-13 | Bayer Aktiengesellschaft | Process for the preparation of chlorinated polymers |
| US5077345A (en) * | 1990-03-01 | 1991-12-31 | Exxon Chemical Patents Inc. | Halogenation of polymers with improved neutralization |
| CN1174846A (en) * | 1996-08-06 | 1998-03-04 | 拜尔公司 | Halogenated butyl rubbers having low halogen content |
| CN1249768A (en) * | 1997-03-06 | 2000-04-05 | 埃克森化学专利公司 | Stabilization of halogenated rubber |
-
2006
- 2006-12-20 CN CNB2006101353453A patent/CN100443506C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4144203A (en) * | 1973-11-29 | 1979-03-13 | Bayer Aktiengesellschaft | Process for the preparation of chlorinated polymers |
| US5077345A (en) * | 1990-03-01 | 1991-12-31 | Exxon Chemical Patents Inc. | Halogenation of polymers with improved neutralization |
| CN1174846A (en) * | 1996-08-06 | 1998-03-04 | 拜尔公司 | Halogenated butyl rubbers having low halogen content |
| CN1249768A (en) * | 1997-03-06 | 2000-04-05 | 埃克森化学专利公司 | Stabilization of halogenated rubber |
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