CN85101756A - Process for purifying rubber - Google Patents
Process for purifying rubber Download PDFInfo
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- CN85101756A CN85101756A CN85101756.8A CN85101756A CN85101756A CN 85101756 A CN85101756 A CN 85101756A CN 85101756 A CN85101756 A CN 85101756A CN 85101756 A CN85101756 A CN 85101756A
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- extraction agent
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Abstract
The present invention relevant purifies the method for ethene-dience rubber with extraction process, and extraction agent is to select for use its threshold temperature to be lower than the material of 435K.The temperature of extraction treatment is than the critical temperature height of extraction agent.Selected pressure will be on the emergent pressure of extraction agent.
Description
The invention relates to a kind of purifying method of rubber.This rubber is at least by vinyl group, and each group carbonatoms is formed by 3-8 alkene-1 group and diolefine group.Vinyl group is meant by ethene by the group in the polymkeric substance of polymerization be combined in addition, group in the polymkeric substance that alkene-1 group refers to be formed by alkene-1 polymerization that has 3-8 carbon atom in one or more each group, diolefine group refer to that one or more diolefine are by the group in the polymerization institute synthetic polymkeric substance.Reach hereinafter in the claim, this ethene-alkene-dience rubber abbreviates EADM rubber usually as.The present invention relates to the purifying method of ethylene-propylene-dience rubber (EPDM rubber) specially.
The alkene-1 that this EADM rubber has a 3-8 carbon atom by ethene, one or more per molecule is propylene particularly, with one or more diolefine, as cyclopentadiene, dicyclopentadiene, 1, the 4-hexadiene, 5-ethylidene norbornene-2,5-vinyl norbornene-2 or the like polymerization preparation, this polymerization is carried out in organic solvent usually, as polymerization in the alcohol of special boiling point, the polymkeric substance that generates is separated usually, and removes catalyzer in the water by the organic solution of polymkeric substance is brought into.US Patent specification 3,350 has been described a kind of available method No. 370, and its content Description herein.After above-mentioned polymerization, the EPDM rubber that is generated thus is wet bits saccharoid, and the bits grain is of a size of 2-5mm, this bits grain contains a large amount of impurity, be monomer residuum, particularly diolefine residuum, and other organic impuritys are as being used to carry out the solvent of this polyreaction and a large amount of water.Pure EADM rubber contains 90%(weight at least) vinyl group, alkene-1 group and the diolefine group that every group has 3-8 carbon atom, vinyl group.Weight ratio between alkene-1 group and the diolefine group is respectively 1: (0.15-3): (0.005-0.6).
Use various known dry technologies, be easy to remove the water that is contained in this bits grain, but, make its content be lower than the 0.2%(weight of pure EADM rubber gross weight as removing organic impurity) then difficulty is bigger.
In above-mentioned US Patent specification, propose to remove method that these organic impuritys purify the bits grain in 3,350,370 and be and place the bits grain water base suspension then with the steam processing that suspends.But consequently this method can not fully be removed impurity.
The present invention provides a kind of very simple and effective solution to these purifying problems.According to the present invention, purify a kind ofly at least by from ethene, from each group the alkene-1 of 3-8 carbon atom is arranged, the method for the rubber that the group of deriving out from diolefine is formed is characterized in that calculating by the per kilogram impurity in the rubber, and this rubber is used 20Nm at least
3(NPT) extraction agent is handled, and its temperature is higher than the critical temperature of this extraction agent, and pressure is higher than the emergent pressure of this extraction agent, and this extraction agent is selected from the material that critical temperature is lower than 435K.Reach the Nm in the following claim herein
3(NPT) represent that pressure is 1 crust, related substance m when temperature is 273K
3The volume number.The suitable material of enumerating is SO
2, N
2O, NO
2, NO, CO, CH
4, N
2, CO
2, the mixture of ethene, propylene and these components and these components with contain be less than the 50%(volume) the mixture of other component.
The critical temperature of said mixture must be lower than 435K.Preferably in the above-mentioned substance be: CO
2, ethene, propylene and the mixture of two or three material wherein.CO
2Be unusual effective extracting, and low price.Produce in a family that among the worker of EADM rubber ethene always can obtain, ethene is not only as extraction agent, and after its superiority was that also ethene is used as extraction agent, no matter whether carry out purifying treatment, this ethene also can be used as monomer, is used to prepare EADM rubber.Propylene has the advantage the same with ethene, critical temperature herein and emergent pressure.
An advantage of the present invention is to purify before the rubber, can separate rubber from most of water with the method that these those of skill in the art were familiar with, and preferably water-content is lower than the 5%(weight of gum).Rather effectively water-eliminating method be filter, pressure filter filters, centrifuging and evaporation or with the method for steaming.
The time of handling with extraction agent is with more suitable between 1 minute to 5 hours.In general, the time of processing is short more, and the degree of purification is just low more, can increase the treatment time, but does not obtain satisfied degree of purification.The Best Times of handling depends on the concentration of impurity in the rubber, desired minimum foreign matter content, rubber and extraction agent contact density, the size of temperature and rubber particles.
When handling with extraction agent, suitable temperature is between the critical temperature and 600K of selected extraction agent, then is optimum temps between the 300-470K.
When handling with extraction agent, used convenient pressure the emergent pressure of extraction agent and 10 times between the emergent pressure of extraction agent, angle only from implementing, reach such high pressure can be with expensive high-tension apparatus.Pressure is the most suitable between the 100-500 crust.
Purify assorted pressure of per kilogram in the EADM rubber, the amount of extraction agent is at 40-1500Nm
3(NPT) be advisable between.The very few meeting of general extraction dosage makes degree of purification too low, and amount only increases expense at most and do not obtain significantly good decontamination effect improving.
Learn for No. 68146 and No. 71793 by european patent application, from the ethene and propylene xln that contain polymkeric substance, remove material odorous, can be respectively under appropriate condition and temperature and at the medium that is used for removing odoriferous substance, handling should be with particulate dispersive polymeric material, and temperature is lower than 10 ℃ of Tcs at least.Opposite with these crystalline polymers, this EADM rubber is the diffusion of organic impurity in the unbodied material, and its performance is different fully, and expands in the presence of extraction agent.From unbodied EADM rubber, remove this problem of a large amount of organic impuritys, in above-mentioned patent application, do not relate to.Thus, unexpected really by the effective ways of removing impurity in the EADM rubber that can illustrate in this example.
For reaching good degree of purification with economical and practical method, operation has superiority on critical temperature and the emergent pressure being higher than.
Method of the present invention can be further detailed with following non-limitative example and comparative experiments.
Example 1:
Is the 13.46g mean particle size EPDM bits grain input 50cm of 3mm
3High pressure.Except 1.20%(weight) water, this bits grain also includes organic impurity.This organic impurity contains 0.61%(weight) carbonatoms be 6 compound and 1.32%(weight) diolefinic monomer.
Pressure is the 200bar(crust), temperature is 333K, CO
2With 0.600Nm per hour
3(NPT) speed is by this bits grain, and the time is 30 minutes.
After the extraction treatment, analyze the EPDM bits grain that stays again.It only contain be lower than 0.01(weight) carbonatoms is 6 compound and 0.01%(weight) organic impurity of diolefinic monomer.
The example II:
The EPDM bits grain that 16.89g is identical with routine I is sent into 50cm
3High pressure.Pressure is 200bar, and temperature is 333K, CO
2With 0.56Nm per hour
3(NPT) speed is through this bits grain, and the time is 15 minutes.
After the extraction treatment, analyze the EPDM bits grain that stays.It only contain be lower than 0.01%(weight) carbonatoms is 6 compound and 0.03%(weight) organic impurity of diolefinic monomer.
The example III:
The EPDM bits grain that 13.66g is identical with routine I is sent into 50cm
3High pressure.
Pressure is 150bar, and temperature is 313K, CO
2With 0.594Nm per hour
3(NPT) speed is through this bits grain.Time is 30 minutes.
After the extraction treatment, analyze the EPDM bits grain that stays.It only contain be lower than 0.01(weight) carbonatoms is 6 compound and 0.04%(weight) organic impurity of diolefinic monomer.
The example IV:
The EPDM bits grain that 17.12g is identical with routine I is put into 50cm
3High pressure.
Pressure is that 150bar, temperature are 313K, CO
2With 0.596Nm per hour
3(NPT) speed is through this bits grain.Time is 15 minutes.
After the extraction treatment, analyze the EPDM bits grain that stays.It only contain be lower than 0.01%(weight) carbonatoms is compound and the 0.15%(weight of b) and the organic impurity of diolefinic monomer.
The example V:
The EPDM bits grain that 16.83g is identical with routine I is put into 50cm
3High pressure.
Pressure is 200bar, and temperature is 308K, CO
2With 0.648Nm per hour
3(NPT) speed is through this bits grain, and the time is 15 minutes.
After the extraction treatment, analyze the EPDM bits grain that stays.It only contain be lower than 0.01%(weight) carbonatoms is 6 compound and 0.13%(weight) organic impurity of diolefinic monomer.
The example VI:
The EPDM bits grain that the 20.03g mean particle size is about 3mm is put into 50cm
3High pressure.Except 27%(weight) the water, this bits grain contains 4.6%(weight) carbonatoms is 6 compound and 0.98%(weight) organic impurity of diolefinic monomer.
Pressure is 200bar, and temperature is 333K, CO
2With 0.534Nm per hour
3(NPT) data rate stream is through this bits grain.Time is 3.5 hours.
After the extraction treatment, analyze the EPDM bits grain that stays.It only contains 0.03%(weight) organic impurity of diolefinic monomer.
The example VII:
20.04g, mean particle size is about the EPDM bits grain of 3mm and puts into 50cm
3High pressure.Except that 27%(weight) the water, this bits grain contains 4.1%(weight) carbonatoms is 6 compound and 0.98%(weight) organic impurity of diolefinic monomer.
Pressure is 200bar, and temperature is 333K, CO
2With 0.533Nm per hour
3(NPT) speed is through this bits grain.Time is 2 hours.
After the extraction treatment, analyze the EPDM bits grain that stays.It only contains 0.02%(weight) carbonatoms is 6 compound and 0.03%(weight) organic impurity of diolefinic monomer.
The example VIII:
20.13gEPDM bits grain is put into 50cm
3High pressure.Except that 26%(weight) the water, this bits grain contains 4.4%(weight) carbonatoms is 6 compound and 1.14%(weight) organic impurity of diolefinic monomer.
Pressure is 200bar, and temperature is 333K, CO
2With 0.461Nm per hour
3(NPT) speed is through this bits grain.Time is 1 hour.
After the extraction treatment, analyze remaining EPDM bits grain.It only contains 0.07%(weight) carbonatoms is 6 compound and 0.11%(weight) organic impurity of diolefinic monomer.
The example IX:
The EPDM bits grain that 15.72g is identical with routine I is put into 50cm
3High pressure in.
Pressure is 200bar, and temperature is 313K, and ethene is with 0.603Nm per hour
3(NPT) speed is through this bits grain.Time is 15 minutes.
After handling as the collection, analyze left EPDM bits grain.It only contain be lower than 0.001%(weight) carbonatoms is 6 compound and 0.09%(weight) organic impurity of diolefinic monomer.
Comparative experiments A:
The EPDM that the 29.67g mean particle size is about 3mm considers grain to be worth doing, puts into 50cm
3High pressure in.Except that 29%(weight) water, this bits grain also contains 5.3%(weight) carbonatoms is 6 compound and 0.94%(weight) organic impurity of diolefinic monomer.
Pressure is 200bar, and temperature is 333K, CO
2With 0.536Nm per hour
3(NPT) speed, through this bits grain, the time is 30 minutes.
After the extraction treatment, analyze left EPDM bits grain.It also contains 2.1%(weight) carbonatoms is 6 compound and 0.57%(weight) organic impurity of diolefinic monomer.
Comparative experiments B:
The EPDM bits grain that the 30.03g mean particle size is about 3mm is put into 50Nm
3High pressure.Except that 28%(weight) water, this bits grain also contains 5.5%(weight) carbonatoms is 6 compound and 1.08%(weight) organic impurity of diolefinic monomer.
Pressure is 200bar, and temperature is 333K, CO
2With 0.502Nm per hour
3(NPT) speed is through this bits grain, and the time is 30 minutes.
After the extraction treatment, analyze left EPDM bits grain.It also contains 1.9%(weight) carbonatoms is 6 compound and 0.58%(weight) organic impurity of diolefinic monomer.
Errata
Claims (10)
1, a kind of purifying method of rubber, this rubber are at least by from ethene, have the alkene-1 of 3-8 carbon atom and formed from the group that diolefine derives out from each group, and present method is characterised in that uses 20Nm at least to the per kilogram impurity in the rubber
3(NPT) extraction agent is handled, and when extraction its treatment temp to be higher than the threshold temperature of this extraction agent, pressure will be on the emergent pressure of this extraction agent, this extraction agent is lower than the material of 435K from critical temperature.
2, according to the method for claim 1, it is characterized in that, before handling, remove the water in the rubber to be clean, make water-content be lower than the 5%(weight of this rubber) with said extraction agent.
3,, it is characterized in that with the time that this extraction agent is handled being 1 to assign to 5 hours according to the method for claim 1 or 2.
4, a kind of method according to arbitrary claim among the claim 1-3, the effective extraction temperature that it is characterized in that this extraction agent is between the critical temperature and 600K of this extraction agent.
5, a kind of method according to arbitrary claim among the claim 1-4 is characterized in that, the suitable pressure when handling with this extraction agent the emergent pressure of this extraction agent and 10 times between this emergent pressure.
6, a kind of method according to arbitrary claim among the claim 1-5 is characterized in that, to the per kilogram impurity in this rubber, uses 40-1500Nm
3(NPT) this extraction agent.
7, a kind of method according to any claim among the claim 1-6 is characterized in that, used extraction agent CO
2, ethene, propylene or wherein both mixtures or the mixture of all these three components.
8, a kind of method according to claim 7 is characterized in that this extraction agent is CO
2
9, a kind of method according to claim 7 is characterized in that this extraction agent is the mixture of ethene, propylene or this two component.
10, according to the purification EADM of any method preparation of claim 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85101756 CN1005259B (en) | 1983-11-17 | 1985-04-01 | Process for purifying rubber |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8303942A NL8303942A (en) | 1983-11-17 | 1983-11-17 | PROCESS FOR THE PURIFICATION OF A RUBBER. |
| CN 85101756 CN1005259B (en) | 1983-11-17 | 1985-04-01 | Process for purifying rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85101756A true CN85101756A (en) | 1987-01-31 |
| CN1005259B CN1005259B (en) | 1989-09-27 |
Family
ID=25741490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85101756 Expired CN1005259B (en) | 1983-11-17 | 1985-04-01 | Process for purifying rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1005259B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110248967A (en) * | 2017-02-10 | 2019-09-17 | 赢创德固赛有限公司 | Method of the preparation for the polyalkenamer of packaging applications |
| CN114425185A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Device for removing volatile organic compounds in polymer emulsion |
-
1985
- 1985-04-01 CN CN 85101756 patent/CN1005259B/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110248967A (en) * | 2017-02-10 | 2019-09-17 | 赢创德固赛有限公司 | Method of the preparation for the polyalkenamer of packaging applications |
| CN114425185A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Device for removing volatile organic compounds in polymer emulsion |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1005259B (en) | 1989-09-27 |
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