MXPA96006713A - Process for the removal or elimination of an alkaline metal compound of a polimer cement - Google Patents
Process for the removal or elimination of an alkaline metal compound of a polimer cementInfo
- Publication number
- MXPA96006713A MXPA96006713A MXPA/A/1996/006713A MX9606713A MXPA96006713A MX PA96006713 A MXPA96006713 A MX PA96006713A MX 9606713 A MX9606713 A MX 9606713A MX PA96006713 A MXPA96006713 A MX PA96006713A
- Authority
- MX
- Mexico
- Prior art keywords
- acid
- metal compound
- alkali metal
- cement
- lithium
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000004568 cement Substances 0.000 title claims abstract description 14
- 238000003379 elimination reaction Methods 0.000 title description 2
- 150000002736 metal compounds Chemical class 0.000 title description 2
- 239000002253 acid Substances 0.000 claims abstract description 54
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 19
- 239000011414 polymer cement Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 30
- 229910052744 lithium Inorganic materials 0.000 claims description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000003456 ion exchange resin Substances 0.000 claims description 9
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 229920001429 Chelating resin Polymers 0.000 description 15
- 238000005984 hydrogenation reaction Methods 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000003999 initiator Substances 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- -1 alkali metal alkoxides Chemical class 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N activated carbon Substances [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000000977 initiatory Effects 0.000 description 3
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- IBVPVTPPYGGAEL-UHFFFAOYSA-N 1,3-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=CC(C(C)=C)=C1 IBVPVTPPYGGAEL-UHFFFAOYSA-N 0.000 description 1
- XRBQEYWBWZFUIJ-UHFFFAOYSA-N 2-ethylhexanoic acid;nickel Chemical compound [Ni].CCCCC(CC)C(O)=O XRBQEYWBWZFUIJ-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- 210000002356 Skeleton Anatomy 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N Triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- WMWXXXSCZVGQAR-UHFFFAOYSA-N dialuminum;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3] WMWXXXSCZVGQAR-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000003134 recirculating Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229940086542 triethylamine Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Abstract
The present invention provides a process for removing an alkali metal compound from a polymeric cement, comprising: i) washing the polymer cement with a weak acid to remove the alkali metal compound from the polymeric cement, II) removing the alkali metal compound from the acid and iii) recycle the acid to wash more polymer cement
Description
PROCESS FOR THE REMOVAL OR ELIMINATION OF AN ALKALINE METAL COMPOUND OF A POLYMERIC CEMENT
FIELD OF THE INVENTION
The present invention relates to a process for removing an alkali metal compound from a polymer cement. More specifically, the present invention relates to a process for removing an alkali metal compound from a functionalized low viscosity polymer cement.
BACKGROUND OF THE INVENTION
Acids are frequently used to remove catalytic residues and alkali metal compounds from polymeric cements. Strong acids such as sulfuric acid and phosphoric acid are particularly effective in the washing of hydrogenation catalyst residues (nickel and aluminum) and alkali metal compounds (lithium) from polymeric cements. If it is desired to recycle or recirculate the acids, the ion exchange is used, but it has been found that it is very difficult to remove the lithium from the acids since most of the ion exchange resins have a very low selectivity to remove the lithium. The process is even less effective if the washing step REF: 23810 requires the use of a concentrated acid. Surprisingly, it has now been found that the selectivity of ion exchange processes for the removal of lithium from an acid can be improved when a weak acid such as citric acid or acetic acid is used in the wash step, instead of a strong acid.
DETAILED DESCRIPTION OF THE INVENTION
Accordingly, the present invention relates to a process for removing an alkali metal compound from a polymeric cement, comprising: 1) washing the polymeric cement with a weak acid to remove the alkali metal compound from the polymer cement; ii) remove the alkali metal compound from the acid; and iii) recycling or recirculating the acid to wash more polymeric cement. It should be noted that in the context of the present invention a weak acid is defined as an acid having a pKa greater than 3. Suitably, the weak acid has a pKa of less than 6. Preferably, the weak acid is selected from the group consisting of of citric acid and acetic acid. A further improvement is established when in step ii) the weak acid is contacted with a first functional ion exchange resin to remove the nickel and aluminum compounds from the acid; and the acid thus obtained is then contacted with a second functional ion exchange resin to remove the alkali metal compound from the acid. The second ion exchange resin is more selective for removing the alkali metal compound from the acid than the first ion exchange resin is. Suitably, use is made of a weak acid solution. It has also been found that several ion exchange resins have a higher selectivity to remove lithium than that of other resins. These are AMBERLYST 35 and AMBERLYST 15, (trademarks of Rohm and Haas for strong acid resins, form H +), and BAYER 0C 1501, (a trademark of Miles for a strong acid resin, form H +). It has been found that the removal of lithium from an acid solution is improved in a process where nickel and aluminum are first removed on a resin such as AMBERLITE 200C (a registered trademark of Rohm and Haas for a strong acid resin) and the The lithium is then removed in one of the second ion exchange resins which have a higher selectivity to remove the lithium. The present invention is particularly applicable for low viscosity functionalized polymer cements (described hereinafter) and relates in particular to the removal of lithium after hydrogenation. The polymerization process suitably uses a lithium initiator, which is preferably a protected functional initiator (PFI). PFI diols contain one mole of lithium per mole of polymer, and the termination step produces a lithium salt. The presence of the lithium salt can affect the operation of the hydrogenation, although the magnitude of this impact is still not fully understood. In cases where the operation of hydrogenation is acceptable, the lithium salt can be removed after hydrogenation in the same step used to remove the hydrogenation catalyst, which contains nickel and aluminum. As mentioned hereinabove, the removal of the lithium salts from the polymer cement after the hydrogenation can be effected by washing the cement with a weak acid such as citric acid or acetic acid. This transfers the cations to the acid solution, which must then be treated to remove the salts before recycling. AMBERLYST 35 resin is preferred and has a higher capacity and selectivity towards lithium than AMBERLITE 200C resin. A two-bed configuration, in which a bed of AMBERLITE 200C is followed by a bed of AMBERLYST 35, achieves the best combination or compromise between the selectivity, capacity, and regenerability of the resin in a fixed-bed process. The process is run or operated preferably at a temperature within the range of 21 to 77 ° C, preferably in the range of 50 to 65 ° C. The acid is preferably citric acid in a concentration of 0.2 to 40% by weight or acetic acid in a concentration of 0.2 to 40% by weight, and the lithium salt at a concentration of 0.005 to 5% by weight. The process is carried out preferably at a rate of 2 bed volumes per hour. Any alkali metal compound commonly found in a polymeric cement when an alkali metal compound is used as the catalyst or initiator can be removed from the polymer cement. These include alkali metal hydrides, alkali metal alkoxides and alkali metal hydroxides. It will be understood that a polymer cement is the polymer solution resulting from a polymerization reaction and usually comprises the components such as the polymer formed, the organic solvent (s), the unconverted monomer and the initiator of the polymer. polymerization, residues of the hydrogenation catalyst, etc. Functionalized low viscosity polymer cements can be made by anionic polymerization of the conjugated dienes hydrocarbons with lithium initiators as is well known (see for example US Patent Nos. 4,039,503 and Re. 27,145 the descriptions of which are incorporated herein by reference). reference Polymerization begins with a monolithium, dilithium, or polylithium initiator which builds a living polymeric skeleton at each lithium site Typical polymeric living structures containing polymerized conjugated diene hydrocarbons are: XB Li XAB Li XABA Li Li BYB Li Li ABYBA Li wherein B represents the polymerized units of one or more conjugated diene hydrocarbons such as butadiene or isoprene A represents the polymerized units of one or more vinyl aromatic compounds such as styrene. X is the residue of a monolithium initiator such as sec-butyllithium, and Y e s the residue of a dilithium initiator such as the diacid of sec-butyllithium and m-diisopropenylbenzene. Some structures, including those belonging to polylithium initiators or the random units of styrene and a conjugated diene, generally have a limited practical utility although known in the art. The anionic polymerization of the conjugated diene hydrocarbons is typically controlled with structure modifiers such as diethyl ether or glyme (1,2-diethoxyethane) to obtain the desired amount of 1,4 addition. As described in Re 27,145, the level of the 1,2-addition of a butadiene polymer or copolymer can greatly affect the elastomeric properties after hydrogenation. The initiation of the dilithium with the sec-butyllithium (s BuLi) duct and the midopropenylbenzene also requires the presence of a non-reactive coordinating agent such as diethyl ether, the glyme, or the triethyl amine, otherwise the initiation of the monolithium is achieved. The ether is typically present during the anionic polymerization as described above, and the amount of the ether typically necessary to obtain the specific polymer structures has been sufficient to provide initiation of the dilithium. Alternatively, the anionic polymerization of the conjugated dienes can be effected using protected functional initiators (PFIs) such as those described for example in U.S. Pat. Nos. 5,391,663 and 5,146,168, which are incorporated herein by reference. Anionic polymerization is often terminated by the addition of water to remove lithium as lithium hydroxide (LiOH) or by the addition of an alcohol (ROH) to remove lithium as a lithium alkoxide (LiOR). For polymers having terminal functional groups, the living or active polymer chains are preferably terminated with hydroxyl, carboxyl, phenol, epoxy or amine groups by the reaction with ethylene oxide, carbon dioxide, a protected hydroxystyrene monomer, ethylene oxide. more epichlorohydrin, or the amine compounds listed in US Pat. No. 4,791,174, respectively. The termination of living or active anionic polymers to form functional end groups is described, for example, in U.S. Pat. Nos. 4,417,029, 4,518,753 and 4,753,991 which are incorporated herein by reference. Of particular interest for the present invention are terminal hydroxyl, carboxyl, phenol, epoxy and amine groups. Such polymers with number average molecular weights between 1000 and 20,000, as measured by gel permeation chromatography, are low viscosity functionalized polymers.
The hydrogenation of at least 90%, preferably at least 95%, of the unsaturation in the low molecular weight butadiene polymers is achieved with the nickel catalysts as described for example in U.S. Pat. Nos. 27,145 and 4,970,254, the latter also being incorporated herein by reference. The preferred nickel catalyst is a mixture of nickel 2-ethylhexanoate and triethylaluminum. It is preferable to remove the nickel catalyst after hydrogenation by stirring the polymer solution with the weak acid. The invention will now be illustrated by means of the following Examples.
EXAMPLES
Example 1
Two column experiments were carried out to compare the effectiveness of lithium removal from two acids that have the same normal but different acid strengths. Phosphoric acid and citric acid were selected for this comparison. The levels of lithium, nickel and aluminum in both acids were similar. The conditions were also the same
Process processes such as temperature, flow velocity, column dimensions, specific resin used, etc. In the experiment with 20% by weight phosphoric acid (2.2 N), lithium rupture or penetration occurred after 2 bed volumes (BV) of the acid had been treated. In the experiment with citric acid at 36% by weight (2.2 N), the rupture or penetration of lithium occurred at 16 bed volumes.
Example 2
Two column experiments were carried out with 20% by weight phosphoric acid containing 280 ppm Li and 100 ppm Ni and Al each. In the first experiment, a bed of 20 ce of AMBERLITE 200C was used. In the second experiment, the bed consisted of 10 ce of AMBERLITE 200C followed by 10cc of AMBERLYST 35. All other parameters such as flow rate, temperature, L / D of the bed, etc., were the same in both experiments The results obtained in these tests show that using the two resins in series increased the volume of the acid treated before the rupture or penetration of lithium from 2 bed volumes to 6 bed volumes.
Example 3
The selectivity towards the highest lithium of AMBERLYST 35, AMBERLYST 15, and BAYER OC 1501 was identified in the isothermal tests. The research experiments to select the best resins consisted of agitation tests to balance the resin or the adsorbent with a 2% by weight phosphoric acid solution containing 230 ppm lithium. The weight ratio of the acid to the adsorbent in these tests was 100: 1 and the temperature was 22 ° C. After equilibration, the residual lithium in the acid solution was determined by ion chromatography. From these results, the most effective materials for the removal of lithium were identified. The test included chelating resins, strong acid resins, a weak acid resin, a strong basic resin with and without the addition of loc chelating agents, an inorganic oxide, inorganic ion exchangers, several zeolites, alumina, activated carbon with acid, and activated carbon impregnated with a crowned ether. The results identified the AMBERLYST 35, BAYER 0C 1501, and AMBERLYST 15 as the most effective materials for the removal of lithium. It is not clear why these resins are particularly effective. It seems that one of the key factors is that these strong acid resins are in the H + form. But even among the strong acid resins in the H + form, there seem to be some differences in their effectiveness. It is suspected that these are due to differences in structure (eg, pore size) and / or strength of the acid.
It is noted that in relation to this date the best method known by the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.
Having described the invention as above, priority is claimed as contained in the following
Claims (6)
1. A process for removing an alkali metal compound from a polymer cement, characterized in that it comprises: 1) washing the polymer cement with a weak acid to remove the alkali metal compound from the polymer cement; ii) remove the alkali metal compound from the acid; and iii) recycle the acid to wash more polymeric cement.
2. A process according to claim 1, characterized in that the alkali metal is lithium.
3. A process according to claim 1 or 2, characterized in that the alkali metal compound is removed from the acid by ion exchange.
4. A process according to any of claims 1 to 3, characterized in that the weak acid is selected from the group consisting of citric acid and acetic acid.
5. A process of compliance with any of the. claims 1 to 4, characterized in that the polymeric cement is a functionalized polymeric cement of low viscosity.
6. A process according to any of claims 1 to 5, characterized in that in step ii) the weak acid is contacted with a first functional ion exchange resin to remove the nickel and aluminum compounds of the acid; and the acid thus obtained is then contained with a second functional ion exchange resin to remove the alkali metal compound from the acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US952795P | 1995-12-28 | 1995-12-28 | |
| US009527 | 1995-12-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| MXPA96006713A true MXPA96006713A (en) | 1997-06-01 |
| MX9606713A MX9606713A (en) | 1997-06-28 |
Family
ID=21738201
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| MX9606713A MX9606713A (en) | 1995-12-28 | 1996-12-19 | Removal of lithium from polymer cements. |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US5847072A (en) |
| EP (1) | EP0781784B1 (en) |
| JP (1) | JPH09202674A (en) |
| KR (1) | KR970042618A (en) |
| CN (1) | CN1121422C (en) |
| BR (1) | BR9606167A (en) |
| CA (1) | CA2193777A1 (en) |
| DE (1) | DE69603572T2 (en) |
| ES (1) | ES2134559T3 (en) |
| MX (1) | MX9606713A (en) |
| TW (2) | TW338765B (en) |
| ZA (1) | ZA9610857B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875702B (en) * | 2011-07-13 | 2014-11-19 | 中国石油化工集团公司 | Method for removing metals from polymer |
| CN104245752A (en) | 2012-04-26 | 2014-12-24 | 旭化成化学株式会社 | Method for producing polymer |
| CN111499055B (en) * | 2020-06-17 | 2020-10-27 | 长沙华时捷环保科技发展股份有限公司 | Comprehensive treatment method of lithium rubber synthetic wastewater |
| CN115286733B (en) * | 2022-08-26 | 2023-08-01 | 盘锦三力中科新材料有限公司 | Method for removing metal impurities in polymethacrylic acid resin reaction mixture |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3176037A (en) * | 1961-01-23 | 1965-03-30 | Phillips Petroleum Co | Removal of metal contaminants from polymer solutions |
| USRE27145E (en) | 1969-05-20 | 1971-06-22 | Side-chain | |
| BE788698A (en) * | 1971-09-14 | 1973-03-12 | Shell Int Research | PROCESS FOR THE REMOVAL OF METAL CONTAMINANTS IN A POLYMER |
| US4098990A (en) * | 1974-01-10 | 1978-07-04 | Ruhrchemie Aktiengesellschaft | Process for the purification of low pressure polymerized polyolefin powder using recycled, anion-exchange treated water |
| JPS568869B2 (en) | 1975-02-19 | 1981-02-26 | ||
| US4098991A (en) * | 1975-09-12 | 1978-07-04 | The Firestone Tire & Rubber Company | Removal of catalytic residues from hydrogenated thermoplastic or elastomeric polymers |
| JPS541364A (en) * | 1977-06-06 | 1979-01-08 | Kanegafuchi Chem Ind Co Ltd | Purification of crude polyalkylene oxide |
| US4417029A (en) | 1981-08-03 | 1983-11-22 | Atlantic Richfield Company | Derivatization of star-block copolymers |
| US4518753A (en) | 1982-04-26 | 1985-05-21 | National Research Development Corporation | Anionic polymerization of conjugated dienes in the presence of hindered triaryl boron or aluminum derivatives |
| US4636540A (en) * | 1985-07-08 | 1987-01-13 | Atlantic Richfield Company | Purification of polymer solutions |
| DE3527909A1 (en) | 1985-08-03 | 1987-02-12 | Basf Ag | POLYMERISATES WITH AMINO GROUPS, THEIR PRODUCTION AND USE |
| DE3611421A1 (en) | 1986-04-05 | 1987-10-08 | Basf Ag | POLYMERISATES WITH AMINO GROUPS, THEIR PRODUCTION AND USE |
| GB8722235D0 (en) * | 1987-09-22 | 1987-10-28 | Enichem Elastomers Ltd | Removal of catalyst residues |
| US4992529A (en) * | 1987-10-29 | 1991-02-12 | Shell Oil Company | Method for separating metal contaminants from organic polymers |
| US4970254A (en) | 1988-09-22 | 1990-11-13 | Shell Oil Company | Method for hydrogenating functionalized polymer and products thereof |
| US5073621A (en) * | 1990-04-16 | 1991-12-17 | Shell Oil Company | Removal of group VIII metal catalyst from polymer cements by extraction with aqueous dicarboxylic acid |
| US5212285A (en) * | 1990-06-14 | 1993-05-18 | Shell Oil Company | Removal of hydrogenation catalyst from polymer solutions by catalyzed precipitation |
| US5146168A (en) | 1990-10-01 | 1992-09-08 | Actron Manufacturing Company | Variable sensitivity timing analyzer |
| US5391663A (en) * | 1993-11-22 | 1995-02-21 | Shell Oil Company | Protected functional initiators for making terminally functionalized polymers |
-
1996
- 1996-05-23 US US08/652,261 patent/US5847072A/en not_active Expired - Lifetime
- 1996-12-12 ZA ZA9610857A patent/ZA9610857B/en unknown
- 1996-12-18 DE DE69603572T patent/DE69603572T2/en not_active Expired - Fee Related
- 1996-12-18 EP EP96203601A patent/EP0781784B1/en not_active Expired - Lifetime
- 1996-12-18 ES ES96203601T patent/ES2134559T3/en not_active Expired - Lifetime
- 1996-12-19 MX MX9606713A patent/MX9606713A/en unknown
- 1996-12-23 CA CA002193777A patent/CA2193777A1/en not_active Abandoned
- 1996-12-26 JP JP8359877A patent/JPH09202674A/en not_active Withdrawn
- 1996-12-26 CN CN96123977A patent/CN1121422C/en not_active Expired - Fee Related
- 1996-12-26 BR BR9606167A patent/BR9606167A/en not_active IP Right Cessation
- 1996-12-27 KR KR1019960073922A patent/KR970042618A/en active IP Right Grant
-
1997
- 1997-01-24 TW TW086100790A patent/TW338765B/en active
- 1997-01-24 TW TW086100789A patent/TW403723B/en not_active IP Right Cessation
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