CN1147517C - Selective hydrogenation method for coupling process of preparing styrene block copolymer containing conjugated diene - Google Patents
Selective hydrogenation method for coupling process of preparing styrene block copolymer containing conjugated dieneInfo
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- CN1147517C CN1147517C CNB011285184A CN01128518A CN1147517C CN 1147517 C CN1147517 C CN 1147517C CN B011285184 A CNB011285184 A CN B011285184A CN 01128518 A CN01128518 A CN 01128518A CN 1147517 C CN1147517 C CN 1147517C
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- hydrogenation
- conjugated diene
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- butyl lithium
- polymkeric substance
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Abstract
The present invention provides a selective hydrogenation method for preparing a styrene block polymer containing conjugated diene by a coupling method. In a selective hydrogenation process, the weight concentration of the polymer in a solvent is controlled within a range of 5% to 25%; firstly, a certain quantity of organic alkali metallic compounds are added; H2 is supplied; as a result, the organic alkali metallic compounds are converted into hydride under the condition of the atmosphere of the H2; secondly, a cocatalyst is added for regulating and stabilizing the hydrogenation activity of a main catalyst; thirdly, a compound in the class of dicyclopentadienyl titanium as the main catalyst is added; the selective hydrogenation reaction is sustained for 1 hours to 2 hours at the temperature of 60 DEG C to 90 DEG C and the pressure of 0.5Mpa to 2.5Mpa. The present invention solves the hydrogenation problem of styrene block polymers containing conjugated diene and without containing reactive species; the hydrogenation degree of the conjugated diene block is larger than 95%.
Description
The present invention relates to a kind of selection method for hydrogenation of the styrenic block polymkeric substance that contains conjugated diene by coupling method preparation.
Patent USP4,501,857 introduce a kind of selection method for hydrogenation that contains the styrenic block polymkeric substance of conjugated diene, selected catalyzer is two luxuriant titanium compounds, at with the butyllithium being initiator synthetic line style block polymer, hydrogenation process is directly to add Primary Catalysts to carry out in containing the line style block polymer of active lithium; And be Primary Catalysts solution and butyl lithium solution pre-reaction to be joined in the line style block polymerization composition glue liquid afterwards in 5 minutes again to carry out earlier to the method for hydrogenation of the line style block polymer that do not contain active lithium.
Patent USP4,980,421 introduce a kind of selection method for hydrogenation that contains the styrenic block polymkeric substance of conjugated diene, with two luxuriant titanium compounds is Primary Catalysts, in hydrogenation process, need to emphasize adding alkoxyl group lithium (RO-Li) and organometallic compound (as organoaluminum, organic-magnesium, organic zinc) to make reductive agent simultaneously, its Ti: the Li atomic ratio is (2～1): 20, and Ti and organic-magnesium or aluminium or zinc, mol ratio is (2～1): 20.
Patent CN1,067,898A improves at the shortcoming that above-mentioned patent need be added reductive agent, emphasizes directly to utilize in the linear conjugated diene polymerization process not suspended as yet active initiator atom (active Li) to reduce two luxuriant titanium class catalyzer.
Patent ZL97108079.8, by introducing have the auxiliary agent (as the phthalic acid dioctyl phthalate, phthalic acid two is sad etc.) of different functional groups thus the activity of stablizing two luxuriant titanium class Primary Catalysts active body reaches rapidly and efficiently selects the hydrogenant purpose.
The line style block polymer is meant with vinylbenzene, alpha-methyl styrene etc., with organometallic compound such as n-Butyl Lithium, s-butyl lithium, tert-butyl lithium etc. is that initiator or homopolymerization or copolymerization are first section of block, structure is RLi, adds conjugated diene and continue to aggregate into RR on the basis of RLi
1Li adds monomer polymerizations such as vinylbenzene, alpha-methyl styrene then and becomes RR
1RLi, promptly said line style block polymer, it is to have active organometallic compound.And be meant at RR with the polymkeric substance of coupling method preparation
1Li or RR
1Add the polymkeric substance that dichlorodimethylsilane or trichlorine trimethyl silane or coupling agent couplings such as silicon tetrachloride or haloalkane form two arms or three arms or four arms on the basis of RLi, do not contain spike in these polymkeric substance.
Above-mentioned patent all only relates to the selection method for hydrogenation that the styrenic that contains conjugated diene contains the block polymer of spike, and does not relate to the selection method for hydrogenation by the styrenic block polymkeric substance that contains conjugated diene of coupling method preparation.Patent USP4,501,857 pairs of block polymers that do not contain spike are selected hydrogen to adopt earlier Primary Catalysts solution and butyl lithium solution pre-reaction to be joined in the line style block polymerization composition glue liquid afterwards in 5 minutes again to carry out, this method complex process, long flow path, reach higher degree of hydrogenation, the large usage quantity of Primary Catalysts dicyclopentadiene titanium dichloride, the 100g polymkeric substance adds more than the 0.2mmol.
For reaching the selection hydrogenant purpose to the styrenic block polymkeric substance that contains conjugated diene that is prepared by coupling method, the present invention takes following technical scheme:
1) in selecting hydrogenation process, the weight concentration of controlling polymers in solvent is 5%～25%;
2) add organic alkali metal compound earlier, logical H
2, make organic alkali metal compound under the atmosphere of hydrogen, be converted into hydride, the molar weight of organic alkali metal compound is 4 times～24 times of Primary Catalysts;
3) add promotor, regulate and the hydrogenation activity of stable Primary Catalysts, its molar weight is 1/16～1/8 of a Primary Catalysts;
4) add Primary Catalysts two luxuriant titanium compounds then, the add-on of two luxuriant titanium compounds is: the 100g polymkeric substance adds 0.05mmol～0.2mmol, and two luxuriant titanium compounds are converted into the ligand of catalytic activity under the reductive action of hydride;
5), carried out selective hydrogenation reaction under pressure 0.5Mpa～2.5Mpa 1 hour～2 hours 60 ℃～90 ℃ of temperature.
Wherein organic alkali metal compound can be one or more in n-Butyl Lithium, tert-butyl lithium, s-butyl lithium, the naphthalene lithium; Promotor be adjacent to or m-phthalic acid and C
1-C
12Alcohol generates dibasic ester class, maleic dioctyl phthalate and C
1-C
12Alcohol generates one or more in the dibasic ester class.
Adopt aforesaid method to selection hydrogenation, in 1 hour～2 hours, can make conjugated diene section degree of hydrogenation greater than 95% by the styrenic block polymkeric substance that contains conjugated diene of coupling method preparation.
Below in conjunction with embodiment the present invention is described in detail:
Embodiment 1～9: Different L i/Ti is to the influence of hydrogenation
In the 10L polymeric kettle, be initiator with the n-Butyl Lithium, hexanaphthene is the synthetic SB reactive polymer of solvent, and wherein SB concentration is 18%, and S/B=3/7 (S-vinylbenzene, B-divinyl) uses SiCl
4Make coupling agent coupling star-shaped sbs (its SBS is 525g).Above-mentioned star-shaped sbs glue is changed in the 10L hydrogenation stirred autoclave, heat up and the different n-Butyl Lithiums of measuring of adding, and feed H
2, when temperature rises to 50 ℃, add promotor dimethyl phthalate 0.08mmol, when temperature rises to 70 ℃, add 0.6825mmol dicyclopentadiene titanium dichloride, constant temperature, pressure be 1.04Mpa (gauge pressure) down reaction get the glue sample after 2 hours and analyze.Its result is as follows:
| Embodiment | N-Butyl Lithium/Primary Catalysts | Reaction degree of hydrogenation % | |
| Conjugated diene | Benzene is bad | ||
| 1 | 2/1 | 80.0 | ＜2 |
| 2 | 4/1 | 95.0 | ＜2 |
| 3 | 6/1 | 96.7 | ＜2 |
| 4 | 8/1 | 98.7 | ＜2 |
| 5 | 10/1 | 97.6 | ＜2 |
| 6 | 12/1 | 99.0 | ＜2 |
| 7 | 18/1 | 97.5 | ＜2 |
| 8 | 20/1 | 96.8 | ＜2 |
| 9 | 24/1 | 95.1 | ＜2 |
Annotate: the degree of hydrogenation of conjugated diene is to determine that by the degree of unsaturation (being iodine number) before and after the hydrogenation in the iodimetry,iodometry survey polymkeric substance phenyl ring content that the benzene ring hydrogenation degree is surveyed hydrogenation front and back in the polymkeric substance by ultraviolet spectrophotometry is determined.As follows.
Embodiment 10～12: the hydrogenation of the star-type polymer that forms with different coupling agents
Respectively in the 10L polymeric kettle, with the n-Butyl Lithium is initiator, and hexanaphthene is a solvent, synthetic SB reactive polymer, wherein SB concentration is 18%, the SB molecular weight is 40,000, and S/B is that 3/7 (S-vinylbenzene, B-divinyl) adds dichlorodimethylsilane afterwards respectively, coupling becomes the different structure polymkeric substance to trichlorine monomethyl silane with silicon tetrachloride, above-mentioned glue is put into 10L hydrogenation stirred autoclave respectively be warming up to 50 ℃, add the 5mmol n-Butyl Lithium, and feed H
2, add promotor dimethyl phthalate 0.08mmol again, when temperature rises to 70 ℃, add 0.6825mmol dicyclopentadiene titanium dichloride, constant temperature, pressure be 1.0Mpa (gauge pressure) down reaction get the glue sample after 2 hours and analyze.Its result is as follows:
| Embodiment | The coupling mode | Degree of hydrogenation % | ||
| Molecular weight (ten thousand) | The PB section | The PS section | ||
| 10 | The dichlorodimethylsilane coupling | 8 | 98.2 | ＜3 |
| 11 | The trichlorine monomethyl is silane coupled | 12 | 98.0 | ＜3 |
| 12 | Silicon tetrachloride | 16 | 99.1 | ＜3 |
Embodiment 13～18: the hydrogenation of the star-type polymer of contents of ethylene in the difference
In the 10L still, be initiator with the n-Butyl Lithium, hexanaphthene be solvent synthetic in contents of ethylene be respectively four each 525g of arm SBS of 11%, 18%, 25%, 37%, 45%, wherein S/B is 3/7, molecular weight is 200,000.Add n-Butyl Lithium 6mmol, feed H
2, promotor dimethyl phthalate 0.06mmol, the luxuriant diene titanium dichloride of dicyclo 0.6825mmol at 70 ℃, carries out hydrogenation under the 1.0Mpa, react sampling analysis after 2 hours.The result is as follows:
| Embodiment | Middle contents of ethylene | Degree of hydrogenation % | |
| PB section degree of hydrogenation | PS section degree of hydrogenation | ||
| 13 | 11 | 97.2 | ＜3 |
| 14 | 18 | 98.5 | ＜3 |
| 15 | 25 | 98.7 | ＜3 |
| 16 | 37 | 98.0 | ＜3 |
| 17 | 45 | 99.2 | ＜3 |
| 18 | 55 | 99.5 | ＜3 |
Embodiment 19～22: different lithium alkylides are to the influence of hydrogenation
Adding the 3500ml hexanaphthene in the 10L still, is the synthetic respectively 525g of initiator with the normal-butyl, changes in the hydrogenation still after the S/B=33/67, four arm SBS of molecular weight 200,000, adds different organic alkali metal compound 10mmol, feeds H
2, add promotor dimethyl phthalate 0.08mmol, add 0.6825mmol dicyclopentadiene titanium dichloride again, at 70 ℃, constant temperature and pressure hydrogenation under the 1.0Mpa, sampling analysis after 2 hours.The result is as follows:
| Embodiment | Organolithium | Degree of hydrogenation % | |
| PB section degree of hydrogenation | PS section degree of hydrogenation | ||
| 19 | N-Butyl Lithium | 98.6 | ＜3 |
| 20 | S-butyl lithium | 99.2 | ＜3 |
| 21 | Tert-butyl lithium | 98.6 | ＜3 |
| 22 | How lithium | 97.9 | ＜3 |
Embodiment 23～26: different promotors are to the influence of hydrogenation
Adding the 3500ml hexanaphthene in the 10L still, is the synthetic 525g of initiator with the n-Butyl Lithium, and S/B=33/67, molecular weight change the hydrogenation still over to after 200,000 the four arm SBS, add after the 10mmol n-Butyl Lithium, feed H
2, add different promotor 0.06mmol, add 0.6825mmol dicyclopentadiene titanium dichloride again, at 70 ℃, constant temperature and pressure hydrogenation under the 1.0Mpa, sampling analysis after 2 hours.The result is as follows:
| Embodiment | Promotor | Degree of hydrogenation % | |
| PB section degree of hydrogenation | PS section degree of hydrogenation | ||
| 23 | Dimethyl phthalate | 99.0 | ＜3 |
| 24 | Dimethyl terephthalate (DMT) | 99.2 | ＜3 |
| 25 | Dimethyl isophthalate | 98.6 | ＜3 |
| 26 | Dimethyl maleate | 98.4 | ＜3 |
Embodiment 27～31: different promotor add-ons is to the influence of hydrogenation
Get the glue synthesis condition with embodiment 1～9, glue (containing 525g four arm SBS) is changed in the hydrogenation still add after the 0.06mmol n-Butyl Lithium, feed H
2, the add-on of change promotor dimethyl phthalate adds 0.6825mmol dicyclopentadiene titanium dichloride again, at 70 ℃, and constant temperature and pressure hydrogenation under the 1.0Mpa, sampling analysis after 2 hours.The result is as follows:
| Embodiment | Promotor: Ti (mol) | Degree of hydrogenation % | |
| PB section degree of hydrogenation | PS section degree of hydrogenation | ||
| 27 | 1∶8 | 96 | ＜3 |
| 28 | 1∶10 | 97.2 | ＜3 |
| 29 | 1∶12 | 98.0 | ＜3 |
| 30 | 1∶14 | 96.2 | ＜3 |
| 31 | 1∶16 | 95.3 | ＜3 |
Embodiment 32～36: temperature of reaction and reaction pressure are to the influence of hydrogenation
Glue is synthetic with embodiment 1-9, contains four arm SBS525g in the glue, at catalyzer dicyclopentadiene titanium dichloride 0.6825mmol, promotor dimethyl phthalate 0.08mmol, n-Butyl Lithium 7mmol changes hydrogenation reaction temperature and pressure, sampling analysis after 2 hours.The result is as follows:
| Embodiment | The hydrogenation reaction temperature | Hydrogenation reaction pressure | Degree of hydrogenation % | |
| PB section degree of hydrogenation | PS section degree of hydrogenation | |||
| 32 | 50 | 1.0 | 95.6 | ＜3 |
| 33 | 90 | 1.0 | 96.0 | ＜3 |
| 34 | 70 | 1.0 | 98.9 | ＜3 |
| 35 | 70 | 0.5 | 95.8 | ＜3 |
| 36 | 70 | 2.0 | 98.2 | ＜3 |
Embodiment 37～42: temperature of reaction and reaction pressure are to the influence of hydrogenation
Get the glue synthesis condition with embodiment 1～9, change glue (containing 525g four arm SBS) in hydrogenation still adding 0.06mmol n-Butyl Lithium, feed H
2, add promotor dimethyl phthalate 0.06mmol, add 0.6825mmol dicyclopentadiene titanium dichloride again, at 70 ℃, constant temperature and pressure hydrogenation under the 1.0Mpa changes the time of reacting.The result is as follows:
| Embodiment | Reaction times (minute) | Degree of hydrogenation % | |
| PB section degree of hydrogenation | PS section degree of hydrogenation | ||
| 37 | 15 | 43.2 | ＜3 |
| 38 | 30 | 85.6 | ＜3 |
| 39 | 45 | 89.3 | ＜3 |
| 40 | 60 | 98.1 | ＜3 |
| 41 | 90 | 99.2 | ＜3 |
| 42 | 120 | 99.2 | ＜3 |
Claims (2)
1, a kind of selection method for hydrogenation of the styrenic block polymkeric substance that contains conjugated diene by coupling method preparation is characterized in that:
A: in selecting hydrogenation process, the weight concentration of controlling polymers in solvent is 5%～25%;
B: add organolithium compound earlier, logical H
2, make organolithium compound under the atmosphere of hydrogen, be converted into hydride, the molar weight of organolithium compound is 4 times～24 times of Primary Catalysts;
C: add promotor, regulate and the hydrogenation activity of stable Primary Catalysts, its molar weight is 1/16～1/8 of a Primary Catalysts, promotor can be adjacent to or m-phthalic acid and C
1-C
12Alcohol generates dibasic ester class, maleic dioctyl phthalate and C
1-C
12Alcohol generates one or more in the dibasic ester class;
D: add Primary Catalysts two luxuriant titanium compounds then, the add-on of two luxuriant titanium compounds is: the 100g polymkeric substance adds 0.05mmol～0.2mmol, and two luxuriant titanium compounds are converted into the ligand of catalytic activity under the reductive action of hydride;
E:, carried out selective hydrogenation reaction under pressure 0.5Mpa～2.5Mpa 1 hour～2 hours 60 ℃～90 ℃ of temperature.
2, the selection method for hydrogenation of the styrenic block polymkeric substance that contains conjugated diene by coupling method preparation according to claim 1 is characterized in that organolithium compound can be one or more in n-Butyl Lithium, tert-butyl lithium, s-butyl lithium, the naphthalene lithium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011285184A CN1147517C (en) | 2001-07-25 | 2001-07-25 | Selective hydrogenation method for coupling process of preparing styrene block copolymer containing conjugated diene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011285184A CN1147517C (en) | 2001-07-25 | 2001-07-25 | Selective hydrogenation method for coupling process of preparing styrene block copolymer containing conjugated diene |
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| CN1332183A CN1332183A (en) | 2002-01-23 |
| CN1147517C true CN1147517C (en) | 2004-04-28 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1844178B (en) * | 2005-04-08 | 2012-02-29 | 中国石油化工集团公司 | A kind of method of selective hydrogenation of styrene-conjugated diene block polymer |
| EP2058345B1 (en) | 2006-08-16 | 2013-02-20 | Asahi Kasei Chemicals Corporation | Process for producing block copolymer, and block copolymer or hydrogenated product thereof |
| CN105237696A (en) * | 2015-11-09 | 2016-01-13 | 宁波科元特种橡胶有限公司 | Novel hydrogenated styrene-butadiene-styrene segmented copolymer synthesis method |
| CN105218768A (en) * | 2015-11-10 | 2016-01-06 | 宁波科元特种橡胶有限公司 | Hydrogenated styrene-butadiene-styrene block copolymers synthetic method |
| CN105944676B (en) * | 2016-04-26 | 2019-02-19 | 张玲 | A kind of furandicarboxylic acid heptyl ester purifying preparation method of adsorbent |
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2001
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