CN1410465A - Method of selective hydrogenation containing conjugated diene block copolymer - Google Patents
Method of selective hydrogenation containing conjugated diene block copolymer Download PDFInfo
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- CN1410465A CN1410465A CN 02139784 CN02139784A CN1410465A CN 1410465 A CN1410465 A CN 1410465A CN 02139784 CN02139784 CN 02139784 CN 02139784 A CN02139784 A CN 02139784A CN 1410465 A CN1410465 A CN 1410465A
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- primary catalysts
- tetrahydrofuran
- block copolymer
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- conjugated diene
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Abstract
A process for selectively hydrogenating the block copolymer containing conjugated diolefine features that the tetrahydrofuran is used as the solvent of bicyclopentadiene titanium bichloride as primary catalyst. Its advantages are low energy consumption for post-treatment as tetrahydrofuran has high solubility, low poison of tetrahydrofuran, low cost, and high hydrogenation effect.
Description
Technical field
The present invention relates to a kind of method that conjugated diene block copolymer is selected hydrogenation that contains.
Background technology
Contain the conjugated diene block co-polymer and refer to that mainly with vinylbenzene, divinyl (or isoprene) be monomer, with the lithium alkylide is initiator, the co-polymer that obtains by anionic polymerisation, mainly comprise thermoplastic elastomer SBS, SIS etc., still have two keys to exist in soft section of polyhutadiene in such co-polymer or the polyisoprene, thereby ageing resistance is poor, and its Application Areas is restricted.For improving the ageing resistance of this analog copolymer, usually will contain conjugated diene block copolymer and select hydrogenation, promptly do under the condition of catalyzer at the dicyclopentadiene titanium dichloride, unsaturated pair of key in the co-polymer polymerized conjugated diene block carried out hydrogenation reaction, make it saturated, and hydrogenation reaction does not take place in phenyl ring in the hard section of polystyrene.Promptly at first be that solvent, lithium alkylide are that initiator, tetrahydrofuran (THF) are that activator and the conditioning agent that adds microtexture carry out anionic solution polymerization with vinylbenzene, conjugated diolefine with the hexanaphthene, obtain line style or star-like conjugated diene block copolymer glue, the co-polymer glue is introduced the hydrogenation still, add Primary Catalysts dicyclopentadiene titanium dichloride and promotor, under temperature of reaction is 70 ℃～95 ℃, reaction pressure 1.0Mpa～2.0Mpa, select hydrogenation.
Because of hydrogenation Primary Catalysts dicyclopentadiene titanium dichloride is a pressed powder, in the prior art, U.S. Pat P5,291,990 employing cyclohexane gives are the solvent of Primary Catalysts dicyclopentadiene titanium dichloride, Primary Catalysts is dissolved in the hexanaphthene, add reaction system then, because of the solubleness of Primary Catalysts dicyclopentadiene titanium dichloride in hexanaphthene very low (under 25 ℃, the 1000ml hexanaphthene can only dissolve 0.001g dicyclopentadiene titanium dichloride), to in reaction system, add into a large amount of hexanaphthenes by the required Primary Catalysts of reaction, generally will make the hexanaphthene of system increase by 30%, make the energy consumption of aftertreatment strengthen.
Chinese patent ZL.97108258.8 adopts toluene to make the solvent of Primary Catalysts dicyclopentadiene titanium dichloride, though the solubleness of Primary Catalysts in toluene improves a lot (under 25 ℃, 1000ml toluene solubilized 0.9g dicyclopentadiene titanium dichloride), but toluene is a kind of aromatic solvent, toxicity is bigger, and the boiling point of toluene under normal pressure be that 110.6 ℃ of 76 ℃ of boiling points than hexanaphthene are high, increased the energy consumption of aftertreatment.
Chinese patent 92110490.1 adopts the hexanaphthene suspension method to add Primary Catalysts dicyclopentadiene titanium dichloride, and promptly Primary Catalysts dicyclopentadiene titanium dichloride adds with the solid form, and therefore existence is reinforced inaccurate, causes hydrogenation reaction restive; And the dissolving of Primary Catalysts dicyclopentadiene titanium dichloride in reaction system needs certain hour, reduced the efficient of reaction.
Summary of the invention
The objective of the invention is to overcome the defective that exists in the existing patented technology, select a kind of new solvent for use, improve the solubleness of Primary Catalysts dicyclopentadiene titanium dichloride in this solvent, can guarantee to contain carrying out smoothly of conjugated diene block compound selective hydrogenation reaction, reduce the add-on of solvent simultaneously, reduce the energy consumption of aftertreatment.
For achieving the above object, the present invention adopt tetrahydrofuran (THF) do Primary Catalysts dicyclopentadiene titanium dichloride solvent.
The concrete technical scheme of the present invention is as follows:
With the hexanaphthene is that solvent, lithium alkylide are that initiator, tetrahydrofuran (THF) are that activator and the conditioning agent that adds microtexture carry out anionic solution polymerization with vinylbenzene, conjugated diolefine, obtain line style or star-like conjugated diene block copolymer glue, the co-polymer glue is introduced the hydrogenation still; Obtain 0.9g/1000ml～16g/1000ml Primary Catalysts solution with tetrahydrofuran (THF) dissolving Primary Catalysts dicyclopentadiene titanium dichloride; Add a certain amount of Primary Catalysts dicyclopentadiene titanium dichloride solution and promotor dimethyl phthalate, the amount ratio of promotor and Primary Catalysts is 1: 1～1: 3; Carry out hydrogenation reaction under temperature of reaction is 70 ℃～95 ℃, reaction pressure 1.0Mpa～2.0Mpa, the reaction times was controlled at 1 hour～3 hours.
The present invention has following advantage:
1, tetrahydrofuran (THF) is big to the solubleness of Primary Catalysts dicyclopentadiene titanium dichloride, under 25 ℃, and 1000ml tetrahydrofuran (THF) solubilized 16.0g dicyclopentadiene titanium dichloride, the quantity of solvent of introducing in hydrogenation process is less, can reduce the energy consumption of aftertreatment.
2, the low application that helps industry of the toxicity of tetrahydrofuran (THF).
3, tetrahydrofuran (THF) can be used as the activator of preparation conjugated diene block copolymer glue and the conditioning agent of microtexture, can recycle in solvent, can reduce the cost of product to a certain extent.
4, degree of hydrogenation≤2% of the degree of hydrogenation of conjugated diolefine section 〉=98%, vinylbenzene section
The degree of hydrogenation of conjugated diolefine section adopts iodometric determination
The degree of hydrogenation of vinylbenzene section adopts ultraviolet spectroscopy to measure
Embodiment
Embodiment 1
In the 10L still, add the 3500ml hexanaphthene, the 24ml tetrahydrofuran (THF), 85ml vinylbenzene, the 8mmol n-Butyl Lithium carries out one-step polymerization, add the 580ml divinyl after the 15min and carry out two sections polymerizations, add 85ml vinylbenzene after the 30min and carry out three stage polymerization controlled polymerization temperature at 30 ℃～110 ℃, the glue that obtains is introduced in the hydrogenation still of 10L, the tetrahydrofuran solution that adds Primary Catalysts dicyclopentadiene titanium dichloride, its add-on is pressed 0.13mmol/100gSBS and is calculated, the promotor dimethyl phthalate, its add-on is 0.7mmol/100gSBS, 60 ℃～110 ℃ of temperature of reaction, pressure is under 0.5Mpa～2.0Mpa, carry out hydrogenation reaction, the reaction times is 2 hours.The results are shown in Table 1:
The hydrogenation result of table 1 different catalysts concentration
Claims (1)
1, a kind of method that contains conjugated diene block copolymer selection hydrogenation, it is characterized in that with the hexanaphthene being that solvent, lithium alkylide are that initiator, tetrahydrofuran (THF) are that activator and the conditioning agent that adds microtexture carry out anionic solution polymerization with vinylbenzene, conjugated diolefine, obtain line style or star-like conjugated diene block copolymer glue, the co-polymer glue is introduced the hydrogenation still; Obtain 0.9g/1000ml～16g/1000ml Primary Catalysts solution with tetrahydrofuran (THF) dissolving Primary Catalysts dicyclopentadiene titanium dichloride; Add a certain amount of Primary Catalysts dicyclopentadiene titanium dichloride solution and promotor dimethyl phthalate, the amount ratio of promotor and Primary Catalysts is 1: 1～1: 3; Carry out hydrogenation reaction under temperature of reaction is 70 ℃～95 ℃, reaction pressure 1.0Mpa～2.0Mpa, the reaction times was controlled at 1 hour～3 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB021397848A CN1183176C (en) | 2002-11-19 | 2002-11-19 | Method of selective hydrogenation containing conjugated diene block copolymer |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021397848A CN1183176C (en) | 2002-11-19 | 2002-11-19 | Method of selective hydrogenation containing conjugated diene block copolymer |
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| CN1410465A true CN1410465A (en) | 2003-04-16 |
| CN1183176C CN1183176C (en) | 2005-01-05 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010006509A1 (en) * | 2008-07-15 | 2010-01-21 | 中国石油化工集团公司 | An injection-foamable styrene-base monomer-diolefin copolymer, preparation methods and uses thereof |
| CN103819635A (en) * | 2012-11-19 | 2014-05-28 | 中国石油化工股份有限公司 | Star-shaped hydrogenated butadiene styrene block copolymer, and preparation method and application thereof |
| 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 |
| 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 |
| CN111747854A (en) * | 2020-07-08 | 2020-10-09 | 陈天然 | Method for preparing hexamethylene diamine by catalytic hydrogenation of adiponitrile |
-
2002
- 2002-11-19 CN CNB021397848A patent/CN1183176C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010006509A1 (en) * | 2008-07-15 | 2010-01-21 | 中国石油化工集团公司 | An injection-foamable styrene-base monomer-diolefin copolymer, preparation methods and uses thereof |
| US10240019B2 (en) | 2008-07-15 | 2019-03-26 | China Petrochemical Corporation | Injection-foamable styrenic monomer-diolefin copolymer, a method for the preparation thereof and use thereof |
| CN103819635A (en) * | 2012-11-19 | 2014-05-28 | 中国石油化工股份有限公司 | Star-shaped hydrogenated butadiene styrene block copolymer, and preparation method and application thereof |
| CN103819635B (en) * | 2012-11-19 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of star hydrogenated styrene-butadiene block copolymer and its preparation method and application |
| 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 |
| CN111747854A (en) * | 2020-07-08 | 2020-10-09 | 陈天然 | Method for preparing hexamethylene diamine by catalytic hydrogenation of adiponitrile |
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| Publication number | Publication date |
|---|---|
| CN1183176C (en) | 2005-01-05 |
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