CN1093140C - Catalyst for preparing syndiotactic poly styrene - Google Patents
Catalyst for preparing syndiotactic poly styrene Download PDFInfo
- Publication number
- CN1093140C CN1093140C CN99113808A CN99113808A CN1093140C CN 1093140 C CN1093140 C CN 1093140C CN 99113808 A CN99113808 A CN 99113808A CN 99113808 A CN99113808 A CN 99113808A CN 1093140 C CN1093140 C CN 1093140C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- alkylaluminoxane
- triisobutyl aluminium
- syndiotactic polystyrene
- catalyzer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to a catalyst for preparing syndiotactic polystyrene, which comprises a cyclopentadienyl titanium compound CpTi(OC6H4OCH3)3, alkylaluminium oxyalkane and triisobutyl aluminium. The catalyst has the characteristics that the product of prepared syndiotactic polystyrene has a high molecular weight, and the triisobutyl aluminium in the catalyst has a higher proportion than the alkylaluminium oxyalkane, so that the catalyst cost is low. The catalyst can be used in industrial production.
Description
The present invention relates to prepare the catalyzer of syndiotactic polystyrene.
The homogeneous catalysis system that cyclopentadiene titanium compound and promotor methylaluminoxane (MAO) or boron fluorine cpd are formed is used for syndiotactic polymerization of phenylethylene and can obtains normal polymkeric substance between height, and melting point polymer can reach 270 ℃.This polymkeric substance has chemically-resistant, resistance toheat is good, narrow molecular weight distribution, and grain size stabilized is good, the electrical property excellent characteristics, its over-all properties can be compared with engineering plastics.The appearance of syndiotactic polystyrene (sPS) has caused the broad research of people to its synthetic catalyst system.Reported with Cp in the document EP 210615
*TiCl
3Compound (Cp
*Be the pentamethyl-cyclopentadienyl) be the situation of Primary Catalysts synthesis of syndiotactic polystyrene, but this catalyst system catalytic activity is low, and the molecular weight of the syndiotactic polystyrene that makes is also lower, about about 10～200,000.Reported Cp in the document US 5032650
*Ti (OCH
3)
3Its syndiotactic polystyrene molecular weight that makes of the catalyst system of/MAO is about between 40～700,000, but the large usage quantity of its MAO.Because MAO costs an arm and a leg, therefore how to reduce the MAO consumption, do not influence the focus that the catalyst system performance becomes people's research simultaneously.
The objective of the invention is in order to overcome in the conventional art, the syndiotactic polystyrene molecular weight that makes is lower, and the big defective of MAO consumption simultaneously provides a kind of catalyzer of new preparation syndiotactic polystyrene.This catalyzer can obtain the high-molecular weight syndiotactic polystyrene, and the consumption of MAO can reduce greatly in the catalyzer simultaneously, to reach the purpose of saving cost.
The objective of the invention is to realize by following technical scheme: a kind of catalyzer for preparing syndiotactic polystyrene comprises that molecular formula is the cyclopentadiene titanium compound of I and alkylaluminoxane and the triisobutyl aluminium III that general formula is II:
Cp
*Ti(OC
6H
4OCH
3)
3 I
Triisobutyl aluminium III
Cp in the formula
*Be the pentamethyl-cyclopentadienyl;
R
1For containing the alkyl of 1～4 carbon atom;
X is the oligomerisation degree of alkylaluminoxane, and its value is 6～40;
Wherein the whole alumiunum amount among alkylaluminoxane II and the triisobutyl aluminium III is 200～1000 to the mol ratio of cyclopentadiene titanium compound I, and triisobutyl aluminium III is 1.0～4.0 to the mol ratio of alkylaluminoxane II.
In the technique scheme among the alkylaluminoxane II value preferable range of x be 30～40, R
1Preferred version be methyl; Whole alumiunum amount among alkylaluminoxane II and the triisobutyl aluminium III is 400～600 to the mol ratio preferable range of cyclopentadiene titanium compound I; Triisobutyl aluminium III is 1.0～3.0 to the mol ratio preferable range of alkylaluminoxane II.
Poly-alkylaluminoxane (MAO) II is prepared by the aluminum alkyls control hydrolysis, and hydrolytic reagent can be the water that contains in the inorganic salt of crystal water, and the inorganic salt that contain crystal water can be CaCl
26H
2O, MgCl
26H
2O, CuSO
45H
2O, Al
2(SO
4)
318H
2O, CuSO
42H
2O, MgSO
47H
2O, FeSO
47H
2O, Ti (SO
4)
24H
2O, Ti
2(SO
4)
38H
2O and ZnSO
47H
2O etc.Aluminum alkyls is 1: 1～3.0 for the mole ratio with water, and temperature of reaction is-20～100 ℃, and the reaction times is 5～40 hours, and reaction solvent can be alkane and aromatic hydrocarbons.Aluminum alkyls commonly used has trimethyl aluminium, triethyl aluminum, triisobutyl aluminium etc.Concrete steps are: aluminum alkyls is pressed Al/H
2The O mol ratio is 1: 1～2.5 slowly to be added dropwise to Al under-20～0 ℃
2(SO
4)
318H
2In the toluene solution of O, the dropping time is 0.5～5 hour, after dropwising, makes temperature of reaction rise to 20～100 ℃, under this temperature, reacts 2～40 hours, and reaction with solid filtering, must contain the toluene solution that structure is the alkylaluminoxane of II after finishing.
The preparation method of metallocene compound I is as follows: in the presence of chlorine hydride absorbent, is that solvent make with tetrahydrofuran (THF) or hydrocarbon polymer by corresponding cyclopentadienyl titanous chloride and p methoxy phenol.Chlorine hydride absorbent can be various aminated compoundss, wherein is advisable with alkylamine, for example triethylamine.Hydrocarbon polymer can be aliphatic hydrocarbon or aromatic hydrocarbon, uses aromatic hydrocarbon better, for example benzene, toluene etc.Concrete steps are: the tetrahydrofuran (THF) mixing solutions of triethylamine and p methoxy phenol is slowly dropped in the tetrahydrofuran solution of pentamethyl-cyclopentadienyl titanous chloride, the mole ratio of pentamethyl-cyclopentadienyl titanous chloride and p methoxy phenol is 1: 3.0～3.5, the mole ratio of pentamethyl-cyclopentadienyl titanous chloride and triethylamine is 1: 3.0～3.5, temperature of reaction is 0～60 ℃, reaction times is 1～30 hour, solids removed by filtration, underpressure distillation removes and desolvates, the crude product hexane extraction that obtains gets the xanchromatic solid at-20 ℃ of recrystallizations.
Work as Cp
*Be pentamethyl-cyclopentadienyl, R
1Be methyl, OCH
3When the contraposition of phenyl ring, the ultimate analysis of compound, proton nmr spectra
1HNMR, carbon-13 nmr spectra
13NMR, mass spectrum MS the results are shown in following data;
Ultimate analysis (element analysis)
Calcd?for?C
31H
36O
6Ti，C：67.39 H：6.52
Found： C：66.99 H：6.51
Proton nmr spectra [
1HNMR (CDCl
3)]
δ1.95[S，15H(CH
3)
5C
5] δ3.79[S，9H(OCH
3)
3]
δ6.76[m，12Hph
3]
Carbon-13 nmr spectra [
13CNMR (CDCl
3)]
δ11.49[(CH
3)
5C
5] δ55.76(OCH
3)
δ114.14(ph?C-3.5) δ119.28(ph?C-2.6)
δ125.17(Cp?C) δ153.03(ph?C-4)
δ159.40(ph?C-1)
Mass spectrum [MS (m/z, %intensity)]
552(61.74M
+)，429(100，M-OC
6H
40CH
3 +)
306[11.20?M-2(OC
6H
40CH
3)
+]，135[5.67C
5(CH
3)
5 +]
Polyreaction is preferably carried out between 50～90 ℃ at 30～130 ℃.In order to obtain the polymkeric substance of ideal performance, before reaction, earlier triisobutyl aluminium III, alkylaluminoxane II and cyclopentadiene titanium compound I were placed in the toluene solution normal temperature ageing 10～30 minutes, and then carry out polymerization.Polymerization need be used the regular hour, and from planting several hours somewhat, preferably 1～10 hour, the ideal polymerization time depended on polymerization temperature and other polymerizing condition.
Among the present invention because to adopt a kind of molecular formula be the catalyst system that the cyclopentadiene titanium compound of I, alkylaluminoxane that general formula is II and triisobutyl aluminium III form, make this catalyst system have greater activity, synthetic syndiotactic polystyrene molecular weight can reach 163.7 ten thousand simultaneously, and the reason inventor wherein also is difficult to get across at present.Owing to use the expensive MAO of a triisobutyl aluminium substitution part, especially the mol ratio with triisobutyl aluminium and MAO is increased to more than 1: 1, greatly reduces the cost of catalyst system, has obtained good effect in addition.
The invention will be further elaborated below by embodiment.[embodiment 1]
The preparation of metallocene compound
In thorough drying, repeatedly add 120ml tetrahydrofuran (THF) (THF) respectively in the flask at the bottom of the metathetical 250ml garden through high pure nitrogen, 4.36g (0.118mol) potassium metal and 15ml (0.118mol) pentamethyl-cyclopentadiene refluxed 6 hours, was cooled to stirring at normal temperature 18 hours.After being chilled to 0 ℃, add 15ml (0.118mol) trimethylchlorosilane, reacted 4 hours, filter, with the 80mlTHF washing, THF is removed in vacuum distilling.Slowly add 200ml heptane and 9mlTiCl again
4Mixed solution, refluxed 1 hour, vacuum distilling remove desolvate thick product, under 200 ℃/16mmHg, distil 15.00g pentamethyl-cyclopentadienyl titanous chloride (Cp
*TiCl
3), Cp wherein
*Be the pentamethyl-cyclopentadienyl.
Get the Cp of above-mentioned preparation
*TiCl
33.373g, with the 70mlTHF dissolving, under 0 ℃, slowly drip 4.8ml (3.473g) triethylamine, slowly drip the 70mlTHF solution of 4.268g p methoxy phenol again, normal temperature stirred 18 hours down, filtered, and THF is removed in vacuum distilling, gets red buttery liquid.Red oily liquids was stirred 20 hours down at 50 ℃ with the 140ml hexane, filter, with liquid recrystallization to-18 ℃ of temperature, remove hexane and get yellow crystals 3.86g, the fusing point of yellow crystals is 134.6 ℃.It is mixed with 1 * 10
-5Mol Ti/ml toluene solution is called catalyst A.[embodiment 2]
On 10 liters of mechanical stirring kettles, after 6 hours, be cooled to 55 ℃, N 85 ℃ of bakings earlier
2Pump drainage 3 times adds 1.5 liters of styrene monomers, then 22.5 mmole triisobutyl aluminiums (TiBA), and 22.5 mmole MAO, its oligomerisation degree x is 30.4, the catalyst A that embodiment 1 makes, i.e. 0.075 mmole Cp
*Ti (OC
6H
4OCH
3)
3Be injected in 100 milliliters of toluene solutions with syringe, 20 ℃ of ageings of room temperature 10 minutes, once join in the reactor then, at 310 rev/mins of following stirring reactions after 2 hours, with the ethanol-hydrochloric acid soln stopped reaction of 10% (weight), washing, dry that powder solid 390 restrains, with WatersGPC150 test, its Mw=1.637 * 10
6, molecular weight distribution is 2.12.[embodiment 3]
On 10 liters of mechanical stirring kettles, after 6 hours, be cooled to 55 ℃, N 85 ℃ of bakings earlier
2Pump drainage 3 times adds 1.5 liters of styrene monomers, then 30 mmole TiBA, and 15 mmole MAO, its oligomerisation degree x is 39.8, the catalyst A that embodiment 1 makes, i.e. 0.075 mmole Cp
*Ti (OC
6H
4OCH
3)
3Be injected in 100 milliliters of toluene solutions with syringe, 20 ℃ of ageings of room temperature 10 minutes, once join in the reactor then, at 310 rev/mins of following stirring reactions after 2 hours, with the ethanol-hydrochloric acid soln stopped reaction of 10% (weight), washing, dry that powder solid 406 restrains, with WatersGPC150 test, its Mw=1.496 * 10
6, molecular weight distribution is 1.92.[embodiment 4]
On 10 liters of mechanical stirring kettles, after 6 hours, be cooled to 55 ℃, N 85 ℃ of bakings earlier
2Pump drainage 3 times adds 3 liters of styrene monomers, then 58.5 mmole TiBA, and 58.5 mmole MAO, its oligomerisation degree x is 20, the catalyst A that embodiment 1 makes, i.e. 0.195 mmole Cp
*Ti (OC
6H
4OCH
3)
3Be injected in 100 milliliters of toluene solutions with syringe, 20 ℃ of ageings of room temperature 10 minutes, once join in the reactor then, at 310 rev/mins of following stirring reactions after 2 hours, with the ethanol-hydrochloric acid soln stopped reaction of 10% (weight), washing, dry that powder solid 930 restrains, with WatersGPC150 test, its Mw=1.259 * 10
6, molecular weight distribution is 1.97.[embodiment 5]
On 10 liters of mechanical stirring kettles, after 6 hours, be cooled to 55 ℃, N 85 ℃ of bakings earlier
2Pump drainage 3 times adds 3.5 liters of styrene monomers, then 117 mmole TiBA, and 39 mmole MAO, its oligomerisation degree x is 9.0, the catalyst A that embodiment 1 makes, i.e. 0.195 mmole Cp
*Ti (OC
6H
4OCH
3)
3Be injected in 100 milliliters of toluene solutions with syringe, 20 ℃ of ageings of room temperature 10 minutes, once join in the reactor then, at 310 rev/mins of following stirring reactions after 2 hours, with the ethanol-hydrochloric acid soln stopped reaction of 10% (weight), washing, dry that powder solid 923 restrains, with WatersGPC150 test, its Mw=1.071 * 10
6, molecular weight distribution is 1.92.[embodiment 6]
On 10 liters of mechanical stirring kettles, after 6 hours, be cooled to 60 ℃, N 85 ℃ of bakings earlier
2Pump drainage 3 times adds 3 liters of styrene monomers, then 30 mmole TiBA, and 30 mmole MAO, its oligomerisation degree x is 25, the catalyst A that embodiment 1 makes, i.e. 0.15 mmole Cp
*Ti (OC
6H
4OCH
3)
3Be injected in 100 milliliters of toluene solutions with syringe, 20 ℃ of ageings of room temperature 10 minutes, once join in the reactor then, at 310 rev/mins of following stirring reactions after 2 hours, with the ethanol-hydrochloric acid soln stopped reaction of 10% (weight), washing, dry that powder solid 793 restrains, with WatersGPC150 test, its Mw=1.363 * 10
6, molecular weight distribution is 2.10.[comparative example 1]
All polymerizing conditions are identical with embodiment 5, only Primary Catalysts Cp
*TiCl
3Replaced C p
*Ti (OC
6H
4OCH
3)
3, the syndiotactic polystyrene that obtains at last (sPS) is tested with WatersGPC150, its Mw=1.73 * 10
5, molecular weight distribution is 1.95.[comparative example 2]
All polymerizing conditions are identical with embodiment 5, except Primary Catalysts Cp
*Ti (OCH
3)
3Replaced C p
*Ti (OC
6H
4OCH
3)
3, the syndiotactic polystyrene that obtains at last (sPS) 801 grams are with WatersGPC150 test, its Mw=6.47 * 10
5, molecular weight distribution is 2.01.[comparative example 3]
All polymerizing conditions are identical with embodiment 4, except Primary Catalysts Cp
*Ti (OCH
3)
3Replaced C p
*Ti (OC
6H
4OCH
3)
3, the syndiotactic polystyrene that obtains at last (sPS) 918 grams are with WatersGPC150 test, its Mw=3.856 * 10
5, molecular weight distribution is 2.13.
Claims (4)
1, a kind of catalyzer for preparing syndiotactic polystyrene comprises that molecular formula is the cyclopentadiene titanium compound of I and alkylaluminoxane and the triisobutyl aluminium III that general formula is II:
Cp
*Ti(OC
6H
4OCH
3)
3 I
Triisobutyl aluminium III
Cp in the formula
*Be the pentamethyl-cyclopentadienyl;
R
1For containing the alkyl of 1～4 carbon atom;
X is the oligomerisation degree of alkylaluminoxane, and its value is 6～40;
Wherein the whole alumiunum amount among alkylaluminoxane II and the triisobutyl aluminium III is 200～1000 to the mol ratio of cyclopentadiene titanium compound I, and triisobutyl aluminium III is 1.0～4.0 to the mol ratio of alkylaluminoxane II.
2, according to the catalyzer of the described preparation syndiotactic polystyrene of claim 1, the value that it is characterized in that x among the alkylaluminoxane II is 30～40, R
1Be methyl.
3,, it is characterized in that the whole alumiunum amount among alkylaluminoxane II and the triisobutyl aluminium III is 400～600 to the mol ratio of cyclopentadiene titanium compound I according to the catalyzer of the described preparation syndiotactic polystyrene of claim 1.
4,, it is characterized in that triisobutyl aluminium III is 1.0～3.0 to the mol ratio of alkylaluminoxane II according to the catalyzer of the described preparation syndiotactic polystyrene of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113808A CN1093140C (en) | 1999-06-24 | 1999-06-24 | Catalyst for preparing syndiotactic poly styrene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113808A CN1093140C (en) | 1999-06-24 | 1999-06-24 | Catalyst for preparing syndiotactic poly styrene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1288016A CN1288016A (en) | 2001-03-21 |
| CN1093140C true CN1093140C (en) | 2002-10-23 |
Family
ID=5276958
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99113808A Expired - Lifetime CN1093140C (en) | 1999-06-24 | 1999-06-24 | Catalyst for preparing syndiotactic poly styrene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1093140C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539878A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Method for preparing syndiotactic polystyrene polymer with doublet broad molecular weight distribution |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1210109A (en) * | 1997-09-03 | 1999-03-10 | 中国石油化工总公司 | Titanium metallocene compounds |
| CN1235975A (en) * | 1998-05-20 | 1999-11-24 | 中国石油化工总公司 | Metallocene compound |
| CN1235984A (en) * | 1998-05-20 | 1999-11-24 | 中国石油化工总公司 | Catalyst for preparing syndiotactic polystyrene |
| CN1253956A (en) * | 1998-11-18 | 2000-05-24 | 中国石油化工集团公司 | Syndiotactic polymerization process of phenylethylene |
-
1999
- 1999-06-24 CN CN99113808A patent/CN1093140C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1210109A (en) * | 1997-09-03 | 1999-03-10 | 中国石油化工总公司 | Titanium metallocene compounds |
| CN1235975A (en) * | 1998-05-20 | 1999-11-24 | 中国石油化工总公司 | Metallocene compound |
| CN1235984A (en) * | 1998-05-20 | 1999-11-24 | 中国石油化工总公司 | Catalyst for preparing syndiotactic polystyrene |
| CN1253956A (en) * | 1998-11-18 | 2000-05-24 | 中国石油化工集团公司 | Syndiotactic polymerization process of phenylethylene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1288016A (en) | 2001-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4157033B2 (en) | Novel multinuclear semimetallocene catalyst and method for producing styrenic polymer using the same | |
| CN1093140C (en) | Catalyst for preparing syndiotactic poly styrene | |
| CN1130394C (en) | Catalyst for preparation of syndiotactic polystyrene | |
| CN1065870C (en) | Metallocene compound | |
| CN1076733C (en) | Catalyst for preparing syndiotactic polystyrene | |
| CN1208354C (en) | Metallocene titanium compound and use thereof | |
| CN1117106C (en) | Syndiotactic poly styrene polymer | |
| CN1207315C (en) | Catalyst for preparing syndiotacti polystyrene | |
| CN1098271C (en) | Cyclopentadiene titanium compound | |
| CN1176928C (en) | Metallocene-titanium metal compound and uses thereof | |
| CN1095476C (en) | Titanium metallocene catalyst for preparation of various densities polyethylene | |
| CN1233667C (en) | Metallocene titanium compound and use thereof | |
| CN1065872C (en) | Cyclopentadiene titanium compound | |
| CN1241959C (en) | Catalyst for preparing syndiotactic polysterol | |
| CN1259327C (en) | Cyclopentadienyl metal titanium compound and its use | |
| CN1211404C (en) | Cyclopentadienyl titanium compound | |
| CN1176927C (en) | Metallocene titanium compound | |
| CN1055935C (en) | Process for preparing styrene-ethylene block copolymer | |
| CN1176926C (en) | Cyclopentadienyl titanium compound | |
| CN1117105C (en) | Catalyst for preparing syndiotactic polystyrene | |
| CN1252101C (en) | Catalyst for preparing syndiotactic polystyrene | |
| US6921734B2 (en) | Titanocene complexes and its catalyst for preparing syndiotactic polystyrene | |
| CN1076734C (en) | Catalyst for preparing syndiotactic polystyrene | |
| CN1055097C (en) | Catalyst for preparing m-stereospecific polymerized styrene | |
| CN1269368A (en) | Catalyst for preparing medium-molecular weight atactic polypropylene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20021023 |