CN1056625C - Styrene-propene block copolymer and preparing process thereof - Google Patents
Styrene-propene block copolymer and preparing process thereof Download PDFInfo
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- CN1056625C CN1056625C CN97106212A CN97106212A CN1056625C CN 1056625 C CN1056625 C CN 1056625C CN 97106212 A CN97106212 A CN 97106212A CN 97106212 A CN97106212 A CN 97106212A CN 1056625 C CN1056625 C CN 1056625C
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Abstract
The present invention relates to a styrene-propene block copolymer and a preparing method thereof, wherein the styrene chain segment of the copolymer has a syndiotactic structure; the length of the styrene chain segment is from 50 to 90 mol%. propene gas or styrene monomers are first led in a reactor; a catalyst contains a cyclopentadienyl titanium compound, alkyl aluminoxyane and alkylaluminium; the rest of raw material of propene gas or styrene monomers is added at the temperature of 20 to 80DEGC; the total pressure is kept within a range of 0.1 to 1.0MPa for reacting for obtaining completed products. The technique has the characteristic of high catalyzing efficiency; the maximum catalyzing efficiency reaches 8.75Kg. polymer/g at normal pressure; when the pressure force of propene is 1.0MPa, the catalyzing efficiency reaches 14.80Kg. polymer/g. the technique can be used for preparing the industrial production of the styrene-propylene block copolymer.
Description
The present invention relates to styrene-propene block copolymer and preparation technology thereof.
The styrene-propene multipolymer is a kind of type material, and wherein the vinylbenzene segment has syndiotactic structure, makes material have high temperature resistant and corrosion resistance nature, can be applicable in the mechanicalss such as automobile component, high temperature resistant mechanicals, electrical equipment, electronic unit.The vinylbenzene segment is the structure of random (J.Appl.Polym.Sci, 1983,28,961) and isotactic (CN851022928) in the styrene-propene block copolymer that in the past made.Document US 5260394 proposes to carry out vinylbenzene and copolymerization of propylene by transistion metal compound and alkylaluminoxane catalyst system, have only and formerly carry out under the prepolymerized condition of ethene and propylene, add styrene monomer again, effective block polymerization could take place, simultaneously catalytic activity and catalytic efficiency are all lower, are respectively 0.45 kg of polymer/gram titanium hour and 1.78 kg of polymer/gram titanium.
In order to overcome the shortcoming that above-mentioned document exists, the purpose of this invention is to provide and a kind ofly prepare styrene-propene block copolymer and preparation technology thereof by vinylbenzene and two kinds of monomers of propylene, wherein the vinylbenzene segment has syndiotactic structure in the multipolymer, and this technology has catalytic activity and the high characteristics of catalytic efficiency simultaneously.
The objective of the invention is to realize by following technical scheme: a kind of styrene-propene block copolymer, comprise vinylbenzene segment and propylene segment, wherein the vinylbenzene segment has syndiotactic structure, and the length of vinylbenzene segment is 50～90% (moles).
Another object of the present invention is to realize by following technical scheme: when the preparation styrene-propene block copolymer, at first in reactor, feed propylene gas or styrene monomer, to contain cyclopentadiene titanium compound and the general formula that molecular formula is I is the alkylaluminoxane of II, and general formula is that the organo-aluminium compound of III is a catalyzer, 20～80 ℃ of temperature, pressure is under 0.1～1.0MPa condition, adds remaining another benzene feedstock vinyl monomer or feed the propylene gas reaction to make
R
1Ti(OR
2)
3 I
Al (R
4)
3R in the III formula
1Be cyclopentadienyl;
R
2Be alkyl, the aryl of 6～20 carbon atoms, alkaryl, the aralkyl of 1～20 carbon atom;
R
3For containing the alkyl of 1～4 carbon atom;
R
4For containing the alkyl of 1～4 carbon atom;
X is the oligomerisation degree of alkylaluminoxane, and its value is 6～40;
Wherein the aluminium among the alkylaluminoxane II is 100～2000 to the mol ratio of cyclopentadiene titanium compound I, and aluminium is 10～500 to the mol ratio of cyclopentadiene titanium compound I among the organo-aluminium compound III.
In the technique scheme among the alkylaluminoxane II value of X be 15～30, R
3Be methyl; R among the organo-aluminium compound III
4Be methyl, ethyl, isobutyl-; Aluminium among the alkylaluminoxane II is 200～1750 to the mol ratio of cyclopentadiene titanium compound I; Aluminium is 200～500 to the mol ratio of cyclopentadiene titanium compound I among the organo-aluminium compound III.
Catalyst component I cyclopentadiene titanium compound prepares in order to the below method: reacted in the presence of amine compound by corresponding cyclopentadienyl three halogenated titaniums and alcohol or phenol and obtain.Concrete steps are: the mixture of alcohol or phenol and amine compound slowly is added drop-wise in cyclopentadienyl three halogenated titaniums that diluted by aromatic hydrocarbon, the dropping time is 0.5～5 hour, cyclopentadienyl three halogenated titaniums are 1: 1～3 with the mole ratio of alcohol, the mole ratio of amine compound and alcohol or phenol is about 1～2: 1, under 0～80 ℃ of condition, react then, reaction times is 5～40 hours, remove solid in the reaction product with filtering method, and remove with underpressure distillation and to desolvate, the crude product that obtains extracts with the alkane of 5～7 carbon, and after removing volatilizable thing, product is glassy yellow mucus or solid, and promptly structural formula is R
1Ti (OR
2)
3Organic titanic compound I, this product wiring solution-forming such as toluene solution can be directly used in and carry out polyreaction.
The halogen element of cyclopentadienyl three halogenated titaniums that adopt among the above-mentioned preparation method can be fluorine, chlorine, bromine, iodine.Used cyclopentadienyl can be the many methyl cyclopentadienyls that contain 0～5 methyl.Used alcohol or phenol are methyl alcohol, ethanol, propyl alcohol, butanols, phenol, phenylcarbinol, phenylethyl alcohol etc.Used amine compound is triethylamine, diethylamine etc.Used solvent is an aromatic hydrocarbon, and commonly used is benzene.
The preparation method of catalyst component II alkylaluminoxane (MAO): by the reaction of aluminum organic compound and water and get.Aluminum organic compound commonly used has aluminum alkyls, as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three hexyl aluminium and trioctylaluminum, and haloalkyl aluminium, as a Chlorodimethyl aluminium, aluminium diethyl monochloride and sesquialter ethyl aluminum chloride etc.
Reactants water 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
20, CuSO
45H
2O, Al
2(SO)
318H
2O, CaSO
42H
2O, MgSO
47H
2O, FeSO
47H
2O, Ti (SO
4)
24H
2O, Ti
2(SO
4)
38H
2O and ZnSO
47H
2O etc.The mole ratio of aluminum alkyls and water is 1: 0.5～2.5, and temperature of reaction is-20～100 ℃, and the reaction times is 10～40 hours.Concrete steps are: the inorganic salt and the thinner toluene that will contain crystal water join in the reactor, under-20～0 ℃ of temperature, slowly splash into the toluene solution of aluminum alkyls then, the dropping time is 0.5～5 hour, after dropwising, temperature is raised to greater than 30 ℃, make to be reflected under 30～100 ℃ of temperature and finish, the reaction times is 10～40 hours.After reaction finishes, will have solid solution and filter, filtrate obtains white solid product after boiling off volatilizable thing, promptly obtains the alkylaluminoxane that structural formula is II.R wherein
3Be C
1～C
4Alkyl, the value of the oligomerisation degree X of alkylaluminoxane (MAO) is 6～30.
Utilize the polyreaction mode of catalyzer of the present invention can adopt solution polymerization, slurry polymerization and mass polymerization.For solution polymerization and slurry polymerization, suitable solvent or thinner comprise: alkane, and as hexane, heptane, octane and hexanaphthene etc.Aromatic hydrocarbon has benzene,toluene,xylene and ethylbenzene etc.Halogenated alkane has 1,2-ethylene dichloride and chlorobenzene etc.
The present invention is the organo-aluminium compound of III owing to added the 3rd component in cyclopentadiene titanium compound I and alkylaluminoxane II, vinylbenzene and propylene catalytic efficiency have been improved greatly, catalytic efficiency is up to 8.75 kg of polymer/gram titanium under the normal pressure, when propylene pressure during to 1.0MPa, catalytic efficiency has been obtained good reaction effect up to 14.8 kg of polymer/gram titanium.
[embodiment 1]
The preparation of cyclopentadiene titanium compound
Churned mechanically 500ml reactor is housed after toasting dry and nitrogen purge, add 6.5 gram (30 millimole) cyclopentadienyl titanous chlorides, 200ml benzene, under the stirring at room, in one hour, drip by 9.72 gram phenylcarbinols (7.8 gram 2-methyl butanols, 5.3 gram n-propyl alcohols), the solution that 12.5ml triethylamine (90 millimole) and 50ml benzene are formed.Drip beginning horse back adularescent solid and separate out, after dropwising, continue stirring and also be warming up to back flow reaction 20 hours, after reaction finishes, reactant is cooled to the room temperature filtration.Filtrate is left the brown dope after boiling off solvent with the decompression method, with this dope of 300ml n-hexane extraction, boils off the normal hexane in the extraction liquid then.Obtain the jonquilleous cyclopentadienyl three benzyloxy titaniums of 11.1 grams respectively, 9.7 gram jonquilleous cyclopentadienyl three (2-methyl butoxy) titaniums and the brown cyclopentadienyl tripropoxy titanium of 6.5 grams.The toluene solution that is made into 0.02M is standby.
The preparation of MAO
Be equipped with and add 62.0 grams in the 1L reactor of induction stirring through ground Al
2(SO
4)
318H
2O and 120ml toluene, under-10 ℃ of stirrings, dripping 400ml concentration is the trimethyl aluminium toluene solution of 3.1M.Rate of addition is 5 ml/min, drips off in 80 minutes.Improve temperature of reaction then gradually, in 1 hour, make temperature reach 60 ℃, and continue reaction 24 hours.Reaction mixture solids removed by filtration, filtrate were taken out 2 hours with vacuum pump under 20 ℃, removed part toluene, under 40 ℃ volatile matters such as toluene were removed then, obtained the white solid that 27.5 grams are referred to as MAO, productive rate about 39%.[embodiment 2]
The preparation of MAO
With the similar method of embodiment 1, that different is Al
2(SO
4)
318H
2The consumption of O is 83.5 grams, and reaction mixture was at first taken out 4 hours with vacuum pump under 40 ℃ through the filtrate that obtains after filtering, and drained at 80 ℃ then, obtains 24.7 gram white solids, and productive rate is 35%.[embodiment 3]
In the 250ml reaction flask, add 50ml toluene, the compound titanium solution 1ml of embodiment 1 preparation, MAO 0.2 gram of embodiment 2 preparations feeds propylene, in 50 ℃ of following polymerizations 10 minutes (under the 0.105MPa pressure), then, adding concentration is 2M triisobutyl aluminium 1ml, 10ml vinylbenzene, 50 ℃ of following polymerizations 2 hours, obtain polymkeric substance 6.3 gram, catalytic efficiency is 6.59 kg of polymer/gram titanium, and catalytic activity is 3.29 kg of polymer/gram titanium hour.Propylene chain link content is 15mol% in the copolymerization product, 255 ℃ of melting point polymers.[embodiment 4]
In the 250ml reaction flask, add 50ml toluene, the compound titanium solution 1ml of embodiment 1 preparation, MAO 0.2 gram of embodiment 2 preparations, 0.5ml concentration is the 0.5M trimethyl aluminium, feed propylene, in 50 ℃ of following polymerizations 20 minutes (under the 0.105MPa pressure), then, adding concentration is the triisobutyl aluminium 1ml of 2M, vinylbenzene 10ml 50 ℃ of following polymerizations 2 hours, obtains polymkeric substance 4.4 grams, catalytic efficiency is 4.6 kg of polymer/gram titanium, and catalytic activity is 2.3 kg of polymer/gram titanium hour.Propylene chain link content is 40mol% in the copolymerization product, 255 ℃ of melting point polymers.[embodiment 5]
In the 250ml reaction flask, add 50ml toluene, embodiment 1 preparation cyclopentadiene tripropoxy titanium solution 1ml, MAO 0.2 gram of embodiment 2 preparations, 1.0ml concentration is the 0.5M trimethyl aluminium, feed propylene to saturated, 50 ℃ of polymerization temperatures, total pressure is 0.105MPa, reacted 20 minutes, and added vinylbenzene 10ml, reacted 2 hours, obtain polymerisate 4.3 grams, catalytic efficiency is 4.5 kg of polymer/gram titanium, and catalytic activity is 2.25 kg of polymer/gram titanium hour, propylene content 28mol% in the polymerisate.[embodiment 6]
In the 250ml reaction flask, add 10ml toluene, 10ml vinylbenzene, 0.5ml concentration is the triisobutyl aluminium of 2M, the titanium compound toluene solution 1ml of embodiment 1 preparation and MAO filtrate 0.2 gram 60 ℃ of following polymerizations 1 hour, feed propylene gas to saturated, total pressure 0.105MPa, reacting did not have obviously absorption in 1 hour, obtained polymkeric substance 2.0 grams, and catalytic efficiency is 2.09 kg of polymer/gram titanium.[embodiment 7]
250ml three-necked flask that charge cavity, gas introduction tube and magnetic stir bar be housed after heating, vacuum-drying deoxygenation, is fed nitrogen, make system pressure keep 760mmHg.The MAO 4.0mmol that adds embodiment 2 preparations then, the cyclopentadienyl tripropoxy titanium 20 μ mol that 1ml trimethyl aluminium (0.5M) and embodiment 1 are prepared, 20ml toluene, reacted 15 minutes down at 30 ℃, be warming up to 60 ℃, feed the metering propylene monomer, regulate the feeding speed of propylene by control valve, entire reaction is carried out under 900mmHg pressure, stop to feed propylene after 10 minutes, add 15ml vinylbenzene, polymerization 2 hours, with the ethanol termination reaction that contains 1%HCl, product is through washing, vacuum-drying.Product weighs 5.8 grams, and catalytic efficiency is 6.35 kg of polymer/gram titanium, and crude product dissolves 9.0wt% with the butanone extracting 8 hours of boiling, and is cooled to 30 ℃, and 0.18 gram polymer crystallization precipitation is arranged.This precipitation is analyzed through 13C-RMR, and a sPS segmental feature unicuspid peak is arranged at δ=145/988ppm place; An aPP segmental feature multiplet appears to the 20.039ppm place in δ=20.635.Because sPS and aPP homopolymer are insoluble to the butanone that boils, and aPP in 30 ℃ of butanone, do not have the precipitation separate out, so this polymkeric substance can only be the sPS-b-aPP segmented copolymer.Tm＝248.8℃，Tg＝89℃，(DSC)。Go out by 13C-NMR spectrogram calculated by peak area that the mol ratio of components of vinylbenzene and propylene chain link is 68.4: 31.6 in the multipolymer.The former product insoluble part of butanone of boiling, through the heptane extracting 8 hours of boiling, soluble part is pure aPP through Infrared spectroscopy, insoluble part is pure sPS through Infrared spectroscopy.[embodiment 8]
250ml three-necked flask that charge cavity, gas introduction tube and magnetic stir bar be housed after heating, vacuum-drying dehydrogenation, is fed nitrogen, make system pressure keep 760mmHg.The MAO 4.0mmol that adds embodiment 2 preparation then, the cyclopentadienyl tripropoxy titanium 20 μ mol that 2ml trimethyl aluminium (1.0M) and embodiment 1 are prepared, 20ml toluene, reacted 15 minutes down at 30 ℃, be warming up to 60 ℃, feed the metering propylene monomer, after the pre-polymerization 10 minutes, add 15ml vinylbenzene and 4.0mmol triisobutyl aluminium simultaneously, polymerization 2 hours, product weighs 8.4 grams, catalytic efficiency is 8.75 kg of polymer/gram titanium, the butanone extracting 8 hours of boiling is cooled to 30 ℃, and throw out weighs 1.51 grams.Tm＝238.9℃，Tg＝89℃。Analyze sPS65.8mol%, aPP34.2mol% through 13C-NMR.The insoluble part of the butanone that boils is with the heptane extracting 8 hours of boiling, and is solvable.After draining heptane, use 40 ℃ of tetrahydrofuran (THF) extractings 4 hours again, soluble part polymkeric substance 0.82 gram is analyzed sPS28.5mol%, aPP71.5% through 13C-NMR.Dsc analysis does not have the crystallization melting peak, Tg=78 ℃.[embodiment 9]
The MAO 4.0mmol that in the 250ml reaction flask, adds embodiment 2 preparations, trimethyl aluminium 0.7ml (0.5M) and cyclopentadiene titanium compound cyclopentadiene three titanium isopropoxides 20 μ mol, 20ml toluene, 50 ℃ of temperature, under the pressure 0.105MPa, propylene prepolymerization 10 minutes adds 15ml vinylbenzene and 4.0mmol triisobutyl aluminium.Copolyreaction product 6.8 grams, catalytic efficiency is 7.1 kg of polymer/gram titanium, and propylene chain link content is 31mol% in the polymkeric substance, and melting point polymer is 245 ℃.[embodiment 10]
The MAO 4.0mmol that in the 250ml reaction flask, adds embodiment 2 preparations, trimethyl aluminium 0.7ml (0.5M) and cyclopentadienyl three titanium n-butoxide 20 μ mol, 20ml toluene, 50 ℃ of temperature, under the pressure 0.105MPa, propylene prepolymerization 10 minutes adds 15ml vinylbenzene and 4.0mmol triisobutyl aluminium.Copolyreaction product 8.1 grams, catalytic efficiency is 8.47 kg of polymer/gram titanium, and propylene chain link content is 23mol% in the polymkeric substance, and melting point polymer is 251 ℃.[embodiment 11]
The MAO 4.0mmol that in the 250ml reaction flask, adds embodiment 2 preparations, trimethyl aluminium 1ml (0.6M) and cyclopentadienyl three isobutoxy titaniums 20 μ mol, 20ml toluene, 50 ℃ of temperature, under the pressure 0.105MPa, propylene prepolymerization 10 minutes adds 15ml vinylbenzene and 4.0mmol triisobutyl aluminium.Copolyreaction product 6.3 grams, catalytic efficiency is 6.59 kg of polymer/gram titanium, melting point polymer is 242 ℃.[embodiment 12]
The MAO 4.0mmol that in the 250ml reaction flask, adds embodiment 2 preparations, trimethyl aluminium 0.4ml (1M) and cyclopentadienyl three tert.-butoxy titaniums 20 μ mol, 20ml toluene, 50 ℃ of temperature, under the pressure 0.105MPa, propylene prepolymerization 10 minutes adds 15ml vinylbenzene and 4.0mmol triisobutyl aluminium.Copolyreaction product 3.2 grams, catalytic efficiency is 3.35 kg of polymer/gram titanium, and propylene chain link content is 40mol% in the polymkeric substance, and melting point polymer is 236 ℃.[embodiment 13]
In the 250ml reaction flask, add toluene 20ml, feed propylene to saturated, total pressure 0.11MPa, the MAO 3.52mmol that adds embodiment 2 preparations, 0.48mmol trimethyl aluminium, the cyclopentadienyl tripropoxy titanium 16.8 μ mol of embodiment 1 preparation, 50 ℃ of following pre-polymerizations 10 minutes stop logical propylene, add the 2.8mmol triethyl aluminum, 10ml vinylbenzene, polymerization 2 hours, copolyreaction product 4.4 grams, catalytic efficiency is 5.5 kg of polymer/gram titanium, in the copolyreaction product, syndiotactic polystyrene/Atactic Polypropelene segmented copolymer 0[embodiment 14]
In the 250ml reaction flask, add toluene 20ml, feed ethene to saturated, total pressure 0.11MPa, the MAO 3.52mmol that adds embodiment 2 preparations, 0.48mmol trimethyl aluminium, the cyclopentadienyl tripropoxy titanium 16.8 μ mol of embodiment 1 preparation, 50 ℃ of following pre-polymerizations 10 minutes, stop logical propylene, add 2.8mmolTMA, 10ml vinylbenzene, polymerization 2 hours, copolyreaction product 5.8 grams, catalytic efficiency is 7.2 kg of polymer/gram titanium, in the copolyreaction product, and syndiotactic polystyrene 4.4 grams, Atactic Polypropelene 1.05 grams, poly-35 grams of a rule.[embodiment 15]
Add toluene 200ml in 1 liter reactor, feeding propylene to pressure is 0.50MPa.The MAO 10.0mmol that adds embodiment 2 preparations, 5ml (1.0M) trimethyl aluminium, the cyclopentadienyl tripropoxy titanium 50.0 μ mol of embodiment 1 preparation, 50 ℃ of following prepolymerizations 10 minutes stop logical propylene, add the 10mmol triisobutyl aluminium, 150ml vinylbenzene, polymerization 2 hours gets polymkeric substance 32.9 grams, and catalytic efficiency is 13.7 kg of polymer/gram titanium.[embodiment 16]
Get polymkeric substance 35.5 grams except that feeding propylene other polymerizing condition to pressure is 1.0MPa with embodiment 15, catalytic efficiency is 14.8 kg of polymer/gram titanium.
Claims (6)
1. a vinylbenzene-propylene-based block copolymer comprises vinylbenzene segment and propylene segment, it is characterized in that the vinylbenzene segment has syndiotactic structure, and the length of vinylbenzene segment is 50～90% (moles).
2. the preparation technology of a vinylbenzene-propylene-based block copolymer, at first in reactor, feed propylene gas or styrene monomer, to contain the alkylaluminoxane that cyclopentadiene titanium compound that molecular formula is I and general formula be II is catalyzer, under 20～80 ℃ of temperature, add remaining another benzene feedstock vinyl monomer or feed propylene gas, keeping total pressure is that 0.1～1.0MPa reaction makes, and it is characterized in that also containing in the catalyzer organo-aluminium compound that general formula is III;
R
1Ti(OR
2)
3 I
Al (R
4)
3R in the III formula
1Be cyclopentadienyl;
R
2Be alkyl, the aryl of 6～20 carbon atoms, alkaryl, the aralkyl of 1～20 carbon atom;
R
3For containing the alkyl of 1～4 carbon atom;
R
4For containing the alkyl of 1～4 carbon atom;
X is the oligomerisation degree of alkylaluminoxane, and its value is 6～40;
Wherein the aluminium among the alkylaluminoxane II is 100～2000 to the mol ratio of cyclopentadiene titanium compound I, and aluminium is 10～500 to the mol ratio of cyclopentadiene titanium compound I among the organo-aluminium compound III.
3. according to the preparation technology of the described styrene-propene block copolymer of claim 2, the value that it is characterized in that X among the alkylaluminoxane II is 15～30, R
3Be methyl.
4. according to the preparation technology of the described styrene-propene block copolymer of claim 2, it is characterized in that the R among the organo-aluminium compound III
4Be methyl, ethyl, isobutyl-.
5. according to the preparation technology of the described styrene-propene block copolymer of claim 2, it is characterized in that aluminium among the alkylaluminoxane II is 200～1750 to the mol ratio of cyclopentadiene titanium compound I.
6. according to the preparation technology of the described styrene-propene block copolymer of claim 2, it is characterized in that aluminium among the organo-aluminium compound III is 200～500 to the mol ratio of cyclopentadiene titanium compound I.
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|---|---|---|---|
| CN97106212A CN1056625C (en) | 1997-01-10 | 1997-01-10 | Styrene-propene block copolymer and preparing process thereof |
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|---|---|---|---|
| CN97106212A CN1056625C (en) | 1997-01-10 | 1997-01-10 | Styrene-propene block copolymer and preparing process thereof |
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| CN1056625C true CN1056625C (en) | 2000-09-20 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5260394A (en) * | 1989-03-20 | 1993-11-09 | Idemitsu Kosan Co., Ltd. | Styrene copolymer and process for production thereof |
| EP0707014A1 (en) * | 1993-07-02 | 1996-04-17 | Idemitsu Kosan Company Limited | Process for producing aromatic vinyl compound copolymer |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5260394A (en) * | 1989-03-20 | 1993-11-09 | Idemitsu Kosan Co., Ltd. | Styrene copolymer and process for production thereof |
| EP0707014A1 (en) * | 1993-07-02 | 1996-04-17 | Idemitsu Kosan Company Limited | Process for producing aromatic vinyl compound copolymer |
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