CN1353119A - Process for treating low-isotactic alpha-olefine polymer - Google Patents
Process for treating low-isotactic alpha-olefine polymer Download PDFInfo
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- CN1353119A CN1353119A CN 00130280 CN00130280A CN1353119A CN 1353119 A CN1353119 A CN 1353119A CN 00130280 CN00130280 CN 00130280 CN 00130280 A CN00130280 A CN 00130280A CN 1353119 A CN1353119 A CN 1353119A
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Abstract
A process for treating low-isotactic alpha-olefin polymer which is liable to block valve and pipeline features that the transform rate of alpha-olefine or polymerizing is controlled, and the liquid medium and alpha-olefin monomer are filled in flash evaporator in advance. Its product has uniform granularity, and can be used as modifier of hot-fusible adhesive, water-proof asphalt material, etc.
Description
The present invention relates to a kind of treatment process of low-isotactic alpha-olefine polymer.Particularly relate to viscosity low-isotactic alpha-olefine polymer that a kind of liquid phase noumenal method produces the discharging conveying and the method for Separation and Recovery.
Low-isotactic alpha-olefine polymer comprises low-isotactic alpha-olefine homopolymer and low-isotactic alpha-olefine multipolymer, and low-isotactic alpha-olefine polymer is meant the alpha-olefinic polymer that the low regularity chain preface the rule distributes except between high isotactic and height.Directly the synthetic low-isotactic alpha-olefine polymer is that a kind of short distance by different lengths, different distributions is long in order apart from unordered isotactic and block homopolymer or multipolymer that the rule chain link is formed.
Low-isotactic alpha-olefine polymer has different forms and purposes according to its degree of isotacticity height with the molecular weight size.Than low grade and normally unbodied, can be used for fields such as hotmelt, modified asphalt waterproof material, building sealant and rubber-plastics material performance improver than the product of small molecular weight.The product of higher degree of isotacticity and larger molecular weight is low-crystallinity normally, can be used as that thermoplastic elastomer is used for film, long filament, fiber, sheet material and other requires elastic purposes.
Usually adopt Ziegler-Natta catalyst or metallocene catalyst to produce low-isotactic alpha-olefine polymer.The stereoselectivity of metallocene catalyst is higher, can make dispersed little polymkeric substance.
The low-isotactic alpha-olefine polymer surfaces of tacky, clinging power is strong, tends to be bonded to the parts of processing unit inside, as the wall of container, pipe or valve, forms caking, causes the danger of skinning and obstruction.The discharging conveying of the low-isotactic alpha-olefine polymer mixture of viscosity and Separation and Recovery are more much more difficult than high isotactic product after polymerization.For this reason, usually adopt solution method, slurry process or vapor phase process to produce.But adopt solution method or slurry polymerization technology, the polymeric kettle per unit area yield is low, after the polymerization solvent remove the cost height, environmental pollution is big; Adopt gas phase polymerization technology, facility investment is big, and technology is complicated, is not suitable for periodical operation.As adopt the liquid phase noumenal method polymerization technique, above-mentioned shortcoming can be avoided, but the discharging conveying of viscosity low-isotactic alpha-olefine polymer mixture and Separation and Recovery problem must be solved and for addressing this problem other correlation technique difficult problems of bringing.
Be to solve the discharging conveying and the Separation and Recovery problem of sticky polymers, US5216121 (1993) adopt make polymkeric substance and carrier mutually the mixture of (liquid monomer and/or solvent) when airtight pressurized by flash distillation almost moment be cooled to that it does not glue, the second-order transition temperature of easy handling or following temperature range and be separated with carrier.Its shortcoming is to need strict control flash distillation parameter.CN87105522 (1988) adopts one-period discharge valve or the sharp ripple blipper of cloth valve to be similar to from reactor and discharges material continuously.At as close as possible Bu Libo valve place, making the material of being discharged is that 177～218 ℃ the amorphous polyolefin of the degassing contacts and enters flash zone with temperature directly.Discharge the unreacted material from flash zone.The amorphous polyolefin part of the degassing is discharged into the product storage tank by liquid-level controller, and part is returned with the material of discharging from polymeric kettle and contacted.Its shortcoming is a flash zone temperature height, the energy consumption height.US4,316,008 (1980), CN1170729A (1998) all adopts in polymerization and make catalyst deactivation and purified polymer by adding entry after isolating unreacted monomer.Its shortcoming is can not directly give off polymkeric substance simply after isolating unreacted monomer.
The object of the present invention is to provide a kind of treatment process of easy low-isotactic alpha-olefine polymer.The low isotactic polymer of the viscosity that adopts this treatment process to solve to obtain by liquid phase noumenal method discharging carry and the Separation and Recovery process in the obstruction and the skinning problem that cause.Make the catalyst deactivation that remains in the polymkeric substance simultaneously.
The present invention relates to a kind of treatment process of low-isotactic alpha-olefine polymer, may further comprise the steps:
(1) making carbonatoms under the liquid-phase bulk polymerization condition is that the 'alpha '-olefin monomers of 3-6 forms the material that contains low-isotactic alpha-olefine polymer in reaction zone;
(2) material that contains low-isotactic alpha-olefine polymer that step (1) is obtained is sent into the flash distillation still, flashes off unreacted monomer;
(3) from the flash distillation still, discharge the low-isotactic alpha-olefine polymer that is dispersed in the liquid medium; Wherein the monomeric transformation efficiency of control is 20～60% in step (1); Before the material that will contain low-isotactic alpha-olefine polymer is sent into the flash distillation still, add liquid medium in advance in the flash distillation still in step (2): the alcohol and/or the carbonatoms that contain the water of 0～0.3% (w) tensio-active agent or water and/or carbonatoms and be 1-6 are the ketone of 3-6; In step (2), charge into 'alpha '-olefin monomers simultaneously in advance.
The present invention's monomer conversion when the controlled polymerization keeps the carrier of an amount of unreacted liquid monomer as the low-isotactic alpha-olefine homopolymer, material is discharged from polymeric kettle be transported to the flash distillation still and can carry out smoothly.If monomer conversion too low (as being lower than 20%), the yield of polymkeric substance is too low, is unfavorable for industrialization; If monomeric transformation efficiency too high (as being higher than 60%), the concentration height of the polymkeric substance of gained, easily sticking wall, easily generation skinning or obstruction in discharge process thereafter also are unfavorable for industrialization in reactor.The transformation efficiency of liquid monomer of the present invention is controlled to be 20～60%, and preferred 30～50%.Generally can reach the purpose of controlling the liquid monomer transformation efficiency by add-on and the regulation polymeric reaction condition that calculates catalyzer.
The present invention before the flash separation, adds certain liquid medium as dispersible carrier in the unreacted liquid monomer from polymeric blends.The viscous material of separating out after the liquid monomer flash distillation enters this liquid medium immediately, keeps dispersion state, prevents caking, blocking pipe and valve when avoiding discharging.The low-isotactic alpha-olefine polymer of sloughing the unreacted liquid monomer can be discharged the flash distillation still with this liquid medium and be entered next step operation: filtration, drying, pelletizing, moulding.The liquid medium that adds can make catalyzer and promotor decompose and inactivation, termination reaction and purified polymer simultaneously.
Liquid medium of the present invention is that water and/or carbonatoms are that alcohol and/or the carbonatoms of 1-6 is the ketone of 3-6, is preferably the mixture of water and alcohol or water and ketone.The proportioning of water and alcohol or water and ketone is 20: 80～80: 20 (v/v), is preferably 40: 60～60: 40 (v/v).Alcohol of the present invention is preferably methyl alcohol and ethanol; Ketone of the present invention is preferably acetone.
Liquid medium of the present invention also can be the aqueous solution that contains 0～0.3% (w/w) tensio-active agent.All can be used for the present invention as long as help low-isotactic alpha-olefine polymer dispersive tensio-active agent in water.Those skilled in the art know that all the working concentration of surfactant soln should be according to the increase and decrease as one feels fit of material deployment conditions.Be preferably 0.05～0.2% (w/w).Be used for tensio-active agent of the present invention and be generally anionic or non-ionic type, preferably low bubble or still.The example of aniorfic surfactant has sodium stearate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, poly alkyl alcohol oxyethane ether sodium sulfate etc.; Examples of nonionic surfactants has Fatty Alcohol(C12-C14 and C12-C18) oxyethane ether, nonyl phenol EO ether, sorbitan fatty acid ester, sucrose fatty ester, alkyl alcohol polyethylene oxide poly(propylene oxide) ether etc.Wherein better with nonionic surface active agent with polyoxyethylene glycol and polyether structure, as SP-169 (stearyl alcohol poly(propylene oxide) polyethylene oxide ether), BP-2000 (propylene glycol polyoxyethylene polyoxytrimethylene ether) etc.
The consumption of liquid medium of the present invention is 1～5 times of low-isotactic alpha-olefine homopolymer quality, is preferably 2～3 times.
The liquid monomer flash distillation will be separated out the low-isotactic alpha-olefine polymer material of viscosity in transport pipe, causes adhesion and caking, makes pipeline and valve blockage.For addressing this problem, the present invention charges into polymerization single polymerization monomer in advance in the flash distillation still, and the amount of charging into connects material under the temperature polymerization single polymerization monomer vapor liquid equilibrium pressure for well to reach the flash distillation still, to prevent or to reduce liquid monomer flash distillation when the discharging transferring polymer mixture.Those skilled in the art know that all the temperature the when temperature that connects material of when utilizing pressure difference convey materials flash distillation still usually should be than the polymeric kettle blowing is low.Generally should hang down 10～40 ℃, be preferably low 15～25 ℃.At this moment the design of flash distillation still should tolerate the saturated vapor pressure of liquid monomer when connecting material, and the flash distillation still should tolerate the pressure of 3.0～4.0MPa usually.The flash distillation still also should be with cooling and heating unit, so that control temperature and the flash distillation speed of connecting material by heating or cooling.Flash vaporization point is generally 10～60 ℃, is preferably 20～50 ℃.
The inventive method is applicable to the processing of the low-isotactic alpha-olefine homopolymer or the low-isotactic alpha-olefine multipolymer of liquid phase noumenal method gained, is specially adapted to the processing of the low-isotactic alpha-olefine homopolymer or the low-isotactic alpha-olefine multipolymer of batch liquid bulk polymerization gained.When method of the present invention was used to handle low-isotactic alpha-olefine homopolymer (as LIPP), the monomer that charges in advance in the flash distillation still was at the used 'alpha '-olefin monomers of polymerization zone (as propylene); When method of the present invention is used to handle the low-isotactic alpha-olefine multipolymer, the monomer that charges in advance in the flash distillation still preferably uses dominant 'alpha '-olefin monomers in low-isotactic alpha-olefine multipolymer content at one or more used 'alpha '-olefin monomers of polymerization zone.
The catalyzer that prior art has been disclosed any to can be used for producing low-isotactic alpha-olefine polymer all can be used for the present invention.Polymerisation catalyst system as low-isotactic alpha-olefine polymer can be a Ziegler-Natta catalyst, also can be metallocene catalyst.The present invention can adopt the LIPP catalyst system of being narrated by CN1146461A.It is that a kind of Ziegler-Natta type titanium is a carried catalyst, with Mg (OC
2H
5)
2With AlCl
3Generate carrier, again with TiCl
4Reaction generates solid catalytic ingredient, and promotor is a trialkylaluminium.This catalyst system is active high, and selectivity is good, and the life-span is long.Its component is:
(1). a kind of with Mg (OC
2H
5)
2With AlCl
3Reaction generates carrier, again with TiCl
4The solid catalytic ingredient that reaction obtains.
(2). a kind of general formula is R
mAlX
3-mAlkylaluminium cpd as promotor.Wherein R is C
1-C
9Alkyl, X is a halogen, m=1～3.
(3). the mol ratio of aluminum alkyls and solid catalyst (al-ti ratio) is 50～1500 during polymerization, is preferably 100～1000.
The present invention is not particularly limited the temperature of reaction of polymerization zone.The temperature range that prior art is disclosed to can be used for preparing low-isotactic alpha-olefine polymer all can be used for the present invention.Can between 50～80 ℃, carry out homopolymerization or copolyreaction as the present invention.
The present invention preferably adopts batch liquid bulk polymerization.This method is convenient except switching product grade, help in time producing outside the readily marketable products according to the market requirement, can also avoid when adopting solution method or slurry process the polymeric kettle per unit area yield low, solvent removes the cost height after the polymerization, environmental pollution big and when adopting gas phase polymerization technology facility investment big, technology is complicated, is not suitable for shortcomings such as periodical operation.
A concrete polymerization procedure is: the stainless steel polymeric kettle of 5L belt stirrer and chuck is vacuumized the thorough pump drainage displacement of inflated with nitrogen three times under 80 ℃.2/5 propylene, triisobutyl aluminium, catalyzer, hydrogen and the remaining propylene that add metering successively.Be warming up to specified temperature, finishing reaction behind the reaction certain hour under the stirring velocity of regulation.Finally can obtain the little sticking LIPP homopolymer product of white particulate.Polyreaction can be carried out under a certain temperature between 50～80 ℃.The concentration of hydrogenation in the controlled polymerization reaction can be regulated the molecular weight of LIPP homopolymer.
The heptane method of the boiling isotactic index of the LIPP homopolymer that obtains thus is＜15%,
13The mmmm% of C-NMR is 40～60, and weight-average molecular weight is 2.0～11.0 * 10
4, molecular weight distribution is 5～11.Catalytic activity is 3.0～6.0 * 10
4Gram polypropylene/gram catalyzer.
Isotactic index adopts the heptane dissolution method of boiling to measure.The granulated samples of drying constant weight is refluxed in the heptane that boils after the dissolving, and the weight percentage of dissolution residual substance is not an isotactic index.Because the meltage of LIPP homopolymer in the heptane that boils is bigger, can not adopts extraction process used when measuring the isotactic polypropylene homopolymer isotactic index, and should adopt dissolution method.
13Bruker AM-300 type NMR spectrometer with superconducting magnet is adopted in the chain preface measure of spread of C-NMR, and 120 ℃ of probe temperatures, solvent are that deuterium is for orthodichlorobenzene.Can obtain the upright structure degree of five unit sequences and characterize isotactic mmmm% by the chemical shift of measuring and calculating polypropylene methyl district.
The Water 150C of company type GPC instrument is adopted in molecular weight and measure of spread thereof.Condition determination is: (series connection of 7.8 * 300mm), four posts, 135 ℃ of column temperatures, solvent are orthodichlorobenzene to Styragel HT post, flow velocity 1ml/min, sample concentration 0.25% (wt), sample size 200ml..
The present invention will be described further with the example of following LIPP.Scope of the present invention is not subjected to the restriction of these examples.
Used solid catalyst is that embodiment 1 makes in the LIPP method for preparing catalyst of narrating according to CN1146461A in the following example.Catalyzer is formed (w%): Ti5.0, Mg18.4, Cl53.1, Si17.0
Embodiment 1.
5L is vacuumized the thorough pump drainage displacement of inflated with nitrogen three times under 80 ℃ with the stainless steel polymeric kettle of magnetic coupling agitator and chuck.Add the 1.5L liquid propylene successively, 9.7ml concentration is the n-heptane solution of 2mol/L triisobutyl aluminium, the 0.0133g solid catalyst, and 1.75L hydrogen and remaining propylene, the liquid propylene total amount that makes adding is 3.0L.Be warming up to 70 ℃, stir down reaction finishes reaction after 2 hours.In 10L flash distillation still, add the aqueous ethanolic solution of 1L ethanol/water=60/40 (v/v), charge into liquid propene 0.5L, be warming up to 50 ℃, can reach the vapor liquid equilibrium pressure (about 2.0MPa) under this temperature that connects material.Plugging in the flash distillation still, is not taken place in the discharge of pipes of the material in the polymeric kettle by φ 15mm.Mixed 10 minutes.The purging valve of opening on the flash distillation still makes the liquid propylene flash distillation.Flash distillation is opened bottom valve after finishing, and LIPP along with aqueous ethanolic solution is emitted the flash distillation still plugging does not take place.Obtain the little sticking LIPP product of 355 gram white particulate after the drying.Propylene conversion is 23.7%.
Embodiment 2.
In the polymeric kettle of the warp abundant pump drainage identical with embodiment 1, add the 1.5L liquid propylene successively, 5.8ml concentration is the n-heptane solution of 2mol/L triisobutyl aluminium, the 0.0190g solid catalyst, 1.75L hydrogen and remaining propylene, the liquid propylene total amount that makes adding is 3.0L.Be warming up to 70 ℃, stir down reaction finishes reaction after 2 hours.The polymeric kettle temperature is cooled to 60 ℃.In 10L flash distillation still, add the aqueous ethanolic solution of 2L ethanol/water=40/60 (v/v), charge into liquid propene 0.4L, be warming up to 40 ℃, can reach the vapor liquid equilibrium pressure (about 1.6MPa) under this temperature that connects material.Plugging in the flash distillation still, is not taken place in the discharge of pipes of the material in the polymeric kettle by φ 15mm.Make the liquid propylene flash distillation as embodiment 1.Finally obtain the little sticking LIPP product of 520 gram white particulate.Propylene conversion 34.6%.
Embodiment 3.
In the polymeric kettle of the warp abundant pump drainage identical with embodiment 1, add the 1.5L liquid propylene successively, 25.7ml concentration is the n-heptane solution of 2mol/L triisobutyl aluminium, the 0.0379g solid catalyst, 1.75L hydrogen and remaining propylene, the liquid propylene total amount that makes adding is 3.8L.Be warming up to 65 ℃, stir down reaction finishes reaction after 2 hours.In 10L flash distillation still, add the aqueous acetone solution of 1L acetone=70/30 (v/v), charge into liquid propene 0.4L, be warming up to 40 ℃, can reach the vapor liquid equilibrium pressure (about 1.6MPa) under this temperature that connects material.Plugging in the flash distillation still, is not taken place in the discharge of pipes of the material in the polymeric kettle by φ 15mm.Make the liquid propylene flash distillation as embodiment 1.Finally obtain the little sticking LIPP product of 685 gram white particulate.Propylene conversion 36%.The isotactic index that the heptane dissolution method of boiling is measured is 15%,
13The mmmm% that C-NMR records is 42.3, and the weight-average molecular weight that the GPC method records is 2.56 * 10
4, molecular weight distribution is 11.4.
Embodiment 4.
Polymerizing condition is identical with embodiment 1.It is about 50 ℃ that polymerization finishes back maintenance polymeric kettle temperature.In 10L flash distillation still, add 1L 0.15% (w) SP-169 (the Tianjin petrochemical complex institute product) aqueous solution.Charge into liquid propene 0.35L, can reach the vapor liquid equilibrium pressure (about 1.2MPa) under this temperature that connects material (room temperature).Material in the polymeric kettle is discharged in the flash distillation still, plugging does not take place.Make the liquid propylene flash distillation as embodiment 1.Flash distillation is opened bottom valve after finishing, and LIPP along with aqueous dispersant is emitted the flash distillation still plugging does not take place.
Embodiment 5
Polymerizing condition is identical with embodiment 1.It is about 50 ℃ that polymerization finishes back maintenance polymeric kettle temperature.In 10L flash distillation still, add 2L 0.05% (w/w) BP-2000 (Nanjing, the Nanjing petrochemical corporation (complex) product) aqueous solution.Charge into liquid propylene as embodiment 4, the material in the polymeric kettle is discharged in the flash distillation still, plugging does not take place.Make the liquid propylene flash distillation as embodiment 1.Flash distillation is opened bottom valve after finishing, and LIPP along with water phase surfactant mixture is emitted the flash distillation still plugging does not take place.
Embodiment 6
Polymerizing condition is identical with embodiment 1.It is about 50 ℃ that polymerization finishes back maintenance polymeric kettle temperature.In 10L flash distillation still, add 2L 0.2% (w/w) Sodium dodecylbenzene sulfonate (Nanjing, the Nanjing petrochemical corporation (complex) product) aqueous solution.Charge into liquid propene as embodiment 4, the material in the polymeric kettle is discharged in the flash distillation still, plugging does not take place.Make the liquid propylene flash distillation as embodiment 1.Flash distillation is opened bottom valve after finishing, and LIPP along with aqueous dispersant is emitted the flash distillation still plugging does not take place.
Embodiment 7
The polymeric kettle of 500L band magnetic coupling agitator and chuck is through fully adding the 150L liquid propylene after the displacement.Successively pour n-heptane solution and the 1.829g solid catalyst that 468ml concentration is the 2.9mol/L triisobutyl aluminium again with remaining 200L propylene.Add 200L hydrogen.Be warming up to 75 ℃ (3.3MPa), stir reaction down 135 minutes.Meanwhile, 1000L flash distillation still is fully replaced the back 300L of adding clear water with purity nitrogen, and charge into propylene to the following gas-liquid equilibrium pressure of the temperature that connects material (20 ℃).Material in the polymeric kettle is passed through the discharge of pipes of φ 80mm in the flash distillation still.Stirred 15 minutes.The purging valve of opening on the flash distillation still makes the liquid propylene flash distillation.Open flash distillation still chuck circulating hot-water pump simultaneously, control flash distillation speed makes the interior temperature of charge of flash distillation still remain 10～20 ℃.After finishing, flash distillation uses the remaining propylene in the nitrogen emptying product.Open bottom valve, emit LIPP, plugging does not take place.Get the little sticking LIPP product of 96.1kg white particulate after the drying.Catalytic activity is the 52520gPP/g catalyzer.Propylene conversion is 54.9%.The isotactic index that the heptane dissolution method of boiling is measured is 14.5%,
13The mmmm% that C-NMR records is 57.0, and the weight-average molecular weight that the GPC method records is 11.3 * 10
4, molecular weight distribution is 9.96.Comparative Examples 1
Polymerizing condition is identical with embodiment 2, does not just add propylene in the flash distillation still in advance, but adds the propylene gas-liquid equilibrium pressure of nitrogen under the temperature that connects material (40 ℃), and the result is with the generation plugging when polymerization reaction kettle is put into the flash distillation still of the material after the polymerization.Comparative Examples 2
Polymerizing condition is identical with embodiment 2, and the controlled polymerization transformation efficiency is 70%, and the result with the material after the polymerization plugging is taking place when polymerization reaction kettle is put into the flash distillation still.
Claims (10)
1. the treatment process of a low-isotactic alpha-olefine polymer may further comprise the steps:
(1) making carbonatoms under the liquid-phase bulk polymerization condition is that the 'alpha '-olefin monomers of 3-6 forms the material that contains low-isotactic alpha-olefine polymer in reaction zone;
(2) material that contains low-isotactic alpha-olefine polymer that step (1) is obtained is sent into the flash distillation still, flashes off unreacted monomer;
(3) from the flash distillation still, discharge the low-isotactic alpha-olefine polymer that is dispersed in the liquid medium; It is characterized in that the monomeric transformation efficiency of control is 20～60% in step (1); Before the material that will contain low-isotactic alpha-olefine polymer is sent into the flash distillation still, add liquid medium in advance in the flash distillation still in step (2): the alcohol and/or the carbonatoms that contain the water of 0～0.3% (weight percent) tensio-active agent or water and/or carbonatoms and be 1-6 are the ketone of 3-6; In step (2), charge into 'alpha '-olefin monomers simultaneously in advance.
2. the treatment process of low-isotactic alpha-olefine polymer according to claim 1 is characterized in that described low-isotactic alpha-olefine polymer is the low-isotactic alpha-olefine homopolymer.
3. the treatment process of low-isotactic alpha-olefine polymer according to claim 1 is characterized in that described low-isotactic alpha-olefine polymer is a LIPP.
4. the treatment process of low-isotactic alpha-olefine polymer according to claim 1 is characterized in that described low-isotactic alpha-olefine polymer is the low-isotactic alpha-olefine multipolymer.
5. according to the treatment process of each described low-isotactic alpha-olefine polymer of claim 1-4, it is characterized in that the monomeric transformation efficiency of control is 30～50% in step (1).
6. according to the treatment process of each described low-isotactic alpha-olefine polymer of claim 1-4, the consumption that it is characterized in that liquid medium is 1～5 times of low-isotactic alpha-olefine polymer quality, is preferably 2～3 times.
7. according to the treatment process of each described low-isotactic alpha-olefine polymer of claim 1-4, it is characterized in that described liquid medium is the mixture of water and alcohol or water and ketone, the proportioning of water and alcohol or water and ketone is 20: 80～80: 20 (v/v), is preferably 40: 60～60: 40 (v/v).
8. according to the treatment process of each described low-isotactic alpha-olefine polymer of claim 1-4, it is characterized in that described alcohol is methyl alcohol or ethanol, described ketone is acetone.
9. according to the treatment process of each described low-isotactic alpha-olefine polymer of claim 1-4, it is characterized in that described tensio-active agent is the tensio-active agent with polyoxyethylene glycol or polyether structure.
10. according to the treatment process of each described low-isotactic alpha-olefine polymer of claim 1-4, it is characterized in that making the amount that charges into 'alpha '-olefin monomers in advance to reach the flash distillation still gas-liquid equilibrium pressure under the temperature that connects material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532366A (en) * | 2010-12-09 | 2012-07-04 | 中国石油化工股份有限公司 | Method for reducing viscosity of conjugated diene polymer solution |
| CN103172766A (en) * | 2011-12-20 | 2013-06-26 | 中国石油化工股份有限公司 | Additive capable of stopping polymerization reaction and/or reducing polymer solution viscosity and method |
| CN105153341A (en) * | 2015-07-10 | 2015-12-16 | 常州市宏硕电子有限公司 | Process and system for producing polybutene alloy |
-
2000
- 2000-11-03 CN CNB001302809A patent/CN1137158C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532366A (en) * | 2010-12-09 | 2012-07-04 | 中国石油化工股份有限公司 | Method for reducing viscosity of conjugated diene polymer solution |
| CN103172766A (en) * | 2011-12-20 | 2013-06-26 | 中国石油化工股份有限公司 | Additive capable of stopping polymerization reaction and/or reducing polymer solution viscosity and method |
| CN103172766B (en) * | 2011-12-20 | 2016-02-10 | 中国石油化工股份有限公司 | Stop additive and the method for polyreaction and/or reduction polymer solution viscosity |
| CN105153341A (en) * | 2015-07-10 | 2015-12-16 | 常州市宏硕电子有限公司 | Process and system for producing polybutene alloy |
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| Publication number | Publication date |
|---|---|
| CN1137158C (en) | 2004-02-04 |
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