CN103665221A - Preparation method of propene polymer composition - Google Patents
Preparation method of propene polymer composition Download PDFInfo
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- CN103665221A CN103665221A CN201210331183.6A CN201210331183A CN103665221A CN 103665221 A CN103665221 A CN 103665221A CN 201210331183 A CN201210331183 A CN 201210331183A CN 103665221 A CN103665221 A CN 103665221A
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Abstract
The invention relates to a preparation method of a propene polymer composition. The method is characterized in that in the presence of catalyst components and hydrogen, firstly the propene homopolymer is produced in three or more than three reactors, then the propene polymer is produced in a final reactor, the multiple reactors comprise liquid reactors and gas reactors, the reaction temperature of the liquid reactor is 60-85 DEG C, the pressure of the liquid reactor is 2-5 MPa, the reaction temperature of the gas reactor is 70-90 DEG C, the pressure of the gas reactor is 1-3 MPa, the number-average molecular weight of the polymer is not less than the average molecular weight of the homopolymer, the ratio of the melt index of the final polymer and the melt index of the homopolymer is 0.3 to 1.0, and the catalyst component adopts the catalyst disclosed in the patent CN1453298A. The propene polymer composition is fewer in xylene soluble matters, the melt temperature is low, the molecular weight is widely distributed, the modulus of the polymer is high, the processing is favored, and a BOPP (biaxially-oriented polypropylene) film of 12 micrometers can be stretched at a high speed (420m/min or more).
Description
Technical field
The present invention relates to the preparation method of prolylene polymer composition.
Background technology
It is generally acknowledged for the production of the degree of isotacticity of the prolylene polymer composition of BOPP film lower, melt temperature is lower, molecular weight distribution is wide, more be beneficial to BOPP film high-speed stretch moulding, therefore on market, the alfon as BOPP PP Pipe Compound is all that degree of isotacticity is very low, but its xylene soluble part is mostly more than 3.5%, although make like this fusing point of polymkeric substance decrease, but solubles content is high, limited its range of application, as be applied in food service industry will contaminated food, certainly, also there is now a kind of method in alfon, to add propylene copolymer, wherein best bet is that the molecular weight of multipolymer wherein will be higher than the molecular weight of homopolymer, as Chinese patent CN1810871A discloses a kind of production method and characteristic thereof of using the prolylene polymer composition of endless tube explained hereafter BOPP film, the xylene soluble part of polymkeric substance is lower, the deflection of BOPP film is good, but the fusing point of polymkeric substance is low not, or melting distributes and need to more optimize, problem due to catalyst system also makes the width of the molecular weight distribution of produced polymkeric substance need further to be improved in addition.At Chinese patent searching database, also retrieve the patent documentation of associated viscera simultaneously, as patent No. CN1718598A, patent name is a kind of preparation method of homopolymerization polypropylene bidirection drawing film special material, patent No. CN1810871A, patent name is prolylene polymer composition and its biaxially oriented film of preparing, amounts to 11 pieces of patent documentation numbers.
Summary of the invention
The invention provides a kind of catalyzer of propylene polymerization, and the production method of prolylene polymer composition, the catalyzer of the application of the invention and polymerization technique, make the xylene soluble part of gained prolylene polymer composition lower, molecular weight distribution is wide, but the modulus of polymkeric substance is higher, good combination property, makes prolylene polymer composition high-speed stretch at a lower temperature become film.
Technical scheme of the present invention is as follows:
A kind ofly prepare polyacrylic catalyzer, it is the reaction product of Primary Catalysts, promotor and external donor compound, wherein Primary Catalysts is a kind of ingredient of solid catalyst, this ingredient of solid catalyst comprises magnesium, titanium, halogen and electron donor, described magnesium is magnesium dihalide, described electron donor is 2,4-pentanediol dibenzoate or 3,5-heptanediol dibenzoate; Described promotor is triethyl aluminum; Described external donor compound is Cyclohexylmethyldimethoxysilane; Ratio between described Primary Catalysts, promotor and external donor compound, take aluminium: titanium: the molar ratio computing between silicon is 1:0.05 ~ 0.005:0.5 ~ 0.002, described Primary Catalysts is prepared as follows: in the reactor of fully replacing through high pure nitrogen, add successively magnesium chloride 60kg, toluene 112L, epoxy chloropropane 50L, tributyl phosphate (TBP) 157L, under stirring, be warming up to 50 ℃, and maintain 2.5 hours, solid dissolves completely.Add Tetra hydro Phthalic anhydride 17.5kg, continue to maintain 1 hour, solution is cooled to below-25 ℃, in 1 hour, drip TiCl
4700L, is slowly warming up to 80 ℃, separates out gradually solids in temperature-rise period, adds 2,4-pentanediol dibenzoate 75mol to 80 ℃, and holding temperature 1 hour, after filtration, adds toluene 700l, and washing, obtains solid sediment, then adds toluene 750L, TiCl
4500L, is warmed up to 100 ℃, processes two hours, after venting filtrate, then adds toluene 750L, TiCl
4500L, is warmed up to 100 ℃, processes two hours, and venting filtrate, then add hexane 800L, boiling state washed twice, adds hexane 800L, after normal temperature washed twice, obtains ingredient of solid catalyst.
A kind of preparation method of prolylene polymer composition, it is at above-mentioned catalyzer, under the existence of hydrogen, in more than three or three multiple reactors, first carry out the production of alfon, in the end in a reactor, carry out the production of propylene copolymer, wherein multiple reactor comprises Liquid-phase reactor and Gas-phase reactor, wherein the temperature of reaction in Liquid-phase reactor is 60 ℃～85 ℃, pressure is 2MPa～5MPa, temperature of reaction in Gas-phase reactor is 70 ℃～90 ℃, pressure is 1MPa～3MPa, and the molecular-weight average of multipolymer is not less than the molecular-weight average of homopolymer, finally obtain the melting index of polymkeric substance and the melting index of homopolymer than the prolylene polymer composition for the production of BOPP film that is 0.3～1.0.
The above-mentioned catalyzer of the present invention can be referring to Chinese patent CN1453298A.
Usually, the ratio between cocatalyst component organo-aluminium compound and external electron donor component silicoorganic compound, can control the degree of isotacticity of propene polymer effectively.
Preparation method for prolylene polymer composition of the present invention, preferably on Mitsui autoclave Hypol continuous polymerization technique device, prepare, described HYPOL process unit comprises three still techniques and four still techniques, three still techniques are comprised of three reactors, one of them liquid phase still and two gas phase stills, four still techniques are comprised of two liquid phase stills and two gas phase stills.
For successive polymerization reaction of the present invention, catalyzer preferably carries out prepolymerization continuous or intermittence, by the prepolymerization with propylene, can effectively control the particle form of polymkeric substance in reaction process, reduce the fragmentation of polymer beads, and the polymerization activity of effectively bringing into play catalyzer.Prepolymerization reaction generally carries out under relatively mild condition, and preferable polymerization temperature is lower than 30 ℃, and pre-polymerization multiple is controlled within 1～10 times.
Comparatively preferred embodiment of preparation method of prolylene polymer composition of the present invention is: first carry out propylene homopolymerization, and then in the end in a reactor, carry out ethene and copolymerization of propylene, it is 10～200 that the two ratio of Primary Catalysts and promotor organo-aluminium compound be take the molar ratio computing of aluminium/titanium, is preferably 20～100; It is 2～50 that the two ratio of promotor organo-aluminium compound and external electron donor silicoorganic compound be take the molar ratio computing of aluminium/silicon, is preferably 3～20; During copolymerization, the mass ratio of ethene and propylene is 0.001 ~ 0.03, is preferably 0.002～0.01; During copolymerization, the mass ratio of hydrogen add-on and propylene add-on is 0 ~ 0.0001, does not preferably add hydrogen; Pre-polymerization multiple is 1～10; Liquid reactive temperature is controlled at 60 ~ 85 ℃, and pressure-controlling is at 2MPa～5MPa, and the temperature of gas-phase reaction is controlled at 70 ℃～90 ℃, and pressure-controlling is at 1MPa～3MPa.
The prepared prolylene polymer composition of preparation method of the present invention, the xylene soluble part that it is characterized in that composition is 2.0% ~ 3.5%, ethylene content is 0.4wt% ~ 0.7wt%, fusing point is 153 ℃～162 ℃, and the rheology polydispersity index PI of the composition of employing rheometer measurement is 5.0 ~ 6.5.
Preferably, the xylene soluble part of the prepared prolylene polymer composition of preparation method of the present invention is 2.0% ~ 3.0%, ethylene content is 0.4wt% ~ 0.6wt%, and fusing point is 155 ℃～160 ℃, and the rheology polydispersity index PI of the composition of employing rheometer measurement is 5.3 ~ 6.0.
The invention provides a kind of catalyzer, adopt the xylene soluble part of the prolylene polymer composition that the production method of the prolylene polymer composition of catalyzer of the present invention produces lower, melt temperature is also lower, molecular weight distribution is wide, but the modulus of polymkeric substance is higher, make prolylene polymer composition be very beneficial for processing, can be at a high speed (420m/min and more than) when stretching 12 um left and right BOPP film, the deflection of gained BOPP film is fine.In addition, in polymer production, in Gas-phase reactor, carry out the production of multipolymer, can reduce the possibility of sticky still, therefore use method of the present invention, make to produce more smooth.
Embodiment
the preparation of Primary Catalysts:
embodiment 1:in the reactor of fully replacing through high pure nitrogen, add successively magnesium chloride 60kg, toluene 112L, epoxy chloropropane 50L, tributyl phosphate (TBP) 157L.Under stirring, be warming up to 50 ℃, and maintain 2.5 hours, solid dissolves completely.Add Tetra hydro Phthalic anhydride 17.5kg, continue to maintain 1 hour.Solution is cooled to below-25 ℃, in 1 hour, drips TiCl
4700L.Slowly be warming up to 80 ℃, in temperature-rise period, separate out gradually solids.Add 2,4-pentanediol dibenzoate 75mol, holding temperature 1 hour to 80 ℃.After filtration, add toluene 700l, washed twice, obtains solid sediment.Then add toluene 750L, TiCl
4500L, is warmed up to 100 ℃, processes two hours, after venting filtrate, then adds toluene 750L, TiCl
4500L, is warmed up to 100 ℃, processes venting filtrate two hours.Add hexane 800L, boiling state washed twice, adds hexane 800L, after normal temperature washed twice, obtains ingredient of solid catalyst again.
embodiment 2:with 3,5-heptanediol dibenzoate, replace 2,4-pentanediol dibenzoate, and add 3,5-heptanediol dibenzoate 75mol at 80 ℃, other condition is with embodiment 1.
comparative example 1:with n-butyl phthalate, replace 2,4-pentanediol dibenzoate, other condition is with embodiment 1.
the production of propylene polymerization composition
embodiment 3: on the Mitsui Hypol process unit that contains two liquid phase stills and two gas phase stills, carry out long run test, the volume of four stills is respectively 32m
3, 32 m
3, 105 m
3with 165 m
3.First by the catalyzer of embodiment 1 preparation in hexane solution lower than 15 ℃, under the condition that in triethyl aluminum and Primary Catalysts, titanium mol ratio is 3, carry out propylene pre-polymerization, obtain pre-polymerization multiple and be 3 prepolymer, then it is added to reaction unit continuously, according to activity, adjust the add-on of catalyzer, make device produce load keep 10 tons of polymkeric substance/hour.The mol ratio 1/50/8 of Primary Catalysts (in titanium content), cocatalyst component triethyl aluminum, three kinds of raw materials of Cyclohexylmethyldimethoxysilane, only in the 4th reactor, add ethene, ethene add-on is 48kg/h, and the temperature of reaction of four stills is respectively 70 ℃, 65 ℃, 75 ℃, 80 ℃.By the hydrogen regulating valve of four reactors, regulate hydrogen add-on respectively, make the melting index of four still resulting polymers be respectively 3.2g/10min, 3.0g/10min, 3.5g/10min, 3.0g/10min.
embodiment 4: identical with embodiment 3, just catalyst activity component is used the catalyst activity component to embodiment 2 preparations.
embodiment 5: identical with embodiment 3, just only in the first reactor, add ethene, ethene add-on is 50kg/h, regulates hydrogen add-on, makes the melting index of four still resulting polymers be respectively 0.35g/10min, 0.9g/10min, 2.4g/10min, 3.0g/10min.
comparative example 2:identical with embodiment 3, just catalyst activity component is used the catalyst activity component of comparative example 1 preparation.
table 1 polymkeric substance and BOPP film performance
From the data of table 1, can find out, adopt the xylene soluble part of the prolylene polymer composition that preparation method of the present invention obtains few, the molecular weight distribution of composition is wide, melt temperature is low, the modulus of composition and BOPP film is very high, makes the prolylene polymer composition can high-speed stretch 12 um left and right BOPP films, and during stretching, energy consumption is low, the thin film strength of gained BOPP is very high, and deflection is fine.
Claims (2)
1. the preparation method of a prolylene polymer composition, it is characterized in that: it is under the existence of catalyst component and hydrogen, in more than three or three multiple reactors, first carry out the production of alfon, in the end in a reactor, carry out the production of propylene copolymer, wherein multiple reactor comprises Liquid-phase reactor and Gas-phase reactor, wherein the temperature of reaction in Liquid-phase reactor is 60 ℃～85 ℃, pressure is 2MPa～5MPa, temperature of reaction in Gas-phase reactor is 70 ℃～90 ℃, pressure is 1MPa～3MPa, and the number-average molecular weight of multipolymer is not less than the molecular-weight average of homopolymer, the final melting index of polymkeric substance and the melting index of homopolymer ratio are 0.3～1.0, described catalyst component adopts the disclosed catalyzer of patent CN1453298A.
2. the preparation method of prolylene polymer composition according to claim 1, is characterized in that: described multiple reactor is the Mitsui Hypol process unit of two liquid phase stills and two gas phase stills.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110016097A (en) * | 2018-01-10 | 2019-07-16 | 中国石油化工股份有限公司 | A kind of low leachable, low melting point, Narrow Molecular Weight Distribution, ethylene-propylene random copolymer of thermal oxidation stability and its preparation method and application |
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| CN1453298A (en) * | 2003-04-21 | 2003-11-05 | 中国石油化工股份有限公司 | Catalyst for olefine polymerizing reaction and its components |
| CN101245114A (en) * | 2003-12-05 | 2008-08-20 | 中国石化扬子石油化工有限公司 | Propylene supercritical polymerization catalyst system and process for producing polypropelene composition |
| CN101735351A (en) * | 2008-11-07 | 2010-06-16 | 中国石油天然气股份有限公司 | Method for preparing high-fluidity wide-distribution polypropylene and product thereof |
| CN102050892A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for controlling production of broad-distribution polyolefin |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1453298A (en) * | 2003-04-21 | 2003-11-05 | 中国石油化工股份有限公司 | Catalyst for olefine polymerizing reaction and its components |
| CN101245114A (en) * | 2003-12-05 | 2008-08-20 | 中国石化扬子石油化工有限公司 | Propylene supercritical polymerization catalyst system and process for producing polypropelene composition |
| CN101735351A (en) * | 2008-11-07 | 2010-06-16 | 中国石油天然气股份有限公司 | Method for preparing high-fluidity wide-distribution polypropylene and product thereof |
| CN102050892A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for controlling production of broad-distribution polyolefin |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110016097A (en) * | 2018-01-10 | 2019-07-16 | 中国石油化工股份有限公司 | A kind of low leachable, low melting point, Narrow Molecular Weight Distribution, ethylene-propylene random copolymer of thermal oxidation stability and its preparation method and application |
| CN110016097B (en) * | 2018-01-10 | 2021-12-31 | 中国石油化工股份有限公司 | Ethylene-propylene random copolymer with low dissolution, low melting point, narrow molecular weight distribution and stable thermal oxygen, and preparation method and application thereof |
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Application publication date: 20140326 |