CN103951770A - Preparation method of bi-modally distributed polypropylene (PP) - Google Patents
Preparation method of bi-modally distributed polypropylene (PP) Download PDFInfo
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- CN103951770A CN103951770A CN201410168366.XA CN201410168366A CN103951770A CN 103951770 A CN103951770 A CN 103951770A CN 201410168366 A CN201410168366 A CN 201410168366A CN 103951770 A CN103951770 A CN 103951770A
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Abstract
The invention discloses a preparation method of bi-modally distributed polypropylene (PP) with good surface morphology. The preparation method has the beneficial effects that the PP resin with a bio-modal distribution characteristic is prepared in a single reactor by utilizing a supported bimetallic catalyst system, combining with a specific aluminum alkyl/alkylaluminoxane bi-cocatalyst system and carrying out a simple polymerization process by a one-step method; regulation of relative contents of high molecular weight and low molecular weight PP components in a polymer can be achieved by regulating the components of double co-catalysts or addition of hydrogen; meanwhile, the bi-modal PP also has the characteristics of high melting point (155-165 DEG C), good polymer particle shape, high polymer bulk density (0.3-0.5g/cm<3>) and the like.
Description
Technical field
The present invention relates to the polyacrylic preparation method of a kind of bimodal distribution.
Background technology
Bimodal distribution polypropylene refers to and in polypropylene, contains high molecular weight polypropylene component and low-molecular-weight polypropylene component simultaneously, thereby makes the molecular weight distribution of polymkeric substance present bimodal feature.This specific character makes bimodal distribution polypropylene possess the features such as good rigidly, melt strength is moderate, processing characteristics is good simultaneously, make it be widely used in the multiple fields such as automotive material, wrapping material, tubing, especially suitablely in thermoforming and film series products, apply.At present, the polyacrylic production technique of bimodal distribution mainly contains the Spherizone technique of the Borstar technique of Borealis company, the Unipol technique of Dow company and Basell company.These techniques are all used Ziegler-Natta catalyst, wherein Borstar technique and Unipol process using is two (many) reactors in series methods, and Spherizone technique is multizone circulating reactor method, in reactor, be divided into raising section and two reaction zones of landing section, the polymerizing condition in each district is different, and its effect is equal to double-reactor series connection method substantially.Domestic also relevant for the patent report (CN101230114A, CN1657149A) of Bimodal Polypropylene Manufacturing Process, be also the improvement to reactors in series method substantially.
How to utilize single reaction vessel to prepare to have the polypropylene of bimodal distribution is the problem that people pay close attention to always, and this is because single reactor technique is simple and cost is also lower.The key of this technology is that catalyst system need to have two or more active centre, and the polymericular weight that its catalyzing propone polymerization obtains differs larger, thereby obtains having the polypropylene product of bimodal distribution.At present, there are reports in the work of this respect, for example, adopt metallocene catalyst (the Journal of Molecular Catalysis A:Chemistry with dual-core architecture, 1998,128,279-287), or adopt two or more hybrid catalyst system.Hybrid catalyst system can be mixing (Macromolecular Symposia, 2001,173, the 179-194 of two kinds of metallocene catalysts; Polymer, 2007,48,1893-1902), can be also metallocene catalyst and (Journal of Applied Polymer Science, 1998,67, the 2213-2222 of mixing of Ziegler-Natta catalyst; Applied Organometallic Chemistry, 1998,401-408).Use dinuclear catalyst or the mixed system of two kinds of metallocene catalysts, cost is all higher, can not meet the needs of large-scale industrial production; And the blending means of utilizing metallocene catalyst and Ziegler-Natta catalyst of bibliographical information, because the metallocene catalyst lacking wherein produces polyacrylic morphology Control, what in fact obtain is the mixture of the polypropylene GRANULES of Ziegler-Natta catalyst and the polypropylene powder of metallocene catalyst, is unfavorable for industrializing implementation.
Consider widely used MgCl in current polypropylene industrial
2carrier model TiCl
4catalyzer not only has high catalytic activity for propylene polymerization, thereby but also can control well polymer morphology and obtain the uniform polypropylene of particle scale, therefore if the muriate of metallocene (Zr) compound and Ti is carried on to MgCl simultaneously
2on obtain a kind of carrier model dual metal catalyzer, and select suitable polymerizing condition to bring into play the catalytic activity of Zr component and Ti component simultaneously, thereby control it and obtain respectively the polypropylene with different molecular weight, be expected to realize and in single reaction vessel, prepare the bimodal distribution acrylic resin that polymer morphology is good.
Summary of the invention
The object of the invention is to the deficiency for bimodal distribution polypropylene technology for existing single reaction vessel legal system, propose a kind ofly can effectively control polymer morphology and be applicable to the polyacrylic preparation method of industrial bimodal distribution.
The polyacrylic method of bimodal distribution of preparing provided by the present invention, comprises the steps:, under bimetallic catalyst and the common existence of promotor, propylene is carried out to polyreaction, obtains described bimodal distribution polypropylene;
Wherein, described promotor is two co-catalyst system that aluminum alkyls and alkylaluminoxane form;
Described aluminum alkyls is the trialkylaluminium except triethyl aluminum and trimethyl aluminium, at least one of preferred triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum and tri-n-octylaluminium; At least one in described alkylaluminoxane preferable methyl aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide; The addition of described aluminum alkyls, with the molar ratio computing of Ti in Al and described bimetallic catalyst, is Al:Ti=10～20000:1, and preferably 50～2000:1, most preferably is 50～700:1; The addition of described alkylaluminoxane, with the molar ratio computing of Zr in Al and described bimetallic catalyst, is Al:Zr=10～20000:1, and preferably 100～10000:1, most preferably is 250～4400:1.
Described bimetallic catalyst is made by following component (i) to the raw material of component (v):
Component (i): the muriate of Ti, wherein, the quality percentage composition of Ti element in described bimetallic catalyst is 0.5～10%, is preferably 0.5～3%, specifically can be 1.7%; The muriate of described Ti is selected from TiCl
3, TiCl
4and TiOCl
3in at least one;
Component (ii): the Zr-π key compound of atom centered by transition metal Zr, wherein, the quality percentage composition of transition metal Zr in described bimetallic catalyst is 0.03～5%, is preferably 0.1～1%, specifically can be 0.52%; It is described that to take the Zr-π key compound of atom centered by transition metal Zr be Me
2si (Ind)
2zrCl
2, Me
2si (2-Me-4-Ph-Ind)
2zrCl
2, CH
2(3-t-Bu-Ind)
2zrCl
2, Me
2c (3-t-Bu-Ind)
2zrCl
2, CH
2(3--Ind)
2zrCl
2, CH
2(3-i-Pr-Ind)
2zrCl
2, Me
2si (2-Me-4-Naph-Ind)
2zrCl
2, Me
2si (2-Me-Benz-Ind)
2zrCl
2, wherein, Me=methyl, Bu=butyl, Ph=phenyl, Ind=indenyl, Pr=propyl group, Naph=naphthyl, Et=ethyl, Benz=phenyl, preferably Me
2c (3-t-Bu-Ind)
2zrCl
2;
Component (iii): MgCl
2, wherein, the quality percentage composition of metallic element Mg in described bimetallic catalyst is 5～25%;
Component (iv): alkylaluminoxane, wherein, the quality percentage composition of the metal element A l in described alkylaluminoxane in described bimetallic catalyst is 0.1～30%, is preferably 10～20%, specifically can be 15.9%; In described alkylaluminoxane, aikyiaiurnirsoxan beta is that repeated structural unit is-(R) line style of AlO-or the compound of non-linearity; Wherein, the number of described repeated structural unit is 1～50, and preferably 5～20, R is the aryl that carbonatoms is 1～12 alkyl, carbonatoms is 3～12 cycloalkyl or carbonatoms are 6～18, preferable methyl aikyiaiurnirsoxan beta;
Component (v): internal electron donor, wherein, the quality percentage composition of described internal electron donor in described bimetallic catalyst is 1～30%, is preferably 10～20%, is specially 13.1%; Described internal electron donor is diethyl succinate, Polycizer W 260, diethyl phthalate, n-butyl phthalate, diisobutyl phthalate, 2,2-diisobutyl-1,3-Propanal dimethyl acetal or 9,9-bis-(methoxymethyl) fluorenes (BMMF), preferably BMMF.
This bimetallic catalyst can be prepared as follows and obtain:
1) spherical MgCl
2the preparation of muriate/electron donor mixture of/Ti
Can prepare according to the disclosed method of CN1110281A, CN1047302A, CN1091748A or US4399054: the muriate that spherical alcohol is closed to magnesium chloride support and described Ti at-20～10 ℃ is uniformly mixed, react 0.5～3 hour, corresponding to every gram of spherical alcohol, close magnesium chloride support, the muriatic consumption of described Ti is 10～50ml; After being warmed up to 50～90 ℃, add described internal electron donor (corresponding to every gram of spherical alcohol, to close magnesium chloride support, the consumption of described internal electron donor is 0.3～2.0g), be warmed up to after 100～150 ℃, react 0.5～3 hour, and then add described Ti compound (corresponding to every gram of spherical alcohol, to close magnesium chloride support, the muriatic consumption of described Ti is 5～50ml), at 100～150 ℃, react 0.5～3 hour, filter and obtain spherical mixture; The spherical mixture of gained can not wash, and can use alkane (as pentane, hexane or heptane etc.) fully to wash yet.
2) preparation of bimetallic catalyst
Can prepare according to the disclosed method of CN1982341A, CN101045760A: mixed solution and step 1 after described component (iv), component (ii) are fully stirred) the spherical mixture that obtains mixes, or after component (iv) is mixed with spherical mixture component, then add component (ii) to mix; Mixing temperature is-30 ℃～80 ℃, stirs, and then filters, and fully washs, is dried with alkane or aromatic hydrocarbon solvent containing 5～10 carbon atoms, finally obtains bimetallic catalyst;
Every gram of step 1 wherein) the spherical mixture correspondence 1 * 10 obtaining
-6mol～5.6 * 10
-4mol component (ii), is preferably 2 * 10
-5mol～1.0 * 10
-4mol.
In aforesaid method, the add-on of described bimetallic catalyst is 0.001～0.1% of described propylene quality, preferably 0.05～0.1%, be specially 0.07%, 0.003%.
Described polyreaction specifically can be bulk polymerization or slurry polymerization.
Described slurry polymerization carries out in organic solvent, and it is at least one in 4～10 alkane that described organic solvent is selected from carbonatoms, preferably at least one of hexane, heptane.
When adopting slurry polymerization, described method also comprises to the step that adds acid alcohol solution (being acidifying ethanol) termination reaction in the reaction system of described slurry polymerization.Hydrochloric acid soln and ethanol that described acid alcohol solution can be specifically 37% by mass concentration are obtained by mixing according to volume ratio 10:1.
In described polyreaction, polymerization temperature is 25 ℃～120 ℃, preferably 45 ℃～90 ℃, and most preferably 60 ℃～80 ℃; Polymerization time is 0.1～10 hour, preferably 0.5～3 hour, and most preferably 0.5～1 hour; The pressure of propylene is 0.1～5Mpa, specifically can be 0.4Mpa.
In described polymerization procedure, also can further pass into hydrogen with regulate polymer molecular weight, hydrogen pressure can be 0.005～0.5MPa.
The present invention utilizes carrier model dual metal catalyst system, and the two co-catalyst system of corresponding selection, by above-mentioned simple polymerization process, prepares bimodal distribution polypropylene in single reaction vessel.The method generates two kinds of polypropylene with different molecular weight on same catalyzer simultaneously.Meanwhile, by regulating the additional proportion of the two promotors of aluminum alkyls and alkylaluminoxane, and the hydrogen add-on in polymerization, can realize the adjusting of high and low molecular weight polypropylene component relative content.Bimodal distribution polypropylene of the present invention, also has polymer particle form spherical in shape, the high (0.3～0.5g/cm of bulk density
3) etc. feature.
Accompanying drawing explanation
Fig. 1 is the GPC curve of embodiment 1-6 and comparative example 1-2 resulting polymers.
Fig. 2 is the DSC heating curve for the second time of embodiment 1-7 and comparative example 1-2 resulting polymers.
Fig. 3 is the electron scanning micrograph of embodiment 1-3 resulting polymers particle.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and biomaterial, if no special instructions, all can obtain from commercial channels.
Hydrochloric acid soln and ethanol that in following embodiment, acidifying ethanol used is 37% by mass concentration are obtained by mixing according to volume ratio 10:1.
In following embodiment, used catalyst A is bimetallic catalyst, prepares by the following method and obtains: under nitrogen protection, add the TiCl of 150ml in bottom in sand core filter and churned mechanically 500ml reaction flask
4, be cooled to-20 ℃, add 10g ball type carrier MgCl
2, react 1 hour, be warming up to 60 ℃, add 9 of 2.5g, 9-bis-(methoxymethyl) fluorenes (BMMF), is slowly warming up to 120 ℃, reacts after 2 hours and filters, then add the TiCl of 150ml
4, in 110 ℃ of reactions 2 hours, use normal hexane washed product for 60 ℃, obtain component a, 1g component a is reacted 1 hour with 34mmol methylaluminoxane (MAO) at 0 ℃, simultaneously by 0.22g CH
2(3-t-Bu-Ind)
2zrCl
2react 2 hours at 0 ℃ with 17mmol methylaluminoxane (MAO), join subsequently in the reaction system containing component a, 20 ℃ of reactions 2 hours, after obtaining product and fully washing with normal hexane and toluene, under room temperature, vacuum-drying is 1 hour, the bimetallic catalyst A obtaining.It consists of: TiCl
4(component i), CH
2(3-t-Bu-Ind)
2zrCl
2(component ii), MgCl
2(component iii), methylaluminoxane MAO (component iv), 9,9-bis-(methoxymethyl) fluorenes BMMF (component v), content is: Ti=1.70wt%, Zr=0.52wt%, Al=15.9wt%, Mg=14.5%, BMMF=13.1wt%.
Comparative example 1
Under vacuum state, 30g propylene gas is filled with in reactor, add successively 50ml solvent heptane, (addition of this promotor is with the molar ratio computing of Ti in Al and catalyzer for single promotor triisobutyl aluminium 0.4mmol, for Al:Ti=50:1) and 20mg catalyst A (be propylene weight 0.07%), propylene constant pressure carries out polyreaction at 0.4MPa, temperature of reaction is 60 ℃, 0.5 hour reaction times; After having reacted, add acidifying ethanol to stop polyreaction, with after distilled water and ethanol repetitive scrubbing polymkeric substance, by polymkeric substance vacuum-drying at 60 ℃, obtain 7.7g polypropylene.
This polypropylene molecule amount is distributed as unimodal distribution (Fig. 1), and molecular weight is 79.35 ten thousand, and molecular weight distribution coefficient is 4.75, and its DSC curve has a melting peak (Fig. 2), at 159.8 ℃, and the polypropylene obtaining corresponding to the polymerization of Ti catalytic.Polymer stacks density 0.39g/cm
3.
Comparative example 2
Under vacuum state, 30g propylene gas is filled with in reactor, add successively 50ml solvent heptane, (addition of this promotor is with the molar ratio computing of Ti in Al and catalyzer for single promotor triethyl aluminum 0.4mmol, for Al:Ti=50:1) and 20mg catalyst A (be propylene weight 0.07%), propylene constant pressure carries out polyreaction at 0.4MPa, temperature of reaction is 60 ℃, 0.5 hour reaction times; After having reacted, add acidifying ethanol to stop polyreaction, with after distilled water and ethanol repetitive scrubbing polymkeric substance, by polymkeric substance vacuum-drying at 60 ℃, obtain 7.8g polypropylene.
This polypropylene molecule amount is distributed as unimodal distribution (Fig. 1), and molecular weight is 64.79 ten thousand, and molecular weight distribution coefficient is 6.44, and its DSC curve has a melting peak (Fig. 2), at 159.9 ℃, and the polypropylene obtaining corresponding to the polymerization of Ti catalytic.Polymer stacks density 0.38g/cm
3.
Comparative example 3
Under vacuum state, 30g propylene gas is filled with in reactor, (addition of this promotor is with the molar ratio computing of Ti in Al and catalyzer to add successively 50ml solvent heptane, promotor triethyl aluminum 0.4mmol, for Al:Ti=50:1), (addition of this promotor is with the molar ratio computing of Zr in Al and catalyzer for promotor methylaluminoxane 0.6mmol, for Al:Zr=500:1) and 20mg catalyst A (be propylene weight 0.07%), propylene constant pressure carries out polyreaction at 0.4MPa, temperature of reaction is 60 ℃, 0.5 hour reaction times; After having reacted, add acidifying ethanol to stop polyreaction, with after distilled water and ethanol repetitive scrubbing polymkeric substance, by polymkeric substance vacuum-drying at 60 ℃, obtain 8.0g polypropylene.
This polypropylene molecule amount is distributed as unimodal distribution (Fig. 1), molecular weight is 63.11 ten thousand, and molecular weight distribution coefficient is 6.37, and a melting peak (Fig. 2) has also only appearred in its DSC curve, at 158.8 ℃, the polypropylene obtaining corresponding to the polymerization of Ti catalytic.The molecular weight and molecualr weight distribution coefficient of this polymkeric substance is very close to comparative example polymkeric substance 2 simultaneously, illustrate that now Zr catalyst activity is suppressed by triethyl aluminum, show, when utilizing bimetallic catalyst to prepare bimodal distribution polypropylene, can not use triethyl aluminum as promotor.
Embodiment 1
Under vacuum state, 30g propylene gas is filled with in reactor, (addition of this promotor is with the molar ratio computing of Ti in Al and catalyzer to add successively 50ml solvent heptane, promotor triisobutyl aluminium 0.4mmol, for Al:Ti=50:1), (addition of this promotor is with the molar ratio computing of Zr in Al and catalyzer for promotor methylaluminoxane 0.3mmol, for Al:Zr=250:1) and 20mg catalyst A (be propylene weight 0.07%), propylene constant pressure carries out polyreaction at 0.4MPa, temperature of reaction is 60 ℃, 0.5 hour reaction times; After having reacted, add acidifying ethanol to stop polyreaction, with after distilled water and ethanol repetitive scrubbing polymkeric substance, by polymkeric substance vacuum-drying at 60 ℃, obtain 9.5g bimodal distribution polypropylene.
This bimodal polypropylene presents good spherical morphology, and diameter is about 300 μ m (Fig. 3).Compare with comparative example 1, the product of the present embodiment presents obvious bimodal distribution (Fig. 1), weight-average molecular weight is 48.14 ten thousand, and molecular weight distribution coefficient 11.68 contains the low-molecular-weight polypropylene being obtained by Zr catalyzed polymerization and the high molecular weight polypropylene being obtained by Ti catalyzed polymerization simultaneously.There are two melting peaks in its DSC curve, respectively at 150.4 ℃ and 158.7 ℃ (Fig. 2).Polymer stacks density 0.40g/cm
3.
Embodiment 2
Under vacuum state, 30g propylene gas is filled with in reactor, (addition of this promotor is with the molar ratio computing of Ti in Al and catalyzer to add successively 50ml solvent heptane, promotor triisobutyl aluminium 0.4mmol, for Al:Ti=50:1), (addition of this promotor is with the molar ratio computing of Zr in Al and catalyzer for promotor methylaluminoxane 0.6mmol, for Al:Zr=500:1) and 20mg catalyst A (be propylene weight 0.07%), propylene constant pressure carries out polyreaction at 0.4MPa, temperature of reaction is 60 ℃, 0.5 hour reaction times; After having reacted, add acidifying ethanol to stop polyreaction, with after distilled water and ethanol repetitive scrubbing polymkeric substance, by polymkeric substance vacuum-drying at 60 ℃, obtain 10.3g bimodal distribution polypropylene.
This bimodal polypropylene presents good spherical morphology, diameter is about 300 μ m (Fig. 3), and present obvious bimodal distribution (Fig. 1), weight-average molecular weight is 27.86 ten thousand, molecular weight distribution coefficient 12.01, there are two melting peaks (Fig. 2) in its DSC curve, respectively at 150.1 ℃ and 158.8 ℃.Meanwhile, than embodiment 1, on its GPC curve, the ratio of high/low molecular weight polypropylene changes.Polymer stacks density 0.40g/cm
3.
Embodiment 3
Under vacuum state, 30g propylene gas is filled with in reactor, (addition of this promotor is with the molar ratio computing of Ti in Al and catalyzer to add successively 50ml solvent heptane, promotor triisobutyl aluminium 0.4mmol, for Al:Ti=50:1), (addition of this promotor is with the molar ratio computing of Zr in Al and catalyzer for promotor methylaluminoxane 1.2mmol, for Al:Zr=1000:1) and 20mg catalyst A (be propylene weight 0.07%), propylene constant pressure carries out polyreaction at 0.4MPa, temperature of reaction is 60 ℃, 0.5 hour reaction times; After having reacted, add acidifying ethanol to stop polyreaction, with after distilled water and ethanol repetitive scrubbing polymkeric substance, by polymkeric substance vacuum-drying at 60 ℃, obtain 14.6g bimodal distribution polypropylene.
This bimodal polypropylene presents good spherical morphology, and diameter is about 300 μ m (Fig. 3), contains the low-molecular-weight polypropylene being obtained by Zr catalyzed polymerization and the high molecular weight polypropylene being obtained by Ti catalyzed polymerization simultaneously, and both are about 1:1.1 by relative weight ratio.Polymericular weight presents bimodal distribution (Fig. 1), and weight-average molecular weight is 19.12 ten thousand, molecular weight distribution coefficient 11.45, and there are two melting peaks (Fig. 2) in its DSC curve, respectively at 149.6 ℃ and 157.9 ℃.Polymer stacks density 0.39g/cm
3.
Embodiment 4
Under vacuum state, 30g propylene gas is filled with in reactor, add successively 50ml solvent heptane, (addition of this promotor is with the molar ratio computing of Ti in Al and catalyzer for promotor triisobutyl aluminium 0.4mmol, for Al:Ti=50:1), (addition of this promotor is with the molar ratio computing of Zr in Al and catalyzer for promotor methylaluminoxane 0.6mmol, for Al:Zr=500:1), 0.02MPa hydrogen (be propylene add-on 0.03%) and 20mg catalyst A (for propylene weight 0.07%), propylene constant pressure carries out polyreaction at 0.4MPa, temperature of reaction is 60 ℃, 0.5 hour reaction times, after having reacted, add acidifying ethanol to stop polyreaction, with after distilled water and ethanol repetitive scrubbing polymkeric substance, by polymkeric substance vacuum-drying at 60 ℃, obtain 14.8g bimodal distribution polypropylene.
Polymericular weight presents bimodal distribution (Fig. 1), weight-average molecular weight 18.97 ten thousand, molecular weight distribution coefficient 11.16.There are two melting peaks (Fig. 2) in its DSC curve, respectively at 149.3 ℃ and 157.1 ℃.Polymer stacks density 0.40g/cm
3.
Embodiment 5
Under vacuum state, 30g propylene gas is filled with in reactor, add successively 50ml solvent heptane, (addition of this promotor is with the molar ratio computing of Ti in Al and catalyzer for promotor triisobutyl aluminium 0.4mmol, for Al:Ti=50:1), (addition of this promotor is with the molar ratio computing of Zr in Al and catalyzer for promotor methylaluminoxane 0.6mmol, for Al:Zr=500:1), 0.05MPa hydrogen (be propylene add-on 0.07%) and 20mg catalyst A (for propylene weight 0.07%), propylene constant pressure carries out polyreaction at 0.4MPa, temperature of reaction is 60 ℃, 0.5 hour reaction times, after having reacted, add acidifying ethanol to stop polyreaction, with after distilled water and ethanol repetitive scrubbing polymkeric substance, by polymkeric substance vacuum-drying at 60 ℃, obtain 15.3g bimodal distribution polypropylene.
Polymericular weight presents obvious bimodal distribution (Fig. 1), and weight-average molecular weight is 6.95 ten thousand, and molecular weight distribution coefficient is 5.19.There are two melting peaks (Fig. 2) in its DSC curve, respectively at 147.9 ℃ and 158.3 ℃.Polymer stacks density 0.41g/cm
3.
Embodiment 6
Under vacuum state, liquid propene 300g is filled with in reactor, (addition of this promotor is with the molar ratio computing of Ti in Al and catalyzer to add successively 2.5mmol promotor triisobutyl aluminium, for Al:Ti=700:1), (addition of this promotor is with the molar ratio computing of Zr in Al and catalyzer for promotor methylaluminoxane 2.5mmol, for Al:Zr=4400:1) and 10mg catalyst A, temperature of reaction kettle is risen to 80 ℃ and carry out polyreaction, 1 hour reaction times; After having reacted, the residual propylene monomer of emptying, obtains 210g bimodal distribution polypropylene.Its DSC curve presents two melting peaks (Fig. 2), respectively at 155.4 ℃ and 160.6 ℃.Polymer stacks density 0.44g/cm
3.
Claims (7)
1. prepare the polyacrylic method of bimodal distribution, comprise the steps:, under bimetallic catalyst and the common existence of promotor, propylene is carried out to polyreaction, obtain described bimodal distribution polypropylene;
Wherein, described promotor is two co-catalyst system that aluminum alkyls and alkylaluminoxane form;
Described aluminum alkyls is the trialkylaluminium except triethyl aluminum and trimethyl aluminium; Described alkylaluminoxane is selected from least one in methylaluminoxane and isobutyl aluminium alkoxide; The addition of described aluminum alkyls, with the molar ratio computing of Ti in Al and described bimetallic catalyst, is Al:Ti=10～20000:1; The addition of described alkylaluminoxane, with the molar ratio computing of Zr in Al and described bimetallic catalyst, is Al:Zr=10～20000:1;
Described bimetallic catalyst is made by following component (i) to the raw material of component (v):
Component (i): the muriate of Ti, wherein, the quality percentage composition of Ti element in described bimetallic catalyst is 0.5～10%; The muriate of described Ti is selected from TiCl
3, TiCl
4and TiOCl
3in at least one;
Component (ii): the Zr-π key compound of atom centered by transition metal Zr, wherein, the quality percentage composition of transition metal Zr in described bimetallic catalyst is 0.03～5%; It is described that to take the Zr-π key compound of atom centered by transition metal Zr be Me
2si (Ind)
2zrCl
2, Me
2si (2-Me-4-Ph-Ind)
2zrCl
2, CH
2(3-t-Bu-Ind)
2zrCl
2, Me
2c (3-t-Bu-Ind)
2zrCl
2, CH
2(3-Et-Ind)
2zrCl
2, CH
2(3-i-Pr-Ind)
2zrCl
2, Me
2si (2-Me-4-Naph-Ind)
2zrCl
2, Me
2si (2-Me-Benz-Ind)
2zrCl
2, wherein, Me=methyl, Bu=butyl, Ph=phenyl, Ind=indenyl, Pr=propyl group, Naph=naphthyl, Et=ethyl, Benz=phenyl;
Component (iii): MgCl
2, wherein, the quality percentage composition of metallic element Mg in described bimetallic catalyst is 5～25%;
Component (iv): alkylaluminoxane, wherein, the quality percentage composition of the metal element A l in described alkylaluminoxane in described bimetallic catalyst is 0.1～30%; In described alkylaluminoxane, aikyiaiurnirsoxan beta is that repeated structural unit is-(R) line style of AlO-or the compound of non-linearity; Wherein, the number of described repeated structural unit is 1～50, and R is the aryl that carbonatoms is 1～12 alkyl, carbonatoms is 3～12 cycloalkyl or carbonatoms are 6～18;
Component (v): internal electron donor, wherein, the quality percentage composition of described internal electron donor in described bimetallic catalyst is 1～30%; Described internal electron donor is diethyl succinate, Polycizer W 260, diethyl phthalate, n-butyl phthalate, diisobutyl phthalate, 2,2-diisobutyl-1,3-Propanal dimethyl acetal or 9,9-bis-(methoxymethyl) fluorenes.
2. method according to claim 1, is characterized in that: described aluminum alkyls is selected from least one of triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum and tri-n-octylaluminium;
The addition of described aluminum alkyls, with the molar ratio computing of Ti in Al and described bimetallic catalyst, is Al:Ti=50～2000:1, is preferably 50～700:1; The addition of described alkylaluminoxane, with the molar ratio computing of Zr in Al and described bimetallic catalyst, is Al:Zr=100～10000:1, is preferably 250～4400:1;
In described component (ii), described to take the Zr-π key compound of atom centered by transition metal Zr be Me
2c (3-t-Bu-Ind)
2zrCl
2;
In described component (iv), described alkylaluminoxane is methylaluminoxane;
In described component (v), described internal electron donor is 9,9-bis-(methoxymethyl) fluorenes.
3. method according to claim 1 and 2, is characterized in that: the add-on of described bimetallic catalyst is 0.001～0.1% of described propylene quality, preferably 0.05～0.1%.
4. according to the method described in any one in claim 1-3, it is characterized in that: described polyreaction is bulk polymerization or slurry polymerization;
In described polyreaction, polymerization temperature is 25 ℃～120 ℃, preferably 45 ℃～90 ℃, and most preferably 60 ℃～80 ℃; Polymerization time is 0.1～10 hour, preferably 0.5～3 hour, and most preferably 0.5～1 hour; The pressure of propylene is 0.1～5MPa.
5. method according to claim 4, is characterized in that: described slurry polymerization carries out in organic solvent, and it is at least one in 4～10 alkane that described organic solvent is selected from carbonatoms, preferably hexane and/or heptane.
6. according to the method described in claim 4 or 5, it is characterized in that: described polyreaction is slurry polymerization, described method also comprises to the step that adds acid alcohol solution termination reaction in the reaction system of described slurry polymerization.
7. according to the method described in any one in claim 1-6, it is characterized in that: in described polyreaction, also in reaction system, pass into hydrogen, hydrogen pressure is 0.005～0.5MPa.
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| CN113583059A (en) * | 2021-07-28 | 2021-11-02 | 武汉科技大学 | Application of binuclear iron complex, bimodal polypropylene composite film and capacitor film |
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| CN101337997A (en) * | 2008-08-13 | 2009-01-07 | 中国科学院化学研究所 | Carrier model dual metal composite catalyst and method for preparing same |
| CN102127176A (en) * | 2011-01-28 | 2011-07-20 | 中国科学院化学研究所 | High-melt-strength polypropylene and preparation method thereof |
| CN102382217A (en) * | 2011-08-30 | 2012-03-21 | 浙江大学 | Method for preparing double-peak or broad-peak polyethylene with adjustable molecular weight |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101337997A (en) * | 2008-08-13 | 2009-01-07 | 中国科学院化学研究所 | Carrier model dual metal composite catalyst and method for preparing same |
| CN102127176A (en) * | 2011-01-28 | 2011-07-20 | 中国科学院化学研究所 | High-melt-strength polypropylene and preparation method thereof |
| CN102382217A (en) * | 2011-08-30 | 2012-03-21 | 浙江大学 | Method for preparing double-peak or broad-peak polyethylene with adjustable molecular weight |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113583059A (en) * | 2021-07-28 | 2021-11-02 | 武汉科技大学 | Application of binuclear iron complex, bimodal polypropylene composite film and capacitor film |
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