CN105623075A - Method for preparing impact-resistant polypropylene material with high melt strength - Google Patents
Method for preparing impact-resistant polypropylene material with high melt strength Download PDFInfo
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Abstract
The invention provides a method for preparing an impact-resistant polypropylene material with high melt strength. The method comprises the steps of carrying out a homopolymerization reaction of propylene in the presence of a first propylene homopolymer so as to obtain a propylene homopolymer component containing the first propylene homopolymer and a second propylene homopolymer, and then, carrying out a copolymerization reaction of ethylene-1-butylene in the presence of the propylene homopolymer component so as to obtain the polypropylene material containing an ethylene-1-butylene copolymer. According to the method, a homopolymerized polypropylene continuous phase, which has a specific melt index, contains a large amount of ultrahigh-molecular-weight ingredients and is extremely wide in molecular weight distribution, is prepared through using external electron donors of different types and use levels, in combination with a chain transfer agent, i.e., hydrogen gas of different use levels separately at different polymerization stages, then, ethylene and 1-butylene copolymerization is further carried out so as to obtain a rubber phase dispersed in the continuous phase, and then, the impact-resistant polypropylene material with high melt strength, high rigidity and high toughness is obtained and is extensive in application.
Description
Technical field
The preparation method that the present invention relates to polypropylene material, the preparation method being specifically related to the impact polypropylene material of a kind of high fondant-strength.
Background technology
Impact polypropylene has rigidity and the higher heat resisting temperatures such as the high/low temperature impact strength of excellence, higher hot strength, bending modulus, have been widely used in a lot of fields, such as molding or the automobile component of extrusion molding, appliances parts, container and household articles etc. Impact polypropylene is relatively low due to its melt strength, is generally used for injection processing, and during for blow molding, there is mold base size unstable, and products thickness inequality even cannot the problem such as molding.
The conventional way improving melt strength of polypropylene is to reduce melt index, i.e. raising polypropylene molecule amount, but this can bring material molten and extrusion difficulty. Still an alternative is that and widen molecular weight distribution, as US7365136 and US6875826 reports a kind of method preparing wide molecular weight distribution, high fondant-strength homopolymerization and atactic copolymerized polypropene, it selects alkoxy silane to be external electron donor (such as dicyclopentyl dimethoxyl silane), by regulating density of hydrogen in the reactor of multiple series connection, come regulatory molecule amount size and distribution, it is achieved improve the effect of melt strength of polypropylene. WO9426794 discloses the method that the reactor of multiple series connection prepares high fondant-strength homopolymerization and random polypropylene, it prepares the high melt strength, propylene of wide molecular weight distribution or bimodal distribution by regulating the concentration of hydrogen in different reactor, the character of catalyst does not adjust at each reactor, thus preparation process needs a large amount of hydrogen.
The preparation method that CN102134290 and CN102134291 discloses the distribution of a kind of wide molecular weight, high fondant-strength HOPP, it adopts multiple tandem reactor by controlling external electron donor component in the kind in differential responses stage and ratio, in conjunction with the control of molecular weight regulator hydrogen usage, it is prepared for wide molecular weight, high fondant-strength HOPP or atactic copolymerized polypropene.
China applies for a patent 201210422726.5 and there was reported and realize the regulation and control to catalyst isotactic index between different reactor and hydrogen response by silanes and the two distinct types of external electron donor of two ethers reasonably combined, obtains the preparation method with wide molecular weight distribution, high fondant-strength HOPP or random polypropylene.
Above-mentioned patent report is the preparation method of high fondant-strength HOPP or atactic copolymerized polypropene, that is, although the HOPP prepared by these methods or atactic copolymerized polypropene possess higher melt strength, but rigidity, toughness or erosion-resisting characteristics are not enough, thus limiting obtained polyacrylic application. Therefore it provides impact polypropylene with the high fondant-strength of rubber components and rubber disperse phase structure, high rigidity and toughness and preparation method thereof will be significant.
Summary of the invention
The present inventor is through further investigation, it is provided that the preparation method of the intensity impact polypropylene material of a kind of high melt, the polypropylene material prepared by the method also has high rigidity and high tenacity feature simultaneously. This polypropylene material applies to the excellent material in the fields such as automobile component, medical apparatus and instruments, household articles.
According to the present invention, it is provided that a kind of method preparing high fondant-strength impact polypropylene material as above, including:
The first step: propylene homo reacts, including:
First stage: under comprising the effect of Ziegler-Natta catalyst of the first external electron donor, under hydrogen presence or absence, carry out propylene homo reaction, obtain comprising the reaction logistics of the first Noblen;
Second stage: add the second external electron donor and carry out complex reaction with the catalyst in described reaction logistics, then under the existence of the first Noblen and hydrogen, carry out propylene homo reaction, produce the second Noblen, obtain the propylene homopolymer component comprising the first Noblen and the second Noblen; Wherein,
Described first Noblen and described propylene homopolymer component at 230 DEG C, under the load of 2.16kg measure melt index respectively 0.001-0.4g/10min and 0.1-15g/10min;
Second step: ethylene-1-butylene copolyreaction, including carrying out ethylene-1-butylene gas phase copolymerization under the existence of described propylene homopolymer component and hydrogen, produce ethylene-butene-1 copolymer component, obtain the polypropylene material comprising described propylene homopolymer component and ethylene-butene-1 copolymer (Ethylene/1-butene copolymer) component.
In method provided by the invention, first prepare propylene homopolymer component as continuous phase, there is provided certain rigidity for polypropylene material, on the basis of propylene homopolymer component, then prepare ethylene-butene-1 copolymer component as rubber phase, i.e. dispersion phase, it is possible to increase the toughness of polypropylene product.
In the first phase, the consumption of hydrogen can be such as 0-200ppm. In second stage, the consumption of hydrogen is 2000-20000ppm.
Method provided by the invention carries out preferably in the reactor of two or more serial operations.
The method according to the invention is the method for the direct catalytic polymerization of Ziegler-Natta catalyst. In multiple reactors of series connection, two or more different types of external electron donors are used respectively by adopting, select suitable external electron donor consumption, the consumption of chain-transferring agent hydrogen different in association reaction, preparation has HOPP continuous phase particular melt index, pole wide molecular weight distribution containing a large amount of super high molecular weight components. The molecular weight distribution M of preferred described homopolymerization componentw/Mn(weight-average molecular weight/number-average molecular weight)=6-20, molecular weight more than the content of 5,000,000 fraction more than or equal to 1.5 weight %, and less than or equal to 5 weight %; Molecular weight less than the content of 50,000 fraction more than or equal to 15.0 weight %, and less than or equal to 40 weight %; Mz+1/Mn((Z+1)-average molecular weight/number-average molecular weight) more than or equal to 70, and less than 150. And carry out the combined polymerization of ethylene and 1-butylene on this basis further, obtain the rubber phase being scattered in continuous phase, the composition of rubber phase, structure and content etc. are controlled, it is thus achieved that there is the impact polypropylene material of high fondant-strength effect by controlling the reaction condition of copolyreaction.
In method provided by the invention, the catalyst used is Ziegler-Natta catalyst, it is preferable that have the catalyst of high stereoselective. The Ziegler-Natta catalyst of high stereoselective described herein refers to the catalyst of the Noblen that may be used for preparing isotactic index more than 95%. This kind of catalyst usually contains the solid catalyst activity component of (1) titaniferous, and it is mainly composed of magnesium, titanium, halogen and internal electron donor; (2) organo-aluminum compound cocatalyst component; (3) external electron donor component.
Solid catalyst activity component (can claim again major catalyst) in the Ziegler-Natta catalyst used in the method for the present invention can be well known in the art. The operational this kind of instantiation containing active solid catalyst component (1) such as can referring in patent documentation CN85100997, CN98126383.6, CN98111780.5, CN98126385.2, CN93102795.0, CN00109216.2, CN99125566.6, CN99125567.4 and CN02100900.7. The full content of these patent documentations is incorporated by reference in the present invention.
The preferred alkyl aluminum compound of organo-aluminum compound in the Ziegler-Natta catalyst used in the method for the present invention, more preferably trialkylaluminium, for instance at least one in triethyl aluminum, triisobutyl aluminium, three n-butylaluminum and three hexyl aluminum etc.
The active solid catalyst component of titaniferous and the mol ratio of organo-aluminum compound in the Ziegler-Natta catalyst used in the method for the present invention are calculated as 10:1��500:1 with aluminum/titanium, it is preferable that 25:1��100:1.
According to the present invention, it is R that described first external electron donor is preferably selected from formula1R2Si(OR3)2Compound at least one; Wherein, R2With R1It is each independently selected from C1-C6Straight or branched alkyl, C3-C8Cycloalkyl and C5-C12Heteroaryl, R3For C1-C3Straight chain aliphatic. instantiation includes but are not limited to methyl-cyclopentyl-dimethoxysilane, ethyI-cyclopentyl-dimethoxysilane, n-pro-pyl-cyclopenta-dimethoxysilane, two (2-methyl butyl)-dimethoxysilane, two (3-methyl butyl)-dimethoxysilane, 2-methyl butyl-3-methyl butyl-dimethoxysilane, two (2, 2-Dimethyl-propyl)-dimethoxysilane, 2-methyl butyl-2, 2-Dimethyl-propyl-dimethoxysilane, 3-methyl butyl-2, 2-Dimethyl-propyl-dimethoxysilane dimethyldimethoxysil,ne, dimethyldiethoxysilane, second, isobutyl dimethoxy silane, methylcyclohexyl dimethoxy silane, methyl-isobutyl dimethoxysilane, Dicyclohexyldimethoxysilane, methyl-isopropyl dimethoxysilane, isopropyl-cyclopenta dimethoxysilane, dicyclopentyl dimethoxyl silane, isopropyl-isobutyl group dimethoxysilane, diisopropyl dimethoxy silane etc.
The mol ratio of described organo-aluminum compound and the first external electron donor is calculated as 1:1��100:1 with aluminum/silicon, it is preferred to 10:1��60:1.
In the method according to the invention, the catalyst comprising the first external electron donor can be added directly in homopolymerization device, it is also possible to after the pre-contact known altogether through industry and/or prepolymerization, is then added in homopolymerization device. Described prepolymerization refers to that catalyst carries out the prepolymerization of certain multiplying power at a lower temperature, to obtain desirable particle shape and dynamic behavior control. Described prepolymerization can be the continuous prepolymerization of liquid-phase bulk, it is also possible to be batch pre-polymerization in the presence of an inert solvent. Prepolymerization temperature is generally-10��50 DEG C, it is preferred to 5��30 DEG C. Pre-contacting steps was optionally set before prepolymerization technology. Described pre-contacting steps refers to that promoter in catalyst system, external electron donor and major catalyst (solid active center component) carry out the complex reaction of catalyst system, to obtain the catalyst system with polymerization activity. The temperature of pre-contacting steps generally controls as-10��50 DEG C, it is preferred to 5��30 DEG C.
According to the present invention, described second external electron donor at least one in the compound as shown in chemical general formula (I), (II) and (III);
Wherein R1And R2It is each independently selected from C1-C20Straight chain, branching or in the aliphatic group of ring-type one, R3��R4��R5��R6��R7And R8It is each independently selected from hydrogen atom, halogen atom, C1-C20Straight or branched alkyl, C3-C20Cycloalkyl, C6-C20Aryl, C7-C20Alkaryl and C7-C20One in aralkyl; R9��R10And R11It is each independently C1-C3Straight chain aliphatic, R12For C1-C6Straight or branched alkyl or C3-C8Naphthene group. the instantiation of the second external electron donor includes but are not limited to 2,2-diisobutyl-1,3-dimethoxy propane, 2,2-phenyl-1,3-dimethoxy propane, 2,2-benzyl-1,3-dimethoxy propane, 2-isopropyl-2-isopentyl-1,3-dimethoxy propane, double, two (the cyclohexyl methyl)-1,3-dimethoxy propane of 2,2-, 2-isopropyl-2-3,7-dimethyl octyl-dimethoxy propane, 2,2-isopropyl-1,3-dimethoxy propane, 2-isopropyl-2-cyclohexyl methyl-1,3-dimethoxy propane, 2,2-diisobutyl-1,3-di ethyl propyl ether, 2,2-diisobutyl-1,3-dipropoxy propane, 2-isopropyl-2-isopentyl-1,3-di ethyl propyl ether, 2-isopropyl-2-isopentyl-1,3-dipropoxy propane, double, two (the cyclohexyl methyl)-1,3-di ethyl propyl ether of 2,2-, n-pro-pyl triethoxysilane, isopro-pyltriethoxysilane, isobutyl triethoxy silane, trimethoxysilane, isobutyl group tripropoxy silane, isobutyl group three butoxy silane, t-butyltriethoxysilane, tert-butyl group tripropoxy silane, the tert-butyl group three butoxy silane, cyclohexyltriethyloxysilane, cyclohexyl tripropoxy silane, tetraethoxysilane, tetramethoxy-silicane, tetrapropoxysilane, four butoxy silanes etc.
The mol ratio of described organo-aluminum compound and the second external electron donor is calculated as 1:1��60:1 with aluminum/silicon or with aluminum/oxygen, it is preferred to 5:1��30:1.
Some embodiments according to the present invention, the mol ratio of described second external electron donor and the first external electron donor is 1-30, it is preferred to 5-30.
In the method for the invention, it is preferable that before the homopolymerization of second stage, make to be fully contacted with the catalytic component in first stage product to electronics outside second. In some preferred embodiments, second dispatch from foreign news agency daughter can be added in after first stage reactor on the feeding line before second stage reactor, or the feed pipe front end at second stage reactor, its objective is first to carry out pre-contact reaction with the catalyst in the product of first stage before second stage is reacted.
For high fondant-strength impact polypropylene, owing to being the material of heterogeneous structure, the factor affecting melt strength just becomes complex. The method according to the invention, the ratio of the melt index of the polypropylene material of propylene homopolymer component and ethylene-butene-1 copolymer component that what the melt index of the Noblen preferably obtained through the first step and second step obtained comprise is more than or equal to 0.6, and less than or equal to 1. It is also preferred that the weight ratio of described first Noblen and the second Noblen is 40:60-60:40. It is further preferred that the weight ratio of described ethylene-butene-1 copolymer component and propylene homopolymer component is 11-80:100. By being set to include that there is different melt index by the propylene homopolymer component of the impact polypropylene material of the present invention, and there is the combination of at least two Noblen of special ratios relation, the polypropylene material making the composition present invention has specific dispersion phase, under the combination further of this dispersion phase and rubber phase, produce that both there is high melt strength, there is the impact polypropylene material of good rigidity and toughness simultaneously.
According to the invention it is preferred to described propylene homopolymer component has the feature that at 230 DEG C, the melt index measured under the load of 2.16kg is 0.1-15g/10min, it is preferable that 0.1-6g/10min; Molecular weight distribution Mw/Mn=6-20; Molecular weight more than the content of 5,000,000 fraction more than or equal to 1.5 weight %, and less than or equal to 5 weight %; Molecular weight less than the content of 50,000 fraction more than or equal to 15.0 weight %, and less than or equal to 40 weight %; Mz+1/MnMore than or equal to 70, and less than 150.
In second step, it is 0.2-0.8 that the consumption of 1-butylene is preferably the ratio of the 1-butylene cumulative volume with 1-butylene and ethylene. Preferably, in second step, the volume ratio of the total amount of hydrogen and 1-butylene and ethylene is 0.02-1. Meanwhile, as it has been described above, in the first phase, the consumption of hydrogen can be such as 0-200ppm. In second stage, the consumption of hydrogen can be 2000-20000ppm. In the present invention, possessing high fondant-strength to obtain, be provided simultaneously with the impact polypropylene material of higher rigidity and toughness, the control of dispersion phase and the composition of continuous phase, structure or performance is particularly significant. The present invention can be prepared and had, by these preferred conditions, the rubber phase being advantageously implemented the molecular weight distribution of the purpose of the present invention, ethylene contents, thus obtaining the impact polypropylene material with better performance.
In a preferred embodiment of the invention, the productivity of the first Noblen and the second Noblen is 40:60-60:40. The productivity ratio of ethylene-butene-1 copolymer component and propylene homopolymer component is 11-80:100.
The polyreaction of the first step in Liquid-liquid, or can carry out in gas phase-gas phase, or adopts liquid-gas combination technique to carry out. When carrying out liquid phase polymerization, polymerization temperature is 0��150 DEG C, and 60��100 DEG C as well; Polymerization pressure should be higher than that propylene saturated vapour pressure under corresponding polymerization temperature. When gas-phase polymerization, polymerization temperature is 0��150 DEG C, and 60��100 DEG C as well; Polymerization pressure can be normal pressure or higher, it is preferable that pressure is 1.0��3.0MPa (gauge pressure, lower same).
The polyreaction of second step carries out in the gas phase. This Gas-phase reactor can be gas-phase fluidized-bed, gas phase moving bed, or bubble agitation bed bioreactor. The temperature of polymerization is 0��150 DEG C, and 60��100 DEG C as well. Polymerization pressure is lower than any pressure of liquefaction under partial pressure of propylene.
According to the preferred embodiments of the invention, the reaction temperature of first stage is 50-100 DEG C, it is preferable that 60-85 DEG C; The reaction temperature of second stage is 55-100 DEG C, it is preferable that 60-85 DEG C; The reaction temperature of second step is 55-100 DEG C, it is preferable that 60-85 DEG C.
The method according to the invention, polyreaction can continuously perform, it is also possible to interval carries out.
The method according to the invention, the M of the room temperature trichloro-benzenes soluble substance of the polypropylene material obtained through second stepwM with room temperature trichloro-benzenes insoluble matterwRatio more than 0.5, and less than 1, it is preferable that more than 0.5, and less than 0.8; Butene content in ethylene-butene-1 copolymer is more than or equal to 20 weight %, and less than or equal to 45 weight %. Rigidity and the toughness of the polypropylene material so obtained obtain further optimization, ensure possess higher melt strength simultaneously. In the present invention, room temperature xylene soluble content method described in ASTMD5492 measures. At this, it is readily appreciated that, so-called " butene content in ethylene-butene-1 copolymer " can be understood as in the ethylene-butene-1 copolymer formed by vinyl monomer and 1-butylene monomer copolymerization, is made up of the weight content of part butene monomers.
The method according to the invention, the polypropylene material obtained through second step is at 230 DEG C, and the melt index measured under the load of 2.16kg is 0.1-15g/10min, it is preferable that 0.1-6g/10min; The molecular weight distribution M of described materialw/MnLess than or equal to 10, and more than or equal to 4; Mz+1/MwMore than 10, and less than 20.
In a preferred embodiment of the invention, the method for the present invention also includes adopting �� or �� crystalline substance nucleator that preparation-obtained impact polypropylene material is modifiied further, to improve rigidity or the toughness of polyacrylic resin material further. The �� being suitable for is brilliant and �� crystalline substance is nucleater modified, is the technology known altogether in the industry. The weight of usual nucleator and the ratio of polypropylene gross weight are (0.005��3): 100.
Present invention also offers the impact polypropylene material of a kind of high fondant-strength prepared according to method as defined above, including propylene homopolymer component and ethylene-butene-1 copolymer component, wherein said propylene homopolymer component at least includes the first Noblen and the second Noblen; The weight ratio of ethylene-butene-1 copolymer component and propylene homopolymer component is 11-80:100, and the butene content in ethylene-butene-1 copolymer is more than or equal to 20 weight %, and less than or equal to 45 weight %.
The present invention adopts ethylene-1-butylene-random copolymer as rubber components, further, the present inventor finds through lot of experiments, in the impact polypropylene material of the present invention, the weight ratio using ethylene-butene-1 copolymer component and propylene homopolymer component is 11-80:100, and effect is better; Further, when making the butene content in ethylene-butene-1 copolymer more than or equal to 20 weight %, and during less than or equal to 45 weight %, it is thus achieved that rigidity and the good impact polypropylene material of toughness. The polypropylene product of the present invention has good rigid-tough balance.
The room temperature xylene soluble content of the impact polypropylene material according to the present invention is preferably greater than 10 weight %, and less than 30 weight %; The M of room temperature trichloro-benzenes soluble substancewM with room temperature trichloro-benzenes insoluble matterwRatio be preferably greater than 0.5, and less than 1, it is preferable that more than 0.5, less than 0.8. The rigidity of polypropylene material and toughness obtain further optimization, are provided simultaneously with higher melt strength.
The melt index scope of the impact polypropylene material of the present invention is preferably controlled in 0.1-15g/10min, it is preferable that 0.1-10g/10min, it is also preferred that 0.1-6.0g/10min. Described melt index, at 230 DEG C, measures under the load of 2.16kg. For high fondant-strength impact polypropylene, owing to being the material of heterogeneous structure, the factor affecting melt strength just becomes complex. The inventors discovered that, in order to ensure the high fondant-strength of product, the molecular weight distribution M of described impact polypropylene materialw/MnIt is preferably lower than or equal to 10, and more than or equal to 4, Mz+1/MwMore than 10, and less than 20, it is preferable that more than 10, less than 15.
In some preferred embodiments, the butene content of the impact polypropylene material of the present invention is 5-20 weight %.
Impact polypropylene material according to the present invention, molecular weight polydispersity index (PI) is 4-8, it is preferable that 4.5-6.
According to impact polypropylene material provided by the invention, it is obtained by reacting the propylene homopolymer component comprising the first Noblen and the second Noblen by carrying out propylene homo under the existence of the first Noblen, then carries out the material that ethylene-1-butylene copolyreaction obtains comprising ethylene-butene-1 copolymer under the existence of described propylene homopolymer component and prepares. As can be seen here, the impact polypropylene material of the present invention is not the simple mixing of propylene homopolymer component and ethylene-butene-1 copolymer component, but the globality polypropylene material comprising Noblen and ethylene-butene-1 copolymer obtained after the enterprising step in the basis of specific propylene homopolymer component carries out specific ethylene-1-butylene copolyreaction.
The polypropylene material of the present invention also has good heat resistance, adopts the melting peak temperature T of the DSC final acrylic resin measuredmMore than or equal to 158 DEG C.
In the preparation method of the impact polypropylene material of the present invention, the second external electron donor added can react with the catalytic active center in first stage homopolymerization products material, generate new catalytic active center, continue to cause propylene polymerization to become and the homopolymer polymer of first stage products obtained therefrom mass difference great disparity in second stage. Second external electron donor has higher hydrogen response than the first external electron donor, it is possible under a small amount of hydrogen exists, prepare high fusion index polymer. Therefore, can pass through to adjust the addition of the external electron donor consumption of different phase, kind and hydrogen when two reactors adding series connection or intermittently operated, do not need with special catalyst, the present invention just can when little hydrogen consumption, obtain containing a large amount of super high molecular weight fraction, the relatively HOPP component of wide molecular weight distribution. Then pass through suitable 1-butylene/(1-butylene+ethylene) of selection, hydrogen/(1-butylene+ethylene) and temperature and pressure, the basis of HOPP component occurs ethylene-1-butylene copolyreaction further, obtains the high fondant-strength impact polypropylene of the rubber components with particular characteristic containing certain content. The Nomenclature Composition and Structure of Complexes of rubber phase component controls to ensure that it possesses high fondant-strength, and the certain content of rubber components ensure that its relatively high impact resistance, and molecular weight distribution suitable in addition also makes polymer have good processing characteristics. That is, the present invention is by arranging multiple propylene homo stage of reaction, and select each suitable response parameter and the reaction condition of each homopolymerization and copolyreaction, thus producing suitable continuous phase and rubber domain and their syntagmatic, obtain the polypropylene material with premium properties on this basis.
Impact polypropylene material provided by the invention, owing to having high melt strength, also has high rigidity and high tenacity feature, thus applies to the excellent material in the fields such as automobile component, medical apparatus and instruments, household articles. The preparation method of high fondant-strength impact polypropylene material provided by the invention is simply effective, it is easy to operation.
Detailed description of the invention
Following by specific embodiment, the present invention is described further, but does not constitute any limitation of the invention.
In embodiment, the relevant data of polymer obtain by following method of testing:
1. polymer room temperature xylene soluble content (namely characterizing rubber-phase content) method described in ASTMD5492 measures;
2. resin stretched intensity presses the measurement of GB/T1040.2 method;
3. melt mass flow rate (also known as melt index, MFR): method described in ASTMD1238, with CEAST company 7026 type fusion index instrument, at 230 DEG C, measures under 2.16kg load;
4. bending modulus: method measures described in GB/T9341;
5. simply supported beam notch impact strength: method measures described in GB/T1043.1;
6. ethylene contents and butene content: adopt nuclear magnetic resonance method determination. Adopting Bruker company AVANCEIII400MHz nuclear magnetic resonance chemical analyser of Switzerland (NMR), 10 millimeters of probes measure. Solvent is deuterated o-dichlorohenzene, and about 250mg sample is placed in 2.5ml deuterated solvent, forms homogeneous solution in 140 DEG C of oil bath heating for dissolving samples. Gathering 13C-NMR, probe temperature 125 DEG C, adopt 90 �� of pulses, sampling time AQ is 5 seconds, and time delay, D1 was 10 seconds, scanning times more than 5000 times. Other operation, spectral peak identifications etc. perform conventional NMR requirement of experiment, list of references includes EricT.Hsieh, andJamesC.Randall, Ethylene-1-ButeneCopolymers.1.ComonomerSequenceDistribut ion, Macromolecules, 15,353-360 (1982).
7. melt strength: adopt the Rheotens melt strength instrument that GeottfertWerkstoffPruefmaschinen company of Germany produces to measure. Polymer is after single screw extrusion machine fusion plastification, the downward melt extrusion material strip of head is turned to then through equipped with 90 �� of 30/2 draw ratio mouth die, this material strip is clamped in one group to carry out uniaxial tension between two rollers of constant acceleration opposite direction rotating, measure and record the power of melt drawn process by the load cell being connected with draw roll, the maximal force recorded when being stretched to melt fracture is defined as melt strength.
8. molecular weight polydispersity index (PI): resin sample is molded at 200 DEG C the thin slice of 2mm; adopt ARES (the senior flow graph extension system) flow graph of U.S. RheometricScientificInc; under 190 DEG C and nitrogen protection, sample is carried out dynamic frequency scanning; select parallel plate fixtures; determine that suitable strain amplitude is to ensure that experiment carries out in linear zone, measure the change with frequency such as the storage modulus (G ') of sample, Loss modulus (G "). Molecular weight polydispersity index PI=105/Gc, wherein Gc(unit: Pa) is G ' frequency curve and G " modulus value of frequency curve point of intersection.
9. molecular weight (Mw��Mn) and molecular weight distribution (Mw/Mn, Mz+1/Mw): adopt the GPCIR instrument (IR5 concentration detector) that PolymerLaboratories company of Britain produces PL-GPC220 chromatograph of gel permeation or PolymerChar company of Spain product to measure molecular weight and the molecular weight distribution of sample, chromatographic column is 3 series connection PLgel13umOlexis posts, solvent and mobile phase are 1, 2, 4-trichloro-benzenes (the antioxidant 2 containing 250ppm, 6-dibutyl paracresol), column temperature 150 DEG C, flow velocity 1.0ml/min, PL company EasiCalPS-1 Narrow distribution polystyrene standard substance are adopted to carry out universal calibration. wherein the preparation process of room temperature trichloro-benzenes soluble substance is as follows: precise sample and trichloro-benzenes solvent, dissolves 5 hours at 150 DEG C, adopts quantitative glass filter paper filtering, obtain the solution of room temperature trichloro-benzenes soluble substance for measuring at 25 DEG C after standing 15 hours. GPC area under the curve is corrected by the polypropylene adopting concentration known, it is determined that the content of room temperature trichloro-benzenes soluble substance, and the molecular weight data of room temperature trichloro-benzenes insoluble matter adopts the GPC data of raw sample and the GPC data of room temperature trichloro-benzenes soluble substance to calculate and obtain.
Embodiment 1
Propylene polymerization carries out on polypropylene plant, and the capital equipment of this device includes prepolymerization reactor, the first annular-pipe reactor, the second annular-pipe reactor and the 3rd Gas-phase reactor. Polymerization and step are as follows.
(1) prepolymerization
Major catalyst (DQC-401 catalyst, Beijing Ao Da branch company of middle Effect of Catalysis In Petrochemistry agent company provide), promoter (triethyl aluminum), the first external electron donor (isopropyl cyclopenta dimethoxysilane, IPCPMS) through 6 DEG C, after 20min pre-contact, be added continuously continuous stirring autoclave prepolymerization reactor and carry out pre-polymerization reactor. Triethyl aluminum (TEA) flow entering prepolymerization reactor is 6.33g/hr, and isopropyl cyclopenta dimethoxysilane flow is 0.3g/hr, and major catalyst flow is 0.6g/hr, TEA/IPCPMS ratio is 50 (mol/mol). Prepolymerization carries out under propylene liquid-phase bulk environment, and temperature is 15 DEG C, and the time of staying is about 4min, and under this condition, the pre-polymerization multiple of catalyst is about 80��120 times.
(2) first step: propylene homo closes reaction
First stage: pre-polymerization rear catalyst closes reaction, the polymeric reaction temperature of the first annular-pipe reactor 70 DEG C, reaction pressure 4.0MPa continuously into completing first stage propylene homo in the first annular-pipe reactor; Not hydrogenation in the charging of the first annular-pipe reactor, the density of hydrogen 10ppm of on-line chromatograph detection, obtain the first Noblen A.
Second stage: the isobutyl triethoxy silane (IBTES) adding 0.63g/hr with the propylene of the second annular-pipe reactor mixes with the reaction logistics from the first annular-pipe reactor, TEA/IBTES ratio is 5 (mol/mol), and wherein IBTES is the second external electron donor. The polymeric reaction temperature of the second annular-pipe reactor 70 DEG C, reaction pressure 4.0MPa; Being additionally added a certain amount of hydrogen with propylene feed, in on-line chromatograph detection charging, density of hydrogen is 3300ppm, produces the second Noblen B, obtain the propylene homopolymer component comprising the first Noblen and the second Noblen in the second annular-pipe reactor.
(3) second step: second fourth copolymerization
A certain amount of hydrogen, H is added in the 3rd reactor2/(C2+C4)=0.06 (v/v), C4/(C2+C4)=0.45 (v/v) (C2And C4Refer to ethylene and 1-butylene respectively), reaction temperature 75 DEG C, continues to cause Ethylene/1-butene copolymerization at the 3rd reactor, produces ethylene-butene-1 copolymer component C.
End product contains the first Noblen, the second Noblen and ethylene-butene-1 copolymer component, removes activity the heat drying of unreacted catalyst through wet nitrogen, obtains polymer powders. By the powder that obtains of polymerization adds the calcium stearate of the IRGAFOS168 additive of 0.1wt%, the IRGANOX1010 additive of 0.1wt% and 0.05wt%, use double screw extruder pelletize. Resulting polymers analyzes result and polymer physics performance is listed in table 1 and table 2.
Embodiment 2
The catalyst that embodiment 2 uses, pre-complexation, polymerization process condition and auxiliary formula and addition and embodiment 1 are identical. Difference from Example 1 is in that: in second stage, the amounts of hydrogen in the second reactor becomes 7000ppm, H in second step Gas-phase reactor2/(C2+C4) it is adjusted to 0.20 (v/v). Resulting polymers analyzes result and polymer physics performance is listed in table 1 and table 2.
Embodiment 3
The catalyst that embodiment 3 uses, pre-complexation, polymerization process condition and auxiliary formula and addition and embodiment 1 are identical. Difference from Example 1 is in that: in second stage, the amounts of hydrogen in the second reactor becomes 10000ppm, H in second step Gas-phase reactor2/(C2+C4) it is adjusted to 0.51 (v/v). Resulting polymers analyzes result and polymer physics performance is listed in table 1 and table 2.
Embodiment 4
The catalyst that embodiment 4 uses, pre-complexation, polymerization process condition and auxiliary formula and addition and embodiment 1 are identical. Difference from Example 1 is in that: the second external electron donor is changed to 2 ,-isopropyl-2-isopentyl-1,3-dimethoxy propane (IPPMP), and addition is constant, and in second stage, the amounts of hydrogen in the second reactor is adjusted to 4000ppm. Resulting polymers analyzes result and polymer physics performance is listed in table 1 and table 2.
Embodiment 5
The catalyst that embodiment 5 uses, pre-complexation, polymerization process condition and auxiliary formula and addition and embodiment 3 are identical. Difference from Example 3 is in that: the first external electron donor is changed to isopropyl-2-isobutyl group-dimethoxysilane (IPBMS), and addition is constant. Resulting polymers analyzes result and polymer physics performance is listed in table 1 and table 2.
Embodiment 6
The catalyst that embodiment 6 uses, pre-complexation, polymerization process condition and auxiliary formula and addition and embodiment 1 are identical. Difference from Example 1 is in that: in second stage, the amounts of hydrogen in the second reactor becomes 6000ppm, H in second step Gas-phase reactor2/(C2+C4) it is adjusted to 0.15 (v/v), C4/(C2+C4) it is adjusted to 0.25 (v/v). Resulting polymers analyzes result and polymer physics performance is listed in table 1 and table 2.
From the result shown in table 1 and table 2 it can be seen that the polypropylene material that the method according to the invention prepares has higher melt strength, there is higher hot strength, bending modulus, notch impact strength simultaneously. Therefore, the impact polypropylene material of high fondant-strength, high rigidity and high tenacity can be prepared by method provided by the invention. This polypropylene material possessing premium properties is with a wide range of applications.
Although the present invention is described in detail, but it will be understood by those skilled in the art that the amendment in spirit and scope of the invention will be apparent from. However, it should be understood that each several part of each side of present invention record, difference detailed description of the invention (scheme) and the various features enumerated can be combined or all or part of exchange. In each above-mentioned detailed description of the invention, those can suitably combine with other embodiment with reference to the embodiment of another embodiment, and this is by understand by those skilled in the art. Additionally, it will be understood to those of skill in the art that description above is only the mode of example, it is no intended to the restriction present invention.
Claims (11)
1. a preparation method for high fondant-strength impact polypropylene material, including:
The first step: propylene homo reacts, including:
First stage: under comprising the effect of Ziegler-Natta catalyst of the first external electron donor, under hydrogen presence or absence, carry out propylene homo reaction, obtain comprising the reaction logistics of the first Noblen;
Second stage: add the second external electron donor and carry out complex reaction with the catalyst in described reaction logistics, then under the existence of the first Noblen and hydrogen, carry out propylene homo reaction, produce the second Noblen, obtain the propylene homopolymer component comprising the first Noblen and the second Noblen;
Wherein,
Described first Noblen and described propylene homopolymer component at 230 DEG C, under the load of 2.16kg measure melt index respectively 0.001-0.4g/10min and 0.1-15g/10min;
Second step: ethylene-1-butylene copolyreaction, including carrying out ethylene and 1-butylene gas phase copolymerization under the existence of described propylene homopolymer component and hydrogen, produce ethylene-butene-1 copolymer component, obtain the polypropylene material comprising described propylene homopolymer component and ethylene-butene-1 copolymer component.
2. method according to claim 1, it is characterised in that described first external electron donor is R selected from formula1R2Si(OR3)2Compound at least one; Wherein, R2With R1It is each independently selected from C1-C6Straight or branched alkyl, C3-C8Cycloalkyl and C5-C12Heteroaryl, R3For C1-C3Straight chain aliphatic.
3. method according to claim 1 and 2, it is characterised in that described second external electron donor at least one in the compound as shown in chemical general formula (I), (II) and (III);
Wherein, R1And R2It is each independently selected from C1-C20Straight chain, branching or in the aliphatic group of ring-type one, R3��R4��R5��R6��R7And R8It is each independently selected from hydrogen atom, halogen atom, C1-C20Straight or branched alkyl, C3-C20Cycloalkyl, C6-C20Aryl, C7-C20Alkaryl and C7-C20One in aralkyl; R9��R10And R11It is each independently C1-C3Straight chain aliphatic, R12For C1-C6Straight or branched alkyl or C3-C8Naphthene group.
4. the method according to any one in claim 1-3, it is characterised in that the mol ratio of described second external electron donor and the first external electron donor is 5-30.
5. the method according to any one in claim 1-4, it is characterised in that described first external electron donor is selected from methyl-cyclopentyl-dimethoxysilane, ethyI-cyclopentyl-dimethoxysilane, n-pro-pyl-cyclopenta-dimethoxysilane, two (2-methyl butyl)-dimethoxysilane, two (3-methyl butyl)-dimethoxysilane, 2-methyl butyl-3-methyl butyl-dimethoxysilane, two (2,2-Dimethyl-propyl)-dimethoxysilane, 2-methyl butyl-2,2-Dimethyl-propyl-dimethoxysilane, 3-methyl butyl-2,2-Dimethyl-propyl-dimethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, second, isobutyl dimethoxy silane, methylcyclohexyl dimethoxy silane, methyl-isobutyl dimethoxysilane, Dicyclohexyldimethoxysilane, methyl-isopropyl dimethoxysilane, isopropyl-cyclopenta dimethoxysilane, dicyclopentyl dimethoxyl silane, at least one in isopropyl-isobutyl group dimethoxysilane and diisopropyl dimethoxy silane,
Described second external electron donor is selected from 2,2-diisobutyl-1,3-dimethoxy propane, 2,2-phenyl-1,3-dimethoxy propane, 2,2-benzyl-1,3-dimethoxy propane, 2-isopropyl-2-isopentyl-1,3-dimethoxy propane, double, two (the cyclohexyl methyl)-1,3-dimethoxy propane of 2,2-, 2-isopropyl-2-3,7-dimethyl octyl-dimethoxy propane, 2,2-isopropyl-1,3-dimethoxy propane, 2-isopropyl-2-cyclohexyl methyl-1,3-dimethoxy propane, 2,2-diisobutyl-1,3-di ethyl propyl ether, 2,2-diisobutyl-1,3-dipropoxy propane, 2-isopropyl-2-isopentyl-1,3-di ethyl propyl ether, 2-isopropyl-2-isopentyl-1,3-dipropoxy propane, double, two (the cyclohexyl methyl)-1,3-di ethyl propyl ether of 2,2-, n-pro-pyl triethoxysilane, isopro-pyltriethoxysilane, isobutyl triethoxy silane, trimethoxysilane, isobutyl group tripropoxy silane, isobutyl group three butoxy silane, t-butyltriethoxysilane, tert-butyl group tripropoxy silane, the tert-butyl group three butoxy silane, cyclohexyltriethyloxysilane, cyclohexyl tripropoxy silane, tetraethoxysilane, tetramethoxy-silicane, at least one in tetrapropoxysilane and four butoxy silanes.
6. the method according to any one in claim 1-5, it is characterized in that, the ratio of the melt index of the polypropylene material comprising propylene homopolymer component and ethylene-butene-1 copolymer component that the melt index of the propylene homopolymer component obtained through the first step obtains with second step is more than or equal to 0.6, and less than or equal to 1.
7. the method according to any one in claim 1-6, it is characterised in that the weight ratio of described first Noblen and the second Noblen is 40:60-60:40; The weight ratio of described ethylene-butene-1 copolymer component and propylene homopolymer component is 11-80:100.
8. the method according to any one in claim 1-7, it is characterised in that described propylene homopolymer component has the feature that
At 230 DEG C, the melt index measured under the load of 2.16kg is 0.1-15g/10min, it is preferable that 0.1-6g/10min;
Molecular weight distribution Mw/Mn=6-20;
Molecular weight more than the content of 5,000,000 fraction more than or equal to 1.5 weight %, and less than or equal to 5 weight %;
Molecular weight less than the content of 50,000 fraction more than or equal to 15.0 weight %, and less than or equal to 40 weight %;
Mz+1/MnMore than or equal to 70, and less than 150.
9. the method according to any one in claim 1-8, it is characterised in that the M of the room temperature trichloro-benzenes soluble substance of the polypropylene material obtained through second stepwM with room temperature trichloro-benzenes insoluble matterwRatio more than 0.5, and less than 1; Butene content in ethylene-butene-1 copolymer is more than or equal to 20 weight %, and less than or equal to 45 weight %.
10. the method according to any one in claim 1-9, it is characterised in that in second step, the ratio of 1-butylene and the cumulative volume of 1-butylene and ethylene is 0.2-0.8; The ratio of hydrogen and the cumulative volume of 1-butylene and ethylene is 0.02-1.
11. the method according to any one in claim 1-10, it is characterised in that the reaction temperature of first stage is 50-100 DEG C, it is preferable that 60-85 DEG C; The reaction temperature of second stage is 55-100 DEG C, it is preferable that 60-85 DEG C; The reaction temperature of second step is 55-100 DEG C, it is preferable that 60-85 DEG C.
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| CN112745583A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | High-gloss impact-resistant polypropylene composition and preparation method thereof |
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| CN112745580A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | High-fluidity, high-impact-resistance and high-temperature-resistance polypropylene material as well as preparation method and application thereof |
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| CN112745583A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | High-gloss impact-resistant polypropylene composition and preparation method thereof |
| CN112745581B (en) * | 2019-10-30 | 2022-07-26 | 中国石油化工股份有限公司 | High-fluidity high-crystallization impact-resistant polypropylene material and preparation method thereof |
| CN112745582B (en) * | 2019-10-30 | 2022-07-26 | 中国石油化工股份有限公司 | Ultrahigh impact polypropylene material and preparation method thereof |
| CN112745583B (en) * | 2019-10-30 | 2022-07-29 | 中国石油化工股份有限公司 | High-gloss impact-resistant polypropylene composition and preparation method thereof |
| CN112745580B (en) * | 2019-10-30 | 2022-09-09 | 中国石油化工股份有限公司 | High-fluidity, high-impact-resistance and high-temperature-resistance polypropylene material as well as preparation method and application thereof |
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