CN104448537A - Polypropylene composition and preparation method thereof and products made from polypropylene composition - Google Patents
Polypropylene composition and preparation method thereof and products made from polypropylene composition Download PDFInfo
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Abstract
The present invention relates to a polypropylene composition and a preparation method thereof and products made from the polypropylene composition. The polypropylene composition comprises 70-95% by weight of crystalline polypropylene A and 5-30% by weight of ethane-propylene elastomeric copolymer B, wherein both of molecular weight distribution indexes of the polypropylene composition and the crystalline polypropylene A are over 4 and the melt index ratio of the polypropylene composition to the crystalline polypropylene is in the range of from 0.7 to 1.3. According to the invention, the polypropylene composition is high in impact resistance and good in transparency with no effect on any other properties, and the preparation method is economical.
Description
Technical field
The present invention relates to a kind of polypropene composition, the preparation method of this polypropene composition, use polypropene composition prepared by the method, and the goods obtained by this polypropene composition.
Background technology
Polypropylene material is all used widely because of advantages such as it is of fine quality, inexpensive, high temperature resistant, easy machine-shapings in industry-by-industry.In fields such as toy, packaging, medicine equipment, daily necessities, people wish to use transparency resin preferably.Homo-polypropylene can be made to obtain good transparency by adding transparent base.Use the monomer such as ethene, butylene to carry out random copolymerization to polypropylene, the monomer due to copolymerization destroys the regularity of propylene monomer arrangement on molecular chain, reduces fusing point and the degree of crystallinity of acrylic resin, further increases the transparency of material.But atactic copolymerized polypropene is similar to homo-polypropylene, its shock resistance is poor, can not provide good shock strength especially at low temperatures.
Introduce ethylene-propylene elastomeric multipolymer by mechanically mixing or successive polymerization, polyacrylic shock strength can be improved and obtain high impact copolymer.Usual impact polypropylene is by ziegler natta catalyst preparation in multi-step polymerization reaction.The ethylene-propylene elastomeric multipolymer that the method is produced and homo-polypropylene can be separated and cause the mist degree of the finished product to increase, in addition, usually there is very uneven composition, so this multipolymer does not have the transparency usually by the binary ethylene-propylene elastomeric multipolymer of Conventional Ziegler-Natta catalyst preparing.
Typically, the transparency of high impact copolymer is all very poor, does not almost have what transparency to say.Particularly, relative to atactic copolymerized polypropene lower than 20% mist degree, the mist degree of the impact polypropylene of heterophasic copolymer up to 98%(" polypropylene handbook " (Chemical Industry Press, in June, 2008 first version, the 259th page).
Homogeneous catalyst, its Typical Representative is metallocene catalyst, has single active center's point feature.The alfon produced by homogeneous catalyst polymerization and multipolymer have very narrow molecular weight distribution, general weight-average molecular weight and the ratio of number-average molecular weight are 2.5 ~ 3.5(" polypropylene--principle, process technologies ", Sinopec press, in June, 2007 first version, the 208th page).And alfon prepared by Ziegler-Natta catalyst and molecular weight of copolymer wider distribution, general weight-average molecular weight and the ratio of number-average molecular weight be greater than 4(" polypropylene handbook " (Chemical Industry Press, in June, 2008 first version, the 15th page).The multipolymer produced by homogeneous catalyst polymerization has very narrow chemical constitution distribution (" polypropylene handbook " (Chemical Industry Press, in June, 2008 first version, 72nd page), the binary ethylene-propylene elastomeric multipolymer prepared with it has and forms very uniformly, and transparency is fine.Therefore homogeneous catalyst is adopted relatively easily to produce the good high impact copolymer of transparency.But homogeneous catalyst poor morphology, can not use common industrialization polypropylene plant to produce; Even if carry out load by carrier to homogeneous catalyst, morphology Control remains the problem being difficult to solve.The cost consumption of homogeneous catalyst will, far above Ziegler-Natta catalyst, therefore be difficult to fall competition with Ziegler-Natta catalyst at its product of field of industrial production.
US4634740A discloses to adopt and to obtain with special catalyst and the method that mixes in the molten state with polypropylene of the propylene-ethylene copolymers with 70-85 % by weight special ethylene content.And point out, lower or higher ethylene content all can not produce required result in the copolymer.Prepare such composition to need to synthesize homopolymer and multipolymer respectively, then mix in molten state.This obviously needs to expend more energy, produces higher cost.In addition owing to lacking highly active catalyzer synthesizing ethylene-propylene elastomeric copolymer, also catalyst residue must be removed to polymkeric substance deliming.
For overcoming above-mentioned deficiency, CN1045983A discloses the transparent polypropylene composition at low temperatures with shock resistance, this transparent polypropylene composition (sequential co-polymerization) directly can be prepared when being polymerized, and use take magnesium dichloride as the highly active ziegler natta catalyst of carrier.Said composition comprises crystallization atactic propene copolymer, ethene and propylene and/or C
4-C
8the elastocopolymer of alhpa olefin, the ethene wherein containing 20-70 % by weight.According to this invention, the ratio that in elastocopolymer, the numerical value of ethylene content is dissolved in the limiting viscosity of the elastocopolymer of dimethylbenzene and the limiting viscosity (I.V.) of random copolymer of propylene under being multiplied by room temperature is included in a default scope.The method is equivalent to the polypropylene homopolymer main part of impact polypropylene being replaced by random copolymerization, and this obviously can make the rigidity of the finished product, hardness and resistance toheat decline.
CN1380893A discloses a kind of prolylene polymer composition, it comprises: A) propylene of 70-90% (weight percent) and ethylene atactic copolymer, ethene containing 1-6%, the content that under room temperature, (about 23 DEG C) are insoluble to xylene moiety is no less than 93%; B) propylene of 10%-30% (weight percent) and ethylene copolymer, the ethene containing 8-18%; Wherein, relative to the weight percent of (B) of (A) and (B) gross weight, and relative to the weight percent of ethene in (B) of (B) gross weight, the latter is by general formula C
2b represents, ratio (B)/C between the two
2b is 2.5 or lower.The homopolymer main part of impact polypropylene is replaced by the polypropylene of random copolymerization by the method, and this obviously can make the rigidity of the finished product, hardness and resistance toheat decline.
CN1861674A discloses a kind of polypropene composition and the goods thereof with excellent impact resistance, modulus in flexure and transparency.Said composition comprises: the high crystalline random copolymer of (a) 80-95 % by weight, and this high crystalline random copolymer is be selected from least one in the propylene-1-butylene random copolymers of the ethylene-propylene random copolymer containing 1-5 % by weight ethene and the 1-butylene containing 2-12 % by weight; (b) the ethylene-propylene elastomeric multipolymer of 5-20 % by weight, this ethylene-propylene elastomeric multipolymer contains 30-50 % by weight ethene, and wherein, the melting index of component (b) and component (a) is than being 1.5-35.The polypropene composition of this invention is applicable to producing cold storage container, freezing container, food container, extrusion moulding product, blow-molded article, film, thin slice and bottle stopper etc.The homopolymer main part of impact polypropylene is also replaced by the polypropylene of random copolymerization by the method, and the rigidity of the finished product, hardness and resistance toheat also can be made to decline.
CN101506297A discloses a kind of polypropene composition and goods thereof, and said composition has the optimum balance of mechanical property and transparency, and therefore said composition is particularly suitable for packing purposes.Said composition comprises: a) propylene copolymer (A), it has the fusing point of less than 160 DEG C and the modulus in flexure of below 1000MPa, and b) ethylene-propylene elastomeric multipolymer (B), based on the weight of ethylene-propylene elastomeric multipolymer (B), its propylene content is 80-92wt%.Wherein, component is a) random copolymers, and the rigidity of the finished product, hardness and resistance toheat can be made to decline.Components b) for adopting single site catalysts to produce from polyolefin elastic multipolymer, this composition obviously needs to mix in molten state.This needs to expend more energy, has higher cost.
CN1957036A discloses a kind of flexible propylene copolymer compositions with high-clarity.Described propylene copolymer compositions comprises A) propylene copolymer of 50%-80% weight, described propylene copolymer comprises the alhpa olefin with 2-10 carbon atom of the 0.05-0.99% weight being different from propylene; And B) a kind of propylene copolymer of 20%-50% weight, described a kind of propylene copolymer comprises the alhpa olefin that the 7.01-20.0% weight being different from propylene has 2-10 carbon atom; Described propylene copolymer compositions has following characteristic: (i) MFR (230 DEG C/2.16kg) [g/10 minute] is 1-20; (ii) tensile E modulus is 400-800MPa (ISO527-2:1993).Said composition has good toughness, but metallocene catalyst must be used to produce, and this catalyzer has higher cost, and is not easy to use on common polyolefin device due to the speciality of its homogeneous phase.Although use little comonomer, rigidity, the hardness of the finished product are very low.
CN1659224A discloses a kind of propylene copolymer compositions, it comprises: A) comprise the propene polymer being different from the alkene of propylene and the B of 0-10% weight) at least one comprises the propylene copolymer being different from the alkene of propylene of 5-40% weight, wherein propene polymer A and propylene copolymer B are as the existence be mutually separated, and haze value≤30% of propylene copolymer compositions, based on the path length of the propylene copolymer compositions of 1 millimeter, and the fragility/tough transition temperature of propylene copolymer compositions be≤-15 DEG C.Said composition has good toughness, but metallocene catalyst must be used to produce, and this catalyzer has higher cost, and is not easy to use on common polyolefin device due to the speciality of its homogeneous phase.Although use little comonomer, rigidity, the hardness of the finished product are very low.
Therefore need badly to find and a kind ofly while not reducing other performance, high shock resistance and the good transparency can be had concurrently, and the polypropene composition of preparation method's economy, this also will expand the use range of polypropene composition.
Summary of the invention
An object of the present invention is to provide a kind of polypropene composition, this polypropene composition while not reducing other performance, can have high shock resistance and the good transparency concurrently, and preparation method's economy.
Another object of the present invention is to provide the preparation method of above-mentioned polypropene composition, the method achieves the polypropene composition adopting continuous polymerization preparation to have high shock resistance and the good transparency concurrently.
The invention provides a kind of polypropene composition, with the gross weight of this polypropene composition for benchmark, said composition contains:
The crystalline polypropylene A of (a) 70-95 % by weight, this crystalline polypropylene A is selected from least one in alfon and random copolymer of propylene, with the gross weight of propylene random co-polymer for benchmark, this propylene random co-polymer contains the alpha-olefin structural unit with 4-10 carbon atom of the propylene structural unit of 97-99.9 % by weight, the ethylene unit unit of 0-1 % by weight and 0-2 % by weight, and ethylene unit unit is 0.1-3 % by weight with the total content of the alpha-olefin structural unit with 4-10 carbon atom, and
The ethylene-propylene elastomeric multipolymer B of (b) 5-30 % by weight, with the gross weight of ethylene-propylene elastomeric multipolymer B for benchmark, this ethylene-propylene elastomeric multipolymer B contains the alpha-olefin structural unit with 4-10 carbon atom of the propylene structural unit of 60-92 % by weight, the ethylene unit unit of 8-25 % by weight and 0-15 % by weight
Wherein, the molecular weight distributing index of described polypropene composition and described crystalline polypropylene A is all greater than 4, and the melting index of described polypropene composition is 0.7-1.3 with the ratio of the melting index of described crystalline polypropylene A.
Preferably, described polypropene composition obtains with continuous polymerization under existing at the ziegler natta catalyst with high stereoselective.
Present invention also offers a kind of preparation method of polypropene composition, this preparation method comprises:
(1) under the first olefin polymerization conditions, by the first monomer a and the ziegler natta catalyst contact reacts with high stereoselective, and remove unreacted monomer the mixture obtained after contact reacts, obtain the first mixture containing crystalline polypropylene A; And
(2) under alkene gas-phase polymerization condition, described the first mixture contact reacts containing crystalline polypropylene A that second comonomer b and step (1) are obtained, obtain the second mixture containing crystalline polypropylene A and ethylene-propylene elastomeric multipolymer B, and unreacted monomer is removed from this second mixture, obtain polypropene composition;
Wherein, in step (1), first monomer a contains propylene and optional ethene and/or has the alpha-olefin of 4-10 carbon atom, the crystalline polypropylene A that step (1) is obtained contains the alpha-olefin structural unit with 4-10 carbon atom of the propylene structural unit of 97-100 % by weight, the ethylene unit unit of 0-1 % by weight and 0-2 % by weight
Wherein, in step (2), second comonomer b contains propylene and ethene and/or has the alpha-olefin of 4-10 carbon atom, the ethylene-propylene elastomeric multipolymer B that step (2) is obtained contains the alhpa olefin structural unit that the propylene structural unit of 60-92 % by weight, 8-25 % by weight ethylene unit unit and 0-15 % by weight have 4-10 carbon atom
With the ultimate production of described polypropene composition for benchmark, the weight of the crystalline polypropylene A that step (1) is obtained is 70-95%, the weight of the ethylene-propylene elastomeric multipolymer B that step (2) obtains is 5-30%, described first olefin polymerization conditions and described alkene gas-phase polymerization condition make the molecular weight distributing index of described polypropene composition and described crystalline polypropylene A all be greater than 4, and the melting index of described polypropene composition is 0.7-1.3 with the ratio of the melting index of described crystalline polypropylene A.
Present invention also offers the polypropene composition prepared by aforesaid method.
Present invention provides a kind of goods, these goods are obtained by polypropene composition provided by the invention.
In the prior art, in order to obtain the polypropene composition having high shock resistance and the good transparency concurrently, each component must be prepared respectively, then carry out blended thus obtained in the molten state, or expensive metallocene catalyst must be used to produce transparent impact polypropylene.In the present invention, the polypropene composition provided while not reducing other performance, can have high shock resistance and the good transparency concurrently, thus overcomes the above-mentioned defect existed in prior art.
And method of the present invention can prepare the above-mentioned polypropene composition having high shock resistance and the good transparency concurrently by conventional Ziegler Natta catalyst, significantly reduces production cost.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Fig. 1 is the atomic force microscopy of polypropene composition prepared by embodiment 1.
Fig. 2 is the atomic force microscopy of polypropene composition prepared by embodiment 3.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of polypropene composition, with the gross weight of this polypropene composition for benchmark, said composition contains:
The crystalline polypropylene A of (a) 70-95 % by weight, this crystalline polypropylene A is selected from least one in alfon and random copolymer of propylene, with the gross weight of propylene random co-polymer for benchmark, this propylene random co-polymer contains the alpha-olefin structural unit with 4-10 carbon atom of the propylene structural unit of 97-99.9 % by weight, the ethylene unit unit of 0-1 % by weight and 0-2 % by weight, and ethylene unit unit is 0.1-3 % by weight with the total content of the alpha-olefin structural unit with 4-10 carbon atom, and
The ethylene-propylene elastomeric multipolymer B of (b) 5-30 % by weight, with the gross weight of ethylene-propylene elastomeric multipolymer B for benchmark, this ethylene-propylene elastomeric multipolymer B contains the alpha-olefin structural unit with 4-10 carbon atom of the propylene structural unit of 60-92 % by weight, the ethylene unit unit of 8-25 % by weight and 0-15 % by weight
Wherein, the molecular weight distributing index of described polypropene composition and described crystalline polypropylene A is all greater than 4, and the melting index of described polypropene composition is 0.7-1.3 with the ratio of the melting index of described crystalline polypropylene A.
In the preferred case, described polypropene composition obtains with continuous polymerization under existing at the ziegler natta catalyst with high stereoselective.Described continuous polymerization refers to the step that preparation process comprises at least two orders and carries out, wherein, component (a) (i.e. crystalline polypropylene A) and component (b) (i.e. ethylene-propylene elastomeric multipolymer B) are prepared separately in a separate step, and, except the first step, a rear step is carried out under the established polymkeric substance of previous step and the existence of catalyzer that uses in a previous step.
Under above-mentioned preferable case, because described polypropene composition adopts the ziegler natta catalyst with high stereoselective to obtain, the molecular weight distribution of its molecular weight distribution and its component (a) and component (b) is all greater than 4, be preferably greater than 4.5, be more preferably 4.5-20(" polypropylene handbook " (Chemical Industry Press, in June, 2008 first version, the 15th page).In the present invention, molecular weight distribution represents with the ratio of weight-average molecular weight with number-average molecular weight.
In the present invention, the melting index of described polypropene composition is 0.7-1.3 with the ratio of the melting index of described crystalline polypropylene A, is preferably 0.75-1.2.Particularly, the melting index of described polypropene composition can be 0.1-100g/10min, is preferably 0.5-50g/10min.In the present invention, melting index measures according to ASTMD1238-99 method.
In the preferred case, described polypropene composition contains: the crystalline polypropylene A of (a) 70-90 % by weight, and the ethylene-propylene elastomeric multipolymer B of (b) 10-30 % by weight.
In the present invention, the alpha-olefin of the described 4-10 of a having carbon atom can for this area commonly use various can with the compound of propylene and ethene generation copolymerization, the example can be but be not limited to: at least one in butylene (as 1-butylene), amylene (as 1-amylene), 4-methyl-1-pentene, hexene (as 1-hexene), heptene (as 1-heptene) and octene (as 1-octene), most preferably is 1-butylene.
In described polypropene composition of the present invention, except propylene structural unit, described crystalline polypropylene A can also contain the structural unit of alpha-olefin comonomer.Because co-monomer content is less, described polypropene composition demonstrates good resistance toheat.Described crystalline polypropylene A can be selected from alfon, ethylene-propylene random copolymer containing 0.1-1 % by weight ethylene unit unit or have the random copolymer of propylene of the alhpa olefin structural unit of 4-10 carbon atom containing 0.1-2 % by weight.When described crystalline polypropylene A be above-mentioned optional alfon or random copolymer of propylene time, the fusing point of described crystalline polypropylene A is greater than 150 DEG C, makes described polypropene composition have the fusing point being greater than 150 DEG C, thus demonstrates good resistance toheat.In the preferred case, described crystalline polypropylene A is alfon, and under this preferable case, described polypropene composition has good rigidity and resistance toheat concurrently.
In described polypropene composition of the present invention, described ethylene-propylene elastomeric multipolymer B can containing a small amount of alpha-olefin structural unit with 4-10 carbon atom, such as, with the gross weight of ethylene-propylene elastomeric multipolymer B for benchmark, described ethylene-propylene elastomeric multipolymer B can contain the alpha-olefin structural unit with 4-10 carbon atom of 0.1-15 % by weight, 0.1-5 % by weight or 0.1-3 % by weight.Under preferable case, described ethylene-propylene elastomeric multipolymer B does not comprise the alpha-olefin structural unit with 4-10 carbon atom substantially; Further preferably, with the gross weight of described ethylene-propylene elastomeric multipolymer B for benchmark, described ethylene-propylene elastomeric multipolymer B contains the propylene structural unit of 75-92 % by weight and the ethylene unit unit of 8-25 % by weight; Still more preferably, described ethylene-propylene elastomeric multipolymer B contains the ethylene unit unit of 10-18 % by weight and the propylene structural unit of 82-90 % by weight.
Described polypropene composition of the present invention, can observe described polypropene composition by atomic force microscope and have two phase structure.Described ethylene-propylene elastomeric multipolymer B is preferably less than the Granular composite of 0.5 μm in described polypropene composition with median size.In the present invention, described median size (i.e. granular size) is determined by atomic force microscopy.
In the present invention, the mist degree of described polypropene composition is preferably less than 60%, is more preferably less than 30%, is preferably less than 20% further.Described mist degree records according to ASTM D1003 method, the result namely recorded on the injected sample thin slice of 1mm.
In the present invention, with the gross weight of polypropene composition for benchmark, this polypropene composition can also contain the nucleator of 0.1-1 % by weight.Described nucleator can be the nucleator that various this area routine uses, such as: two (2,4-di-tert-butyl-phenyl) sodium phosphate, 2,2 '-methylene radical-two (4,6-di-n-butyl phenol) the aryl phosphoric acids salt nucleator such as sodium phosphate, methylene-bis (2,4-di-tert-butyl-phenyl) aluminum phosphate; The Sorbitol Nucleators such as the derivative that two benzal sorbyl alcohols or its alkyl replace, can enumerate Millad3905, Millad3940 and Millad3988 etc. of Milliken company as commercially available product; Carboxylic acid metal's salt nucleators such as Sodium Benzoate, p-tert-butyl benzoic acid carboxyl aluminium.Polypropene composition containing nucleator has higher modulus in flexure and the transparency.
In the present invention, described polypropene composition can also containing oxidation inhibitor to improve the antioxidant of polypropene composition.The various oxidation inhibitor that described oxidation inhibitor can be commonly used for this area, are not particularly limited.Usually, described oxidation inhibitor can be the combination of primary antioxidant and auxiliary antioxidant, and wherein, described primary antioxidant has the function of catching polymkeric substance peroxy radical, can be selected from hindered phenol system oxidation inhibitor; Described auxiliary antioxidant can hydroperoxide effectively in decomposing copolymer, prevent its homolysis from producing new free radical, cause the carrying out of Auto-oxidation reaction, such as can one or more for being selected from phosphorous acid ester system oxidation inhibitor and monothioester system oxidation inhibitor.In the present invention, the example of described oxidation inhibitor can include but not limited to: 2, 6-di-tert-butyl-4-methy phenol, β-(3, 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester is (namely, antioxidant 1010), two [the 3-(3 of sulfo-diethylene, 5-di-tert-butyl-hydroxy phenyl) propionic ester, 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1, 3, 5-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl)-1, 3, 5-triazine-2, 4, 6 (1H, 3H, 5H)-triketone, three (2-methyl-4-hydroxyl-5-tert.-butylbenzene) butane and 2, 2 '-methylene-bis (4-methyl-6-tert-butylphenol).Particularly, the example of described auxiliary antioxidant can be but be not limited to: three [2,4-di-tert-butyl-phenyl] phosphorous acid ester is (namely, irgasfos 168), four (2,4-di-tert-butylphenol)-4,4 '-xenyl diphosphites, three nonylated phenyl phosphorous acid esters, two (2,4-DTBP) pentaerythritol diphosphites, the two octadecyl of thio-2 acid and Tyox B.From the angle improving further antioxidant property, described antioxidant preferably using described phenol system oxidation inhibitor as primary antioxidant, using phosphorous acid ester and/or monothioester as auxiliary antioxidant.The ratio of described primary antioxidant and described auxiliary antioxidant can be that the routine of this area is selected.Usually, the weight ratio of described primary antioxidant and described auxiliary antioxidant can be 1:0.5-2.The content of described oxidation inhibitor can be the routine selection of this area, and such as: with the gross weight of polypropene composition for benchmark, the content of described oxidation inhibitor can be 0.15-0.8 % by weight, is preferably 0.2-0.4 % by weight.
In the present invention, described polypropene composition can also containing static inhibitor to improve the static resistance of polypropene composition.Static inhibitor can be but be not limited to mono-glycerides class, oxyethyl group amine.The content of described static inhibitor can be the routine selection of this area, and such as: with the gross weight of polypropene composition for benchmark, the content of described static inhibitor can be 0.02-1 % by weight.
In the present invention, composition of the present invention can also containing tinting material to improve the aesthetic property of polypropene composition.Tinting material adds according to the needs of end article usually.
The invention provides a kind of preparation method of polypropene composition, this preparation method can comprise the following steps:
(1) under the first olefin polymerization conditions, by the first monomer a and the ziegler natta catalyst contact reacts with high stereoselective, and remove unreacted monomer the mixture obtained after contact reacts, obtain the first mixture containing crystalline polypropylene A; And
(2) under alkene gas-phase polymerization condition, described the first mixture contact reacts containing crystalline polypropylene A that second comonomer b and step (1) are obtained, obtain the second mixture containing crystalline polypropylene A and ethylene-propylene elastomeric multipolymer B, and unreacted monomer is removed from this second mixture, obtain polypropene composition;
Wherein, in step (1), first monomer a contains propylene and optional ethene and/or has the alpha-olefin of 4-10 carbon atom, the crystalline polypropylene A that step (1) is obtained contains the alpha-olefin structural unit with 4-10 carbon atom of the propylene structural unit of 97-100 % by weight, the ethylene unit unit of 0-1 % by weight and 0-2 % by weight
Wherein, in step (2), second comonomer b contains propylene and ethene and/or has the alpha-olefin of 4-10 carbon atom, the ethylene-propylene elastomeric multipolymer B that step (2) is obtained contains the alhpa olefin structural unit that the propylene structural unit of 60-92 % by weight, 8-25 % by weight ethylene unit unit and 0-15 % by weight have 4-10 carbon atom
With the ultimate production of described polypropene composition for benchmark, the weight of the crystalline polypropylene A that step (1) is obtained is 70-95%, the weight of the ethylene-propylene elastomeric multipolymer B that step (2) obtains is 5-30%, described first olefin polymerization conditions and described alkene gas-phase polymerization condition make the molecular weight distributing index of described polypropene composition and described crystalline polypropylene A all be greater than 4, and the melting index of described polypropene composition is 0.7-1.3 with the ratio of the melting index of described crystalline polypropylene A.
In the preferred case, by controlling described first olefin polymerization conditions and described alkene gas-phase polymerization condition makes the melting index of described polypropene composition be 0.1-100g/10min, 0.5-50g/10min is more preferably.Described first olefin polymerization conditions and described alkene gas-phase polymerization condition make the melting index of described polypropene composition be 0.75-1.3 with the ratio of the melting index of described crystalline polypropylene A, are preferably 0.75-1.2.
In described method provided by the invention, described in have 4-10 carbon atom alpha-olefin can with describe above identical.
The present inventor finds in research process: when adopting ziegler natta catalyst at least to comprise the propylene polymerization of two sequential steps, by controlling polymerizing condition, make the melting index of polypropene composition and crystalline polypropylene A than in specified range and by the specific composition of crystallization control polypropylene A and ethylene-propylene elastomeric multipolymer B and content, the polypropene composition of formation can have the high transparency and resistance to impact shock.
Preparation in accordance with the present invention, in one embodiment, described first monomer a is propylene, makes the crystalline polypropylene A obtained under the first olefin polymerization conditions be alfon.
Preparation in accordance with the present invention, in a preferred embodiment, described second comonomer b is propylene and ethene, makes the ethylene-propylene elastomeric multipolymer B obtained under alkene gas-phase polymerization condition contain the propylene structural unit of 75-92 % by weight and the ethylene unit unit of 8-25 % by weight; Further preferably, ethylene-propylene elastomeric multipolymer B is made to contain the propylene structural unit of 82-90 % by weight and the ethylene unit unit of 10-18 % by weight.
In the present invention, " there is the ziegler natta catalyst of high stereoselective " and refer to the catalyzer can prepared isotactic index and be greater than the alfon of 95%.
According to method of the present invention, described in have that the ziegler natta catalyst of high stereoselective can commonly use for this area variously can carry out the catalyzer of isotactic polymerization by catalyzing propone.Usually, described in there is high stereoselective ziegler natta catalyst contain: the solid catalyst active ingredient of (1) titaniferous, its main component is magnesium, titanium, halogen and internal electron donor; (2) organo-aluminium compound cocatalyst component; And the external electron donor component that (3) are optional.
The operational this kind of specific examples containing active solid catalyst component is disclosed in CN85100997, CN98126383.6, CN98111780.5, CN98126385.2, CN93102795.0, CN00109216.2, CN99125566.6, CN99125567.4, CN02100900.7.Described catalyzer can directly use, and also can add after pre-complexing and prepolymerization.Catalyzer described in CN85100997, CN98111780.5 and CN02100900.7, has advantage especially for catalyzer of the present invention.
Organo-aluminium compound as the cocatalyst component of catalyzer is preferably alkylaluminium cpd, is more preferably selected from least one in trialkylaluminium (as: trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, trioctylaluminum etc.), aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, dichloro one aluminium triethyl and ethyl aluminum dichloride.
With Ti/Al molar ratio computing, the solid catalyst active ingredient of titaniferous and the ratio of organo-aluminium compound cocatalyst component can be 1:25 to 1:1000.
The external donor compound of catalyst component is optionally preferably silicoorganic compound, and its general formula is R
nsi (OR')
4-n, 0 < n≤3 in formula, wherein, R and R' is identical or different, and is selected from alkyl, cycloalkyl, aryl and haloalkyl independently of one another, and R also can be halogen or hydrogen atom.Particularly, described silicoorganic compound can be but be not limited only to: tetramethoxy-silicane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, isopropyl methyl dimethoxysilane, two phenoxy group dimethoxysilane, diphenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, 2-ethyl piperidine base-2-t-butyldimethoxysilane, (1, 1, the fluoro-2-propyl group of 1-tri-)-2-ethyl piperidine base dimethoxysilane, (1, 1, the fluoro-2-propyl group of 1-tri-)-methyl dimethoxysilane etc.
With Al/Si molar ratio computing, described alkylaluminium cpd can be 3:1 to 100:1 with the ratio of described silicoorganic compound.
Described three kinds of components with the ziegler natta catalyst of high stereoselective can directly join in polymerization reactor, also after the known pre-complexing of industry and/or prepolymerization, then can join in reactor.Prepolymerization can be carried out continuously under liquid-phase bulk condition, also can carry out in inert solvent discontinuous.Pre-polymerization reactor can be continuous stirred tank, annular-pipe reactor etc.Prepolymerized temperature can control between-10 to 60 DEG C, and preferred temperature is 0 to 40 DEG C.Prepolymerized multiple can control at 0.5 to 1000 times, and preferred multiple is 1.0 to 500 times.
Preparation in accordance with the present invention, the first olefinic polymerization and alkene gas-phase polymerization can carry out continuously, also may be carried out batchwise.Successive polymerization can use plural tandem reactor to carry out.
First olefinic polymerization can be carried out in liquid phase, also can carry out in gas phase.First olefinic polymerization reactor used can be Liquid-phase reactor, also can be Gas-phase reactor.Liquid-phase reactor can be annular-pipe reactor and stirred-tank reactor etc., and Gas-phase reactor can be horizontal type agitated bed reactor, vertical mixing bed bioreactor and fluidized-bed reactor etc., and above Liquid-phase reactor and Gas-phase reactor also can at random matched combined.
Preparation in accordance with the present invention, described first olefin polymerization conditions can comprise: temperature is 50-100 DEG C, is preferably 60-95 DEG C; Pressure is 1-8MPa, is preferably 1.2-5.5MPa; Time is 30-180 minute, is preferably 45-120 minute.In the present invention, pressure refers to reactor gauge pressure.
The reactor of alkene gas-phase polymerization can be horizontal type agitated bed reactor, vertical mixing bed bioreactor, fluidized-bed reactor etc., and above Gas-phase reactor can at random matched combined.
Preparation in accordance with the present invention, described alkene gas-phase polymerization condition can comprise: temperature is 50-100 DEG C, is preferably 60-95 DEG C; Pressure is 1-4MPa, is preferably 1.2-3.5MPa; Time is 10-180 minute, is preferably 10-90 minute.
In the present invention, the preparation method of described polypropene composition can also comprise: carry out granulation to the polypropene composition that step (2) obtains, and adds nucleator when polypropene composition granulation.Preferably, the nucleator of 0.1-1 % by weight (preferred 0.2-0.5 % by weight) is contained in the polypropene composition that the consumption of described nucleator obtains after making granulation.Described nucleator can with describe above identical.
In the present invention, in order to improve the antioxidant of the polypropene composition of preparation, when the preparation method of described polypropene composition can also be included in polypropene composition granulation, add oxidation inhibitor.Preferably, the oxidation inhibitor of 0.15-0.8 % by weight (preferred 0.2-0.4 % by weight) is contained in the polypropene composition that the consumption of described oxidation inhibitor obtains after making granulation.Described oxidation inhibitor can with describe above identical.
In the present invention, other auxiliary agents such as static inhibitor and/or tinting material are added when the preparation method of described polypropene composition can also be included in polypropene composition granulation.
Present invention also offers the polypropene composition prepared by aforesaid method.
Present invention also offers the goods be made up of above-mentioned polypropene composition.These goods have the good transparency and shock resistance.Described goods can be cold storage container, freezing container, food container, extrusion moulding product, blow-molded article, fiber, film, thin slice or bottle stopper.
Below will be described the present invention by embodiment.
Experimental result in embodiment obtains according to following testing method, all operates under room temperature environment in following testing method when being not particularly limited:
Melting index (MFR): according to ASTM D1238,230 DEG C, measure under 2.16kg load.
Co-monomer content: measure by fourier infrared method.
Xylene soluble content: measure by ASTM D5492-98.
Melting temperature (Tm): use the DSC7 type differential scanning calorimeter instrument of Perkin Elmer company to measure, test specification is from 50 DEG C to 200 DEG C, first sample is risen to 200 DEG C to eliminate thermal history by the speed of 10 DEG C/min, 50 DEG C are down to again by the speed of 10 DEG C/min, record its Tc and crystallization enthalpy, rise to 200 DEG C by the speed of 10 DEG C/min again, record its fusing point and melting enthalpy.
Tensile strength: measure injected sample according to ASTM D638.
Modulus in flexure: measure injected sample according to ASTM D790.
Cantilever beam impact strength (Izod notch shock): according to ASTD D256, measures injected sample respectively at 23 DEG C and-20 DEG C.
Heat-drawn wire (HDT): measure according to ASTM D648.
Mist degree: according to ASTM D1003, measures the mist degree of the injected sample of 1 mm thick.
Transmittance: according to ASTM D1003, measures the transmittance of the injected sample of 1 mm thick.
Atomic force microscopy: polypropylene injection moulding batten is ultrathin section(ing) after cryogenic freezing is to subzero 50 degrees Celsius, observes tangent plane.Vecco company of U.S. Naonscope IIIa type multiple mode scanning force microscope, J scanner head, tapping-mode, sweep limit 10 microns × 10 microns or 5 microns × 5 microns, gather phasor.
Molecular weight distributing index Mw/Mn: adopt Polymer Laboratories company of Britain to produce the molecular weight distribution of PL-GPC220 gel permeation chromatograph working sample, chromatographic column is 3 series connection Plgel10 μm of MIXED-B post, solvent and moving phase are 1,2,4-trichlorobenzene, column temperature 150 DEG C, adopt PL company EasiCal PS-1 Narrow distribution polystyrene standard specimen to carry out universal calibration, detector adopts the infrared concentration detector of IR5 of POLYCHAR company.
Polypropene composition in the present invention and embodiment obtains by the following method, and material amounts wherein and polymeric reaction condition are listed in table 1.
Polyreaction is carried out on set of horizontal type gas phase polypropylene pilot plant, polymerization reactor be two series connection Horizontal stirring reactors, polymerization process and step as follows:
Primary Catalysts (the active solid catalyst component of titaniferous) adopts the method that in CN1258683A, embodiment 1 describes to obtain, and internal electron donor compound wherein adopts diisobutyl phthalate.
Primary Catalysts, promotor (triethyl aluminum), external electron donor add Horizontal stirring reactor continuously and carry out polyreaction under the carrying of propylene.Catalyzer enters from first stirring tank front end, and under the condition of gas phase, polymerization generates crystalline polypropylene A, and reaction heat is vaporized by the propylene sprayed and taken away.The polymkeric substance generated is discharged by the end of stirring tank.Catalyzer and polymkeric substance move in reactor in the mode close to plug flow, and polymerization temperature is 66 DEG C, reaction pressure 2.3MPa, and the residence time is 90 minutes.
Polymkeric substance is discharged from first reactor, by being equipped with the equipment of transfer between two reactors, polymkeric substance is transferred to second Horizontal stirring reactor.Polymkeric substance enters from second stirring tank front end, and under the condition of gas phase, polymerization generates ethylene-propylene elastomeric multipolymer B, and reaction heat is vaporized by the propylene sprayed and taken away.The polymkeric substance generated is discharged by the end of stirring tank.Catalyzer and polymkeric substance move in reactor in the mode close to plug flow, and polymerization temperature is 66 DEG C, reaction pressure 2.2MPa, are 60 minutes during stop.
The polymkeric substance be obtained by reacting, after degassed, wet nitrogen deactivation process, obtains polymeric articles.
Adopt hydrogen as molecular weight regulator in two reactors, use the composition (ethene, propylene, butylene and hydrogen) of gas in the continuous analysis reactor of gas-chromatography
The calcium stearate (purchased from Ciba company limited) of the IRGAFOS168 additive (purchased from Ciba company limited) of 0.1 weight part, the IRGANOX1010 additive (purchased from Ciba company limited) of 0.1 weight part and 0.05 weight part is added respectively in powder according to obtained polypropene composition 100 weight part, and the Millad3988 additive (concrete consumption is see table 2) added purchased from Milliken company, use twin screw extruder granulation.
Injection moulding machine preparation meets the injected sample of ASTM standard, and measures its physical properties, and measurement result is as shown in table 2.
Comparative example 1
Polyreaction is carried out on above-mentioned horizontal pneumatic heterophasic polypropylene pilot plant, and reaction is carried out according to the method described above.The external electron donor adopted is diisopropyl dimethoxy silane, and the first reactor polyreaction is propylene homo, and polymerization temperature is 66 DEG C, reaction pressure 2.3MPa, and the residence time is 90 minutes.Second reactor also carries out propylene homo, and polymerization temperature is 66 DEG C, reaction pressure 2.2MPa, and the residence time is 60 minutes.The polymkeric substance be obtained by reacting, after degassed, wet nitrogen deactivation process, obtains polymeric articles.Reaction conditions and product property as shown in table 1.Product adds additive granulation, and after making injected sample, test performance is as shown in table 2.
Comparative example 2
Carry out polyreaction according to the method for comparative example 1, be second, isobutyl dimethoxy silane unlike the external electron donor adopted, and do not use the second reactor, reaction conditions and product property as shown in table 1.Product adds additive granulation, and after making injected sample, test performance is as shown in table 2.
Embodiment 1
Polyreaction is carried out on above-mentioned horizontal pneumatic heterophasic polypropylene pilot plant, and reaction is carried out according to the method described above.The external electron donor that polyreaction adopts is second, isobutyl dimethoxy silane, and the first reactor is that propylene homo prepares component (a), and polymerization temperature is 66 DEG C, reaction pressure 2.3MPa, and the residence time is 90 minutes.Second reactor is that copolymerization of propylene prepares component (b), adds ethene and propylene in reactor, and polymerization temperature is 66 DEG C, reaction pressure 2.2MPa, and the residence time is 60 minutes.The polymkeric substance be obtained by reacting, after degassed, wet nitrogen deactivation process, obtains polypropene composition.Reaction conditions and product property as shown in table 1.Polypropene composition adds additive granulation, and after making injected sample, test performance is as shown in table 2.As shown in Figure 1, as can be seen from the figure, described polypropene composition has two phase structure to the atomic force microscopy of the polypropene composition of preparation, and shows that component (b) is highly dispersed in composition with the particle diameter of about 0.2 micron.
Embodiment 2
Polyreaction is carried out on above-mentioned horizontal pneumatic heterophasic polypropylene pilot plant, and reaction is carried out according to the method described above.The external electron donor that polyreaction adopts is diisopropyl dimethoxy silane, and the first reactor is that propylene homo prepares component (a), and polymerization temperature is 66 DEG C, reaction pressure 2.3MPa, and the residence time is 90 minutes.Second reactor is that copolymerization of propylene prepares component (b), adds ethene and propylene in reactor, and polymerization temperature is 66 DEG C, reaction pressure 2.2MPa, and the residence time is about 60 minutes.The polymkeric substance be obtained by reacting, after degassed, wet nitrogen deactivation process, obtains polypropene composition.Reaction conditions and product property as shown in table 1.Polypropene composition adds additive granulation, and after making injected sample, test performance is as shown in table 2.
Embodiment 3
Polypropene composition is prepared, unlike the composition and the content that change component (b) according to the method for embodiment 2.Reaction conditions and product property as shown in table 1.Product adds additive granulation, and after making injected sample, test performance is as shown in table 2.As shown in Figure 2, as can be seen from the figure, described polypropene composition has two phase structure to the atomic force microscopy of the polypropene composition of preparation, and shows that component (b) is highly dispersed in composition with the particle diameter of about 0.3 micron.
Embodiment 4
Polypropene composition is prepared, unlike the composition and the content that change component (b) according to the method for embodiment 2.Reaction conditions and product property as shown in table 1.Product adds additive granulation, and after making injected sample, test performance is as shown in table 2.
Embodiment 5
Prepare polypropene composition according to the method for embodiment 1, the external electron donor of employing is second, isobutyl dimethoxy silane, unlike the composition and the content that change component (b).Reaction conditions and product property as shown in table 1.Product adds additive granulation, and after making injected sample, test performance is as shown in table 2.
Embodiment 6
Polyreaction is carried out on above-mentioned horizontal pneumatic heterophasic polypropylene pilot plant, and reaction is carried out according to the method described above.The external electron donor that polyreaction adopts is Cyclohexyl Methyl Dimethoxysilane, and the first reactor is that propylene homo prepares component (a), and polymerization temperature is 66 DEG C, reaction pressure 2.3MPa, and the residence time is 90 minutes.Second reactor is that copolymerization of propylene prepares component (b), adds ethene, propylene and butylene in reactor, and polymerization temperature is 66 DEG C, reaction pressure 2.2MPa, and the residence time is 60 minutes.The polymkeric substance be obtained by reacting, after degassed, wet nitrogen deactivation process, obtains polypropene composition.Reaction conditions and product property as shown in table 1.Polypropene composition adds additive granulation, and after making injected sample, test performance is as shown in table 2.
Table 1
Note: P is diisopropyl dimethoxy silane; B is second, isobutyl dimethoxy silane; C is Cyclohexyl Methyl Dimethoxysilane; MFR
a+b/ MFR
arefer to the melting index ratio of polypropene composition and crystalline polypropylene A.
Table 2
As can be seen from the result of table 1 and table 2, polypropene composition of the present invention is improved largely relative to the homo-polypropylene shock resistance of comparative example, while not reducing other performance, has the good transparency concurrently.
Claims (19)
1. a polypropene composition, is characterized in that, with the gross weight of this polypropene composition for benchmark, said composition contains:
The crystalline polypropylene A of (a) 70-95 % by weight, this crystalline polypropylene A is selected from least one in alfon and random copolymer of propylene, with the gross weight of propylene random co-polymer for benchmark, this propylene random co-polymer contains the alpha-olefin structural unit with 4-10 carbon atom of the propylene structural unit of 97-99.9 % by weight, the ethylene unit unit of 0-1 % by weight and 0-2 % by weight, and ethylene unit unit is 0.1-3 % by weight with the total content of the alpha-olefin structural unit with 4-10 carbon atom, and
The ethylene-propylene elastomeric multipolymer B of (b) 5-30 % by weight, with the gross weight of ethylene-propylene elastomeric multipolymer B for benchmark, this ethylene-propylene elastomeric multipolymer B contains the alpha-olefin structural unit with 4-10 carbon atom of the propylene structural unit of 60-92 % by weight, the ethylene unit unit of 8-25 % by weight and 0-15 % by weight
Wherein, the molecular weight distributing index of described polypropene composition and described crystalline polypropylene A is all greater than 4, and the melting index of described polypropene composition is 0.7-1.3 with the ratio of the melting index of described crystalline polypropylene A.
2. polypropene composition according to claim 1, wherein, described polypropene composition obtains with continuous polymerization under existing at the ziegler natta catalyst with high stereoselective.
3. polypropene composition according to claim 1, wherein, with the gross weight of this polypropene composition for benchmark, said composition contains:
The crystalline polypropylene A of (a) 70-90 % by weight, and
The ethylene-propylene elastomeric multipolymer B of (b) 10-30 % by weight.
4. according to the polypropene composition in claim 1-3 described in any one, wherein, described crystalline polypropylene A is alfon.
5. according to the polypropene composition in claim 1-3 described in any one, wherein, with the gross weight of described ethylene-propylene elastomeric multipolymer B for benchmark, this ethylene-propylene elastomeric multipolymer B contains the ethylene unit unit of 10-18 % by weight and the propylene structural unit of 82-90 % by weight.
6. according to the polypropene composition in claim 1-3 described in any one, wherein, the melting index of described polypropene composition is 0.1-100g/10min.
7. according to the polypropene composition in claim 1-4 described in any one, wherein, with the gross weight of this polypropene composition for benchmark, the nucleator of described polypropene composition also containing 0.1-1 % by weight.
8. the mist degree that according to the polypropene composition in claim 1-4 described in any one, wherein, described polypropene composition measures according to ASTM D1003 method is less than 60%.
9. according to the polypropene composition in claim 1-4 described in any one, wherein, described ethylene-propylene elastomeric multipolymer B is less than the Granular composite of 0.5 μm in described polypropene composition with median size.
10. a preparation method for polypropene composition, this preparation method comprises the following steps:
(1) under the first olefin polymerization conditions, by the first monomer a and the ziegler natta catalyst contact reacts with high stereoselective, and remove unreacted monomer the mixture obtained after contact reacts, obtain the first mixture containing crystalline polypropylene A; And
(2) under alkene gas-phase polymerization condition, described the first mixture contact reacts containing crystalline polypropylene A that second comonomer b and step (1) are obtained, obtain the second mixture containing crystalline polypropylene A and ethylene-propylene elastomeric multipolymer B, and unreacted monomer is removed from this second mixture, obtain polypropene composition;
Wherein, in step (1), first monomer a contains propylene and optional ethene and/or has the alpha-olefin of 4-10 carbon atom, the crystalline polypropylene A that step (1) is obtained contains the alpha-olefin structural unit with 4-10 carbon atom of the propylene structural unit of 97-100 % by weight, the ethylene unit unit of 0-1 % by weight and 0-2 % by weight
Wherein, in step (2), second comonomer b contains propylene and ethene and/or has the alpha-olefin of 4-10 carbon atom, the ethylene-propylene elastomeric multipolymer B that step (2) is obtained contains the alhpa olefin structural unit that the propylene structural unit of 60-92 % by weight, 8-25 % by weight ethylene unit unit and 0-15 % by weight have 4-10 carbon atom
With the ultimate production of described polypropene composition for benchmark, the weight of the crystalline polypropylene A that step (1) is obtained is 70-95%, the weight of the ethylene-propylene elastomeric multipolymer B that step (2) obtains is 5-30%, described first olefin polymerization conditions and described alkene gas-phase polymerization condition make the molecular weight distributing index of described polypropene composition and described crystalline polypropylene A all be greater than 4, and the melting index of described polypropene composition is 0.7-1.3 with the ratio of the melting index of described crystalline polypropylene A.
11. methods according to claim 10, wherein, the crystalline polypropylene A that step (1) obtains is alfon.
12. methods according to claim 10, wherein, the ethylene-propylene elastomeric multipolymer B that step (2) obtains contains the ethylene unit unit of 10-18 % by weight and the propylene structural unit of 82-90 % by weight.
13. according to the method in claim 10-12 described in any one, wherein, described in there is 4-10 carbon atom alpha-olefin be 1-butylene.
14. methods according to claim 10, wherein, described first olefin polymerization conditions comprises: temperature is 50-100 DEG C, and pressure is 1-8MPa, and the time is 30-180 minute.
15. methods according to claim 10, wherein, described alkene gas-phase polymerization condition comprises: temperature is 50-100 DEG C, and pressure is 1-4MPa, and the time is 10-180 minute.
16. according to the method in claim 10-15 described in any one, wherein, the polypropene composition that described method also comprises step (2) obtains carries out granulation, and add nucleator when polypropene composition granulation, the nucleator containing 0.1-1 % by weight in the polypropene composition obtained after the consumption of described nucleator makes granulation.
17. polypropene compositions prepared by the method in claim 10-16 described in any one.
18. 1 kinds of goods, these goods are obtained by the polypropene composition in claim 1-9 and 17 described in any one.
19. goods according to claim 18, wherein, described goods are cold storage container, freezing container, food container, extrusion moulding product, blow-molded article, fiber, film, thin slice or bottle stopper.
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