CN105623078A - Polymer membrane and preparation method thereof - Google Patents
Polymer membrane and preparation method thereof Download PDFInfo
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- CN105623078A CN105623078A CN201410608743.7A CN201410608743A CN105623078A CN 105623078 A CN105623078 A CN 105623078A CN 201410608743 A CN201410608743 A CN 201410608743A CN 105623078 A CN105623078 A CN 105623078A
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Abstract
The invention discloses a polymer membrane, and a preparation method thereof. The polymer membrane is composed of a polypropylene composition; and the polypropylene composition contains, (a) 40 to 70wt% of a crystalline polypropylene A, wherein the crystalline polypropylene A is at least one selected from a propylene homopolymer and a propylene random copolymer, and (b) 30 to 60wt% of an ethylene-propylene elastic copolymer B. The molecular weight distribution indexes of the polypropylene composition and the crystalline polypropylene A are both larger than 4; melt mass-flow rate of the polypropylene composition at 230 DEG C under loading of 2.16kg ranges from 5 to 10g/10min, and the ratio of the melt mass-flow rate ratio of the polypropylene composition to the melt mass-flow rate ratio of the crystalline polypropylene A ranges from 0.7 to 1.3; the polymer membrane contains a nucleating agent; and in 100 weight parts of the polypropylene composition, the content of the nucleating agent ranges from 200 to 2000ppm. The polymer membrane possesses relatively high transparency, excellent shock resistance, and excellent performance uniformity in the axial direction and the radial direction.
Description
Technical field
The present invention relates to a kind of polymeric film and the preparation method of this polymeric film.
Background technology
TPO thin film is widely used in fields such as packaging for foodstuff, refrigeration package, frozen-pack, medical apparatus and instruments, article of everyday use packagings, and these fields usually require that thin film has the good transparency. Obtain the thin film made by propylene copolymer with the monomer random copolymerization such as ethylene, butylene and generally there is good transparency, in HOPP, add transparencizing agent also can prepare the thin film of the high grade of transparency. But as packing film, should also have good erosion-resisting characteristics, to prevent thin film from being destroyed under external force percussion. Random polypropylene and HOPP are limited to its molecular structure, and shock resistance is all not ideal enough.
In order to improve the shock resistance of thin film, CN1675257A mentions interpolation 10-50% ultra-low density polyethylene (ULDPE) in syndiotactic polypropylene and improves the impact property of thin film, although this method can improve shock resistance while keeping the transparency, but syndiotactic polypropylene and ULDPE production method are complex, and ULDPE addition is high, cause that production process is complex, it is easy to go wrong, and this method is relatively costly. CN1861674A refer to the ethylene-propylene elastomeric copolymers of highly crystalline random copolymer and the 5-20% adopting 80-95% blended, thus improving erosion-resisting characteristics and the transparency of goods, but first the method needs blending step, second said composition main body is random copolymer, rigidity and the heat resistance of goods can be reduced, and for packing film, it is necessary to rigidity and deflection make it not easily pleating in rolling and packaging process preferably.
In order to improve erosion-resisting characteristics and the toughness of thin film, thin film is prepared also by multi-layer co-extruded method, just have employed three-layer co-extruded method such as CN101913279A and prepare laminated film, thin film middle level is the elastomer blended in 1:10-1:3 ratio and PP, good shock resistance is provided by elastomer, but this method one is both to have needed to be layered to carry out the blended of different formulations, two is exist when elastomer content is higher to be difficult to finely dispersed possibility, and influences whether optics and the mechanical property of thin film.
Usual impact polypropylene is by ziegler natta catalyst preparation in multi-step polymerization reacts. In the impact polypropylene that the method produces, ethylene-propylene elastomeric copolymer and HOPP can be separated and cause that the mist degree of final products increases, additionally, it is generally of very uneven composition, so this copolymer does not generally have the transparency by the binary ethylene-propylene elastomeric copolymer of Conventional Ziegler-Natta catalyst preparing. This Film Haze resulting in the production of common impact polypropylene is significantly high, it is impossible to meet the requirement simultaneously improving thin film erosion-resisting characteristics and the transparency.
Metallocene catalyst is adopted to produce impact polypropylene, although toughness and transparency product all preferably can be obtained, but metallocene catalyst is relatively costly relative to Ziegler-Natta catalyst, and cannot produce with most polyolefin device. Owing to the polypropylene molecule amount distribution of preparation is very narrow, the processing fluidity in film-forming process is poorer than the polypropylene that Ziegler-Natta catalyst produces, and therefore cannot be widely used.
Accordingly, it would be desirable to a kind of transparency and shock resistance are good, and there is the thin film of high stiffness and deflection, method for preparing raw material economy that this kind of thin film adopts and strong adaptability, and film-forming process relative ease.
Summary of the invention
The inventors found that, the content increasing ethylene-propylene elastomeric copolymer can improve the erosion-resisting characteristics of thin film, but under ziegler natta catalyst exists, during the polypropene composition of high ethylene-propylene elastomeric copolymer level prepared with continuous polymerization, the ethylene-propylene elastomeric molecular weight of copolymer that copolymer uses is all smaller, this makes ethylene-propylene elastomeric copolymer particle be easier to tacky situation occur, so adopting continuous polymerization to be difficult to obtain ethylene-propylene elastomeric copolymer level account for the polypropene composition of more than polypropene composition gross weight 30 weight %, and polymer itself is tacky that film surface also can be made tacky, preparation to thin film, rolling and use procedure cause difficulty, also the use safety of thin film can be jeopardized. and so high ethylene-propylene elastomeric copolymer level can have a strong impact on optical property and the deflection of thin film.
In order to solve the problems referred to above of prior art, the invention provides a kind of polymeric film and the preparation method of this polymeric film.
According to the first aspect of the invention, the invention provides a kind of polymeric film, this polymeric film is formed by polypropene composition, and described polypropene composition contains:
The crystalline polypropylene A of (a) 40-70 weight %, this crystalline polypropylene A at least one in Noblen and random copolymer of propylene, with the gross weight of propylene random co-polymer for benchmark, the alpha-olefin construction unit with 4-10 carbon atom of propylene construction unit, the ethylene unit unit of 0-6 weight % and 0-12 weight % that this propylene random co-polymer contains 82-99.9 weight %, and the total content of ethylene unit unit and the alpha-olefin construction unit with 4-10 carbon atom is 0.1-18 weight %;
The ethylene-propylene elastomeric copolymer B of (b) 30-60 weight %, with the gross weight of ethylene-propylene elastomeric copolymer B for benchmark, the alpha-olefin construction unit with 4-10 carbon atom of propylene construction unit, the ethylene unit unit of 8-25 weight % and 0-15 weight % that this ethylene-propylene elastomeric copolymer B contains 60-92 weight %
Wherein, the molecular weight distributing index of described polypropene composition and described crystalline polypropylene A is all higher than 4, described polypropene composition melt mass flow rate at 230 DEG C, under 2.16kg load effect is 5-10g/10min, is 0.7-1.3 with the ratio of the melt mass flow rate of described crystalline polypropylene A;
And described polymeric film contains nucleator, relative to the described polypropene composition of 100 weight portions, the content of described nucleator is 200-2000ppm.
According to the second aspect of the invention, the preparation method that the invention provides above-mentioned polymeric film, the method comprises the following steps:
(1) under the first olefin polymerization conditions, by the first monomer a and the ziegler natta catalyst haptoreaction with high stereoselective, and the mixture obtained after haptoreaction removes unreacted monomer, obtain the first mixture containing crystalline polypropylene A, wherein, described first monomer a contains propylene and optional ethylene and/or has the alpha-olefin of 4-10 carbon atom;
(2) when alkene gas-phase polymerization, by second comonomer b described the first mixture haptoreaction containing crystalline polypropylene A obtained with step (1), obtain the second mixture containing crystalline polypropylene A and ethylene-propylene elastomeric copolymer B, and remove unreacted monomer from this second mixture, obtain polypropene composition, wherein, described second comonomer b contains propylene and ethylene and/or has the alpha-olefin of 4-10 carbon atom, obtains polypropene composition;
(3) polypropene composition nucleator, step (2) obtained and optional antioxidant and coalescents mix and extruding pelletization, and the pellet obtained is made polymeric film.
According to the third aspect of the present invention, present invention also offers polymeric film prepared by said method.
The polymeric film of the present invention not only has the higher transparency, and has good shock resistance. It addition, in the polymeric film of the present invention, ethylene-propylene elastomeric copolymer can be distributed in crystalline polypropylene matrix with less size uniform, it is ensured that this polymeric film axially and radially goes up the uniformity of performance.
In the preparation process in accordance with the present invention: first, the preparation process of polypropene composition can a step complete, it is not necessary to uses multiple different component to carry out proportioning blended, enormously simplify the flow process that elastomer selects and processes; Secondly, only need to adopt Ziegler-Natta catalyst, ethylene-propylene elastomeric copolymer just can be made to be distributed in crystalline polypropylene matrix with less size uniform, compared with preparing polyacrylic technique with use metallocene catalyst, this method reduce production cost, the impact resistance that thin film is high can either be given, the transparency of its excellence can be kept again.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, is used for explaining the present invention, but is not intended that limitation of the present invention together with detailed description below. In the accompanying drawings:
Fig. 1 is the atomic force microscope images of the polypropene composition of embodiment 1 preparation.
Detailed description of the invention
Hereinafter the specific embodiment of the present invention is described in detail. It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
According to the first aspect of the invention, the invention provides a kind of polymeric film, this polymeric film is formed by polypropene composition, it is characterised in that described polypropene composition contains:
The crystalline polypropylene A of (a) 40-70 weight %, this crystalline polypropylene A at least one in Noblen and random copolymer of propylene, with the gross weight of propylene random co-polymer for benchmark, the alpha-olefin construction unit with 4-10 carbon atom of propylene construction unit, the ethylene unit unit of 0-6 weight % and 0-12 weight % that this propylene random co-polymer contains 82-99.9 weight %, and the total content of ethylene unit unit and the alpha-olefin construction unit with 4-10 carbon atom is 0.1-18 weight %;
The ethylene-propylene elastomeric copolymer B of (b) 30-60 weight %, with the gross weight of ethylene-propylene elastomeric copolymer B for benchmark, the alpha-olefin construction unit with 4-10 carbon atom of propylene construction unit, the ethylene unit unit of 8-25 weight % and 0-15 weight % that this ethylene-propylene elastomeric copolymer B contains 60-92 weight %
Wherein, the molecular weight distributing index of described polypropene composition and described crystalline polypropylene A is all higher than 4, described polypropene composition melt mass flow rate at 230 DEG C, under 2.16kg load effect is 5-10g/10min, is 0.7-1.3 with the ratio of the melt mass flow rate of described crystalline polypropylene A;
And described polymeric film contains nucleator, relative to the described polypropene composition of 100 weight portions, the content of described nucleator is 200-2000ppm.
A preferred embodiment of the invention, described polypropene composition is by preparing with continuous polymerization under existing at the ziegler natta catalyst with high stereoselective. Described continuous polymerization refers to that preparation process includes the step that at least two order carries out, wherein, component (a) (i.e. crystalline polypropylene A) and component (b) (i.e. ethylene-propylene elastomeric copolymer B) are each prepared in a separate step, and, except the first step, later step carries out under the established polymer of previous step and the existence of catalyst that uses in a previous step.
Under above-mentioned preferable case, owing to described polypropene composition adopts the ziegler natta catalyst with high stereoselective to prepare, the molecular weight distribution of described polypropene composition and the molecular weight distribution of its component (a) are all higher than 4, preferably it is all higher than 4.5, more preferably 4.5-20 (" polypropylene handbook " (Chemical Industry Press it is, in June, 2008 first edition, 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 alpha-olefin of the described 4-10 of having carbon atom can be commonly used in the art various can be copolymerized the compound of conjunction with propylene and ethylene, the example can be but be not limited to: at least one in butylene (such as 1-butylene), amylene (such as 1-amylene), 4-methyl-1-pentene, hexene (such as 1-hexene), heptene (such as 1-heptene) and octene (such as 1-octene), it is most preferred that for 1-butylene.
In described polypropene composition, described crystalline polypropylene A can be selected from least one in Noblen and random copolymer of propylene. When comonomer structural unit content is less, described polypropene composition demonstrates good heat resistance. With the gross weight of described random copolymer of propylene for benchmark, described random copolymer of propylene preferably comprises the alpha-olefin construction unit with 4-10 carbon atom of the propylene construction unit of 97-99.9 weight %, the ethylene unit unit of 0-2 weight % and 0-1 weight %, and the total content of ethylene unit unit and the alpha-olefin construction unit with 4-10 carbon atom is 0.1-3 weight %. Under above-mentioned preferable case, the fusing point of described crystalline polypropylene A is more than 150 DEG C so that described polypropene composition has the fusing point more than 150 DEG C, thus demonstrating good heat resistance.
It is further preferred that described crystalline polypropylene A is Noblen, described polypropene composition so can be made to have good rigidity and heat resistance concurrently, improve described polymer film strength and deflection further.
In described polypropene composition, described crystalline polypropylene A can derive the construction unit to other olefin comonomers containing more, polypropene composition so can be made to demonstrate better toughness, so that described polymeric film has better pliability and impact resistance.
In described polypropene composition, described ethylene-propylene elastomeric copolymer B can contain a small amount of alpha-olefin construction unit with 4-10 carbon atom, such as, with the gross weight of ethylene-propylene elastomeric copolymer B for benchmark, described ethylene-propylene elastomeric copolymer B can contain the alpha-olefin construction unit with 4-10 carbon atom of 0.1-15 weight %, 0.1-5 weight % or 0.1-3 weight %. Under preferable case, described ethylene-propylene elastomeric copolymer B does not substantially comprise the alpha-olefin construction unit with 4-10 carbon atom; It is further preferred that with the gross weight of described ethylene-propylene elastomeric copolymer B for benchmark, described ethylene-propylene elastomeric copolymer B contains the propylene construction unit of 75-92 weight % and the ethylene unit unit of 8-25 weight %; It is further preferred that described ethylene-propylene elastomeric copolymer B contains the propylene construction unit of 82-90 weight % and the ethylene unit unit of 10-18 weight %.
Polymeric film according to the present invention, the ratio of described polypropene composition and the MFR of described crystalline polypropylene A is 0.7-1.3, it is preferred to 0.75-1.2. Specifically, the MFR of described polypropene composition is 5-10g/10min. In the present invention, MFR, all in accordance with ASTMD1238-13 method, at 230 DEG C, records under 2.16kg counterweight effect.
In the present invention, by atomic force microscope it is observed that described polypropene composition has a two phase structure, and described ethylene-propylene elastomeric copolymer B preferably with the mean diameter Granular composite less than 0.5 ��m in described polypropene composition. In the present invention, described mean diameter (i.e. granular size) is determined by atomic force microscopy.
In the present invention, containing nucleator in described polymeric film, with the gross weight of described polypropene composition for benchmark, the content of described nucleator is 200-2000ppm, it is preferred to 200-1000ppm.
According to the present invention, described nucleator can be various nucleator commonly used in the art, it is preferable that described nucleator is at least one in Sorbitol Nucleator and aryl phosphoric acids salt nucleator.
The instantiation of described Sorbitol Nucleator can include but not limited to: 1, 3:2, 4-bis-(benzylidene)-D-glucitol, 1, 3:2, 4-bis-(4-methylbenzene subunit)-D-glucitol, 1, 3:2, 4-bis-(3, 4-dimethylbenzylidene)-D-glucitol, 1, 3:2, 4-bis-(4-ethylo benzene methylene)-D-glucitol, double, two-1, 3:2, 4-(4 '-propyl group benzal)-1-allyl sorbitol, double, two-1, 3:2, 4-(4 '-ethylbenzylidene)-1-allyl sorbitol, double, two-1, 3:2, 4-(4 '-propoxyl group benzal)-1-allyl sorbitol, double, two-1, 3:2, 4-(4 '-propyl group benzal)-1-propyl group sorbitol, double, two-1, 3:2, 4-(4 '-propoxyl group benzal)-1-propyl group sorbitol. preferred described Sorbitol Nucleator is 1,3:2,4-bis-(3,4-dimethylbenzylidene)-D-glucitol (can purchased from American Milliken Co., the trade mark is Millad3988) and/or double, two-1,3:2,4-(4 '-propyl group benzal)-1-propyl group sorbitol (can purchased from American Milliken Co., the trade mark is NX8000). more preferably described Sorbitol Nucleator is double, two-1,3:2,4-(4 '-propyl group benzal)-1-propyl group sorbitol.
The instantiation of described aryl phosphoric acids salt nucleator can include but not limited to: 2,2 '-methylene-bis-(4,6-di-tert-butyl-phenyl) sodium phosphate, 2,2 '-ethidine-bis-(4,6-di-tert-butyl-phenyl) sodium phosphate, 2,2 '-methylene-bis-(4,6-di-tert-butyl-phenyl) lithium phosphate, 2,2 '-ethidine-bis-(4,6-di-tert-butyl-phenyl) lithium phosphate, 2,2 '-ethidine-bis-(4-isopropyl-6-di-tert-butyl-phenyl) sodium phosphate, 2,2 '-methylene-bis-(4-methyl-6-di-tert-butyl-phenyl) lithium phosphate, 2,2 '-methylene-bis-(4-ethyl-6-di-tert-butyl-phenyl) lithium phosphate, double, two [2,2 '-thiobis (4-methyl-6-di-tert-butyl-phenyl) calcium phosphate], double, two [2,2 '-thiobis (4-ethyl-6-di-tert-butyl-phenyl) calcium phosphate], double, two [2,2 '-thiobis (4,6-di-tert-butyl-phenyl) calcium phosphate], double, two [2,2 '-thiobis (4,6-di-tert-butyl-phenyl) magnesium phosphate], double, two [2,2 '-thiobis (4,6-bis-t-octyl phenyl) magnesium phosphate], 2,2 '-Ding pitch base-bis-(4,6-3,5-dimethylphenyl) sodium phosphate, 2,2 '-t-octyl methylene-bis-(4,6-3,5-dimethylphenyl) sodium phosphate, 2,2 '-t-octyl methylene-bis-(4,6-di-tert-butyl-phenyl) sodium phosphate, double, two [2,2 '-methylene-bis-(4,6-di-tert-butyl-phenyl) calcium phosphate], double, two [2,2 '-methylene-bis-(4,6-di-tert-butyl-phenyl) magnesium phosphate], double, two [2,2 '-methylene-bis-(4,6-di-tert-butyl-phenyl) barium phosphates], 2,2 '-methylene-bis-(4-methyl-6-tert butyl phenyl) sodium phosphate, 2,2 '-methylene-bis-(4-ethyl-6-tert-butyl-phenyl) sodium phosphate, double, two [4,4 '-dimethyl-6,6 '-di-t-butyl-2,2 '-xenyl) calcium phosphate], 2,2 '-ethidine-bis-(4-m-butyl-6-tert-butyl-phenyl) sodium phosphate, 2,2 '-methylene-bis-(4,6-3,5-dimethylphenyl) sodium phosphate, 2,2 '-methylene-bis-(4,6-diethyl phenyl) sodium phosphate, 2,2 '-ethidine-bis-(4,6-di-tert-butyl-phenyl) potassium phosphate, double, two [2,2 '-ethidine-bis-(4,6-di-tert-butyl-phenyl) calcium phosphate], double, two [2,2 '-ethidine-bis-(4,6-di-tert-butyl-phenyl) magnesium phosphate], double, two [2,2 '-ethidine-bis-(4,6-di-tert-butyl-phenyl) barium phosphates], hydroxyl-bis-[2,2 '-ethidine-bis-(4,6-di-tert-butyl-phenyl) aluminum phosphate], three pairs [2,2 '-ethidine-bis-(4,6-di-tert-butyl-phenyl) aluminum phosphate], hydroxyl-bis-[2,4,8,10-tetra-(1,1 '-dimethyl ethyl)-6-hydroxyl-12H-dibenzo [d, g] dioxy phospha eight ring-6-oxygen] closes aluminum. described aryl phosphoric acids salt nucleator is preferably 2,2 '-methylene-bis-(4,6-di-tert-butyl-phenyl) sodium phosphate, hydroxyl-bis-[2,2 '-ethidine-bis-(4,6-di-tert-butyl-phenyl) aluminum phosphate] and hydroxyl-bis-[2,4,8,10-tetra-(1,1 '-dimethyl ethyl)-6-hydroxyl-12H-dibenzo [d, g] dioxy phospha eight ring-6-oxygen] close at least one in aluminum.
Described aryl phosphoric acids salt nucleator can be commercially available, such as, can be NA-11 (2 purchased from the trade mark of rising sun electrification company of Japan, 2 '-methylene-bis-(4,6-di-tert-butyl-phenyl) sodium phosphate) and/or NA-21 (hydroxyl-bis-[2,4,8,10-tetra-(1,1 '-dimethyl ethyl)-6-hydroxyl-12H-dibenzo [d, g] dioxy phospha eight ring-6-oxygen] close aluminum) nucleator.
In the present invention, adding the non-oxidizability in man-hour to improve described polymeric film, it is preferable that possibly together with antioxidant in described polymeric film. Described antioxidant can be various antioxidant commonly used in the art, it does not have is particularly limited to. Can be such as antioxidant 1076, antioxidant 1010, irgasfos 168, sulphur ester antioxidant (such as DLTP, DSTP) etc. Relative to the described polypropene composition of 100 weight portions, the content of described antioxidant can be 0.1-0.8 weight portion, it is preferred to 0.2-0.4 weight portion.
According to the present invention, in order to improve other performances (such as stability, antistatic behaviour etc.) of described polymeric film, described polymeric film is preferably possibly together with coalescents. Described coalescents can be selected from least one in halogen-resistant agent, light stabilizer, heat stabilizer, coloring agent, filler, slipping agent, antiplastering aid and antistatic additive. The concrete kind of described coalescents is the selection that this area is conventional, does not repeat them here.
In the present invention, relative to the described polypropene composition of 100 weight portions, the content of described coalescents can be 0.01-0.2 weight portion, it is preferred to 0.05-0.15 weight portion.
In the present invention, the mist degree of described polymeric film can less than 9%, it is preferable that less than 7%. Described mist degree is the result that the method according to GB/T2410-2008 records.
According to the present invention, described polymeric film can be cast film, it is also possible to for two-phase oriented film. It addition, the polymeric film of the present invention can also as at least one of which in multilamellar cast film or multilamellar two-phase oriented film, except the layer that described polymeric film is formed, the film of other layers can be made up of the pp material that this area is conventional. Usual described pp material can be selected from least one in HOPP, ethylene-propylene copolymer, propylene and other alpha olefin copolymers, and the concrete kind of the described pp material of other layers is the selection that this area is conventional, does not repeat them here.
According to second aspect of the present invention, the preparation method that the invention provides above-mentioned polymeric film, the method comprises the following steps:
(1) under the first olefin polymerization conditions, by the first monomer a and the ziegler natta catalyst haptoreaction with high stereoselective, and the mixture obtained after haptoreaction removes unreacted monomer, obtain the first mixture containing crystalline polypropylene A, wherein, described first monomer a contains propylene and optional ethylene and/or has the alpha-olefin of 4-10 carbon atom;
(2) when alkene gas-phase polymerization, by second comonomer b described the first mixture haptoreaction containing crystalline polypropylene A obtained with step (1), obtain the second mixture containing crystalline polypropylene A and ethylene-propylene elastomeric copolymer B, and remove unreacted monomer from this second mixture, obtain polypropene composition, wherein, described second comonomer b contains propylene and ethylene and/or has the alpha-olefin of 4-10 carbon atom;
(3) polypropene composition nucleator, step (2) obtained and optional antioxidant and coalescents mix and extruding pelletization, and the pellet obtained is made polymeric film.
In the present invention, there is with continuous polymerization synthesis the polypropene composition of higher ethylene-propylene elastomeric copolymer level by selecting specific ziegler natta catalyst to realize, ethylene-propylene elastomeric copolymer level can reach more than 30 weight %, polymeric film is made to have extraordinary impact resistance, the preparation of thin film and use procedure still can be made to be smoothed out simultaneously, and good optical property can be kept.
The present inventor it have also been found that, after adding nucleator in described polypropene composition, the ethylene-propylene elastomeric copolymer being possible to prevent high-load is reunited in membrane-film preparation process, it is made to disperse uniformly with little particle diameter in crystalline polypropylene portion, it is to avoid the defect that the optical property because reuniting or dispersion inequality causes declines. And the nucleator of certain content, it is possible to make the melt containing high-load ethylene-propylene elastomeric copolymer reach the rate of cooling being suitable for, make polymeric film both keep good impact property, there is again higher deflection and intensity. It addition, nucleator itself also has the effect promoting crystallizable homopolypropylene portion crystallization, thus improve described polymer film strength further.
Preparation in accordance with the present invention, in one embodiment, described first monomer a is propylene so that the crystalline polypropylene A obtained under the first olefin polymerization conditions is Noblen.
Preparation in accordance with the present invention, in a preferred embodiment, described second comonomer b is propylene and ethylene so that the ethylene-propylene elastomeric copolymer B obtained when alkene gas-phase polymerization contains the propylene construction unit of 75-92 weight % and the ethylene unit unit of 8-25 weight %; It is further preferred that make the ethylene unit unit of the ethylene-propylene elastomeric copolymer B propylene construction unit containing 82-90 weight % and 10-18 weight %.
In the present invention, " there is the ziegler natta catalyst of high stereoselective " and refer to the catalyst of the Noblen preparing isotactic index more than 95%.
In the present invention, the ziegler natta catalyst described in high stereoselective can contain:
(i) ingredient of solid catalyst, it is mainly composed of magnesium, titanium, halogen and internal electron donor;
(ii) organo-aluminum compound; And
(iii) optional external donor compound,
The mean diameter of the described ziegler natta catalyst with high stereoselective can more than 30 ��m, it is preferable that more than 40 ��m.
Preferably, the ziegler natta catalyst that magnesium diaikoxide compound is prepared as carrier is adopted to have advantage for the present invention.
Described ingredient of solid catalyst prepares preferably by following steps:
(a) under inert gas shielding, with magnesium and alcohol for raw material, back flow reaction under the existence of halogenating agent, obtain magnesium diaikoxide compound;
B (), under inert diluent exists, magnesium diaikoxide compound step (a) obtained carries out haptoreaction with titanium compound and internal electron donor compound;
Described magnesium diaikoxide compound is spherical particle, and mean diameter is 10-150um, particle size distribution index SPAN < 1.1.
The preparation process of above-mentioned preferred ziegler natta catalyst and described ingredient of solid catalyst is identical with described in patent application CN102453150A.
The described ziegler natta catalyst with high stereoselective can directly use, it is also possible to adds after pre-complexation and prepolymerization.
Organo-aluminum compound as the cocatalyst component of catalyst is preferably alkyl aluminum compound, is more preferably selected from least one in trialkylaluminium (such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, trioctylaluminum), aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, dichloro one aluminium ethide and ethyl aluminum dichloride.
With Ti/Al molar ratio computing, the ratio of described ingredient of solid catalyst and described organo-aluminum compound cocatalyst component can be 1:25 to 1:1000.
The external donor compound of catalyst component optionally is preferably organo-silicon compound, and its formula is RnSi(OR')4-n, 0 < n��3 in formula, wherein, R and R' is identical or different, and is each independently selected from alkyl, cycloalkyl, aryl and haloalkyl, and R can also be halogen or hydrogen atom. specifically, described organo-silicon 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, the ratio of described alkyl aluminum compound and described organo-silicon compound can be 3:1 to 100:1.
Three kinds of components of the described ziegler natta catalyst with high stereoselective can be added directly in polymer reactor, it is also possible to after the known pre-complexation of industry and/or prepolymerization, is then added in reactor. Prepolymerization can continuously perform when liquid-phase bulk, it is also possible to carries out in atent solvent discontinuous. Pre-polymerization reactor can be continuous stirred tank, annular-pipe reactor etc. Prepolymerized temperature can control between-10 to 60 DEG C, it is preferred that temperature is 0 to 40 DEG C. Prepolymerized multiple can control at 0.5 to 1000 times, it is preferred that multiple is 1.0 to 500 times.
In the above-mentioned methods, the first olefinic polymerization and alkene gas-phase polymerization can continuously perform, it is also possible to interval carries out. Continuous polymerization can use plural tandem reactor to carry out.
First olefinic polymerization can carry out in liquid phase, it is also possible to carries out in gas phase. Reactor used by first olefinic polymerization can be Liquid-phase reactor, it is also possible to for Gas-phase reactor. Liquid-phase reactor can be annular-pipe reactor and stirred tank reactor etc., and Gas-phase reactor can be that horizontal type agitated bed reactor, vertical mixing bed bioreactor and fluidized-bed reactor etc., above Liquid-phase reactor and Gas-phase reactor can also at random matched combined.
Preparation in accordance with the present invention, described first olefin polymerization conditions may include that temperature is 50-100 DEG C, it is preferred to 60-95 DEG C; Pressure is 1-8MPa, it is preferred to 1.2-5.5MPa; Time is 30-180 minute, it is preferred to 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 may include that temperature is 50-100 DEG C, it is preferred to 60-95 DEG C; Pressure is 1-4MPa, it is preferred to 1.2-3.5MPa; Time is 10-180 minute, it is preferred to 10-90 minute.
In the preparation process in accordance with the present invention, the process of the mixing of polypropene composition and optional antioxidant and coalescents extruding pelletization of step (2) being obtained generally may include that mixs homogeneously described polypropene composition and optional antioxidant with coalescents in homogenizer, the material of mix homogeneously is added to melting mixing in double screw extruder uniform extruding pelletization, dry, thus obtaining pellet. Wherein, the processing temperature of described double screw extruder may be controlled to 170-230 DEG C.
Preparation in accordance with the present invention, described pellet is made the method for polymeric film be referred to prior art and carry out, such as can adopt extrusion the tape casting that described pellet is processed or described pellet is processed by biaxial tension method, thus preparing the polymeric film of the present invention.
According to one embodiment of the present invention, it is possible to adopt extrusion the tape casting that described pellet is processed. The process of described extrusion the tape casting can include delivering in extruder by described pellet, and the extruded machine die orifice of pellet sequentially passes through casting roller, carry-over pinch rolls after flowing out, then through cutting edge and rolling, thus preparing described polymeric film. Wherein, the temperature of extrusion curtain coating may be controlled to 170-230 DEG C, and the temperature of casting roller can be 10-50 DEG C. The detailed process that described extrusion curtain coating method prepares thin film is selection commonly used in the art, does not repeat them here.
According to the third aspect of the present invention, present invention also offers polymeric film prepared by said method. Polymeric film prepared by the preparation method of the present invention only need to adopt Ziegler-Natta catalyst, and ethylene-propylene elastomeric copolymer just can be made to be distributed in crystalline polypropylene matrix with less size uniform. The polymeric film prepared by the method for the present invention had both had higher impact resistance, had again the transparency of excellence.
Hereinafter will be described the present invention by embodiment.
Experimental result in embodiment and comparative example obtains according to following method of testing, and following method of testing all operates when being not particularly limited under room temperature environment:
Melt index (MFR): according to ASTMD1238-13,230 DEG C, measure under 2.16kg load.
Co-monomer content: measure by fourier infrared method.
Xylene soluble content: measure by ASTMD5492-98.
Melting temperature (Tm): use the DSC7 type differential scanning calorimeter instrument of PerkinElmer company to measure, test scope 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, it is down to 50 DEG C again by the speed of 10 DEG C/min, record its crystallization temperature and crystallization enthalpy, rise to 200 DEG C by the speed of 10 DEG C/min again, record its fusing point and melting enthalpy.
Cantilever beam impact strength (Izod notch shock): according to ASTMD256-10, point measurement injected sample at 23 DEG C.
The mechanical property of polymeric film: test according to GB/T1040.3-2006.
The mist degree of polymeric film: according to the method test of regulation in GB/T2410-2008.
The glossiness of polymeric film: according to the method test of regulation in ASTMD2457-08.
The dart impact performance of polymeric film: test according to the method for GB/T9639.1-2008.
Atomic force microscopy: polypropene composition injection moulding batten is ultrathin section after freezing is to subzero 50 degrees Celsius, observes tangent plane. U.S. Vecco company NaonscopeIIIa type multiple mode scanning force microscope, J probe, tapping-mode, sweep limits is 5 microns �� 5 microns, gathers phasor.
Molecular weight distributing index Mw/Mn: adopt PolymerLaboratories company of Britain to produce PL-GPC220 chromatograph of gel permeation and measure the molecular weight distribution of sample, chromatographic column is Plgel10 ��m of MIXED-B post of 3 series connection, solvent and mobile phase are 1,2,4-trichloro-benzenes, column temperature 150 DEG C, adopts PL company EasiCalPS-1 Narrow distribution polystyrene standard specimen to carry out universal calibration, and detector adopts the infrared concentration detector of IR5 of POLYCHAR company.
Polypropene composition in the present invention and comparative example thereof obtains by the following method, and material amounts therein and polymeric reaction condition are listed in table 1.
Polyreaction carries out on set of horizontal type gas phase polypropylene pilot-plant, and polymer reactor is the Horizontal stirring reactor of two series connection, and in case of no particular description, polymerization and step are as follows:
Major catalyst (the active solid catalyst component of titaniferous) adopts the method that in CN102453150A, embodiment 1 describes to obtain, and internal electron donor compound therein adopts n-butyl phthalate.
Major catalyst, promoter (triethyl aluminum), external electron donor are added continuously Horizontal stirring reactor under the carrying of propylene and carry out polyreaction. Catalyst enters from first stirred tank front end, and when gas phase, polymerization generates crystalline polypropylene A, and reaction heat is taken away by the propylene vaporization sprayed. The polymer generated is discharged by the end of stirred tank. Catalyst and polymer to move in the way of laminar flow in reactor, and polymerization temperature is 66 DEG C, reaction pressure 2.3MPa, and the time of staying is 90 minutes.
Polymer is discharged from first reactor, by between two reactors equipped with transfer equipment, polymer is transferred to second Horizontal stirring reactor. Polymer enters from second stirred tank front end, and when gas phase, polymerization generates ethylene-propylene elastomeric copolymer B, and reaction heat is taken away by the propylene vaporization sprayed. The polymer generated is discharged by the end of stirred tank. Catalyst and polymer to move in the way of laminar flow in reactor, and polymerization temperature is 66 DEG C, reaction pressure 2.2MPa, is 60 minutes during stop.
Degassed, the wet nitrogen deactivation of the polymer being obtained by reacting obtains polymeric articles after processing.
Adopt hydrogen as molecular weight regulator in two reactors, use the composition (ethylene, propylene, butylene and hydrogen) of gas in the continuous analysis reactor of gas chromatogram
The Izod notch impact strength of polypropene composition injection moulding batten is in Table 2.
Embodiment 1
(1) preparation of polypropene composition
Polyreaction carries out on above-mentioned horizontal pneumatic heterophasic polypropylene pilot-plant, and the catalyst particle size of use is 59 microns, and reaction carries 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 time of staying is about 90 minutes. Second reactor is that copolymerization of propylene prepares component (b), adds ethylene, propylene in reactor, and polymerization temperature is 85 DEG C, reaction pressure 2.2MPa, and the time of staying is 60 minutes. Degassed, the wet nitrogen deactivation of the polymer being obtained by reacting obtains polypropene composition after processing. Reaction condition and composition properties are as shown in table 1. The atomic force microscopy of the polypropene composition of preparation is as it is shown in figure 1, it can be seen that described polypropene composition has two phase structure, and shows that component (b) is highly dispersed in compositions with the particle diameter of about 0.3 micron.
(2) preparation of polymeric film
According to the calcium stearate (purchased from Ciba company limited) being separately added into the nucleant agent N X8000 (purchased from Milliken Co.) of 200ppm, the IRGAFOS168 additive (purchased from Ciba company limited) of 0.1 weight portion, the IRGANOX1010 additive (purchased from Ciba company limited) of 0.1 weight portion and 0.05 weight portion in the powder of obtained polypropene composition 100 weight portion, add mix homogeneously in agitator, with WP25 type double screw extruder pelletize, in the course of processing, the temperature of screw rod controls between 170-230 DEG C.
The pellet obtained is added in hot-air oven and is dried, and the addition of dried pellet is melt extruded purchased from the curtain coating extrusion equipment that model is LCR400 of Labtech company of Sweden, then through casting roller flow casting molding, the each zone temperatures of extruder controls at 210 DEG C, 230 DEG C, 230 DEG C, 230 DEG C, 230 DEG C respectively, draping district temperature controls at 230 DEG C, head temperature controls at 230 DEG C, casting roller temperature controls at 25 DEG C, forming the polymeric film that average thickness is 25 microns, its performance is as shown in table 2.
Embodiment 2
(1) preparation of polypropene composition
Polypropene composition is prepared, the difference is that the composition and the content that change component (b) according to the method for embodiment 1. Reaction condition and composition properties are as shown in table 1.
(2) preparation of polymeric film
With embodiment 1, the difference is that the content adding NX8000 is 500ppm. Obtaining the polymeric film that average thickness is 25 microns, its performance is as shown in table 2.
Embodiment 3
(1) preparation of polypropene composition
Polyreaction carries out on above-mentioned horizontal pneumatic heterophasic polypropylene pilot-plant, and the catalyst particle size of use is 35 microns, and reaction carries out according to the method described above. The external electron donor adopted is diisopropyl dimethoxy silane, and the first reactor polyreaction is propylene and ethylene random copolymerization, and polymerization temperature is 66 DEG C, reaction pressure 2.3MPa, and the time of staying is 90 minutes. Second reactor is that copolymerization of propylene prepares component (b), adds ethylene, propylene in reactor, and polymerization temperature is 66 DEG C, reaction pressure 2.2MPa, and the time of staying is about 60 minutes. Degassed, the wet nitrogen deactivation of the polymer being obtained by reacting obtains polypropene composition after processing. Reaction condition and composition properties are as shown in table 1.
(2) preparation of polymeric film
With embodiment 2. Obtaining the polymeric film that average thickness is 25 microns, its performance is as shown in table 2.
Embodiment 4
(1) preparation of polypropene composition
With embodiment 3.
(2) preparation of polymeric film
With embodiment 1. The difference is that the content adding NX8000 is 1000ppm. Obtaining the polymeric film that average thickness is 25 microns, its performance is as shown in table 2.
Comparative example 1
(1) preparation of polypropene composition
Polyreaction carries out on above-mentioned horizontal pneumatic heterophasic polypropylene pilot-plant, and the catalyst particle size of use is 59 microns, and reaction carries 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 85 DEG C, reaction pressure 2.3MPa, and the time of staying is about 90 minutes. Second reactor is that copolymerization of propylene prepares component (b), adds ethylene, propylene in reactor, and polymerization temperature is 66 DEG C, reaction pressure 2.2MPa, and the time of staying is 60 minutes. Degassed, the wet nitrogen deactivation of the polymer being obtained by reacting obtains polymeric articles after processing. Reaction condition product property is as shown in table 1.
(2) preparation of polymeric film
With embodiment 1. The difference is that without nucleator. Obtaining the polymeric film that average thickness is 25 microns, its performance is as shown in table 2.
Comparative example 2
(1) preparation of polypropene composition
With comparative example 1.
(2) preparation of polymeric film
With embodiment 2. Obtaining the polymeric film that average thickness is 25 microns, its performance is as shown in table 2.
Comparative example 3
The HOPP FC801 (MFR is 7.8g/10min, 230 DEG C, under 2.16kg load) using oil of SPC replaces polypropene composition. It is 100 listed as parts by weight according to FC801, it is separately added into the propylene-based elastomeric (trade mark Vistamaxx3000 of 30 weight portions, purchased from Exxonmobil company), the IRGAFOS168 additive (purchased from Ciba company limited) of 0.1 weight portion, the IRGANOX1010 additive (purchased from Ciba company limited) of 0.1 weight portion and 0.05 weight portion calcium stearate (purchased from Ciba company limited), add mix homogeneously in agitator, with WP25 type double screw extruder pelletize, in the course of processing, the temperature of screw rod controls between 170-230 DEG C.
Other steps are with embodiment 1. Obtaining the polymeric film that average thickness is 25 microns, its performance is as shown in table 2.
Table 1
Note: P is diisopropyl dimethoxy silane; MFRa+b/MFRaRefer to the melt index ratio of polypropene composition and crystalline polypropylene A.
Table 2
*: Izod notch impact strength refers to the Izod notch impact strength of the injection batten of polypropene composition pellet.
Can be seen that from table 1 and 2, relative to the thin film of preparation in comparative example 1 and 2, the thin film of embodiment not only has good shock resistance, and has good optical property, and under close component (b) content, the mist degree of comparative example and glossiness are all very poor. Comparative example 3 is polypropylene homopolymer and elastomer mixing prepares thin film, it can be seen that the shock resistance of embodiment thin film to be significantly larger than comparative example 3, and other performances are close with it, and by more advantage on the preparation method cost of the present invention.
Claims (16)
1. a polymeric film, this polymeric film is formed by polypropene composition, it is characterised in that described polypropene composition contains:
The crystalline polypropylene A of (a) 40-70 weight %, this crystalline polypropylene A at least one in Noblen and random copolymer of propylene, with the gross weight of propylene random co-polymer for benchmark, the alpha-olefin construction unit with 4-10 carbon atom of propylene construction unit, the ethylene unit unit of 0-6 weight % and 0-12 weight % that this propylene random co-polymer contains 82-99.9 weight %, and the total content of ethylene unit unit and the alpha-olefin construction unit with 4-10 carbon atom is 0.1-18 weight %;
The ethylene-propylene elastomeric copolymer B of (b) 30-60 weight %, with the gross weight of ethylene-propylene elastomeric copolymer B for benchmark, the alpha-olefin construction unit with 4-10 carbon atom of propylene construction unit, the ethylene unit unit of 8-25 weight % and 0-15 weight % that this ethylene-propylene elastomeric copolymer B contains 60-92 weight %
Wherein, the molecular weight distributing index of described polypropene composition and described crystalline polypropylene A is all higher than 4, described polypropene composition melt mass flow rate at 230 DEG C, under 2.16kg load effect is 5-10g/10min, is 0.7-1.3 with the ratio of the melt mass flow rate of described crystalline polypropylene A;
And described polymeric film contains nucleator, relative to the described polypropene composition of 100 weight portions, the content of described nucleator is 200-2000ppm.
2. polymeric film according to claim 1, wherein, described polypropene composition is by preparing with continuous polymerization under existing at the ziegler natta catalyst with high stereoselective.
3. polymeric film according to claim 2, wherein, described polypropene composition, crystalline polypropylene A molecular weight distribution be all higher than 4.5, it is preferable that be 4.5-20.
4. the polymeric film according to any one in claim 1-3, wherein, described crystalline polypropylene A is Noblen; Described ethylene-propylene elastomeric copolymer B contains the propylene construction unit of 75-92 weight % and the ethylene unit unit of 8-25 weight %.
5. the polymeric film according to any one in claim 1-4, wherein, described ethylene-propylene elastomeric copolymer B with the mean diameter Granular composite less than 0.5 ��m in described polypropene composition.
6. polymeric film according to claim 1, wherein, described nucleator at least one in Sorbitol Nucleator and aryl phosphoric acids salt nucleator.
7. the polymeric film according to any one in claim 1-6, wherein, described polymeric film is possibly together with antioxidant; Relative to the described polypropene composition of 100 weight portions, the content of described antioxidant is 0.1-0.8 weight portion, it is preferred to 0.2-0.4 weight portion.
8. the polymeric film according to any one in claim 1-7, wherein, described polymeric film is possibly together with coalescents, described coalescents at least one in halogen-resistant agent, light stabilizer, heat stabilizer, coloring agent, filler, slipping agent, antiplastering aid and antistatic additive; Relative to the described polypropene composition of 100 weight portions, the content of described coalescents is 0.01-0.2 weight portion, it is preferred to 0.05-0.15 weight portion.
9. the polymeric film according to any one in claim 1-8, wherein, the mist degree that described polymeric film measures according to the method for GB/T2410-2008 is less than 9%, it is preferable that less than 7%.
10. preparing a method for polymeric film described in any one in claim 1-9, the method comprises the following steps:
(1) under the first olefin polymerization conditions, by the first monomer a and the ziegler natta catalyst haptoreaction with high stereoselective, and the mixture obtained after haptoreaction removes unreacted monomer, obtain the first mixture containing crystalline polypropylene A, wherein, described first monomer a contains propylene and optional ethylene and/or has the alpha-olefin of 4-10 carbon atom;
(2) when alkene gas-phase polymerization, by second comonomer b described the first mixture haptoreaction containing crystalline polypropylene A obtained with step (1), obtain the second mixture containing crystalline polypropylene A and ethylene-propylene elastomeric copolymer B, and remove unreacted monomer from this second mixture, obtain polypropene composition, wherein, described second comonomer b contains propylene and ethylene and/or has the alpha-olefin of 4-10 carbon atom;
(3) polypropene composition nucleator, step (2) obtained and optional antioxidant and coalescents mix and extruding pelletization, and the pellet obtained is made polymeric film.
11. method according to claim 10, wherein, described in there is the particle diameter of ziegler natta catalyst of high stereoselective more than 30 microns.
12. method according to claim 10, wherein, described in there is high stereoselective the carrier of ziegler natta catalyst be magnesium diaikoxide compound.
13. the method according to any one in claim 10-12, wherein, described in there is the ziegler natta catalyst of high stereoselective contain:
(i) ingredient of solid catalyst;
(ii) organo-aluminum compound; And
(iii) optional external donor compound,
Described ingredient of solid catalyst is prepared by following steps:
(a) under inert gas shielding, with magnesium and alcohol for raw material, back flow reaction under the existence of halogenating agent, obtain magnesium diaikoxide compound;
B (), under inert diluent exists, magnesium diaikoxide compound step (a) obtained carries out haptoreaction with titanium compound and internal electron donor compound;
Described magnesium diaikoxide compound is spherical particle, and mean diameter is 10-150um, particle size distribution index SPAN < 1.1.
14. method according to claim 10, wherein, described first olefin polymerization conditions includes: temperature is 50-100 DEG C, and pressure is 1-8MPa, and the time is 30-180 minute; Preferably, described first olefin polymerization conditions includes: temperature is 60-95 DEG C, and pressure is 1.2-5.5MPa, and the time is 45-120 minute.
15. method according to claim 10, wherein, described alkene gas-phase polymerization condition includes: temperature is 50-100 DEG C, and pressure is 1-4MPa, and the time is 10-180 minute; Preferably, described alkene gas-phase polymerization condition includes: temperature is 60-95 DEG C, and pressure is 1.2-3.5MPa, and the time is 10-90 minute.
16. the polymeric film that in claim 10-15 prepared by method described in any one.
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| CN112694678A (en) * | 2019-10-22 | 2021-04-23 | 中国石油化工股份有限公司 | Polypropylene composition for power pipe and preparation method thereof |
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| CN115991027A (en) * | 2021-10-20 | 2023-04-21 | 中国石油化工股份有限公司 | Polypropylene composite film and preparation method and application thereof |
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