CN103087423A - Composition for polymer film and polymer film and multilayer film - Google Patents
Composition for polymer film and polymer film and multilayer film Download PDFInfo
- Publication number
- CN103087423A CN103087423A CN2011103490437A CN201110349043A CN103087423A CN 103087423 A CN103087423 A CN 103087423A CN 2011103490437 A CN2011103490437 A CN 2011103490437A CN 201110349043 A CN201110349043 A CN 201110349043A CN 103087423 A CN103087423 A CN 103087423A
- Authority
- CN
- China
- Prior art keywords
- weight
- content
- olefin
- propylene
- alpha
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention provides a composition for a polymer film, a polymer film and a multilayer film; the composition comprises propylene polymer and a film forming additive; on a basis of the total amount of the propylene polymer, the content of the propylene structure unit is 80-95 wt%; the content of the ethylene structure unit is 1-10 wt%; the content of the alpha-olefin structure unit is 1-19 wt%; the propylene polymer comprises 1-20 wt% of xylene soluble substances, and 80-99 wt% of xylene insoluble substances; the crystallization temperature of the xylene soluble substance is 40-65 DEG C, and the melting temperature is 80-97 DEG C; the crystallization temperature of the xylene insoluble substance is 85-105 DEG C, and the melting temperature is 125-135 DEG C. The composition of the invention has good film forming capability, and the polymer film formed by the composition has a low initial heat-sealing temperature and good thermal adhesion resistance. The polymer film of the invention is suitable for being used as a heat-sealing layer for a heat shrinkable film or a multilayer film.
Description
Technical field
The present invention relates to a kind of polymkeric substance film composition, the invention still further relates to a kind of polymeric film that is formed by said composition, the invention further relates to a kind of multilayer film that contains described polymeric film.
Background technology
A kind of orientation that is stretched in process of production of heat-shrinkable film, and the thermoplastic film who in use is subjected to thermal contraction.Heat-shrinkable film is widely used in food, books and packing, prevent product breakage and dirty in, the outward appearance that can also fully show packed article.At present, usually adopt polyolefine (for example: polyethylene, polypropylene) to prepare heat-shrinkable film.The propylene terpolymers that propylene, ethene and the alpha-olefin except propylene is carried out copolymerization and form, due to the structural unit of introducing derived from ethylene on the macromolecular chain of alfon with can reduce the Tc of alfon derived from the structural unit of the alpha-olefin except propylene, improve the performance of alfon product, thereby have unique advantage for the preparation of heat-shrinkable film the time.
Although compare with polypropylene, the heat-sealing temperature of propene polymer is lower, but by the initial heat-sealing temperature of the film of existing propene polymer preparation still higher (being generally more than 115 ℃), and at high temperature be easy to inter-adhesive, therefore adopting the film that is prepared by existing propene polymer when carrying out slaking, be easy between film be sticked together, the follow-up course of processing is had a negative impact, and affect the outward appearance of packing material, reduce Package Quality.
Therefore, for the polymeric film of the propene polymer preparation that is formed by propylene, ethene and alpha-olefine polymerizing, need to reduce on the one hand the initial heat-sealing temperature of film, need on the other hand to improve the high temperature resistance blocking under warming performance of film.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of polymkeric substance film composition is provided, the good film-forming property of this polymkeric substance film composition, and the initial heat-sealing temperature of the polymeric film that forms is low and heat resistanceheat resistant adhesion performance is good.
the present inventor finds in research process: for by propylene, the propene polymer that ethene and alpha-olefine polymerizing form, the solvend of propene polymer in dimethylbenzene and the content of insolubles, Tc and melt temperature (the particularly Tc of the solvend of propene polymer in dimethylbenzene) have significant impact for initial heat-sealing temperature and the heat resistanceheat resistant adhesion performance of the film that is formed by this propene polymer, by controlling the solvend of propene polymer in dimethylbenzene and the content of dimethylbenzene insolubles, Tc and melt temperature (particularly improving the Tc of the solvend of propene polymer in dimethylbenzene), can obtain both had low initial heat-sealing temperature, the propene polymer that has again excellent heat resistanceheat resistant adhesion performance.Completed the present invention based on above-mentioned discovery.
The invention provides a kind of polymkeric substance film composition, said composition contains propene polymer and film coalescence aid, wherein, described propene polymer contain derived from propylene propylene structural unit, derived from ethylene the ethene structural unit and derived from C
4-C
8The alpha-olefin structural unit of alpha-olefin, take the total amount of described propene polymer as benchmark, the content of described propylene structural unit is the 80-95 % by weight, and the content of described ethene structural unit is the 1-10 % by weight, and the content of described alpha-olefin structural unit is the 1-19 % by weight;
Take the total amount of described propene polymer as benchmark, the xylene soluble part content of described propene polymer is the 1-20 % by weight, and the dimethylbenzene insolubles content of described propene polymer is the 80-99 % by weight;
The Tc of described xylene soluble part is 40-65 ℃, and melt temperature is 80-97 ℃; The Tc of described dimethylbenzene insolubles is 85-105 ℃, and melt temperature is 125-135 ℃.
The present invention also provides a kind of polymeric film, and this polymeric film is formed by composition of the present invention.
The present invention further provides a kind of multilayer film, this multilayer film comprises substrate layer and at least one the lip-deep hot sealing layer that is positioned at described substrate layer, and described hot sealing layer is formed by polymeric film provided by the invention.
According to the good film-forming property of polymkeric substance film composition of the present invention, the polymeric film that is formed by said composition not only has low initial heat-sealing temperature, but also has good heat resistanceheat resistant adhesion performance.
The initial heat-sealing temperature of the polymeric film that is formed by propene polymer of the present invention particularly, can for lower than 115 ℃, be generally 105-115 ℃; At the temperature of 130-139 ℃, there is no or substantially do not have adhesion phenomenon between the polymeric film that is formed by propene polymer of the present invention.
Propene polymer according to the present invention is applicable to prepare polymeric film, and this polymeric film is particularly suitable for the hot sealing layer as heat-shrinkable film or multilayer film.
Description of drawings
Accompanying drawing is to be used to provide a further understanding of the present invention, and consists of the part of specification sheets, is used from explanation the present invention with following embodiment one, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is that wherein, X-coordinate is granularity according to the size distribution curve of the solid ingredient of using in embodiments of the invention 1, and ordinate zou is volume fraction;
Fig. 2 is the size distribution curve of the solid ingredient of use in Comparative Examples 1, and wherein, X-coordinate is granularity, and ordinate zou is volume fraction.
Embodiment
The invention provides a kind of polymkeric substance film composition, said composition contains propene polymer and film coalescence aid, described propene polymer contain derived from propylene propylene structural unit, derived from ethylene the ethene structural unit and derived from C
4-C
8The alpha-olefin structural unit of alpha-olefin.
In the present invention, the propylene structural unit of derived from propylene refers to the structural unit that formed by propylene; The ethene structural unit of derived from ethylene refers to the structural unit that formed by ethene; Derived from C
4-C
8The alpha-olefin structural unit of alpha-olefin refer to the structural unit that formed by alpha-olefin.
In the present invention, term " propene polymer " refers to the random copolymers that formed by propylene, ethene and alpha-olefine polymerizing.
According to polymkeric substance film composition of the present invention, take the total amount of described propene polymer as benchmark, the content of described propylene structural unit is the 80-95 % by weight, and the content of described ethene structural unit is the 1-10 % by weight, and the content of described alpha-olefin structural unit is the 1-19 % by weight.Preferably, take the total amount of described propene polymer as benchmark, the content of described propylene structural unit is the 85-95 % by weight, and the content of described ethene structural unit is the 1-5 % by weight, and the content of described alpha-olefin structural unit is the 1-10 % by weight.
According to polymkeric substance film composition of the present invention, take the total amount of described propene polymer as benchmark, the xylene soluble part content of described propene polymer is the 1-20 % by weight, and the dimethylbenzene insolubles content is the 80-99 % by weight.Preferably, take the total amount of described propene polymer as benchmark, the xylene soluble part content of described propene polymer is the 1-15 % by weight, and the dimethylbenzene insolubles content is the 85-99 % by weight.More preferably, take the total amount of described propene polymer as benchmark, the xylene soluble part content of described propene polymer is the 2-15 % by weight, and the dimethylbenzene insolubles content is the 85-98 % by weight.Further preferably, take the total amount of described propene polymer as benchmark, the xylene soluble part content of described propene polymer is the 3-10 % by weight, and the dimethylbenzene insolubles content is the 90-97 % by weight.
In the present invention, described xylene soluble part content is to measure according to the method stipulated in GB/T 24282-2009, and the dimethylbenzene insolubles content is the difference between the weight of the gross weight of propene polymer and xylene soluble part.
According to polymkeric substance film composition of the present invention, the solvend of described propene polymer in dimethylbenzene (namely, xylene soluble part) Tc is high, can reach 40-65 ℃, and the melt temperature of the solvend of propene polymer according to the present invention in dimethylbenzene is 80-97 ℃; The Tc of the insolubles (that is, dimethylbenzene insolubles) of propene polymer according to the present invention in dimethylbenzene is 85-105 ℃, and melt temperature is 125-135 ℃.
In the present invention, described Tc and melt temperature are all to adopt determine with dsc method
Of the present invention a kind of preferred embodiment in, take the total amount of described propene polymer as benchmark, the content of described propylene structural unit is the 85-95 % by weight, and the content of described ethene structural unit is the 1-5 % by weight, and the content of described alpha-olefin structural unit is the 1-10 % by weight; Take the total amount of described propene polymer as benchmark, the xylene soluble part content of described propene polymer is the 1-15 % by weight, and the dimethylbenzene insolubles content is the 85-99 % by weight; The Tc of described xylene soluble part is 40-65 ℃, and melt temperature is 80-97 ℃; The Tc of described dimethylbenzene insolubles is 85-105 ℃, and melt temperature is 125-135 ℃.Not only have lower initial heat-sealing temperature according to this polymeric film that preferred embodiment forms, but also have higher heat resistanceheat resistant adhesion performance; And the film that is formed by described propene polymer has more good comprehensive mechanical property, can obtain good balance between rigidity and snappiness.
According to polymkeric substance film composition of the present invention, the melt mass flow rate of described propene polymer can reach 0.5-30 gram/10 minute, and therefore polymkeric substance film composition according to the present invention also has good processing characteristics.In the present invention, described melt mass flow rate is to measure according to the method for stipulating in GB/T 3682-2000.Particularly, probe temperature is 230 ℃, and load is 2.16 kilograms.
According to the present invention, described alpha-olefin can for this area commonly used various can with the compound of propylene and ethene generation copolymerization.The example of described alpha-olefin can for but be not limited to: 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-heptene and 1-octene.Preferably, described alpha-olefin is 1-butylene.
According to polymkeric substance film composition of the present invention, described propene polymer can be by in gas-phase polymerization reactor, under the alkene gas-phase polymerization condition, with propylene, ethene be selected from C
4-C
8Alpha-olefin contact and make with olefin polymerization catalyst system.
according to the present invention, described propylene, mutual ratio between ethene and alpha-olefin so that the preparation propene polymer in the propylene structural unit, the amount of ethene structural unit and alpha-olefin structural unit can satisfy previously described requirement and be as the criterion, for example: described propylene, the consumption of ethene and alpha-olefin makes in the propene polymer of final preparation, take the total amount of described propene polymer as benchmark, the content of described propylene structural unit is the 80-95 % by weight, the content of described ethene structural unit is the 1-10 % by weight, the content of described alpha-olefin structural unit is the 1-19 % by weight.Determine that according to the content of each structural unit in the propene polymer of expection the method for the relative consumption of propylene, ethene and alpha-olefin is known in the field.
According to the present invention, when preparing described propene polymer by single step reaction, take the total amount of propylene, ethene and alpha-olefin as benchmark, the amount of described propylene can be the 75-95 % by weight, the amount of described ethene can be the 1-10 % by weight, and the amount of described alpha-olefin can be the 1-25 % by weight.When the consumption of described propylene, ethene and alpha-olefin is within above-mentioned scope, take the total amount of propene polymer of preparation as benchmark, the content of described propylene structural unit is the 80-95 % by weight, the content of described ethene structural unit is the 1-10 % by weight, and the content of described alpha-olefin structural unit is the 1-19 % by weight; Take the total amount of described propene polymer as benchmark, the xylene soluble part content of described propene polymer is the 1-20 % by weight, and the dimethylbenzene insolubles content is the 80-99 % by weight; The Tc of described xylene soluble part is 40-65 ℃, and melt temperature is 80-97 ℃ (being preferably 85-97 ℃); The Tc of described dimethylbenzene insolubles is 85-105 ℃, and melt temperature is 125-135 ℃.
More preferably, take the total amount of propylene, ethene and alpha-olefin as benchmark, the consumption of described propylene is the 80-95 % by weight, and the consumption of described ethene is the 1-5 % by weight, and the consumption of described alpha-olefin is the 1-15 % by weight.The propene polymer of preparation thus, take the total amount of described propene polymer as benchmark, the content of described propylene structural unit is the 85-95 % by weight, and the content of described ethene structural unit is the 1-5 % by weight, and the content of described alpha-olefin structural unit is the 1-10 % by weight; Take the total amount of described propene polymer as benchmark, the xylene soluble part content of described propene polymer is the 1-15 % by weight, and the dimethylbenzene insolubles content of described propene polymer is the 85-99 % by weight; The Tc of described xylene soluble part is 40-65 ℃, and melt temperature is 80-97 ℃ (being preferably 85-97 ℃); The Tc of described dimethylbenzene insolubles is 85-105 ℃, and melt temperature is 125-135 ℃.
According to the present invention, described olefin polymerization catalyst system can be this area various catalyst systems that can catalyzing propone carry out organic vertical structure polymerization commonly used.Usually, described olefin polymerization catalyst system contains solid ingredient, external donor compound and organo-aluminium compound, and described solid ingredient contains carrier and the titanium compound and the internal electron donor compound that load on described carrier.
The present inventor is finding in research process: for vapour phase polymerization, the globule size of described solid ingredient and size-grade distribution are for the content of the solvend of propene polymer in dimethylbenzene of final preparation, and the Tc of xylene soluble part and dimethylbenzene insolubles and melt temperature have significant impact, and then initial heat-sealing temperature and the heat resistanceheat resistant adhesion performance of the propene polymer of the final preparation of impact; And, it is inter-adhesive in reactor that granularity by selecting described solid ingredient and size-grade distribution can also suppress the polymer beads that forms in gas-phase polymerization processes effectively, and then can make production to carry out swimmingly continuously, the composition of the propene polymer of preparation is even, stable performance.
the present inventor finds in research process: granularity (that is, the granular size that makes described solid ingredient, for spherical solid ingredient, described granularity is particle diameter) be the 10-50 micron, take the total amount of described solid ingredient as benchmark, the content that granularity is in the solid ingredient within the scope of 14-30 micron is 80-100 volume %, and when the size distribution curve of described solid ingredient is unimodal, the solvend of propene polymer in dimethylbenzene and the content of insolubles of preparation, within melt temperature and Tc can be in scope mentioned above, initial heat-sealing temperature by the polymeric film of this propene polymer preparation can be for (being generally 105-115 ℃) below 115 ℃, and this polymeric film has good heat resistanceheat resistant adhesion performance.
In the present invention, described granularity and size distribution curve are to adopt laser fineness gage to measure.In the present invention, the X-coordinate of described size distribution curve is granularity, and ordinate zou is volume fraction (that is, take the total amount of solid ingredient that be used for to measure as benchmark, having the volume fraction of the solid ingredient of a certain specified particle size).In the present invention, the size distribution curve of described solid ingredient is unimodally to refer to that take granularity as X-coordinate, the size distribution curve that obtains take volume fraction as ordinate zou is normal distribution, only exists one to be bell peak.
The present inventor also finds in research process: take the cumulative volume of described solid ingredient as benchmark, the amount that granularity is in the solid ingredient within the scope of 14-30 micron is 90-100 volume %, the polymkeric substance of preparation not only forms, performance is more even, and granular size is also more even, and the propene polymer of preparation also has better film forming properties; The polymeric film that forms has more excellent heat resistanceheat resistant adhesion performance.Most preferably, take the cumulative volume of described solid ingredient as benchmark, the amount that granularity is in the solid ingredient within the scope of 14-30 micron is 100 volume %.
According to the present invention, can adopt the whole bag of tricks (for example: screening) make the particle diameter of described solid ingredient be in scope mentioned above within and to make the size distribution of described solid ingredient be unimodal distribution.This paper repeats no more.
According to the present invention, the composition of described solid ingredient can be selected for the routine of this area, is not particularly limited.Usually, described solid ingredient contains carrier and loads on titanium compound and internal electron donor compound on described carrier.
According to the present invention, described carrier can be that the routine of this area selects, for example can for magnesium compound (for example: magnesium halide) or silica gel.When described carrier is silica gel, can titanium compound and internal electron donor is compound loaded on silica gel, thus prepare described solid ingredient.Described silica gel can for this area various silica gel commonly used, be not particularly limited.
When described carrier is magnesium compound, thereby can prepare described solid ingredient by titanium compound and internal electron donor compound and magnesium compound are reacted, namely described solid ingredient is the reaction product of titanium compound and internal electron donor compound and magnesium compound.Described magnesium compound can be selected for the routine of this area.For example, described magnesium compound can be the magnesium compound shown in formula I,
R
2-Mg-R
1 (I)
In formula I, R
1And R
2Can be chlorine, bromine, iodine, C separately
1-C
5Straight or branched alkoxyl group and C
1-C
5The straight or branched alkyl in a kind of.
In the present invention, C
1-C
5The straight or branched alkoxyl group include but not limited to: methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, isopentyloxy, uncle's pentyloxy and neopentyl oxygen.
In the present invention, C
1-C
5The straight or branched alkyl example can for but be not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl and neo-pentyl.
Preferably, in formula I, R
1And R
2Respectively do for oneself a kind of in chlorine, bromine and iodine, namely described carrier is magnesium halide.Most preferably, in formula I, R
1And R
2Be chlorine, namely described magnesium compound is magnesium dichloride.
Of the present invention a kind of preferred embodiment in, described carrier is magnesium compound, described solid ingredient contains magnesium compound and loads on titanium compound and internal electron donor compound on described magnesium compound, be that described solid ingredient contains titanium, magnesium and internal electron donor compound, be the reaction product of titanium compound and internal electron donor compound and magnesium compound.More preferably, described magnesium compound is magnesium halide.
According to the present invention, described titanium compound can be various titanium compounds commonly used in olefin polymerization catalysis.Preferably, described titanium compound is the titanium compound shown in formula II,
TiX
1 m(OR
3)
4-m (II)
In formula II, X
1Can be in chlorine, bromine and iodine a kind of, R
3Can be C
1-C
5The straight or branched alkyl, m can be the integer of 0-4.In formula II, m for example can be 0,1,2,3 or 4.
In the present invention, the example of described titanium compound can for but be not limited to: one or more in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium and trichlorine one ethanolato-titanium.
Preferably, in formula II, X
1A kind of in chlorine, bromine and iodine, R
3Be C
1-C
5The straight or branched alkyl, m is the integer of 1-4, for example: described titanium compound can be one or more in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, a chlorine triethoxy titanium, dichloro diethoxy titanium and trichlorine one ethanolato-titanium.
Further preferably, in formula II, X
1A kind of in chlorine, bromine and iodine, m is 4, for example: described titanium compound can be one or more in titanium tetrachloride, titanium tetrabromide and titanium tetra iodide.Most preferably, in formula II, m is 4, and X
1Be chlorine, namely described titanium compound is titanium tetrachloride.
According to the present invention, described internal electron donor compound can be the various internal electron donor compounds that field of olefin polymerisation is commonly used, and for example: described internal electron donor compound can be one or more in the Bisphthalate based compound.Preferably, described internal electron donor compound is one or more in diisobutyl phthalate, n-butyl phthalate, n-propyl phthalate, diisopropyl phthalate, diethyl phthalate and dimethyl phthalate.
According to the present invention, in described solid ingredient, the content of each component can be selected for the routine of this area.For example, when described carrier is magnesium compound, take the total amount of described solid ingredient as benchmark, in described solid ingredient, content take the titanium compound of titanium can be as the 0.5-4.5 % by weight, the content of internal electron donor compound can be the 6-15 % by weight, can be as the 80.5-93.5 % by weight take the content of the magnesium compound of magnesium; Preferably, take the total amount of described solid ingredient as benchmark, take the content of the titanium compound of titanium as the 1.5-3.5 % by weight, the content of internal electron donor compound is the 7-10 % by weight, take the content of the magnesium compound of magnesium as the 86.5-91.5 % by weight.
According to the present invention, described olefin polymerization catalyst system also contains organo-aluminium compound and external donor compound except containing solid ingredient.
According to the present invention, described organo-aluminium compound can be this area various organo-aluminium compounds commonly used.Usually, described organo-aluminium compound can be one or more in the organo-aluminium compound shown in formula III,
In formula III, R
4, R
5And R
6Can be chlorine and C separately
1-C
5The straight or branched alkyl in a kind of, and R
4, R
5And R
6In at least one is C
1-C
5The straight or branched alkyl.
Preferably, described organo-aluminium compound is one or more in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium and diethyl aluminum chloride.Further preferably, described organo-aluminium compound is triethyl aluminum.
According to the present invention, described external donor compound can be selected for the routine of this area.For example, described external donor compound can be for can be as one or more in carboxylic acid, acid anhydrides, ester, ketone, ether, alcohol, organo phosphorous compounds and the silicoorganic compound of the external donor compound of olefin polymer catalyst system.Preferably, described external donor compound is one or more compounds that are selected from silicoorganic compound.Further preferably, described external donor compound is one or more in dicyclo amyl group dimethoxy silane, diisopropyl dimethoxy silane, diisobutyl dimethoxy silicon and Cyclohexyl Methyl Dimethoxysilane.
According to the present invention, in described olefin polymerization catalyst system, the mol ratio between described solid ingredient, organo-aluminium compound and external donor compound is not particularly limited, and can select for the routine of this area.
Preferably, the mol ratio of the aluminium in described organo-aluminium compound and the titanium in described solid ingredient is 1-300: 1; The mol ratio of described organo-aluminium compound and described external donor compound is 1-40: 1.
According to the present invention, described alkene gas-phase polymerization condition can be selected for the routine of this area.Preferably, described alkene gas-phase polymerization condition comprises: temperature can be 55-85 ℃, is preferably 60-80 ℃; Pressure can be 1-8MPa, is preferably 1.2-7.5MPa.
According to the present invention, the contact of described propylene, ethene and alpha-olefin is preferably carried out under hydrogen exists, and hydrogen can be regulated the molecular weight (that is, melt mass flow rate) of the propene polymer of preparation as molecular weight regulator.The present invention is not particularly limited for the consumption of described hydrogen, can carry out appropriate selection according to the molecular weight of the propene polymer of expecting.Preferably, the mol ratio of described hydrogen and described propylene can be 0.013-0.027: 1.When the mol ratio of described hydrogen and described propylene was within above-mentioned scope, the melt mass flow rate of the propene polymer of preparation generally can be in the scope of 0.5-30 gram/10 minute.
According to the present invention, described alpha-olefin can for this area commonly used various can with the compound of propylene and ethene generation copolymerization.The example of described alpha-olefin can for but be not limited to: 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-heptene and 1-octene.Preferably, described alpha-olefin is 1-butylene.
According to the present invention, the quantity of described gas-phase polymerization reactor can be carried out appropriate selection according to practical application.For example: gas-phase polymerization reactor can be one, also can be a plurality of (for example: 2).The method according to this invention, at described gas-phase polymerization reactor when being a plurality of, described a plurality of gas-phase polymerization reactors each other can be for being connected in parallel, also can be for being connected in series.When being connected in series, the product of contact of previous gas-phase polymerization reactor output contacts with another part propylene, ethene and alpha-olefin in next gas-phase polymerization reactor at described a plurality of gas-phase polymerization reactors.
According to of the present invention a kind of preferred embodiment in, described gas-phase polymerization reactor is two gas-phase polymerization reactors that are connected in series, the method according to this invention comprises:
Under the first alkene gas-phase polymerization condition, first part's propylene, first part's ethene and first part alpha-olefin are carried out first with described olefin polymerization catalyst system contact in first gas-phase polymerization reactor; And
Contact described first and send in second gas-phase polymerization reactor after the mixture that obtains is removed unreacted monomer, under the second alkene gas-phase polymerization condition, make described product of contact carry out second with second section propylene, second section ethene and second section alpha-olefin and contact.
This preferred embodiment in, take the total amount of described first part propylene, first part's ethene and first part's alpha-olefin as benchmark, the amount of described first part propylene is the 80-95 % by weight, the amount of described first part ethene is the 1-5 % by weight, and the amount of described first part alpha-olefin is the 1-15 % by weight;
Take the total amount of described second section propylene, second section ethene and second section alpha-olefin as benchmark, the amount of described second section propylene is the 75-95 % by weight, the amount of described second section ethene is the 1-10 % by weight, and the amount of described second section alpha-olefin is the 1-15 % by weight.Thus in the propene polymer of preparation, take the total amount of described propene polymer as benchmark, the content of described propylene structural unit is the 80-95 % by weight, and the content of described ethene structural unit is the 1-10 % by weight, and the content of described alpha-olefin structural unit is the 1-19 % by weight.
This preferred embodiment in, described the first alkene gas-phase polymerization condition and described the second alkene gas-phase polymerization condition can be that the routine of this area selects.Usually, described the first alkene gas-phase polymerization condition and described the second alkene gas-phase polymerization condition comprise separately: temperature can be 55-85 ℃, is preferably 60-80 ℃; Pressure can be 1-8MPa, is preferably 1.2-7.5MPa.
This preferred embodiment in, described first part alpha-olefin and described second section alpha-olefin can be selected from alpha-olefin mentioned above separately.Preferably, described first part's alpha-olefin and described second section alpha-olefin are 1-butylene.
According to the present invention, described gas-phase polymerization reactor can be this area various gas-phase polymerization reactors commonly used, for example: fluidized-bed reactor and horizontal type agitated bed gas-phase polymerization reactor.Olefine polymerizing process according to the present invention is particularly suitable for implementing in horizontal type agitated bed gas-phase polymerization reactor.
Of the present invention a kind of preferred embodiment in, described gas-phase polymerization reactor is horizontal type agitated bed gas-phase polymerization reactor, and described horizontal type agitated bed reactor is two horizontal type agitated bed gas-phase polymerization reactors mutually being connected in series.
According to polymkeric substance film composition of the present invention, said composition also contains film coalescence aid except containing the propylene polymerization beyond the region of objective existence, forms film with auxiliary described propene polymer, perhaps gives the polymeric film of formation with certain performance or function.
The present invention is not particularly limited for the consumption of described film coalescence aid, can carry out appropriate selection according to the kind of described film coalescence aid.Usually, with respect to the 100 described propene polymers of weight part, the total amount of described auxiliary agent can be the 0.05-5 weight part.Preferably, with respect to the 100 described propene polymers of weight part, the total amount of described auxiliary agent is the 0.08-2.5 weight part.
According to polymeric film of the present invention, appropriate selection is carried out in the kind of the polymeric film that described film coalescence aid can form as required and concrete application scenario.Usually, described film coalescence aid can be for being selected from one or more the auxiliary agent in oxidation inhibitor, stablizer, opening agent and slipping agent.
Described oxidation inhibitor, stablizer, opening agent and slipping agent can be selected for the routine of this area separately, are not particularly limited.
In the present invention, described oxidation inhibitor can for this area various oxidation inhibitor commonly used, be 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 the polymkeric substance peroxy radical, can be that oxidation inhibitor and amine are one or more in oxidation inhibitor for being selected from hindered phenol; Described auxiliary antioxidant is the hydroperoxide in decomposing copolymer effectively, prevent the carrying out that its homolysis produces new free radical, causes Auto-oxidation reaction, can be for example that oxidation inhibitor and monothioester are one or more in oxidation inhibitor for being selected from phosphorous acid ester.in the present invention, the example of described oxidation inhibitor can include but not limited to: 2, the 6-di-tert-butyl-4-methy phenol, β-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester is (namely, antioxidant 1010), the sulfo-diethylene is two, and [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, 1, 3, 5-trimethylammonium-2, 4, 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1, 3, 5-three (3, the 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 for but be not limited to: three [2, the 4-di-tert-butyl-phenyl] phosphorous acid ester is (namely, irgasfos 168), four (2, the 4-di-tert-butylphenol)-4,4 '-xenyl diphosphites, three nonylated phenyl phosphites, two (2,4-DTBP) pentaerythritol diphosphites, the two stearyl alcohol esters of thio-2 acid and Tyox B.From the angle of further raising antioxidant property, described antioxidant preferably with described phenol be oxidation inhibitor and/or amine be oxidation inhibitor as primary antioxidant, with phosphorous acid ester and/or monothioester as auxiliary antioxidant.The ratio of described primary antioxidant and described auxiliary antioxidant can be selected for the routine of this area.Usually, the weight ratio of described primary antioxidant and described auxiliary antioxidant can be 1: 0.5-4.The consumption of described oxidation inhibitor can be selected for the routine of this area, and for example: with respect to the 100 described propene polymers of weight part, the content of described oxidation inhibitor can be the 0.01-0.5 weight part, is preferably the 0.03-0.5 weight part.
In the present invention, described stablizer can prevent that product from aging additive in use occuring, and comprises photostabilizer and thermo-stabilizer for commonly used various in this area.the example of described photostabilizer can include but not limited to: benzophenone is stablizer, for example: ESCALOL 567 (UV-9), Octabenzone (UV-531), triazine is stablizer, for example: 2,4,6-three (2-hydroxyl-4-butoxy phenyl)-1,3,5-triazines (triazine-5), the nickel salt quencher, for example: dithiocarbamic acid nickel salt and two (3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester) nickel (Irgastab-2002), benzotriazole is stablizer, for example: 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole (UV-P), 2 '-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorobenzotriazole (UV-326), hindered amine is stablizer, for example: three (1, 2, 2, 6, 6-pentamethyl-piperidyl) phosphorous acid ester (GW540), poly-succinic (4-hydroxyl-2, 2, 6, 6-tetramethyl--1-piperidines ethanol) ester (photostabilizer 622), poly-[(6-morpholinyl-1, 3, 5-triazine-2, the 4-yl)-((2, 2, 6, 6-tetramethyl--4-piperidyl) imido) hexane-((2, 2, 6, 6-tetramethyl--4-piperidyl) imido)] (photostabilizer 3346) and poly-[[6-[(1, 1, 3, the 3-tetramethyl butyl) amine]-1, 3, 5-triazine-2, 4-two bases] [(2, 2, 6, 6-tetramethyl--4-piperidines) imines]-1, 6-two dihexyls [(2, 2, 6, 6-tetramethyl--4-piperidines) imines]]] (photostabilizer 944), salicylate is stablizer, for example: dihydroxyphenyl propane sasapyrin (UV Absorber BAD) and Whitfield's ointment-4-tertiary butyl phenyl ester (UV light absorber TBS).The example of described thermo-stabilizer can include but not limited to: metallic soap is stablizer, for example: hydrotalcite, sodium stearate, Magnesium Stearate, calcium stearate, strontium stearate, barium stearate, Zinic stearas, cadmium stearate, aluminum stearate, lithium stearate, lead stearate, cobalt stearate, aluminium hydroxy distearate, the inferior tin of stearic acid, calcium laurate, barium laurate, zinc laurate, cadmium laurate, calcium benzoate and Zinc dibenzoate.The amount of described stablizer can be carried out appropriate selection according to kind and the concrete application scenario of the polymeric film of final preparation.Usually, with respect to the 100 described propene polymers of weight part, the amount of described stablizer can be the 0.01-0.5 weight part, is preferably the 0.02-0.5 weight part.
In the present invention, described opening agent refers to realize the reagent of the function that the film with mutual driving fit separates.Described opening agent can be that the routine of this area selects, and for example, described opening agent can be one or more in silicon-dioxide, diatomite, talcum, calcium carbonate and secondary calcium phosphate.Preferably, described opening agent is silicon-dioxide.The amount of described opening agent can be carried out appropriate selection according to the character of concrete film-forming process and described propene polymer.Usually, with respect to the propene polymer of 100 weight parts, the amount of described opening agent can be the 0.05-1 weight part, is preferably the 0.1-1 weight part.
In the present invention, described slipping agent can be the various auxiliary agents that can realize reducing frictional coefficient between film.The kind that can realize the slipping agent of above-mentioned functions is known in the field, and for example: described slipping agent can be one or more in the two amine hydroxybenzenes of calcium stearate, polyethylene wax, erucicamide, amine hydroxybenzene, stearic amide, methylene bis stearylamide, ethylene bis stearic acid amide, ethylene, glyceryl monostearate, pentaerythritol tetrastearate, curing Viscotrol C, stearic acid stearyl ester, stearyl alcohol, Zinic stearas, Magnesium Stearate, lead stearate, stearic acid, docosoic acid, 12-oxystearic acid, solid paraffin and microcrystalline wax.The present invention is not particularly limited for the amount of described slipping agent, can select for the routine of this area.Usually, with respect to the described propene polymer of 100 weight parts, the amount of described slipping agent can be the 0.05-1 weight part, is preferably the 0.1-1 weight part.
According to the good film-forming property of polymkeric substance film composition of the present invention, can adopt this area the whole bag of tricks commonly used to form polymeric film.Thus, the present invention also provides the application of a kind of polymkeric substance film composition according to the present invention in the preparation polymeric film.
Of the present inventionly further provide a kind of polymeric film that is formed by polymkeric substance film composition of the present invention.
Can adopt the ordinary method of this area to prepare described polymeric film.For example, described propene polymer pellet can be mixed with film coalescence aid, to obtain containing the described raw material of propene polymer, then described raw material is extruded, the polymeric film that obtains not stretching carries out unilateral stretching with the described polymkeric substance that does not stretch or two-way stretch can prepare the polymeric film of stretching.This paper no longer describes in detail.
Not only have high heat seal strength according to polymeric film of the present invention, but also have excellent heat resistanceheat resistant adhesion performance, also have simultaneously low heat-sealing temperature.Therefore, described polymeric film is particularly preferably heat-shrinkable film.
The present invention also provides a kind of multilayer film, at least one lip-deep hot sealing layer that this multilayer film contains substrate layer and is positioned at described substrate layer, and wherein, described hot sealing layer is polymeric film provided by the invention.
Can adopt this area the whole bag of tricks commonly used to form described multilayer film, for example can be by polymeric film of the present invention and described substrate layer be carried out hot pressing, thus obtain described multilayer film.
According to multilayer film of the present invention, described substrate layer can be this area various polymeric films commonly used.When multilayer film according to the present invention was used as heat-shrinkable film, described substrate layer was preferably the polymeric film that is formed by polyethylene (being preferably Low Density Polyethylene).
Multilayer film according to the present invention is particularly suitable for as heat-shrinkable film.
Describe the present invention in detail below in conjunction with embodiment.
Following examples relate to following testing method.
1, the granularity of catalyst solid constituent and size distribution curve: measure being purchased on the Chengdu bass reaches the laser fineness gage of Instr Ltd..
2, melt mass flow rate: be to measure according to the method for stipulating in GB/T 3682-2000.Particularly, probe temperature is 230 ℃, and load is 2.16 kilograms.
3, melt temperature and Tc: be to measure according to the method for stipulating in ASTM D3418-03, be specially:
Be on the differential scanning calorimeter of TA-9900 in the model that is purchased from U.S. Du-Pont company, with about 5mg sample, at N
2Under protection, be warming up to 180 ℃ with the speed of 10 ℃/min, constant temperature 3min at this temperature then with 10 ℃/min cooling, obtains the Tc of sample; Then heat up with 10 ℃/min, obtain the melt temperature of sample.
4, xylene soluble part content: be to measure according to the method for stipulating in GB/T 24282-2009;
5, hexane solubles content: take 4 gram samples, limit of error ± 0.001g, particle shape is 1mm * 1mm * 1mm, joins apparatus,Soxhlet's, after the normal hexane boiling, drip washing is after 4 hours, and is cooling, carries out weighing.
6, the ethene structural unit content in propene polymer and 1-butylene structural unit content: be to adopt the carbon-13 nmr spectra method to measure.Wherein, solvent is that deuterium is for orthodichlorobenzene; Carbon-13 nmr spectra test is carried out being purchased on the nuclear magnetic resonance spectrometer that model from Switzerland Bruker company is BRUKER400.Test condition comprises: operating frequency is 100.62MHz, 30 ° of pulses, and the burst length is 3s, and the proton noise is uncoupled entirely, and spectrum width is 15000Hz, and accumulative frequency is 4000 times, calibrates with the isolated mesomethylene carbon in 30.0ppm place.
7, the testing method of initial heat-sealing temperature is:
It is that 15mm, thickness are the film of 30 μ m that propene polymer is made width, take 1 ℃ as the interval, as initial probe temperature, with two mutual pressings of film, the heat-sealing time is 1s with 105 ℃, heat-sealing pressure is 0.45MPa, fixed temperature and humidity was placed after 48 hours, utilized the Instron5566 material-testing machine, and the spacing jig of trier is from being 50mm, trial speed is 300mm/min, the needed power value when measure sample is opened.Be that the initial probe temperature of 7N when above is as initial heat-sealing temperature with the power that records.
8, the testing method of heat resistanceheat resistant adhesion performance:
It is that 15mm, thickness are the film of 30 μ m that propene polymer is made width, film and copy paper (are purchased the Paper Co., Ltd from Ya Long, model is A4, operative norm Q/320583WYYL004) be cut into respectively the bar that width is 15mm ± 0.1mm, length 100mm ± 1; With film and copy paper pressing, wherein, pressing time is 0.5s, pressing pressure is 0.3-0.45MPa, and pressing utilized the Instron5566 material-testing machine after 30 minutes, needed power value when measure sample is opened, the spacing jig of trier is from being 50mm, trial speed is 300mm/min.Power value when the sample of measuring is opened is as the measurement index of the heat resistanceheat resistant adhesion performance of this film, and wherein, the value of power is less, and heat resistanceheat resistant adhesion performance is just better.
Embodiment 1
The present embodiment is used for explanation according to polymkeric substance film composition of the present invention and polymeric film and multilayer film.
(1) preparation of propene polymer
Employing is purchased the catalyst solid constituent that reaches petrochemical industry company limited from Beijing Austria, before using, this catalyst solid constituent is sieved, so that the granularity of described catalyst solid constituent is the 10-50 micron, and granularity is that the amount of the solid ingredient within the scope of 14-30 micron is 87 volume %; The size distribution curve of the solid ingredient of collecting as shown in Figure 1, is unimodal distribution.
Take the total amount of described solid ingredient as benchmark, the titanium content in described solid ingredient is 2.5 % by weight, and the content of di-n-butyl terephthalate is 9 % by weight.
Catalyst solid constituent is added 50m continuously with 0.61g/h
3Continuous horizontal type agitated bed Gas-phase reactor in, add continuously triethyl aluminum with pump, its add-on makes aluminium in triethyl aluminum and the mol ratio Al/Ti=30 of the titanium in catalyst solid constituent, add continuously Cyclohexyl Methyl Dimethoxysilane (wherein, the mol ratio of triethyl aluminum and Cyclohexyl Methyl Dimethoxysilane is 20: 1).Then, pass into propylene, ethene, 1-butylene and hydrogen in the described reactor and carry out polyreaction, wherein, the pressure in reactor is 1.4MPa, and the temperature in reactor is 65 ℃, the hydrogen in reactor/propylene mol ratio (H
2/ C
3) be 0.018, take the total amount of propylene, ethene and 1-butylene as benchmark, the content of propylene is 85.0 % by weight, and the content of ethene is 3.3 % by weight, and the content of 1-butylene is 11.7 % by weight.Propylene, ethene, 1-butylene and the hydrogen mean residence time in reactor is 60min, and the reactor material level is 70%.
The phenomenon that polymer beads stops up the material discharge line of reactor does not appear in polymerization process.The composition of the propene polymer of preparation and character are shown in table 1.
(2) preparation of polymeric film
The propene polymer of step (1) preparation is mixed with film coalescence aid in table 2, adopt casting method to form polymeric film in the mixture that obtains, the concrete technology flow process is: with the melting in forcing machine of described mixture, with melt by the slit on T font head (slit gap is 0.4-0.65mm) film extrusion.The film of extruding is attached to cooling roller with the pressurized air that air knife sprays.By in the process of cooling roller, extruded film is due to the stretching thinning at extruded film, is the film of 30 microns and finally form thickness.
The initial heat-sealing temperature of the polymeric film of mensuration preparation and heat resistanceheat resistant adhesion performance are shown in table 1.
Comparative Examples 1
Adopt the method identical with embodiment 1 to prepare propene polymer and polymeric film, different is, in step (1), solid ingredient is sieved processing before use, solid ingredient is sieved processing, the granularity that makes the solid ingredient that obtains is the 7-320 micron, and granularity is that the amount of the solid ingredient within the scope of 14-30 micron is 65 volume %; As shown in Figure 2, size-grade distribution is that multimodal distributes.In reaction process, the mutual adhesion caking of polymkeric substance forces to produce to stop.Film occuring in film process tear phenomenon, can not obtain complete film.
The composition of the propene polymer of preparation and character are shown in table 1.
Comparative Examples 2
Adopt the method identical with embodiment 1 to prepare propene polymer and polymeric film, different is, in step (1), solid ingredient is sieved before use, so that the granularity of catalyst solid constituent is the 0.7-100 micron, and granularity is that the amount of the solid ingredient within the scope of 14-30 micron is 82 volume %, and size-grade distribution is that multimodal distributes.In reaction process, the mutual adhesion caking of polymkeric substance forces to produce to stop.
The composition of the propene polymer of preparation and character are shown in table 1.The initial heat-sealing temperature of the polymeric film of preparation and heat resistanceheat resistant adhesion performance are shown in table 1.
Embodiment 2
The present embodiment is used for explanation according to polymkeric substance film composition of the present invention and polymeric film and multilayer film.
Adopt the method identical with embodiment 1 to prepare propene polymer and polymeric film, different is, in step (1), granularity is that the amount of the solid ingredient within the scope of 14-30 micron is 90 volume %.
The phenomenon that polymer beads stops up the material discharge line of reactor does not appear in polymerization process.The composition of the propene polymer of preparation and character are shown in table 1.The initial heat-sealing temperature of the polymeric film of preparation and heat resistanceheat resistant adhesion performance are shown in table 1.
Embodiment 3
The present embodiment is used for explanation according to polymkeric substance film composition of the present invention and polymeric film and multilayer film.
Adopt the method identical with embodiment 1 to prepare propene polymer, different is, in step (1), granularity is that the amount of the solid ingredient within the scope of 14-30 micron is 100 volume %.
The phenomenon that polymer beads stops up the material discharge line of reactor does not appear in polymerization process.The composition of the propene polymer of preparation and character are shown in table 1.The initial heat-sealing temperature of the polymeric film of preparation and heat resistanceheat resistant adhesion performance are shown in table 1.
Embodiment 4
The present embodiment is used for explanation according to polymkeric substance film composition of the present invention and polymeric film and multilayer film.
Adopt the method identical with embodiment 1 to prepare propene polymer and polymeric film, different is, in step (1), and the aluminium in triethyl aluminum and the mol ratio Al/Ti=35 of the titanium in catalyst solid constituent.
The phenomenon that polymer beads stops up the material discharge line of reactor does not appear in polymerization process.The composition of the propene polymer of preparation and character are shown in table 1.The initial heat-sealing temperature of the polymeric film of preparation and heat resistanceheat resistant adhesion performance are shown in table 1.
Embodiment 5
The present embodiment is used for explanation according to polymkeric substance film composition of the present invention and polymeric film and multilayer film.
Adopt the method identical with embodiment 1 to prepare propene polymer and polymeric film, different is that in step (1), the mol ratio of triethyl aluminum and Cyclohexyl Methyl Dimethoxysilane is 25: 1.
The phenomenon that polymer beads stops up the material discharge line of reactor does not appear in polymerization process.The composition of the propene polymer of preparation and character are shown in table 1.The initial heat-sealing temperature of the polymeric film of preparation and heat resistanceheat resistant adhesion performance are shown in table 1.
Embodiment 6
The present embodiment is used for explanation according to polymkeric substance film composition of the present invention and polymeric film and multilayer film.
Adopt the method identical with embodiment 1 to prepare propene polymer and polymeric film, different is in step (1), to use second, isobutyl dimethoxy silane to replace Cyclohexyl Methyl Dimethoxysilane.
The phenomenon that polymer beads stops up the material discharge line of reactor does not appear in polymerization process.The composition of the propene polymer of preparation and character are shown in table 1.The initial heat-sealing temperature of the polymeric film of preparation and heat resistanceheat resistant adhesion performance are shown in table 1.
Embodiment 7
The present embodiment is used for explanation according to polymkeric substance film composition of the present invention and polymeric film and multilayer film.
Adopt the method identical with embodiment 1 to prepare propene polymer and polymeric film, different is, the granularity of described solid ingredient is the 10-50 micron, and granularity is that the amount of the solid ingredient within the scope of 14-30 micron is 80 volume %, and the size distribution curve of solid ingredient is unimodal distribution.
The phenomenon that polymer beads stops up the material discharge line of reactor does not appear in polymerization process.The composition of the propene polymer of preparation and character are shown in table 1.The initial heat-sealing temperature of the polymeric film of preparation and heat resistanceheat resistant adhesion performance are shown in table 1.
Embodiment 8
The present embodiment is used for explanation according to polymkeric substance film composition of the present invention and polymeric film and multilayer film.
Adopt the method identical with embodiment 1 to prepare polymeric film, different is, the granularity of catalyst solid constituent is the 10-50 micron, and wherein, granularity is that the amount of the solid ingredient within the scope of 14-30 micron is 81 volume %, and size distribution curve is unimodal distribution.
Take the total amount of described solid ingredient as benchmark, the titanium content in described solid ingredient is 2.6 % by weight, and the content of dibutyl terephthalate is 9.2 % by weight.
Catalyst solid constituent is added 50m continuously with 0.65g/h
3Continuous horizontal type agitated bed Gas-phase reactor in, add continuously triethyl aluminum with pump, its add-on makes aluminium in triethyl aluminum and the mol ratio Al/Ti=28 of the titanium in catalyst solid constituent, add continuously diisopropyl dimethoxy silane (wherein, the mol ratio of triethyl aluminum and diisopropyl dimethoxy silane is 23).Then, pass into propylene, ethene, 1-butylene and hydrogen in the described reactor and carry out polyreaction, wherein, the pressure in reactor is 1.7MPa, and the temperature in reactor is 67 ℃, the hydrogen in reactor/propylene mol ratio (H
2/ C
3) be 0.022, take the total amount of propylene, ethene and 1-butylene as benchmark, the content of propylene is 85 % by weight, and the content of ethene is 3 % by weight, and the content of 1-butylene is 12 % by weight.Propylene, ethene, 1-butylene and the hydrogen mean residence time in reactor is 45min, and the reactor material level is 60%.
The phenomenon that polymer beads stops up the material discharge line of reactor does not appear in polymerization process.The composition of the propene polymer of preparation and character are shown in table 1.The initial heat-sealing temperature of the polymeric film of preparation and heat resistanceheat resistant adhesion performance are shown in table 1.
Embodiment 9
The present embodiment is used for explanation according to polymkeric substance film composition of the present invention and polymeric film and multilayer film.
Adopt the method identical with embodiment 1 to prepare polymeric film, different is to adopt following methods to prepare propene polymer.
The granularity of catalyst solid constituent is the 10-50 micron, and wherein, granularity is that the amount of the solid ingredient within the scope of 14-30 micron is 82 volume %, and the size distribution curve of the solid ingredient of collecting is unimodal distribution.
Take the total amount of described solid ingredient as benchmark, the titanium content in described solid ingredient is 2.7 % by weight, and the content of di-n-butyl terephthalate is 11.1 % by weight.
Catalyst solid constituent is added 50m continuously with 0.63g/h
3Continuous horizontal type agitated bed Gas-phase reactor in, add continuously triethyl aluminum with pump, its add-on makes aluminium in triethyl aluminum and the mol ratio Al/Ti=36 of the titanium in catalyst solid constituent, add continuously diisopropyl dimethoxy silane (wherein, the mol ratio of triethyl aluminum and diisopropyl dimethoxy silane is 25).Then, pass into propylene, ethene, 1-butylene and hydrogen in the described reactor and carry out polyreaction, wherein, the pressure in reactor is 2.0MPa, and the temperature in reactor is 68 ℃, the hydrogen in reactor/propylene mol ratio (H
2/ C
3) be 0.018, take the total amount of propylene, ethene and 1-butylene as benchmark, the content of propylene is 80 % by weight, and the content of ethene is 4 % by weight, and the content of 1-butylene is 16 % by weight.Propylene, ethene, 1-butylene and the hydrogen mean residence time in reactor is 45min, and the reactor material level is 65%.
The phenomenon that polymer beads stops up the material discharge line of reactor does not appear in polymerization process.The composition of the propene polymer of preparation and character are shown in table 1.The initial heat-sealing temperature of the polymeric film of preparation and heat resistanceheat resistant adhesion performance are shown in table 1.
The present embodiment is used for explanation according to polymkeric substance film composition of the present invention and polymeric film and multilayer film.
Adopt the method identical with embodiment 9 to prepare propene polymer and polymeric film, different is, in step (1), take the total amount of propylene, ethene and 1-butylene as benchmark, the content of propylene is 75 % by weight, and the content of ethene is 5 % by weight, and the content of 1-butylene is 20 % by weight.
The phenomenon that polymer beads stops up the material discharge line of reactor does not appear in polymerization process.The composition of the propene polymer of preparation and character are shown in table 1.The initial heat-sealing temperature of the polymeric film of preparation and heat resistanceheat resistant adhesion performance are shown in table 1.
Embodiment 11
The present embodiment is used for explanation according to polymkeric substance film composition of the present invention and application and polymeric film.
Adopt the method identical with embodiment 1 to prepare propene polymer and polymeric film, different is, produces propene polymer with two horizontal type agitated bed reactors that mutually are connected in series, and concrete operations are as follows.
Catalyst solid constituent is added 50m continuously with 0.71g/h
3First continuous horizontal type agitated bed Gas-phase reactor in, add continuously triethyl aluminum with pump, its add-on makes aluminium in triethyl aluminum and the mol ratio Al/Ti=45 of the titanium in catalyst solid constituent, add continuously diisopropyl dimethoxy silane (wherein, the mol ratio of triethyl aluminum and diisopropyl dimethoxy silane is 23).Then, pass into propylene, ethene, 1-butylene and hydrogen in the described reactor and carry out polyreaction, wherein, the pressure in reactor is 2.2MPa, and the temperature in reactor is 68 ℃, the hydrogen in reactor/propylene mol ratio (H
2/ C
3) be 0.033, take the total amount of propylene, ethene and 1-butylene as benchmark, the content of propylene is 90 % by weight, and the content of ethene is 2 % by weight, and the content of 1-butylene is 8 % by weight.Propylene, ethene, 1-butylene and the hydrogen mean residence time in reactor is 45min, and the reactor material level is 60%.
The product of above-mentioned first continuous horizontal type agitated bed Gas-phase reactor output is sent in the second continuous horizontal type agitated bed Gas-phase reactor.Wherein, in second continuous horizontal type agitated bed Gas-phase reactor: pressure is 1.6MPa, temperature is 63 ℃, hydrogen/propylene mol ratio is 0.010, take the total amount of propylene, ethene and 1-butylene as benchmark, the content of propylene is 75 % by weight, and the content of ethene is 7 % by weight, and the content of 1-butylene is 18 % by weight.Propylene, ethene, 1-butylene and the hydrogen mean residence time in reactor is 60min, and the reactor material level is 65%.
The phenomenon that polymer beads stops up the material discharge line of reactor does not appear in polymerization process.The composition of the propene polymer of preparation and character are shown in table 1.The initial heat-sealing temperature of the polymeric film of preparation and heat resistanceheat resistant adhesion performance are shown in table 1.
Claims (17)
1. polymkeric substance film composition, said composition contains propene polymer and film coalescence aid, it is characterized in that, described propene polymer contain derived from propylene propylene structural unit, derived from ethylene the ethene structural unit and derived from C
4-C
8The alpha-olefin structural unit of alpha-olefin, take the total amount of described propene polymer as benchmark, the content of described propylene structural unit is the 80-95 % by weight, and the content of described ethene structural unit is the 1-10 % by weight, and the content of described alpha-olefin structural unit is the 1-19 % by weight;
Take the total amount of described propene polymer as benchmark, the xylene soluble part content of described propene polymer is the 1-20 % by weight, and the dimethylbenzene insolubles content of described propene polymer is the 80-99 % by weight;
The Tc of described xylene soluble part is 40-65 ℃, and melt temperature is 80-97 ℃; The Tc of described dimethylbenzene insolubles is 85-105 ℃, and melt temperature is 125-135 ℃.
2. composition according to claim 1, wherein, take the total amount of described propene polymer as benchmark, the content of described propylene structural unit is the 85-95 % by weight, the content of described ethene structural unit is the 1-5 % by weight, and the content of described alpha-olefin structural unit is the 1-10 % by weight.
3. composition according to claim 2, wherein, take the total amount of described propene polymer as benchmark, the xylene soluble part content of described propene polymer is the 1-15 % by weight, the dimethylbenzene insolubles content of described propene polymer is the 85-99 % by weight.
4. composition according to claim 1, wherein, described propene polymer prepares by the following method: in gas-phase polymerization reactor, under the alkene gas-phase polymerization condition, with propylene, ethene be selected from C
4-C
8Alpha-olefin contact with olefin polymerization catalyst system;
Described olefin polymerization catalyst system contains solid ingredient, external donor compound and organo-aluminium compound, and described solid ingredient contains carrier and loads on titanium compound and internal electron donor compound on described carrier;
The consumption of described propylene, ethene and alpha-olefin makes in the propene polymer of final preparation, take the total amount of described propene polymer as benchmark, the content of described propylene structural unit is the 80-95 % by weight, the content of described ethene structural unit is the 1-10 % by weight, and the content of described alpha-olefin structural unit is the 1-19 % by weight;
The granularity of described solid ingredient is the 10-50 micron, take the total amount of described solid ingredient as benchmark, the content that granularity is in the solid ingredient within the scope of 14-30 micron is 80-100 volume %, and the size distribution curve of described solid ingredient is unimodal, described size distribution curve is take granularity as X-coordinate, take volume fraction as ordinate zou.
5. composition according to claim 4, wherein, take the total amount of described solid ingredient as benchmark, the amount that granularity is in the solid ingredient within the scope of 14-30 micron is 90-100 volume %.
6. composition according to claim 4, wherein, the mol ratio of the titanium in the aluminium in described organo-aluminium compound and described solid ingredient is 1-300: 1, the mol ratio of described organo-aluminium compound and described external donor compound is 1-40: 1.
7. composition according to claim 4, wherein, described alkene gas-phase polymerization condition comprises: temperature is 55-85 ℃, pressure is 1-8MPa.
8. composition according to claim 4, wherein, described gas-phase polymerization reactor comprises two gas-phase polymerization reactors that are connected in series, with propylene, ethene be selected from C
4-C
8The mode that contacts with olefin polymerization catalyst system of alpha-olefin comprise:
Under the first alkene gas-phase polymerization condition, first part's propylene, first part's ethene and first part alpha-olefin are carried out first with described olefin polymerization catalyst system contact in first gas-phase polymerization reactor; And
Contact described first and send in second gas-phase polymerization reactor after the mixture that obtains is removed unreacted monomer, under the second alkene gas-phase polymerization condition, carry out second with second section propylene, second section ethene and second section alpha-olefin and contact;
Wherein, take the total amount of described first part propylene, first part's ethene and first part's alpha-olefin as benchmark, the amount of described first part propylene is the 80-95 % by weight, and the amount of described first part ethene is the 1-5 % by weight, and the amount of described first part alpha-olefin is the 1-15 % by weight;
Take the total amount of described second section propylene, second section ethene and second section alpha-olefin as benchmark, the amount of described second section propylene is the 75-95 % by weight, the amount of described second section ethene is the 1-10 % by weight, and the amount of described second section alpha-olefin is the 1-15 % by weight.
9. composition according to claim 8, wherein, described the first alkene gas-phase polymerization condition and described the second alkene gas-phase polymerization condition comprise separately: temperature is 55-85 ℃, and pressure is 1-8MPa.
10. according to claim 1, the described composition of any one in 2,4 and 8, wherein, described alpha-olefin is 1-butylene.
11. according to claim 4 or 8 described compositions, wherein, described gas-phase polymerization reactor is horizontal type agitated bed gas-phase polymerization reactor.
12. composition according to claim 1, wherein, with respect to the 100 described propene polymers of weight part, the total amount of described film coalescence aid is the 0.05-5 weight part.
13. according to claim 1 or 12 described compositions, wherein, described film coalescence aid is one or more the auxiliary agent that is selected from oxidation inhibitor, stablizer, opening agent and slipping agent.
14. composition according to claim 13, wherein, with respect to the 100 described propene polymers of weight part, the content of described oxidation inhibitor is the 0.01-0.5 weight part, the content of described stablizer is the 0.01-0.5 weight part, the content of described opening agent is 0.05-1 part, and the consumption of described slipping agent is 0.05-1 part.
15. a polymeric film, this polymeric film is formed by the described composition of any one in claim 1-14.
16. a multilayer film, this multilayer film comprise substrate layer and at least one the lip-deep hot sealing layer that is positioned at described substrate layer, described hot sealing layer is formed by the described polymeric film of claim 15.
17. multilayer film according to claim 16, wherein, described substrate layer is formed by polyethylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110349043.7A CN103087423B (en) | 2011-11-07 | 2011-11-07 | A kind of polymkeric substance film composition and polymeric film and multilayer film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110349043.7A CN103087423B (en) | 2011-11-07 | 2011-11-07 | A kind of polymkeric substance film composition and polymeric film and multilayer film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103087423A true CN103087423A (en) | 2013-05-08 |
| CN103087423B CN103087423B (en) | 2015-10-28 |
Family
ID=48200579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110349043.7A Active CN103087423B (en) | 2011-11-07 | 2011-11-07 | A kind of polymkeric substance film composition and polymeric film and multilayer film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103087423B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105584179A (en) * | 2016-01-12 | 2016-05-18 | 东莞市华宇包装有限公司 | Low-temperature shrink film and preparation method thereof |
| CN105585772A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Polypropylene resin, preparation method and application thereof, and automobile instrument board material |
| CN105584178A (en) * | 2016-01-12 | 2016-05-18 | 东莞市华宇包装有限公司 | Color shrink film and preparation method thereof |
| CN105644095A (en) * | 2016-01-12 | 2016-06-08 | 东莞市华宇包装有限公司 | Hot-running film and preparation method thereof |
| CN109265594A (en) * | 2017-07-17 | 2019-01-25 | 中国石油天然气股份有限公司 | Second the third fourth ternary polymerized polypropylene and its preparation method and application |
| CN109438833A (en) * | 2018-10-09 | 2019-03-08 | 中国石油化工股份有限公司 | A kind of polypropylene casting membrane material of improvement and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033059A (en) * | 1987-10-28 | 1989-05-24 | 住友化学工业株式会社 | The ingredient of solid catalyst that is used for olefinic polymerization |
| CN1898307A (en) * | 2003-12-24 | 2007-01-17 | 佩特罗基米卡库伊欧公司 | Sealing layer resin compositions |
-
2011
- 2011-11-07 CN CN201110349043.7A patent/CN103087423B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033059A (en) * | 1987-10-28 | 1989-05-24 | 住友化学工业株式会社 | The ingredient of solid catalyst that is used for olefinic polymerization |
| CN1898307A (en) * | 2003-12-24 | 2007-01-17 | 佩特罗基米卡库伊欧公司 | Sealing layer resin compositions |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105585772A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Polypropylene resin, preparation method and application thereof, and automobile instrument board material |
| CN105585772B (en) * | 2014-10-21 | 2018-05-15 | 中国石油化工股份有限公司 | A kind of acrylic resin and its preparation method and application and automobile instrument plate material |
| CN105584179A (en) * | 2016-01-12 | 2016-05-18 | 东莞市华宇包装有限公司 | Low-temperature shrink film and preparation method thereof |
| CN105584178A (en) * | 2016-01-12 | 2016-05-18 | 东莞市华宇包装有限公司 | Color shrink film and preparation method thereof |
| CN105644095A (en) * | 2016-01-12 | 2016-06-08 | 东莞市华宇包装有限公司 | Hot-running film and preparation method thereof |
| CN109265594A (en) * | 2017-07-17 | 2019-01-25 | 中国石油天然气股份有限公司 | Second the third fourth ternary polymerized polypropylene and its preparation method and application |
| CN109265594B (en) * | 2017-07-17 | 2021-07-30 | 中国石油天然气股份有限公司 | Ethylene-propylene-butylene-terpolymer polypropylene and preparation method and application thereof |
| CN109438833A (en) * | 2018-10-09 | 2019-03-08 | 中国石油化工股份有限公司 | A kind of polypropylene casting membrane material of improvement and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103087423B (en) | 2015-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103087423B (en) | A kind of polymkeric substance film composition and polymeric film and multilayer film | |
| KR100845583B1 (en) | Polymer film comprising a propylene random copolymer | |
| CN102532381B (en) | Polymerization method of anti-impact propylene copolymer having high melt flowability | |
| US20090018267A1 (en) | Polypropylene Composition Comprising a Propylene Homopolymer Component | |
| CN102532380B (en) | Method for preparing high-fluidity anti-impact polypropylene | |
| US20050197456A1 (en) | Sealing layer resin compositions | |
| WO2007071447A1 (en) | Polyolefin composition | |
| CN102050990A (en) | PP Resin composition and film thereof for preparing packaging film | |
| CN102453180B (en) | Preparation method and application of propylene/butene random copolymer | |
| CN101255256A (en) | Propylene-based copolymer material, film made therefrom, and method for producing propylene-based copolymer material | |
| KR20150086319A (en) | Pp compounds with alleviated or eliminated tiger stripe and retained excellent mechanical properties | |
| CN103087419A (en) | Polypropylene composition, and stretch film prepared through using it | |
| CN103087421B (en) | A kind of polymkeric substance film composition and polymeric film | |
| CA3037512C (en) | Polypropylene composition | |
| CN103772571A (en) | Preparation method of propylene-alpha-olefin random copolymer | |
| SG173099A1 (en) | Pe mib film zn/cr | |
| EP3950739B1 (en) | Polypropylene sheet | |
| CN114573902A (en) | Polyethylene composition and preparation method thereof | |
| CN102459453B (en) | Polyolefin compositions | |
| CN103087242B (en) | Propylene polymer, preparation method and application thereof | |
| CN102464750A (en) | Propylene random copolymer and stretched film prepared from propylene random copolymer | |
| CN114058113B (en) | High-impact transparent polypropylene resin and preparation method thereof | |
| CN103087239B (en) | A kind of propene polymer and its preparation method and application | |
| EP2935414B1 (en) | Polyethylene composition having high mechanical properties | |
| US20220356379A1 (en) | Resin composition for tackifier or adhesive and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |