CN108623917B - Polypropylene composition, preparation method thereof and polymer film - Google Patents
Polypropylene composition, preparation method thereof and polymer film Download PDFInfo
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- CN108623917B CN108623917B CN201710178004.2A CN201710178004A CN108623917B CN 108623917 B CN108623917 B CN 108623917B CN 201710178004 A CN201710178004 A CN 201710178004A CN 108623917 B CN108623917 B CN 108623917B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
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- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C08L2203/162—Applications used for films sealable films
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Abstract
The invention relates to the field of propylene polymers, and discloses a polypropylene composition, a preparation method thereof, the polypropylene composition prepared by the method and a polymer film. The polypropylene composition contains a random copolymer, and when the total weight of the random copolymer is 100 wt%, the content of a structural unit derived from 1-butene in the random copolymer is 10 to 20 wt%, the content of a structural unit derived from propylene is 80 to 90 wt%, and the content of a structural unit derived from ethylene is 0 to 5 wt%. The polypropylene composition provided by the invention has low content of n-hexane soluble substances; the polymer film prepared from the polypropylene composition has the advantages of low initial heat sealing temperature, low haze, high light transmittance and high specular gloss.
Description
Technical Field
The invention relates to the field of propylene polymers, in particular to a polypropylene composition and a preparation method thereof, and the polypropylene composition and a polymer film prepared by the method.
Background
Polypropylene materials with good transparency are propylene homopolymers, random copolymers of propylene and ethylene or random copolymers of propylene and 1-butene, especially random copolymers of propylene and ethylene and random copolymers of propylene and 1-butene, and because polypropylene films have excellent optical properties, mechanical properties and packaging adaptability, they are widely used in the fields of food packaging containers and the like at present. The polypropylene film may be prepared by a film processing technique of unidirectional or biaxial stretching. The film should not contain too much soluble substances in the preparation process or the packaging use process, because the molecular weight of the soluble substances is generally low, the soluble substances cannot be crystallized at normal temperature, are easy to migrate to the surface of the film, can be adhered to a conveying roller in the preparation process of the film, cause too much parking cleaning, and can pollute the packaged articles in the use process.
CN102453180A discloses a film made of butene and propylene copolymer. Selecting a high-stereospecificity selection Ziegler-Natta catalyst, and directly polymerizing propylene and 1-butene in the reaction to obtain the propylene/butene random copolymer with the content of 1-butene of 0.1-5 mol%. The films prepared with the random copolymers have better transparency and lower soluble content, but the patent application mentions that the use of a higher amount of butene copolymerized with propylene still leaves something to be desired, as well as transparency and stiffness which affect the appearance of the package.
CN103087237A discloses a process for the preparation of a propylene-butene-1 random copolymer with up to 6 mol% of butene-1 as a comonomer, which patent mentions that the random copolymer products prepared have a low xylene solubles content at room temperature, but does not refer to polymerization with higher butene content and product introduction.
In addition, films used as packaging should also have excellent physical and mechanical properties such as ease of heat sealing, high tensile strength, and processability on high speed equipment. The n-hexane soluble content and melting temperature of the propylene polymer have a significant influence on the initial heat-sealing temperature and heat-bonding resistance of a film formed of the propylene polymer, and have a great influence on the stiffness and gloss of the prepared film.
It is therefore very desirable to develop a polypropylene composition which can be used to prepare films having a low soluble content, good transparency, easy heat sealing and good mechanical properties.
Disclosure of Invention
In order to overcome the defects that the content of soluble substances is low and the heat sealing performance and the mechanical performance are excellent and cannot be realized simultaneously in the prior art, the invention provides the polypropylene composition, the preparation method thereof and the polymer film.
Specifically, the present invention provides a polypropylene composition comprising a random copolymer, wherein the content of a structural unit derived from 1-butene is 10 to 20% by weight, the content of a structural unit derived from propylene is 80 to 90% by weight, and the content of a structural unit derived from ethylene is 0 to 5% by weight, based on 100% by weight of the total weight of the random copolymer.
The present invention also provides a process for the preparation of a polypropylene composition comprising mixing a random copolymer and optionally a film-forming auxiliary agent, wherein the random copolymer is obtained by polymerising propylene, 1-butene and optionally ethylene in the presence of a ziegler-natta catalyst; when the total weight of the propylene, the 1-butene and the ethylene is 100 wt%, the 1-butene is used in an amount of 10-20 wt%, the propylene is used in an amount of 80-90 wt%, and the ethylene is used in an amount of 0-5 wt%.
The invention also provides a polypropylene composition obtained by the preparation method.
The invention also provides a polymer film which is formed by heating, melting and extruding the polypropylene composition.
The polypropylene composition provided by the invention has low content of n-hexane soluble substances, can be used for packaging materials, and can avoid pollution of packages caused by precipitation of the soluble substances in the processing process.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The present invention provides a polypropylene composition comprising a random copolymer, wherein the content of a structural unit derived from 1-butene is 10 to 20% by weight, the content of a structural unit derived from propylene is 80 to 90% by weight, and the content of a structural unit derived from ethylene is 0 to 5% by weight, based on 100% by weight of the total weight of the random copolymer.
Preferably, in order to obtain a film having a lower soluble content and better heat sealability and transparency, the content of the structural unit derived from 1-butene is 11 to 18% by weight, the content of the structural unit derived from propylene is 81 to 89% by weight, and the content of the structural unit derived from ethylene is 0 to 1% by weight, based on 100% by weight of the total weight of the random copolymer. More preferably, the content of the structural unit derived from 1-butene is 12 to 15% by weight, the content of the structural unit derived from propylene is 85 to 88% by weight, and the content of the structural unit derived from ethylene is 0% by weight in the random copolymer, based on the total weight of the random copolymer taken as 100% by weight.
According to the invention, the random copolymer may have a melt mass flow rate at 230 ℃ under a load of 2.16kg of 0.1 to 20g/10min, preferably 2 to 10g/10min, more preferably 4 to 6g/10 min. In the present invention, the melt mass flow rate is determined according to the method specified in GB/T3682-2000. Wherein the test conditions include: the temperature was 230 ℃ and the load was 2.16 kg.
According to the present invention, the polypropylene composition may have a n-hexane soluble content of 0.01 to 10 wt%, preferably 0.1 to 2 wt%, based on 100 wt% of the total weight of the polypropylene composition. In the present invention, the content of the n-hexane solubles can be measured by the following method: preparing a sample to be detected into a size of 1mm multiplied by 1mm, weighing 5 g (+ -0.001 g) of the sample to be detected, adding the sample to a conical flask with a plug, adding 200ml of normal hexane, heating the solution to 48 +/-2 ℃ in a constant-temperature water bath, soaking for 2 hours, taking out the flask, and placing the flask to room temperature. And (3) supplementing the liquid in the conical flask to the original volume of 200mL by using the same batch of n-hexane solvent to obtain n-hexane leaching liquid, respectively taking 100mL of the n-hexane leaching liquid and 100mL of blank liquid, placing the n-hexane leaching liquid and the blank liquid in an evaporation dish with constant weight, and evaporating the solution in the evaporation dish by using a water bath. And (3) placing the evaporating dish in a drying box at 105 ℃ for drying for 2 hours, cooling to room temperature, weighing the evaporating dish and the dissolved substance, and calculating the content of the dissolved substance.
According to the present invention, the random copolymer may be obtained commercially or may be prepared by various methods known to those skilled in the art. In a specific preparation process, the melt mass flow rate of the random copolymer can be controlled by the addition amount of hydrogen, and the content of each structural unit can be controlled by the amount of the monomer, which can be known by those skilled in the art and will not be described herein again.
According to the present invention, the polypropylene composition may further comprise an antioxidant and an acid scavenger. The content of the antioxidant and/or acid scavenger is not particularly limited and may be conventionally selected in the art. For example, the random copolymer may be contained in an amount of 99.3 to 100% by weight, preferably 99.7 to 99.87% by weight, based on 100% by weight of the total weight of the polypropylene composition; the content of the antioxidant can be 0 to 0.2 weight percent, and preferably 0.1 to 0.2 weight percent; the acid scavenger may be contained in an amount of 0 to 0.1% by weight, preferably 0.03 to 0.1% by weight.
According to the present invention, the antioxidant may be any of various known substances capable of preventing or retarding the aging of the polypropylene composition, and for example, may be a phenolic antioxidant and/or a phosphite antioxidant.
The kind of the phenolic antioxidant is not particularly limited in the present invention, and for example, the phenolic antioxidant may be one or more selected from the group consisting of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (abbreviated as antioxidant 1010), 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene (abbreviated as antioxidant 330), 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid (abbreviated as antioxidant 3114) and n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (abbreviated as antioxidant 1076), and is particularly preferably pentaerythritol [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene.
According to the present invention, the kind of the phosphite antioxidant is not particularly limited, and for example, the phosphite antioxidant may be one or more selected from tris (2, 4-di-t-butylphenyl) phosphite (abbreviated as antioxidant 168), bis (2, 4-di-t-butylphenol) pentaerythritol diphosphite (abbreviated as antioxidant 626) and bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite (abbreviated as antioxidant PEP-36), and tris (2, 4-di-t-butylphenyl) phosphite is particularly preferable.
The type of the acid acceptor in the present invention is also not particularly limited, and may be, for example, one or more selected from sodium stearate, calcium stearate, zinc stearate, and hydrotalcite is preferable.
In the preparation of polymeric films, it is also common in the art to use an opening agent and a slip agent, the specific type and amount being well known to those skilled in the art. However, the polypropylene composition of the present invention preferably does not contain an opening agent and a slip agent because the molecular weight of the opening agent and the slip agent is small relative to the polymer and the precipitation of small molecules greatly affects the production of a film.
Wherein, the opening agent refers to an agent capable of realizing the function of separating the films which are mutually adhered, and the opening agent can be one or more of silicon dioxide, diatomite, talc, calcium carbonate and calcium hydrogen phosphate. The slip agent may be any of a variety of additives that can effect a reduction in the coefficient of friction between films. The types of slip agents that can achieve the above-described functions are well known in the art, for example: the slip agent may be one or more of calcium stearate, polyethylene wax, erucamide, oleamide, stearamide, methylene bis stearamide, ethylene bis oleamide, glyceryl monostearate, pentaerythritol tetrastearate, solidified castor oil, stearyl stearate, stearyl alcohol, zinc stearate, magnesium stearate, lead stearate, stearic acid, behenic acid, 12-hydroxystearic acid, paraffin wax and microcrystalline wax.
The invention also provides a process for the preparation of a polypropylene composition, wherein the process comprises mixing a random copolymer and optionally a film-forming auxiliary agent, wherein the random copolymer is obtained by polymerising propylene, 1-butene and optionally ethylene in the presence of a ziegler-natta catalyst;
when the total weight of the propylene, the 1-butene and the ethylene is 100 wt%, the 1-butene is used in an amount of 10-20 wt%, the propylene is used in an amount of 80-90 wt%, and the ethylene is used in an amount of 0-5 wt%.
According to the present invention, the amount of the Ziegler-Natta catalyst may be selected according to the total amount of the monomers, for example, the amount of the Ziegler-Natta catalyst may be 0.01 to 0.05% by weight, preferably 0.02 to 0.03% by weight, based on 100% by weight of the total amount of the propylene, 1-butene and ethylene. In addition, the kind of the Ziegler-Natta catalyst can be selected conventionally in the field as long as it can initiate copolymerization of propylene and 1-butene and copolymerization of ethylene, and it is known to those skilled in the art and will not be described herein.
Preferably, in order to obtain a film having a lower soluble content and better heat sealability and transparency, 1-butene is used in an amount of 11 to 18% by weight, propylene is used in an amount of 81 to 89% by weight, and ethylene is used in an amount of 0 to 1% by weight, based on 100% by weight of the total of propylene, 1-butene and ethylene.
More preferably, 1-butene is used in an amount of 12 to 15 wt%, propylene is used in an amount of 85 to 88 wt%, and ethylene is used in an amount of 0 wt%, based on 100 wt% of the total weight of propylene, 1-butene and ethylene.
According to the invention, the random copolymer may have a melt mass flow rate at 230 ℃ under a load of 2.16kg of 0.1 to 20g/10min, preferably 2 to 10g/10min, more preferably 4 to 6g/10 min. In the present invention, the melt mass flow rate is determined according to the method specified in GB/T3682-2000. Wherein the test conditions include: the temperature was 230 ℃ and the load was 2.16 kg.
According to the present invention, the polypropylene composition may have a n-hexane soluble content of 0.01 to 10 wt%, preferably 0.1 to 2 wt%, based on 100 wt% of the total weight of the polypropylene composition. In the present invention, the content of the n-hexane solubles can be measured by the following method: preparing a sample to be detected into a size of 1mm multiplied by 1mm, weighing 5 g (+ -0.001 g) of the sample to be detected, adding the sample to a conical flask with a plug, adding 200ml of normal hexane, heating the solution to 48 +/-2 ℃ in a constant-temperature water bath, soaking for 2 hours, taking out the flask, and placing the flask to room temperature. And (3) supplementing the liquid in the conical flask to the original volume of 200mL by using the same batch of n-hexane solvent to obtain n-hexane leaching liquid, respectively taking 100mL of the n-hexane leaching liquid and 100mL of blank liquid, placing the n-hexane leaching liquid and the blank liquid in an evaporation dish with constant weight, and evaporating the solution in the evaporation dish by using a water bath. And (3) placing the evaporating dish in a drying box at 105 ℃ for drying for 2 hours, cooling to room temperature, weighing the evaporating dish and the dissolved substance, and calculating the content of the dissolved substance.
According to the present invention, in general, it is usually necessary to introduce hydrogen into the polymerization system during the olefin polymerization reaction to control the melt mass flow rate of the polymer within a desired range. Accordingly, the polymerization and contact reactions are carried out in the presence of hydrogen in an amount sufficient to control the melt index of the resulting random copolymer within the above range, which is known to those skilled in the art and will not be described herein.
The conditions of the polymerization reaction are not particularly limited in the present invention, and for example, the conditions of the polymerization reaction include: the polymerization temperature can be 55-85 ℃, preferably 60-80 ℃; the polymerization pressure may be 1 to 8MPa, preferably 1.2 to 7.5 MPa; the polymerization time may be from 0.5 to 3 hours, preferably from 1 to 2 hours.
In the present invention, the pressures are gauge pressures.
In the present invention, the coalescing agent comprises an antioxidant and/or an acid acceptor. The amount of the antioxidant and the acid acceptor can be selected conventionally in the field. For example, the random copolymer may be contained in an amount of 99.3 to 100% by weight, preferably 99.7 to 99.87% by weight, based on 100% by weight of the total weight of the polypropylene composition; the antioxidant may be used in an amount of 0 to 0.2 wt%, preferably 0.1 to 0.2 wt%.
In addition, the kinds of the antioxidant and the acid acceptor can be reasonably selected according to the above, and will not be described in detail herein.
The invention also provides a polypropylene composition obtained by the preparation method.
The invention also provides a polymer film which is formed by heating, melting and extruding the polypropylene composition.
According to the invention, the method for heating, melting and extruding the polypropylene composition into a film comprises the following steps: adopting a tape casting method to form a polymer film, and the specific flow is as follows: the mixture is melted in an extruder, and the melt is extruded into a film through a slit (the slit gap is 0.4-0.65mm) on a T-shaped head. The extruded film was attached to a cooling roll with compressed air ejected from an air knife. During the passage of the extruded film through the cooling roll, the extruded film is finally formed into a film having a desired thickness (for example, a thickness of 30 μm) due to the stretching and thinning effect.
In addition, in order to make the obtained polypropylene composition more uniform, preferably, the polypropylene composition provided by the invention further comprises adding the random copolymer of propylene and 1-butene and optionally the antioxidant and/or the acid neutralizer into various existing mixing devices to stir and mix uniformly before heating and melting the polypropylene composition. The mixing device may be, for example, a stirrer, a kneader, an open mill, an internal mixer, or the like. The temperature and time of the agitation mixing are well known to those skilled in the art, for example, the temperature of the agitation mixing may be 25 to 65 ℃, the time of the agitation mixing may be 5 to 30 minutes, and the rotation speed of the agitation mixing may be 50 to 300 rpm.
The present invention will be described in detail below by way of examples. In the following examples, relevant parameters were tested by the following methods:
1) 1-butene structural unit and ethylene structural unit in random polymer: nuclear magnetic resonance carbon spectrometry, wherein the solvent is deuterated o-dichlorobenzene; the NMR carbon spectrum measurements were carried out on a NMR spectrometer model BRUKER400 from Bruker, Switzerland. The test conditions included: the working frequency is 100.62MHz, the pulse is 30 degrees, the pulse time is 3s, the proton noise is fully decoupled, the spectrum width is 15000Hz, the accumulation times are 4000 times, and the calibration is carried out by isolated methylene carbon at 30.0 ppm.
2) Melt mass flow rate: the test temperature is 230 ℃ and the load is 2.16kg according to GB/T3682-2000.
3) Content of n-hexane soluble matter: weighing 5 g (+ -0.001 g) of a sample to be detected, adding the sample to a conical flask with a plug, adding 200ml of n-hexane, heating the solution to 48 +/-2 ℃ in a constant-temperature water bath, soaking for 2 hours, taking out the flask, and placing the flask to room temperature. And (3) supplementing the liquid in the conical flask to the original volume of 200mL by using the same batch of n-hexane solvent to obtain n-hexane leaching liquid, respectively taking 100mL of the n-hexane leaching liquid and 100mL of blank liquid, placing the n-hexane leaching liquid and the blank liquid in an evaporation dish with constant weight, and evaporating the solution in the evaporation dish by using a water bath. And (3) placing the evaporating dish in a drying box at 105 ℃ for drying for 2 hours, cooling to room temperature, weighing the evaporating dish and the dissolved substance, and calculating the content of the dissolved substance.
4) Initial heat-seal temperature: the polypropylene composition is made into a film with the width of 15mm and the thickness of 30 mu m, the two films are mutually pressed by taking 2 ℃ as an interval and 105 ℃ as an initial testing temperature, the heat sealing time is 1s, the heat sealing pressure is 0.3MPa, after the films are placed for 48 hours under constant temperature and humidity, an Instron5566 material testing machine is utilized, the distance between clamps of the testing machine is 50mm, the testing speed is 300mm/min, and the required force value when a sample is uncovered is measured. The initial test temperature at which a force of 2.5N or more was measured was taken as the initial heat-seal temperature.
5) Light transmittance and haze: the measurement was carried out according to the method specified in GB/T2410-2008, wherein the test sample film had a thickness of 30 μm.
6) Specular gloss: the measurement was carried out according to the method of ASTM D523-2008.
7) Melting temperature: according to GB/T19466.3-2004 Differential Scanning Calorimetry (DSC) part 3: and (4) measuring the melting and crystallization temperatures and the heat content.
In the following examples and comparative examples:
the solid catalyst component is purchased from Odapetrochemical company Limited in Beijing, and the antioxidant is 1010 and 168; hydrotalcite was purchased from dalianhaichen chemical mineral limited; silica was obtained from Yumin silica gel reagent factory, and erucamide was obtained from Japanese grass, David.
Example 1
This example illustrates the polypropylene composition, the process for preparing the same and the polymer film provided by the present invention
(1) Preparation of Polypropylene composition
The solid catalyst component, available from Odapetrochemical Co., Ltd, Beijing, was continuously fed at a rate of 0.61g/h to a volume of 50m3In the continuous horizontal stirred bed gas phase reactor of (3), triethylaluminum was continuously fed by means of a pump in such an amount that the molar ratio of aluminum in the triethylaluminum to titanium in the solid catalyst component, Al/Ti, was 30. Subsequently, propylene, 1-butene and hydrogen were introduced into a reactor to conduct polymerization reaction, wherein the pressure in the reactor was 1.4MPa, the temperature in the reactor was 65 ℃ and the hydrogen/propylene weight ratio (H) in the reactor was set2/C3) 0.018, the content of propylene was 88.0% by weight and the content of 1-butene was 12% by weight, based on the total amount of propylene and 1-butene. The average residence time of the propylene, 1-butene and hydrogen in the reactor is 60min, and the reaction is carried outThe level in the vessel was 70%.
No polymer particles were found to clog the reactor discharge line during the polymerization. Uniformly mixing 100 g of the obtained random copolymer of propylene and 1-butene with 0.05 g of antioxidant 1010, 0.1 g of antioxidant 168 and 0.05 g of hydrotalcite, adding the mixed material into a feeder of a double-screw extruder, feeding the material into a double screw through the feeder, uniformly melting and mixing the material by a screw, extruding, granulating and drying, wherein the temperature of the screw is controlled at 215 ℃ in the processing process. The composition and properties of the resulting polypropylene compositions are listed in table 1.
(2) Preparation of Polymer films
And (2) preparing the polypropylene composition prepared in the step (1) into a polymer film by adopting a tape casting method. The specific process is as follows: the polypropylene composition is melted in an extruder, and the melt is extruded into a film through a slit (the slit gap is 0.4-0.65mm) on a T-shaped head. The extruded film was attached to a cooling roll with compressed air ejected from an air knife. During the passage of the extruded film through the cooling roll, the extruded film finally formed a film having a thickness of 30 μm due to the stretching-thinning effect.
The initial heat-seal temperature, haze, light transmittance and specular gloss of the resulting polymer films are listed in table 2.
Example 2
This example illustrates the polypropylene composition, the process for preparing the same and the polymer film provided by the present invention
A propylene polymer was produced in the same manner as in example 1, except that in the step (1), the content of propylene was 85% by weight and the content of 1-butene was 15% by weight, based on the total amount of propylene and 1-butene. During the extrusion granulation, 0.1 g of antioxidant 1010, 0.1 g of antioxidant 168 and 0.03 g of hydrotalcite were added.
The composition and properties of the resulting polypropylene compositions are listed in table 1. The initial heat-seal temperature, haze, light transmittance and specular gloss of the resulting polymer films are listed in table 2.
Example 3
This example illustrates the polypropylene composition, the process for preparing the same and the polymer film provided by the present invention
A propylene polymer was produced in the same manner as in example 1, except that in the step (1), the content of propylene was 86.8% by weight and the content of 1-butene was 13.2% by weight, based on the total amount of propylene and 1-butene. During the extrusion granulation, 0.05 g of antioxidant 1010, 0.05 g of antioxidant 168 and 0.1 g of hydrotalcite were added.
The composition and properties of the resulting polypropylene compositions are listed in table 1. The initial heat-seal temperature, haze, light transmittance and specular gloss of the resulting polymer films are listed in table 2.
Examples 4 to 8
This example illustrates the polypropylene composition, the process for preparing the same and the polymer film provided by the present invention
The catalyst, polymerization conditions, polymer granulation conditions and formulation, and membrane preparation process used were the same as in example 1. Except that the content of the structural units in the copolymer was varied, as shown in Table 1. The initial heat-seal temperature, haze, light transmittance and specular gloss of the resulting polymer films are listed in table 2.
Example 9
This example illustrates the polypropylene composition, the process for preparing the same and the polymer film provided by the present invention
The procedure is as in example 1, except that no antioxidant 1010 and no antioxidant 168 are used. The composition and properties of the resulting polypropylene compositions are listed in table 1. The initial heat-seal temperature, haze, light transmittance and specular gloss of the resulting polymer films are listed in table 2.
Example 10
This example illustrates the polypropylene composition, the process for preparing the same and the polymer film provided by the present invention
The procedure is as in example 1 except that the polypropylene composition is prepared by mixing the components further comprising 0.1 grams of silica and 0.1 grams of erucamide. The composition and properties of the resulting polypropylene compositions are listed in table 1. The initial heat-seal temperature, haze, light transmittance and specular gloss of the resulting polymer films are listed in table 2.
Comparative examples 1 to 3
This comparative example serves to illustrate a reference polypropylene composition, a process for its preparation and a polymer membrane.
The catalyst, polymerization conditions, polymer granulation conditions and formulation, and membrane preparation process used were the same as in example 1. Except that the content of the structural units in the copolymer was varied, as shown in Table 1. The initial heat-seal temperature, haze, light transmittance and specular gloss of the resulting polymer films are listed in table 2.
Comparative example 4
This comparative example serves to illustrate a reference polypropylene composition, a process for its preparation and a polymer membrane.
A propylene polymer was produced in the same manner as in example 1, except that in the step (1), the content of propylene was 75.0% by weight and the content of 1-butene was 25% by weight, based on the total amount of propylene and 1-butene.
In the polymerization process, polymer particles block a reactor to form a caking phenomenon, and polymerization and granulation cannot be carried out.
TABLE 1
TABLE 2
| Initial Heat-sealing temperature (. degree. C.) | Haze (%) | Light transmittance (%) | Specular gloss (%) | |
| Example 1 | 114 | 0.28 | 92.9 | 149 |
| Example 2 | 112 | 0.22 | 93.8 | 141 |
| Example 3 | 113 | 0.25 | 93.1 | 143 |
| Example 4 | 118 | 0.37 | 92.8 | 131 |
| Example 5 | 110 | 0.22 | 93.5 | 135 |
| Example 6 | 111 | 0.36 | 91.9 | 128 |
| Example 7 | 110 | 0.30 | 92.8 | 124 |
| Example 8 | 104 | 0.24 | 91.3 | 120 |
| Example 9 | 115 | 0.56 | 90.8 | 122 |
| Example 10 | 114 | 1.16 | 90.5 | 131 |
| Comparative example 1 | 122 | 1.18 | 88.9 | 131 |
| Comparative example 2 | 121 | 1.57 | 88.2 | 118 |
| Comparative example 3 | 103 | 0.86 | 89.4 | 115 |
As can be seen from the results of the examples and the comparative examples, the polypropylene composition provided by the invention has low content of n-hexane solubles; the polymer film prepared from the polypropylene composition has the advantages of low initial heat sealing temperature, low haze, high light transmittance and high specular gloss. Specifically, the indexes of starting n-hexane solubles, initial heat-sealing temperature, haze, light transmittance and specular gloss of examples 1 to 3, which are the most preferred embodiments, are optimized in combination, and instead of examples 4 to 10, which are the preferred embodiments, the effect of one or more of the above indexes is slightly decreased, whereas in the case of comparative examples 1 to 4, which are the embodiments of the present invention, n-hexane solubles are more and/or haze is high and/or transmittance is poor and/or specular gloss is low.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (11)
1. A polypropylene composition comprising a random copolymer, an antioxidant and an acid acceptor, wherein the content of a structural unit derived from 1-butene in the random copolymer is 12 to 15% by weight, the content of a structural unit derived from propylene is 85 to 88% by weight, and the content of a structural unit derived from ethylene is 0% by weight, based on 100% by weight of the total weight of the random copolymer;
when the total weight of the polypropylene composition is 100 wt%, the content of the random copolymer is 99.7-99.87 wt%, the content of the antioxidant is 0.1-0.2 wt%, and the content of the acid acceptor is 0.03-0.1 wt%;
the polypropylene composition does not contain a mouth-opening agent and a slipping agent;
the content of n-hexane soluble matters in the polypropylene composition is 0.1-2 wt% when the total weight of the polypropylene composition is 100 wt%.
2. The polypropylene composition according to claim 1, wherein the melt mass flow rate of the random copolymer at 230 ℃ under a load of 2.16kg is from 0.1 to 20g/10 min.
3. The polypropylene composition according to claim 2, wherein the melt mass flow rate of the random copolymer at 230 ℃ under a 2.16kg load is from 2 to 10g/10 min.
4. The polypropylene composition according to claim 3, wherein the melt mass flow rate of the random copolymer at 230 ℃ under a load of 2.16kg is from 4 to 6g/10 min.
5. A process for the preparation of a polypropylene composition, comprising mixing a random copolymer, an antioxidant and an acid scavenger, wherein said random copolymer is obtained by polymerizing propylene, 1-butene and optionally ethylene in the presence of a ziegler-natta catalyst;
when the total weight of the propylene, the 1-butene and the ethylene is 100 weight percent, the using amount of the 1-butene is 12 to 15 weight percent, the using amount of the propylene is 85 to 88 weight percent, and the using amount of the ethylene is 0 weight percent;
when the total weight of the polypropylene composition is 100 wt%, the content of the random copolymer is 99.7-99.87 wt%, the dosage of the antioxidant is 0.1-0.2 wt%, and the dosage of the acid acceptor is 0.03-0.1 wt%; the content of n-hexane soluble matters in the polypropylene composition is 0.1-2 wt% when the total weight of the polypropylene composition is 100 wt%.
6. The production method according to claim 5, wherein the melt mass flow rate of the random copolymer at 230 ℃ under a load of 2.16kg is from 0.1 to 20g/10 min.
7. The production method according to claim 6, wherein the melt mass flow rate of the random copolymer under a 2.16kg load at 230 ℃ is 2 to 10g/10 min.
8. The production method according to claim 7, wherein the melt mass flow rate of the random copolymer under a 2.16kg load at 230 ℃ is 4 to 6g/10 min.
9. The production method according to any one of claims 5 to 8, wherein the conditions of the polymerization reaction include: the polymerization temperature is 55-85 ℃, the polymerization pressure is 1-8MPa, and the polymerization time is 0.5-3 hours.
10. Polypropylene composition obtainable by the process according to any one of claims 5 to 9.
11. A polymer film, wherein the polymer film is formed by heating, melting and extruding the polypropylene composition according to any one of claims 1 to 4 and 10.
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