CN111849077B - Polypropylene composition for blow molding, polypropylene film and preparation method - Google Patents

Polypropylene composition for blow molding, polypropylene film and preparation method Download PDF

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CN111849077B
CN111849077B CN201910341029.9A CN201910341029A CN111849077B CN 111849077 B CN111849077 B CN 111849077B CN 201910341029 A CN201910341029 A CN 201910341029A CN 111849077 B CN111849077 B CN 111849077B
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polypropylene
weight
impact polypropylene
parts
propylene homopolymer
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CN111849077A (en
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郭鹏
吕明福
徐耀辉
张师军
解娜
毕福勇
权慧
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/28—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of blown tubular films, e.g. by inflation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—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
    • C08J2423/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08J2423/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres

Abstract

The invention belongs to the field of blow molding matte polypropylene films, and discloses a polypropylene composition for blow molding, a polypropylene film and a preparation method thereof. The composition comprises 100 weight parts of impact-resistant polypropylene, 0.05 to 0.5 weight part of composite antioxidant, 0.25 to 10 weight parts of mixed olefin-maleic anhydride copolymer microspheres and 0.05 to 2 weight parts of guanidine salt composite antibacterial agent; wherein the particle size of the mixed olefin-maleic anhydride copolymerized microsphere is 0.05-2 μm. The invention can prepare the polypropylene matte film by blow molding, has improved surface roughness, reduced glossiness, high transverse tensile strength and longitudinal tensile strength, high elongation at break, good delustering performance and antibacterial performance.

Description

Polypropylene composition for blow molding, polypropylene film and preparation method
Technical Field
The invention belongs to the field of blow molding matte polypropylene films, and particularly relates to a polypropylene composition for blow molding, a polypropylene film prepared from the composition and a method for preparing a polypropylene blow molding film.
Background
The polypropylene (PP) film has higher mechanical strength, good heat resistance and grease resistance and better transparency, is widely used in industry and daily life, and is particularly suitable for bags for cooking food, microwave food packaging, medical high-temperature cooking sterilization, large heavy packaging and the like.
The extrusion blow molding film has the advantages of simple process, less equipment and cost advantage. However, polypropylene films have long been produced primarily by extrusion cast mono-and biaxially oriented techniques. Due to the low melt viscosity and melt strength of ordinary polypropylene resins, extrusion blow molding into films is difficult. In recent years, with the progress of polymerization and catalyst technologies, high melt strength polypropylene resins suitable for extrusion blow molding have been developed. Because the melt strength and viscosity of the polypropylene resin are much higher than those of common polypropylene, the polypropylene film can be produced on the conventional polypropylene blown film equipment.
In order to improve the applicability of polypropylene blown film, at present, a method of adding ethylene monomer in the polymerization process of propylene is adopted to produce a copolymer, and the copolymer is used as a raw material to produce a polypropylene blown film. Due to the addition of the ethylene monomer, the toughness of the film is improved, but the difference between the longitudinal and transverse tear strengths of the film is still large, and the heat resistance of the film is greatly reduced.
The matt film as a paper-like film has the advantages of low glossiness, high haze, comfortable hand feeling, quiet and elegant appearance, excellent printing performance, strong color sense and the like, and is called as a natural glossy film. The method is mainly used for packaging high-grade food, gifts, candies and the like, and the flyleaves of printed paper and hardcover books for large-scale outdoor advertisements. The extinction film is firstly processed for the second time by methods of mechanical knurling, solvent etching and the like to obtain an extinction effect, and the extinction effect is also obtained by adding extinction agents such as superfine calcium carbonate, silicon dioxide and the like. However, the mechanical properties of the film, especially the tear resistance in the TD and MD directions, are often reduced by special processes such as mechanical knurling and solvent etching or by the addition of a matting agent.
Therefore, a method for preparing a blown polypropylene matte film is needed.
Disclosure of Invention
The invention aims to overcome the defect that the polypropylene film can only be prepared by casting, biaxial stretching and other processes in the prior art.
The invention also aims to solve the problems of low impact resistance and tear resistance, low tensile strength and poor extinction property of the polypropylene film in the prior art.
In order to achieve the above object, the present invention provides in a first aspect a polypropylene composition for blow molding, comprising 100 parts by weight of an impact polypropylene, 0.05 to 0.5 parts by weight of a complex antioxidant, 0.25 to 10 parts by weight of mixed olefin-maleic anhydride copolymerized microspheres, and 0.05 to 2 parts by weight of a guanidinium salt complex antibacterial agent;
wherein the particle size of the mixed olefin-maleic anhydride copolymerized microsphere is 0.05-2 μm.
In a second aspect, the present invention provides a polypropylene film made from the composition of the present invention.
Preferably, the polypropylene film is a polypropylene blown film, more preferably, the polypropylene blown film is a blown polypropylene matte film.
In a third aspect the present invention provides a process for the preparation of a polypropylene blown film comprising: the composition of the invention is extruded and pelletized and then blown into a film.
According to the technical scheme, the invention provides the composition which uses the impact-resistant polypropylene and is mixed with the mixed olefin-maleic anhydride copolymer microspheres to realize the blow molding film forming to prepare the polypropylene matte film, and the polypropylene matte film has the advantages of improved surface roughness, reduced glossiness, high transverse tensile strength and longitudinal tensile strength, good tear resistance, good puncture resistance, good delustering performance and antibacterial performance.
Description of the drawings:
FIG. 1 is an SEM photograph of the surface topography of a blown polypropylene film obtained in example 4;
FIG. 2 is an SEM photograph of the surface morphology of a blown polypropylene film prepared in comparative example 12.
Detailed Description
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 invention provides a polypropylene composition for blow molding, which comprises 100 weight parts of impact-resistant polypropylene, 0.05 to 0.5 weight part of composite antioxidant, 0.25 to 10 weight parts of mixed olefin-maleic anhydride copolymerized microspheres and 0.05 to 2 weight parts of guanidine salt composite antibacterial agent;
wherein the particle size of the mixed olefin-maleic anhydride copolymerized microsphere is 0.05-2 μm.
Preferably, the composition contains 100 weight parts of impact polypropylene, 0.1 to 0.3 weight part of composite antioxidant, 0.25 to 2.5 weight parts of mixed olefin-maleic anhydride copolymerized microspheres and 0.05 to 1.5 weight parts of guanidine salt composite antibacterial agent;
wherein the particle size of the mixed olefin-maleic anhydride copolymerized microsphere is 0.2-1 μm.
Mixed olefin-maleic anhydride copolymer microspheres
The particle size can be measured by a scanning electron microscope method.
The composition provided by the invention can be suitable for preparing a polypropylene film by a blow molding film forming method, and can have improved mechanical properties and optical properties. The copolymer microspheres containing the mixed olefin and the maleic anhydride can improve the surface roughness of the prepared polypropylene film, increase diffuse reflection and reduce glossiness. Preferably, the content of the maleic anhydride structural unit in the mixed olefin-maleic anhydride copolymerized microsphere is 30 to 70 mol%, preferably 48 to 55 mol%. In the mixed olefin-maleic anhydride copolymerized microsphere, the maleic anhydride structural unit can be in a main chain, a side chain or an end group. The content of the maleic anhydride structural unit can be determined by1H and13c nuclear magnetic measurement. The mixed olefin-maleic anhydride copolymerized microsphere may further contain an olefin structural unit formed by at least one of 1-butene, 1, 3-butadiene and isobutene. The content of the olefin structural unit in the mixed olefin-maleic anhydride copolymerized microsphere can be determined by1H and13c nuclear magnetic measurement. The olefin building block content may be from 30 to 70 mol%. Preferably, the olefin building block content is from 45 to 52 mol%.
In the present invention, preferably, the mixed olefin-maleic anhydride copolymerized microspheres are a copolymer of maleic anhydride and carbon tetraene prepared by copolymerizing mixed carbon four and maleic anhydride in the presence of nitrogen, an initiator and an organic solvent. Preferably, the mixed olefin-maleic anhydride copolymerized microspheres are copolymer microspheres of maleic anhydride, n-butene and isobutene. Preferably, the mixed olefin-maleic anhydride copolymerized microspheres mainly contain structural units derived from n-butene and isobutylene in an amount of 30 to 70 mol%, and preferably, the structural units derived from n-butene and isobutylene are present in an amount of 45 to 52 mol%.
The mixed olefin-maleic anhydride copolymerized microspheres used in the invention can use mixed C4 as a raw material, wherein the mixed C can be obtained from various petroleum processing and refining processes, and can be C4A mixture of hydrocarbon compounds. Preferably, the mixed carbon four contains at least one of 1-butene, isobutene, 1, 3-butadiene, n-butane, isobutane, cis-2-butene and trans-2-butene, and may be, for example, liquefied fuel produced in a petroleum refining process, cracked gas produced by cracking naphtha, gas produced by producing olefins from methanol, and the like. The composition of the mixed C.sub.D can be analyzed by gas chromatography using Agilent's 7890A Gas Chromatograph (GC).
Preferably, the compositional content of the mixed C.sub.D can be 1-99 wt% of 1-butene, 1-99 wt% of isobutylene, 0-99 wt% of 1, 3-butadiene, 0-50 wt% of 1, 2-butadiene, 0-99 wt% of n-butane, 1-99 wt% of isobutane, 5-20 wt% of vinyl acetylene, 0-99 wt% of cis-2-butene, and 1-99 wt% of trans-2-butene.
According to a preferred embodiment of the present invention, the composition content of the mixed C.sub.D may be 5-10 wt% of 1-butene, 5-15 wt% of isobutene, 10-20 wt% of 1, 3-butadiene, 5-15 wt% of 1, 2-butadiene, 0.5-5 wt% of n-butane, 0.5-2 wt% of isobutane, 20-40 wt% of cis-2-butene, 2-10 wt% of trans-2-butene, 5-20 wt% of vinyl acetylene.
According to another preferred embodiment of the present invention, the composition content of the mixed C.sub.D may be 0.1-2 wt% of 1-butene, 10-30 wt% of isobutene, 0.01-0.1 wt% of 1, 3-butadiene, 0.5-5 wt% of n-butane, 30-40 wt% of isobutane, 20-40 wt% of cis-2-butene, 5-20 wt% of trans-2-butene.
According to another preferred embodiment of the present invention, the compositional content of mixed C.sub.D may be 5-15 wt% of 1-butene, 0.5-3 wt% of isobutene, 20-30 wt% of n-butane, 15-30 wt% of cis-2-butene, 35-45 wt% of trans-2-butene.
In the present invention, 1-butene, isobutylene and 1, 3-butadiene among the mixed carbons can be copolymerized with maleic anhydride. Preferably, the weight ratio of the mixed C4 to the maleic anhydride is (0.2-3): 1; preferably (0.8-3): 1.
in the invention, the initiator is used in an amount which ensures that the copolymerization reaction is carried out. Preferably, the initiator is used in an amount of 0.05 to 20 mol% based on the maleic anhydride. The initiator may be dibenzoyl peroxide or azobisisobutyronitrile.
In the present invention, the organic solvent is an inert solvent that does not participate in the copolymerization reaction, and provides a dispersion medium for the copolymerization reaction. Preferably, the concentration of maleic anhydride in the organic solvent is from 5% to 25% by weight; preferably 10 wt% to 20 wt%. The organic solvent is preferably at least one of isoamyl acetate, butyl acetate, isopropyl acetate and ethyl acetate.
In the present invention, the copolymerization reaction conditions may be such that the copolymerization reaction of the mixed carbon four and maleic anhydride is achieved. Preferably, the copolymerization reaction temperature is 50-100 ℃, preferably 70-90 ℃; the copolymerization pressure is 0.2-2MPa, preferably 0.5-1 MPa; the copolymerization reaction time is 5-10 h.
In the invention, a certain amount of mixed C4 is introduced into a reaction kettle containing a certain amount of maleic anhydride, an initiator and an organic solvent to carry out copolymerization reaction under the conditions of nitrogen atmosphere and the copolymerization reaction, and then the reaction product is subjected to flash separation and centrifugal separation to obtain the mixed olefin-maleic anhydride copolymerized microsphere. Wherein, the mixed C4, the maleic anhydride, the initiator and the organic solvent are used in the same amount as described above. The flash separation may be carried out in a flash separator at about 25 ℃ and 0 MPa. The centrifugation may be carried out at a rotation speed of about 4000rpm for about 20 min. The obtained microspheres can be further washed by hexane and filtered by a sand core to obtain a filter cake, and after the filter cake is dried in vacuum at about 90 ℃ for about 8 hours, the obtained product is the mixed olefin-maleic anhydride copolymerized microspheres with the particle size of 0.05-2 mu m, preferably 0.2-2 mu m, and the composition structure and the content of the mixed olefin-maleic anhydride copolymerized microspheres can be further analyzed and used for the impact polypropylene.
Guanidine salt composite antibacterial agent
The guanidine salt composite antibacterial agent contained in the composition provided by the invention can provide the polypropylene blown film obtained by the invention with antibacterial performance, and is also helpful for improving the mechanical and/or optical performance of the further prepared polypropylene film together with the mixed olefin-maleic anhydride copolymerized microspheres. Preferably, the guanidine salt composite antibacterial agent contains a guanidine salt polymer, a zinc salt and/or a copper salt, an anti-migration agent, nano-scale powder rubber and a dispersing agent.
Preferably, the zinc salt and/or the copper salt is 0.01 to 40 parts by weight, the anti-migration agent is 0.1 to 10 parts by weight, the nano-sized powder rubber is 0.5 to 100 parts by weight, and the dispersant is 0.1 to 10 parts by weight, relative to 100 parts by weight of the guanidine salt polymer. Preferably, the zinc salt and/or the copper salt, the anti-migration agent, the nano-scale powder rubber and the dispersant are 5 to 25 parts by weight, 0.5 to 5 parts by weight, 4.5 to 50 parts by weight and 0.5 to 5 parts by weight, respectively, relative to 100 parts by weight of the guanidine salt polymer.
In the present invention, the guanidine salt polymer may be selected from at least one of an inorganic acid salt and/or an organic acid salt of polyhexamethylene (bis) guanidine, and polyoxyethylene guanidine; preferably at least one selected from the group consisting of polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine phosphate, polyhexamethylene (bis) guanidine acetate, polyhexamethylene (bis) guanidine propionate, polyhexamethylene (bis) guanidine stearate, polyhexamethylene (bis) guanidine laurate, polyhexamethylene (bis) guanidine benzoate and polyhexamethylene (bis) guanidine sulfonate; further preferred is polyhexamethylene (bis) guanidine hydrochloride and/or polyhexamethylene (bis) guanidine propionate.
In the invention, the zinc salt and/or the copper salt can be inorganic zinc salt and/or inorganic copper salt; preferably at least one selected from the group consisting of zinc sulfate, zinc nitrate, zinc chloride, copper sulfate, copper nitrate and copper chloride; further preferably zinc sulfate and/or copper sulfate.
In the present invention, the anti-migration agent may be a blocked polyisocyanate, preferably at least one selected from the group consisting of phenol blocked polyisocyanate, caprolactam blocked polyisocyanate, and butanone oxime blocked polyisocyanate.
In the invention, the nano-scale powder rubber can be at least one of fully vulcanized styrene-butadiene rubber, fully vulcanized carboxyl styrene-butadiene rubber, fully vulcanized nitrile-butadiene rubber, fully vulcanized carboxyl nitrile-butadiene rubber, fully vulcanized acrylate rubber, fully vulcanized ethylene vinyl acetate rubber, fully vulcanized silicon rubber and fully vulcanized butadiene-styrene-pyridine rubber which are subjected to radiation crosslinking; preferably fully vulcanized styrene-butadiene rubber and/or fully vulcanized silicone rubber.
In the invention, the content control of the nano-powder rubber can help to reduce the moisture absorption of the guanidine salt composite antibacterial agent during storage, and increase the operability and the use timeliness in practical application.
In the invention, the dispersant can be nano-scale inorganic powder, preferably at least one selected from nano-scale calcium carbonate, silicon dioxide, montmorillonite, zinc oxide, talcum powder, titanium dioxide, carbon nano tube, graphene, carbon fiber, boron nitride, zirconium dioxide, wollastonite and zeolite; further preferred is nanoscale calcium carbonate and/or nanoscale fumed silica.
In the invention, the preparation method of the guanidine salt composite antibacterial agent comprises the following steps:
a. contacting an aqueous solution of a guanidinium polymer with an aqueous solution of a zinc salt and/or a copper salt to form a transparent liquid mixture;
b. mixing the liquid mixture obtained in the step a with a latex solution after radiation crosslinking, and then adding an anti-migration agent to obtain a mixture;
c. and c, carrying out spray drying on the mixture obtained in the step b to obtain solid powder, and then mixing the solid powder with a dispersing agent to obtain the guanidine salt composite antibacterial agent.
Wherein the latex can be determined according to the type of the finally required powdered rubber, and the latex can be at least one of styrene-butadiene latex, carboxylic styrene-butadiene latex, butyronitrile latex, carboxylic butyronitrile latex, acrylate latex, ethylene vinyl acetate latex, silicon rubber latex and styrene-butadiene-pyridine latex; preferably styrene-butadiene latex and/or silicone rubber latex.
A large number of experiments show that the guanidine salt composite antibacterial agent can be prepared more smoothly when the concentrations of a guanidine salt polymer aqueous solution, a zinc salt and/or copper salt aqueous solution and a latex solution are in a certain range. The concentrations of the guanidine salt polymer aqueous solution, the zinc salt and/or copper salt aqueous solution and the latex emulsion are not high enough, otherwise, the uniform stirring is not facilitated, the coagulation phenomenon can occur, and the subsequent spray drying operation can not be carried out; the concentration should not be too low, otherwise, the production efficiency will be low, and water and energy resources will be wasted. Specifically, the mass concentration of the aqueous solution of the guanidinium polymer may be 10% to 40%, preferably 15% to 25%. The mass concentration of the aqueous solution of the zinc salt and/or the copper salt can be 15-30%, and preferably 20-25%. The mass concentration of the latex solution is 30-40%.
Wherein the spray drying may be carried out in a spray dryer. The mixing of the solid powder and the dispersing agent can be carried out in a high-speed stirrer, and the guanidine salt composite antibacterial agent of the invention is obtained after high-speed stirring and dispersing.
The aqueous guanidinium polymer solution may be obtained by dissolving a guanidinium polymer solid in water or may be obtained commercially directly. Preferably, the weight ratio of the guanidine salt polymer in the guanidine salt polymer aqueous solution, the zinc salt and/or copper salt in the zinc salt and/or copper salt aqueous solution, the solid solution in the latex solution, the anti-migration agent and the dispersant is 100: 0.01-40: 0.5-100: 0.1-10: 0.1 to 10; the preferable weight ratio is 100: 5-25: 4.5-50: 0.5-5: 0.5-5.
The guanidine salt composite antibacterial agent obtained by the preparation method of the guanidine salt composite antibacterial agent has the characteristics of good fluidity and low moisture absorption, and the prepared polypropylene film has good antibacterial and mildew-proof effects and improved water resistance.
Impact polypropylene
In the composition provided by the invention, the polypropylene with high melt strength is used, and the prepared polypropylene blown film has good mechanical and/or optical properties. Preferably, the impact polypropylene has a melt strength greater than 0.1N, preferably from 0.15 to 0.25N.
According to the invention, the impact polypropylene preferably has an Izod notched impact of 70 to 100KJ/m at 23 ℃2。
According to the invention, preferably, M of the impact polypropylenew/Mn(weight average molecular weight/number average molecular weight) satisfies 4. ltoreq. Mw/Mn10 or less, preferably 5 < Mw/MnLess than 9; m of the impact polypropylenez+1/Mw(Z +1 average molecular weight/weight average molecular weight) satisfies 10 < Mz+1/Mw< 20, preferably 10 < Mz+1/Mw＜15。
According to the present invention, preferably the impact polypropylene has a room temperature xylene solubles content of more than 10 wt% and less than 30 wt%, preferably more than 10 wt% and less than 22 wt%; and M of room temperature trichlorobenzene solubles of said impact polypropylenewM with trichlorobenzene insolubles at room temperaturewThe ratio of (d) is greater than 0.4 and less than 1, preferably greater than 0.5 and less than 0.8.
In the present invention, the impact polypropylene may comprise a propylene homopolymer component and a propylene-ethylene copolymer component. The propylene homopolymer component can be used as a continuous phase, and the propylene-ethylene copolymer component can be used as a rubber phase (namely a dispersed phase), so that the toughness of the polypropylene blown film can be improved. For the impact polypropylene, factors affecting melt strength become complicated due to the material having a multi-phase structure of a continuous phase and a dispersed phase. The inventor of the invention finds that the impact-resistant polypropylene with the molecular weight relationship and the molecular weight distribution characteristics of the components can have excellent rigidity and toughness and higher melt strength, and further, the composition of the invention can be used for preparing a polypropylene blown film through blow molding, and the polypropylene blown film prepared by the composition has high rigidity, toughness and melt strength, particularly has stronger impact resistance and tensile resistance, and has stronger tear strength and low transverse and longitudinal tear strength difference.
In the present invention, as described above, the content of the rubber phase (i.e., the content of the propylene-ethylene copolymer component) in the impact polypropylene may be calculated as the room temperature xylene soluble content. For ease of characterization, the molecular weight of the rubber phase is based on the molecular weight of the trichlorobenzene solubles. While the composition of the rubber phase (i.e. the composition of the propylene-ethylene copolymer component) is characterized by the ethylene content in the xylene solubles. Preferably, the room temperature xylene solubles of the impact polypropylene have an ethylene content of more than 25 wt.% and less than 50 wt.%, preferably more than 30 wt.% and less than 50 wt.%. The "ethylene content in the room-temperature xylene soluble matter" means the weight content of the ethylene monomer constituent part in the room-temperature xylene soluble matter, and in the present invention, corresponds to the weight content of the ethylene monomer constituent part in the rubber phase, and can be measured by the CRYSTEX method.
According to the present invention, preferably the ethylene content in the impact polypropylene is 5-15 wt%. The ethylene content in the impact polypropylene is understood here to be the weight content of the fraction composed of ethylene monomer in the impact polypropylene.
According to the present invention, the impact polypropylene may also define other performance parameters to ensure that the blown polypropylene film required by the present invention is obtained. Preferably, the impact polypropylene has a melt flow rate of 0.1 to 15g/10min, preferably 0.1 to 6g/10min, measured at 230 ℃ and under a load of 2.16 kg.
According to the present invention, preferably the impact polypropylene has a molecular weight Polydispersity Index (PI) of 4 to 8, preferably 4.5 to 6.
In the present invention, preferably, the impact polypropylene also has good heat resistance, and the melting peak temperature T of the final polypropylene resin is determined by DSCmGreater than or equal to 158 ℃.
According to the present invention, preferably, the propylene homopolymer component comprises a first propylene homopolymer and a second propylene homopolymer. Wherein the first propylene homopolymer has a melt flow rate of 0.001 to 0.4g/10min, measured at 230 ℃ and under a load of 2.16 kg.
According to the present invention, preferably, the propylene homopolymer component has a melt flow rate, measured at 230 ℃ and under a load of 2.16kg, of from 0.1 to 15g/10 min; and the weight ratio of the first propylene homopolymer to the second propylene homopolymer is from 40:60 to 60: 40. By arranging the propylene homopolymer component to comprise a combination of at least two propylene homopolymers having different melt flow rates and having a specific ratio relationship, the impact polypropylene of the present invention can be provided with a specific continuous phase and, in the further combination of this continuous phase and the propylene-ethylene copolymer (dispersed phase, rubber component), results in a polypropylene blown film having both high melt strength and good stiffness and toughness, and thus being suitable for the production of polypropylene blown films having good tear and stretch resistance.
In the present invention, preferably, the impact polypropylene is obtained by the following method: performing a propylene homopolymerization reaction in the presence of a first propylene homopolymer to obtain a propylene homopolymer component containing the first propylene homopolymer and a second propylene homopolymer; performing a propylene-ethylene copolymerization reaction in the presence of the propylene homopolymer component to obtain the impact polypropylene comprising a propylene homopolymer component and a propylene-ethylene copolymer component. It follows that the impact polypropylene provided by the present invention is not a simple blend of a propylene homopolymer component and a propylene-ethylene copolymer component, but is instead a unitary polypropylene material comprising a propylene homopolymer and a propylene-ethylene copolymer obtained after further specific propylene-ethylene copolymerization reactions on the basis of a specific propylene homopolymer component.
In the present invention, it is preferable that the propylene-ethylene copolymer component employs a propylene-ethylene random copolymer. As mentioned above, the impact polypropylene of the present invention can be used as a rubber component to ensure better tear resistance and stretch resistance. Moreover, the inventor of the present invention has found through a great deal of experiments that the impact polypropylene has a good effect when the weight ratio of the propylene-ethylene copolymer component to the propylene homopolymer component is 11-40: 100. Further, it is preferred that the ratio of the melt flow rate of the propylene homopolymer component to the impact polypropylene, as measured at 230 ℃ and under a load of 2.16kg, is from 0.6 to 1.
In the present invention, preferably, by the above-mentioned method for preparing the impact polypropylene, it is possible to first prepare, as a continuous phase, a propylene homopolymer component having a specific melt flow rate, a very broad molecular weight distribution containing a large amount of an ultrahigh molecular weight component, preferably the molecular weight distribution M of the homopolymer componentw/Mn6-20, the content of fractions with molecular weight greater than 500 ten thousand is 1.5-5% by weight; the content of the fraction with molecular weight less than 5 ten thousand is 15-40 wt%; mz+1/MnIs 70 or more and less than 150; then, copolymerization reaction of propylene and ethylene is further carried out on the basis of the rubber phase dispersed in the continuous phase, and the composition and the structure of the rubber phase are controlled by controlling the reaction conditions of the copolymerization reaction, preferably the molecular weight distribution M of the obtained impact resistant polypropylenew/MnIs 4-10; mz+1/MwIs greater than 10 and less than 20, preferably greater than 10 and less than 15; the room temperature xylene solubles content of the impact polypropylene is greater than 10 wt% and less than 30 wt%; and room temperature trichlorobenzene solubleswM with trichlorobenzene insolubles at room temperaturewThe ratio of (d) is greater than 0.4 and less than 1, preferably greater than 0.5 and less than 0.8. Thereby obtaining impact polypropylene having a high melt strength effect.
For purposes of the present invention, the relevant disclosure of the impact polypropylene is set forth in CN105623077A, which is incorporated herein by reference in its entirety.
Composite antioxidant
In the present invention, the complex antioxidant may include at least one selected from hindered phenol antioxidants, phosphite antioxidants, and thioester antioxidants. Specifically, the hindered phenol antioxidant may be monophenol, bisphenol, and polyphenol; the phosphite antioxidant comprises alkyl phosphite and aryl phosphite; the sulfofat antioxidant comprises a sulfofat antioxidant, a sulfophenol antioxidant and a sulfobisphenol antioxidant. The hindered phenol antioxidant, phosphite antioxidant and thioester antioxidant are known substances and are commercially available. For example, antioxidant 1010 (hindered phenol antioxidant), antioxidant 168 (phosphite antioxidant). Preferably, the composite antioxidant can also be added with calcium stearate to increase the antioxidant effect of the polypropylene. For example, the composite antioxidant is preferably composed of a mixture of the antioxidant 1010, the antioxidant 168 and calcium stearate in a weight ratio of 2:2: 1.
Other auxiliaries
In the invention, the composition can also contain other auxiliary agents, and the performance of the polypropylene is not affected. The auxiliary may be at least one selected from a slipping agent, an antistatic agent, a lubricant and a plasticizer. Preferably, the composition further comprises glycerol monostearate in an amount of 1 to 10% by weight of the copolymer microspheres. May help to improve the dispersibility of the mixed olefin-maleic anhydride copolymerized microspheres in the impact polypropylene.
According to the present invention, the composition may further include 0 to 5 parts by weight of a linear low density polyethylene. Preferably, the linear low density polyethylene has a Melt Flow Rate (MFR) in the range of 0.1 to 3g/10min at 190 ℃ and under a load of 2.16 kg. Commercially available, for example, Chinese petrochemical 7042(MFR 2g/10 min).
In a second aspect, the invention provides a polypropylene film made from said composition.
Preferably, the polypropylene film is a polypropylene blown film, more preferably, the polypropylene blown film is a blown polypropylene matte film.
According to the invention, the polypropylene blown film is a thin film whose thickness can be adjusted according to the needs and the specific process. Preferably, the polypropylene blown film has a thickness of 5 to 100 μm, preferably 15 to 60 μm.
According to the invention, the polypropylene blown film preferably has a tensile stress at break of more than 15MPa, preferably more than 25MPa, and may for example be in the range of 25 to 100 MPa.
According to the present invention, it is preferable that the polypropylene blown film has a longitudinal tensile strength of 63MPa or more and a transverse tensile strength of 60MPa or more; preferably, the longitudinal tensile strength is 65MPa or more and the transverse tensile strength is 63MPa or more; preferably, the tensile strength in the machine direction is 65.2 to 70.3MPa, and the tensile strength in the transverse direction is 63.6 to 68.2 MPa.
According to the present invention, preferably, the polypropylene blown film has a longitudinal elongation at break of 670% or more and a transverse elongation at break of 640% or more; preferably, the elongation at break in the machine direction is 700% or more and the elongation at break in the transverse direction is 680% or more; preferably, the elongation at break in the machine direction is 702-765% and the elongation at break in the transverse direction is 683-744%.
According to the present invention, it is preferable that the polypropylene blown film has a tensile elastic modulus in the machine direction of 810MPa or more and a tensile elastic modulus in the transverse direction of 699MPa or more. Preferably, the modulus of elasticity in longitudinal stretching is 850MPa or more, and the modulus of elasticity in transverse stretching is 750MPa or more; preferably, the longitudinal tensile elastic modulus is 852-891MPa, and the transverse tensile elastic modulus is 752-801 MPa.
In the present invention, preferably, the polypropylene blown film has a gloss of 9% or more; the oxidation induction period is more than 33min, preferably 33.2-41.7 min.
In the invention, the polypropylene film also has antibacterial property.
In a third aspect the present invention provides a process for the preparation of a polypropylene blown film comprising: the composition is extruded and granulated, and then blown into a film.
In the present invention, the impact polypropylene may be obtained as described above and in CN 105623077A. The mixed olefin-maleic anhydride copolymerized microspheres can be obtained by copolymerizing mixed C4 and maleic anhydride according to the method described above. The guanidine salt complex antibacterial agent can be prepared by steps a-c according to the aforementioned method.
In the present invention, the method for preparing the polypropylene blown film may include adding the guanidine salt composite antibacterial agent prepared in advance to the process of preparing the mixed olefin-maleic anhydride copolymerized microspheres before the extrusion granulation to obtain a composite of the mixed olefin-maleic anhydride copolymerized microspheres and the guanidine salt composite antibacterial agent. Preferably, the weight ratio of the mixed olefin-maleic anhydride copolymerized microspheres to the guanidine salt composite antibacterial agent is 1: (2-5), can have better extinction and antibacterial synergistic effects.
In the invention, the impact-resistant polypropylene and the composite antioxidant can be mixed and granulated, preferably, the weight ratio of the impact-resistant polypropylene to the composite antioxidant is 100: (0.05-0.5), preferably 100: (0.1-0.3) to obtain a base resin, and then extruding and granulating the compound and other components in the composition, such as linear low-density polypropylene and glycerol monostearate. A polypropylene film satisfying the object of the present invention can be produced.
The method for preparing a polypropylene blown film according to an embodiment of the present invention comprises:
I) mixing and granulating impact polypropylene and a composite antioxidant, wherein the weight ratio of the impact polypropylene to the composite antioxidant is preferably 100: (0.05-0.5) to obtain a base resin;
II) preparing the mixed olefin-maleic anhydride copolymerized microspheres, and mixing the mixed olefin-maleic anhydride copolymerized microspheres with the prepared guanidine salt composite antibacterial agent to obtain a composite of the mixed olefin-maleic anhydride copolymerized microspheres and the guanidine salt composite antibacterial agent, wherein the weight ratio of the mixed olefin-maleic anhydride copolymerized microspheres to the guanidine salt composite antibacterial agent is 1: (2-5);
III) mixing the base resin obtained in the step I) and the compound obtained in the step II), extruding and granulating, and then carrying out blow molding on the obtained granules to form a film.
The extrusion granulation can be preferably performed by a twin-screw extruder, and then the film blowing by a film blowing machine is performed to form the film.
Preferably, the extrusion temperature is 150 ℃ to 240 ℃, preferably 170 ℃ to 220 ℃.
Preferably, the blown film temperature is 170-230 ℃, preferably 185-220 ℃. The extrusion temperature refers to the extrusion temperature set by the extrusion equipment, such as an extruder. The film blowing temperature refers to the film opening temperature of film blowing equipment such as a film blowing machine.
Preferably, the blow-up ratio is from 1.5 to 3, preferably from 2 to 2.5, during the blown film process.
According to the invention, the film blowing machine can be a lower blowing water-cooled type, a flat blowing water-cooled type or a traditional upper blowing water-cooled type polypropylene film blowing machine set.
The polypropylene composition for blow molding provided by the invention can be used for obtaining a polypropylene blown film by using a common blow molding process, and changes the current situation that most polypropylene film molding can only depend on processes such as casting, biaxial stretching and the like. The polypropylene film obtained by the invention has the characteristics of strong impact resistance and tearing resistance, high tensile strength, good delustering performance and antibacterial property, and is particularly suitable for packaging high-grade foods, gifts, candies and the like; book leaf and beverage bottle printing and packaging fields. In addition, the obtained polypropylene film is of a non-crosslinked structure, can be recycled according to common polypropylene modified materials, does not cause secondary pollution, and meets the requirement of circular economy.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the following test methods were obtained using the equipment and associated data:
film blowing machine: collin blow Film Line Type 180/400, Germany.
A double-screw extruder: ZSK-25 from Kekuilong Nanjing mechanical Co.
1) The content of xylene soluble substances at room temperature and the content of ethylene in xylene soluble substances at room temperature (namely the content of a characteristic rubber phase and the content of ethylene in the rubber phase) are measured by a CRYSTEX method, a series of samples with different contents of xylene soluble substances at room temperature are selected as standard samples to be corrected by a CRYST-EX instrument (IR 4+ detector) produced by Spanish Polymer Char company, and the content of the xylene soluble substances at room temperature of the standard samples is measured by ASTM D5492. The infrared detector carried by the instrument can detect the weight content of the propylene in the soluble substance and is used for representing the ethylene content (ethylene content in a rubber phase) in the xylene soluble substance at room temperature, namely 100 percent to the weight content of the propylene.
2) Melt tensile tester: rheotens TM 97, Goettfert, Germany; the tensile strength of the resin was measured according to GB/T1040.2.
3) Melt flow rate MFR (also called melt index): measured according to ASTM D1238, using a melt index apparatus model 7026 from CEAST, at 190 ℃ or 230 ℃ under a load of 2.16 kg;
4) flexural modulus: measured according to the method described in GB/T9341;
5) impact strength of the simply supported beam notch: measured according to the method described in GB/T1043.1;
6) ethylene content: measured by infrared spectroscopy (IR), wherein the standard is calibrated by NMR. The NMR method was carried out using an AVANCE III 400MHz NMR spectrometer (NMR), 10 mm probe, from Bruker, Switzerland. The solvent is deuterated o-dichlorobenzene, about 250mg of the sample is placed in 2.5ml of deuterated solvent, and the sample is dissolved by heating in an oil bath at 140 ℃ to form a uniform solution. Collecting13C-NMR, probe temperature 125 ℃, adopting 90-degree pulse, sampling time AQ of 5 seconds, delay time D1 of 10 seconds, and scanning times of more than 5000 times. Other manipulations, spectral peak identification, etc. were performed as required for commonly used NMR experiments.
7) Molecular weight Polydispersity Index (PI): the resin sample is molded into a 2mm slice at 200 ℃, dynamic frequency scanning is carried out on the sample at 190 ℃ under the protection of nitrogen by adopting an ARES (advanced rheometer extended system) rheometer of Rheometric Scientific Inc in America, a parallel plate clamp is selected, appropriate strain amplitude is determined to ensure that the experiment is carried out in a linear region, and the change of storage modulus (G '), energy consumption modulus (G') and the like of the sample along with the frequency is measured. The molecular weight polydispersity index PI is 105/Gc, where Gc (unit: Pa) is the modulus value at the intersection of the G' -frequency curve and the G "-frequency curve.
8) Molecular weight (M)w，Mn) And molecular weight distribution (M)w/Mn，Mz+1/Mw): the molecular weight and molecular weight distribution of the sample were measured by PL-GPC 220 gel permeation chromatograph manufactured by Polymer Laboratories, UK, or GPCIR apparatus manufactured by Polymer Char, Spanish (IR5 concentration Detector), the columns were 3 PLgel 13 μm Olexis columns in series, the solvent and mobile phase were 1,2, 4-trichlorobenzene (containing 250ppm of antioxidant 2, 6-dibutyl-p-cresol), the column temperature was 150 ℃ and the flow rate was 1.0mL/min, and the calibration was carried out universally by EasiCal PS-1 narrow distribution polystyrene standard manufactured by PL. The preparation process of the room temperature trichlorobenzene soluble substance comprises the following steps: accurately weighing sample and trichlorobenzene solvent, dissolving at 150 deg.C for 5 hr, standing at 25 deg.C for 15 hr, and quantitatively adding glass fiberThe filter paper was filtered to obtain a solution of trichlorobenzene solubles at room temperature for assay. The content of trichlorobenzene soluble matter at room temperature was determined by correcting the GPC curve area with polypropylene of known concentration, and the molecular weight data of trichlorobenzene insoluble matter at room temperature was calculated from the GPC data of the original sample and the GPC data of the soluble matter.
9) The tensile strength, elongation at break and tensile modulus of elasticity of the film were measured according to the methods specified in GB/T1040.3-2006.
10) Film gloss was measured according to the method specified in ASTM D2457-2008.
11) Surface morphology of the film: the surface of the gold-sprayed film was observed with a Scanning Electron Microscope (SEM) of S4800, hitachi, japan.
12) And (3) antibacterial testing: the detection is carried out according to QB/T2591-2003A 'antibacterial property test method and antibacterial effect of antibacterial plastics': escherichia coli (Escherichia coli) ATCC 25922, Staphylococcus aureus (Staphylococcus aureus) ATCC 6538.
The sample piece is soaked in hot water at 50 ℃ for 16h before the antibacterial test. The test procedure was as follows: and (3) sterilizing a sample to be detected by using 75% ethanol, drying the sample, and diluting the strain into a bacterial suspension with a proper concentration by using sterile water for later use. 0.2mL of the bacterial suspension was dropped on the surface of the sample, and a polypropylene film (4.0 cm. times.4.0 cm) having a thickness of 0.1mm was coated thereon to form a uniform liquid film between the sample and the film. Culturing at 37 deg.C under relative humidity of 90% for 18-24 h. The bacterial liquid is washed by sterile water, diluted to a proper concentration gradient, and 0.1mL of the bacterial liquid is uniformly coated on the prepared sterile agar culture medium. Culturing at 37 deg.C for 18-24h, and observing the result. The negative control was replaced with a sterile plate and the other operations were identical.
13) Polypropylene EPS30R, China petrochemical Tianjin division, Melt Flow Rate (MFR) 1.5g/10min (230 ℃, 2.16 kg).
14) Polyethylene 7042, Chinese petrochemical, melt flow rate 2g/10min (190 ℃, 2.16 kg).
Preparation example 1 (base resin HMSPP601)
The propylene polymerization reaction is carried out on a polypropylene device, and the main equipment of the device comprises a prepolymerization reactor, a first loop reactor, a second loop reactor and a third gas-phase reactor. The polymerization method and the steps are as follows.
(1) Prepolymerization reaction
The main catalyst (DQC-401 catalyst, supplied by Oda, Beijing of China petrochemical catalyst Co.), cocatalyst (triethylaluminum) and first external electron donor (dicyclopentyl-dimethoxysilane, DCPMS) were precontacted at 6 ℃ for 20min, and then continuously added into a continuous stirred tank type prepolymerization reactor to perform a prepolymerization reactor. The Triethylaluminum (TEA) flow into the prepolymerization reactor was 6.33g/hr, the dicyclopentyl-dimethoxysilane flow was 0.3g/hr, the procatalyst flow was 0.6g/hr, and the TEA/DCPMS ratio was 50 (mol/mol). The prepolymerization is carried out in a propylene liquid phase bulk environment, the temperature is 15 ℃, the residence time is about 4min, and the prepolymerization multiple of the catalyst under the condition is about 80-120 times.
(2) The first step is as follows: homopolymerization of propylene
The first stage is as follows: continuously feeding the prepolymerized catalyst into a first loop reactor to complete the first-stage propylene homopolymerization, wherein the polymerization temperature of the first loop reactor is 70 ℃, and the reaction pressure is 4.0 MPa; and (3) adding no hydrogen into the feed of the first loop reactor, wherein the concentration of the hydrogen detected by an online chromatographic method is less than 10ppm, so as to obtain a first propylene homopolymer A.
And a second stage: the second stage of propylene homopolymerization was carried out in a second loop reactor connected in series with the first loop reactor. Tetraethoxysilane (TEOS) was added at 0.63g/hr with propylene from the second loop reactor and mixed with the reactant stream from the first loop reactor at a TEA/TEOS ratio of 5(mol/mol), where TEOS is the second external electron donor. The polymerization temperature of the second loop reactor is 70 ℃, and the reaction pressure is 4.0 MPa; a quantity of hydrogen was also added with the propylene feed, and the hydrogen concentration in the feed was 3000ppm, as detected by on-line chromatography, to produce a second propylene homopolymer B in the second loop reactor, yielding a propylene homopolymer component comprising a first propylene homopolymer and a second propylene homopolymer (polymer (a + B)).
(3) The second step is that: propylene-ethylene copolymerization
A certain amount of hydrogen and H is added into the third reactor2/(C2+C3)＝0.06(mol/mol)，C2/(C2+C3)＝0.3(mol/mol)(C2And C3Respectively referring to ethylene and propylene), and the ethylene/propylene copolymerization is continuously initiated in the third reactor at a reaction temperature of 75 ℃ to produce the propylene-ethylene copolymer component C.
The final product comprised the first propylene homopolymer, the second propylene homopolymer and the propylene-ethylene copolymer component (polymer (a + B + C)), which was deactivated by wet nitrogen and dried by heating to give an impact polypropylene SPP601, and the analysis results and physical properties are shown in tables 1 and 2.
Adding 0.1 wt% of antioxidant 168, 0.1 wt% of antioxidant 1010 and 0.05 wt% of calcium stearate into the impact polypropylene powder, and granulating by using a double-screw extruder. Obtaining the base resin HMSPP601 (the weight ratio of the impact-resistant polypropylene SPP601 to the composite antioxidant is 100: 0.25).
Preparation example 2 (base resin HMSPP602)
The base resin HMSPP602 is prepared according to the method described in preparation example 1, and the catalyst, pre-complexing, polymerization process conditions and the like used are the same as those of preparation example 1, except that: the amount of hydrogen in the second reactor in the second stage was 13000ppm, and the amount of H in the gas phase reactor in the second stage was 13000ppm2/(C2+C3) The temperature was adjusted to 0.49 (mol/mol). The first external electron donor was replaced by methyl-isopropyl-dimethoxysilane (MIPMS), and the amount added was unchanged.
The analysis results and physical properties of the impact polypropylene SPP602 are shown in tables 1 and 2.
In the base resin HMSPP602, the impact polypropylene SPP 602: the weight ratio of the composite antioxidant is 100: 0.25.
preparation example 3 (base resin HMSPP603)
The base resin HMSPP603 is prepared according to the method described in preparation example 1, and the catalyst, pre-complexing, polymerization process conditions and the like used are the same as those of preparation example 1, except that: the second external electron donor was changed to 2, 2-diisobutyl-1, 3-Dimethoxypropane (DIBMP), the amount of the added electron donor was unchanged, and the amount of hydrogen in the second reactor was adjusted to 3600ppm in the second stage.
The analysis results and physical properties of the impact polypropylene SPP603 are shown in tables 1 and 2.
Of the base resin HMSPP603, the impact polypropylene SPP 603: the weight ratio of the composite antioxidant is 100: 0.25.
in the preparation process as provided in the above preparation examples, the obtained first polypropylene homopolymer A has a melt flow rate of 0.001-0.4g/10min, measured at 230 ℃ and under a load of 2.16 kg. And wherein the weight ratio of the first polypropylene homopolymer a to the second propylene homopolymer B satisfies 40:60 to 60: 40.
Preparation example 4
And preparing the guanidine salt composite antibacterial agent.
1# of composite antibacterial agent:a. 1000.0g of polyhexamethylene guanidine hydrochloride (practice Co., Ltd., Shanghai) was dissolved in water to prepare an aqueous solution having a mass concentration of 20%; 50.0g of zinc sulfate is prepared into an aqueous solution with the mass concentration of 25 percent, and 125.0g of styrene-butadiene latex solution is directly used after radiation crosslinking, and the concentration is 40 percent. b. Adding the prepared guanidine salt polymer aqueous solution into a container containing a zinc-containing aqueous solution, stirring while adding until the guanidine salt polymer aqueous solution and the zinc-containing aqueous solution are uniformly mixed to form a transparent liquid mixture. c. Adding the liquid mixture of step b to the latex solution while stirring until uniformly mixed, and then adding 5.0g of an anti-migration agent (Coresi wound) to the mixture
Figure BDA0002040703370000151
2794 XP). d. C, drying the mixture obtained in the step c by using a spray dryer to obtain solid powder; transferring the obtained solid powder to a high-speed stirrer, adding 5.0g of fumed silica serving as a dispersing agent, and mixing and dispersing at a high speed to obtain the guanidine salt composite antibacterial agent 1 #.
Composite antibacterial agent 2 #:a. 1000.0g of polyhexamethylene guanidine propionate (Utility Co., Ltd., Shanghai mountain) was dissolved in water to prepare an aqueous solution having a mass concentration of 40%; 100.0g of zinc acetate is prepared into an aqueous solution with the mass concentration of 15 percent, 150.0g of butyronitrile latex solution is directly used after radiation crosslinking, and the concentration is 30% of the total weight of the composition. b. Adding the prepared guanidine salt polymer aqueous solution into a container containing a zinc-containing aqueous solution, stirring while adding until the guanidine salt polymer aqueous solution and the zinc-containing aqueous solution are uniformly mixed to form a transparent liquid mixture. c. And c, adding the liquid mixture obtained in the step b into the latex solution, and stirring while adding until the mixture is uniformly mixed. Then, 5.0g of an anti-migration agent (Colesine) was added to the mixture
Figure BDA0002040703370000152
2794 XP). d. C, drying the mixture obtained in the step c by using a spray dryer to obtain solid powder; transferring the obtained solid powder to a high-speed stirrer, adding 15.0g of nano calcium carbonate as a dispersing agent, and mixing and dispersing at a high speed to obtain the guanidine salt composite antibacterial agent No. 2.
Composite antibacterial agent 3 #:a. 1000.0g of polyhexamethylene biguanide hydrochloride (practice Co., Ltd., Shanghai mountain) was dissolved in water to prepare an aqueous solution having a mass concentration of 10%; 200.0g of zinc nitrate is prepared into an aqueous solution with the mass concentration of 30%, 125.0g of silicone rubber latex solution is directly used after radiation crosslinking, and the concentration is 40%. b. Adding the prepared guanidine salt polymer aqueous solution into a container containing a zinc-containing aqueous solution, stirring while adding until the guanidine salt polymer aqueous solution and the zinc-containing aqueous solution are uniformly mixed to form a transparent liquid mixture. c. And c, adding the liquid mixture obtained in the step b into the latex solution, and stirring while adding until the mixture is uniformly mixed. Then, 5.0g of an anti-migration agent (Colesine) was added to the mixture
Figure BDA0002040703370000161
2794 XP). d. C, drying the mixture obtained in the step c by using a spray dryer to obtain solid powder; and transferring the obtained solid powder into a high-speed stirrer, adding 30.0g of talcum powder serving as a dispersing agent, and mixing and dispersing at a high speed to obtain the guanidine salt composite antibacterial agent # 3.
Preparation example 5
Preparing the composite of the mixed olefin-maleic anhydride copolymer microspheres and the guanidine salt composite antibacterial agent.
The mixed C-C A comprises (by weight percent) 1, 2-butadiene, 8.92%; 1, 3-butadiene, 14.14%; 1-butene, 8.38%; trans-2-butene, 5.84%; cis-2-butene, 31.7%; vinyl acetylene, 10.99%; isobutane, 1.3%; isobutene, 12.78%; n-butane 2.58%, others, 3.37%.
The mixed C-B comprises the following components in percentage by weight: 1, 3-butadiene, 0.06%; trans-2-butene, 12.67%; isobutane, 37.09%; 19.48 percent of isobutene; cis-2-butene, 27.79%; 1-butene, 1.02%; others, 1.89%.
The mixed C-C comprises the following components in percentage by weight: trans-2-butene, 40.83%; cis-2-butene, 18.18%; 24.29 percent of n-butane; 1-butene, 9.52%; isobutene, 2.78%; others, 4.4%.
Composite of microspheres and antimicrobial agent
Under the protection of nitrogen, 14kg of mixed C-IV A is introduced into a 200L reaction kettle containing 20kg of organic reaction liquid of maleic anhydride, 2.4kg of azodiisobutyronitrile and 100L of isoamyl acetate for copolymerization reaction, the copolymerization reaction pressure is 0.9MPa, the copolymerization reaction temperature is 70 ℃, and the copolymerization reaction time is 6 h;
and introducing the copolymerization reaction product into a flash separator for gas-liquid separation at the temperature of 25 ℃ and under the pressure of 0MPa, continuously carrying out liquid-solid separation on the obtained liquid-solid mixture in a centrifugal separator at the rpm of 4000 for 20min to obtain a solid product, washing with hexane, and carrying out vacuum drying on a filter cake obtained by suction filtration through a sand core funnel for 8h at the temperature of 90 ℃ to obtain the mixed olefin-maleic anhydride copolymer microsphere powder 101. Testing the microsphere powder, wherein the content of the maleic anhydride structural unit is 48 mol%; the average particle diameter was 0.2. mu.m.
Mixing the mixed olefin-maleic anhydride copolymer microsphere powder 101 and the composite antibacterial agent 1# according to the mixture ratio in the table 3, wherein the weight ratio is 1: (2-5).
Microsphere and antimicrobial agent composite
Under the protection of nitrogen, 13.5kg of mixed C-IV B is introduced into a 200L reaction kettle containing 20kg of maleic anhydride, 4kg of dibenzoyl peroxide and 100L of organic reaction liquid of isoamyl acetate for copolymerization reaction, the copolymerization reaction pressure is 1MPa, the copolymerization reaction temperature is 80 ℃, and the copolymerization reaction time is 6 h;
and introducing the copolymerization reaction product into a flash separator for gas-liquid separation at 30 ℃ and 0MPa, continuously performing liquid-solid separation on the obtained liquid-solid mixture in a centrifugal separator at 4000rpm for 20min to obtain a solid product, washing with hexane, and performing vacuum drying on a filter cake obtained by suction filtration of a sand core funnel for 8h at 90 ℃ to obtain the mixed olefin-maleic anhydride copolymer microsphere powder 102. Testing the microsphere powder, wherein the content of the maleic anhydride structural unit is 51 mol%; the average particle diameter was 1 μm.
Mixing the mixed olefin-maleic anhydride copolymer microsphere powder 102 and the composite antibacterial agent 2# according to the mixture ratio in the table 3, wherein the weight ratio is 1: (2-5).
Microsphere and antimicrobial agent composite
Introducing 15kg of mixed C-C into a 200L reaction kettle containing 20kg of maleic anhydride, 4.5kg of dibenzoyl peroxide and 100L of isoamyl acetate to carry out copolymerization reaction at the copolymerization reaction pressure of 1.5MPa and the copolymerization reaction temperature of 80 ℃ for 10 h;
and introducing the copolymerization reaction product into a flash separator for gas-liquid separation at the temperature of 27 ℃ and under the pressure of 0MPa, continuously performing liquid-solid separation on the obtained liquid-solid mixture in a centrifugal separator at 8000rpm for 20min to obtain a solid product, washing with hexane, and performing vacuum drying on a filter cake obtained by suction filtration of a sand core funnel at the temperature of 90 ℃ for 8h to obtain mixed olefin-maleic anhydride copolymer microsphere powder 103. Testing the microsphere powder, wherein the content of the maleic anhydride structural unit is 55 mol%; the average particle diameter was 2 μm.
Mixing the mixed olefin-maleic anhydride copolymer microsphere powder 103 and the composite antibacterial agent 3# according to the mixture ratio in the table 3, wherein the weight ratio is 1: (2-5).
Examples 1-15, optimization examples 1-6, comparative examples 1-12
Preparation of polypropylene composition for blow molding and blown polypropylene film
The components were mixed in a high speed mixer to a mixture according to the components and amounts of the polypropylene composition listed in table 3; feeding the mixed materials into a double-screw extruder, and then mixing and granulating by using the double-screw extruder, wherein the temperature of each section of the extruder is set as follows: 190 deg.C, 200 deg.C, 210 deg.C, 215 deg.C (handpiece). The resulting pellets were dried to obtain a granular polypropylene composition. The polypropylene composition pellets were subjected to an oxidative induction period test. And then, carrying out injection molding on the polypropylene composition by an injection molding machine to obtain a test sample strip, and carrying out thermal deformation test. The test results are shown in Table 4.
The obtained pellets are extruded and blown on a film blowing machine, and the temperature of each section of the film blowing machine is set as follows: 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃ (die temperature). The blown film test results are shown in Table 5.
Wherein, the surface topography of the SEM electron microscope is observed in example 4 and comparative example 12, and the results are shown in figures 1 and 2.
As can be seen from the data results of the above examples, optimization examples, comparative examples, FIGS. 1-2, and tables 1-5, the polypropylene composition for blow molding provided by the present invention contains the mixed olefin-maleic anhydride copolymerized microspheres as the delustering agent, and the polypropylene film prepared by blow molding can contain maleic anhydride structural units in the composition structure, so as to realize the antibacterial blow molded polypropylene film with good mechanical properties, matte effect and thermo-oxidative aging resistance.
As can be seen from the results shown in tables 1 and 2, the impact polypropylene prepared according to the method of the present invention has high melt strength, tensile strength and flexural modulus, and high notched impact strength. Can be used for polypropylene blown films.
As can be seen from the data results of tables 3 and 4, the polypropylene compositions for blow molding of the present invention obtained in the examples and the optimized examples can have good heat distortion properties and oxidation resistance.
As can be seen from the results in Table 5, the polypropylene composition for blow molding provided by the invention uses the mixed olefin-maleic anhydride copolymerized microspheres as the delustering agent, not only can realize blow molding film formation, but also can prepare a polypropylene blown film with the thickness of 10-50 μm. Particularly, when the film thickness is only 10 mu m, the film still has good mechanical property, good matte effect and thermal-oxidative aging resistance, and simultaneously has the performances of longitudinal (MD) tensile strength being more than or equal to 63MPa, Transverse (TD) tensile strength being more than or equal to 60MPa and glossiness being 9-15%, and the blown film can keep good antibacterial property before and after being boiled in water, thereby having good industrial application prospect of being used as a matte film.
Comparative example 12 was set for comparison of the surface topography of the film in the present invention. Comparative example 12 differs from example 4 only in that no mixed olefin-maleic anhydride copolymerized microspheres were added. As shown in the SEM photographs of FIGS. 1 and 2, it can be seen that the surface appearance of the blown polypropylene film prepared by the example 4 containing the mixed olefin-maleic anhydride copolymerized microspheres is rough, and the glossiness of the film can be effectively reduced, so that the matte effect is obtained; comparative example 10 a blown polypropylene film made without the mixed olefin-maleic anhydride copolymerized microspheres had a smooth surface, without the gloss being affected and without matte effect.
Comparative examples 7-9 blown polypropylene films with low gloss and good mechanical properties could not be obtained using polypropylene not defined by the present invention. Comparative example 11 when polyhexamethylene biguanide hydrochloride was used alone in the same amount as the antibacterial agent, the obtained film had poor antibacterial properties and was not suitable for the field of packaging materials having high requirements for antibacterial properties.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Figure BDA0002040703370000201
Figure BDA0002040703370000211
Figure BDA0002040703370000221
Figure BDA0002040703370000231
Figure BDA0002040703370000241
Figure BDA0002040703370000251
Figure BDA0002040703370000261

Claims (45)

1. A polypropylene composition for blow molding comprises 100 weight parts of impact polypropylene, 0.05 to 0.5 weight part of composite antioxidant, 0.25 to 10 weight parts of mixed olefin-maleic anhydride copolymer microspheres and 0.05 to 2 weight parts of guanidine salt composite antibacterial agent; the mixed olefin is from mixed C4;
wherein the particle size of the mixed olefin-maleic anhydride copolymerized microsphere is 0.05-2 μm;
the guanidine salt composite antibacterial agent contains a guanidine salt polymer, zinc salt and/or copper salt, an anti-migration agent, nano-powder rubber and a dispersing agent;
relative to 100 parts by weight of the guanidine salt polymer, 0.01-40 parts by weight of the zinc salt and/or the copper salt, 0.1-10 parts by weight of the anti-migration agent, 0.5-100 parts by weight of the nanoscale powder rubber and 0.1-10 parts by weight of the dispersing agent are used.
2. The composition of claim 1, wherein the composition comprises 100 parts by weight of the impact polypropylene, 0.1 to 0.3 parts by weight of the complex antioxidant, 0.25 to 2.5 parts by weight of the mixed olefin-maleic anhydride copolymerized microspheres, and 0.05 to 1.5 parts by weight of the guanidine salt complex antibacterial agent;
wherein the particle size of the mixed olefin-maleic anhydride copolymerized microsphere is 0.2-1 μm.
3. The composition according to claim 1 or 2, wherein the content of the maleic anhydride structural unit in the mixed olefin-maleic anhydride copolymerized microsphere is 30 to 70 mol%.
4. The composition of claim 1 or 2, wherein the mixed olefin-maleic anhydride copolymerized microspheres are a copolymer of maleic anhydride and a carbon tetraene prepared by copolymerization of mixed carbon four and maleic anhydride in the presence of nitrogen, an initiator and an organic solvent.
5. The composition of claim 4, wherein the mixed olefin-maleic anhydride copolymerized microspheres are copolymer microspheres of maleic anhydride and n-butene, isobutylene.
6. The composition of claim 3, wherein the mixed olefin-maleic anhydride copolymerized microspheres are a copolymer of maleic anhydride and a carbon tetraene prepared by copolymerization of mixed carbon four and maleic anhydride in the presence of nitrogen, an initiator and an organic solvent.
7. The composition of claim 6, wherein the mixed olefin-maleic anhydride copolymerized microspheres are copolymer microspheres of maleic anhydride and n-butene, isobutylene.
8. The composition of claim 4, wherein the weight ratio of mixed C4 to maleic anhydride is (0.2-3): 1;
and/or the amount of the initiator is 0.05-20 mol% of the maleic anhydride;
and/or the concentration of maleic anhydride in the organic solvent is 5-25 wt%;
and/or the copolymerization reaction temperature is 50-100 ℃; the copolymerization pressure is 0.2-2 MPa; the copolymerization reaction time is 5-10 h.
9. The composition of claim 8, wherein the weight ratio of mixed carbon four to maleic anhydride is (0.8-3): 1;
and/or the concentration of maleic anhydride in the organic solvent is 10-20 wt%;
and/or the copolymerization reaction temperature is 70-90 ℃; the copolymerization pressure is 0.5-1 MPa.
10. The composition of any of claims 5-7, wherein the weight ratio of mixed C4 to maleic anhydride is (0.2-3): 1;
and/or the amount of the initiator is 0.05-20 mol% of the maleic anhydride;
and/or the concentration of maleic anhydride in the organic solvent is 5-25 wt%;
and/or the copolymerization reaction temperature is 50-100 ℃; the copolymerization pressure is 0.2-2 MPa; the copolymerization reaction time is 5-10 h.
11. The composition of claim 10, wherein the weight ratio of mixed carbon four to maleic anhydride is (0.8-3): 1;
and/or the concentration of maleic anhydride in the organic solvent is 10-20 wt%;
and/or the copolymerization reaction temperature is 70-90 ℃; the copolymerization pressure is 0.5-1 MPa.
12. The composition of any of claims 1,2, 5-9, 11, wherein the impact polypropylene isM w /M n Meet the requirement of not more than 4M w /M n Less than or equal to 10; of the impact polypropyleneM z+1 /M w Satisfies 10 <M z+1 /M w ＜20；
And/or the impact polypropylene has a room temperature xylene solubles content of greater than 10 weight percent% and less than 30% by weight; and room temperature trichlorobenzene solubles of said impact polypropyleneM w With trichlorobenzene insolubles at room temperatureM w The ratio of (A) to (B) is greater than 0.4 and less than 1;
and/or the room temperature xylene solubles of the impact polypropylene have an ethylene content of more than 25 wt% and less than 50 wt%;
and/or the ethylene content in the impact-resistant polypropylene is 5-15 wt%;
and/or the impact polypropylene has a melt flow rate of 0.1 to 15g/10min, measured at 230 ℃ and under a load of 2.16 kg;
and/or the impact polypropylene has a molecular weight polydispersity index of 4 to 8;
and/or the melt strength of the impact polypropylene is greater than 0.1N;
and/or the impact polypropylene has an Izod notched impact of 70-100kJ/m at 23 DEG C2。
13. The composition of claim 12, wherein the impact polypropylene isM w /M n Satisfies 5 <M w /MnLess than 9; of the impact polypropyleneM z+1 /M w Satisfies 10 <M z+1 /M w ＜15；
And/or the impact polypropylene has a room temperature xylene solubles content of greater than 10 wt% and less than 22 wt%; and room temperature trichlorobenzene solubles of said impact polypropyleneM w With trichlorobenzene insolubles at room temperatureM w The ratio of (A) to (B) is greater than 0.5 and less than 0.8;
and/or the room temperature xylene solubles of the impact polypropylene have an ethylene content of more than 30 wt% and less than 50 wt%;
and/or the impact polypropylene has a melt flow rate of 0.1 to 6g/10min, measured at 230 ℃ and under a load of 2.16 kg;
and/or the impact polypropylene has a molecular weight polydispersity index of 4.5 to 6;
and/or the melt strength of the impact polypropylene is from 0.15 to 0.25N.
14. The composition of claim 3, wherein the impact polypropylene isM w /M n Meet the requirement of not more than 4M w /M n Less than or equal to 10; of the impact polypropyleneM z+1 /M w Satisfies 10 <M z+1 /M w ＜20；
And/or the impact polypropylene has a room temperature xylene solubles content of greater than 10 wt% and less than 30 wt%; and room temperature trichlorobenzene solubles of said impact polypropyleneM w With trichlorobenzene insolubles at room temperatureM w The ratio of (A) to (B) is greater than 0.4 and less than 1;
and/or the room temperature xylene solubles of the impact polypropylene have an ethylene content of more than 25 wt% and less than 50 wt%;
and/or the ethylene content in the impact-resistant polypropylene is 5-15 wt%;
and/or the impact polypropylene has a melt flow rate of 0.1 to 15g/10min, measured at 230 ℃ and under a load of 2.16 kg;
and/or the impact polypropylene has a molecular weight polydispersity index of 4 to 8;
and/or the melt strength of the impact polypropylene is greater than 0.1N;
and/or the impact polypropylene has an Izod notched impact of 70-100kJ/m at 23 DEG C2。
15. The composition of claim 14, wherein the impact polypropylene isM w /M n Satisfies 5 <M w /MnLess than 9; of the impact polypropyleneM z+1 /M w Satisfies 10 <M z+1 /M w ＜15；
And/or, room temperature two of said impact polypropyleneA toluene solubles content of greater than 10 wt% and less than 22 wt%; and room temperature trichlorobenzene solubles of said impact polypropyleneM w With trichlorobenzene insolubles at room temperatureM w The ratio of (A) to (B) is greater than 0.5 and less than 0.8;
and/or the room temperature xylene solubles of the impact polypropylene have an ethylene content of more than 30 wt% and less than 50 wt%;
and/or the impact polypropylene has a melt flow rate of 0.1 to 6g/10min, measured at 230 ℃ and under a load of 2.16 kg;
and/or the impact polypropylene has a molecular weight polydispersity index of 4.5 to 6;
and/or the melt strength of the impact polypropylene is from 0.15 to 0.25N.
16. The composition of claim 4, wherein the impact polypropylene isM w /M n Meet the requirement of not more than 4M w /M n Less than or equal to 10; of the impact polypropyleneM z+1 /M w Satisfies 10 <M z+1 /M w ＜20；
And/or the impact polypropylene has a room temperature xylene solubles content of greater than 10 wt% and less than 30 wt%; and room temperature trichlorobenzene solubles of said impact polypropyleneM w With trichlorobenzene insolubles at room temperatureM w The ratio of (A) to (B) is greater than 0.4 and less than 1;
and/or the room temperature xylene solubles of the impact polypropylene have an ethylene content of more than 25 wt% and less than 50 wt%;
and/or the ethylene content in the impact-resistant polypropylene is 5-15 wt%;
and/or the impact polypropylene has a melt flow rate of 0.1 to 15g/10min, measured at 230 ℃ and under a load of 2.16 kg;
and/or the impact polypropylene has a molecular weight polydispersity index of 4 to 8;
and/or the melt strength of the impact polypropylene is greater than 0.1N;
and/or the impact polypropylene has an Izod notched impact of 70-100kJ/m at 23 DEG C2。
17. The composition of claim 16, wherein the impact polypropylene isM w /M n Satisfies 5 <M w /MnLess than 9; of the impact polypropyleneM z+1 /M w Satisfies 10 <M z+1 /M w ＜15；
And/or the impact polypropylene has a room temperature xylene solubles content of greater than 10 wt% and less than 22 wt%; and room temperature trichlorobenzene solubles of said impact polypropyleneM w With trichlorobenzene insolubles at room temperatureM w The ratio of (A) to (B) is greater than 0.5 and less than 0.8;
and/or the room temperature xylene solubles of the impact polypropylene have an ethylene content of more than 30 wt% and less than 50 wt%;
and/or the impact polypropylene has a melt flow rate of 0.1 to 6g/10min, measured at 230 ℃ and under a load of 2.16 kg;
and/or the impact polypropylene has a molecular weight polydispersity index of 4.5 to 6;
and/or the melt strength of the impact polypropylene is from 0.15 to 0.25N.
18. The composition of claim 10, wherein the impact polypropylene isM w /M n Meet the requirement of not more than 4M w /M n Less than or equal to 10; of the impact polypropyleneM z+1 /M w Satisfies 10 <M z+1 /M w ＜20；
And/or the impact polypropylene has a room temperature xylene solubles content of greater than 10 wt% and less than 30 wt%; and room temperature trichlorobenzene solubles of said impact polypropyleneM w With trichlorobenzene at room temperatureOf dissolved substancesM w The ratio of (A) to (B) is greater than 0.4 and less than 1;
and/or the room temperature xylene solubles of the impact polypropylene have an ethylene content of more than 25 wt% and less than 50 wt%;
and/or the ethylene content in the impact-resistant polypropylene is 5-15 wt%;
and/or the impact polypropylene has a melt flow rate of 0.1 to 15g/10min, measured at 230 ℃ and under a load of 2.16 kg;
and/or the impact polypropylene has a molecular weight polydispersity index of 4 to 8;
and/or the melt strength of the impact polypropylene is greater than 0.1N;
and/or the impact polypropylene has an Izod notched impact of 70-100kJ/m at 23 DEG C2。
19. The composition of claim 18, wherein the impact polypropylene isM w /M n Satisfies 5 <M w /MnLess than 9; of the impact polypropyleneM z+1 /M w Satisfies 10 <M z+1 /M w ＜15；
And/or the impact polypropylene has a room temperature xylene solubles content of greater than 10 wt% and less than 22 wt%; and room temperature trichlorobenzene solubles of said impact polypropyleneM w With trichlorobenzene insolubles at room temperatureM w The ratio of (A) to (B) is greater than 0.5 and less than 0.8;
and/or the room temperature xylene solubles of the impact polypropylene have an ethylene content of more than 30 wt% and less than 50 wt%;
and/or the impact polypropylene has a melt flow rate of 0.1 to 6g/10min, measured at 230 ℃ and under a load of 2.16 kg;
and/or the impact polypropylene has a molecular weight polydispersity index of 4.5 to 6;
and/or the melt strength of the impact polypropylene is from 0.15 to 0.25N.
20. The composition of any of claims 1,2, 5-9, 11, 13-19, wherein the impact polypropylene is obtained by:
performing a propylene homopolymerization reaction in the presence of a first propylene homopolymer to obtain a propylene homopolymer component containing the first propylene homopolymer and a second propylene homopolymer;
performing a propylene-ethylene copolymerization reaction in the presence of the propylene homopolymer component to obtain the impact polypropylene comprising a propylene homopolymer component and a propylene-ethylene copolymer component;
wherein the first propylene homopolymer has a melt flow rate of 0.001 to 0.4g/10min, measured at 230 ℃ and under a load of 2.16 kg;
the propylene homopolymer component has a melt flow rate of 0.1 to 15g/10min measured at 230 ℃ and under a load of 2.16 kg; and the weight ratio of the first propylene homopolymer to the second propylene homopolymer is from 40:60 to 60: 40.
21. The composition of claim 3, wherein the impact polypropylene is obtained by:
performing a propylene homopolymerization reaction in the presence of a first propylene homopolymer to obtain a propylene homopolymer component containing the first propylene homopolymer and a second propylene homopolymer;
performing a propylene-ethylene copolymerization reaction in the presence of the propylene homopolymer component to obtain the impact polypropylene comprising a propylene homopolymer component and a propylene-ethylene copolymer component;
wherein the first propylene homopolymer has a melt flow rate of 0.001 to 0.4g/10min, measured at 230 ℃ and under a load of 2.16 kg;
the propylene homopolymer component has a melt flow rate of 0.1 to 15g/10min measured at 230 ℃ and under a load of 2.16 kg; and the weight ratio of the first propylene homopolymer to the second propylene homopolymer is from 40:60 to 60: 40.
22. The composition of claim 4, wherein the impact polypropylene is obtained by:
performing a propylene homopolymerization reaction in the presence of a first propylene homopolymer to obtain a propylene homopolymer component containing the first propylene homopolymer and a second propylene homopolymer;
performing a propylene-ethylene copolymerization reaction in the presence of the propylene homopolymer component to obtain the impact polypropylene comprising a propylene homopolymer component and a propylene-ethylene copolymer component;
wherein the first propylene homopolymer has a melt flow rate of 0.001 to 0.4g/10min, measured at 230 ℃ and under a load of 2.16 kg;
the propylene homopolymer component has a melt flow rate of 0.1 to 15g/10min measured at 230 ℃ and under a load of 2.16 kg; and the weight ratio of the first propylene homopolymer to the second propylene homopolymer is from 40:60 to 60: 40.
23. The composition of claim 10, wherein the impact polypropylene is obtained by:
performing a propylene homopolymerization reaction in the presence of a first propylene homopolymer to obtain a propylene homopolymer component containing the first propylene homopolymer and a second propylene homopolymer;
performing a propylene-ethylene copolymerization reaction in the presence of the propylene homopolymer component to obtain the impact polypropylene comprising a propylene homopolymer component and a propylene-ethylene copolymer component;
wherein the first propylene homopolymer has a melt flow rate of 0.001 to 0.4g/10min, measured at 230 ℃ and under a load of 2.16 kg;
the propylene homopolymer component has a melt flow rate of 0.1 to 15g/10min measured at 230 ℃ and under a load of 2.16 kg; and the weight ratio of the first propylene homopolymer to the second propylene homopolymer is from 40:60 to 60: 40.
24. The composition of claim 12, wherein the impact polypropylene is obtained by:
performing a propylene homopolymerization reaction in the presence of a first propylene homopolymer to obtain a propylene homopolymer component containing the first propylene homopolymer and a second propylene homopolymer;
performing a propylene-ethylene copolymerization reaction in the presence of the propylene homopolymer component to obtain the impact polypropylene comprising a propylene homopolymer component and a propylene-ethylene copolymer component;
wherein the first propylene homopolymer has a melt flow rate of 0.001 to 0.4g/10min, measured at 230 ℃ and under a load of 2.16 kg;
the propylene homopolymer component has a melt flow rate of 0.1 to 15g/10min measured at 230 ℃ and under a load of 2.16 kg; and the weight ratio of the first propylene homopolymer to the second propylene homopolymer is from 40:60 to 60: 40.
25. The composition of any one of claims 1,2, 5-9, 11, 13-19, 21-24, further comprising 0-5 parts by weight of a linear low density polyethylene;
and/or the linear low density polyethylene has a melt flow rate at 190 ℃ under a load of 2.16kg in the range of 0.1 to 3g/10 min.
26. The composition of claim 3, further comprising 0-5 parts by weight of a linear low density polyethylene;
and/or the linear low density polyethylene has a melt flow rate at 190 ℃ under a load of 2.16kg in the range of 0.1 to 3g/10 min.
27. The composition of claim 4, further comprising 0-5 parts by weight of a linear low density polyethylene;
and/or the linear low density polyethylene has a melt flow rate at 190 ℃ under a load of 2.16kg in the range of 0.1 to 3g/10 min.
28. The composition of claim 10, further comprising 0-5 parts by weight of a linear low density polyethylene;
and/or the linear low density polyethylene has a melt flow rate at 190 ℃ under a load of 2.16kg in the range of 0.1 to 3g/10 min.
29. The composition of claim 12, further comprising 0-5 parts by weight of a linear low density polyethylene;
and/or the linear low density polyethylene has a melt flow rate at 190 ℃ under a load of 2.16kg in the range of 0.1 to 3g/10 min.
30. The composition of claim 20, further comprising 0-5 parts by weight of a linear low density polyethylene;
and/or the linear low density polyethylene has a melt flow rate at 190 ℃ under a load of 2.16kg in the range of 0.1 to 3g/10 min.
31. The composition of any one of claims 1,2, 5-9, 11, 13-19, 21-24, and 26-30, wherein the zinc salt and/or copper salt is 5-25 parts by weight, the anti-migration agent is 0.5-5 parts by weight, the nano-sized powder rubber is 4.5-50 parts by weight, and the dispersant is 0.5-5 parts by weight, relative to 100 parts by weight of the guanidinium polymer.
32. The composition according to claim 3, wherein the zinc salt and/or copper salt is 5 to 25 parts by weight, the anti-migration agent is 0.5 to 5 parts by weight, the nano-sized powder rubber is 4.5 to 50 parts by weight, and the dispersant is 0.5 to 5 parts by weight, relative to 100 parts by weight of the guanidine salt polymer.
33. The composition according to claim 4, wherein the zinc salt and/or copper salt is 5 to 25 parts by weight, the anti-migration agent is 0.5 to 5 parts by weight, the nano-sized powder rubber is 4.5 to 50 parts by weight, and the dispersant is 0.5 to 5 parts by weight, relative to 100 parts by weight of the guanidine salt polymer.
34. The composition of claim 10, wherein the zinc salt and/or copper salt is 5 to 25 parts by weight, the anti-migration agent is 0.5 to 5 parts by weight, the nano-sized powder rubber is 4.5 to 50 parts by weight, and the dispersant is 0.5 to 5 parts by weight, relative to 100 parts by weight of the guanidine salt polymer.
35. The composition of claim 12, wherein the zinc salt and/or copper salt is 5 to 25 parts by weight, the anti-migration agent is 0.5 to 5 parts by weight, the nano-sized powder rubber is 4.5 to 50 parts by weight, and the dispersant is 0.5 to 5 parts by weight, relative to 100 parts by weight of the guanidine salt polymer.
36. The composition of claim 20, wherein the zinc salt and/or copper salt is 5 to 25 parts by weight, the anti-migration agent is 0.5 to 5 parts by weight, the nano-sized powder rubber is 4.5 to 50 parts by weight, and the dispersant is 0.5 to 5 parts by weight, relative to 100 parts by weight of the guanidine salt polymer.
37. The composition of claim 25, wherein the zinc salt and/or copper salt is 5-25 parts by weight, the anti-migration agent is 0.5-5 parts by weight, the nano-sized powder rubber is 4.5-50 parts by weight, and the dispersant is 0.5-5 parts by weight, relative to 100 parts by weight of the guanidinium polymer.
38. A polypropylene film made from the composition of any one of claims 1-37.
39. The polypropylene film of claim 38, wherein the polypropylene film is a polypropylene blown film.
40. The polypropylene film of claim 39, wherein the polypropylene blown film is a blown polypropylene matte film.
41. The polypropylene film according to any one of claims 38 to 40, wherein the polypropylene blown film has a thickness of 5 to 100 μm;
and/or the longitudinal tensile strength of the polypropylene blown film is above 63MPa, and the transverse tensile strength is above 60 MPa;
and/or the polypropylene blown film has a longitudinal elongation at break of 670% or more and a transverse elongation at break of 640% or more;
and/or the polypropylene blown film has a longitudinal tensile elastic modulus of 810MPa or more and a transverse tensile elastic modulus of 699MPa or more.
42. The polypropylene film according to claim 41, wherein the polypropylene blown film has a thickness of 10-50 μm.
43. A method of making a polypropylene blown film comprising: extrusion granulation of a composition according to any one of claims 1 to 37 followed by blow moulding to form a film.
44. The method as claimed in claim 43, wherein the extrusion temperature is 150-240 ℃;
and/or the film blowing temperature is 170-230 ℃;
and/or a blow-up ratio of 1.5 to 3.
45. The method as claimed in claim 44, wherein the extrusion temperature is 170-220 ℃;
and/or the film blowing temperature is 185-220 ℃;
and/or a blow-up ratio of 2 to 2.5.
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