CN113549260A - Composition containing polypropylene homopolymer, polypropylene material, preparation method and application thereof - Google Patents
Composition containing polypropylene homopolymer, polypropylene material, preparation method and application thereof Download PDFInfo
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- CN113549260A CN113549260A CN202010333643.3A CN202010333643A CN113549260A CN 113549260 A CN113549260 A CN 113549260A CN 202010333643 A CN202010333643 A CN 202010333643A CN 113549260 A CN113549260 A CN 113549260A
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- 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
- C08L23/12—Polypropene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F110/06—Propene
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
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Abstract
The invention relates to the field of polyolefin materials, and discloses a composition containing a polypropylene homopolymer, a polypropylene homopolymer material, and a preparation method and application thereof. The composition containing the polypropylene homopolymer contains the polypropylene homopolymer and an antioxidant, and the composition optionally also contains an acid acceptor; the polypropylene homopolymer is prepared by catalysis of a metallocene catalyst. The polypropylene homopolymer material provided by the invention is obviously improved in the aspects of glossiness, optical performance, sanitation, corona performance and the like.
Description
Technical Field
The invention relates to the field of polyolefin materials, in particular to a composition containing a polypropylene homopolymer, a method for preparing a polypropylene homopolymer material by using the composition, the polypropylene homopolymer material prepared by the method, and application of the polypropylene homopolymer material in a polypropylene cast film.
Background
Cast polypropylene film (CPP) is a non-stretched, non-oriented cast film produced by melt cast quenching. Compared with the blown film, the production speed is fast, the yield is high, the film transparency, the gloss and the thickness uniformity are excellent, the heat sealing performance, the oil resistance, the boiling resistance, the scratch resistance and the packaging machinery applicability are good, meanwhile, because the film is flat extruded, the subsequent processes such as printing, compounding and the like are very convenient, and the film can be widely applied to the packaging of textiles, flowers, foods and daily necessities, and can also be used as a high-temperature boiling film, a composite film inner layer heat sealing material, a metallized base film and the like.
The PP is a non-polar polymer and does not contain a polar group, so that the surface energy of the film is very low, the wetting tension (also called surface tension) is only 29-30 dynes, the surface energy is low, and the film is not easy to be wetted by ink or adhesive, and therefore, the critical surface tension of the CPP film is required to be greater than or equal to the surface tension of the ink or adhesive so as to ensure that the ink or adhesive is fully wetted on the surface of the CPP film. Therefore, the CPP film must be surface-treated during the production process to achieve a surface tension of at least 38 dynes or more. So far, the most widely used method for treating the surface of plastic film at home and abroad is the corona treatment method.
The corona treatment is that high-frequency high-voltage electric spark treatment is carried out to break chain molecules on the surface of the film, free radicals generated during chain breaking and air corona products are subjected to oxidation and crosslinking reaction to generate polar groups on the surface of the film, and partial polar groups are injected into the film to coarsen the surface, so that the surface tension of the film is increased. After the film is produced, in the stress recovery process, the surface tension of the film is reduced by further crystallization of film molecules; the surface tension of the film is reduced by the migration of the migrating additive in the film to the surface of the film; the surface tension of the film is also reduced by the movement process of polar groups on the surface of the film. I.e. what we often say is the decay of the corona value.
Compared with metallocene homopolymerized polypropylene, common homopolymerized polypropylene produced by the Ziegler-Natta catalyst has higher crystallinity, molecules are in a thermodynamic stable state and have more stable chemical properties, and ink or adhesive molecules are difficult to generate diffusion on the surfaces of the ink or the adhesive molecules, so that the adhesion effect of the ink, the adhesive and the like on the surface of a film is not ideal.
The core layer, i.e. the intermediate layer, also called the support layer, of the CPP film is mainly used for providing the film with certain mechanical properties. The support layer is firstly required to have excellent rigidity, so that the core layer is made of multi-homopolymer, and secondly, the good optical properties (low haze and high gloss) of the multi-layer co-extruded CPP film are mainly provided by the intermediate layer.
When the ordinary homo-polypropylene forming CPP film produced by the Ziegler-Natta catalyst is used for high-end products in the fields of electronic packaging, food packaging, cosmetic packaging and the like, the problems of poor glossiness and optical performance, slightly low sanitation and the like exist, and the problems of difficult corona and quick corona attenuation also exist.
Disclosure of Invention
The object of the present invention is to improve the optical, hygienic and corona properties of the products of the prior art compositions containing polypropylene homopolymers.
In order to achieve the above object, the first aspect of the present invention provides a composition comprising a polypropylene homopolymer, the composition comprising the polypropylene homopolymer and an antioxidant, and optionally further comprising an acid acceptor;
relative to 100 parts by weight of the polypropylene homopolymer, the content of the antioxidant is 0.02-0.4 part by weight, and the content of the acid acceptor is 0-0.3 part by weight;
the polypropylene homopolymer is prepared by catalyzing with a metallocene catalyst, the metallocene catalyst is a dinuclear metallocene compound, and the compound has a structure shown in a formula (1),
wherein, in the formula (1),
two M are the same and are Ti, Zr or Hf;
each X is the same and is fluorine, chlorine or bromine;
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10and R11Each independently is H, substituted or unsubstituted C1-C8Alkyl, substituted or unsubstituted C2-C8Alkenyl, substituted or unsubstituted C7-C20Aralkyl, substituted or unsubstituted C6-C20An aryl group;
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10and R11Wherein the substituents optionally present are each independently selected from C1-C4At least one of alkyl groups of (a);
R12and R13Each independently is H, methyl or ethyl.
A second aspect of the invention provides a process for preparing a polypropylene homopolymer material, the process comprising: the components of the polypropylene homopolymer-containing composition of the first aspect are melt blended at 180 ℃ and 230 ℃ and then extruded, pelletized and dried.
A third aspect of the invention provides a polypropylene homopolymer material obtainable by the process of the second aspect.
A fourth aspect of the invention provides the use of a polypropylene homopolymer material according to the third aspect in cast polypropylene films.
The polypropylene homopolymer material provided by the invention is obviously improved in the aspects of transparency, sanitation, corona performance and the like. The invention utilizes the characteristics of narrow molecular weight distribution, low crystallinity and the like of the polypropylene homopolymer prepared by the metallocene catalyst, adopts the metallocene catalyst to develop the polypropylene homopolymer product for the CPP film, realizes better optical performance, better sanitation and good corona performance of the CPP film, simultaneously has lower melting temperature and is beneficial to reducing the energy consumption of processing.
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.
In the present invention, C1-C8The alkyl group represents a linear, branched or cyclic alkyl group having 1 to 8 total carbon atoms. For each carbon atom, all possible isomeric structures exist. Such as methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, and the like. It is to be understood that the invention is not limited to the above-listed groups.
In the present invention, C2-C8The alkenyl group means an alkenyl group having 2 to 8 total carbon atoms, such as vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl and the like. It is to be understood that the invention is not limited to the above-listed groups.
In the present invention, C2-C4Alkenyl means alkenyl having 2-4 total carbon atoms, e.g. vinylPropenyl, butenyl and the like. It is to be understood that the invention is not limited to the above-listed groups.
In the present invention, C7-C20The aralkyl group means an aralkyl group having 7 to 20 total carbon atoms, which contains an alkyl group and an aryl group, wherein the alkyl moiety is a linking site, such as benzyl, phenethyl, α -methylphenylethyl and the like. It is to be understood that the invention is not limited to the above-listed groups.
In the present invention, C6-C20The aryl group means an aryl group having 6 to 20 carbon atoms in total, such as a phenyl group or the like. It is to be understood that the invention is not limited to the above-listed groups.
In the present invention, C1-C4The alkyl group of (b) represents a linear, branched or cyclic alkyl group having 1 to 4 total carbon atoms. For each carbon atom, all possible isomeric structures exist. Such as methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and the like. It is to be understood that the invention is not limited to the above-listed groups.
As mentioned above, the first aspect of the present invention provides a composition comprising a polypropylene homopolymer, wherein the composition comprises the polypropylene homopolymer and an antioxidant, and optionally further comprises an acid acceptor;
relative to 100 parts by weight of the polypropylene homopolymer, the content of the antioxidant is 0.02-0.4 part by weight, and the content of the acid acceptor is 0-0.3 part by weight;
the polypropylene homopolymer is prepared by catalyzing with a metallocene catalyst, the metallocene catalyst is a dinuclear metallocene compound, and the compound has a structure shown in a formula (1),
wherein, in the formula (1),
two M are the same and are Ti, Zr or Hf;
each X is the same and is fluorine, chlorine or bromine;
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10and R11Each independently is H, substituted or unsubstituted C1-C8Alkyl, substituted or unsubstituted C2-C8Alkenyl, substituted or unsubstituted C7-C20Aralkyl, substituted or unsubstituted C6-C20An aryl group;
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10and R11Wherein the substituents optionally present are each independently selected from C1-C4At least one of alkyl groups of (a);
R12and R13Each independently is H, methyl or ethyl.
Several preferred embodiments are provided below for the metallocene catalysts described in the present invention.
Embodiment mode 1:
in formula (1), two M are the same and are Ti, Zr or Hf;
each X is the same and is fluorine, chlorine or bromine;
R1、R2、R3、R4、R7、R8、R9and R11Each independently is H, substituted or unsubstituted C1-C4Alkyl, substituted or unsubstituted C2-C4Alkenyl, substituted or unsubstituted C7-C20Aralkyl, substituted or unsubstituted C6-C20An aryl group;
R1、R2、R3、R4、R7、R8、R9and R11Wherein the substituents optionally present are each independently selected from C1-C4At least one of alkyl groups of (a);
R12and R13Each independently is H, methyl or ethyl;
R5is phenyl; and is
R6And R10Are all hydrogen.
Embodiment mode 2:
in formula (1), two M are the same and are Ti, Zr or Hf;
each X is the same and is chlorine;
R1and R11Are both methyl;
R2、R3、R4、R6、R7、R8、R9and R10Are all H;
R5is phenyl; and is
R12And R13Each independently is H, methyl or ethyl.
Embodiment mode 3:
in formula (1), two M are the same and are Ti, Zr or Hf;
each X is the same and is chlorine;
R1and R11Are both methyl;
R2、R3、R4、R6、R7、R8、R9and R10Are all H;
R5is phenyl; and is
R12And R13Are all methyl.
In order to achieve the superior effects of low crystallinity and low melting point of the homopolymer, it is preferred that the polypropylene homopolymer has 2, 1-insertion. The 2, 1-insertion can be detected by nuclear magnetism.
Preferably, the polypropylene homopolymer has a melting temperature of less than or equal to 155 ℃, more preferably, the polypropylene homopolymer has a melting temperature of less than or equal to 151 ℃.
Preferably, the polypropylene homopolymer has a melt mass flow rate (230 ℃, 2.16kg) of 4 to 10g/10 min; more preferably, the polypropylene homopolymer has a melt mass flow rate (230 ℃, 2.16kg) of 6 to 9g/10 min.
In a preferred embodiment, the antioxidant is present in an amount of 0.05 to 0.2 parts by weight and the acid scavenger is present in an amount of 0.01 to 0.1 parts by weight, relative to 100 parts by weight of the polypropylene homopolymer.
Preferably, the antioxidant is a phenolic antioxidant and a phosphite antioxidant.
Preferably, the content weight ratio of the phenolic antioxidant to the phosphite antioxidant is 1 (1-2).
Preferably, the phenolic antioxidant is selected from at least one of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (referred to as antioxidant 1010), 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid (referred to as antioxidant 3114) and n-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (referred to as antioxidant 1076), more preferably pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (referred to as antioxidant 1010).
Preferably, the phosphite antioxidant is at least one selected from the group consisting of tris [ 2.4-di-tert-butylphenyl ] phosphite (referred to as antioxidant 168), bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite (referred to as antioxidant 626) and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (referred to as antioxidant PEP-36), more preferably tris [ 2.4-di-tert-butylphenyl ] phosphite (referred to as antioxidant 168).
Preferably, the acid scavenger is hydrated talc.
As previously mentioned, a second aspect of the present invention provides a process for the preparation of a polypropylene homopolymer material, which process comprises: the components of the polypropylene homopolymer-containing composition of the first aspect are melt blended at 180 ℃ and 230 ℃ and then extruded, pelletized and dried.
In the second aspect of the present invention, the characteristics of the polypropylene homopolymer-containing composition described in the first aspect, such as the types and contents of the components, are not repeated, and are completely the same as the corresponding ones described in the first aspect, and those skilled in the art should not be construed as limiting the present invention.
Preferably, the method of the present invention comprises: mixing a polypropylene homopolymer, a phenol antioxidant, a phosphite antioxidant and an acid absorption agent, feeding the obtained mixture into a double-screw extruder, adjusting the rotating speed of a screw, and respectively controlling the temperature of each section; and melting, shearing, dispersing, compressing, exhausting and plasticizing the mixture in a screw and a cylinder of the extruder, extruding the mixture through a die head, cooling by water, drying (air drying) and granulating to obtain the polypropylene homopolymer material.
Illustratively, polypropylene homopolymer, phenolic antioxidant and phosphite antioxidant good acid absorbent are mixed for 0.5-5min at 20-30 ℃ and at 200-400rpm, the obtained mixture is fed into a double-screw extruder, the rotating speed of a screw is adjusted to 100-200rpm, and the temperature of each section is respectively controlled between 180 ℃ and 230 ℃; and melting, shearing, dispersing, compressing, exhausting and plasticizing the mixture in a screw and a cylinder of the extruder, extruding the mixture through a die head, cooling by water, drying (air drying) and granulating to obtain the polypropylene homopolymer material.
In a preferred embodiment, the process further comprises preparing said polypropylene homopolymer by an operation comprising:
(1) introducing propylene and hydrogen into a first liquid phase polymerization reaction kettle to carry out a first contact reaction in the presence of the metallocene catalyst to obtain a first material;
(2) introducing hydrogen and the first material into a second liquid-phase polymerization reaction kettle to carry out second contact reaction to obtain a second material;
(3) introducing hydrogen and the second material into a third gas-phase polymerization reaction kettle to carry out a third contact reaction to obtain a third material;
(4) introducing hydrogen and the third material into a fourth gas-phase polymerization reaction kettle to perform a fourth contact reaction to obtain a fourth material;
(5) and introducing the fourth material into a gas-solid separation unit, a deactivation unit and a drying unit in sequence for treatment to obtain the polypropylene homopolymer.
Preferably, in the present invention, the polypropylene homopolymer is produced in a system comprising two liquid-phase polymerizers and two gas-phase polymerizers connected in series in this order.
Preferably, in step (1), the conditions of the first contact reaction include: the polymerization temperature is 50 ℃ to 80 ℃, the polymerization pressure is 1.5 MPa to 4MPa, and the polymerization time is 0.5h to 2 h.
Preferably, in step (1), the hydrogen is used in an amount of 0.0001 to 0.01 parts by weight, relative to 100 parts by weight of the propylene.
Preferably, in step (1), the first contacting reaction is also carried out in the presence of an alkylaluminum cocatalyst, preferably at least one selected from the group consisting of triisobutylaluminum, triethylaluminum, trimethylaluminum, tri-n-hexylaluminum.
Preferably, in step (2), the conditions of the second contact reaction include: the polymerization temperature is 50 ℃ to 80 ℃, the polymerization pressure is 1.5 MPa to 4MPa, and the polymerization time is 0.5h to 2 h.
Preferably, in the step (2), the hydrogen is used in an amount of 0 to 0.01 parts by weight relative to 100 parts by weight of the propylene in the step (1).
Preferably, in step (3), the conditions of the third contact reaction include: the polymerization temperature is 50 ℃ to 90 ℃, the polymerization pressure is 0.5 MPa to 2MPa, and the polymerization time is 0.5h to 2 h.
Preferably, in the step (3), the hydrogen is used in an amount of 0 to 0.01 parts by weight relative to 100 parts by weight of the propylene in the step (1).
Preferably, the method further comprises: before the step (3), the second material is introduced into the middle of the washing tower to reversely contact with the circulating propylene entering from the lower part of the washing tower, the material containing the catalyst and the polypropylene is led out from the top of the washing tower and then circulates back to the first liquid phase kettle, and the washed second material is led out from the bottom of the washing tower and then enters the third gas phase polymerization reaction kettle to carry out the third contact reaction. Illustratively, before the step (3), the second material is introduced into the middle part of a washing tower to reversely contact with the circulating propylene entering from the lower part of the washing tower, the material containing the insufficiently reacted lighter short-circuit catalyst and polypropylene is led out from the top of the washing tower, is pressurized by a propylene circulating pump and then circulates back to the first liquid phase kettle, and the heavy catalyst and the washed second material are led out from the bottom of the washing tower and then enter the third gas phase polymerization kettle to perform the third contact reaction.
Preferably, in step (4), the conditions of the fourth contact reaction include: the polymerization temperature is 50 ℃ to 90 ℃, the polymerization pressure is 0.5 MPa to 2MPa, and the polymerization time is 0.5h to 2 h.
Preferably, in the step (4), the hydrogen is used in an amount of 0 to 0.01 parts by weight relative to 100 parts by weight of the propylene in the step (1).
Preferably, the hydrogen is used in the step (1), the step (2), the step (3) and the step (4) in an amount of 0.0001 to 0.01 parts by weight, independently of each other.
Exemplarily, in the step (5), the fourth material is firstly introduced into a gas-solid separation unit for gas-solid separation, and the solid material after gas-solid separation is introduced into a deactivation unit; then the mixture enters a drying unit to inactivate an active catalyst in the material and take away volatile components; finally, the deactivated and dried material is introduced into a granulation unit to obtain the metallocene homopolymer.
Preferably, in step (5), the treatment carried out in the deactivation unit is carried out in the presence of nitrogen containing from 1 to 5% by volume of water vapour, more preferably from 1 to 3% by volume of water vapour.
Preferably, in step (5), the conditions in the drying unit include: the drying temperature is 90-130 deg.C, and the drying time is 0.5-3 h. More preferably, the conditions in the drying unit include: the drying temperature is 100-120 ℃, and the drying time is 0.5-2 h.
As mentioned previously, a third aspect of the present invention provides a polypropylene homopolymer material obtainable by the process of the second aspect.
As mentioned before, the fourth aspect of the present invention provides the use of the polypropylene homopolymer material of the third aspect in cast polypropylene films.
The polypropylene homopolymer material provided by the invention is obviously improved in the aspects of optical performance, sanitary performance, corona performance and the like.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available ones unless otherwise specified.
Unless otherwise specified, room temperature hereinafter means 25. + -. 3 ℃.
Phenol antioxidant: pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (referred to as antioxidant 1010) (hereinafter, in examples, referred to as antioxidant-1) was purchased from BASF corporation.
Phenol antioxidant: 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid (referred to as antioxidant 3114) (hereinafter, in the examples, referred to as antioxidant-2) was purchased from BASF corporation.
Phosphite ester antioxidant: tris [2, 4-di-tert-butylphenyl ] phosphite (referred to as antioxidant 168) (hereinafter, referred to as antioxidant-3 in the examples) was purchased from BASF corporation.
Phosphite ester antioxidant: bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite (referred to as antioxidant 626) (hereinafter, referred to as antioxidant-4) was purchased from BASF corporation.
Acid-absorbing agent: hydrotalcite (hereinafter, referred to as acid acceptor 1 in the examples) was purchased from Kyowa corporation under the trade designation DHT-6.
In the present invention, the transparency is characterized by the haze, which is the percentage of the total transmitted light intensity of the transmitted light intensity which deviates from the incident light by more than 2.5 degrees, and the greater the haze means that the film gloss and transparency, especially the imaging degree, are reduced, indicating that the transparency of the material is worse.
In the present invention, the product appearance is also characterized by specular gloss. Gloss is the surface characteristic of an object, and is dependent on the specular reflectance of light by the surface, and specular reflection is a reflection phenomenon in which the reflection angle is equal to the incident angle. Gloss is a physical quantity that evaluates the ability of a material surface to reflect light under a set of geometrically specified conditions. It therefore states a reflective property with directional selectivity.
In the invention, the sanitation is characterized by a normal hexane extract percentage value measured by a GB 9693 method, the normal hexane extract is used for representing the performance of small molecule precipitation, and the higher the percentage value is, the poorer the sanitation of the material is, and the better the sanitation is.
In the present invention, the corona performance represents the printing performance, characterized by the wetting tension. The higher the wetting tension, the better the corona treatment effect of the material and the easier the printing.
In the following examples and comparative examples:
melt Flow Rate (MFR) measured according to the method of GB/T3682.1-2018;
the melting temperature is measured according to the method of GB/T19466.3;
specular gloss is measured according to the method of GB/T8807;
the haze is measured according to the method of GB/T2410, and the sample is a polypropylene film with the thickness of 30 mu m obtained by casting;
the hygiene characterization data was measured according to the method of GB 9693.
The wetting tension is measured according to the method of GB/T14216. The wetting tension was measured after subjecting the cast polypropylene film to corona treatment at a current intensity of 8A at a speed of 8m/s on a corona treatment device of the SDCD16-3-20 type.
The amounts of the components used in the following examples are all parts by weight, and each part by weight represents 10g, unless otherwise specified.
Preparation example 1
(1) Preparation of metallocene catalysts
To 100mL of a toluene solution containing 2.96g of the compound A represented by the formula (A) and 1.48g of the compound B represented by the formula (B) was added dropwise 4.41mL of a butyllithium/hexane solution (2.86mol/L) at 0 ℃ and the mixture was allowed to slowly warm to room temperature to react for 12 hours, thereby obtaining a mother liquor containing a large amount of orange-red precipitates. The precipitation mother liquor was cooled to-25 ℃. 2.39g of zirconium tetrachloride was slowly added, the reaction was stirred, held at-25 ℃ for 0.5h, and slowly raised to 25 ℃ for 24 h. The precipitate was filtered, washed with 50mL of toluene and the filtrates combined. Distilling under reduced pressure to remove part of the solvent, adding hexane dropwise until precipitate is generated, adding appropriate amount of toluene to dissolve the precipitate, crystallizing the obtained solution at-20 deg.C, filtering to obtain orange red crystal, and drying to obtain the metallocene catalyst represented by formula (2) with yield of 71% based on the compound A represented by formula (A).
(2) Preparation of Polypropylene homopolymer
In the preparation of this polypropylene homopolymer, the total amount of ethylene parts by weight was found to be 1.5 parts by weight relative to 100 parts by weight of propylene.
50g of a metallocene catalyst represented by the formula (2), 10g of triisobutylaluminum, 100 parts by weight of liquid propylene and 0.004 part by weight of hydrogen were charged into a first liquid phase polymerization reactor to perform a first contact reaction, and after the propylene was vaporized, the heat of reaction in the reactor was removed. The temperature of the first polymerization reaction kettle is 68 ℃, the pressure is 2.8MPa, and the residence time of the materials in the reaction kettle is 1.0 hour, so as to obtain a first material.
And introducing the first material into a second liquid-phase polymerization reaction kettle, and introducing 0.001 part by weight of hydrogen to perform a second contact reaction, wherein the temperature of the second polymerization reaction kettle is 68 ℃, the pressure is 2.8MPa, and the polymerization time is 1.0 hour to obtain a second material.
And introducing the second material into a third gas-phase polymerization reaction kettle, and introducing 0.002 weight part of hydrogen to perform a third contact reaction, wherein the temperature of the third polymerization reaction kettle is 75 ℃, the pressure is 1.8MPa, and the polymerization time is 1.0 hour to obtain a third material.
And introducing the third material into a fourth gas-phase polymerization reaction kettle, and introducing 0.001 part by weight of hydrogen to perform a fourth contact reaction, wherein the temperature of the fourth polymerization reaction kettle is 78 ℃, the pressure is 1.2MPa, and the polymerization time is 1.0 hour to obtain a fourth material.
The fourth material was deactivated by means of nitrogen containing 2% by volume of water vapor and subsequently introduced into a drying unit and dried at 110 ℃ for 1 hour to give a metallocene homopolymer H1.
Preparation examples 2 to 6
A polymerization process similar to that of preparation example 1 was employed except that the addition ratio of hydrogen was constant in four polymerization reactors with respect to 100 parts by weight of propylene, and accordingly a metallocene homopolymer was obtained, and the total amount of hydrogen (parts by weight) was as shown in Table 1.
TABLE 1
| Preparation example 1 | Preparation example 2 | Preparation example 3 | Preparation example 4 | Preparation example 5 | Preparation example 6 | |
| Polypropylene homopolymer nomenclature | H1 | H2 | H3 | H4 | H5 | H6 |
| Total amount of hydrogen (parts by weight) | 0.008 | 0.009 | 0.010 | 0.011 | 0.006 | 0.013 |
Comparative preparation example 1
(1) Preparation of comparative metallocene catalysts
4.41mL of a butyllithium/hexane solution (2.86mol/L) was added dropwise to 100mL of a toluene solution containing 2.96g of the compound A represented by the formula (A) at 0 ℃ and the mixture was slowly warmed to room temperature to react for 12 hours, thereby obtaining a mother solution containing a large amount of orange-red precipitates. The precipitation mother liquor was cooled to-25 ℃. 2.39g of zirconium tetrachloride was slowly added, the reaction was stirred, held at-25 ℃ for 0.5h, and slowly raised to 25 ℃ for 24 h. The precipitate was filtered, washed with 50mL of toluene and the filtrates combined. Distilling under reduced pressure to remove part of the solvent, adding hexane dropwise until precipitate is generated, adding an appropriate amount of toluene to dissolve the precipitate, crystallizing the obtained solution at-20 deg.C, filtering to obtain orange red crystals, and drying to obtain the metallocene catalyst represented by the formula (3) with a yield of 70% based on the compound A represented by the formula (A).
(2) Preparation of comparative homopolymer
In a similar manner to step (2) of production example 1 except that the metallocene catalyst of step (1) of production example 1 was replaced with the same molar amount of the comparative metallocene catalyst represented by formula (3), comparative homopolymer DH1 was obtained.
Example 1
Mixing polypropylene homopolymer, phenolic antioxidant, phosphite antioxidant and acid acceptor at content ratio shown in Table 2 at 25 deg.C and 300rpm for 1min, feeding the obtained mixture into a twin-screw extruder, adjusting screw rotation speed to 150rpm, and controlling temperature of each section at 180 deg.C, 190 deg.C, 200 deg.C and 190 deg.C respectively; and melting, shearing, dispersing, compressing, exhausting and plasticizing the mixture in a screw and a cylinder of the extruder, extruding the mixture through a die head, cooling by water, drying (air drying) and granulating to obtain the polypropylene homopolymer material S1.
The remaining examples and comparative examples were carried out by the same procedure as in example 1, except that the formulation of the composition for preparing the polypropylene homopolymer material was different, unless otherwise specified, and the specific conditions are shown in Table 2.
TABLE 2
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| Polypropylene homopolymer | ||||||
| Species of | H1 | H2 | H3 | H4 | H1 | H1 |
| Dosage of | 100 | 100 | 100 | 100 | 100 | 100 |
| Phenolic antioxidants | ||||||
| Species of | Antioxidant-1 | Antioxidant-1 | Antioxidant-1 | Antioxidant-1 | Antioxidant-1 | Antioxidant-1 |
| Dosage of | 0.05 | 0.05 | 0.03 | 0.02 | 0.1 | 0.1 |
| Phosphite antioxidant | ||||||
| Species of | Antioxidant-3 | Antioxidant-3 | Antioxidant-3 | Antioxidant-3 | Antioxidant-3 | Antioxidant-3 |
| Dosage of | 0.05 | 0.1 | 0.03 | 0.04 | 0.1 | 0.1 |
| Acid-absorbing agent | ||||||
| Species of | Acid scavenger 1 | Acid scavenger 1 | Acid scavenger 1 | Acid scavenger 1 | Acid scavenger 1 | Acid scavenger 1 |
| Dosage of | 0.03 | 0.05 | 0.01 | 0.1 | 0.1 | 0.01 |
| Polypropylene homopolymer Material nomenclature | S1 | S2 | S3 | S4 | S5 | S6 |
Table 2 (continuation 1)
| Example 1 | Example 7 | Example 8 | Example 9 | Example 10 | |
| Polypropylene homopolymer | |||||
| Species of | H1 | H1 | H1 | H1 | H1 |
| Dosage of | 100 | 100 | 100 | 100 | 100 |
| Phenolic antioxidants | |||||
| Species of | Antioxidant-1 | Antioxidant-1 | Antioxidant-1 | Antioxidant-1 | Antioxidant-1 |
| Dosage of | 0.05 | 0.01 | 0.2 | 0.05 | 0.05 |
| Phosphite antioxidant | |||||
| Species of | Antioxidant-3 | Antioxidant-3 | Antioxidant-3 | Antioxidant-3 | Antioxidant-3 |
| Dosage of | 0.05 | 0.01 | 0.2 | 0.05 | 0.05 |
| Acid-absorbing agent | |||||
| Species of | Acid scavenger 1 | Acid scavenger 1 | Acid scavenger 1 | Acid scavenger 1 | Acid scavenger 1 |
| Dosage of | 0.03 | 0.03 | 0.03 | 0.3 | 0 |
| Polypropylene homopolymer Material nomenclature | S1 | S7 | S8 | S9 | S10 |
Table 2 (continuation 2)
| Example 1 | Example 11 | Example 12 | Example 13 | Example 14 | Comparative example 1 | |
| Polypropylene homopolymer | ||||||
| Species of | H1 | H5 | H6 | H1 | H1 | DH1 |
| Dosage of | 100 | 100 | 100 | 100 | 100 | 100 |
| Phenolic antioxidants | ||||||
| Species of | Antioxidant-1 | Antioxidant-1 | Antioxidant-1 | Antioxidant-1 | Antioxidant-2 | Antioxidant-1 |
| Dosage of | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
| Phosphite antioxidant | ||||||
| Species of | Antioxidant-3 | Antioxidant-3 | Antioxidant-3 | Antioxidant-4 | Antioxidant-3 | Antioxidant-3 |
| Dosage of | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
| Acid-absorbing agent | ||||||
| Species of | Acid scavenger 1 | Acid scavenger 1 | Acid scavenger 1 | Acid scavenger 1 | Acid scavenger 1 | Acid scavenger 1 |
| Dosage of | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 |
| Polypropylene homopolymer Material nomenclature | S1 | S11 | S12 | S13 | S14 | DS1 |
Comparative example 2
A commercially available polypropylene homopolymer material is adopted, is homopolymerized polypropylene of Beijing Yanshan division of China petrochemical, has the trade name of F1904Y, is a polypropylene homopolymer material obtained by a polymer prepared by a Ziegler-Natta catalyst, and is named as DS 2.
The melt flow rate, melting temperature, 2, 1-insertion content, specular gloss, hygiene, haze, wetting tension and wetting tension after standing for 30 days were measured for the polypropylene homopolymer materials of the above examples (S1-S14) and the polypropylene homopolymer materials of the comparative examples (DS1-DS2), and specific material properties are shown in table 3.
TABLE 3
As can be seen from table 3, compared with the prior art, the material obtained by the present invention has lower haze, better mirror surface gloss, better hygienic property and reduced corona decay, is helpful for corona treatment of the film, has low melting temperature, and can reduce the processing temperature during use, thereby reducing energy consumption.
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.
Claims (12)
1. A composition comprising a polypropylene homopolymer, wherein the composition comprises the polypropylene homopolymer and an antioxidant, and the composition optionally further comprises an acid acceptor;
relative to 100 parts by weight of the homopolymer, the content of the antioxidant is 0.02-0.4 part by weight, and the content of the acid acceptor is 0-0.3 part by weight;
the polypropylene homopolymer is prepared by catalyzing with a metallocene catalyst, the metallocene catalyst is a dinuclear metallocene compound, and the compound has a structure shown in a formula (1),
wherein, in the formula (1),
two M are the same and are Ti, Zr or Hf;
each X is the same and is fluorine, chlorine or bromine;
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10and R11Each independently is H, substituted or unsubstituted C1-C8Alkyl, substituted or unsubstituted C2-C8Alkenyl, substituted or unsubstituted C7-C20Aralkyl, substituted or unsubstituted C6-C20An aryl group;
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10and R11Wherein the substituents optionally present are each independently selected from C1-C4At least one of alkyl groups of (a);
R12and R13Each independently is H, methyl or ethyl.
2. The composition of claim 1, wherein, in formula (1), both M are the same and are Ti, Zr, or Hf;
each X is the same and is fluorine, chlorine or bromine;
R1、R2、R3、R4、R7、R8、R9and R11Each independently is H, substituted or unsubstituted C1-C4Alkyl, substituted or unsubstituted C2-C4Alkenyl, substituted or unsubstituted C7-C20Aralkyl, substituted or unsubstituted C6-C20An aryl group;
R1、R2、R3、R4、R7、R8、R9and R11Wherein the substituents optionally present are each independently selected from C1-C4At least one of alkyl groups of (a);
R12and R13Each independently is H, methyl or ethyl;
R5is phenyl; and is
R6And R10Are all hydrogen.
3. The composition of claim 1, wherein, in formula (1), both M are the same and are Ti, Zr, or Hf;
each X is the same and is chlorine;
R1and R11Are both methyl;
R2、R3、R4、R6、R7、R8、R9and R10Are all H;
R5is phenyl; and is
R12And R13Each independently is H, methyl or ethyl.
4. The composition of claim 1, wherein, in formula (1), both M are the same and are Ti, Zr, or Hf;
each X is the same and is chlorine;
R1and R11Are both methyl;
R2、R3、R4、R6、R7、R8、R9and R10Are all H;
R5is phenyl; and is
R12And R13Are all methyl.
5. The composition according to any one of claims 1 to 4, wherein the antioxidant is contained in an amount of 0.05 to 0.2 parts by weight and the acid acceptor is contained in an amount of 0.01 to 0.1 parts by weight, relative to 100 parts by weight of the homopolymer.
6. The composition of any one of claims 1-5, wherein the antioxidant is a phenolic antioxidant and a phosphite antioxidant;
preferably, the content weight ratio of the phenolic antioxidant to the phosphite antioxidant is 1: (1-2);
preferably, the phenolic antioxidant is selected from at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid and n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate;
more preferably, the phenolic antioxidant is selected from pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ];
preferably, the phosphite antioxidant is at least one selected from the group consisting of tris [2, 4-di-tert-butylphenyl ] phosphite, bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite;
more preferably, the phosphite antioxidant is selected from tris [2, 4-di-tert-butylphenyl ] phosphite;
preferably, the acid scavenger is hydrated talc.
7. A method of preparing a polypropylene material, the method comprising:
the polypropylene homopolymer-containing composition as claimed in any one of claims 1 to 6, wherein the components are melt-blended at 180 ℃ and 230 ℃ and then extruded, pelletized and dried.
8. The method of claim 7, further comprising preparing the polypropylene homopolymer by an operation comprising:
(1) introducing propylene and hydrogen into a first liquid phase polymerization reaction kettle to carry out a first contact reaction in the presence of the metallocene catalyst to obtain a first material;
(2) introducing hydrogen and the first material into a second liquid-phase polymerization reaction kettle to carry out second contact reaction to obtain a second material;
(3) introducing hydrogen and the second material into a third gas-phase polymerization reaction kettle to carry out a third contact reaction to obtain a third material;
(4) introducing hydrogen and the third material into a fourth gas-phase polymerization reaction kettle to perform a fourth contact reaction to obtain a fourth material;
(5) and introducing the fourth material into a gas-solid separation unit, a deactivation unit and a drying unit in sequence for treatment to obtain the polypropylene homopolymer.
9. The method of claim 8, wherein, in step (1), the conditions of the first contact reaction comprise: the polymerization temperature is 50 ℃ to 80 ℃, the polymerization pressure is 1.5 MPa to 4MPa, and the polymerization time is 0.5h to 2 h;
preferably, in the step (1), the hydrogen is used in an amount of 0.0001 to 0.01 parts by weight relative to 100 parts by weight of the propylene;
preferably, in step (2), the conditions of the second contact reaction include: the polymerization temperature is 50 ℃ to 80 ℃, the polymerization pressure is 1.5 MPa to 4MPa, and the polymerization time is 0.5h to 2 h;
preferably, in the step (2), the hydrogen is used in an amount of 0 to 0.01 parts by weight relative to 100 parts by weight of the propylene in the step (1);
preferably, in step (3), the conditions of the third contact reaction include: the polymerization temperature is 50 ℃ to 90 ℃, the polymerization pressure is 0.5 MPa to 2MPa, and the polymerization time is 0.5h to 2 h;
preferably, in the step (3), the hydrogen is used in an amount of 0 to 0.01 parts by weight relative to 100 parts by weight of the propylene in the step (1);
preferably, in step (4), the conditions of the fourth contact reaction include: the polymerization temperature is 50 ℃ to 90 ℃, the polymerization pressure is 0.5 MPa to 2MPa, and the polymerization time is 0.5h to 2 h;
preferably, in the step (4), the hydrogen is used in an amount of 0 to 0.01 parts by weight relative to 100 parts by weight of the propylene in the step (1);
preferably, in step (5), the treatment carried out in the deactivation unit is carried out in the presence of nitrogen containing from 1 to 5% by volume of water vapour;
preferably, in step (5), the conditions in the drying unit include: the drying temperature is 90-130 deg.C, and the drying time is 0.5-3 h.
10. The method of claim 8 or 9, wherein the method further comprises:
before the step (3), the second material is introduced into the middle of the washing tower to reversely contact with the circulating propylene entering from the lower part of the washing tower, the material containing the catalyst and the polypropylene is led out from the top of the washing tower and then circulates back to the first liquid phase kettle, and the washed second material is led out from the bottom of the washing tower and then enters the third gas phase polymerization reaction kettle to carry out the third contact reaction.
11. Polypropylene homopolymer material obtainable by the process according to any one of claims 7 to 10.
12. Use of the polypropylene homopolymer material of claim 11 in cast polypropylene films.
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