CN107805340B - Polyolefin composition and polyolefin material - Google Patents
Polyolefin composition and polyolefin material Download PDFInfo
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- CN107805340B CN107805340B CN201610815316.5A CN201610815316A CN107805340B CN 107805340 B CN107805340 B CN 107805340B CN 201610815316 A CN201610815316 A CN 201610815316A CN 107805340 B CN107805340 B CN 107805340B
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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
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- 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
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Abstract
The invention belongs to the field of polyolefin, and particularly relates to a polyolefin composition and a polyolefin material. The polyolefin composition comprises a polyolefin component and a nucleating agent; the polyolefin component comprises, component (a): 65 to 80% by weight of a propylene homopolymer or a propylene copolymer; and component (b): 20-35 wt% of an ethylene/1-butene copolymer; the propylene copolymer contains up to 5% by weight of ethylene and/or 1-butene; the ethylene/1-butene copolymer has a 1-butene content of 20 to 30% by weight and a xylene solubles content at room temperature of 50 to 70% by weight; the nucleating agent is HPN-20E. The flexural modulus of the polyolefin material is more than 1050MPa, the transverse shrinkage and the longitudinal shrinkage are both less than 0.8 percent, and the ratio of the two is less than 1.1.
Description
Technical Field
The invention belongs to the field of polyolefin materials, and particularly relates to a polyolefin composition and a polyolefin material.
Background
Polypropylene materials have been widely used in the fields of automobiles, electronic and electrical appliances, medical materials, building materials, food packaging and the like because of their small relative density, good mechanical properties and processability, high heat resistance and chemical corrosion resistance. However, since the crystallized polypropylene has an increased specific gravity and a reduced volume as a crystalline polymer, the homopolypropylene tends to exhibit a large molding shrinkage, generally in the range of 1.7 to 2.2%. While a higher mold shrinkage means that the dimensional stability of the article is relatively poor, thus making the polypropylene somewhat limited in processing applications. For example, when polypropylene is used for producing interior and exterior automotive trim products, if the problem of large polypropylene molding shrinkage is not solved, the product size is reduced and deformed, so that the appearance and the sealing property of the product are affected, and even potential safety hazards can be caused.
In order to solve the above problems, a common solution is to add a certain amount of glass fiber or inorganic filler to the homo-polypropylene material, and then mechanically blend the materials. The method can obviously reduce the molding shrinkage of the polypropylene and also can greatly enhance the strength of the polypropylene. However, the anisotropy of the molding shrinkage of the glass fiber-modified polypropylene tends to be relatively large. Moreover, the polypropylene modified by glass fiber has the problems that the material is no longer transparent, becomes brittle, and has poor fluidity.
In addition, it is also possible to add a certain amount of rubber or other elastomer component to the homopolypropylene material, in which case the reduction in the molding shrinkage of the polypropylene is mainly determined by the type, content and dispersion state of the added rubber or elastomer in the polypropylene matrix.
CN1832999A discloses a polyolefin composition comprising (percent by weight): (A) 60-85% of a broad molecular weight distribution propylene polymer (component A) having a polydispersity index of 5-15 and a Melt Flow Rate (MFR) of 20-78g/10min (according to ASTM-D1238, condition L); and (B) 15-40% of a partially xylene-soluble ethylene-propylene copolymer rubber (component B) containing at least 65% by weight of ethylene. The invention discloses that the polyolefin composition has a higher flexural modulus and furthermore exhibits lower transverse and machine direction shrinkage. However, in the field requiring high dimensional stability, the shrinkage ratio is not low enough, and the transverse shrinkage ratio/longitudinal shrinkage ratio in the examples is larger than 1.17, which shows large anisotropy of shrinkage ratio, which is not favorable for molding angular articles (such as plastic lunch boxes).
CN1132865C, CN101541879B and CN101959665A disclose a series of polyolefin compositions characterized in that as continuous phase or matrix is a crystalline polypropylene comprising homopolypropylene or propylene with up to 15 wt% ethylene; as the rubber phase, an elastomeric copolymer of ethylene and an α -olefin (mainly, an elastomeric copolymer of ethylene and butene-1) is used. The polypropylene compositions disclosed in the above patent documents tend to have a low molding shrinkage, but both of the transverse shrinkage and the longitudinal shrinkage are more than 1.15.
In addition, in order to further improve the rigidity and/or impact property of the material, a certain content of nucleating agent is often added. For example, CN101541879B mentions the addition of 0.09 wt% benzoic acid nucleating agent. The impact strength and stiffness of the polyolefin composition after the addition of the nucleating agent are significantly improved, but the properties are deteriorated in terms of molding shrinkage: firstly, the transverse shrinkage rate is obviously increased; secondly, the transverse shrinkage/longitudinal shrinkage even reaches 1.45. In fact, in the field of plastic processing, the addition of nucleating agents, although improving the mechanical properties of polypropylene, often leads to poor processability of polypropylene, and in particular to a general increase in molding shrinkage anisotropy, which limits the shaping and application of the material.
Disclosure of Invention
In view of the above problems in the prior art, the inventors of the present invention have unexpectedly found that when a HPN-20E nucleating agent is added to a polymer composition having a propylene homopolymer or a crystalline propylene copolymer (containing up to 5 wt% of ethylene and/or 1-butene) as a continuous phase or a matrix and an elastic copolymer of ethylene and a certain amount of 1-butene as a dispersed phase, not only can the rigidity of the polymer material be increased, but also the molding shrinkage rate and anisotropy can be reduced. In view of this, the present invention provides a polyolefin composition and a polyolefin material.
According to a first aspect of the present invention, there is provided a polyolefin composition comprising a polyolefin component and a nucleating agent; the polyolefin component comprises a polyolefin comprising a polyolefin of,
component (a): 65 to 80% by weight of a propylene homopolymer or a propylene copolymer; and
a component (b): 20-35 wt% of an ethylene/1-butene copolymer;
wherein the propylene copolymer contains at most 5% by weight of ethylene and/or 1-butene, and component (a) has an MFR of 20 to 50g/10min as measured at 230 ℃ under 2.16 kg;
the ethylene/1-butene copolymer has a 1-butene content of 20-30 wt%, is partially soluble in xylene at room temperature, and has a xylene solubles content of 50-70 wt%;
the nucleating agent is HPN-20E;
preferably, the nucleating agent is present in an amount of 0.05 to 5 wt%, based on the total weight of the polyolefin composition.
According to a second aspect of the present invention, there is provided a polyolefin material obtained by melt blending and shaping said polyolefin composition.
Compared with polypropylene compositions without adding or adding other nucleating agents beneficial to forming, the polyolefin material prepared by the polyolefin composition has higher rigidity and lower molding shrinkage, and the anisotropy of the shrinkage is obviously reduced; specifically, the polyolefin material has a flexural modulus of more than 1050MPa, a transverse shrinkage and a longitudinal shrinkage of less than 0.8%, and the ratio of the two is 1.1 or less, preferably not more than 1.06.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
According to a first aspect of the present invention, there is provided a polyolefin composition comprising a polyolefin component and a nucleating agent; the polyolefin component comprises a polyolefin comprising a polyolefin of,
component (a): 65 to 80% by weight of a propylene homopolymer or a propylene copolymer; and
a component (b): 20-35 wt% of an ethylene/1-butene copolymer;
wherein the propylene copolymer contains at most 5% by weight of ethylene and/or 1-butene, and component (a) has an MFR of 20 to 50g/10min as measured at 230 ℃ under 2.16 kg;
the ethylene/1-butene copolymer has a 1-butene content of 20-30 wt%, is partially soluble in xylene at room temperature, and has a xylene solubles content of 50-70 wt%;
the nucleating agent is HPN-20E.
In the present invention, HPN-20E is available from Millad, and the nucleating agent is also called
HPN-20E or Hyperform HPN-20E.
In the present invention, the nucleating agent is contained in an amount of 0.05 to 5% by weight, based on the total weight of the polyolefin composition.
Preferably, the content of the nucleating agent is 0.1-2 wt% based on the total weight of the polyolefin composition, so that the comprehensive mechanical property of the polyolefin material can be ensured, and the raw material cost can be reduced.
According to the invention, the propylene homopolymer or propylene copolymer of component (a) is a crystalline polymer as the continuous phase or matrix in the polyolefin composition. Preferably, component (a) has an MFR of 20 to 30g/10min, measured at 230 ℃ under 2.16 kg.
When the component (a) is a propylene copolymer, it is preferred that the comonomer (i.e., ethylene and/or 1-butene) content therein is 0.8 to 3% by weight.
From the viewpoint of improving the comprehensive mechanical properties of the polyolefin material, it is preferable that the component (a) is a propylene homopolymer.
According to the invention, the ethylene/1-butene copolymer of component (b) is an elastomeric copolymer as the dispersed phase in the polyolefin composition. Preferably, the ethylene/1-butene copolymer has a xylene solubles content at room temperature of from 60 to 70% by weight.
In the present invention, the MFR of the polyolefin component measured at 230 ℃ under 2.16kg is usually 10 to 20g/10min, preferably 15 to 18g/10 min.
In the present invention, the intrinsic viscosity value of the xylene soluble fraction of the polyolefin component at room temperature is generally in the range of from 0.8 to 1.5dL/g, preferably in the range of from 0.9 to 1.4 dL/g.
In the present invention, the total content of xylene-soluble fractions of the polyolefin component at room temperature may be from 15 to 25% by weight, preferably from 17 to 24% by weight.
According to one embodiment, the polyolefin component is prepared by a process comprising the steps of:
1) subjecting propylene, or propylene and ethylene and/or 1-butene to a first polymerization reaction in the presence of an olefin polymerization catalyst, optionally in the presence of a molecular weight regulator, to obtain a reaction stream comprising component (a);
2) subjecting ethylene and 1-butene to a second polymerization reaction in the presence of said reactant stream, optionally in the presence of a molecular weight regulator, to produce said polyolefin component comprising component (b) and component (a).
In the present invention, the molecular weight regulator is preferably hydrogen gas.
The olefin polymerization catalyst may be selected from Ziegler-Natta (Ziegler-Natta) catalysts. The Ziegler-Natta catalyst may comprise: an active solid catalyst component, an organoaluminum compound, and optionally an external electron donor compound.
According to the present invention, the Ziegler-Natta catalyst is preferably a Ziegler-Natta catalyst having high stereoselectivity. By "high stereoselectivity" is meant that a propylene homopolymer having an isotactic index greater than 95% can be produced. Such Ziegler-Natta catalysts may be selected with reference to the prior art, for example, the catalysts described in CN93102795.0, CN00109216.2, CN200410062291.3, CN200610113863.5, cn200610113864.x, CN200410073621.9, CN200410073623.8, cn200510117429.x, CN200610067177.9, CN201010152784.1, CN02100900.7, CN102453150A, CN1213080C, CN 102603933A. Among them, the catalysts described in CN93102795.0, CN102453150A and CN1213080C are particularly advantageous for use as the olefin polymerization catalyst of the present invention.
Generally, the active solid catalyst component generally comprises magnesium, titanium, halogen and optionally an internal electron donor compound.
According to a particular embodiment, the active solid catalyst component is prepared by the following process: in the adduct of magnesium dichloride with alcohol (MgCl)2nROH, where n is preferably from 2.0 to 3.5 and R is C1-C12The alkyl) carrier is loaded with a titanium compound and an internal electron donor compound, and the alcohol can be ethanol, propanol, isopropanol, butanol, isobutanol, isooctanol and the like.
As a cocatalyst in the Ziegler-Natta catalyst, the organoaluminum compound may be an alkylaluminum compound having the general formula AlR1 nX3-nIn the formula, R1Is hydrogen or C1-C20X is halogen, n is a number greater than 1 and n is less than or equal to 3. Specifically, the alkyl aluminum compound may be selected from one or more of Triethylaluminum (TEA), tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichlorochloride. Preferably, the alkyl aluminum compound is at least one of triethyl aluminum, triisobutyl aluminum and tri-n-butyl aluminum.
The molar ratio of the active solid catalyst component to the organoaluminum compound can be 1: 25 to 1: 100 in terms of titanium/aluminum.
The external electron donor compound may be selected from organosilicon compounds.
According to one embodiment, the organosilicon compound has the formula R2 kSi(OR3)4-kWherein k is more than or equal to 0 and less than or equal to 3; r2Selected from alkyl, cycloalkyl, aryl, haloalkyl, amino, halogen or hydrogen, R3Selected from alkyl, cycloalkyl, aryl, haloalkyl or amino. The organosilicon compound is specificallyNon-limiting examples of (a) include: tetramethoxysilane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, methylisopropyldimethoxysilane, diphenoxydimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, (1,1, 1-trifluoro-2-propyl) -methyldimethoxysilane, and the like.
In addition, the organosilicon compound can also be selected from 2-ethylpiperidinyl-2-tert-butyldimethoxysilane and/or (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyl dimethoxysilane.
According to one embodiment, the weight ratio of the organoaluminum compound to the silicone compound is 2-150: 1.
The Ziegler-Natta catalyst can be directly contacted with a polymerization monomer for polymerization reaction, and can also be subjected to pre-complexation (pre-contact) and/or prepolymerization for polymerization reaction. Preferably, the Ziegler-Natta catalyst is pre-complexed and/or prepolymerised prior to use.
The pre-complexing may be carried out in a reactor, for example in a continuous stirred tank; other means of achieving adequate mixing may be chosen, for example, by means of a loop reactor, a section of pipe containing a static mixer, or even a section of pipe where the material is in a turbulent state. Wherein the temperature of the pre-complexing can be controlled between-10 ℃ and 60 ℃, and the preferable temperature is 0-30 ℃; the pre-complexing time can be controlled within 0.1-180min, and the preferable time is 5-30 min.
The Ziegler-Natta catalyst, with or without pre-complexing, may also be prepolymerized to produce a prepolymerized catalyst. The prepolymerised catalyst is a prepolymer produced by prepolymerising a ziegler-natta catalyst, optionally with pre-complexing, with a prepolymerised olefin.
The term "prepolymerized olefin" means ethylene and/or alpha-olefin used in a prepolymerization reaction with a Ziegler-Natta catalyst to obtain a prepolymerized catalyst. Wherein, the prepolymerized olefin is preferably one or more of ethylene, propylene and 1-butene, and is more preferably propylene.
The prepolymerization can be carried out continuously under liquid phase bulk conditions or intermittently in an inert solvent. Wherein, the reactor for prepolymerization can be a continuous stirred tank, a loop reactor, etc. The temperature of the prepolymerization can be controlled between-10 ℃ and 60 ℃, preferably 0-40 ℃. The ratio of the preliminary polymerization may be controlled to 0.5 to 1000 olefin polymer/g active solid catalyst component, and preferably 1.0 to 500 olefin polymer/g active solid catalyst component.
In the present invention, the first polymerization reaction (preparation component (a)) may be a liquid-phase polymerization reaction or a gas-phase polymerization reaction. The second polymerization reaction (preparation of component (b)) is a gas phase polymerization reaction.
According to the invention, the process for preparing the polyolefin component can be carried out either in a continuous polymerization process (continuous polymerization) or in a batch polymerization process.
The continuous polymerization can be effected in at least two reactors connected in series.
Specifically, the first polymerization reaction may be carried out in two or more reactors. Accordingly, the reactor employed for this step may be a liquid phase reactor or a gas phase reactor. The second polymerization reaction can also be carried out in more than two reactors, and the reactor used in the step is a gas phase reactor. The reactor for preparing the component (b) is connected downstream of the reactor for preparing the component (a) in terms of the direction of flow.
The batch polymerization process means that the component (a) and the component (b) are prepared in different reactors in sequence. Accordingly, component (a) may be prepared in a liquid phase reactor or a gas phase reactor, and component (b) is prepared in the gas phase reactor in the presence of a reactant stream comprising component (a).
In the present invention, the liquid phase reactor may be selected from a loop reactor or a stirred tank reactor.
In the present invention, the gas phase reactor may be selected from a horizontal stirred bed reactor, a vertical stirred bed reactor, a fluidized bed reactor, or the like. In addition, the gas phase reactors can be matched and used at will.
According to the invention, the temperature of the liquid phase polymerization reaction may be between 0 and 150 ℃, preferably between 40 and 100 ℃; the polymerization pressure should be above the saturation vapor pressure of the comonomer at the corresponding polymerization temperature.
According to the invention, the temperature of the gas-phase polymerization reaction may be between 0 and 150 ℃, preferably between 40 and 100 ℃; the polymerization pressure may be not less than normal pressure, and is preferably from 0.5 to 2.5 MPa.
The pressure values referred to in the present invention are gauge pressures.
According to the present invention, the process of step 2) may further include: after the second polymerization reaction is finished, the obtained material is subjected to degassing and wet nitrogen deactivation treatment, so that a dried polyolefin component is obtained.
According to the present invention, the polyolefin composition may further contain an antioxidant and/or an acid scavenger (e.g., calcium stearate).
The antioxidant can be selected from hindered phenol antioxidants and/or phosphite antioxidants.
Examples of the hindered phenolic antioxidant may include, but are not limited to: 2, 6-di-tert-butyl-4-methylphenol, n-octadecyl- β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), thiodiethylenebis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, Tris (2-methyl-4-hydroxy-5-tert-butylphenol) butane and 2, 2' -methylenebis (4-methyl-6-tert-butylphenol).
Examples of the phosphite based antioxidant may include, but are not limited to: tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168) and p- (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite.
Preferably, the antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or tris (2, 4-di-tert-butylphenyl) phosphite.
Typically, the antioxidant is used in an amount of 0.05 to 2 weight percent, based on the total weight of the polyolefin composition.
In addition, the polyolefin composition may further contain other additives such as light stabilizer, heat stabilizer, colorant, etc. according to the needs of practical application, and the specific kinds and amounts of the additives are well known in the art and will not be described herein.
According to a second aspect of the present invention, there is provided a polyolefin material obtained by melt blending and shaping said polyolefin composition.
In the present invention, the main improvement of the polyolefin material is the use of a novel polyolefin composition, and the melt blending and shaping means and conditions can be selected conventionally in the art. The melt blending and molding can be carried out in various apparatuses which integrate the melting and molding functions, for example, a twin-screw extruder and a single-screw extruder. The molding may be extrusion molding or injection molding. In the forming process, the polyolefin material can be extruded into shapes of sheets, columns, granules and the like according to actual needs.
The present invention will now be described in detail by way of specific examples, which are intended to be illustrative only and not limiting of the invention.
In the following examples and comparative examples,
melt index (MFR): measured according to ASTM D1238 at 230 ℃ under a load of 2.16 kg.
Comonomer content: measured by Fourier infrared method.
Molar ratio of gases in the gas phase reactor: measured by gas chromatography.
Xylene solubles content at room temperature: measured according to ASTM D5492-98.
Intrinsic viscosity values were measured using a relative viscometer (available from Reineckia technologies, Inc., model VISCOTEK Y501) at 135 deg.C under the following test conditions: the concentration of the polyolefin component was 0.01g/mL and the solvent was decalin.
Tensile strength: the injection molded samples were measured according to ASTM D638.
Flexural modulus: injection molded samples were measured according to ASTM D790.
Cantilever beam impact strength: injection molded samples were measured according to ASTD D256 at 23 ℃ and-20 ℃ respectively.
Transverse and longitudinal shrinkage: injection molded samples were measured according to GB/T17037.4-2003. Specifically, the dimensional difference between a dried sample and a mold cavity in which the sample was molded was measured at a laboratory temperature after the sample was molded for 48 hours, wherein the sample was a 60mm × 60mm × 2mm square piece, and the length l1 and the width b1 of the test sample and the length l of the mold cavity were measured0And width b0(ii) a Mold shrinkage S parallel to the melt flow directionMpMeasured in the middle of the sample width; molding shrinkage S perpendicular to the melt flowMnMeasured in the middle of the length of the sample, the calculation formula is: sMp＝100*(l0-l1)/l0，SMn＝100*(b0-b1)/b0。
Unless otherwise indicated, each of the above tests was performed under ambient conditions at room temperature.
Example 1
This example illustrates the polyolefin compositions and polyolefin materials of the present invention.
The titanium-containing active solid catalyst component (procatalyst) was prepared by the method described in example 1 in CN93102795.0, and its Ti content: 2.2 wt%, di-n-butyl phthalate (DIBP) content: 11.2% by weight.
The polymerization was carried out on a set of polypropylene pilot plants.
The polymerization method and the steps are as follows:
pre-polymerization: the method comprises the steps of carrying out precontacting reaction on a main catalyst, a cocatalyst (triethyl aluminum (TEA)) and an external electron donor compound (methyl cyclohexyl dimethoxy silane (CHMMS)) for 20min at 10 ℃, and then continuously adding the main catalyst, the cocatalyst and the external electron donor compound into a prepolymerization reactor to carry out prepolymerization reaction, wherein the flow rate of TEA is 6g/hr, the flow rate of CHMMS is 1.02g/hr, and the flow rate of the main catalyst is 0.36 g/hr. The prepolymerization was carried out in a bulk environment of propylene liquid phase (propylene flow rate 12kg/hr) at 15 deg.C for a residence time of 4 min.
Continuously feeding the prepolymerized catalyst into a loop reactor, and finishing homopolymerization of propylene in the loop reactor, wherein the polymerization temperature is 70 ℃, the reaction pressure is 4.0MPa, hydrogen is added into the feed of the loop reactor, and the hydrogen concentration detected by an online chromatograph is 0.39 mol%.
After the loop reactor reaction, the obtained material enters a fluidized bed gas phase reactor for copolymerization of ethylene and butylene, the polymerization temperature is 75 ℃, the reaction pressure is 1.0MPa, wherein the ratio of butylene/(ethylene + butylene) is 0.3 (volume ratio), hydrogen is added into the gas phase reactor, and the concentration of hydrogen in the gas phase reactor circulating gas is 25 mol% through online chromatographic detection.
And degassing the polymer material obtained by the reaction, and deactivating by wet nitrogen to obtain the polyolefin component. Specific process conditions and the composition of the polyolefin component are shown in table 1.
Adding 0.1 wt% of IRGAFOS 168, 0.1 wt% of IRGANOX1010, 0.05 wt% of calcium stearate, and 0.15 wt% of Millad nucleating agent HPN-20E to the polyolefin component to obtain a polyolefin composition; the polyolefin composition is granulated by a double-screw extruder to prepare the polyolefin material.
In addition, the polyolefin material was molded into injection-molded samples meeting the above test standards by an injection-molding machine, and the properties thereof were measured, with the results shown in Table 2.
Example 2
This example illustrates the polyolefin compositions and polyolefin materials of the present invention.
Polyolefin compositions and polyolefin materials were prepared according to the method of example 1, except that: the copolymerization of propylene and ethylene was completed in a loop reactor, with an ethylene concentration of 2 mol% and a hydrogen concentration of 0.48 mol% as measured by on-line chromatography. The specific process conditions and the composition of the polyolefin component are shown in table 1, and the properties of the polyolefin material are shown in table 2.
Example 3
This example illustrates the polyolefin compositions and polyolefin materials of the present invention.
Polyolefin compositions and polyolefin materials were prepared according to the method of example 1, except that: the copolymerization of propylene and 1-butene was completed in a loop reactor, and the concentration of 1-butene was 3 mol% and the hydrogen concentration was 0.35 mol% as determined by on-line chromatography. The specific process conditions and the composition of the polyolefin component are shown in table 1, and the properties of the polyolefin material are shown in table 2.
Comparative example 1
The polyolefin component and the polyolefin material were prepared according to the method of example 1, except that: subsequently, no nucleating agent is added to the resulting polyolefin component, thereby producing a polyolefin material. The properties of the polyolefin material are shown in Table 2
Comparative example 2
Polyolefin compositions and polyolefin materials were prepared according to the method of example 1, except that: the nucleating agent adopted in the composition is Millad nucleating agent HPN-68L, and the addition amount is 0.15 weight percent, so that the polyolefin material is prepared. The properties of the polyolefin material are shown in table 2.
Comparative example 3
Polyolefin compositions and polyolefin materials were prepared according to the method of example 1, except that: the nucleating agent adopted in the composition is a composite nucleating agent VP101B (produced by Beijing chemical research institute of petrochemical China), and the addition amount is 0.15 wt%, so that the polyolefin material is prepared. The properties of the polyolefin material are shown in table 2.
Comparative example 4
Polyolefin compositions and polyolefin materials were prepared according to the method of example 1, except that: the polymerization pressure in the gas phase reactor was adjusted to 0.95MPa, butene/(ethylene + butene) 0.26 (volume ratio), and the hydrogen concentration in the gas phase reactor recycle gas was 19.8 mol% as measured by online chromatography. The specific process conditions and the composition of the polyolefin component prepared are shown in table 1, and the properties of the polyolefin material are shown in table 2.
As can be seen from the data in table 2 below, the polyolefin material prepared in the example has a transverse shrinkage and a longitudinal shrinkage of less than 0.8%, and the ratio of the transverse shrinkage and the longitudinal shrinkage does not exceed 1.06. Compared with the comparative examples 1 to 3, the shrinkage and the anisotropy of the shrinkage of the polypropylene material can be obviously reduced by adopting the HPN-20E, and the material has good comprehensive mechanical properties; comparing example 1 with comparative example 4, when the content of 1-butene in component (b) is less than 20% by weight, the addition of HPN-20E rather increases the shrinkage anisotropy of the material. From the results of tables 1 and 2, it is understood that the polyolefin composition of the present invention comprising HPN-20E and the polyolefin component not only enables the material to satisfy higher rigidity, but also reduces the molding shrinkage and the anisotropy of shrinkage of the material.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention. In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (13)
1. A polyolefin composition, characterized in that the polyolefin composition consists of a polyolefin component, an antioxidant, an acid scavenger and a nucleating agent; the polyolefin component comprises a polyolefin comprising a polyolefin of,
component (a): 65 to 80% by weight of a propylene homopolymer or a propylene copolymer; and
a component (b): 20-35 wt% of an ethylene/1-butene copolymer;
wherein the propylene copolymer contains at most 5% by weight of ethylene and/or 1-butene, and component (a) has an MFR of 20 to 50g/10min as measured at 230 ℃ under 2.16 kg;
the ethylene/1-butene copolymer has a 1-butene content of 20-30 wt%, is partially soluble in xylene at room temperature, and has a xylene solubles content of 50-70 wt%;
the nucleating agent is HPN-20E.
2. The polyolefin composition according to claim 1, wherein the nucleating agent is present in an amount of 0.05 to 5 wt. -%, based on the total weight of the polyolefin composition.
3. The polyolefin composition according to claim 1, wherein the polyolefin component has an MFR of 10 to 20g/10min, measured at 230 ℃ under 2.16 kg.
4. The polyolefin composition of claim 1, wherein the polyolefin component has an intrinsic viscosity value of xylene soluble fraction at room temperature of from 0.8 to 1.5 dL/g.
5. The polyolefin composition according to claim 1, wherein the total content of xylene moieties of the polyolefin component soluble at room temperature is from 15 to 25% by weight.
6. The polyolefin composition according to any of claims 1-5, wherein the polyolefin component is prepared by a process comprising the steps of:
1) subjecting propylene, or propylene and ethylene and/or 1-butene to a first polymerization reaction in the presence of an olefin polymerization catalyst, optionally in the presence of a molecular weight regulator, to obtain a reaction stream comprising component (a);
2) subjecting ethylene and 1-butene to a second polymerization reaction in the presence of said reactant stream, optionally in the presence of a molecular weight regulator, to produce said polyolefin component comprising component (b) and component (a).
7. The polyolefin composition according to claim 6, wherein the olefin polymerization catalyst is a Ziegler-Natta catalyst.
8. Polyolefin composition according to claim 7 wherein the Ziegler-Natta catalyst comprises: an active solid catalyst component comprising magnesium, titanium and halogen, and optionally an internal electron donor compound, an organoaluminum compound, and optionally an external electron donor compound.
9. Polyolefin composition according to claim 7 wherein the Ziegler-Natta catalyst is pre-complexed and/or pre-polymerized before use.
10. The polyolefin composition according to claim 6, wherein the first polymerization reaction is a liquid phase polymerization reaction or a gas phase polymerization reaction and the second polymerization reaction is a gas phase polymerization reaction.
11. Polyolefin composition according to claim 10 wherein the temperature of the liquid phase polymerization is from 40 to 100 ℃.
12. Polyolefin composition according to claim 10 wherein the gas phase polymerization is at a temperature of 40 to 100 ℃ and a polymerization pressure of 0.5 to 2.5 MPa.
13. A polyolefin material obtained by melt blending and shaping the polyolefin composition according to any one of claims 1 to 12.
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| CN110669292A (en) * | 2019-10-29 | 2020-01-10 | 中国石油化工股份有限公司 | Preparation method of toughened polypropylene resin |
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