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CN106279989B - Glass fiber reinforcement prolylene polymer composition, sheet material prepared therefrom or pipe and its application - Google Patents

Glass fiber reinforcement prolylene polymer composition, sheet material prepared therefrom or pipe and its application Download PDF

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Publication number
CN106279989B
CN106279989B CN201610694926.4A CN201610694926A CN106279989B CN 106279989 B CN106279989 B CN 106279989B CN 201610694926 A CN201610694926 A CN 201610694926A CN 106279989 B CN106279989 B CN 106279989B
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ultra
composition
molecular weight
particle size
propylene polymer
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CN106279989A (en
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李化毅
李倩
孙同兵
朱才镇
刘瑞刚
赵宁
徐坚
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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Priority to PCT/CN2017/075496 priority patent/WO2018032745A1/en
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    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • 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
    • C08J2323/12—Polypropene
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention provides a kind of glass fiber reinforcement prolylene polymer composition, sheet material prepared therefrom or pipe and its application, the composition includes super high molecular weight ultra-fine grain diameter acrylic polymers and glass fibre；The viscosity average molecular weigh (Mv) of the super high molecular weight ultra-fine grain diameter acrylic polymers is greater than 1 × 106；The super high molecular weight ultra-fine grain diameter acrylic polymers is spheric granules, and average grain diameter is 10 μm -200 μm, and standard deviation is 2 μm -15 μm, and heap density is 0.1g/mL-0.4g/mL.The sheet material or pipe have excellent resistance to low temperature, shock resistance and creep resistance.In addition, the mechanical performance of the sheet material or pipe is also very excellent due to the humidification of glass fibre.Therefore, sheet material of the invention is especially suitable for numerous areas such as automobile, electronic devices, and the pipe is particularly suitable for fields such as water supply and drainage, oil drillings.

Description

Glass fiber reinforced propylene polymer composition, sheet or tube made therefrom and use thereof
Technical Field
The invention relates to a propylene composition and application thereof, in particular to a glass fiber reinforced propylene polymer composition, a sheet or a pipe prepared from the glass fiber reinforced propylene polymer composition and application of the glass fiber reinforced propylene polymer composition.
Background
Polypropylene is one of the most commonly used plastic varieties at present, has relatively balanced comprehensive performance, and is widely used in the fields of automobiles, electric appliances, building materials and the like. Because of regular structure and high crystallization, the melting point of polypropylene can reach 167 ℃, and the polypropylene has excellent heat resistance and corrosion resistance, but has poor low temperature resistance and impact resistance and is easy to age.
In recent years, glass fiber reinforced polypropylene (GFPP) has been receiving attention from many researchers because of its advantages of improved rigidity, impact strength, creep resistance, low warpage, dynamic fatigue resistance, and dimensional stability, and although glass fiber reinforced polypropylene can improve its low temperature resistance, it still has the problems of poor compatibility between glass fiber and polypropylene, low impact resistance, and low creep resistance, and a new glass fiber reinforced polypropylene composite material is yet to be developed.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a novel glass fiber reinforced propylene polymer composition, which is capable of providing a sheet or a tube having excellent low temperature resistance, and excellent mechanical properties (especially impact resistance and creep resistance) and thermal properties.
In order to solve the above technical problems, the present invention provides a glass fiber reinforced propylene polymer composition comprising an ultra-high molecular weight ultra-fine particle size propylene polymer and glass fibers;
the viscosity average molecular weight (Mv) of the ultra-high molecular weight ultrafine particle size propylene polymer is more than 1 x 106(ii) a The ultra-high molecular weight ultrafine particle size propylene polymer is spherical particles, the average particle size is 10-200 mu m, the standard deviation is 2-15 mu m, and the bulk density is 0.1-0.4 g/mL.
Preferably, the particle size distribution of the ultra-high molecular weight ultra-fine particle size propylene polymer is approximately normal distribution.
According to the invention, the ultra-high molecular weight ultrafine particle size propylene polymer is a propylene homopolymer or a propylene copolymer, and the comonomer in the propylene copolymer is C2-20α -olefins such as one or more of ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, or 1-dodecene preferably the comonomer is one or both of ethylene and 1-butene, the comonomer content being from 0 to 10 mol%, preferably from 0 to 5 mol%.
According to the invention, the viscosity average molecular weight (Mv) of the ultra-high molecular weight ultrafine particle size propylene polymer is 1.5X 10 or more6Preferably 1.5X 106～4.0×106(ii) a The molecular weight distribution Mw/Mn of the ultra-high molecular weight ultrafine particle size propylene polymer is 2-15, preferably 3-10, and further preferably 4-8.
According to the present invention, the average particle diameter of the ultra-high molecular weight ultrafine particle size propylene polymer is preferably 20 μm to 180 μm, more preferably 30 μm to 150 μm, and further preferably 40 to 120 μm; the standard deviation is preferably 5 μm to 15 μm, more preferably 6 μm to 12 μm, and further preferably 8 μm to 10 μm; the bulk density of the ultra-high molecular weight ultrafine particle size propylene polymer is preferably 0.15g/mL-0.35g/mL, and more preferably 0.2g/mL-0.3 g/mL.
According to the invention, the glass fibers are glass fibers treated with a coupling agent, such as a silane coupling agent (e.g. gamma-aminopropyltriethoxysilane KH550, gamma- (2, 3-glycidoxy) propyltrimethoxysilane KH560, gamma-methacryloxypropyltrimethoxysilane KH570, N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane KH792, N- (β -aminoethyl) -gamma-aminopropylmethyldimethoxysilane DL602, vinyltrimethoxysilane A-171, vinyltriethoxysilane A-151, etc.), titanate coupling agents (e.g. one or more of tri (dioctylphosphatoxy) isopropyl titanate, di (dioctylphosphatoxy) ethylene titanate, diisostearoylethylene titanate) or aluminate coupling agents preferably, the coupling agent is selected from silane coupling agents, particularly preferably gamma-aminopropyltriethoxysilane KH550, vinyltrimethoxysilane A-171, vinyltriethoxysilane A-151, etc. in order to better disperse the glass fibers, the coupling agent may be added to the glass fibers in a liquid coupling system, such as a diluent, such as a white oil (1-6) or a diluent, such as a diluent, for example, 1-6.
According to the invention, the glass fibers have a length of 0.5mm to 10mm, for example 1mm to 3mm, or 3mm to 5mm, or 5mm to 7mm, etc.
According to the invention, the composition comprises the following components in percentage by weight: 10-95 wt% of ultra-high molecular weight ultrafine particle size propylene polymer and 5-90 wt% of glass fiber. Preferably, the glass fiber is present in an amount of 10 to 80 wt%, more preferably 40 to 70 wt%.
The invention also provides a sheet or tube prepared from the composition.
The invention also provides a preparation method of the sheet, which comprises the following steps: the ultra-high molecular weight ultrafine particle size propylene polymer and the glass fiber are uniformly mixed in a high-speed stirrer, added into an extruder, extruded through a sheet die, cooled and stretched to prepare the sheet material.
The invention also provides a preparation method of the pipe, which comprises the following steps: the ultra-high molecular weight ultrafine particle size propylene polymer and the glass fiber are uniformly mixed in a high-speed stirrer, added into an extruder, extruded through a pipe die, cooled and stretched to prepare the pipe of the invention.
Preferably, the wall thickness of the tube is between 0.1mm and 10mm, preferably between 0.5mm and 5 mm.
The invention further provides application of the sheet, and the sheet can be applied to the fields of automobiles, electronic devices and the like.
The invention further provides the application of the pipe, which is used in the fields of water supply and drainage, oil drilling and the like, for example, as a water supply and drainage pipe or a mining wear-resistant pipe and the like.
The invention has the beneficial effects that:
the invention provides a glass fiber reinforced propylene polymer composition, and a sheet or a pipe prepared from the composition has excellent low-temperature resistance (such as long-term use at minus 30 ℃ to minus 175 ℃), and impact resistance (such as impact strength (7.5J) of a simple beam notch higher than 10.0 KJ/m)2) And creep resistance (e.g., creep of 2.5% or less). In addition, the sheet or tube is also excellent in mechanical properties (such as flexural strength, flexural modulus, tensile strength, heat distortion temperature and the like) due to the reinforcing effect of the glass fibers. Therefore, the sheet of the present invention is particularly suitable for use in many fields such as automobiles and electronic devices, and the pipe is particularly suitable for use in fields such as water supply and drainage, oil drilling, and the like.
Detailed Description
[ method for producing catalyst ]
The catalyst used in the process for producing an ultra-high molecular weight, ultra-fine particle size propylene polymer according to the present invention can be produced by the method disclosed in the patent application (application No. 201510271254.1) filed by the applicant, the entire contents of which are incorporated herein by reference.
Specifically, the catalyst is prepared by a method comprising the following steps:
(a) mixing magnesium halide, an alcohol compound, an auxiliary agent, part of internal electron donor and a solvent to prepare a mixture I;
(b) adding the mixture I into a reactor, preheating to-30 ℃, and dropwise adding a titanium compound; or adding a titanium compound into a reactor, preheating to-30 ℃, and dropwise adding the mixture I;
(c) after the dropwise addition is finished, the reaction system is heated to 90-130 ℃ after 30 minutes-3 hours, and the rest internal electron donor is added for continuous reaction;
(d) filtering liquid in the reaction system, adding the residual titanium compound, and continuing the reaction;
(e) after the reaction is finished, the catalyst is obtained by post-treatment.
In the present invention, said step (b) is replaced by the following step (b'):
(b') preparing a mixture II comprising nanoparticles, a dispersant and a solvent;
adding the mixture I and the mixture II into a reactor to obtain a mixture of the mixture I and the mixture II, preheating to-30 ℃, and dropwise adding a titanium compound; or,
adding a titanium compound into a reactor, preheating to-30 ℃, and dropwise adding the mixture of the mixture I and the mixture II.
In the present invention, said mixture I is preferably prepared as follows: mixing magnesium halide and an alcohol compound in an organic solvent, heating and preserving heat, adding an auxiliary agent and part of internal electron donor, and reacting at a certain temperature to obtain a stable and uniform mixture I. The alcohol compound is selected from C1-C15Fatty alcohol compound of (2), C3-C15And C6-C15The aromatic alcohol compound (b) is preferably one or more selected from methanol, ethanol, ethylene glycol, n-propanol, isopropanol, 1, 3-propanediol, butanol, isobutanol, hexanol, heptanol, n-octanol, isooctanol, nonanol, decanol, sorbitol, cyclohexanol, and benzyl alcohol, and more preferably ethanol, butanol, hexanol, and isooctanol. The internal electron donor is at least one of monoester, diester, monoether and diether compounds, and is more preferably selected from diester or diether. The solvent is at least one of linear alkane with 5-20 carbons, branched alkane with 5-20 carbons, aromatic hydrocarbon with 6-20 carbons or halogenated hydrocarbon thereof, preferably at least one of toluene, chlorobenzene, dichlorobenzene or decane. In the present invention, magnesium halide is preparedThe catalyst capable of directly obtaining submicron polyolefin particles has the function of a carrier, is one of the components of the traditional Ziegler-Natta catalyst, can enable the prepared catalyst to have proper shape, size and mechanical strength, and simultaneously, the carrier can enable active components to be dispersed on the surface of the carrier, so that higher specific surface area is obtained, and the catalytic efficiency of the active components per unit mass is improved. In addition, the alcohol compound serves to dissolve the magnesium halide, which is a carrier. In the preparation of the mixture I, the temperature of the obtained mixed solution is preferably 110 ℃ to 130 ℃, more preferably 130 ℃, the incubation time is preferably 1 to 3 hours, more preferably 2 to 3 hours, and the reaction time after addition of the auxiliary agent and the like is 0.5 to 2 hours, more preferably 1 hour. Thus, the magnesium halide is dissolved by the alcohol compound at high temperature to give a mixture I.
In the present invention, said mixture II is preferably prepared as follows: and adding the nano particles, the dispersing agent and the solvent into a reaction vessel, and carrying out ultrasonic treatment to obtain a uniform mixture II. The nano particles are preferably at least one of nano silicon dioxide, nano titanium dioxide, nano zirconium dioxide, nano nickel oxide, nano magnesium chloride or nano carbon spheres, and more preferably are nano silicon dioxide and nano titanium dioxide. The particle size of the nanoparticles is preferably 1 to 80nm, more preferably 10 to 50 nm. The addition mass of the nanoparticles is preferably 0% to 200%, more preferably 0% to 20%, relative to the addition mass of the magnesium halide. The time of the ultrasonic treatment is preferably 2 hours. In the present invention, the nanoparticles are introduced as seeds in order to accelerate the shaping of the support and to reduce the particle size of the catalyst particles; both the dispersing agent and the solvent, including sonication, are intended to aid in the dispersion of the nanoparticles, thus facilitating the function of the seed for each nanoparticle.
In the present invention, in the mixture II in the step (b'), the nanoparticles are selected from at least one of nano silicon dioxide, nano titanium dioxide, nano zirconium dioxide, nano nickel oxide, nano magnesium chloride or nano carbon spheres.
Preferably, the nanoparticles have a particle size of 1 to 80nm, preferably 2 to 60 nm, more preferably 3 to 50 nm.
The addition mass of the nanoparticles is more than 0% and less than or equal to 200% relative to the addition mass of the magnesium halide, and preferably, the addition amount of the nanoparticles ranges from more than 0% to less than or equal to 20%.
In the present invention, in the mixture II in the step (b'), the solvent is at least one selected from linear alkanes having 5 to 20 carbons, branched alkanes having 5 to 20 carbons, aromatic hydrocarbons having 6 to 20 carbons, and halogenated hydrocarbons thereof.
The dispersing agent is selected from titanium tetrachloride, silicon tetrachloride or a mixture of the titanium tetrachloride and the silicon tetrachloride.
In step (a), the mixing is carried out under heating and stirring to obtain a uniform and stable transparent mixture I.
In step (b'), ultrasonic dispersion treatment is performed at the time of deployment.
In the step (b) or (b'), the dropwise addition is carried out slowly.
In step (b) or (b'), the reaction preheating temperature is preferably from-20 ℃ to 30 ℃, more preferably from-20 ℃ to 20 ℃.
The reaction time of step (c) is 1 to 5 hours, preferably 2 to 3 hours.
The reaction of step (d) is continued for a period of 1 to 5 hours, preferably 2 to 3 hours.
The post-treatment in the step (e) can be washing the obtained product by using hexane and then drying; wherein the number of washing may be 1 to 10, preferably 3 to 6.
In the step (a), the magnesium halide is at least one selected from magnesium chloride, magnesium bromide and magnesium iodide.
In the step (a), the auxiliary agent may be a titanate compound.
In step (b) or (b'), the titanium compound has a general formula shown in formula I:
Ti(R)nX(4-n)
formula I
Wherein R is C1-C12 branched chain or straight chain alkyl, X is halogen, and n is 0, 1, 2 or 3.
In step (d), preferably, the temperature of the reaction system is raised to 90 to 130 ℃ over 40 minutes to 3 hours, more preferably, the temperature of the reaction system is raised to 100 to 120 ℃ over 40 minutes to 2 hours.
According to the scheme, the preparation method of the Ziegler-Natta catalyst is simple in process and easy for industrial production. In addition, the Ziegler-Natta catalyst prepared by the invention can prepare propylene polymer particles with the average particle size of 10-200 μm, higher sphericity, narrower particle size distribution and low bulk density (0.1-0.4 g/mL) during propylene polymerization. According to research, the catalyst prepared by the invention is used for propylene polymer particles obtained by propylene polymerization, the particle size is reduced by 20-30 times compared with other particles, the particle size distribution is obviously narrowed, and the bulk density can be as low as 0.1 g/mL.
[ ultra-high molecular weight ultrafine particle size propylene Polymer and Process for producing the same ]
As described above, the composition of the present invention employs an ultra-high molecular weight, ultra-fine particle size propylene polymer having a viscosity average molecular weight (Mv) of greater than 1X 106The propylene polymer is spherical particles, the average particle diameter is 10-200 mu m, the standard deviation is 2-15 mu m, and the bulk density is 0.1-0.4 g/mL. Preferably, the particle size distribution of the propylene polymer approximates a normal distribution. The average particle diameter is preferably 20 μm to 180 μm, more preferably 30 μm to 150 μm, and further preferably 40 to 120 μm. The standard deviation is preferably 5 μm to 15 μm, more preferably 6 μm to 12 μm, and further preferably 8 μm to 10 μm. The bulk density is preferably 0.15g/mL-0.35g/mL, and more preferably 0.2g/mL-0.3 g/mL. The propylene polymer with the ultrahigh molecular weight and the particle size and the bulk density is particularly suitable for graft modification, and on one hand, the modification space of the propylene polymer is greatly expanded; on the other hand, theThe processability of the polymer is obviously improved, and the polymer is suitable for preparing products in a wider range; thus, the application field of the polymer is effectively expanded.
Meanwhile, the propylene polymer of the invention also has the following excellent properties: firstly, the wear resistance is very excellent and is several times higher than the wear resistance index of metals such as common carbon steel, copper and the like; secondly, due to the fact that the molecular weight is ultrahigh, the molecular chain is overlong, and the impact strength of the material is high; thirdly, the chemical resistance of the propylene polymer is stronger than that of common polyolefin; finally, the material has a wider range of use temperature, and can keep good toughness and strength at lower or higher temperature.
As described above, the present invention provides a method for preparing the above ultra-high molecular weight ultra-fine particle size propylene polymer, comprising the steps of:
under the action of a catalyst, propylene or propylene and a comonomer are subjected to polymerization reaction, wherein the polymerization reaction temperature is 30-105 ℃, and the volume fraction of the propylene is more than or equal to 98%;
the catalyst is prepared by the preparation method of the catalyst.
The present inventors have found, through studies, that the particle size of the propylene polymer can be controlled well with simple control of the preparation process of the catalyst, but the molecular weight of the propylene polymer to be prepared is not high, and many attempts have been made by the inventors to increase the molecular weight of the polymer while controlling the particle size, and as a result, it has been found that controlling the polymerization temperature and the monomer purity is a simple and effective method, and does not affect the effective control of the particle size of the polymer, and even contributes to the preparation of polymers in a narrower particle size range and a lower bulk density range.
According to research, the temperature of the polymerization reaction is controlled to be 30-105 ℃, the volume fraction of the propylene is controlled to be more than or equal to 98%, and the ultrahigh molecular weight propylene polymer can be prepared while the particle size is controlled. Further preferably, the temperature of the polymerization reaction is 40-80 ℃. More preferably, the volume fraction of propylene is greater than or equal to 99%; still more preferably, 99.8% or higher; still more preferably, 99.9% or more. For copolymerization, it is advantageous to control the content of carbon monoxide in the comonomer to be less than 5ppm, carbon dioxide to be less than 15ppm and the content of conjugated diene to be less than 10 ppm.
In the present invention, the propylene volume fraction is determined by the standard GB/T3392. The propylene volume fraction is an important indicator of the purity of the propylene monomer.
In one embodiment of the present invention, there is provided a method for preparing an ultra-high molecular weight, ultra-fine particle size propylene polymer, comprising the steps of:
under the action of a catalyst, propylene or propylene and a comonomer are subjected to polymerization reaction, wherein the polymerization reaction temperature is 30-105 ℃, and the volume fraction of the propylene is more than or equal to 98%;
the catalyst is prepared by a method comprising the following steps:
(a) mixing magnesium halide, an alcohol compound, an auxiliary agent, part of internal electron donor and a solvent to prepare a mixture I;
(b) adding the mixture I into a reactor, preheating to-30 ℃, and dropwise adding a titanium compound; or adding a titanium compound into a reactor, preheating to-30 ℃, and dropwise adding the mixture I;
(c) after the dropwise addition is finished, the reaction system is heated to 90-130 ℃ after 30 minutes-3 hours, and the rest internal electron donor is added for continuous reaction;
(d) filtering liquid in the reaction system, adding the residual titanium compound, and continuing the reaction;
(e) after the reaction is finished, post-treating to obtain the catalyst;
wherein the resulting propylene polymer has a viscosity average molecular weight (Mv) of greater than1×106(ii) a The propylene polymer is spherical particles, the average particle size is 10-200 mu m, the standard deviation is 2-15 mu m, and the bulk density is 0.1-0.4 g/mL.
In the present invention, the particle size distribution of the propylene polymer is approximately normal.
In the present invention, the comonomer is C2-20α -olefins such as one or more of ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, or 1-dodecene preferably the comonomer is one or both of ethylene and 1-butene, the comonomer content being from 0 to 10 mol%, preferably from 0 to 5 mol%.
In the invention, the temperature of the polymerization reaction is preferably 40-80 ℃.
In the present invention, the volume fraction of propylene is 99% or more, more preferably 99.8% or more, and still more preferably 99.9% or more.
In the present invention, the comonomer (e.g., ethylene or 1-butene) has a carbon monoxide content of less than 5ppm, a carbon dioxide content of less than 15ppm, and a conjugated diene content of less than 10 ppm.
[ measurement of parameters ]
The creep resistance is measured by the method of Chinese national standard GB11546-89 and ISO 899-1981.
The impact resistance is measured by GB/T1043.1-2008.
The flexural strength and flexural modulus were determined using GB/T9341-2008.
Tensile strength was measured by GB/T1040-2006.
The heat distortion temperature was measured by GB/T1634.2-2004.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various other respects, all without departing from the spirit of the present invention.
Preparation example 1 propylene homopolymer and preparation thereof
4.94g of anhydrous magnesium chloride, 18.9g of isooctyl alcohol and 30ml of decane are sequentially added into a reactor fully replaced by high-purity nitrogen, the temperature is raised to 130 ℃ under stirring and maintained for 2 hours, then 2.65g of tetrabutyl titanate and 2.05g of diisobutyl phthalate are added, the reaction is carried out for 1 hour at the temperature of 130 ℃, and finally the mixture is cooled to room temperature to form a uniform transparent solution, namely a mixture I.
200ml of titanium tetrachloride was added to the reaction vessel, stirred and preheated to 0 ℃ and the mixture I was added dropwise to the titanium tetrachloride over about 2 hours. After the dropwise addition, the temperature was raised to 110 ℃ within 2 hours. 1.23g of diisobutylphthalate as an internal electron donor was added. After reacting at this temperature for 2 hours, the reaction liquid was removed, and 200ml of titanium tetrachloride was added again to react for 2 hours. And finally, removing reaction liquid, washing the remaining solid substance with hexane at 60 ℃ for 10 times, and drying to obtain the catalyst.
Bulk polymerization of propylene:
under the protection of high-purity nitrogen, a 5L high-pressure reaction kettle is dried and deaerated, 20mg of the catalyst, 12ml of triethyl aluminum and 3ml of external electron Donor Donor-P are added, 1200g of propylene is added, wherein the volume fraction of the propylene is 99.9%, the polymerization reaction starts, the system temperature is maintained at 45 ℃, and the reaction time is 60 minutes, so that the propylene homopolymer disclosed by the invention is prepared.
Preparation example 2 propylene-ethylene copolymer and preparation thereof
The catalyst was prepared in the same manner as in preparation example 1.
Propylene-ethylene copolymerization:
under the protection of high-purity nitrogen, a 5L high-pressure reaction kettle is dried and deaerated, 20mg of the catalyst and 12ml of triethyl aluminum and 3ml of external electron Donor Donor-P are added, 1200g of propylene is then added, and 40g of ethylene is introduced, wherein the volume fraction of the propylene is 99.9%, the content of carbon monoxide in ethylene gas is less than 5ppm, the content of carbon dioxide is less than 15ppm, and the content of conjugated diene is less than 10ppm, the polymerization reaction is started, the system temperature is maintained at 75 ℃, and the reaction time is 60 minutes, so that the propylene-ethylene copolymer is prepared.
Preparation example 3 propylene homopolymer and preparation thereof
The catalyst was prepared in the same manner as in preparation example 1.
Bulk polymerization of propylene:
under the protection of high-purity nitrogen, a 5L high-pressure reaction kettle is dried and deaerated, 20mg of the catalyst, 12ml of triethyl aluminum and 3ml of external electron Donor Donor-P are added, 1200g of propylene is added, wherein the volume fraction of the propylene is 99.9%, the polymerization reaction starts, the system temperature is maintained at 55 ℃, and the reaction time is 60 minutes, so that the propylene homopolymer disclosed by the invention is prepared.
Preparation example 4 propylene homopolymer and preparation thereof
The catalyst was prepared in the same manner as in preparation example 1.
Bulk polymerization of propylene:
under the protection of high-purity nitrogen, a 5L high-pressure reaction kettle is dried and deaerated, 20mg of the catalyst, 12ml of triethyl aluminum and 3ml of external electron Donor Donor-P are added, 1200g of propylene is added, wherein the volume fraction of the propylene is 99.9%, the polymerization reaction starts, the system temperature is maintained at 65 ℃, and the reaction time is 60 minutes, so that the propylene homopolymer disclosed by the invention is prepared.
TABLE 1 Properties of propylene polymers of preparation examples 1 to 4
Preparation example 5
Adding glass fiber and coupling agent into a mixer, and stirring for 30 min; adding diluent, and stirring for 30 min; the treated glass fiber of the present invention is obtained. Wherein the coupling agent is gamma-aminopropyl triethoxysilane KH 550; the length of the glass fiber is 3-5 mm; the diluent is white oil. The weight ratio of the diluent to the coupling agent is 3: 1; the amount of the coupling agent used was 2 parts by weight relative to 100 parts by weight of the glass fiber.
Preparation example 6
Adding glass fiber and coupling agent into a mixer, and stirring for 30 min; adding diluent, and stirring for 30 min; the treated glass fiber of the present invention is obtained. Wherein the coupling agent is vinyltrimethoxysilane A-171; the length of the glass fiber is 3-5 mm; the diluent is white oil. The weight ratio of the diluent to the coupling agent is 4: 1; the amount of the coupling agent used was 1 part by weight relative to 100 parts by weight of the glass fiber.
Preparation example 7
Adding glass fiber and coupling agent into a mixer, and stirring for 30 min; adding diluent, and stirring for 30 min; the treated glass fiber of the present invention is obtained. Wherein the coupling agent is vinyl triethoxysilane A-151; the length of the glass fiber is 3-5 mm; the diluent is liquid paraffin. The weight ratio of the diluent to the coupling agent is 6: 1; the amount of the coupling agent used was 3 parts by weight per 100 parts by weight of the glass fiber.
Examples 1-12 glass fiber reinforced propylene Polymer compositions
The compositions and amounts of the compositions of examples 1-12 of the present invention are listed in Table 2.
TABLE 2
Examples 13 to 24
Sheets were prepared using the compositions of examples 1-12, respectively.
Taking the composition of example 1a as an example, 6Kg of the propylene homopolymer of preparation example 1 and 4Kg of the glass fiber of preparation example 5 were uniformly mixed by a high-speed stirrer, added to an extruder, extruded through a slot die, cooled and stretched to obtain a sheet of the present invention. Wherein the processing temperature of the extruder is 180-240 ℃.
The results of the performance testing of the sheets prepared in examples 13-24 are shown in Table 3.
TABLE 3
Table 3 (continuation 1)
Table 3 (continuation 2)
Table 3 (continuation 3)
Examples 25 to 36
Tubes were prepared using the compositions of examples 1-12, respectively.
Taking the composition of example 1a as an example, 6Kg of the propylene homopolymer of preparation example 1 and 4Kg of the glass fiber of preparation example 5 were uniformly mixed by a high-speed stirrer, added to an extruder, extruded through a pipe die, cooled and stretched to obtain the pipe of the present invention. Wherein the processing temperature of the extruder is 180-240 ℃. The wall thickness of the tube is between 0.5mm and 5 mm.
The performance test results for the tubes prepared in examples 25-36 are similar to the corresponding sheet properties.

Claims (36)

1. A glass fiber reinforced propylene polymer composition comprising an ultra high molecular weight, ultra fine particle size propylene polymer and glass fibers;
the viscosity average molecular weight (Mv) of the ultra-high molecular weight ultrafine particle size propylene polymer is more than 1 x 106(ii) a The ultra-high molecular weight ultrafine particle size propylene polymer is spherical particles, the average particle size is 10-200 μm, the standard deviation is 2-15 μm, and the bulk density is 0.1-0.4 g/mL; the particle size distribution of the ultra-high molecular weight ultrafine particle size propylene polymer is approximate to normal distribution;
wherein, the ultra-high molecular weight ultra-fine particle size propylene polymer is prepared by the method comprising the following steps:
under the action of a catalyst, propylene or propylene and a comonomer are subjected to polymerization reaction, wherein the polymerization reaction temperature is 30-105 ℃, and the volume fraction of the propylene is more than or equal to 99%;
the catalyst is prepared by a preparation method of the catalyst, which comprises the following steps:
(a) mixing magnesium halide and an alcohol compound in an organic solvent, heating and preserving heat, adding an auxiliary agent and part of internal electron donor, and reacting at a certain temperature to obtain a mixture I;
(b) adding the mixture I into a reactor, preheating to-30 ℃, and dropwise adding a titanium compound; or adding a titanium compound into a reactor, preheating to-30 ℃, and dropwise adding the mixture I;
(c) after the dropwise addition is finished, the reaction system is heated to 90-130 ℃ after 30 minutes-3 hours, and the rest internal electron donor is added for continuous reaction;
(d) filtering liquid in the reaction system, adding a titanium compound, and continuing the reaction;
(e) after the reaction is finished, post-treating to obtain the catalyst;
alternatively, the catalyst is prepared by a preparation method of the catalyst, which comprises the following steps:
(a) mixing magnesium halide and an alcohol compound in an organic solvent, heating and preserving heat, adding an auxiliary agent and part of internal electron donor, and reacting at a certain temperature to obtain a mixture I;
(b') preparing a mixture II comprising nanoparticles, a dispersant and a solvent;
adding the mixture I and the mixture II into a reactor to obtain a mixture of the mixture I and the mixture II, preheating to-30 ℃, and dropwise adding a titanium compound; or,
adding a titanium compound into a reactor, preheating to-30 ℃, and dropwise adding a mixture of the mixture I and the mixture II;
(c) after the dropwise addition is finished, the reaction system is heated to 90-130 ℃ after 30 minutes-3 hours, and the rest internal electron donor is added for continuous reaction;
(d) filtering liquid in the reaction system, adding a titanium compound, and continuing the reaction;
(e) after the reaction is finished, the catalyst is obtained by post-treatment.
2. The composition of claim 1, wherein the ultra-high molecular weight, ultra-fine particle size propylene polymer is a propylene homopolymer or a propylene copolymer, and the comonomer in the propylene copolymer is one or more of ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, or 1-dodecene.
3. The composition of claim 2, wherein the comonomer is one or both of ethylene and 1-butene.
4. The composition of claim 2, wherein the comonomer is present in an amount of 0 to 10 mole percent.
5. The composition of claim 1, wherein said ultra-high molecular weight, ultra-fine particle size propylene polymer has a viscosity average molecular weight (Mv) of 1.5 x 10 or more6(ii) a The molecular weight distribution Mw/Mn of the ultra-high molecular weight ultrafine particle size propylene polymer is 2-15.
6. The composition of claim 5, wherein said ultra-high molecular weight, ultra-fine particle size propylene polymer has a viscosity average molecular weight (Mv) of 1.5 x 106～4.0×106。
7. The composition of claim 5, wherein the ultra-high molecular weight ultra-fine particle size propylene polymer has a molecular weight distribution Mw/Mn of 3 to 10.
8. The composition of claim 7, wherein the ultra-high molecular weight ultra-fine particle size propylene polymer has a molecular weight distribution Mw/Mn of 4 to 8.
9. The composition of claim 1, wherein the ultra-high molecular weight, ultra-fine particle size propylene polymer has an average particle size of 20 μm to 180 μm.
10. The composition of claim 9 wherein said ultra high molecular weight, ultra fine particle size propylene polymer has an average particle size of 30 μm to 150 μm.
11. The composition of claim 10 wherein said ultra high molecular weight, ultra fine particle size propylene polymer has an average particle size of 40 to 120 μm.
12. The composition of claim 1, wherein the standard deviation is from 5 μ ι η to 15 μ ι η.
13. The composition of claim 12, wherein the standard deviation is 6 μ ι η to 12 μ ι η.
14. The composition of claim 13, wherein the standard deviation is 8 μ ι η to 10 μ ι η.
15. The composition of claim 1, wherein the ultra-high molecular weight, ultra-fine particle size propylene polymer has a bulk density of 0.15g/mL to 0.35 g/mL.
16. The composition of claim 15, wherein said ultra-high molecular weight, ultra-fine particle size propylene polymer has a bulk density of from 0.2g/mL to 0.3 g/mL.
17. The composition of claim 1, wherein the glass fiber is a coupling agent treated glass fiber.
18. The composition of claim 17, wherein the coupling agent is one or more of a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent.
19. The composition of claim 18, wherein the silane coupling agent is selected from the group consisting of gamma-aminopropyltriethoxysilane KH550, gamma- (2, 3-glycidoxy) propyltrimethoxysilane KH560, gamma-methacryloxypropyltrimethoxysilane KH570, N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane KH792, N- (β -aminoethyl) -gamma-aminopropylmethyldimethoxysilane DL602, vinyltrimethoxysilane A-171, vinyltriethoxysilane A-151, and one or more titanate coupling agents selected from the group consisting of isopropyl tri (dioctylphosphato) titanate, ethylene bis (isostearyl) titanate.
20. The composition as claimed in claim 17, wherein a diluent is added to the system of glass fibers and coupling agent, wherein the diluent is selected from white oil or liquid paraffin.
21. The composition of claim 20, wherein the weight ratio of the diluent to the coupling agent is (1-10): 1.
22. The composition of claim 21, wherein the weight ratio of the diluent to the coupling agent is (3-6): 1.
23. The composition of claim 1, wherein the glass fibers have a length of 0.5mm to 10 mm.
24. The composition of claim 23, wherein the glass fibers have a length of 1mm to 3mm, or 3mm to 5mm, or 5mm to 7 mm.
25. The composition according to any one of claims 1 to 24, wherein the composition comprises the following components in percentage by weight: 10-95 wt% of ultra-high molecular weight ultrafine particle size propylene polymer and 5-90 wt% of glass fiber.
26. The composition of claim 25, wherein the glass fiber is present in the composition in an amount of 10 to 80 wt.%.
27. The composition of claim 26, wherein the glass fiber is present in the composition in an amount of 40 to 70 wt.%.
28. A sheet prepared from the composition of any one of claims 1-27.
29. A tube prepared from the sheet of claim 28.
30. The tube of claim 29, wherein the tube has a wall thickness of between 0.1mm and 10 mm.
31. The tube of claim 30, wherein the tube has a wall thickness between 0.5mm and 5 mm.
32. A method of making the sheet of claim 28, comprising the steps of: and uniformly mixing the ultrahigh molecular weight ultrafine particle size propylene polymer and the glass fiber in a high-speed stirrer, adding the mixture into an extruder, extruding the mixture through a sheet die, and cooling and stretching to obtain the sheet.
33. A method of producing a pipe as claimed in any one of claims 29 to 31, wherein the method comprises the steps of: and uniformly mixing the ultrahigh molecular weight ultrafine particle size propylene polymer and the glass fiber in a high-speed stirrer, adding the mixture into an extruder, extruding the mixture through a pipe die, and cooling and stretching to obtain the pipe.
34. Use of the sheet according to claim 28, characterized in that it is used in the automotive, electronic field.
35. Use of a pipe according to any of claims 29-31, characterized in that the pipe is used in the fields of water supply and drainage, oil drilling.
36. Use according to claim 35, wherein the pipe is used as a water supply drain or a mining wear pipe.
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