WO2018032745A1

WO2018032745A1 - Ultra-high molecular weight, ultra-fine particle size propene polymer, preparation method therefor and use thereof

Info

Publication number: WO2018032745A1
Application number: PCT/CN2017/075496
Authority: WO
Inventors: 李化毅; 李倩; 孙同兵; 朱才镇; 刘瑞刚; 赵宁; 徐坚
Original assignee: 中国科学院化学研究所
Priority date: 2016-08-19
Filing date: 2017-03-02
Publication date: 2018-02-22

Abstract

Provided are an ultra-high molecular weight, ultra-fine particle size propene polymer, a preparation method therefor and a use thereof. The viscosity average molecular weight (Mv) of the propene polymer is greater than 1 × 10⁶, and the propene polymer is spherical particles with a mean particle size of 10-200 µm, a standard deviation of 2-15 µm and a bulk density of 0.1-0.4 g/mL. Using the propene polymer as a basic polypropene, a graft-modified propene polymer is prepared by means of a solid phase grafting method; and a reinforced propene polymer composition comprising the propene polymer and glass fibres, a sheet or pipe prepared therefrom; a solubility-enhancing ultra-high molecular weight, ultra-fine particle size propene polymer; and a fibre and a film prepared therefrom may also be obtained.

Description

[Invention name established by ISA according to Rule 37.2] Ultrahigh molecular weight ultrafine particle size propylene polymer and preparation method and application thereof

Technical field

The invention belongs to the field of polyolefin polymer materials, and particularly relates to an ultrahigh molecular weight ultrafine particle size propylene polymer and a preparation method and application thereof.

Background technique

Ultra-high molecular weight propylene polymer (UHMWPP) and ultra-high molecular weight propylene polymer (UHMWPE) are both flexible chain polymers with excellent structure and excellent crystallization properties, while UHMWPP has better adhesion and temperature than UHMWPE. Higher, lower creep and other advantages. However, since the viscosity of the ultrahigh molecular weight polymer in the molten state is extremely high and the melt flow property is extremely poor (its melt flow index is almost zero), it is difficult to process by a general hot working method. After several decades of development, UHMWPE's processing technology has evolved from initial press-sintering to extrusion, blow molding and injection, solution spinning and other forming methods, but the processing and application of UHMWPP has been slow. On the one hand, it is difficult to synthesize ultra-high molecular weight propylene polymer. Under the usual polymerization conditions, only propylene polymer resin having a molecular weight of several hundred thousand can be obtained. On the other hand, UHMWPP is more difficult to process than UHMWPE.

The development of new processing methods is one of its solutions, and how to prepare UHMWPP with better processing performance and easier processing is also a more fundamental and more effective solution with good development prospects.

Therefore, there is an urgent need for a new preparation method of UHMWPP, which enables the preparation of UHMWPP with excellent performance and ensures that it does not degrade its properties when processed into profiles, films, fibers or filter materials. Processing performance and broader application prospects.

Polypropylene is a general-purpose plastic, which is famous for its high output, wide application and low cost. However, polypropylene has poor cold resistance, weather resistance, light resistance, dyeability, adhesion, antistatic property and hydrophilicity. And the compatibility with other polar polymers, inorganic fillers and reinforcing materials is also very poor. These shortcomings restrict the application of polypropylene in the field of packaging materials, automotive industry, electronics industry and medical equipment.

In order to improve the properties of polypropylene and expand its range of applications, it is necessary to modify the polypropylene. There are many methods for modifying polypropylene, and graft modification is one of the most important ones. The graft modification process includes chemical grafting, mechanical grafting, photografting, etc., wherein the chemical grafting includes solution grafting, solid phase grafting, melt grafting, gas phase grafting, suspension grafting and the like. The study of solid phase grafted polypropylene started late. In the late 1980s, Rengarajan et al first reported the preparation of maleic anhydride functionalized polypropylene by solid phase grafting, followed by solid phase grafting. The monomer of the modified polypropylene includes styrene, glycidyl methacrylate, 4-vinylpyridine, acrylonitrile, methyl 2-hydroxyethyl acrylate, and the like. In recent years, this method has been used by more and more researchers to modify polypropylene. Compared with other grafting processes, solid phase grafting can not only introduce polar functional groups while maintaining the original properties of polypropylene. And it has the advantages of low temperature, low pressure, low cost, high grafting rate and no need for solvent recovery.

However, a major difficulty faced by solid phase grafting modified polypropylene is that the grafting modified polypropylene prepared by conventional techniques or techniques has a low effective grafting rate, and the current reports in the literature generally only It can reach 1%, and it is apparent that the modification of such a low graft ratio has a limited improvement in the performance of polypropylene. In recent years, researchers have developed a series of solid phase grafting processes to increase the grafting rate, for example: supercritical carbon dioxide assisted solid phase grafting, grinding disc force chemical reactor graft modified polypropylene, ultrasonic assisted Solid phase grafting method, comonomer melt grafting method, radiation grafting method and the like. Although these methods can reduce the grafting temperature and grafting time and increase the grafting rate to some extent, the entire reaction process is too complicated, and new media or equipment are introduced, which greatly increases the production cost and is difficult to be Achieve large scale and low cost production. Therefore, it is very important to study the low-cost preparation of grafted polypropylene with high grafting rate by conventional methods.

Polypropylene fibers include long fibers, short fibers, nonwoven fabrics, and the like. Among them, polypropylene long fiber has good gloss, soft handfeel, good drape and low density. It is suitable for the knitting industry. When it is interwoven with cotton, viscose, silk, spandex, etc. into cotton cover C, silk cover C and other products, it is made. Ideal material for high-end sportswear, T-shirts, etc.; polypropylene staple fiber and cotton blend can be made into cotton cloth, bed sheets, and viscose blended for blankets, polypropylene pure and blended wool, carpet, cotton wool and tobacco filter. Tsui. Polypropylene non-woven fabrics are used in disposable medical and hygiene products, disposable anti-fouling garments, agricultural fabrics, furniture fabrics or linings for footwear, or in the fields of medical hygiene, thermal insulation materials, filter materials, etc. Although the conventional polypropylene fiber has many advantages such as light weight, high strength, good elasticity, wear resistance, corrosion resistance, good insulation, and good heat retention, it also has defects of heat resistance, low temperature resistance and poor aging resistance. Moreover, its hygroscopicity and dyeing properties are also poor. In the current prior art, ethylene copolymerization, addition of blending modifiers (such as adding ethylene propylene rubber, EPDM, POE, EVA or SBS, etc.) are used to improve the low temperature resistance, but these methods are improving the low temperature resistance. Performance, will affect other excellent properties of polypropylene, such as strength and modulus.

The molding process of chemical fibers includes melt spinning, solution spinning, gel spinning, and the like. Drafting is an important process in chemical fiber forming processes. The drawing can make the polymer in the chemical fiber produce anisotropy in mechanics, optics, heat, etc., and effectively increase the strength of the chemical fiber. For melt spinning, the drafting process mainly uses hot roll drafting, hot plate drafting and hot box drawing; for some fibers that are difficult to plasticize, in addition to the above drafting mode, pressurized steam drawing or Heat bath drafting. It is also a research direction to improve the above-mentioned many disadvantages of polypropylene through the adjustment of processing methods.

Polypropylene film, especially biaxially oriented polypropylene film, has excellent resistance to bending fatigue, high heat resistance, good chemical properties, purity and non-toxicity, good transparency, etc., and is mainly used in the field of packaging films. However, its low temperature resistance is low and the low temperature impact strength is low.

In addition, polypropylene microporous membranes are also widely used in battery separators, electrolytic capacitor separators, various filters, waterproof and moisture permeable fabrics, reverse osmosis filtration membranes, ultrafiltration membranes, microfiltration membranes, and the like. When used in a separator for a battery, the film is required to have excellent permeability, mechanical properties, heat shrinkage resistance, melting characteristics, etc. How to obtain a polypropylene microporous film having excellent properties has been pursued by researchers. The goal.

Polypropylene is one of the most widely used general-purpose plastics, and it has a relatively balanced overall performance. It is widely used in the fields of automobiles, electrical appliances, and building materials. Due to the regular structure and high crystallization, the melting point of polypropylene can be as high as 167 ° C, excellent heat and corrosion resistance, but at the same time low temperature resistance, poor impact resistance, easy to age.

Glass fiber reinforced polypropylene (GFPP) has attracted more and more researchers' attention in recent years due to its advantages of improved rigidity, impact strength, creep resistance, low warpage, dynamic fatigue resistance and dimensional stability. Although glass fiber reinforced polypropylene can improve its low temperature resistance, there are still problems such as poor compatibility of glass fiber and polypropylene, low impact resistance and low creep resistance, and a new type of glass fiber reinforced polypropylene composite material is to be developed.

Summary of the invention

One of the objects of the present invention is to provide an ultrahigh molecular weight ultrafine particle size propylene polymer powder and a process for preparing the same, which powder has excellent processability.

A second object of the present invention is to provide a graft-modified ultrahigh molecular weight ultrafine particle size propylene polymer and a solid phase grafting method thereof, which can prepare a graft having a higher graft ratio simply and efficiently. A propylene polymer that is more effective in modifying propylene polymers.

A third object of the present invention is to provide a glass fiber reinforced propylene polymer composition and a sheet and a tube thereof, and the sheet or tube prepared from the composition has excellent low temperature resistance and various mechanical properties (especially It is excellent in impact resistance and creep resistance) and thermal properties.

A fourth object of the present invention is to provide a solubilized ultrahigh molecular weight ultrafine particle size propylene polymer having a process property which is more excellent in processability and easier to process, and a process for producing the same.

A fifth object of the present invention is to provide a fiber prepared by solubilizing ultrahigh molecular weight ultrafine particle size propylene polymer which is excellent in low temperature resistance, excellent in various mechanical properties and thermal properties, and a preparation method thereof.

A sixth object of the present invention is to provide a film prepared by solubilizing ultrahigh molecular weight ultrafine particle size propylene polymer which is excellent in low temperature resistance, excellent in various mechanical properties and thermal properties, and a preparation method thereof. Further, the film of the present invention is particularly suitable for use in a battery separator because of its excellent mechanical properties, thermal properties, permeability, melting properties and the like.

A first aspect of the present invention provides a method for preparing an ultrahigh molecular weight ultrafine particle size propylene polymer powder, which comprises the steps of: polymerizing propylene or propylene with a comonomer under the action of a catalyst, wherein The temperature of the polymerization reaction is 30-105 ° C, and the volume fraction of the propylene is 98% or more;

The catalyst is prepared by a process comprising the following steps:

(a) mixing magnesium halide, an alcohol compound, an auxiliary, a part of the internal electron donor and a solvent to prepare a mixture I;

(b) adding the above mixture I to the reactor, preheating to -30 ° C ~ 30 ° C, adding titanium compound; or, adding titanium compound in the reactor, preheating to -30 ° C ~ 30 ° C, dropping The above mixture I;

(c) after the completion of the dropwise addition, the reaction system is heated to 90 ° C to 130 ° C over 0.5 to 3 hours, and the remaining internal electron donor is added to continue the reaction;

(d) filtering out the liquid of the reaction system, adding the remaining titanium compound, and continuing the reaction;

(e) after completion of the reaction, post-treatment to obtain the catalyst;

The propylene polymer obtained has a viscosity average molecular weight (Mv) of more than 1×10 ⁶ ; the propylene polymer powder is spherical particles having an average particle diameter of 10 μm to 200 μm, a standard deviation of 2 μm to 15 μm, and a bulk density of 0.1. g/mL - 0.4 g / mL.

According to the invention, the particle size distribution of the propylene polymer powder approximates a normal distribution.

According to the invention, the comonomer is a C _2-20 alpha-olefin such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-oxime One or more of an alkene, 1-decene, 1-undecene or 1-dodecene. Preferably, the comonomer is one or both of ethylene and 1-butene. The comonomer has a molar percentage of from 0 to 10 mol%, preferably from 0 to 5 mol%.

According to the invention, the temperature of the polymerization reaction is preferably from 40 to 80 °C.

According to the invention, the volume fraction of propylene is 99% or more, more preferably 99.8% or more, still more preferably 99.9% or more.

According to the present invention, the comonomer (e.g., ethylene or 1-butene) has a carbon monoxide content of less than 5 ppm, a carbon dioxide content of less than 15 ppm, and a conjugated diene content of less than 10 ppm.

A second aspect of the present invention provides an ultrahigh molecular weight ultrafine particle size propylene polymer powder obtained by the above-described method for producing an ultrahigh molecular weight ultrafine particle size propylene polymer powder, the viscosity average molecular weight of the propylene polymer (Mv) is more than 1 × 10 ⁶ ; the propylene polymer powder is spherical particles having an average particle diameter of 10 μm to 200 μm, a standard deviation of 2 μm to 15 μm, and a bulk density of 0.1 g/mL to 0.4 g/mL. Preferably, the particle size distribution of the propylene polymer powder approximates a normal distribution.

According to the present invention, the propylene polymer is a propylene homopolymer or a propylene copolymer, and the comonomer in the propylene copolymer is a C _2-20 α-olefin such as ethylene, 1-butene, 1-pentene, One or more of 1-hexene, 1-heptene, 1-octene, 1-decene, 1-decene, 1-undecene or 1-dodecene. Preferably, the comonomer is one or both of ethylene and 1-butene. The comonomer has a molar percentage of from 0 to 10 mol%, preferably from 0 to 5 mol%.

According to the present invention, the propylene polymer has a viscosity average molecular weight (Mv) of 1.5 × 10 ^{6 or more} , preferably 1.5 × 10 ⁶ to 4.0 × 10 ⁶ ; and the molecular weight distribution Mw / Mn of the propylene polymer is 2 - 15, preferably from 3 to 10, and more preferably from 4 to 8.

According to the invention, the average particle diameter of the propylene polymer powder is preferably from 20 μm to 180 μm, more preferably from 30 μm to 150 μm; the standard deviation is preferably from 5 μm to 15 μm, more preferably from 6 μm to 12 μm, still more preferably 8 μm - 10 μm; the bulk density of the powder is preferably from 0.15 g/mL to 0.35 g/mL.

A third aspect of the present invention provides a method for preparing an ultrahigh molecular weight ultrafine particle size grafted propylene polymer by solid phase grafting, comprising the steps of:

In the container, adding propylene polymer, grafting monomer, initiator and interface agent, stirring and mixing uniformly; heating to carry out solid phase grafting reaction; obtaining the grafted propylene polymer;

The propylene polymer is a powder having a spherical particle shape, an average particle diameter of 10 μm to 200 μm, a standard deviation of 2 μm to 15 μm, a bulk density of 0.1 g/mL to 0.4 g/mL, and a viscosity average of the propylene polymer. The molecular weight (Mv) is greater than 1 × 10 ⁶ . Preferably, the particle size distribution of the propylene polymer powder approximates a normal distribution.

According to the invention, the average particle diameter of the propylene polymer is preferably from 20 μm to 180 μm, more preferably from 30 μm to 150 μm; the standard deviation is preferably from 5 μm to 15 μm, more preferably from 6 μm to 12 μm, still more preferably from 8 μm to 10 μm.

According to the invention, the bulk density of the propylene polymer powder is preferably from 0.15 g/mL to 0.35 g/mL.

According to the invention, the agitation mixing time is from 30 minutes to 5 hours. The purpose of the agitation is to enable the reactants to be thoroughly mixed well. In principle, the longer the stirring time, the more favorable the reaction, and the preferred stirring time is from 1 hour to 5 hours.

According to the present invention, the solid phase grafting reaction is carried out at a temperature of from 60 to 140 ° C for a period of from 0.5 to 5 hours. The reaction is preferably carried out at 70 to 120 ° C for 0.5 to 3.5 hours. More preferably, it is reacted at 90 to 110 ° C for 2 to 3 hours.

According to the invention, the propylene polymer is selected from the group consisting of propylene homopolymers, propylene copolymers or mixtures thereof. The comonomer of the propylene copolymer is one or more of α-olefins other than propylene, for example, one, two or three. The α-olefin is, for example, ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene or 1-decene. The copolymer is, for example, a propylene-ethylene copolymer, a propylene-1-butene copolymer or a propylene-ethylene-1-butene terpolymer.

According to the invention, the grafting monomer is a siloxane-based compound or a vinyl-based unsaturated compound.

According to the invention, the vinyl-based unsaturated compound is, for example, a styrene compound, a vinyl-based unsaturated organic acid, a vinyl-based unsaturated organic ester, a vinyl-based unsaturated organic acid anhydride, or a mixture thereof. Preferred are acrylic acid (AA), methacrylic acid (MAA), methyl acrylate (MA), methyl methacrylate (MMA), ethyl acrylate (EA), ethyl methacrylate (MEA), butyl acrylate ( One or more of BA), butyl methacrylate (BMA), maleic anhydride (MAH), maleic acid, styrene (St), and pentaerythritol triacrylate (PETA).

According to the invention, the siloxane-based compound is, for example, vinyltrimethylsilane, vinyltriethylsilane, divinyldimethylsilane, (triethylsilyl)acetylene, allyltrimethyl Silane or the like is preferably one or both of vinyltrimethylsilane and vinyltriethylsilane.

According to the present invention, the graft monomer is added in an amount of 0.2% by weight to 15% by weight, preferably 0.5% by weight to 12% by weight, more preferably 1% by weight to 8% by weight based on the mass of the propylene polymer powder.

According to the invention, the initiator is an azo initiator or a peroxide initiator, preferably one or more of azobisisobutyronitrile, benzoyl peroxide or cumene peroxide. . The initiator is added in an amount of from 0.1% by weight to 10% by weight based on the mass of the propylene polymer powder, preferably from 2% by weight to 9% by weight, more preferably from 3% by weight to 8% by weight.

According to the invention, the interfacial agent is an organic solvent which has a swelling action on the propylene polymer. Preferred are the following organic solvents which have a swelling action on the propylene polymer: an ether solvent, a ketone solvent, an aromatic hydrocarbon solvent or an alkane solvent; more preferably a chlorobenzene, a polychlorinated benzene, a C6 or higher alkane or a cycloalkane , benzene, alkyl substituted benzene, fatty ether, fatty ketone, or decahydronaphthalene; still more preferably benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, diethyl ether, acetone, hexane, cyclohexane, decalin, One or more of heptane. For example, it is xylene or a mixture of xylene and tetrahydrofuran. The interface agent is added in an amount of 0.1 to 30% by weight, preferably 10 to 25% by weight based on the mass of the propylene polymer powder.

A fourth aspect of the present invention provides a grafted propylene polymer prepared by the above method for preparing an ultrahigh molecular weight ultrafine particle size grafted propylene polymer by a solid phase grafting method, wherein the graft monomer is effective The grafting rate is >0.5%; the base polymer is a propylene polymer; the propylene polymer is a powder having a spherical particle shape, an average particle diameter of 10 μm to 200 μm, a standard deviation of 2 μm to 15 μm, and a bulk density of 0.1 g/ mL-0.4 g/mL; the propylene polymer has a viscosity average molecular weight (Mv) of more than 1 × 10 ⁶ .

According to the invention, in particular, the effective graft ratio is from 1.0% to 6.5%, more preferably from 4.0% to 6.5%.

According to the invention, the bulk density of the propylene polymer is preferably from 0.15 g/mL to 0.35 g/mL.

According to the present invention, the siloxane-based compound is, for example, vinyltrimethylsilane, vinyltriethylsilane, Divinyldimethylsilane, (triethylsilyl)acetylene, allyltrimethylsilane or the like is preferably one or both of vinyltrimethylsilane and vinyltriethylsilane.

According to the invention, the grafted propylene polymer has a water contact angle of 90 or less. For example, the water contact angle is 70° to 82°.

A fifth aspect of the present invention provides a glass fiber reinforced propylene polymer composition comprising an ultrahigh molecular weight ultrafine particle size propylene polymer and glass fibers;

The ultrahigh molecular weight ultrafine particle size propylene polymer has a viscosity average molecular weight (Mv) of more than 1×10 ⁶ ; the ultrahigh molecular weight ultrafine particle size propylene polymer is spherical particles, and the average particle diameter is 10 μm to 200 μm. The difference is from 2 μm to 15 μm, and the bulk density is from 0.1 g/mL to 0.4 g/mL.

Preferably, the particle size distribution of the ultrahigh molecular weight ultrafine particle size propylene polymer approximates a normal distribution.

According to the present invention, the ultrahigh molecular weight ultrafine particle size propylene polymer is a propylene homopolymer or a propylene copolymer, and the comonomer in the propylene copolymer is a C _2-20 alpha olefin such as ethylene or 1-butyl. One or more of alkene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-decene, 1-undecene or 1-dodecene . Preferably, the comonomer is one or both of ethylene and 1-butene. The comonomer has a molar percentage of from 0 to 10 mol%, preferably from 0 to 5 mol%.

According to the present invention, the ultrahigh molecular weight ultrafine particle size propylene polymer has a viscosity average molecular weight (Mv) of 1.5 × 10 ^{6 or more} , preferably 1.5 × 10 ⁶ to 4.0 × 10 ⁶ ; The molecular weight distribution Mw/Mn of the particle size propylene polymer is 2 to 15, preferably 3 to 10, and more preferably 4 to 8.

According to the present invention, the ultrahigh molecular weight ultrafine particle size propylene polymer preferably has an average particle diameter of from 20 μm to 180 μm, more preferably from 30 μm to 150 μm, still more preferably from 40 to 120 μm; and the standard deviation is preferably from 5 μm to 15 μm. More preferably, it is 6 μm to 12 μm, and further preferably 8 μm to 10 μm; the bulk density of the ultrahigh molecular weight ultrafine particle size propylene polymer is preferably from 0.15 g/mL to 0.35 g/mL, and further preferably from 0.2 g/mL to 0.3. g/mL.

According to the invention, the glass fibers are glass fibers treated with a coupling agent. The coupling agent is, for example, a silane coupling agent (such as γ-aminopropyltriethoxysilane KH550, γ-(2,3-epoxypropoxy)propyltrimethoxysilane KH560, γ-methyl propylene. Acyloxypropyltrimethoxysilane KH570, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane KH792, N-(β-aminoethyl)-γ-aminopropylmethyldi Methoxysilane DL602, vinyl trimethoxysilane A-171, vinyl triethoxysilane A-151, etc.), titanate coupling agent (such as tris(dioctyl pyrophosphoryloxy) titanic acid One or more of isopropyl ester, bis(dioctylphosphoryloxy) titanate, ethylene diisostearyl titanate or an aluminate coupling agent. Preferably, the coupling agent is selected from a silane coupling agent, and particularly preferably γ-aminopropyltriethoxysilane KH550, vinyltrimethoxysilane A-171, vinyltriethoxysilane A-151, etc. . Further, in order to better disperse the glass fibers in the coupling agent, a diluent may be added to the system of the glass fibers and the coupling agent, for example, selected from white oil or liquid paraffin. The weight ratio of the diluent to the coupling agent is, for example, (1 to 10): 1, preferably (3 to 6): 1.

According to the invention, the glass fibers have a length of from 0.5 to 10 mm, for example from 1 to 3 mm, or from 3 to 5 mm, or 5-7mm and so on.

According to the present invention, the weight percentage of each component in the composition is 10 to 95% by weight of the ultrahigh molecular weight ultrafine particle size propylene polymer and 5 to 90% by weight of the glass fiber. Preferably, the glass fiber is contained in an amount of 10 to 80% by weight, more preferably 40 to 70% by weight.

A sixth aspect of the invention provides a sheet or tube prepared from the above composition.

A seventh aspect of the present invention provides a method for producing the above-mentioned sheet, comprising the steps of: uniformly mixing the ultrahigh molecular weight ultrafine particle size propylene polymer and the glass fiber in a high speed mixer, and adding and extruding In the machine, the sheet of the present invention is obtained by extrusion through a sheet die, cooling and stretching.

An eighth aspect of the present invention provides a method for producing the above tube, comprising the steps of: uniformly mixing the ultrahigh molecular weight ultrafine particle size propylene polymer and the glass fiber in a high speed mixer, and adding the extruder The tube of the present invention is obtained by extrusion through a pipe mold, cooling, and stretching.

Preferably, the tube has a wall thickness of between 0.1 mm and 10 mm, preferably between 0.5 mm and 5 mm.

A ninth aspect of the present invention provides a use of the above sheet, which can be used in many fields such as automobiles, electronic devices, and the like.

A tenth aspect of the present invention provides a use of the above pipe for use in water supply drainage, oil drilling, and the like, for example, as a water supply drain pipe or a mine wear pipe.

An eleventh aspect of the present invention provides a method for producing a solubilized ultrahigh molecular weight ultrafine particle size propylene polymer selected from one of the methods (1) or (2): the method (1) ) includes the following steps:

(1a) under the action of a catalyst and a dispersion medium, propylene or propylene and a comonomer are polymerized, wherein the polymerization temperature is 30-105 ° C, the volume fraction of the propylene is 98% or more;

(1b) after the end of the polymerization of the step (1a), adding a solvent, and then removing the dispersion medium by fractional distillation to obtain the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer;

The method (2) comprises the following steps:

(2a) under the action of a catalyst, a dispersion medium and a solvent, a polymerization reaction of propylene or propylene with a comonomer, wherein the polymerization temperature is 30-105 ° C, and the volume fraction of the propylene is 98% or more;

(2b) after the completion of the polymerization in the step (2a), the dispersion medium is removed by fractional distillation to obtain the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer;

In the above method (1) or method (2), the boiling point of the dispersion medium is lower than the boiling point of the solvent and at least 5 ° C lower;

In the above method (1) or method (2), the catalyst is prepared by the method for preparing the above catalyst.

In the present invention, the polymer obtained by the polymerization of propylene and the polymer obtained by polymerizing propylene and a comonomer are collectively referred to as a propylene polymer.

According to the present invention, the propylene polymer obtained has a viscosity average molecular weight (Mv) of more than 1 × 10 ⁶ ; the propylene polymer is spherical particles, an average particle diameter of 10 μm to 200 μm, a standard deviation of 2 μm to 15 μm, and a bulk density. It is 0.1 g/mL to 0.4 g/mL; the weight percentage of the solvent in the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer is more than 0 and less than or equal to 98% by weight.

According to the present invention, the weight percentage of the solvent in the propylene polymer is more than 0 and less than or equal to 80% by weight, preferably more than 0 and less than or equal to 50% by weight, more preferably from 10 to 50% by weight, still more preferably from 20 to 40% by weight. .

According to the invention, the particle size distribution of the propylene polymer approximates a normal distribution.

In the above preparation method, the polymerization reaction is carried out by a slurry method.

In the above preparation method, the dispersion medium may be at least one of n-pentane, cyclohexane, benzene, toluene, xylene, n-hexane, n-heptane, petroleum ether and the like.

In the above preparation method, the solvent may be cyclohexane, n-hexane, n-heptane, benzene, toluene, xylene, dichlorobenzene, trichlorobenzene, 1,1,1-trichloroethane, white oil. At least one of paraffin, kerosene, olefin mineral oil and decalin.

According to the invention, the temperature of the polymerization reaction is preferably from 40 to 80 ° C, more preferably from 50 to 75 ° C.

According to the invention, the volume fraction of propylene is 99% or more, preferably 99.2% or more, further preferably 99.5% or more, more preferably 99.8% or more, still more preferably 99.9% or more.

According to a twelfth aspect of the present invention, there is provided a solubilized ultrahigh molecular weight ultrafine particle size propylene polymer obtained by the above-described method for preparing a solubilized ultrahigh molecular weight ultrafine particle size propylene polymer, said propylene polymer The viscosity average molecular weight (Mv) is greater than 1×10 ⁶ ; the propylene polymer is spherical particles having an average particle diameter of 10 μm to 200 μm, a standard deviation of 2 μm to 15 μm, and a bulk density of 0.1 g/mL to 0.4 g/mL; The weight percentage of the solvent in the propylene polymer is more than 0 and less than or equal to 98% by weight.

According to the present invention, the propylene polymer has a viscosity average molecular weight (Mv) of more than 1.5 × 10 ⁶ , preferably 1.5 × 10 ⁶ to 4.0 × 10 ⁶ ; and the molecular weight distribution Mw / Mn of the propylene polymer is 2 to 15 It is preferably 3 to 10, and more preferably 4 to 8.

According to the invention, the average particle diameter of the propylene polymer is preferably from 20 μm to 180 μm, more preferably from 30 μm to 150 μm, still more preferably from 40 to 120 μm; the standard deviation is preferably from 5 μm to 15 μm, more preferably from 6 μm to 12 μm, It is also preferably from 8 μm to 10 μm; the bulk density of the propylene polymer is preferably from 0.15 g/mL to 0.35 g/mL, and more preferably from 0.2 g/mL to 0.3 g/mL.

According to a thirteenth aspect of the invention, there is provided a fiber comprising a solubilized ultrahigh molecular weight ultrafine particle size propylene polymer as described above.

According to the invention, the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer is obtained by a production method selected from one of the above methods (1) or (2).

According to the invention, in addition to the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer, the raw material further includes an antioxidant. Preferably, the antioxidant is added in an amount of 0.01 to 1 part by weight, more preferably 0.02 to 0.5 part by weight, per 100 parts by weight of the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer. Specifically, the fiber is obtained from the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer containing an antioxidant.

A fourteenth aspect of the present invention provides a method of producing the above fiber, comprising the steps of:

1) dissolving a raw material containing the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer in a solvent to obtain a spinning solution or gel; 2) spinning by a jelly spinning method to obtain a gel fiber; Drawing; producing the fiber.

According to the invention, in step 1), in order to avoid degradation of the ultrahigh molecular weight propylene polymer during dissolution and use, an antioxidant is added during the dissolution process. The amount of the antioxidant added is 0.01 to 1 part by weight, more preferably 0.02 to 0.5 part by weight, per 100 parts by weight of the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer.

In one embodiment, prior to the drawing step of step 3), the step of extracting the solvent by a coagulant or an extractant is included. Preferably, the coagulant or extractant is selected from a low boiling organic solvent such as one or more of the following low boiling organic solvents: petroleum ether, dichloromethane, cyclohexane, and the like.

Wherein, the drafting in the step 3) is carried out by a hot box or a hot roll, or a hot bath drawing method may be employed.

For the heat bath drawing mode therein, preferably, the hot bath medium used is selected from the group consisting of a polyol (preferably having a boiling point of 120-220 ° C) and a polyoxyethylene oligomer (preferably, a relative molecular weight of 88-5000 g/mol). a polyoxypropylene oligomer (preferably, having a relative molecular weight of 116 to 1200 g/mol), one or more components of mineral oil and silicone oil. Preferably, the hot bath medium temperature T _{L is} set between the glass transition temperature T _g of the polymer matrix and the decomposition temperature T _{d of the} polymer matrix.

In another embodiment, the step 3) is specifically: the gel fiber is subjected to gel wire drawing, solvent extraction, drying, first hot box dry heat drawing, and second hot box dry heat drawing. The fiber of the present invention is obtained by a process such as heat setting and winding.

The drawing temperature in the gel yarn drawing step is 10 to 70 ° C, preferably 25 to 50 ° C; and the draw ratio is 2 to 20 times, preferably 3 to 15 times.

The extractant in the solvent extraction step is selected from a low boiling organic solvent, for example, one or more of the following low boiling organic solvents: petroleum ether, dichloromethane, cyclohexane, and the like.

Among them, the drying in the drying step is dried by hot air, and the hot air temperature is 40 to 100 ° C, preferably 50 to 80 ° C.

Wherein, the temperature in the first hot box dry heat drawing process is 100-200 ° C, preferably 130-180 ° C; the draw ratio is 1-20 times, preferably 1.5-15 times.

Wherein, the temperature in the dry heat drawing step of the second hot box is 110-200 ° C, preferably 130-180 ° C; the draw ratio is 1-5 times, preferably 1.1-3 times.

Among them, the temperature in the heat setting step is 100 to 180 ° C, preferably 120 to 150 ° C.

According to a fifteenth aspect of the invention, there is provided a film comprising, in the raw material, a solubilized ultrahigh molecular weight ultrafine particle size propylene polymer as described above.

According to the invention, in addition to the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer, the raw material further includes an antioxidant. Preferably, the antioxidant is added in an amount of 0.01 to 1 part by weight, more preferably 0.02 to 0.5 part by weight, per 100 parts by weight of the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer. Specifically, the film is prepared from the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer containing an antioxidant.

According to the invention, the film is uniaxially stretched or biaxially stretched. Preferably, the film is biaxially stretched.

A sixteenth aspect of the invention provides a method for producing the above film, comprising the steps of: 1) melting a raw material containing the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer and a solvent for film formation; Mixing to obtain a solution; 2) extruding the solution, forming a shaped body, cooling to obtain a polymer sheet; 3) uniaxial stretching or biaxial stretching to obtain a film.

According to the invention, in step 1), in order to avoid degradation of the ultrahigh molecular weight propylene polymer during dissolution and use, an antioxidant is added during the dissolution process. The amount of the antioxidant added is 0.01 to 1 part by weight, more preferably 0.02 to 0.5 part by weight, per 100 parts by weight of the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer. Specifically, the raw material is composed of the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer and an antioxidant.

A seventeenth aspect of the invention provides the use of a film of the invention for use as a battery separator.

The beneficial effects of the invention:

1. The present invention provides a novel method for preparing ultrahigh molecular weight ultrafine particle size propylene polymer powder, wherein a super method is synthesized by controlling polymerization temperature, monomer purity and adjusting catalyst preparation steps. The high molecular weight ultrafine particle size propylene polymer powder has simple method, easy control and high repeatability, and can be industrialized.

The present invention synthesizes a propylene polymer powder having both an ultrahigh molecular weight and an ultrafine particle size range for the first time. It has been found that a powder having the above characteristics is particularly suitable for processing applications, and is easy to realize graft modification. The application field and scope of application of ultrahigh molecular weight propylene polymers have been greatly expanded. At the same time, the propylene polymer powder also has the following excellent properties: firstly, the wear resistance is excellent, and the wear resistance index of the metal such as carbon steel and copper is several times higher; secondly, due to the high molecular weight, the molecule The chain is extremely long, which makes the impact strength of the material high; again, the chemical resistance of the propylene polymer powder is stronger than that of the general polyolefin; finally, the material has a wide temperature range of use, at a lower or higher temperature. Both maintain good toughness and strength.

2. The present invention provides a graft modified ultrahigh molecular weight ultrafine particle size propylene polymer and a solid phase grafting method thereof. First, compared with the prior art, the selected reaction substrate is ultrahigh molecular weight ultrafine particle size. a propylene polymer powder (in the form of spherical particles having an average particle diameter of 10 μm to 200 μm, a standard deviation of 2 μm to 15 μm, a bulk density of 0.1 g/mL to 0.4 g/mL, and a viscosity average molecular weight of more than 1 × 10 ⁶ ), Compared with common propylene polymer particles (greater than 500 microns), the particle size is smaller, the molecular weight is higher, the specific surface area is greatly increased, and the grafting monomer has more reaction sites, thus preparing the grafted propylene polymer. Has a higher effective graft ratio. Secondly, this method does not require complex pretreatment of the raw materials and design of specific reaction equipment compared to other methods of preparing high graft ratio graft polymers. Finally, the method for preparing a high graft ratio grafted propylene polymer by solid phase grafting provided by the invention has the advantages of simple process, low cost, simple operation and easy industrialized production.

The experimental results show that the grafted propylene polymer prepared by the method provided by the invention has obvious improvement in thermal properties, mechanical properties and polarity, and maintains the original excellent performance of the propylene polymer. The crystallization temperature of the grafted propylene polymer is increased by 8 ° C; the effective graft ratio is more than 0.5% (for example, 4.0% or more); the water contact angle of the grafted propylene polymer is 90 or less (for example, 70 ° to 82) °), and the water contact angle of the base polymer is generally 96 or more, and it is seen that the hydrophilicity and polarity of the grafted propylene polymer of the present invention are remarkably improved.

3. The present invention provides a glass fiber reinforced propylene polymer composition, the sheet or tube prepared from the composition having excellent low temperature resistance (for example, long-term use at minus 30 ° C to minus 175 ° C), Impact resistance (such as simple beam notched impact strength (7.5J) is higher than 10.0KJ/m ² ) and creep resistance (such as creep less than or equal to 2.5%). In addition, the mechanical properties (such as bending strength, flexural modulus, tensile strength, heat distortion temperature, etc.) of the sheet or tube are also excellent 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, electronic devices, and the like, and the tube is particularly suitable for the fields of water supply and drainage, oil drilling, and the like.

4. The present invention provides a novel process for preparing a solubilized ultrahigh molecular weight ultrafine particle size propylene polymer by controlling the polymerization temperature, monomer purity, adjusting the preparation steps of the catalyst, and introducing into the polymerization system. Dispersing medium, synthesizing a solubilized ultra-high molecular weight ultra-fine particle size propylene polymer, the method is simple, easy to control, high repeatability, and can be industrialized.

The present invention synthesizes a propylene polymer having both a solubilizing, ultrahigh molecular weight and ultrafine particle size range for the first time. It has been found that a polymer having the above characteristics is particularly suitable for processing applications, and is easy to realize graft modification. It greatly expands the processing properties of ultra-high molecular weight propylene polymers and the application fields and application scope of the products. At the same time, the propylene polymer also has the following excellent properties: firstly, the wear resistance is excellent, and the wear resistance index of the metal such as carbon steel and copper is several times higher; secondly, the molecular chain is extremely long due to the high molecular weight. Make material The impact strength of the material is high; again, the chemical resistance of the propylene polymer is stronger than that of the general polyolefin; again, the material has a wide temperature range and maintains good toughness at lower or higher temperatures. And strength; finally, the material has low energy consumption during post-forming, film formation, fiber forming, and short process time (for example, complete dissolution at lower temperatures, or rapid dissolution at higher temperatures and shorter times) Thereby effectively reducing or reducing polymer degradation while shortening the dissolution process).

5. The fiber of the present invention uses a solubilized ultrahigh molecular weight ultrafine particle size propylene polymer as a raw material, and the propylene polymer is particularly suitable for processing applications because it is easy to dissolve and has a low dissolution temperature, and is particularly suitable for use in the fiber. Solution or gel jelly spinning of fibers.

The fiber of the present invention has excellent creep resistance due to the use of the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer as a raw material, and has a wide temperature range (suitable for low temperature use and high temperature). Use of temperature).

6. A solubilized ultrahigh molecular weight ultrafine particle size propylene polymer is selected as a raw material in the film of the present invention, and the ultrahigh molecular weight of the raw material brings about a great improvement in product properties and a solvent contained in the raw material. The degree of crystallization of the propylene polymer is limited, so that the propylene polymer is easily melted and dissolved at a lower temperature during processing, and the problem that the conventional ultrahigh molecular weight propylene polymer is easily degraded during processing is inhibited, and is particularly suitable for processing applications. It is especially suitable for hot pressing and drawing processing of the film.

The film of the present invention has excellent creep resistance due to the use of the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer as a raw material, and has a wide temperature range (suitable for low temperature use and high temperature). Use of temperature).

DRAWINGS

Figure 1 is an infrared spectrum of maleic anhydride grafted polypropylene of Example 2.1.

detailed description

[Preparation method of catalyst]

The catalyst used in the preparation method of the present invention can be prepared by the method disclosed in the applicant's already filed patent application (Application No. 201510271254.1), which is incorporated herein by reference in its entirety.

As described above, in the preparation method of the ultrahigh molecular weight ultrafine particle size propylene polymer powder and the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer in the present invention, the catalyst used includes a method comprising the following steps preparation:

(c) After the completion of the dropwise addition, the reaction system is heated to 90 ° C to 130 ° C over 30 minutes to 3 hours, and the remainder is added. The internal electron donor continues to react;

(e) After completion of the reaction, the catalyst is obtained by post treatment.

According to the invention, said step (b) is replaced by the following step (b'):

(b') configuring a mixture comprising nanoparticles, a dispersant, and a solvent II;

Adding the above mixture I and mixture II to the reactor to obtain a mixture of the two, preheating to -30 ° C to 30 ° C, dropping titanium compound; or

A titanium compound was added to the reactor, preheated to -30 ° C to 30 ° C, and a mixture of the above mixture I and mixture II was added dropwise.

In the present invention, the mixture I is preferably prepared by mixing a magnesium halide and an alcohol compound in an organic solvent, heating and maintaining the temperature, and then adding an auxiliary agent and a part of the internal electron donor to obtain a reaction at a certain temperature. Stable homogeneous mixture I.

The alcohol compound is selected from one or more of a C ₁ -C ₁₅ fatty alcohol compound, a C ₃ -C ₁₅ cycloalkanol compound, and a C ₆ -C ₁₅ aromatic alcohol compound, preferably Methanol, ethanol, ethylene glycol, n-propanol, isopropanol, 1,3-propanediol, butanol, isobutanol, hexanol, heptanol, n-octanol, isooctanol, decyl alcohol, decyl alcohol, sorbitol One or more of an alcohol, cyclohexanol and benzyl alcohol, more preferably ethanol, butanol, hexanol and isooctanol.

The internal electron donor is at least one of a monoester, a diester, a monoether, and a diether compound, and more preferably a diester or a diether. Specifically selected from the group consisting of: aromatic carboxylic acid diesters, 1,3-diethers, malonic esters, succinates, glutarates, glycol esters, such as: diisobutyl phthalate, phthalic acid Di-n-butyl formate, 1,3-diether, 9,9-bis(methoxymethyl)anthracene, di-n-butyl 2-isopropylmalonate, 2-mercaptomalonate Ethyl ester, diethyl 2-methyl-2-isopropylmalonate, diisobutyl diisopropyl succinate, diethyl 2,3-diisopropylsuccinate, β-substituted pentyl Diester, 1,3-diol ester, and the like. The above-mentioned internal electron donors are disclosed in the following patents or applications: CN1453298, CN1690039, EP1840138, CN101423566, CN101423570, CN101423571, CN101423572, CN1986576, CN1986576, CN101125898, CN1891722, WO2007147864, CN1831017, CN101560273, EP 2029637, EP2029642, CN1330086, CN1463990, CN1397568, CN1528793, CN1732671, CN1563112, CN1034548, CN1047302, CN1091748, CN1109067, CN94103454, CN1199056, EP03614941990, EP03614931990, WO002617 and the like.

The solvent is selected from the group consisting of a linear alkane of 5-20 carbons, a branched alkane of 5-20 carbons, an aromatic hydrocarbon of 6-20 carbons or at least one of their halogenated hydrocarbons, preferably toluene, chlorobenzene At least one of dichlorobenzene or decane.

In the present invention, the magnesium halide has a carrier function in the preparation of a catalyst capable of directly obtaining submicron-sized polyolefin particles, and is one of the compositions of the conventional Ziegler-Natta catalyst, and the prepared catalyst can have a suitable shape, The size and mechanical strength, at the same time, the carrier can disperse the active component on the surface of the carrier to obtain a higher specific surface area and improve the catalytic efficiency of the active component per unit mass. In addition, the alcohol compound functions to halogenate the carrier. Magnesium dissolves. In the preparation of the mixture I, the temperature at which the mixed solution is obtained is preferably 110 to 130 ° C, more preferably 130 ° C, and the incubation time is preferably 1 to 3 hours, more preferably 2 to 3 hours. The reaction time after the auxiliary or the like is 0.5 to 2 hours, and more preferably 1 hour. Therefore, the magnesium halide is dissolved by the alcohol compound at a high temperature to obtain a mixture I.

According to the invention, the mixture II is preferably prepared by adding nanoparticles, a dispersant and a solvent to a reaction vessel and sonicating to obtain a homogeneous mixture II. The nanoparticles are preferably at least one of nano silica, nano titanium dioxide, nano zirconium dioxide, nano nickel oxide, nano magnesium chloride or nano carbon spheres, more preferably nano silica, nano titanium dioxide. The particle size of the nanoparticles is preferably from 1 to 80 nm, more preferably from 10 to 50 nm. The mass of the preferred nanoparticles added is from 0% to 200%, more preferably from 0% to 20%, based on the mass of the magnesium halide. The time for sonication is preferably 2 h. In the present invention, nanoparticles are introduced as seed crystals for the purpose of accelerating the formation of the carrier and reducing the particle size of the catalyst particles; dispersants and solvents, including sonication, are all used to assist in the dispersion of the nanoparticles, thus promoting the ability of each of the nanoparticles. Play the role of seed crystals.

According to the present invention, in the mixture II of the step (b'), the nanoparticles are at least one selected from the group consisting of nano silica, nano titanium dioxide, nano zirconium dioxide, nano nickel oxide, nano magnesium chloride or nano carbon spheres. .

Preferably, the nanoparticles have a particle size of from 1 to 80 nm, preferably from 2 to 60 nm, more preferably from 3 to 50 nm.

The addition mass of the nanoparticles is greater than 0% to 200% or less with respect to the mass of the magnesium halide added. Preferably, the amount of the nanoparticles added is in the range of more than 0% to less than or equal to 20%.

In the present invention, in the mixture II of the step (b'), the solvent is selected from the group consisting of a linear alkane of 5-20 carbons, a branched alkane of 5-20 carbons, an aromatic hydrocarbon of 6-20 carbons or At least one of their halogenated hydrocarbons.

The dispersant is selected from the group consisting of titanium tetrachloride, silicon tetrachloride or a mixture of the two.

In the step (a), the mixing is carried out under heating and stirring to obtain a uniformly stable transparent mixture I.

In the step (b'), the ultrasonic dispersion treatment is performed at the time of the arrangement.

In the step (b) or (b'), the dropwise addition is a slow dropwise addition.

In the step (b) or (b'), a preferred reaction preheating temperature is -20 ° C to 30 ° C, and more preferably -20 ° C to 20 ° C.

The reaction time of the step (c) is from 1 to 5 hours, preferably from 2 to 3 hours.

The reaction of the step (d) is continued for 1 to 5 hours, preferably 2 to 3 hours.

The post-treatment in the step (e) may be that the obtained product is washed with hexane and then dried; wherein the number of washings may be 1 to 10 times, preferably 3 to 6 times.

In the step (a), the magnesium halide is at least one selected from the group consisting of magnesium chloride, magnesium bromide or magnesium iodide.

In the step (a), the auxiliary agent may be a titanate compound.

In the step (b) or (b'), the formula of the titanium compound is as shown in the formula I:

Ti(R) _n X _(4-n) Formula I

Wherein R is a branched or linear alkyl group of C ₁ -C ₁₂ , X is a halogen, and n is 0, 1, 2 or 3.

In the step (d), preferably, the reaction system is heated to 90 to 130 ° C over a period of from 40 minutes to 3 hours, and more preferably, the reaction system is heated to a temperature of from 100 ° C to 120 ° C over a period of from 40 minutes to 2 hours.

It can be seen from the above scheme that the preparation method of the Ziegler-Natta catalyst according to the present invention is simple in process and easy to industrialize. Moreover, the Ziegler-Natta catalyst prepared by the invention can produce an average particle diameter of 10 μm-200 μm when propylene is polymerized, has a high sphericity, a narrow particle size distribution, and a low bulk density (0.1-0.4 g/mL). ) propylene polymer particles. It has been found through research that the catalyst prepared by the invention is used for the polymerization of propylene polymer to obtain a propylene polymer having a particle size reduction of 20-30 times compared with other particles, a narrow particle size distribution and a bulk density as low as 0.1 g/ mL.

[Preparation method of ultrahigh molecular weight ultrafine particle size propylene polymer powder]

As described above, the present invention provides a method for preparing an ultrahigh molecular weight ultrafine particle size propylene polymer powder, which comprises the steps of: polymerizing propylene or propylene with a comonomer under the action of a catalyst, wherein The temperature of the polymerization reaction is 30-105 ° C, and the volume fraction of the propylene is 98% or more;

The catalyst is prepared by the above-described method for preparing a catalyst.

The invention has found through research that the method for preparing the catalyst can be controlled simply, and the particle size control of the powder can be well realized, but the molecular weight of the prepared propylene polymer is not high, and the particle size is controlled to achieve the same. The inventors have made many attempts to determine the molecular weight of the polymer. It has been found that controlling the temperature of the polymerization reaction and the purity of the monomer is a simple and effective method, and does not affect the particle size of the polymer. Effective control and even help to prepare polymers with a narrower particle size range and lower bulk density range.

It has been found through research that the temperature of the polymerization reaction is controlled at 30-105 ° C, and the volume fraction of propylene is controlled to be 98% or more, and the ultra-high molecular weight propylene polymer can be prepared while controlling the particle diameter. Further preferably, the temperature of the polymerization reaction is 40 to 80 °C. Further preferably, the volume fraction of the propylene is 99% or more; still more preferably, 99.8% or more; still more preferably, 99.9% or more. For copolymerization, it is also advantageous to achieve the object of the present invention to control the comonomer to have a carbon monoxide content of less than 5 ppm, a carbon dioxide of less than 15 ppm, and a conjugated diene content of less than 10 ppm.

In the present invention, the propylene volume fraction is determined by the standard GB/T 3392. The propylene volume fraction is an important indicator of the purity of the propylene monomer.

[Ultra high molecular weight ultrafine particle size propylene polymer powder]

As described above, the present invention provides an ultrahigh molecular weight ultrafine particle size propylene polymer powder.

The ultrahigh molecular weight propylene polymer having the particle size and the bulk density is particularly suitable for graft modification, and on the one hand, greatly expands the modification space of the propylene polymer; on the other hand, the processing property of the polymer is remarkable Improved, suitable for the preparation of a wider range of articles; thus, the field of application of the polymer is effectively expanded.

The ultrahigh molecular weight ultrafine particle size propylene polymer powder of the invention also has the following excellent properties: firstly, the wear resistance is excellent, and the wear resistance index of the metals such as carbon steel and copper is several times higher; secondly, Due to molecular weight High, the molecular chain is extremely long, which makes the impact strength of the material high; again, the chemical resistance of the propylene polymer powder is stronger than that of the general polyolefin; finally, the temperature range of the material is wider, lower or higher. It maintains good toughness and strength at all temperatures.

[Preparation of high graft ratio grafted propylene polymer by solid phase grafting]

As described above, the present invention provides a method for preparing an ultra-high molecular weight ultra-fine particle size grafted propylene polymer by solid phase grafting.

In a preferred embodiment of the present invention, the grafted propylene polymer is prepared by adding an average particle diameter of a viscosity average molecular weight (Mv) of more than 1 × 10 ⁶ in a container of 10 to 200 μm (preferably 20 to 180 μm, more preferably 30 to 150 μm, standard deviation is 2 μm to 15 μm (preferably 5 μm to 15 μm, more preferably 6 μm to 12 μm, still more preferably 8 μm to 10 μm), and bulk density is 0.1 g/mL. 0.4 g/mL (preferably 0.15 g/mL to 0.35 g/mL) of propylene polymer powder; an azo initiator or a peroxy compound initiator (for example, benzoyl peroxide) is added in an amount of propylene 0.1 to 10% by weight (preferably 2 to 9% by weight, more preferably 3 to 8% by weight) based on the mass of the polymer powder; and a grafting monomer selected from a siloxane compound or a vinyl-based unsaturated compound, The vinyl unsaturated compound is, for example, a styrene compound, a vinyl unsaturated organic acid, a vinyl unsaturated organic ester, a vinyl unsaturated organic acid anhydride or a mixture thereof, more preferably acrylic acid (AA), Malay. One or more of anhydride (MAH), methyl methacrylate (MMA), styrene (St), The siloxane-based compound is, for example, vinyltrimethylsilane, vinyltriethylsilane, divinyldimethylsilane, (triethylsilyl)acetylene, allyltrimethylsilane, or the like, preferably One or both of vinyltrimethylsilane and vinyltriethylsilane. The amount added is 0.2 wt% to 15 wt% (preferably 0.5 wt% to 12 wt%, more preferably 1-8 wt%) of the mass of the propylene polymer powder; the interface agent is added to be benzene, toluene, xylene, tetrahydrofuran, diethyl ether One or more of acetone, hexane, heptane, more preferably one or more of toluene, xylene, tetrahydrofuran, diethyl ether, acetone, such as xylene, or a mixture of xylene and tetrahydrofuran, The amount added is 0.1 to 30% by weight (preferably 10 to 25% by weight) based on the mass of the propylene polymer powder. After the raw materials are added, high-speed mechanical stirring is carried out, and the stirring time is related to the efficiency of the stirring paddle. The purpose of the stirring is to uniformly mix the reactants, to make the grafting reaction more fully, and to reduce the occurrence of self-polymerization of the grafting monomer. Therefore, the stirring time is uncertain, and is generally from 30 minutes to 5 hours, preferably from 1 hour to 5 hours. The solid phase grafting reaction is carried out by heating, and the grafting reaction conditions are carried out at 60 to 140 ° C for 0.5 to 5 hours, preferably at 70 to 120 ° C for 0.5 to 3.5 hours, more preferably at 90 to 110 ° C for 2 to 3 hours. Grafting reaction. At the end of the reaction, the product is a grafted propylene polymer having a high graft ratio.

[Preparation method of solubilized ultrahigh molecular weight ultrafine particle size propylene polymer]

As described above, the present invention provides a process for preparing a solubilized ultrahigh molecular weight ultrafine particle size propylene polymer.

The present invention has found through research that the control method of the catalyst can be easily controlled, and the particle size of the polymer can be well controlled, but the molecular weight of the prepared propylene polymer is not high, and the particle size is controlled to achieve the same. The inventors have made many attempts to determine the molecular weight of the polymer. The temperature and monomer purity are a simple and effective method and do not affect the effective control of the particle size of the polymer, and even help to prepare polymerizations in a narrower particle size range and lower bulk density range. Things.

It has been found through research that the temperature of the polymerization reaction is controlled at 30-105 ° C, and the volume fraction of propylene is controlled to be 98% or more, and the ultra-high molecular weight propylene polymer can be prepared while controlling the particle diameter. Further preferably, the temperature of the polymerization reaction is 40 to 80 ° C, and more preferably 50 to 75 ° C. Further preferably, the volume fraction of the propylene is 99% or more; preferably 99.2% or more, further preferably 99.5% or more, still more preferably 99.8% or more; still more preferably 99.9% or more. For copolymerization, it is also advantageous to achieve the object of the present invention to control the comonomer to have a carbon monoxide content of less than 5 ppm, a carbon dioxide of less than 15 ppm, and a conjugated diene content of less than 10 ppm.

In addition, in order to further improve the processability of the ultrahigh molecular weight ultrafine particle size propylene polymer, a means for solubilization is further introduced in the present invention, that is, the present invention introduces a solvent and/or in the process of preparing a propylene polymer. Or dispersion medium, the presence of these small molecules makes the crystal size of the obtained propylene polymer greatly reduced, the molecular chain is more mobile, and the heat is more easily transferred in the subsequent dissolution or melt processing of the product, so that the obtained propylene The polymer can be rapidly dissolved or melted at a lower temperature, thereby shortening the process, and further reducing the dissolution or melting temperature can also significantly reduce the degradation of the propylene polymer, which is very important for ensuring its molecular weight and obtaining high performance propylene polymer products. The essential.

[Soluble-type ultrahigh molecular weight ultrafine particle size propylene polymer]

As described above, the present invention provides a solubilized ultrahigh molecular weight ultrafine particle size propylene polymer.

At the same time, the propylene polymer of the present invention has the following excellent properties: firstly, the wear resistance is excellent, and the wear resistance index of the metal such as carbon steel and copper is several times higher; secondly, the molecular chain is super high, the molecular chain Ultra-long, the impact strength of the material is high; again, the chemical resistance of the propylene polymer is stronger than that of the general polyolefin; again, the material has a wide temperature range and can be maintained at lower or higher temperatures. Good toughness and strength; finally, the material has low energy consumption and short process time in the process of forming, film forming and fiber forming.

[Fiber and preparation method thereof]

As described above, the present invention provides a fiber and a method of preparing the same.

In a preferred embodiment of the present invention, the solution jelly spinning method is exemplified, and the method specifically comprises the steps of: mixing a solubilized ultrahigh molecular weight ultrafine particle size propylene polymer with a solvent to obtain a mixture; The spinning solution is obtained by twin-screw dissolution extrusion (preferably, the temperature of the dissolution extrusion is 120-270 ° C, preferably 150-240 ° C); the spinning solution is directly extruded through a twin-screw, and is spun. Assembly, spinneret extrusion, Cooling bath (for example, a cooling water bath; preferably, the water bath temperature is 0-15 ° C, preferably 2-10 ° C) to obtain a gel fiber; the gel fiber is subjected to gel wire drawing, solvent extraction, drying, and A heat box dry heat drawing, a second hot box dry heat drawing, heat setting and winding, etc., obtain the fiber of the present invention.

The solvent in the mixture is, for example, decalin, white oil or the like.

Further, the mixture has a polymer content of from 3 to 20% by weight, preferably from 5 to 15% by weight. Further, an antioxidant is further added to the mixture, and preferably, the antioxidant is added in an amount of 0.01 to 1 part by weight, more preferably 0.02 to 0.5 part by weight, per 100 parts by weight of the propylene polymer. The antioxidant is an antioxidant for a propylene polymer known in the art, and the antioxidant is composed of a primary antioxidant and a secondary antioxidant, and the primary antioxidant is selected. The self-blocking phenolic antioxidant is selected from the group consisting of thiodipropionic acid diester or phosphite. The hindered phenolic antioxidants are some phenolic compounds with steric hindrance, and their anti-oxidation effects are remarkable, and they do not pollute the products; there are many varieties of such antioxidants, mainly: 2,6-di-tert-butyl 4-methylphenol, bis(3,5-di-tert-butyl-4-hydroxyphenyl) sulfide, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid 〕 pentaerythritol ester and the like. The thiodipropionic acid diester is a kind of auxiliary antioxidant, and is often used together with a hindered phenolic antioxidant, and the effect is remarkable, such as: bisdithiolactyl thiodipropionate, thiodipropionic acid double Tetradecanol ester or bis-octadecyl thiodipropionate. The phosphites are also auxiliary antioxidants, mainly including trioctyl phosphite, tridecyl phosphite, tris(dodecanol) phosphite, and tris(hexadecanol) phosphite.

In the process step of processing the gel fiber into a fiber, the drawing temperature of the gel yarn is 10-70 ° C, preferably 25-50 ° C; the draw ratio is 2-20 times, preferably 3-15 times. The extracting agent is selected from low boiling point extracting agents such as dichloromethane, petroleum ether and cyclohexane. The drying is dried by hot air, and the hot air temperature is 40 to 100 ° C, preferably 50 to 80 ° C. The first hot box has a dry heat drawing temperature of 100 to 200 ° C, preferably 130 to 180 ° C; and a draw ratio of 1 to 20 times, preferably 1.5 to 15 times. The second hot box has a dry heat drawing temperature of 110 to 200 ° C, preferably 130 to 180 ° C; and a draw ratio of 1-5 times, preferably 1.1-3 times. The heat setting temperature is 100-180 ° C, preferably 120-150 ° C.

The fiber of the present invention has excellent mechanical properties and creep resistance, and also has a wide temperature range of use. Specifically, the fiber of the present invention has the following properties: a fineness (dtex) of more than 3.3 (for example, may be 3.6), fracture The strength is greater than or equal to 1.50 GPa (for example, 1.50-2.10 GPa), the modulus is 35 GPa or more (for example, 35-40 GPa), the elongation at break is 2.5-5.0%, and the creep is less than 2% (for example, 1.7% to 1.9%). The crystallinity is 80%-87%, the melting point is 174.5 ° C-180.5 ° C, and the use temperature ranges from -30 ° C to 175 ° C.

[Film and preparation thereof]

As described above, the present invention provides a film and a method of preparing the same.

In a preferred embodiment of the present invention, the melt-kneading in the step (1) is carried out by a twin-screw extruder, and melt-kneading by a twin-screw extruder is well known and will not be described in detail herein. The weight percentage of the propylene polymer in the solution is from 20 to 50% by weight, preferably from 30 to 40% by weight. The solvent for film formation may be cyclohexane, n-hexane, n-heptane, decane, decane, undecane, dodecane, benzene, toluene, xylene, dichlorobenzene, trichlorobenzene, 1, At least one of 1,1-trichloroethane, white oil, liquid paraffin, kerosene, olefin mineral oil, and decalin. The temperature of the melt-kneading varies depending on the polymer and the solvent, and is generally in the range of 130 to 280 °C.

In a preferred embodiment of the present invention, the step (2) is specifically: the solution of the step (1) is supplied to a mold through an extruder, and the solution is extruded from the mold to form a molded body (such as a sheet). After cooling by a cooling drum, a polymer sheet was obtained. The surface temperature of the cooling drum is set to 20 to 40 ° C, and the cooling rate of the molded body through the cooling drum is 20 ° C / s or more.

In a preferred embodiment of the present invention, the stretching in the step (3) means that the polymer sheet of the step (2) is oriented in the transverse direction by a usual tenter method, a drum method or a combination thereof. Stretching is performed at a certain magnification (transverse stretching ratio and longitudinal stretching ratio) in both directions of TD) and the machine direction (machine direction, MD). In the present invention, the transverse stretching ratio and/or the longitudinal stretching ratio are preferably 5 to 6 times, and in the case of biaxial stretching, preferably, the transverse stretching ratio is the same as the longitudinal stretching ratio.

Further, in the raw material, the polymer content is from 3 to 20% by weight, preferably from 5 to 15% by weight. Further, an antioxidant is further added to the raw material. Preferably, the antioxidant is added in an amount of from 0.01 to 1 part by weight, more preferably from 0.02 to 0.5 part by weight, per 100 parts by weight of the propylene polymer. The antioxidant is an antioxidant for a propylene polymer known in the art, and the antioxidant is composed of a primary antioxidant and a secondary antioxidant, and the primary antioxidant is selected. The self-blocking phenolic antioxidant is selected from the group consisting of thiodipropionic acid diester or phosphite. The hindered phenolic antioxidants are some phenolic compounds with steric hindrance, and their anti-oxidation effects are remarkable, and they do not pollute the products; there are many varieties of such antioxidants, mainly: 2,6-di-tert-butyl 4-methylphenol, bis(3,5-di-tert-butyl-4-hydroxyphenyl) sulfide, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid 〕 pentaerythritol ester and the like. The thiodipropionic acid diester is a kind of auxiliary antioxidant, and is often used together with a hindered phenolic antioxidant, and the effect is remarkable, such as: dicodipropionate, thiodipropionate, thiodipropionate Tetradecanol ester or bis-octadecyl thiodipropionate. The phosphites are also auxiliary antioxidants, mainly including trioctyl phosphite, tridecyl phosphite, tris(dodecanol) phosphite, and tris(hexadecanol) phosphite.

[Measurement of performance and parameters]

The properties of the sheets and tubes of the present invention are determined by measurement methods in well-known standards. For example, the creep resistance is measured by the Chinese national standard GB11546-89 and ISO899-1981. Impact resistance, measured by GB/T1043.1-2008. Flexural strength and flexural modulus were measured by GB/T9341-2008. Tensile strength, measured by GB/T1040-2006. The heat distortion temperature was measured by GB/T1634.2-2004.

Characterization method of the grafted propylene polymer of the invention:

Infrared characterization of grafted polymers: A small sample was taken and pressed into a film on a flat vulcanizer to obtain an infrared spectrum on a NICOLET560 type FTIR.

Determination of water contact angle: A small sample was taken and pressed into a film on a flat vulcanizer. A drop of distilled water was dropped on the sample stage to allow the sample film to adhere tightly to the sample stage. 2 μL of deionized water droplets were extracted with a micro-injector and applied to the sample membrane, and the angle was measured 10 seconds later.

Method for determining the effective graft ratio of the graft polymer: accurately weighing 1 g of the dried refined graft sample, Place in a 250 mL flask, add 80 mL of xylene, and heat to reflux until dissolved. After cooling, an excess of 0.1 mol/L KOH-ethanol solution was added, and the mixture was further heated under reflux for 2 hours. After cooling, phenolphthalein was used as an indicator, and titration was carried out with a 0.1 mol/L HCl-isopropanol solution. The amount of alkali added and the amount of acid consumed for neutralization were recorded, and the effective graft ratio of the solid phase graft reaction product was calculated by the following formula.

Where: G is the effective graft ratio of the product; c ₁ is the concentration of KOH-ethanol solution, mol/L; V ₁ is the volume of the excess added KOH-ethanol solution, mL; c ₂ is the concentration of HCl-isopropanol solution , mol / L; V ₂ is the volume of the HCl-isopropanol solution in the titration neutralization base, mL; a is the functionality of the grafting monomer involved in the neutralization reaction; m is the mass of the refined sample, g, M is The relative molecular mass of the monomer.

DSC Characterization: The basic thermal properties of the polymer were determined by TA Instruments' Differential Scanning Calorimeter DSC Q2000. Specific test method: Weigh about 5mg of polymer sample placed in aluminum crucible, in the high purity helium atmosphere, the sample first rapidly heated to 200 ° C, constant temperature 2min. Then, the temperature was lowered to 30 ° C at 20 ° C / min. The temperature was raised to 200 ° C at a constant rate of 20 ° C / min. Save all heating and cooling curves and calculate the relevant thermodynamic parameters.

The fiber properties of the present invention and the properties of the film can be measured by a measurement method in a known standard. For example, the creep resistance of the present invention is measured by the measurement method in the National Standards of the People's Republic of China GB11546-89 and ISO899-1981.

The present invention will be further described in detail below with reference to the specific embodiments of the invention. However, it is to be understood by those skilled in the art that the present invention is not limited to the drawings and the following embodiments.

Preparation Example 1 [Preparation of Catalyst]

In a reactor fully substituted with high-purity nitrogen, 4.94 g of anhydrous magnesium chloride, 18.9 g of isooctanol, 30 ml of decane were sequentially added, and the temperature was raised to 130 ° C with stirring, and maintained for 2 hours, and then 2.65 g of tetrabutyl titanate was added. The ester and 2.05 g of diisobutyl phthalate were further reacted at 130 ° C for 1 hour and finally cooled to room temperature to form a homogeneous clear solution, which was the mixture I.

To the reaction vessel, 200 ml of titanium tetrachloride was added and stirred, and preheated to 0 ° C, and the mixture I was added dropwise to titanium tetrachloride in about 2 hours. After the addition was completed, the temperature was raised and the temperature was raised to 110 ° C in 2 hours. 1.23 g of an internal electron donor diisobutyl phthalate was added. After reacting at this temperature for 2 hours, the reaction liquid was removed, and 200 ml of titanium tetrachloride was again added thereto, and the reaction was carried out for 2 hours. Finally, the reaction liquid was removed, and the remaining solid matter was washed 10 times with hexane at 60 ° C, and dried to obtain a catalyst.

Example 1.1 [Body polymerization of propylene]

Under high purity nitrogen protection, the 5L high pressure reactor was dried and deaerated, and 20 mg of the above catalyst was added. And triethylaluminum 12ml and 3ml external electron donor Donor-P, then add 1200g of propylene, wherein the volume fraction of propylene is 99.9%, the polymerization reaction starts, the system temperature is maintained at 45 ° C, the reaction time is 60 minutes, the obtained catalyst The activity and properties of polypropylene are shown in Table 1.

Example 1.2 [Propylene-ethylene copolymer and its preparation]

Under the protection of high purity nitrogen, the 5L high pressure reactor was dried and deaerated, 20 mg of the above catalyst and 12 ml of triethylaluminum and 3 ml of external electron donor Donor-P were added, then 1200 g of propylene was added, and 40 g of ethylene was introduced thereto. The volume fraction of propylene is 99.9%, the content of carbon monoxide in ethylene gas is less than 5 ppm, the carbon dioxide is less than 15 ppm, and the content of conjugated diene is less than 10 ppm. The polymerization starts, the temperature of the system is maintained at 75 ° C, and the reaction time is 60 minutes. The catalyst activity and the properties of the propylene-ethylene copolymer are shown in Table 1.

Example 1.3 [Body polymerization of propylene]

Under the protection of high purity nitrogen, the 5L autoclave was dried and deaerated, 20 mg of the above catalyst and 12 ml of triethylaluminum and 3 ml of external electron donor Donor-P were added, and then 1200 g of propylene was added, wherein the volume fraction of propylene was 99.9%, the polymerization reaction started, the system temperature was maintained at 55 ° C, and the reaction time was 60 minutes. The obtained catalyst activity and polypropylene properties are shown in Table 1.

Example 1.4 [Body polymerization of propylene]

Under the protection of high purity nitrogen, the 5L autoclave was dried and deaerated, 20 mg of the above catalyst and 12 ml of triethylaluminum and 3 ml of external electron donor Donor-P were added, and then 1200 g of propylene was added, wherein the volume fraction of propylene was 99.9%, the polymerization reaction started, the system temperature was maintained at 65 ° C, and the reaction time was 60 minutes. The obtained catalyst activity and polypropylene properties are shown in Table 1.

Table 1 Catalytic Activity of the Catalyst of Preparation Example 1 and Properties of the Propylene Polymers Prepared in Examples 1.1 to 1.4

Further properties of the propylene polymers of Examples 1.1 to 1.4 were further examined in the present invention, and it was found that: (1) The abrasion resistance indexes of the propylene polymers of Examples 1.1 to 1.4 were all more resistant than those of ordinary carbon steel or copper. The grinding index is several times higher; (2) the impact strength of the propylene polymer of Examples 1.1 to 1.4 is 2-5 times that of ordinary polypropylene; (3) The resistance of the propylene polymer powder of Examples 1.1 to 1.4 The chemical corrosion ability is stronger than that of general polyolefins; (4) The propylene polymer powders of Examples 1.1 to 1.4 have a wide temperature range, which is lower (such as minus 30 ° C) or Good toughness and strength are maintained at high temperatures (eg 130 ° C).

Comparative Example 1.1 to 1.2

A method similar to that of Example 1.1 was employed except that the polymerization temperature and the purity of the monomer were different. The results are shown in Table 2.

Table 2 Properties of propylene polymers in Comparative Examples 1.1 to 1.2

Preparation 2.1 Preparation of ultrahigh molecular weight ultrafine particle size propylene homopolymer powder

Bulk polymerization of propylene:

Under the protection of high purity nitrogen, the 5L autoclave was dried and deaerated, 20 mg of the above catalyst and 12 ml of triethylaluminum and 3 ml of external electron donor Donor-P were added, and then 1200 g of propylene was added, wherein the volume fraction of propylene was 99.9%, the polymerization started, the system temperature was maintained at 55 ° C, and the reaction time was 60 minutes.

The propylene homopolymer powder was a spherical particle having an average particle diameter of 47 μm, a standard deviation of 8.16 μm, a bulk density of 0.206 g/mL, a viscosity average molecular weight of 3.4×10 ⁶ and a molecular weight distribution of 4.1.

Preparation 2.2 Preparation of ultrahigh molecular weight ultrafine particle size propylene-ethylene copolymer powder

The catalyst was prepared in the same manner as in Preparation 2.1.

Propylene-ethylene copolymerization:

Under the protection of high purity nitrogen, the 5L high pressure reactor was dried and deaerated, 20 mg of the above catalyst and 12 ml of triethylaluminum and 3 ml of external electron donor Donor-P were added, then 1200 g of propylene was added, and 40 g of ethylene was introduced thereto. The volume fraction of propylene is 99.9%, the content of carbon monoxide in ethylene gas is less than 5ppm, and the carbon dioxide is less. At 15 ppm, the conjugated diene content was less than 10 ppm, the polymerization started, the system temperature was maintained at 75 ° C, and the reaction time was 60 minutes.

The propylene-ethylene copolymer powder was spherical particles having an average particle diameter of 135 μm, a standard deviation of 8.15 μm, a bulk density of 0.310 g/mL, a viscosity average molecular weight of 2.5×10 ⁶ and a molecular weight distribution of 7.2.

Example 2.1 [Preparation of Grafted Propylene Polymer]

Preparation of PP-g-MAH: In a reactor sufficiently substituted with high-purity nitrogen, 40 g of a polypropylene powder having an average particle diameter of 47 μm prepared in Preparation Example 2.1 (standard deviation of 8.16 μm, viscosity average molecular weight of 3.4) was added. ×10 ⁶ , the bulk density is 0.206 g/mL, the molecular weight distribution is 4.1), 2.0 g of benzoyl peroxide is added, 2.8 g of maleic anhydride (MAH) is added, 4 mL of tetrahydrofuran and 5 mL of xylene are added; then mechanical stirring is started. The mixture was stirred rapidly for 4 hours; finally, the reactor was placed in an oil bath at 110 ° C for 2 hours to obtain a product.

Purification of PP-g-MAH: Weigh about 4g of crude graft, weigh it together with 200mL of xylene and add it to a 500mL distillation flask to dissolve it. It is refluxed for 4h. After cooling, add acetone (about 200mL) and shake it. Then, it was washed once with acetone, and the filtrate was dried in an oven at 50 ° C for 12 hours, and cooled to obtain a purified graft.

Infrared characterization of PP-g-MAH: The infrared spectrum of the refined graft was determined according to the method described above, and the results are shown in Fig. 1, wherein the upper is a polypropylene raw material; the lower is a graft polymer. 1862 cm ^-1 , 1785 cm ^-1 , and 1717 cm ^-1 are characteristic peaks of maleic anhydride, indicating that maleic anhydride was successfully grafted onto the polypropylene chain.

Measurement of water contact angle: The water contact angle was measured in accordance with the aforementioned method, the water contact angle of the polypropylene raw material was 96°, and the water contact angle of the graft polymer was 78°.

Determination of the effective graft ratio of PP-g-MAH: The effective graft ratio of the graft polymer was determined to be 4.56% according to the method described above.

DSC characterization: The relevant thermodynamic parameters of the graft polymer were determined according to the foregoing method. The test results are shown in Table 1. Compared with the polypropylene raw material, the melting temperature of the graft polymer and the polypropylene raw material are basically the same, but the crystallization temperature is improved. At 8 ° C, this is advantageous for the processing of materials.

Table 3 DSC analysis results of polypropylene and graft polymer

Example 2.2 [Preparation of Grafted Propylene Polymer]

Preparation of PP-g-MAH: In a reactor sufficiently substituted with high-purity nitrogen, 40 g of a polypropylene powder having an average particle diameter of 60 μm prepared by the same method as in Preparation 2.1 (standard deviation of 8.16 μm, viscosity average molecular weight) was added. To be 3.5 × 10 ⁶ ), 2.0 g of azobisisobutyronitrile was added, 2.8 g of maleic anhydride (MAH) was added, 3 mL of tetrahydrofuran and 6 mL of xylene were added; then mechanical stirring was started, and rapid stirring was carried out for 4 hours; finally, the reactor was placed. The mixture was reacted for 2 hours in an oil bath at 100 ° C to obtain a product. The effective graft ratio of maleic anhydride of the graft polymer was measured to be 5.25%, and the water contact angle of the graft polymer was 74°.

Example 2.3 [Preparation of Grafted Propylene Polymer]

Preparation of PP-g-AA: In a reactor sufficiently substituted with high-purity nitrogen, 40 g of a polypropylene powder having an average particle diameter of 70 μm prepared by the same method as in Preparation 2.1 (standard deviation of 8.16 μm, viscosity average molecular weight was 3.0×10 ⁶ ), adding 2.0g of benzoyl peroxide, adding 2.8g of acrylic acid (AA), adding 5mL of xylene; then turning on mechanical stirring, stirring rapidly for 4 hours; finally adding the reactor to the oil bath of 120 °C The reaction was carried out for 2 hours to obtain a product. The effective graft ratio of acrylic acid of the graft polymer was measured to be 4.14%, and the water contact angle of the graft polymer was 70°.

Example 2.4 [Preparation of Grafted Propylene Polymer]

Preparation of PP-g-MMA: In a reactor sufficiently substituted with high-purity nitrogen, 40 g of a polypropylene powder having an average particle diameter of 70 μm prepared by the same method as in Preparation 2.1 (standard deviation of 8.16 μm, viscosity average molecular weight) was added. 3.8 × 10 ⁶ ), adding 2.0 g of benzoyl peroxide, adding 2.8 g of methyl methacrylate (MMA), adding 5 mL of xylene; then turning on mechanical stirring, stirring rapidly for 4 hours; finally adding the reactor to 110 The product was obtained by reacting for 2 hours in an oil bath of °C. The effective graft ratio of MMA of the graft polymer was measured to be 6.04%, and the water contact angle of the graft polymer was 72°.

Example 2.5 [Preparation of Grafted Propylene Polymer]

Preparation of propylene-ethylene copolymer grafted maleic anhydride graft polymer: 40 g of propylene-ethylene copolymer powder having an average particle diameter of 135 μm prepared in Preparation 2.2 was added to a reactor which was sufficiently substituted with high purity nitrogen gas. (Standard deviation is 8.15 μm, viscosity average molecular weight is 2.5×10 ⁶ ), 2.0 g of benzoyl peroxide is added, 2.8 g of maleic anhydride (MAH) is added, 4 mL of tetrahydrofuran and 5 mL of xylene are added; then mechanical stirring is started, and fast Stirring for 4 hours; finally adding the reactor to an oil bath at 110 ° C for 2 hours to obtain the product. The effective graft ratio of maleic anhydride of the graft polymer was determined to be 6.16%, and the water contact angle of the graft polymer was 71°.

Example 2.6 [Grafting of propylene polymer preparation]

Preparation of propylene-ethylene-1-butene terpolymer grafted maleic anhydride graft polymer: In a reactor fully substituted with high purity nitrogen, 40 g of an average particle size prepared by the similar method of Preparation 2.2 was prepared. Micron propylene-ethylene-1-butene terpolymer powder (standard deviation 8.16 μm, viscosity average molecular weight 3.4×10 ⁶ ), 2.0 g of benzoyl peroxide was added, and 2.8 g of maleic anhydride (MAH) was added. ), 4 mL of tetrahydrofuran and 5 mL of xylene were added; then mechanical stirring was started, and rapid stirring was carried out for 4 hours; finally, the reactor was placed in an oil bath of 100 ° C for 2 hours to obtain a product. The effective graft ratio of maleic anhydride of the graft polymer was determined to be 4.51%, and the water contact angle of the graft polymer was 82°.

Preparation Example 3.1 [glass fiber]

In the mixer, glass fiber and a coupling agent were added and stirred for 30 minutes; a diluent was further added and stirred for 30 minutes; and the treated glass fiber of the present invention was obtained. Wherein, the coupling agent is γ-aminopropyltriethoxysilane KH550; the length of the glass fiber is 3-5 mm; and the diluent is white oil. The weight ratio of the diluent to the coupling agent is 3:1; the amount of the coupling agent is 2 parts by weight relative to 100 parts by weight of the glass fiber.

Preparation Example 3.2 [glass fiber]

In the mixer, glass fiber and a coupling agent were added and stirred for 30 minutes; a diluent was further added and stirred for 30 minutes; and the treated glass fiber of the present invention was obtained. Wherein, the coupling agent is vinyltrimethoxysilane A-171; the length of the glass fiber is 3-5 mm; and the diluent is white oil. The weight ratio of the diluent to the coupling agent is 4:1; the amount of the coupling agent is 1 part by weight relative to 100 parts by weight of the glass fiber.

Preparation Example 3.3 [glass fiber]

In the mixer, glass fiber and a coupling agent were added and stirred for 30 minutes; a diluent was further added and stirred for 30 minutes; and the treated glass fiber of the present invention was obtained. Wherein, the coupling agent is vinyl triethoxysilane A-151; the length of the glass fiber is 3-5 mm; and the diluent is liquid paraffin. The weight ratio of the diluent to the coupling agent is 6:1; the amount of the coupling agent is 3 parts by weight relative to 100 parts by weight of the glass fiber.

Examples 3.1 to 3.12 [Glass fiber reinforced propylene polymer composition]

The compositions and contents of the compositions of Examples 3.1 to 3.12 of the present invention are shown in Table 4.

Table 4 Different ratios of glass fiber reinforced propylene polymer compositions

实施例Example	丙烯聚合物Propylene polymer	重量百分比Weight percentage	玻璃纤维glass fiber	重量百分比Weight percentage
3.1a3.1a	实施例1.1的丙烯均聚物Propylene homopolymer of Example 1.1	6060	制备例3.1的玻璃纤维Preparation of glass fiber of Example 3.1	4040
3.1b3.1b	实施例1.1的丙烯均聚物Propylene homopolymer of Example 1.1	5050	制备例3.1的玻璃纤维Preparation of glass fiber of Example 3.1	5050
3.1c3.1c	实施例1.1的丙烯均聚物Propylene homopolymer of Example 1.1	4040	制备例3.1的玻璃纤维Preparation of glass fiber of Example 3.1	6060
3.2a3.2a	实施例1.2的丙烯-乙烯共聚物Propylene-ethylene copolymer of Example 1.2	6060	制备例3.1的玻璃纤维Preparation of glass fiber of Example 3.1	4040
3.2b3.2b	实施例1.2的丙烯-乙烯共聚物Propylene-ethylene copolymer of Example 1.2	5050	制备例3.1的玻璃纤维Preparation of glass fiber of Example 3.1	5050
3.2c3.2c	实施例1.2的丙烯-乙烯共聚物Propylene-ethylene copolymer of Example 1.2	4040	制备例3.1的玻璃纤维Preparation of glass fiber of Example 3.1	6060
3.3a3.3a	实施例1.3的丙烯均聚物Propylene homopolymer of Example 1.3	6060	制备例3.1的玻璃纤维Preparation of glass fiber of Example 3.1	4040
3.3b3.3b	实施例1.3的丙烯均聚物Propylene homopolymer of Example 1.3	5050	制备例3.1的玻璃纤维Preparation of glass fiber of Example 3.1	5050
3.3c3.3c	实施例1.3的丙烯均聚物Propylene homopolymer of Example 1.3	4040	制备例3.1的玻璃纤维Preparation of glass fiber of Example 3.1	6060
3.4a3.4a	实施例1.4的丙烯均聚物Propylene homopolymer of Example 1.4	6060	制备例3.1的玻璃纤维Preparation of glass fiber of Example 3.1	4040
3.4b3.4b	实施例1.4的丙烯均聚物Propylene homopolymer of Example 1.4	5050	制备例3.1的玻璃纤维Preparation of glass fiber of Example 3.1	5050
3.4c3.4c	实施例1.4的丙烯均聚物Propylene homopolymer of Example 1.4	4040	制备例3.1的玻璃纤维Preparation of glass fiber of Example 3.1	6060
3.5a3.5a	实施例1.1的丙烯均聚物Propylene homopolymer of Example 1.1	6060	制备例3.2的玻璃纤维Preparation of glass fiber of Example 3.2	4040
3.5b3.5b	实施例1.1的丙烯均聚物Propylene homopolymer of Example 1.1	5050	制备例3.2的玻璃纤维Preparation of glass fiber of Example 3.2	5050
3.5c3.5c	实施例1.1的丙烯均聚物Propylene homopolymer of Example 1.1	4040	制备例3.2的玻璃纤维Preparation of glass fiber of Example 3.2	6060
3.6a3.6a	实施例1.2的丙烯-乙烯共聚物Propylene-ethylene copolymer of Example 1.2	6060	制备例3.2的玻璃纤维Preparation of glass fiber of Example 3.2	4040
3.6b3.6b	实施例1.2的丙烯-乙烯共聚物Propylene-ethylene copolymer of Example 1.2	5050	制备例3.2的玻璃纤维Preparation of glass fiber of Example 3.2	5050

3.6c3.6c	实施例1.2的丙烯-乙烯共聚物Propylene-ethylene copolymer of Example 1.2	4040	制备例3.2的玻璃纤维Preparation of glass fiber of Example 3.2	6060
3.7a3.7a	实施例1.3的丙烯均聚物Propylene homopolymer of Example 1.3	6060	制备例3.2的玻璃纤维Preparation of glass fiber of Example 3.2	4040
3.7b3.7b	实施例1.3的丙烯均聚物Propylene homopolymer of Example 1.3	5050	制备例3.2的玻璃纤维Preparation of glass fiber of Example 3.2	5050
3.7c3.7c	实施例1.3的丙烯均聚物Propylene homopolymer of Example 1.3	4040	制备例3.2的玻璃纤维Preparation of glass fiber of Example 3.2	6060
3.8a3.8a	实施例1.4的丙烯均聚物Propylene homopolymer of Example 1.4	6060	制备例3.2的玻璃纤维Preparation of glass fiber of Example 3.2	4040
3.8b3.8b	实施例1.4的丙烯均聚物Propylene homopolymer of Example 1.4	5050	制备例3.2的玻璃纤维Preparation of glass fiber of Example 3.2	5050
3.8c3.8c	实施例1.4的丙烯均聚物Propylene homopolymer of Example 1.4	4040	制备例3.2的玻璃纤维Preparation of glass fiber of Example 3.2	6060
3.9a3.9a	实施例1.1的丙烯均聚物Propylene homopolymer of Example 1.1	6060	制备例3.3的玻璃纤维Preparation of glass fiber of Example 3.3	4040
3.9b3.9b	实施例1.1的丙烯均聚物Propylene homopolymer of Example 1.1	5050	制备例3.3的玻璃纤维Preparation of glass fiber of Example 3.3	5050
3.9c3.9c	实施例1.1的丙烯均聚物Propylene homopolymer of Example 1.1	4040	制备例3.3的玻璃纤维Preparation of glass fiber of Example 3.3	6060
3.10a3.10a	实施例1.2的丙烯-乙烯共聚物Propylene-ethylene copolymer of Example 1.2	6060	制备例3.3的玻璃纤维Preparation of glass fiber of Example 3.3	4040
3.10b3.10b	实施例1.2的丙烯-乙烯共聚物Propylene-ethylene copolymer of Example 1.2	5050	制备例3.3的玻璃纤维Preparation of glass fiber of Example 3.3	5050
3.10c3.10c	实施例1.2的丙烯-乙烯共聚物Propylene-ethylene copolymer of Example 1.2	4040	制备例3.3的玻璃纤维Preparation of glass fiber of Example 3.3	6060
3.11a3.11a	实施例1.3的丙烯均聚物Propylene homopolymer of Example 1.3	6060	制备例3.3的玻璃纤维Preparation of glass fiber of Example 3.3	4040
3.11b3.11b	实施例1.3的丙烯均聚物Propylene homopolymer of Example 1.3	5050	制备例3.3的玻璃纤维Preparation of glass fiber of Example 3.3	5050
3.11c3.11c	实施例1.3的丙烯均聚物Propylene homopolymer of Example 1.3	4040	制备例3.3的玻璃纤维Preparation of glass fiber of Example 3.3	6060
3.12a3.12a	实施例1.4的丙烯均聚物Propylene homopolymer of Example 1.4	6060	制备例3.3的玻璃纤维Preparation of glass fiber of Example 3.3	4040
3.12b3.12b	实施例1.4的丙烯均聚物Propylene homopolymer of Example 1.4	5050	制备例3.3的玻璃纤维Preparation of glass fiber of Example 3.3	5050
3.12c3.12c	实施例1.4的丙烯均聚物Propylene homopolymer of Example 1.4	4040	制备例3.3的玻璃纤维Preparation of glass fiber of Example 3.3	6060

Example 3.13 to 3.24 [Sheet]

Sheets were prepared using the compositions of Examples 3.1 to 3.12, respectively.

Taking the composition of Example 3.1a as an example, 6 kg of the ethylene homopolymer of Example 1.1 and 4 kg of the glass fiber of Preparation 3.1 were uniformly mixed by a high speed mixer, fed into an extruder, and extruded through a slit die. The sheet of the present invention was obtained by cooling and stretching. Wherein, the processing temperature of the extruder is 180 to 240 °C.

The performance test results of the sheets prepared in Examples 3.13 to 3.24 are shown in Table 3.

Table 5 Performance test results of sheets prepared in Examples 3.13 to 3.24

Example 3.25 to 3.36 [tube]

Tubes were prepared using the compositions of Examples 3.1 to 3.12, respectively.

Taking the composition of Example 3.1a as an example, 6 kg of the ethylene homopolymer of Example 1.1 and 4 kg of the glass fiber of Preparation 3.1 were uniformly mixed by a high speed mixer, fed into an extruder, extruded through a tube die, and cooled. And stretching to obtain the tube of the present invention. Wherein, the processing temperature of the extruder is 180 to 240 °C. The tube has a wall thickness of between 0.5 mm and 5 mm.

The performance test results of the tubes prepared in Examples 3.25 to 3.36 were similar to those of the corresponding sheets.

Example 4.1 [Solubilized propylene homopolymer polymerization]

Using the slurry polymerization process, the polymerization reactor is pretreated (under the protection of high purity nitrogen, the 5L high pressure reactor is dried and deaerated), and 500 g of the dispersion medium cyclohexane is added, 20 mg of the catalyst of the above preparation example 1 and the triethyl group 12 ml of base aluminum and 3 ml of external electron donor Donor-P, after stirring for 2 h, 1200 g of propylene was added, wherein the volume fraction of propylene was 99.9%, the polymerization reaction was started, the system temperature was maintained at 50 ° C, and the reaction time was 60 minutes. After the end of the polymerization reaction, the temperature is cooled and cooled, and the slurry material is directly discharged from the bottom valve, and the required amount of white oil is added, and the distillation is removed. The bulk medium was used to obtain the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer of the present invention, wherein the white oil had a mass percentage of 30% by weight. The properties of the obtained polypropylene are shown in Table 6.

Comparative dissolution test: 10 g of an ultrahigh molecular weight ultrafine particle size propylene polymer containing white oil prepared in Example 4.1 was added to 60 g of white oil, dissolved at 140 ° C, and dissolved in 20 minutes.

7 g of the ultrahigh molecular weight ultrafine particle size propylene polymer prepared in Comparative Example 4.1 was added to 63 g of white oil, dissolved at 140 ° C, and dissolved in 90 minutes.

Example 4.2 [Solubilized propylene-ethylene copolymerization]

Using the slurry polymerization process, the polymerization reactor is pretreated (under the protection of high purity nitrogen, the 5L high pressure reactor is dried and deaerated), and 500 g of the dispersion medium cyclohexane is added, 20 mg of the catalyst of the above preparation example 1 and the triethyl group 12ml of base aluminum and 3ml of external electron donor Donor-P, after stirring for 2h, 1200g of propylene is added, 40g of ethylene is introduced, wherein the volume fraction of propylene is 99.9%, the content of carbon monoxide in ethylene gas is less than 5ppm, and the carbon dioxide is less than 15ppm. And the conjugated diene content was less than 10 ppm, the polymerization reaction was started, the system temperature was maintained at 50 ° C, and the reaction time was 60 min. After the end of the polymerization reaction, the temperature is cooled and cooled, the slurry material is directly discharged from the bottom valve, the required amount of white oil is added, and the dispersion medium is distilled off to obtain the solubilized ultrahigh molecular weight ultrafine particle size propylene-ethylene copolymer of the present invention. The white oil has a mass percentage of 40% by weight. The properties of the obtained propylene-ethylene copolymer are shown in Table 6.

The solubility was measured by a method similar to that in Example 4.1, and the dissolution time of the polymer having a solvent content of 0 was shortened by nearly 80%.

Example 4.3 [Solubilized propylene homopolymer polymerization]

The slurry polymerization process is firstly carried out. The polymerization vessel is pretreated (the high-purity nitrogen gas is used to dry and deoxidize the 5L high pressure reactor), and 500 g of the dispersion medium cyclohexane and the required amount of white oil are added, 20 mg of the above preparation. The catalyst of Example 1 and 12 ml of triethylaluminum and 3 ml of the external electron donor Donor-P, then 1200 g of propylene were added, wherein the volume fraction of propylene was 99.9%, the polymerization started, the temperature of the system was maintained at 46 ° C, and the reaction time was 60. minute. After the polymerization reaction is finished, the temperature is cooled and cooled, the slurry material is directly discharged from the bottom valve, and the dispersion medium is distilled off to obtain the solubilized ultrahigh molecular weight ultrafine particle size propylene homopolymer of the present invention, wherein the white oil has a mass percentage of 30 wt%. %. The properties of the obtained polypropylene are shown in Table 6.

Example 4.4 [Solubilized propylene-ethylene copolymerization]

Using a slurry polymerization process, the polymerization vessel is pretreated (under a high purity nitrogen gas, the 5 L high pressure reactor is dried and deaerated), and 500 g of the dispersion medium cyclohexane and the required amount of white oil are added, 20 mg of the above. Catalyst and triethylaluminum 12ml and 3ml external electron donor Donor-P, after stirring for 2h, add 1200g of propylene to B 40g of olefin, wherein the volume fraction of propylene is 99.9%, the content of carbon monoxide in ethylene gas is less than 5ppm, the carbon dioxide is less than 15ppm, and the content of conjugated diene is less than 10ppm, the polymerization starts, the temperature of the system is maintained at 50 ° C, and the reaction time is It is 60 minutes. After the end of the polymerization reaction, the temperature is cooled and cooled, the slurry material is directly discharged from the bottom valve, and the dispersion medium is distilled off to obtain the solubilized ultrahigh molecular weight ultrafine particle size propylene-ethylene copolymer of the present invention, wherein the mass percentage of the white oil is 40wt%. The properties of the obtained propylene-ethylene copolymer are shown in Table 6.

Table 6 Catalytic Activity of the Catalyst of Preparation Example 1 and Properties of the Propylene Polymers Prepared in Examples 4.1 to 4.4

Further properties of the propylene polymers of Examples 4.1 to 4.4 were further examined in the present invention, and it was found that: (1) The abrasion resistance indexes of the propylene polymers of Examples 4.1 to 4.4 were all more resistant than those of ordinary carbon steel or copper. The grinding index is several times higher; (2) the impact strength of the propylene polymer of Examples 4.1 to 4.4 is 2-5 times that of ordinary polypropylene; (3) The chemical resistance of the propylene polymer of Examples 4.1 to 4.4 The ability is stronger than general polyolefin; (4) The propylene polymer of Examples 4.1 to 4.4 has a wide temperature range and can be kept at a low temperature (such as minus 30 ° C) or a higher temperature (such as 130 ° C). Good toughness and strength.

Comparative Example 4.1 [Propylene homopolymer and its preparation]

Under the protection of high purity nitrogen, the 5L autoclave was dried and deaerated, 20 mg of the above catalyst and 12 ml of triethylaluminum and 3 ml of external electron donor Donor-P were added, and then 1200 g of propylene was added, wherein the volume fraction of propylene was 99.9%, the polymerization reaction was started, the system temperature was maintained at 45 ° C, and the reaction time was 60 minutes, and the propylene homopolymer was obtained.

Comparative Example 4.2-4.3 [Body Polymerization of Propylene]

A method similar to that of Example 4.1 was employed except that the polymerization temperature and the purity of the monomer were different. The results are shown in Table 7.

Table 7 Properties of propylene polymers in Comparative Examples 4.2-4.3

Example 5.1 [Preparation of fibers]

The solubilized ultrahigh molecular weight ultrafine particle size propylene polymer of Example 4.1 was mixed with white oil to obtain a mixture in which the polymer content was 10% by weight; the mixture was subjected to twin screw dissolution extrusion, and the temperature of the dissolution extrusion was carried out. a spinning solution is obtained at 200 ° C; the spinning solution is directly extruded through a twin-screw, extruded through a spinning assembly, a spinneret, and cooled in a cooling water bath (water bath temperature of 5 ° C) to obtain a gel fiber; The gel fiber is subjected to gel filament drawing, solvent extraction, drying, first hot box dry heat drawing, second hot box dry heat drawing, heat setting and winding process to obtain the fiber of the present invention.

In the process step of processing the gel fiber into a fiber, the drawing temperature of the gel filament drawing step is 40 ° C, the draw ratio is 10 times; the extractant in the solvent extraction step is selected from cyclohexane; in the drying step Drying is dried by hot air, the hot air temperature is 70 ° C; the temperature in the first hot box dry heat drawing process is 160 ° C, the draw ratio is 10 times; the temperature in the second hot box dry heat drawing process is 170 ° C, The draw ratio was 2 times; the temperature in the heat setting process was 130 °C.

Example 5.2 [Preparation of fibers]

Others were the same as in Example 5.1 except that an antioxidant was further added to the mixture, and the antioxidant was added in an amount of 0.05 part by weight based on 100 parts by weight of the propylene polymer. The antioxidant is composed of a primary antioxidant and a secondary antioxidant selected from the group consisting of 2,6-di-tert-butyl-4-methylphenol. The secondary antioxidant is selected from the group consisting of bisdidecanoic acid thiodipropionate.

Example 5.3 [Preparation of fibers]

The same as in Example 5.1 except that the polymer was replaced with the copolymer of Example 4.2.

Example 5.4 [Preparation of fibers]

The same as in Example 5.2 except that the polymer was replaced with the copolymer of Example 4.2.

The properties of the fibers prepared in Examples 5.1-5.4 are listed in Table 8.

Table 8 Performance test results of fibers prepared in Examples 5.1-5.4 of the present invention

It can be seen from the data of Table 8 that the fiber of the present invention has excellent creep resistance and wide use temperature, and has great application prospects.

Example 6.1 [Preparation of film]

1) melt-kneading a raw material containing the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer and a solvent for film formation to obtain a solution;

The polymer is a solubilized ultrahigh molecular weight ultrafine particle size propylene polymer as described in Example 4.1, and an antioxidant is added thereto, and the antioxidant is used in an amount of 0.1 part by weight based on 100 parts by weight of the polymer. The oxygen agent is composed of a primary antioxidant and a secondary antioxidant selected from 2,6-di-tert-butyl-4-methylphenol. The auxiliary antioxidant is selected from the group consisting of bisdidecanoic acid thiodipropionate;

The solvent for film formation is liquid paraffin, and the weight percentage of the polymer in the solution is 30% by weight;

The melt-kneading is carried out by a known twin-screw extruder, wherein the temperature of the melt-kneading is from 180 to 250 °C.

2) extruding the solution, forming a shaped body, and cooling to obtain a polymer sheet; specifically, the solution of the step (1) is supplied to a mold through an extruder, and the solution is extruded from the mold to form a molded body (eg, a sheet shape), after cooling by a cooling drum, a polymer sheet is obtained; the surface temperature of the cooling drum is set to 20 to 40 ° C, and the cooling rate of the molded body through the cooling drum is 20 ° C / s or more;

3) uniaxial stretching or biaxial stretching to obtain a film; the stretching is biaxial stretching, which is achieved by a drum method in which the longitudinal stretching ratio is 5 times and the transverse stretching ratio is 5 times.

Example 6.2 [Preparation of film]

A film was prepared in the same manner as in Example 1 except that the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer of Example 4.2 was used in place of Example 4.1.

Examples 6.3 to 6.6 [Preparation of membrane]

Others were the same as in Example 1, and the differences are listed in Table 9.

Table 9 Specific conditions or parameters of Examples 6.3-6.6

实施例Example	聚合物polymer	拉伸方式Stretching method	横向拉伸倍率Lateral stretching ratio	纵向拉伸倍率Longitudinal stretching ratio
6.36.3	实施例4.1Example 4.1	双向拉伸Biaxial stretching	55	66
6.46.4	实施例4.2Example 4.2	双向拉伸Biaxial stretching	55	66
6.56.5	实施例4.1Example 4.1	单向拉伸Unidirectional stretching	--	55
6.66.6	实施例4.1Example 4.1	单向拉伸Unidirectional stretching	--	55

The performance test results for the films of Examples 6.1 to 6.6 are shown in Table 10.

Table 9 Performance test results of the films of Examples 6.1 to 6.6

The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and scope of the present invention are intended to be included within the scope of the present invention.

Claims

A method for preparing ultrahigh molecular weight ultrafine particle size propylene polymer powder, comprising the steps of: polymerizing propylene or propylene with a comonomer under the action of a catalyst, wherein the temperature of the polymerization reaction is 30-105 ° C, the volume fraction of propylene is greater than or equal to 98%;

The catalyst is prepared by a process comprising the following steps:

(a) mixing magnesium halide, an alcohol compound, an auxiliary, a part of the internal electron donor and a solvent to prepare a mixture I;

(b) adding the above mixture I to the reactor, preheating to -30 ° C ~ 30 ° C, adding titanium compound; or, adding titanium compound in the reactor, preheating to -30 ° C ~ 30 ° C, dropping The above mixture I;

(c) after the completion of the dropwise addition, the reaction system is heated to 90 ° C to 130 ° C over 0.5 to 3 hours, and the remaining internal electron donor is added to continue the reaction;

(d) filtering out the liquid of the reaction system, adding the remaining titanium compound, and continuing the reaction;

(e) after completion of the reaction, post-treatment to obtain the catalyst;

The propylene polymer obtained has a viscosity average molecular weight (Mv) of more than 1×10 6 ; the propylene polymer powder is spherical particles having an average particle diameter of 10 μm to 200 μm, a standard deviation of 2 μm to 15 μm, and a bulk density of 0.1. g/mL - 0.4 g / mL.
The production method according to claim 1, wherein the particle size distribution of the propylene polymer powder approximates a normal distribution.

Preferably, the comonomer is a C 2-20 alpha-olefin such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene One or more of 1-decene, 1-undecene or 1-dodecene. Preferably, the comonomer is one or both of ethylene and 1-butene. The comonomer has a molar percentage of from 0 to 10 mol%, preferably from 0 to 5 mol%.

Preferably, the temperature of the polymerization reaction is preferably from 40 to 80 °C.

Preferably, the propylene has a volume fraction of greater than or equal to 99%, more preferably greater than or equal to 99.8%, still more preferably greater than or equal to 99.9%.

Preferably, the comonomer (e.g., ethylene or 1-butene) has a carbon monoxide content of less than 5 ppm, a carbon dioxide content of less than 15 ppm, and a conjugated diene content of less than 10 ppm.
The ultrahigh molecular weight ultrafine particle size propylene polymer powder obtained by the preparation method according to claim 1 or 2, wherein the propylene polymer has a viscosity average molecular weight (Mv) of more than 1 × 10 6 ; The propylene polymer powder is spherical particles having an average particle diameter of 10 μm to 200 μm, a standard deviation of 2 μm to 15 μm, and a bulk density of 0.1 g/mL to 0.4 g/mL. Preferably, the particle size distribution of the propylene polymer powder approximates a normal distribution.
The ultrahigh molecular weight ultrafine particle size propylene polymer powder according to claim 3, wherein the propylene polymer is a propylene homopolymer or a propylene copolymer, and the comonomer in the propylene copolymer is C 2 -20 α-olefin, such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-decene, 1-undecene Or one or more of 1-dodecene. Preferably, the comonomer is one or both of ethylene and 1-butene. The comonomer has a molar percentage of from 0 to 10 mol%, preferably from 0 to 5 mol%.

Preferably, the propylene polymer has a viscosity average molecular weight (Mv) of 1.5×10 6 or more , preferably 1.5×10 6 to 4.0×10 6 ; and the molecular weight distribution Mw/Mn of the propylene polymer is 2-15. It is preferably 3 to 10, and more preferably 4 to 8.

Preferably, the propylene polymer powder preferably has an average particle diameter of from 20 μm to 180 μm, more preferably from 30 μm to 150 μm; the standard deviation is preferably from 5 μm to 15 μm, more preferably from 6 μm to 12 μm, still more preferably from 8 μm to 10 μm. The bulk density of the powder is preferably from 0.15 g/mL to 0.35 g/mL.
A method for preparing ultra-high molecular weight ultra-fine particle size grafted propylene polymer by solid phase grafting method, comprising the steps of:

In the container, adding propylene polymer, grafting monomer, initiator and interface agent, stirring and mixing uniformly; heating to carry out solid phase grafting reaction; obtaining the grafted propylene polymer;

The propylene polymer is a powder having a spherical particle shape, an average particle diameter of 10 μm to 200 μm, a standard deviation of 2 μm to 15 μm, a bulk density of 0.1 g/mL to 0.4 g/mL, and a viscosity average of the propylene polymer. The molecular weight (Mv) is greater than 1 × 10 6 .
The method according to claim 5, wherein the particle size distribution of the propylene polymer powder approximates a normal distribution.

Preferably, the average particle diameter of the propylene polymer is preferably from 20 μm to 180 μm, more preferably from 30 μm to 150 μm; the standard deviation is preferably from 5 μm to 15 μm, more preferably from 6 μm to 12 μm, still more preferably from 8 μm to 10 μm.

Preferably, the bulk density of the propylene polymer powder is preferably from 0.15 g/mL to 0.35 g/mL.

Preferably, the propylene polymer has a viscosity average molecular weight (Mv) of 1.5×10 6 or more , preferably 1.5×10 6 to 4.0×10 6 ; and the molecular weight distribution Mw/Mn of the propylene polymer is 2-15. It is preferably 3 to 10, and more preferably 4 to 8.

Preferably, the agitation mixing time is from 30 minutes to 5 hours. The purpose of the agitation is to enable the reactants to be thoroughly mixed well. In principle, the longer the stirring time, the more favorable the reaction, and the preferred stirring time is from 1 hour to 5 hours.

Preferably, the temperature of the solid phase grafting reaction is from 60 to 140 ° C for a period of from 0.5 hours to 5 hours. The reaction is preferably carried out at 70 to 120 ° C for 0.5 to 3.5 hours. More preferably, it is reacted at 90 to 110 ° C for 2 to 3 hours.

Preferably, the propylene polymer is selected from the group consisting of a propylene homopolymer, a propylene copolymer, or a mixture thereof. The comonomer of the propylene copolymer is one or more of α-olefins other than propylene, for example, one, two or three. The α-olefin is, for example, ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene or 1-decene. The copolymer is, for example, a propylene-ethylene copolymer, a propylene-1-butene copolymer or a propylene-ethylene-1-butene terpolymer.

Preferably, the grafting monomer is a siloxane-based compound or a vinyl-based unsaturated compound.

Preferably, the vinyl-based unsaturated compound is, for example, a styrene compound, a vinyl-based unsaturated organic acid, a vinyl-based unsaturated organic ester, a vinyl-based unsaturated organic acid anhydride, or a mixture thereof. Preferred are acrylic acid (AA), methacrylic acid (MAA), methyl acrylate (MA), methyl methacrylate (MMA), ethyl acrylate (EA), ethyl methacrylate (MEA), butyl acrylate ( One or more of BA), butyl methacrylate (BMA), maleic anhydride (MAH), maleic acid, styrene (St), and pentaerythritol triacrylate (PETA).

Preferably, the siloxane-based compound is, for example, vinyltrimethylsilane, vinyltriethylsilane, divinyldiene Methylsilane, (triethylsilyl)acetylene, allyltrimethylsilane, etc. are preferably one or both of vinyltrimethylsilane and vinyltriethylsilane.

Preferably, the graft monomer is added in an amount of 0.2% by weight to 15% by weight, preferably 0.5% by weight to 12% by weight, more preferably 1% by weight to 8% by weight based on the mass of the propylene polymer powder.

Preferably, the initiator is an azo initiator or a peroxide initiator, preferably one or more of azobisisobutyronitrile, benzoyl peroxide or cumene peroxide. The initiator is added in an amount of from 0.1% by weight to 10% by weight based on the mass of the propylene polymer powder, preferably from 2% by weight to 9% by weight, more preferably from 3% by weight to 8% by weight.

Preferably, the interfacial agent is an organic solvent having a swelling effect on the propylene polymer. Preferred are the following organic solvents which have a swelling action on the propylene polymer: an ether solvent, a ketone solvent, an aromatic hydrocarbon solvent or an alkane solvent; more preferably a chlorobenzene, a polychlorinated benzene, a C6 or higher alkane or a cycloalkane , benzene, alkyl substituted benzene, fatty ether, fatty ketone, or decahydronaphthalene; still more preferably benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, diethyl ether, acetone, hexane, cyclohexane, decalin, One or more of heptane. For example, it is xylene or a mixture of xylene and tetrahydrofuran. The interface agent is added in an amount of 0.1 to 30% by weight, preferably 10 to 25% by weight based on the mass of the propylene polymer powder.
The ultrahigh molecular weight ultrafine particle size grafted propylene polymer prepared by the method of claim 5 or 6, wherein the grafting monomer has an effective graft ratio of >0.5%; and the base polymer is a propylene polymer; The propylene polymer is a powder having a spherical particle shape, an average particle diameter of 10 μm to 200 μm, a standard deviation of 2 μm to 15 μm, a bulk density of 0.1 g/mL to 0.4 g/mL, and a viscosity average molecular weight of the propylene polymer. (Mv) is greater than 1 × 10 6 .
The ultrahigh molecular weight ultrafine particle size grafted propylene polymer according to claim 7, wherein the particle size distribution of the propylene polymer powder approximates a normal distribution.

Preferably, the effective graft ratio is from 1.0% to 6.5%, more preferably from 4.0% to 6.5%.

Preferably, the average particle diameter of the propylene polymer is preferably from 20 μm to 180 μm, more preferably from 30 μm to 150 μm; the standard deviation is preferably from 5 μm to 15 μm, more preferably from 6 μm to 12 μm, still more preferably from 8 μm to 10 μm.

Preferably, the bulk density of the propylene polymer is preferably from 0.15 g/mL to 0.35 g/mL.

Preferably, the propylene polymer has a viscosity average molecular weight (Mv) of 1.5×10 6 or more , preferably 1.5×10 6 to 4.0×10 6 ; and the molecular weight distribution Mw/Mn of the propylene polymer is 2-15. It is preferably 3 to 10, and more preferably 4 to 8.

Preferably, the propylene polymer is selected from the group consisting of a propylene homopolymer, a propylene copolymer, or a mixture thereof. The comonomer of the propylene copolymer is one or more of α-olefins other than propylene, for example, one, two or three. The α-olefin is, for example, ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene or 1-decene. The copolymer is, for example, a propylene-ethylene copolymer, a propylene-1-butene copolymer or a propylene-ethylene-1-butene terpolymer.

Preferably, the grafting monomer is a siloxane-based compound or a vinyl-based unsaturated compound.

Preferably, the vinyl-based unsaturated compound is, for example, a styrene compound, a vinyl-based unsaturated organic acid, a vinyl-based unsaturated organic ester, a vinyl-based unsaturated organic acid anhydride, or a mixture thereof. Preferred are acrylic acid (AA), methacrylic acid (MAA), methyl acrylate (MA), methyl methacrylate (MMA), ethyl acrylate (EA), ethyl methacrylate (MEA), butyl acrylate ( BA), butyl methacrylate (BMA), maleic anhydride (MAH), maleic acid, One or more of styrene (St) and pentaerythritol triacrylate (PETA).

Preferably, the siloxane-based compound is, for example, vinyltrimethylsilane, vinyltriethylsilane, divinyldimethylsilane, (triethylsilyl)acetylene, allyltrimethylsilane Etc., preferably one or both of vinyltrimethylsilane and vinyltriethylsilane.

Preferably, the grafted propylene polymer has a water contact angle of 90 or less. For example, the water contact angle is 70° to 82°.
A glass fiber reinforced propylene polymer composition, comprising the ultrahigh molecular weight ultrafine particle size propylene polymer powder and glass fiber according to claim 3 or 4;

The ultrahigh molecular weight ultrafine particle size propylene polymer has a viscosity average molecular weight (Mv) of more than 1×10 6 ; the ultrahigh molecular weight ultrafine particle size propylene polymer is spherical particles, and the average particle diameter is 10 μm to 200 μm. The difference is from 2 μm to 15 μm, and the bulk density is from 0.1 g/mL to 0.4 g/mL.
The composition according to claim 9, wherein the particle size distribution of the ultrahigh molecular weight ultrafine particle size propylene polymer approximates a normal distribution.

Preferably, the ultrahigh molecular weight ultrafine particle size propylene polymer is a propylene homopolymer or a propylene copolymer, and the comonomer in the propylene copolymer is a C 2-20 α-olefin such as ethylene or 1-butene. One or more of 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-decene, 1-undecene or 1-dodecene. Preferably, the comonomer is one or both of ethylene and 1-butene. The comonomer has a molar percentage of from 0 to 10 mol%, preferably from 0 to 5 mol%.

Preferably, the ultrahigh molecular weight ultrafine particle size propylene polymer has a viscosity average molecular weight (Mv) of 1.5×10 6 or more , preferably 1.5×10 6 to 4.0×10 6 ; The molecular weight distribution Mw/Mn of the radial propylene polymer is 2 to 15, preferably 3 to 10, and more preferably 4 to 8.

Preferably, the ultrahigh molecular weight ultrafine particle size propylene polymer preferably has an average particle diameter of from 20 μm to 180 μm, more preferably from 30 μm to 150 μm, still more preferably from 40 to 120 μm; and the standard deviation is preferably from 5 μm to 15 μm. It is preferably 6 μm to 12 μm, and more preferably 8 μm to 10 μm; the bulk density of the ultrahigh molecular weight ultrafine particle size propylene polymer is preferably from 0.15 g/mL to 0.35 g/mL, and more preferably from 0.2 g/mL to 0.3 g. /mL.

Preferably, the glass fibers are glass fibers treated with a coupling agent. The coupling agent is, for example, a silane coupling agent (such as γ-aminopropyltriethoxysilane KH550, γ-(2,3-epoxypropoxy)propyltrimethoxysilane KH560, γ-methyl propylene. Acyloxypropyltrimethoxysilane KH570, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane KH792, N-(β-aminoethyl)-γ-aminopropylmethyldi Methoxysilane DL602, vinyl trimethoxysilane A-171, vinyl triethoxysilane A-151, etc.), titanate coupling agent (such as tris(dioctyl pyrophosphoryloxy) titanic acid One or more of isopropyl ester, bis(dioctylphosphoryloxy) titanate, ethylene diisostearyl titanate or an aluminate coupling agent. Preferably, the coupling agent is selected from a silane coupling agent, and particularly preferably γ-aminopropyltriethoxysilane KH550, vinyltrimethoxysilane A-171, vinyltriethoxysilane A-151, etc. . Further, in order to better disperse the glass fibers in the coupling agent, a diluent may be added to the system of the glass fibers and the coupling agent, for example, selected from white oil or liquid paraffin. The weight ratio of the diluent to the coupling agent is, for example, (1 to 10): 1, preferably (3 to 6): 1.

Preferably, the glass fibers have a length of from 0.5 to 10 mm, such as from 1 to 3 mm, or from 3 to 5 mm, or from 5 to 7 mm, and the like.

Preferably, the weight percentage of each component in the composition is 10 to 95% by weight of the ultrahigh molecular weight ultrafine particle size propylene polymer and 5 to 90% by weight of the glass fiber. Preferably, the glass fiber is contained in an amount of 10 to 80% by weight, more preferably 40 to 70% by weight.
A sheet characterized in that the sheet is prepared from the composition of claim 9 or 10.
A tube characterized in that the tube is prepared from the composition of claim 9 or 10.
A method of producing a sheet according to claim 11, wherein the method comprises the steps of: uniformly mixing said ultrahigh molecular weight ultrafine particle size propylene polymer and said glass fiber in a high speed mixer, and adding and extruding In the machine, the sheet of the present invention is obtained by extrusion through a sheet die, cooling and stretching.
A method of producing a tube according to claim 12, characterized in that the method comprises the steps of: uniformly mixing the ultrahigh molecular weight ultrafine particle size propylene polymer and the glass fiber in a high speed mixer, and adding the extruder The tube of the present invention is obtained by extrusion through a pipe mold, cooling, and stretching.

Preferably, the tube has a wall thickness of between 0.1 mm and 10 mm, preferably between 0.5 mm and 5 mm.
The use of the sheet according to claim 11 which can be used in many fields such as automobiles, electronic devices and the like.
The use of the tube of claim 12 for use in water supply drainage, oil drilling, and the like, for example as a water supply drain or a mine wear resistant tube.
A method for preparing a solubilized ultrahigh molecular weight ultrafine particle size propylene polymer, characterized in that the method is selected from one of the method (1) or the method (2): the method (1) includes the following step:

(1a) under the action of a catalyst and a dispersion medium, propylene or propylene and a comonomer are polymerized, wherein the polymerization temperature is 30-105 ° C, the volume fraction of the propylene is 98% or more;

(1b) after the end of the polymerization of the step (1a), adding a solvent, and then removing the dispersion medium by fractional distillation to obtain the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer;

The method (2) comprises the following steps:

(2a) under the action of a catalyst, a dispersion medium and a solvent, a polymerization reaction of propylene or propylene with a comonomer, wherein the polymerization temperature is 30-105 ° C, and the volume fraction of the propylene is 98% or more;

(2b) after the completion of the polymerization in the step (2a), the dispersion medium is removed by fractional distillation to obtain the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer;

In the above method (1) or method (2), the boiling point of the dispersion medium is lower than the boiling point of the solvent and at least 5 ° C lower; the temperature difference is set in order to effectively separate the system by fractional distillation. Dispersing medium.
The production method according to claim 17, wherein in the method (1) or the method (2), the catalyst is produced by the method for producing a catalyst according to claim 1.

Preferably, the propylene polymer obtained has a viscosity average molecular weight (Mv) of more than 1×10 6 ; the propylene polymer is spherical particles, an average particle diameter of 10 μm to 200 μm, a standard deviation of 2 μm to 15 μm, and a bulk density of 0.1 g/mL to 0.4 g/mL; the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer has a solvent content of more than 0 and less than or equal to 98% by weight.

Preferably, the propylene polymer has a solvent content of more than 0 and less than or equal to 80% by weight, preferably more than 0 and less than or equal to 50% by weight, more preferably from 10 to 50% by weight, still more preferably from 20 to 40% by weight.

Preferably, the particle size distribution of the propylene polymer approximates a normal distribution.

Preferably, the polymerization is carried out by a slurry process.

Preferably, the dispersion medium may be at least one of n-pentane, cyclohexane, benzene, toluene, xylene, n-hexane, n-heptane, petroleum ether, and the like.

Preferably, the solvent may be cyclohexane, n-hexane, n-heptane, benzene, toluene, xylene, dichlorobenzene, trichlorobenzene, 1,1,1-trichloroethane, white oil, paraffin, At least one of kerosene, olefin mineral oil and decalin.

Preferably, the comonomer is a C 2-20 alpha-olefin such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene One or more of 1-decene, 1-undecene or 1-dodecene. Preferably, the comonomer is one or both of ethylene and 1-butene. The comonomer has a molar percentage of from 0 to 10 mol%, preferably from 0 to 5 mol%.

Preferably, the temperature of the polymerization reaction is preferably from 40 to 80 ° C, more preferably from 50 to 75 ° C.

Preferably, the propylene has a volume fraction of 99% or more, preferably 99.2% or more, further preferably 99.5% or more, more preferably 99.8% or more, still more preferably 99.9% or more.

Preferably, the comonomer (e.g., ethylene or 1-butene) has a carbon monoxide content of less than 5 ppm, a carbon dioxide content of less than 15 ppm, and a conjugated diene content of less than 10 ppm.
The solubilized ultrahigh molecular weight ultrafine particle size propylene polymer obtained by the preparation method according to claim 17 or 18, wherein the propylene polymer has a viscosity average molecular weight (Mv) of more than 1 × 10 6 ; The propylene polymer is spherical particles having an average particle diameter of 10 μm to 200 μm, a standard deviation of 2 μm to 15 μm, a bulk density of 0.1 g/mL to 0.4 g/mL, and a weight percentage of the solvent in the propylene polymer of more than 0. And less than or equal to 98% by weight.
The solubilized ultrahigh molecular weight ultrafine particle size propylene polymer according to claim 19, wherein the propylene polymer has a solvent content of more than 0 and less than or equal to 80% by weight, preferably more than 0. It is 50% by weight or less, more preferably 10 to 50% by weight, still more preferably 20 to 40% by weight.

Preferably, the particle size distribution of the propylene polymer approximates a normal distribution.

Preferably, the propylene polymer is a propylene homopolymer or a propylene copolymer, and the comonomer in the propylene copolymer is a C 2-20 α-olefin such as ethylene, 1-butene, 1-pentene, 1 One or more of hexene, 1-heptene, 1-octene, 1-decene, 1-decene, 1-undecene or 1-dodecene. Preferably, the comonomer is one or both of ethylene and 1-butene. The comonomer has a molar percentage of from 0 to 10 mol%, preferably from 0 to 5 mol%.

Preferably, the propylene polymer has a viscosity average molecular weight (Mv) of more than 1.5×10 6 , preferably 1.5×10 6 to 4.0×10 6 ; and the propylene polymer has a molecular weight distribution Mw/Mn of 2-15. It is preferably 3 to 10, and more preferably 4 to 8.

Preferably, the average particle diameter of the propylene polymer is preferably from 20 μm to 180 μm, more preferably from 30 μm to 150 μm, still more preferably from 40 to 120 μm; the standard deviation is preferably from 5 μm to 15 μm, more preferably from 6 μm to 12 μm, It is preferably 8 μm to 10 μm; the bulk density of the propylene polymer is preferably from 0.15 g/mL to 0.35 g/mL, and more preferably from 0.2 g/mL to 0.3 g/mL.
A fiber comprising, in its raw material, a solubilized ultrahigh molecular weight ultrafine particle size propylene polymer according to claim 19 or 20.

Preferably, the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer adopts the method of claim 17 or 18. The preparation method of one of (1) or method (2) is prepared.

Preferably, the raw material includes an antioxidant in addition to the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer. Preferably, the antioxidant is added in an amount of 0.01 to 1 part by weight, more preferably 0.02 to 0.5 part by weight, per 100 parts by weight of the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer. Specifically, the fiber is obtained from the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer containing an antioxidant.
A method of preparing a fiber according to claim 21, comprising the steps of:

1) dissolving a raw material containing the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer in a solvent to obtain a spinning solution or gel; 2) spinning by a jelly spinning method to obtain a gel fiber; Drawing; producing the fiber.
The preparation method according to claim 22, wherein in the step 1), in order to avoid degradation of the ultrahigh molecular weight propylene polymer during dissolution and use, an antioxidant is added during the dissolution. The amount of the antioxidant added is 0.01 to 1 part by weight, more preferably 0.02 to 0.5 part by weight, per 100 parts by weight of the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer.

Preferably, prior to the step of drawing of step 3), the step of extracting the solvent by a coagulant or an extractant is included. Preferably, the coagulant or extractant is selected from a low boiling organic solvent such as one or more of the following low boiling organic solvents: petroleum ether, dichloromethane, cyclohexane, and the like.

Preferably, the drafting in the step 3) is carried out by a hot box or a hot roll, or a hot bath drafting method.

For the heat bath drawing mode therein, preferably, the hot bath medium used is selected from the group consisting of a polyol (preferably having a boiling point of 120-220 ° C) and a polyoxyethylene oligomer (preferably, a relative molecular weight of 88-5000 g/mol). a polyoxypropylene oligomer (preferably, having a relative molecular weight of 116 to 1200 g/mol), one or more components of mineral oil and silicone oil. Preferably, the hot bath medium temperature T L is set between the glass transition temperature T g of the polymer matrix and the decomposition temperature T d of the polymer matrix.

Preferably, the step 3) is specifically: the gel fiber is subjected to gel wire drawing, solvent extraction, drying, first hot box dry heat drawing, second hot box dry heat drawing, heat setting and rolling. The fiber of the present invention is obtained by a process such as winding.

Preferably, the drawing temperature in the gel filament drawing step is from 10 to 70 ° C, preferably from 25 to 50 ° C; and the draw ratio is from 2 to 20 times, preferably from 3 to 15 times.

Preferably, the extracting agent in the solvent extraction step is selected from a low boiling organic solvent such as one or more of the following low boiling organic solvents: petroleum ether, dichloromethane, cyclohexane, and the like.

Preferably, the drying in the drying step is dried by hot air, and the hot air temperature is 40 to 100 ° C, preferably 50 to 80 ° C.

Preferably, the temperature in the first hot box dry heat drawing process is 100-200 ° C, preferably 130-180 ° C; the draw ratio is 1-20 times, preferably 1.5-15 times.

Preferably, the temperature in the second hot box dry heat drawing process is 110-200 ° C, preferably 130-180 ° C; the draw ratio is 1-5 times, preferably 1.1-3 times.

Preferably, the temperature in the heat setting process is from 100 to 180 ° C, preferably from 120 to 150 ° C.
A film characterized in that the raw material mainly comprises the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer according to claim 19 or 20.

Preferably, the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer adopts the method of claim 17 or 18. The preparation method of one of (1) or method (2) is prepared.

Preferably, the raw material includes an antioxidant in addition to the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer. Preferably, the antioxidant is added in an amount of 0.01 to 1 part by weight, more preferably 0.02 to 0.5 part by weight, per 100 parts by weight of the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer. Specifically, the film is prepared from the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer containing an antioxidant.

Preferably, the film is uniaxially stretched or biaxially stretched. Preferably, the film is biaxially stretched.
The method for producing a film according to claim 24, wherein the preparation method comprises the steps of: 1) melting a raw material containing the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer and a solvent for film formation; Mixing to obtain a solution; 2) extruding the solution, forming a shaped body, cooling to obtain a polymer sheet; 3) uniaxial stretching or biaxial stretching to obtain a film.

Preferably, in step 1), in order to avoid degradation of the ultrahigh molecular weight propylene polymer during dissolution and use, an antioxidant is added during the dissolution process. The amount of the antioxidant added is 0.01 to 1 part by weight, more preferably 0.02 to 0.5 part by weight, per 100 parts by weight of the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer. Specifically, the raw material is composed of the solubilized ultrahigh molecular weight ultrafine particle size propylene polymer and an antioxidant.
The use of the film of claim 24 as a battery separator.