CN106279474A - Solubilising type super high molecular weight micronized polyethylene and preparation method thereof - Google Patents
Solubilising type super high molecular weight micronized polyethylene and preparation method thereof Download PDFInfo
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- CN106279474A CN106279474A CN201610695051.XA CN201610695051A CN106279474A CN 106279474 A CN106279474 A CN 106279474A CN 201610695051 A CN201610695051 A CN 201610695051A CN 106279474 A CN106279474 A CN 106279474A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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Abstract
The invention provides a kind of solubilising type super high molecular weight ultra-fine grain diameter polyethylene and preparation method thereof, the viscosity-average molecular weight (Mv) of described polyethylene is more than 1 × 106；Described polyethylene is spherical or spherical particle, and mean diameter is 10～100 μm, and standard deviation is 2 μm 15 μm, and bulk density is 0.1g/mL～0.3/mL；In described polyethylene, the weight percentage of solvent is more than 0 and less than or equal to 98wt%.The present invention is by controlling the polymerization temperature of ethylene, the purity of monomer ethylene, adjusting the preparation process of catalyst and introduce disperse medium in polymerization system, synthesize a kind of solubilising type super high molecular weight ultra-fine grain diameter polyethylene, the method step height simple, easily controllable, repeated, it is possible to achieve industrialization.
Description
Technical field
The present invention relates to a kind of solubilising type polymer and preparation method thereof, be specifically related to a kind of solubilising type super high molecular weight and surpass
Fine grain polyethylene and preparation method thereof.
Background technology
Ultra-high molecular weight polyethylene (UHMWPE) is by ethylene, divinylic monomer under the effect of Ziegler catalyst, low
The mean molecule quantity that is polymerized of pressure is more than 1,500,000, and molecule has the engineering thermoplastic of excellent combination property of linear structure
Plastics.Molecular weight (molecular weight of HDPE generally only 2～300,000) high for UHMWPE gives the serviceability of its excellence, thus
Ultra-high molecular weight polyethylene is made to have common high density polyethylene (HDPE) and the unexistent special performance of some other engineering plastics, as
Excellent impact resistance, mar proof, chemical resistance, lower temperature resistance, stress cracking resistance, anti-adhesive and self-lubricity
Deng, there is the title of " surprised plastics ".This material combination property is superior, and density is little, and coefficient of friction is the lowest, wear-resistant, low temperature resistant, resistance to
Burn into self-lubrication, shock resistance are peak in all plastics, and anti-wear performance is better than politef, nylon, carbon steel
Deng material, can work under the conditions of-169～+80 DEG C for a long time, physical and mechanical properties is considerably beyond common polythene.Can be extensive
It is applied to metallurgy, electric power, oil, weaving, papermaking, food, chemical industry, machinery, the industry such as electrically.
Although having an excellent combination property when solid-state as the UHMWPE of thermoplastic engineering plastic, but its melt characteristic and
The general thermoplastic such as common polythene is the most completely different, is mainly manifested in the following aspects: 1) melt viscosity height；2) rub
Wiping factor is little；3) critical shear rate is low；4) forming temperature narrow range, oxidizable degraded.Although the process technology warp of UHMWPE
Cross the development of decades, by initial compacting-sinter molding develop into extrusion, be blow molded and inject, solvent spinning molding etc. many
Kind of forming method, but owing to UHMWPE exists problem above, bring difficulty to processing method so that its be applied to section bar,
Hydraulic performance decline is caused during the aspects such as thin film, fiber, filtering material.
Such as along with the increase of ultra-high molecular weight polyethylene content, the viscosity of system is also substantially increased, conventional wet technique
It is difficult to process high viscosity stock solution, limits the application of ultra-high molecular weight polyethylene.Such as in conventional wet method preparation process process
In, first by polyolefin heating for dissolving in paraffin or other solvent, form homogeneous phase solution, use vulcanizer to drop after being pressed into thin slice
, there is liquid-liquid phase separation, then extract-stretch or stretch-extract, obtain porous septum in temperature.Polyolefin is meeting in temperature-fall period
, there is liquid-liquid separation, result in thin film and be difficult to high magnification drawing-off, limit the lifting of barrier film combination property in crystallization.Cause
This, the solution that conventional wet technique is difficult by containing ultra-high molecular weight polyethylene prepares barrier film, and this is primarily due to all mix
Liquid occurs liquid-solid phase to separate or liquid-liquid phase separation in temperature-fall period, and in phase separation, polyolefin can crystallize, and causes thin film
It is difficult to high magnification drawing-off, limits the lifting of barrier film combination property.
Therefore, current research mainly around how preparing the excellent ultra-high molecular weight polyethylene of processing characteristics launches.Portion
Catalyst employed in point research worker preparation method to ultra-high molecular weight polyethylene has carried out widely studied, to be expected to
The ultra-high molecular weight polyethylene aspect preparing high excellent properties makes a breakthrough.Used when preparing ultra-high molecular weight polyethylene
Catalyst is mainly metallocene catalyst and ziegler natta catalyst.But, metallocene catalyst is extremely sensitive to temperature, when
With Cp2ZrCl2Catalyzed ethylene polymerization, when temperature is in time being raised to 70 DEG C for 20 DEG C, and polymer molecular weight drops to 120,000 from 600,000.Meanwhile,
Metallocene catalyst, to reach sufficiently high catalysis activity, needs a large amount of expensive MAO (MAO) as helping
Catalyst, thus add product preparation cost, on the other hand, the compound that promoter MAO not composition is single, produced
It is unstable that journey easily causes properties of product.Ziegler natta catalyst is the industrialization catalysis preparing ultra-high molecular weight polyethylene
Agent, such as, ZhangH.X. etc. [Polym.Bull., 2011,66,627] reports and utilizes the Ziegler containing internal electron donor
The method of ultra-high molecular weight polyethylene prepared by Natta catalyst, but, the internal electron donor fall in this ziegler natta catalyst
The low activity of catalyst.
Therefore, at present in the urgent need to the preparation method of a kind of ultra-high molecular weight polyethylene (UHMWPE) occurs so that the party
Method can prepare the UHMWPE of excellent performance, and ensures that it will not when being processed as section bar, thin film, fiber or filtering material
Reduce its performance, there is more preferable processing characteristics and wider application prospect.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of processing characteristics more excellent, more easily
Ultra-high molecular weight polyethylene of processing and preparation method thereof.
In order to solve above technical problem, the present invention provides the system of a kind of solubilising type super high molecular weight ultra-fine grain diameter polyethylene
Preparation Method, its one in method (1) or method (2)；
Described method (1) comprises the following steps:
(1a) under the effect of catalyst and disperse medium, ethylene carries out polyreaction；Wherein, the temperature of polyreaction
For-20～100 DEG C；Wherein, the carbon monoxide content in ethylene is less than 5ppm, and carbon dioxide is less than 15ppm, and conjugated diene contains
Amount is less than 10ppm；
(1b), after the polymerization of step (1a) terminates, add solvent, then remove described disperse medium by the method for fractional distillation,
Obtain described solubilising type super high molecular weight ultra-fine grain diameter polyethylene；
Described method (2) comprises the following steps:
(2a) under the effect of catalyst, disperse medium and solvent, ethylene carries out polyreaction；Wherein, polyreaction
Temperature is-20～100 DEG C；Wherein, the carbon monoxide content in ethylene is less than 5ppm, and carbon dioxide is less than 15ppm, conjugated diene
Hydrocarbon content is less than 10ppm；
(2b), after the polymerization of step (2a) terminates, remove described disperse medium by the method for fractional distillation, obtain described solubilising
Type super high molecular weight ultra-fine grain diameter polyethylene；
In said method (1) or method (2), the boiling point of described disperse medium is less than the boiling point of described solvent and the lowest by 5
℃；
In said method (1) or method (2), described catalyst is prepared by the method comprised the following steps:
A (), by magnesium halide, alcohol compound, auxiliary agent, the internal electron donor of part and solvent mixing, prepares mixture I；
B () adds above-mentioned mixture I in the reactor, be preheating to-30 DEG C～30 DEG C, drips titanium compound；Or,
Reactor adds titanium compound, is preheating to-30 DEG C～30 DEG C, drips above-mentioned mixture I；
C () is added dropwise to complete after, reaction system was warming up to 90 DEG C～130 DEG C through 30 minutes～3 hours, added remaining interior
Electron donor continues reaction；
D () filters the liquid of reaction system, add remaining titanium compound, continues reaction；
E () has been reacted after, post processing obtains described catalyst.
According to the present invention, the viscosity-average molecular weight (Mv) of the solubilized type super high molecular weight ultra-fine grain diameter polyethylene wherein prepared is big
In 1 × 106；Described solubilising type super high molecular weight ultra-fine grain diameter polyethylene be spherical or spherical particle, mean diameter be 10～
100 μm, standard deviation is 2 μm-15 μm, and bulk density is 0.1g/mL～0.3g/mL；Described solubilising type super high molecular weight ultra-fine grain diameter
In polyethylene, the weight percentage of solvent is more than 0 and less than or equal to 98wt%.
According to the present invention, in described solubilising type super high molecular weight ultra-fine grain diameter polyethylene, the weight percentage of solvent is more than
0 and less than or equal to 80wt%, preferably greater than 0 and less than or equal to 50wt%, more preferably 10-50wt%, still more preferably 20-
40wt%.
According to the present invention, the particle diameter distribution of described solubilising type super high molecular weight ultra-fine grain diameter polyethylene is similar to normal state and divides
Cloth.
In above-mentioned preparation method, described polyreaction uses slurry process.
In above-mentioned preparation method, described disperse medium can be pentane, hexamethylene, benzene,toluene,xylene, normal hexane,
In normal heptane, petroleum ether etc. at least one.
In above-mentioned preparation method, described solvent can be hexamethylene, normal hexane, normal heptane, benzene,toluene,xylene, dichloro
In benzene, trichloro-benzenes, 1,1,1-trichloroethane, white oil, paraffin, kerosene, alkene mineral oil and decahydronaphthalene at least one.
According to the present invention, the temperature of described polyreaction is preferably 0～90 DEG C, preferably 10～85 DEG C, and also preferably 30
～80 DEG C, more preferably 50～80 DEG C.
The present invention also provides for the solubilized type super high molecular weight ultra-fine grain diameter polyethylene prepared by above-mentioned preparation method, described poly-
The viscosity-average molecular weight (Mv) of ethylene is more than 1 × 106；Described polyethylene is spherical or spherical particle, and mean diameter is 10～100
μm, standard deviation is 2 μm-15 μm, and bulk density is 0.1g/mL～0.3/mL；In described polyethylene, the weight percentage of solvent is
More than 0 and less than or equal to 98wt%.
According to the present invention, in described polyethylene, the weight percentage of solvent is more than 0 and less than or equal to 80wt%, is preferably
More than 0 and less than or equal to 50wt%, more preferably 10-50wt%, still more preferably 20-40wt%.
According to the present invention, the particle diameter distribution of described polyethylene is similar to normal distribution.
According to the present invention, the viscosity-average molecular weight (Mv) of described polyethylene is more than or equal to 1.5 × 106, it is therefore preferable to 1.5 × 106
～4.0 × 106；The molecular weight distribution mw/mn of described polyethylene is 2～15, preferably 3～10, also preferably 4～8.
According to the present invention, the mean diameter of described polyethylene is preferably 20 μm-90 μm, also preferably 30-85 μm, more preferably
It is 50 μm-80 μm；Described standard deviation is preferably 5 μm-15 μm, more preferably 6 μm-12 μm, also preferably 8 μm-10 μm；Described poly-
The bulk density of ethylene is preferably 0.15g/mL-0.25g/mL, such as 0.2g/mL.
Beneficial effects of the present invention:
The present invention proposes a kind of method of brand-new preparation solubilising type super high molecular weight ultra-fine grain diameter polyethylene, described method
In by controlling the polymerization temperature of ethylene, the purity of monomer ethylene, adjusting the preparation process of catalyst and draw in polymerization system
Entering disperse medium, synthesized a kind of solubilising type super high molecular weight ultra-fine grain diameter polyethylene, the method step is simple, be prone to control
System, repeatability are high, it is possible to achieve industrialization.
The present invention synthesizes a kind of poly-second simultaneously having lyotropy, super high molecular weight and ultra-fine particle size range concurrently first
Alkene, research finds, the polyethylene possessing above-mentioned characteristic is particularly suitable for processed and applied, and is easily achieved graft modification, greatly
Extend the processing characteristics of ultra-high molecular weight polyethylene and the application of goods thereof and the scope of application.Meanwhile, described poly-second
Alkene is also equipped with following excellent properties: first, and abrasion resistance properties is the most remarkable, than the metals such as general carbon steel and copper abrasion resistance index also
High several times；Secondly as molecular weight superelevation, strand overlength so that the impact strength of material is high；Again, this polyethylene is resistance to
Chemical attack ability is better than general polyolefin；Finally, the use wider range of this material, at lower or higher temperatures
All can keep good toughness and intensity；Finally, this material energy consumption in later stage molding, film forming, fiber forming process is low, technique stream
Time of journey is short (such as, to be completely dissolved, or rapid solution under the higher temperature short period, thus at a lower temperature in contracting
It is effectively reduced while short course of dissolution or decreases depolymerization).
Therefore, use the polyethylene prepared of method of the present invention to have the processing characteristics of excellence, be expected to later stage molding,
The most more energy efficient in film forming, fiber forming process, and technological process can be accelerated, prepare the material of higher performance.
Detailed description of the invention
[preparation method of catalyst]
The catalyst used in the preparation method of the present invention can use the application for a patent for invention (application that applicant has been filed on
Numbers 201510271254.1) prepared by the method disclosed in, it introduces in full herein as reference.
Specifically, the catalyst used in the preparation method of the present invention is prepared by the method comprised the following steps:
A (), by magnesium halide, alcohol compound, auxiliary agent, the internal electron donor of part and solvent mixing, prepares mixture I；
B () adds above-mentioned mixture I in the reactor, be preheating to-30 DEG C～30 DEG C, drips titanium compound；Or,
Reactor adds titanium compound, is preheating to-30 DEG C～30 DEG C, drips above-mentioned mixture I；
C () is added dropwise to complete after, reaction system was warming up to 90 DEG C 130 DEG C through 30 minutes～3 hours, added remaining interior
Electron donor continues reaction；
D () filters the liquid of reaction system, add remaining titanium compound, continues reaction；
E () has been reacted after, post processing obtains described catalyst.
According to the present invention, described step (b) is replaced by following step (b '):
(b ') configure the mixtures II including nanoparticle, dispersant and solvent；
Add above-mentioned mixture I in the reactor and mixtures II obtains the two mixture, be preheating to-30 DEG C～30
DEG C, drip titanium compound；Or,
Add titanium compound in the reactor, be preheating to-30 DEG C～30 DEG C, drip above-mentioned mixture I and mixtures II
Mixture.
In the present invention, described mixture I is preferably prepared as follows: by magnesium halide and alcohol compound organic
Solvent mixes, after heating up and being incubated, adds auxiliary agent and the internal electron donor of part, obtain stablizing equal after uniform temperature is reacted
The mixture I of one.Described alcohol compound is selected from C1-C15Aliphatic alcohols compound, C3-C15Cyclic alkanol compounds and C6-
C15Aromatic alcohol compound in one or more, preferably methanol, ethanol, ethylene glycol, normal propyl alcohol, isopropanol, 1,3-third
In glycol, butanol, isobutanol, hexanol, enanthol, n-octyl alcohol, isooctanol, nonyl alcohol, decanol, sorbitol, Hexalin and benzylalcohol one
Plant or several, more preferably ethanol, butanol, hexanol and isooctanol.Described internal electron donor is monoesters, diester, monoether, two ethers
At least one in compound, preferred selected from diester or diether.Described solvent is selected from the linear paraffin of 5-20 carbon, 5-20
At least one in the branched paraffin of individual carbon, the aromatic hydrocarbon of 6-20 carbon or their halogenated hydrocarbons, preferably toluene, chlorobenzene, dichloro
At least one in benzene or decane.In the present invention, magnesium halide can directly obtain urging of submicron order polyolefin particles in preparation
Agent has the effect of carrier, for one of the composition of traditional Ziegler Natta, the catalyst of preparation can be made to have conjunction
Suitable shape, size and mechanical strength, meanwhile, carrier can make active component be dispersed on carrier surface, it is thus achieved that higher ratio table
Area, improves the catalytic efficiency of unit mass active component.It addition, the effect of described alcohol compound is carrier i.e. halogenation
Magnesium dissolves.In the preparation process of mixture I, described in obtain the temperature of mixed solution and be preferably 110 DEG C-130 DEG C, more preferably
130 DEG C, described temperature retention time is preferably 1-3 hour, more preferably 2-3 hour, and the response time after described addition auxiliary agent etc. is
0.5-2 hour, more preferably 1 hour.Therefore, magnesium halide is at high temperature dissolved by alcohol compound, has obtained mixture I.
According to the present invention, described mixture II is preferably prepared as follows: by nanoparticle, dispersant and solvent
Join in reaction vessel, supersound process, obtain uniform mixture II.Described nanoparticle is preferably nanometer titanium dioxide
At least one in silicon, nano titanium oxide, nano zirconium dioxide, nano-nickel oxide, nanometer magnesium chloride or nano carbon microsphere, more excellent
Elect nano silicon, nano titanium oxide as.The granularity of nanoparticle is preferably 1-80nm, more preferably 10-50nm.Preferably
The addition quality of nanoparticle be 0%-200%, more preferably 0%-20% relative to the addition quality of magnesium halide.Ultrasonic place
The time of reason is preferably 2 hours.In the present invention nanoparticle as crystal seed introduce in order to accelerate carrier molding and
Reduce the particle diameter of catalyst granules；Dispersant and solvent, be provided to help nanoparticle dispersion including supersound process, so promote
Make each nano-particle can play the effect of crystal seed.
According to the present invention, in the mixtures II of described step (b '), described nanoparticle is selected from nano silicon, nanometer
At least one in titanium dioxide, nano zirconium dioxide, nano-nickel oxide, nanometer magnesium chloride or nano carbon microsphere.
Preferably, the granularity of described nanoparticle is 1-80 nanometer, preferably 2-60 nanometer, more preferably 3-50 nanometer.
The addition quality of described nanoparticle is to less than or equal to 200% more than 0% relative to the addition quality of magnesium halide,
Preferably, described nanoparticle addition in the range of more than 0% to less than or equal to 20%.
In the present invention, in the mixtures II of described step (b '), described solvent is selected from the linear paraffin of 5-20 carbon, 5-20
At least one in the branched paraffin of individual carbon, the aromatic hydrocarbon of 6-20 carbon or their halogenated hydrocarbons.
Described dispersant is selected from titanium tetrachloride, Silicon chloride. or both mixture.
In step (a), described in be blended under heated and stirred and carry out, it is thus achieved that the transparent mixture I of stable homogeneous.
Step (b ') in, carry out ultrasonic disperse process during configuration.
In step (b) or (b '), drip as being slowly added dropwise.
In step (b) or (b '), preferably reaction preheating temperature be-20 DEG C 30 DEG C, is more preferably-20 DEG C 20 DEG C.
The response time of step (c) is 1-5 hour, preferably 2-3 hour.
The time continuing reaction of step (d) is 1-5 hour, preferably 2-3 hour.
Post processing in step (e) can be to be carried out products therefrom with hexane, then dries；Wherein, cleaning
Number of times can be 1-10 time, preferably 3-6 time.
In step (a), at least one in magnesium chloride, magnesium bromide or magnesium iodide of described magnesium halide.
In step (a), described auxiliary agent can be titanate ester compound.
In step (b) or (b '), the formula of described titanium compound shown in formula I:
Ti(R)nX(4-n)
Formulas I
Wherein, R is the branched-chain or straight-chain alkyl of C1-C12, and X is halogen, and n is 0,1,2 or 3.
In step (d), it is preferred that reaction system was warming up to 90 DEG C 130 DEG C through 40 minutes 3 hours, the most instead
System is answered to be warming up to 100 DEG C 120 DEG C through 40 minutes 2 hours.
From such scheme it can be seen that the preparation method technique of Ziegler-Natta catalyst involved in the present invention is simple,
It is prone to industrialized production.Further, the Ziegler-Natta catalyst that prepared by the present invention can prepare mean diameter when vinyl polymerization
Being 10～100 μm, sphericity is higher, narrower particle size distribution, the polyethylene particle of bulk density low (being 0.1～0.3g/mL).Pass through
Research finds, catalyst prepared by the present invention is compared and other polyethylene for the polyethylene particle that vinyl polymerization obtains, granularity
Having the reduction of 20-30 times, particle size distribution substantially narrows and bulk density can as little as 0.1g/mL.
[preparation method of solubilising type super high molecular weight ultra-fine grain diameter polyethylene]
As it has been described above, the invention provides the preparation method of a kind of super high molecular weight ultra-fine grain diameter polyethylene, it is selected from side
One in method (1) or method (2)；
Described method (1) comprises the following steps:
(1a) under the effect of catalyst and disperse medium, ethylene carries out polyreaction；Wherein, the temperature of polyreaction
For-20～100 DEG C；Wherein, the carbon monoxide content in ethylene is less than 5ppm, and carbon dioxide is less than 15ppm, and conjugated diene contains
Amount is less than 10ppm；
(1b), after the polymerization of step (1a) terminates, add solvent, then remove described disperse medium by the method for fractional distillation,
Obtain described solubilising type super high molecular weight ultra-fine grain diameter polyethylene；
Described method (2) comprises the following steps:
(2a) under the effect of catalyst, disperse medium and solvent, ethylene carries out polyreaction；Wherein, polyreaction
Temperature is-20～100 DEG C；Wherein, the carbon monoxide content in ethylene is less than 5ppm, and carbon dioxide is less than 15ppm, conjugated diene
Hydrocarbon content is less than 10ppm；
(2b), after the polymerization of step (2a) terminates, remove described disperse medium by the method for fractional distillation, obtain described solubilising
Type super high molecular weight ultra-fine grain diameter polyethylene；
In said method (1) or method (2), the fusing point of described disperse medium is less than the fusing point of described solvent and the lowest by 5
℃；Set such temperature difference, be the disperse medium in order to efficiently separate out in system by the method for fractional distillation.
In said method (1) or method (2), described catalyst is prepared by the preparation method of above-mentioned catalyst.
The present invention is found by research, the simple preparation method controlling described catalyst, really can realize institute very well
State the control of the particle diameter of polyethylene, but the molecular weight of the polyethylene of preparation is the highest, in order to realize improving while controlling particle diameter
The molecular weight of described polymer, inventor has carried out many trials, it has been investigated that, control temperature and the monomer of polyreaction
Purity be a kind of simple and effective method, and do not interfere with effective control of described polymer particle diameter, even help
In preparing narrower particle size range and the polymer of lower bulk density scope.
Being found by research, the temperature of described polyreaction controls at-20～100 DEG C, and it is an oxygen that ethylene moderate purity controls
Change carbon content and be less than 10ppm less than 5ppm, carbon dioxide less than 15ppm and conjugated diene hydrocarbon content, it is possible to realize particle diameter
The polyethylene of super high molecular weight is prepared while control.Preferably, the temperature of described polyreaction is 0～90 DEG C, preferably 10
～85 DEG C, also preferably 30-80 DEG C, more preferably 50-80 DEG C.
It addition, for the processing characteristics improving described super high molecular weight ultra-fine grain diameter polyethylene further, the present invention enters
One step introduces the means of solubilising, say, that the present invention introduces disperse medium during preparing polyethylene, or dispersion is situated between
Matter and solvent, the existence of these little molecules makes the Crystalline size of obtained polyethylene be greatly reduced, and strand is easier to fortune
Dynamic, when follow-up dissolving or melt-processed goods, heat is easier to transmission so that obtained polyethylene can be at relatively low temperature
Degree lower rapid solution or melted, thus shorten technological process, reduce dissolving in addition or melt temperature can also substantially reduce poly-
The degraded of ethylene, this for ensureing its molecular weight, to obtain high performance polyethylene products the most crucial.
[solubilising type super high molecular weight ultra-fine grain diameter polyethylene]
As it has been described above, the invention provides a kind of solubilising type super high molecular weight ultra-fine grain diameter polyethylene, described polyethylene
Viscosity-average molecular weight (Mv) is more than 1 × 106, described polyethylene is spherical or spherical particle, and mean diameter is 10 μm-100 μm, mark
Quasi-difference is 2 μm-15 μm, and bulk density is 0.1g/mL-0.3g/mL；In described polyethylene, the weight percentage of solvent is more than 0
And less than or equal to 98wt%.Preferably, in described polyethylene, the weight percentage of solvent is preferably greater than 0 and is less than or equal to
50wt%, more preferably 10-50wt%, still more preferably 20-40wt%.Preferably, the particle diameter distribution approximation of described polyethylene
In normal distribution.Described mean diameter is preferably 20 μm-90 μm, also preferably 30-85 μm, more preferably 50 μm-80 μm.Described
Standard deviation is preferably 5 μm-15 μm, more preferably 6 μm-12 μm, also preferably 8 μm-10 μm.Described bulk density is preferably 0.15g/
ML-0.25g/mL, such as 0.2g/mL.Possesses the ultra-high molecular weight polyethylene of described particle diameter, bulk density and solvent, especially
It is applicable to graft modification, on the one hand greatly extends the modified space of polyethylene；On the other hand, the processability of described polymer
Can significantly improve, it is adaptable to the preparation of larger range of goods；So, the application of described polymer is the most effectively extended.
Meanwhile, the polyethylene of the present invention is also equipped with following excellent properties: first, and abrasion resistance properties is the most remarkable, and ratio is typically
The highest several times of abrasion resistance index of the metal such as carbon steel and copper；Secondly as molecular weight superelevation, strand overlength so that rushing of material
Hit intensity is high；Again, the resistance to chemical attack ability of this polyethylene is better than general polyolefin；Finally, the use temperature model of this material
Enclose wider, all can keep good toughness and intensity at lower or higher temperatures；Finally, this material is at later stage molding, one-tenth
Energy consumption in film, fiber forming process is low, the time of technological process is short.
Below by way of specific instantiation, embodiments of the present invention being described, those skilled in the art can be by this specification
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also be by different specific embodiment parties
Formula is carried out or applies, the every details in this specification can also application based on different aspect, without departing from this
Various modification or change is carried out under bright spirit.
The ultra-fine Alathon of comparative example 1 super high molecular weight and preparation thereof
1) preparation of catalyst
In the reactor being sufficiently displaced from through high pure nitrogen, it is sequentially added into anhydrous magnesium chloride 4.94g, isooctanol 18.9g,
Decane 30ml, is warming up to 130 DEG C under stirring, and maintains 2 hours, is subsequently adding 2.65g butyl titanate and 2.05g O-phthalic
Acid diisobutyl ester, reacts 1 hour at 130 DEG C again, is finally cooled to room temperature, forms homogeneous transparent solution, is mixture I.
In reactor, add 200ml titanium tetrachloride stir and be preheated to 0 DEG C, mixture I is added drop-wise to four in about 2 hours
In titanium chloride.Drip complete, start to warm up, in 2 hours, be warming up to 110 DEG C.Add internal electron donor phthalic acid two isobutyl
Ester 1.23g.After reacting 2 hours at this temperature, remove reaction liquid, again add 200ml titanium tetrachloride, react 2 hours.?
After remove reaction liquid, remaining solid matter is rinsed 10 times with the hexane of 60 DEG C, is drying to obtain catalyst.
2) slurry polymerization of ethylene:
Under high pure nitrogen is protected, 1L autoclave is dried deoxygenation, is sequentially added into 150mL normal hexane, 20mg
Above-mentioned catalyst and triethyl aluminum 12ml, then pass to ethylene gas and maintain 0.7MPa；Wherein, in ethylene, carbon monoxide contains
Amount is less than 15ppm less than 5ppm, carbon dioxide, and conjugated diene hydrocarbon content is less than 10ppm；Polyreaction starts, and system temperature is tieed up
To hold be 80 DEG C, the response time is 30 minutes, prepares described Alathon.
Embodiment 1
In the reactor being sufficiently displaced from through high pure nitrogen, it is sequentially added into anhydrous magnesium chloride 4.94g, isooctanol 18.9g,
Decane 30ml, is warming up to 130 DEG C under stirring, and maintains 2 hours, is subsequently adding 2.65g butyl titanate and 2.05g O-phthalic
Acid diisobutyl ester, reacts 1 hour at 130 DEG C again, is finally cooled to room temperature, forms homogeneous transparent solution, is mixture I.
In reactor, add 200ml titanium tetrachloride stir and be preheated to 0 DEG C, mixture I is added drop-wise to four in about 2 hours
In titanium chloride.Drip complete, start to warm up, in 2 hours, be warming up to 110 DEG C.Add internal electron donor phthalic acid two isobutyl
Ester 1.23g.After reacting 2 hours at this temperature, remove reaction liquid, again add 200ml titanium tetrachloride, react 2 hours.?
After remove reaction liquid, remaining solid matter is rinsed 10 times with the hexane of 60 DEG C, is drying to obtain catalyst.
The slurry polymerization of ethylene:
Use slurry polymerization technique, first 5L autoclave (under high pure nitrogen is protected, is entered by polymeric kettle pretreatment
Row is dried deoxygenation), add disperse medium hexamethylene 500g, sequentially add 150mL normal hexane, the catalyst and three that 20mg is above-mentioned
Aluminium ethide 12ml, then passes to ethylene gas and maintains 0.7MPa；Wherein, in ethylene, carbon monoxide content is less than 5ppm, titanium dioxide
Carbon is less than 15ppm, and conjugated diene hydrocarbon content is less than 10ppm；Polyreaction starts, and system temperature is maintained 80 DEG C, response time
It it is 30 minutes.Polyreaction cools after terminating, and is expelled directly out slurry material from bottom valve, adds the desired amount of white oil, distillation
Remove disperse medium, obtain the solubilized type super high molecular weight ultra-fine grain diameter Alathon of the present invention, the wherein quality hundred of white oil
Dividing content is 30wt%.Gained polyethylene character is shown in Table 1.
Contrast dissolution experiment: the super high molecular weight ultra-fine grain diameter ethene polymers containing white oil prepared by embodiment 1
10g, adds 60g white oil, dissolves at 140 DEG C, and 20min has dissolved.
Super high molecular weight ultra-fine grain diameter ethene polymers 7g comparative example 1 prepared, adds 63g white oil, molten at 140 DEG C
Solving, 90min has dissolved.
Embodiment 2
Alathon and preparation thereof
The preparation method of catalyst is with embodiment 1.
The slurry polymerization of ethylene:
Use slurry polymerization technique, first 5L autoclave (under high pure nitrogen is protected, is entered by polymeric kettle pretreatment
Row is dried deoxygenation), add disperse medium pentane 500g, sequentially add 150mL normal hexane, the catalyst and three that 20mg is above-mentioned
Aluminium ethide 12ml, then passes to ethylene gas and maintains 0.7MPa；Wherein, in ethylene, carbon monoxide content is less than 5ppm, titanium dioxide
Carbon is less than 15ppm, and conjugated diene hydrocarbon content is less than 10ppm；Polyreaction starts, and system temperature is maintained 70 DEG C, response time
It it is 30 minutes.Polyreaction cools after terminating, and is expelled directly out slurry material from bottom valve, adds the desired amount of white oil, distillation
Remove disperse medium, obtain the solubilized type super high molecular weight ultra-fine grain diameter Alathon of the present invention, the wherein quality hundred of white oil
Dividing content is 40wt%.The character of gained polyethylene is shown in Table 1.
The dissolution time using the similar to Example 1 polymer that method mensuration dissolubility, relatively solvent are 0 shortens
Nearly 80%.
Embodiment 3
Alathon and preparation thereof
The preparation method of catalyst is with embodiment 1.
The slurry polymerization of ethylene:
Use slurry polymerization technique, first 5L autoclave (under high pure nitrogen is protected, is entered by polymeric kettle pretreatment
Row is dried deoxygenation), add disperse medium hexamethylene 500g and the desired amount of white oil, sequentially add catalyst above-mentioned for 20mg and
Triethyl aluminum 12ml, then passes to ethylene gas and maintains 0.7MPa；Wherein, in ethylene, carbon monoxide content is less than 5ppm, dioxy
Change carbon and be less than 10ppm less than 15ppm, conjugated diene hydrocarbon content；Polyreaction starts, system temperature be maintained 50 DEG C, reaction time
Between be 30 minutes.Polyreaction cools after terminating, and is expelled directly out slurry material from bottom valve, and disperse medium is removed in distillation,
To the solubilized type super high molecular weight ultra-fine grain diameter Alathon of the present invention, wherein the weight/mass percentage composition of white oil is 30wt%.
Gained polyethylene character is shown in Table 1.
The dissolution time using the similar to Example 1 polymer that method mensuration dissolubility, relatively solvent are 0 shortens
Nearly 80%.
The detection of scanned Electronic Speculum figure understands, and polyethylene particle prepared by embodiment 1-3 presents preferable sphericity, for spherical
Or class is spherical, and particle diameter distribution is more uniform, and mean diameter is less.
Comparative example 2
Alathon and preparation thereof
The preparation method of catalyst is with embodiment 1.
The polymerisation in bulk of ethylene:
Use method similar to Example 1, be different only in that the purity of polymerization temperature and monomer, wherein, ethylene pure
Degree is: carbon monoxide content is higher than 10ppm, and carbon dioxide is higher than 20ppm, and conjugated diene hydrocarbon content is higher than 20ppm；System temperature
It is maintained 110 DEG C.The character of gained catalyst activity and polyethylene is shown in Table 1.
The catalysis activity of Ziegler-Natta catalyst prepared by table 1 embodiment of the present invention and the character of prepared polyethylene
The present invention have detected some other performance of the polyethylene of embodiment 1-3 the most further, find after testing: (1)
All high than the abrasion resistance index of general carbon steel or the copper several times of the abrasion resistance index of the polyethylene of embodiment 1-3；And the wear-resisting finger of comparative example 1
Number the most slightly reduces；(2) impact strength of the polyethylene of embodiment 1-3 is more than 10KJ/m2, and the impact strength in comparative example 1
Then at 3KJ/m2Left and right；(3) the resistance to chemical attack ability of the polyethylene powder body of embodiment 1-3 is better than general polyolefin, comparative example 1
In polyethylene powder body the most easily degrade；(4) the use temperature range of the polyethylene powder body of embodiment 1-3 is relatively
Width, all can keep good toughness and intensity at the temperature (such as 110 DEG C) of relatively low (such as subzero 30 DEG C) or higher.
Claims (10)
1. the preparation method of a solubilized type super high molecular weight ultra-fine grain diameter polyethylene, it is characterised in that described method is selected from side
One in method (1) or method (2)；
Described method (1) comprises the following steps:
(1a) under the effect of catalyst and disperse medium, ethylene carries out polyreaction；Wherein, the temperature of polyreaction is-20
～100 DEG C；Wherein, the carbon monoxide content in ethylene is less than 5ppm, and carbon dioxide is less than 15ppm, and conjugated diene hydrocarbon content is few
In 10ppm；
(1b), after the polymerization of step (1a) terminates, add solvent, then remove described disperse medium by the method for fractional distillation, obtain
Described solubilising type super high molecular weight ultra-fine grain diameter polyethylene；
Described method (2) comprises the following steps:
(2a) under the effect of catalyst, disperse medium and solvent, ethylene carries out polyreaction；Wherein, the temperature of polyreaction
For-20～100 DEG C；Wherein, the carbon monoxide content in ethylene is less than 5ppm, and carbon dioxide is less than 15ppm, and conjugated diene contains
Amount is less than 10ppm；
(2b) after the polymerization of step (2a) terminates, remove described disperse medium by the method for fractional distillation, obtain described solubilising type and surpass
High molecular ultra-fine grain diameter polyethylene；
In said method (1) or method (2), the boiling point of described disperse medium is less than the boiling point of described solvent and the lowest 5 DEG C；
In said method (1) or method (2), described catalyst is prepared by the method comprised the following steps:
A (), by magnesium halide, alcohol compound, auxiliary agent, the internal electron donor of part and solvent mixing, prepares mixture I；
B () adds above-mentioned mixture I in the reactor, be preheating to-30 DEG C～30 DEG C, drips titanium compound；Or, in reaction
Device adds titanium compound, is preheating to-30 DEG C～30 DEG C, drips above-mentioned mixture I；
C () is added dropwise to complete after, reaction system was warming up to 90 DEG C～130 DEG C through 30 minutes～3 hours, added remaining interior to electricity
Daughter continues reaction；
D () filters the liquid of reaction system, add remaining titanium compound, continues reaction；
E () has been reacted after, post processing obtains described catalyst；
The viscosity-average molecular weight (Mv) of the solubilized type super high molecular weight ultra-fine grain diameter polyethylene wherein prepared is more than 1 × 106；Described increasing
Molten type super high molecular weight ultra-fine grain diameter polyethylene is spherical or spherical particle, and mean diameter is 10～100 μm, and standard deviation is 2 μ
M-15 μm, bulk density is 0.1g/mL～0.3g/mL；The weight of solvent in described solubilising type super high molecular weight ultra-fine grain diameter polyethylene
Amount percentage composition is more than 0 and less than or equal to 98wt%.
Preparation method the most according to claim 1, it is characterised in that the described solubilising type poly-second of super high molecular weight ultra-fine grain diameter
In alkene, the weight percentage of solvent is more than 0 and less than or equal to 80wt%, and preferably greater than 0 and less than or equal to 50wt%, more excellent
Elect 10-50wt% as, still more preferably 20-40wt%.
Preferably, the particle diameter distribution of described solubilising type super high molecular weight ultra-fine grain diameter polyethylene is similar to normal distribution.
Preparation method the most according to claim 1 and 2, it is characterised in that described polyreaction uses slurry process.
Preferably, the temperature 0 of described polyreaction～90 DEG C, preferably 10～85 DEG C, also preferably 30～80 DEG C, more preferably
50～80 DEG C.
4. according to the preparation method described in any one of claim 1-3, it is characterised in that described disperse medium can be pentane,
In hexamethylene, benzene,toluene,xylene, normal hexane, normal heptane, petroleum ether etc. at least one.
5. according to the preparation method described in any one of claim 1-4, it is characterised in that described solvent can be hexamethylene, just oneself
Alkane, normal heptane, benzene,toluene,xylene, dichloro-benzenes, trichloro-benzenes, 1,1,1-trichloroethane, white oil, paraffin, kerosene, alkene mineral
Oil and decahydronaphthalene at least one.
6. the solubilized type super high molecular weight ultra-fine grain diameter polyethylene prepared by preparation method described in any one of claim 1-5, its
Being characterised by, the viscosity-average molecular weight (Mv) of described polyethylene is more than 1 × 106；Described polyethylene is spherical or spherical particle, flat
All particle diameters are 10～100 μm, and standard deviation is 2 μm-15 μm, and bulk density is 0.1g/mL～0.3/mL；Solvent in described polyethylene
Weight percentage is more than 0 and less than or equal to 98wt%.
Solubilising type super high molecular weight ultra-fine grain diameter polyethylene the most according to claim 6, it is characterised in that described polyethylene
The weight percentage of middle solvent is preferably greater than 0 and less than or equal to 50wt%, more preferably 10-50wt%, still more preferably
20-40wt%.
8. according to the solubilized type super high molecular weight ultra-fine grain diameter polyethylene described in claim 6 or 7, it is characterised in that described poly-
The particle diameter distribution of ethylene is similar to normal distribution.
9. according to the solubilized type super high molecular weight ultra-fine grain diameter polyethylene described in any one of claim 6-8, it is characterised in that institute
State the viscosity-average molecular weight (Mv) of polyethylene more than or equal to 1.5 × 106, it is therefore preferable to 1.5 × 106～4.0 × 106；Described polyethylene
Molecular weight distribution mw/mn be 2～15, preferably 3～10, also preferably 4～8.
10. according to the solubilized type super high molecular weight ultra-fine grain diameter polyethylene described in any one of claim 6-9, it is characterised in that
The mean diameter of described polyethylene is preferably 20 μm-90 μm, also preferably 30-85 μm, more preferably 50 μm-80 μm；Described mark
Quasi-difference is preferably 5 μm-15 μm, more preferably 6 μm-12 μm, also preferably 8 μm-10 μm；The bulk density of described polyethylene is preferably
0.15g/mL-0.25g/mL, such as 0.2g/mL.
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| CN201610695051.XA CN106279474B (en) | 2016-08-19 | 2016-08-19 | Solubilized type super high molecular weight micronized polyethylene and preparation method thereof |
| KR1020217006485A KR102317083B1 (en) | 2016-08-19 | 2017-03-02 | Ultra-high molecular weight, ultra-fine particle size polyethylene, preparation method therefor and use thereof |
| JP2019510358A JP7466306B2 (en) | 2016-08-19 | 2017-03-02 | Ultra-high molecular weight, ultra-fine particle polyethylene and its manufacturing method and applications |
| EP17840722.7A EP3489265A4 (en) | 2016-08-19 | 2017-03-02 | Ultra-high molecular weight, ultra-fine particle size polyethylene, preparation method therefor and use thereof |
| PCT/CN2017/075495 WO2018032744A1 (en) | 2016-08-19 | 2017-03-02 | Ultra-high molecular weight, ultra-fine particle size polyethylene, preparation method therefor and use thereof |
| KR1020207029878A KR102292650B1 (en) | 2016-08-19 | 2017-03-02 | Ultra-high molecular weight, ultra-fine particle size polyethylene, preparation method therefor and use thereof |
| KR1020197006903A KR102185631B1 (en) | 2016-08-19 | 2017-03-02 | Polyethylene with ultra high molecular weight and ultra fine particle diameter and its manufacturing method and application |
| US16/279,677 US11530281B2 (en) | 2016-08-19 | 2019-02-19 | Ultra-high molecular weight, ultra-fine particle size polyethylene, preparation method therefor and use thereof |
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