CN106319667A - Fiber prepared with solubilizing type ultra-high molecular weight ultrathin polyethylene and preparation method thereof - Google Patents
Fiber prepared with solubilizing type ultra-high molecular weight ultrathin polyethylene and preparation method thereof Download PDFInfo
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- CN106319667A CN106319667A CN201610695021.9A CN201610695021A CN106319667A CN 106319667 A CN106319667 A CN 106319667A CN 201610695021 A CN201610695021 A CN 201610695021A CN 106319667 A CN106319667 A CN 106319667A
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- molecular weight
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- polyethylene
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Abstract
The invention provides a fiber and a preparation method thereof; the fiber is prepared mainly from solubilizing type ultra-high molecular weight ultrathin polyethylene; the viscosity average molecular weight (Mv) of the polyethylene is more than 1x10<6>, the polyethylene contains spherical or quasi-spherical particles; the mean particle size is 10 Mum-100 Mum, a standard difference is 2 Mum-15 Mum, and bulk density is 0.1 g/mL-0.3 g/mL; a solvent in the solubilizing type ultra-high molecular weight ultrathin polyethylene is more than 0 and less than or equal to 98% by weight. Since the solubilizing type ultra-high molecular weight ultrathin polyethylene is applied as the raw material, the fiber is excellent in creep resisting performance and extremely wide in temperature scale (the fiber is suitable for use at both low temperature and high temperature).
Description
Technical field
The present invention relates to a kind of fiber and preparation method thereof, be specifically related to a kind of solubilising type super high molecular weight ultra-fine grain diameter and gather
Fiber prepared by ethylene and preparation method thereof.
Background technology
Polyethylene fibre includes long fibre, chopped fiber, non-woven fabrics etc..Wherein, polyethylene long fibre good luster, feel are soft
Soft, drapability is good, density is little, it is adaptable to knitting industry, be woven into cotton lid third, wire cover with cotton, viscose, real silk, spandex etc.
During third gradegrade C product, it it is the ideal material making high-grade gym suit, T-shirt etc.；Polyethylene chopped fiber and Cotton Gossypii blending can be made cotton thin
Cloth, sheet, can make woollen blanket with viscose blending, polyethylene is pure spins and wool-mix thread, carpet, cotton-wool and cigarette filter.Polyethylene without
Spin cloth for disposable medical hygienic article, disposable antifouling clothes, agricultural fabric, furniture cloth or the lining etc. of shoe industry, or
Person is used for the field such as health care, heat insulating material formed, filtering material.Although conventional polyethylene fibre has light weight, intensity height, bullet
The plurality of advantages such as property is good, wear-resisting, corrosion-resistant, good insulating, warmth retention property are good, but it there is also heat-resisting, low temperature resistant, ageing-resistant performance
The defect of difference, and its hygroscopicity and dyeability are the most very poor.In current prior art, use is total to propylene copolymerization, interpolation more
The modes such as mixed modification agent (as added EP rubbers, EPDM, POE, EVA or SBS etc.) improve its resistance to low temperature, but these sides
Method, improving resistance to low temperature when, can affect other excellent properties of polyethylene, such as intensity and modulus etc..
The processing and forming of chemical fibre includes wet spinning, dry-wet spinning and melt spinning etc..In chemical fibre molding
In the course of processing, drawing-off is an important technical process.Drawing-off can make the macromolecule in chemical fibre produce mechanics, light
The anisotropy of the aspects such as, calorifics, is effectively improved the intensity of chemical fibre.For melt spinning, drafting process therein
Main employing hot-rolling drawing-off, hot plate drawing-off and hot tank drawing-off；For wet method or dry-wet spinning, in addition to above-mentioned drawing-off mode,
Steam under pressure drawing-off can also be used.Improved above-mentioned many disadvantages of polyethylene by the adjustment of processing mode, be also
Study a more direction at present.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of resistance to low temperature mechanical property excellent, every
Can and the fiber prepared of the most excellent solubilized type super high molecular weight ultra-fine grain diameter polyethylene of thermal property and preparation method thereof.
In order to solve above technical problem, the present invention provides a kind of fiber, mainly includes that solubilising type superelevation is divided in its raw material
Son amount ultra-fine grain diameter polyethylene；
The viscosity-average molecular weight (Mv) of described solubilising type super high molecular weight ultra-fine grain diameter polyethylene is more than 1 × 106；Described solubilising
Type super high molecular weight ultra-fine grain diameter polyethylene is spherical or spherical particle, and mean diameter is 10～100 μm, standard deviation be 2 μm-
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
Percentage composition is more than 0 and less than or equal to 98wt%；
It is a kind of that described solubilising type super high molecular weight ultra-fine grain diameter polyethylene employing is selected from method (1) or method (2)
Preparation method prepares:
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, in described raw material in addition to described solubilising type super high molecular weight ultra-fine grain diameter polyethylene, also include resisting
Oxygen agent.Preferably, the addition of antioxidant relative to 100 weight portion solubilising type super high molecular weight ultra-fine grain diameter polyethylene, for
0.01-1 weight portion, also preferably 0.02-0.5 weight portion.Concrete, described fiber is surpassed by the described solubilising type containing antioxidant
High molecular ultra-fine grain diameter polyethylene prepares.
According to the present invention, in described solubilising type super high molecular weight ultra-fine grain diameter polyethylene, the weight percentage of solvent is preferred
For more than 0 and less than or equal to 80wt%, it is also preferably more than 0 and less than or equal to 50wt%, more preferably 10-50wt%, the most more
It is 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.
According to the present invention, the viscosity-average molecular weight (Mv) of described solubilising type super high molecular weight ultra-fine grain diameter polyethylene is more than or equal to
1.5×106, it is therefore preferable to 1.5 × 106～4.0 × 106；The molecular weight of described solubilising type super high molecular weight ultra-fine grain diameter polyethylene
Distribution Mw/Mn is 2～15, preferably 3～10, also preferably 4～8.
According to the present invention, the mean diameter of described solubilising type super high molecular weight ultra-fine grain diameter polyethylene is preferably 20 μm-90 μ
M, 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 μ
M, also preferably 8 μm-10 μm；The bulk density of described solubilising type super high molecular weight ultra-fine grain diameter polyethylene is preferably 0.15g/mL-
0.25g/mL, such as 0.2g/mL.
The present invention also provides for the preparation method of above-mentioned fiber, and it comprises the following steps:
1) material dissolution comprising described solubilising type super high molecular weight ultra-fine grain diameter polyethylene is obtained spinning in a solvent
Solution or gel；
2) by gel spinning method spinning, gelatinous fibre is obtained；
3) drawing-off；Prepare described fiber.
According to the present invention, step 1) in, in order to avoid ultra-high molecular weight polyethylene degraded in dissolving and using, molten
Solution preocess needs add antioxidant.The addition of antioxidant gathers relative to 100 weight portion solubilising type super high molecular weight ultra-fine grain diameters
Ethylene, for 0.01-1 weight portion, also preferably 0.02-0.5 weight portion.
In one embodiment, step 3) drafting step before, including by coagulator or extractant by solvent extraction
Step.Preferably, lower boiling organic solvent selected by described coagulator or extractant, the most following lower boiling organic molten
One or more in agent: petroleum ether, dichloromethane, hexamethylene etc..
Wherein, described step 3) in drawing-off use hot tank or hot-rolling drawing-off, it would however also be possible to employ heating bath drawing-off mode.
For heating bath drawing-off mode therein, it is preferred that the heating bath medium of employing includes that (preferably boiling point is selected from polyhydric alcohol
120-220 DEG C), polyoxyethylene oligomer (preferably, relative molecular weight is 88-5000g/mol), polyoxypropylene oligomer (excellent
Choosing, relative molecular weight is 116-1200g/mol), one or more components in mineral oil and silicone oil.Preferably, described heat
Bath medium temperature TLIt is set as vitrification point T between polymeric matrixgDecomposition temperature T with polymeric matrixdBetween.
In another embodiment, described step 3) particularly as follows: described gelatinous fibre is through gelatine silk drawing-off, solvent extraction
Take, be dried, the first hot tank dry heat drafting, the second hot tank dry heat drafting, the operation such as thermal finalization and winding, obtain the fibre of the present invention
Dimension.
Wherein, the drawing temperature in gelatine silk drafting process is 10-70 DEG C, preferably 25-50 DEG C；Drafting multiple is 2-20
Times, preferably 3-15 times.
Wherein, lower boiling organic solvent selected by extractant in solvent extraction step, and the most following lower boiling have
One or more in machine solvent: petroleum ether, dichloromethane, hexamethylene etc..
Wherein, being dried by hot air drying in drying process, hot blast temperature is 30-90 DEG C, preferably 40-80 DEG C.
Wherein, the temperature in the first hot tank dry heat drafting operation is 100-160 DEG C, preferably 130-145 DEG C；Drafting multiple is
1-20 times, preferably 1.5-15 times.
Wherein, the temperature in the second hot tank dry heat drafting operation is 110-160 DEG C, preferably 130-145 DEG C；Drafting multiple is
1-5 times, preferably 1.1-3 times.
Wherein, the temperature in heat-setting process is 100-150 DEG C, preferably 120-135 DEG C.
Beneficial effects of the present invention:
In the fiber of the present invention, a kind of solubilising of selection type super high molecular weight ultra-fine grain diameter polyethylene is as raw material, due to described
Polyethylene be prone to dissolve, solution temperature low, be particularly suitable for processed and applied, the wet spinning being particularly suited for described fiber adds
Work.
The fiber of the present invention due to employ described solubilising type super high molecular weight ultra-fine grain diameter polyethylene as raw material, have
Excellent creep resistance, uses temperature range the widest (being both suitable for low temperature to use, be also suitable for the use of higher temperature).
Detailed description of the invention
[preparation method of catalyst]
The catalyst used in the preparation method of the polyethylene of the present invention can use the patent of invention that applicant has been filed on
Prepared by the method disclosed in application (application number 201510271254.1), it introduces in full herein as reference.
Specifically, the catalyst used in the preparation method of the polyethylene of the present invention is by the method system comprised the following steps
Standby:
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.
[solubilising type super high molecular weight ultra-fine grain diameter polyethylene and preparation method thereof]
As it has been described above, the fiber of the present invention have employed a kind of solubilising type super high molecular weight ultra-fine grain diameter polyethylene, non-limit
Fixed, described solubilising type super high molecular weight ultra-fine grain diameter polyethylene uses a kind of preparation in method (1) or method (2)
Method prepares:
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
℃；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.
In an embodiment of the invention, described solubilising type super high molecular weight ultra-fine grain diameter polyethylene uses selected from side
A kind of preparation method in method (1) or method (2) prepares:
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.
In above-mentioned preparation method, described polyreaction uses slurry process.The temperature of described polyreaction is preferably 0～90
DEG C, preferably 10～85 DEG C, also preferably 30～80 DEG C, more preferably 50～80 DEG C.
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.
In an embodiment of the invention, described solubilising type super high molecular weight ultra-fine grain diameter polyethylene has following knot
Structure and performance: 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 μm-100 μm, and standard deviation is 2 μm-15 μm, and bulk density is 0.1g/mL-0.3g/mL；Solvent in described polyethylene
Weight percentage be more than 0 and less than or equal to 98wt%.Preferably, in described polyethylene, the weight percentage of solvent is big
In 0 and less than or equal to 80wt%, preferably greater than 0 arrives less than or equal to 50wt%, more preferably 10-50wt%, still more preferably
20-40wt%.Preferably, the particle diameter distribution of described polyethylene is similar to 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 μ
M, also preferably 8 μm-10 μm.Described bulk density is preferably 0.15g/mL-0.25g/mL, for example, 0.2g/mL.Described polyethylene
Viscosity-average molecular weight (Mv) more than or equal to 1.5 × 106, it is therefore preferable to 1.5 × 106～4.0 × 106；The molecular weight of described polyethylene
Distribution Mw/Mn is 2～15, preferably 3～10, also preferably 4～8.Possesses the superelevation of described particle diameter, bulk density and solvent
Molecular weight polyethylene, is particularly well-suited to graft modification, on the one hand greatly extends the modified space of polyethylene；On the other hand,
The processing characteristics of described polymer significantly improves, it is adaptable to the preparation of larger range of goods；So, described in the most effectively extending
The application of polymer.
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.
[fiber of the present invention and preparation method thereof]
As it has been described above, the invention provides the preparation method of above-mentioned fiber, it comprises the following steps: 1) will comprise described increasing
The material dissolution of molten type super high molecular weight ultra-fine grain diameter polyethylene obtains spinning solution or gel in a solvent；2) spun by frozen glue
Silk method spinning, obtains gelatinous fibre；3) drawing-off；Prepare described fiber.
In step (1), the mixture comprising described solubilising type super high molecular weight ultra-fine grain diameter polyethylene is mixed with solvent
Dissolve, obtain described spinning solution or gel.In the present invention, described solvent is the organic solvent that can dissolve described polyethylene, example
As for decahydronaphthalene, white oil etc..In described spinning solution or gel, polymer content is 3-20wt%, preferably 5-15wt%.
In a preferred embodiment of the present invention, as a example by solution gel spinning method, described method specifically includes
Following steps: solubilising type super high molecular weight ultra-fine grain diameter polyethylene and solvent are mixed to get mixture；By mixture through double spiral shells
Bar dissolves extrusion (preferably, the described temperature dissolving extrusion is 120-270 DEG C, preferably 150-240 DEG C) and obtains spinning solution；Will
Described spinning solution directly through twin-screw extrusion, is extruded, through coagulating bath (such as, cooling bath by filament spinning component, spinneret；
Preferably, bath temperature is 0-15 DEG C, preferably 2-10 DEG C) cooling, obtain gelatinous fibre；By above-mentioned gelatinous fibre through gelatine silk
Drawing-off, solvent extraction, be dried, the first hot tank dry heat drafting, the second hot tank dry heat drafting, the operation such as thermal finalization and winding, obtain
The fiber of the present invention.
In the present invention, in described mixture in addition to described polyethylene, also include antioxidant.Preferably, the interpolation of antioxidant
Amount is relative to 100 weight account polyethylenes, for 0.01-1 weight portion, also preferably 0.02-0.5 weight portion.Concrete, described mixing
Thing is made up of described solubilising type super high molecular weight ultra-fine grain diameter polyethylene and antioxidant.Described antioxidant is as known in the art
For the antioxidant of polyethylene, unrestriced, described antioxidant is made up of primary antioxidant and auxiliary antioxidant, described primary antioxidant
Selected from Hinered phenols antioxidant, described auxiliary antioxidant is selected from thio-2 acid dibasic acid esters or phosphite ester etc..Described Hinered phenols
Antioxidant is that some have the phenolic compound of steric restriction, and their thermal oxidation resistance effect is notable, will not pollute goods；This kind of
The kind of antioxidant is a lot, mainly has: 2,6-di-tert-butyl-4-methy phenols, double (3,5-di-tert-butyl-hydroxy phenyl) sulfur
Ether, four (β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid) pentaerythritol ester etc..Described thio-2 acid dibasic acid esters is that a class is auxiliary
Aid anti-oxidants, normal and Hinered phenols antioxidant use, effect is notable, such as: thio-2 acid Lauryl Alcohol ester, sulfur in pairs are for dipropyl
The double ten four carbon alcohols esters of acid or the double octadecanol ester of thio-2 acid.Described phosphite ester is also auxiliary antioxidant, mainly has: phosphorous
Acid three monooctyl esters, tridecyl phosphite, tricresyl phosphite (Lauryl Alcohol) ester and tricresyl phosphite (16 carbon alcohol) ester etc..
The fiber of the present invention has mechanical property and the creep-resistant property of excellence, it may have wider temperature range,
Specifically, the fiber of the present invention has following performance: fiber number (dtex) 1.5-3.0, fracture strength is more than or equal to 2.0-
3.5GPa, modulus 95-220GPa, elongation at break 3.0-4.5%, creep is less than or equal to 2% (such as 1.0%-2.0%), knot
Crystalline substance degree 95%, fusing point 130 DEG C-140 DEG C, using temperature range is-30 DEG C～135 DEG C.
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 fibre property of the present invention is measured by the assay method in known standard.
As, the creep resistance of the present invention passes through National Standard of the People's Republic of China GB11546-89, ISO899-1981
In assay method measure.
The preparation of preparation example 1 solubilising type super high molecular weight ultra-fine grain diameter polyethylene
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%.
The preparation of embodiment 1 fiber
The solubilized type super high molecular weight ultra-fine grain diameter polyethylene of preparation example 1 and white oil are mixed to get mixture, wherein, poly-
Compound content is 10wt%；Through twin screw, mixture is dissolved extrusion, and the described temperature dissolving extrusion is 200 DEG C, obtains spinning
Solution；By described spinning solution directly through twin-screw extrusion, extruded by filament spinning component, spinneret, cooled water-bath (water-bath temperature
Degree is 5 DEG C) cooling, obtain gelatinous fibre；By above-mentioned gelatinous fibre through gelatine silk drawing-off, solvent extraction, dry, the first hot tank
Dry heat drafting, the second hot tank dry heat drafting, thermal finalization and rolling step, obtain the fiber of the present invention.
Above-mentioned gelatinous fibre is processed as in the processing step of fiber, and the drawing temperature of gelatine silk drafting process is 40 DEG C, leads
Stretching multiple is 10 times；Extractant in solvent extraction step is selected from hexamethylene；Being dried by hot air drying, heat in drying process
Air temperature is 60 DEG C；Temperature in first hot tank dry heat drafting operation is 130 DEG C, and drafting multiple is 10 times；Second hot tank is xeothermic
Temperature in drafting process is 135 DEG C, and drafting multiple is 2 times；Temperature in heat-setting process is 120 DEG C.
The preparation of embodiment 2 fiber
Other are with embodiment 1, are simply also added into antioxidant with solvent mixed process in step (1), antioxidant
Addition, relative to 100 weight account polyethylenes, is 0.05 weight portion.Described antioxidant is by primary antioxidant and auxiliary antioxidant structure
Becoming, described primary antioxidant is selected from 2,6-di-tert-butyl-4-methy phenol.Described auxiliary antioxidant is selected from thio-2 acid in pairs ten
Two carbon alcohol esters.
The performance of fiber prepared by embodiment 1-2 is shown in Table 1.
The performance test results of the fiber of table 1 present invention
From the data of table 1, the fiber of the present invention has the creep resistance of excellence and wider use temperature, has
Application prospect greatly.
Claims (10)
1. a fiber, it is characterised in that mainly include in the raw material of described fiber that solubilising type super high molecular weight ultra-fine grain diameter gathers
Ethylene；
The viscosity-average molecular weight (Mv) of described solubilising type super high molecular weight ultra-fine grain diameter polyethylene is more than 1 × 106；Described solubilising type surpasses
High molecular ultra-fine grain diameter polyethylene is spherical or spherical particle, and mean diameter is 10～100 μm, and standard deviation is 2 μm-15 μ
M, bulk density is 0.1g/mL～0.3g/mL；The weight percent of solvent in described solubilising type super high molecular weight ultra-fine grain diameter polyethylene
Content is more than 0 and less than or equal to 98wt%；
Described solubilising type super high molecular weight ultra-fine grain diameter polyethylene uses a kind of preparation in method (1) or method (2)
Method prepares:
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.
Fiber the most according to claim 1, it is characterised in that ultra-fine except described solubilising type super high molecular weight in described raw material
Outside particle diameter polyethylene, also include antioxidant.Preferably, the addition of antioxidant is relative to 100 weight portion solubilising type supra polymers
Amount ultra-fine grain diameter polyethylene, for 0.01-1 weight portion, also preferably 0.02-0.5 weight portion.Concrete, described fiber is by containing
The described solubilising type super high molecular weight ultra-fine grain diameter polyethylene of antioxidant prepares.
Fiber the most according to claim 1 and 2, 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 preferably greater than 0 and less than or equal to 80wt%, is also preferably more than 0 and is less than or equal to
50wt%, more preferably 10-50wt%, still more preferably 20-40wt%.
4. according to the fiber described in any one of claim 1-3, it is characterised in that described solubilising type super high molecular weight ultra-fine grain diameter
The particle diameter distribution of polyethylene is similar to normal distribution.
5. according to the fiber described in any one of claim 1-4, it is characterised in that described solubilising type super high molecular weight ultra-fine grain diameter
The viscosity-average molecular weight (Mv) of polyethylene is more than or equal to 1.5 × 106, it is therefore preferable to 1.5 × 106～4.0 × 106；Described solubilising type surpasses
The molecular weight distribution mw/mn of high molecular ultra-fine grain diameter polyethylene is 2～15, preferably 3～10, also preferably 4～8.
6. according to the fiber described in any one of claim 1-5, it is characterised in that described solubilising type super high molecular weight ultra-fine grain diameter
The mean diameter of polyethylene is preferably 20 μm-90 μm, also preferably 30-85 μm, more preferably 50 μm-80 μm；Described standard deviation
It is preferably 5 μm-15 μm, more preferably 6 μm-12 μm, also preferably 8 μm-10 μm；Described solubilising type super high molecular weight ultra-fine grain diameter
The bulk density of polyethylene is preferably 0.15g/mL-0.25g/mL, such as 0.2g/mL.
7. the preparation method of fiber described in any one of claim 1-6, it is characterised in that said method comprising the steps of:
1) material dissolution comprising described solubilising type super high molecular weight ultra-fine grain diameter polyethylene is obtained spinning solution in a solvent
Or gel；
2) by gel spinning method spinning, gelatinous fibre is obtained；
3) drawing-off；Prepare described fiber.
Preparation method the most according to claim 7, it is characterised in that except described solubilising type supra polymer in described mixture
Outside amount ultra-fine grain diameter polyethylene, also include antioxidant.
Preparation method the most according to claim 8, it is characterised in that the addition of antioxidant increases relative to 100 weight portions
Molten type super high molecular weight ultra-fine grain diameter, for 0.01-1 weight portion, also preferably 0.02-0.5 weight portion.
Preparation method the most according to claim 8 or claim 9, it is characterised in that step 3) drafting step before, including passing through
Coagulator or extractant are by solvent-extracted step.Preferably, lower boiling organic solvent selected by described coagulator or extractant,
One or more in the most following lower boiling organic solvent: petroleum ether, dichloromethane, hexamethylene etc..
Preferably, described step 3) in drawing-off use hot tank or hot-rolling drawing-off, it would however also be possible to employ heating bath drawing-off mode.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610695021.9A CN106319667B (en) | 2016-08-19 | 2016-08-19 | A kind of fiber and preparation method thereof of solubilising type super high molecular weight micronized polyethylene preparation |
| 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 |
| 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 |
| 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 |
| KR1020207029878A KR102292650B1 (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 |
| KR1020217006485A KR102317083B1 (en) | 2016-08-19 | 2017-03-02 | Ultra-high molecular weight, ultra-fine particle size polyethylene, preparation method therefor and use thereof |
| 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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| CN201610695021.9A CN106319667B (en) | 2016-08-19 | 2016-08-19 | A kind of fiber and preparation method thereof of solubilising type super high molecular weight micronized polyethylene preparation |
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