CN106149085A - A kind of cut resistant superhigh molecular weight polyethylene fibers and preparation technology thereof - Google Patents
A kind of cut resistant superhigh molecular weight polyethylene fibers and preparation technology thereof Download PDFInfo
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- CN106149085A CN106149085A CN201610515744.6A CN201610515744A CN106149085A CN 106149085 A CN106149085 A CN 106149085A CN 201610515744 A CN201610515744 A CN 201610515744A CN 106149085 A CN106149085 A CN 106149085A
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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
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
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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
- 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
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Abstract
The invention discloses a kind of cut resistant ultra-high molecular weight polyethylene composite fibre, it is made up of ultra-high molecular weight polyethylene and inflatable organosilicate clay, modified graphene, antioxidant, wherein, described inflatable silicate clay accounts for 0.1% the 10% of composite fibre gross mass, and described modified graphene accounts for 0.1% the 5% of composite fibre gross mass.The invention provides a kind of with UHMWPE fiber as body (the current anti-cutting grade of its fiber bodies typically can only achieve about 2 grades), the technical scheme of preparation cut resistant fibers, its technological process is simple, and need not other hard fibres compound and just can reach preferable belt cutting-resisting property, thus improve the comfort level of fibre.
Description
Technical field
The present invention relates to a kind of technology using solution spinning to prepare ultra-high molecular weight polyethylene composite fibre, belong to high
Performance fibers field.
Background technology
Superhigh molecular weight polyethylene fibers is one of three big high technical fibre, is that the specific strength commercially produced is the highest
Fiber, be mainly used in the fields such as security protection, aviation, weapons, physical culture.Ultra-high molecular weight polyethylene (Ultra-hig
HMolecular Polyethylene, is called for short UHMWPE) refer to the linear polyethylene that mean molecule quantity is more than 1,500,000.Its link
Structure is typical linear structure, and side chain is few, and well below common polythene, branch point is less than 1/1000, and macromolecular chain surpasses
Long, reach tens thousand of nanometer, be therefore the ideal material preparing flexible chain high strength fibre.
For preventing sharp object from encroaching on, particularly under hypervelocity motion, emergency event context, need a kind of high anti-cutting
The research and development of property fiber and knitting (such as various military-civil facilities, clothing, trick set etc.) thereof are constantly subjected to looking steadily of domestic and international industry
Mesh.From improve the anti-cutting of raw fibre consider patent have CN102828312A, JP2004-19050, WO2008/046476,
CN102037169A, CN102227524A etc., wherein utilize High molecular weight polyethylene, high symmetrical structure polyamide, polyphenyl also more
The high-intensity fibers such as azoles form compound fibre with inorganic metal or glass with core/skin, or with high-elasticity fiber cladding, with hard mineral powder
The mode of grain coating reaches to improve the target of cutting resistance, but causes body-sensing hardening because of addition inorganic metal, glass fibers class, makes
People is without comfort；Patent CN 102037169A (Japan is spun) discloses a kind of lower molecular weight (5-30 ten thousand) polyethylene and adds crosslinking
Agent causes the network structure being cross-linked to form to achieve the goal by free radical, but this method is spun for melted, forms cross linked chain under high temperature
Gel controllability is by no means easy on technological process operates, and follow-up need short fine cladding reach, patent CN18092292A (Du Pont)
Disclosed two stack type compound needle fabrics, the most known high-strength aromatic polymer of the cut resistant fibers component wherein provided
With band cladodification polyethylene blend fibres, but cumbersome complexity is implemented in this blend spinning, and is difficult to during spinning reach uniform；Patent
CN101528998A and 102277669A (DSM) discloses a kind of composite filament including long silk thread and so-called staple fibre, its
In the main staple fibre used be chopped hard fibre have certain draw ratio, including glass fibers, ore deposit (stone) thing fibre or metal
Fiber, does not indicates the chemical attribute of hard fibre, has only said and spun by known rotation technique or injection in this patented technology
Method is spun into, and its diameter is less than 25 μm, and draw ratio is more than 10, is then milled into chopped hard fibre, and this method has been focused on
Improvement in terms of the macro-size pattern processing such as chopped hard fibre draw ratio and diameter, then with ultra-high molecular weight polyethylene
(UHMWPE) solution mixing carries out spinning, and cutting performance anti-to UHMWPE fiber improves positive effect, but the fixed length in this method
It is more difficult that hard fibre preparation technology, cost of manufacture, particularly size distribution control, and the hard fibre that especially part is longer is long when it
When degree is more than UHMWPE fibre diameter, solution is spun flow process stability unfavorable, and the intensity of composite fibre finished product (is included mould
Amount, fracture strength etc.) and serviceability all produce impact；To this, patent CN 102227524A (DSM) proposes with easier
Ring spinning processes further by its cladding being had sheath-cored structure form that the cellosilk such as polyaromatic amide of polarity is formed,
Wherein such as front made cut resistant silk is that core is made, and this improvement has certain effect, but this method is still confined to weave morphosis
Improvement aspect, additionally health is had a certain impact by glass.At present, above-mentioned patent has been generally used main body and has had height
The fundamental mechanics performance of strong high-modulus UHMWPE, aromatic hydrocarbons Fypro etc., fine with other hard fibre or organic elastomer etc.
Compound, the composite filament of preparation is used for finished product and adds and be woven into the species of glove class braiding such as man-hour, for the field of cut resistant, technique
Complicated.
Summary of the invention
Present invention aims to the deficiencies in the prior art, it is provided that one just need not other hard fibres compound
The superhigh molecular weight polyethylene fibers of more preferable belt cutting-resisting property can be reached；
It is a further object of the present invention to provide the preparation technology of above-mentioned cut resistant ultra-high molecular weight polyethylene composite fibre, work
Skill is simple, and the fiber produced has the most wear-resisting, belt cutting-resisting property.
The purpose of the present invention implements by the following technical programs:
A kind of cut resistant ultra-high molecular weight polyethylene composite fibre, by ultra-high molecular weight polyethylene and inflatable organic silicic acid
Salt clay, modified graphene, antioxidant are constituted, wherein,
Described inflatable silicate clay accounts for the 0.1%-10% of total fiber mass, preferably 0.5%-5%, further preferably
3%；
Described modified graphene accounts for the 0.1%-5% of total fiber mass, preferably 0.1%-0.5%, further preferably
0.4%.
Preferably, described inflatable organosilicate clay is in organobentonite, organic rectorite or organic sepiolite
One or more compositionss.Described inflatable organosilicate clay be inflatable silicate clay (such as: bentonite, tired torr
Stone or meerschaum) be uniformly dispersed in water after, with silane coupler, organic quaternary ammonium salt, benzidine, season phosphonium salt etc. through interlayer grain
The method modifications such as son exchange, surface grafting obtain.Inflatable organosilicate clay of the present invention is commercially available.The most permissible
The organosilicate clay of expansion in ultra-high molecular weight polyethylene spinning solvent.
Described solvent is paraffin oil, mineral oil, white oil or kerosene.
Preferably, the particle diameter of described inflatable organosilicate clay is 0.1-50um, preferably 0.2-5um.
Preferably, described modified graphene is one or more the compositions surfaces in silane coupler, organic amine
Modified Graphene,
Wherein, described silane coupler is preferably dodecyltrichlorosilane, dodecyltrimethoxysilane, dodecane
Ethyl triethoxy silicane alkane, tetramethyl four ethylene cyclotetrasiloxane, octamethylcy-clotetrasiloxane, aminopropyl triethoxysilane, ammonia
Propyl trimethoxy silicane, aminopropyl-aminoethyl trimethoxy silane, aminopropyl-aminoethyl triethoxysilane or aminoethyl
Aminoethylaminopropyl trimethoxy silane；Described organic amine is preferably decyl amine, lauryl amine, cetylamine, 18-amine., 1,10-last of the ten Heavenly stems two
Amine or distearyl amine；
It is further preferred that the Graphene that described modified graphene is dodecyltrimethoxysilane surface modification.
Preferably, described modified graphene is prepared as follows forming:
Graphene dispersion is in the mixed solution of water and ethanol, and Graphene and mixed solution mass ratio are 1:(25-100),
Preferably 1:(50-100), the volume ratio of water and ethanol is 1:9；Adding silane coupler, its addition is the 2-of Graphene quality
5%, 500-2000r/min high-speed stirred 1-3h, filters；Filter cake 80-120 degree vacuum drying 2-4h after, comminution by gas stream.
Preferably, the particle diameter of described modified graphene is 0.1-20um, preferably 0.5-5um.
Preferably, the molecular weight of described ultra-high molecular weight polyethylene is 1 × 106g/mol-8×106G/mol, preferably 3 ×
106g/mol-5×106g/mol。
The preparation technology of above-mentioned cut resistant ultra-high molecular weight polyethylene composite fibre, feeds by said ratio, including such as
Lower step:
1) inflatable organosilicate clay solution is prepared
By proportioning, joining in organic solvent by inflatable organosilicate clay, mulser high shear agitation is to glutinous
Soil is uniformly dispersed in a solvent, is configured to the clay organic solvent solution that mass concentration is 0.5%-2%, the quality of preferably 1%
Concentration；
2) modified graphene solution is prepared
By proportioning, being added to by modified graphene in organic solvent, high-speed stirred is disperseed in a solvent to modified graphene
Uniformly, it is configured to the Graphene organic solvent solution of mass concentration 0.1%-0.5%, the mass concentration of preferably 0.2%；
3) mixed at the beginning of liquid liquid
By step 2) gained modified graphene solution joins step 1) in gained inflatable organosilicate clay solution,
High-speed stirred makes modified graphene and inflatable organosilicate clay mix homogeneously；
4) UHMWPE/ inflatable organosilicate clay/Graphene composite solution is prepared
By proportioning, ultra-high molecular weight polyethylene powder and antioxidant powder are joined step 3) in gained mixed liquor, with
Time add solvent so that ultra-high molecular weight polyethylene mass concentration is 5%-8%, and the mass concentration of preferably 6% is slowly warmed up to
240-280 DEG C, high-speed stirred is completely dissolved to ultra-high molecular weight polyethylene powder, prepares spinning solution；
5) gel spinning
The UHMWPE/ inflatable organosilicate clay fully dissolved/Graphene composite solution is used gel spinning method
Carrying out spinning, spinning temperature is 240-280 DEG C, prepares gained gelatine silk and passes through extraction, drawing-off, obtains the compound fibre of the present invention
Dimension.
Preferably, in each step, solvent for use is the solvent of solubilized ultra-high molecular weight polyethylene, preferred paraffinic oils, mineral
Oil, white oil or kerosene, most preferably white oil.
Preferably, described step 1) in, under ultrasound wave state, inflatable organosilicate clay is dispersed in solvent
In；
Preferably, described step 1) in, the speed of stirring is 1000-3500r/min, and mixing time is 1-3h；Preferably,
The speed of stirring is 3000r/min, and mixing time is 2h.
Preferably, described step 2) in, the speed of stirring is 1000-3500r/min, and mixing time is 0.5-2h, preferably
, the speed of stirring is 3000r/min, and mixing time is 1h.
Preferably, described step 3) in, the speed of high-speed stirred is 1000-3000r/min, and mixing time is 0.5-2h；
Preferably, the speed of high-speed stirred is 2000r/min, and mixing time is 1h.
Preferably, described step 4) in, the speed of high-speed stirred is 100-2000r/min；Preferably, temperature rises to 250
DEG C, the speed of speed stirring is 300r/min.
Preferably, described step 5) in, described spinning temperature is 250 DEG C, and concentration of dope is 5%-8%.
The invention has the beneficial effects as follows:
In order to solve the problem of the complicated difficulty of cut resistant fibers preparation in prior art, and need and other hard fibres
The compound problem that can be only achieved certain belt cutting-resisting property, the invention provides a kind of with UHMWPE fiber as body (its fiber
The current anti-cutting grade of body typically can only achieve about 2 grades), the technical scheme of preparation cut resistant fibers, its technological process letter
Single, and need not other hard fibres compound and just can reach preferable belt cutting-resisting property, thus improve the comfortable of fibre
Degree.It is an advantage of the current invention that, by inflatable organosilicate, Graphene is incorporated in superhigh molecular weight polyethylene fibers so that
Superhigh molecular weight polyethylene fibers is without being combined the belt cutting-resisting property that other hard fibres just can reach good again.Specifically have with
The lower technology promise superior function of fiber of the present invention.
(1) it is coated with a series of alkyl segment because of modified graphene surface, can be with inflatable organosilicate surface
Alkyl segment tangles so that Graphene preferably covers on silicate clay surface；
(2) inflatable organosilicate clay can be at paraffin oil, mineral oil, expands and peel off dispersion in white oil equal solvent,
Interlamellar spacing after it expands can allow ultra-high molecular weight polyethylene strand insert；
(3) silicate clay can protect ultra-high molecular weight polyethylene, improves fiber belt cutting-resisting property, and Graphene covers
Clay surface, its hard belt cutting-resisting property that can improve fiber with greasy property further.
Detailed description of the invention
Hereinafter the preferred embodiments of the present invention are illustrated, it will be appreciated that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention
Embodiment 1:
(1) during 2g Graphene joins the mixed solution of 100ml water and ethanol, the volume 1:9,800r/min of water and ethanol
Add 0.1g aminopropyl-aminoethyl triethoxysilane, 800r/min high-speed stirred 2h after high-speed stirred 0.5h, filter.Filter cake
After 100 DEG C of vacuum drying 3h, comminution by gas stream, obtain aminopropyl-aminoethyl triethoxysilane surface modified graphite alkene powder body.
(2) the inflatable organobentonite of 5g is dispersed in 500g white oil under ultrasound wave state, high by mulser
Speed shear agitation, the speed of high shear agitation is 1000r/min, and mixing time is 1h.
(3), during the Graphene of 1g surface modification adds 500g white oil to, high-speed stirred, the speed of high-speed stirred is 1000r/
Min, mixing time is 1h.
(4) joining in (2) by (3), high-speed stirred, the speed of high-speed stirred is 1000r/min, and mixing time is 1h.
(5) 991g ultra-high molecular weight polyethylene powder and 3g antioxidant powder are joined in (4), add 18kg simultaneously
White oil, is slowly warmed up to 250 DEG C, high-speed stirred, and the speed of high-speed stirred is 500r/min, to ultra-high molecular weight polyethylene powder
It is completely dissolved.
(6) gel spinning, uses frozen glue to the UHMWPE/ organosilicate clay fully dissolved/Graphene composite solution
Spin processes carries out spinning, and spinning temperature is 250 DEG C, prepares gained gelatine silk and passes through extraction, drawing-off, obtains the compound fibre of the present invention
Dimension.
Embodiment 2:
(1) during 4g Graphene joins the mixed solution of 200ml water and ethanol, the volume 1:9,800r/min of water and ethanol
Add 0.2g dodecyltrichlorosilane, 800r/min high-speed stirred 2h after high-speed stirred 0.5h, filter.Filter cake is true at 100 DEG C
After empty dry 3h, comminution by gas stream.
(2) the inflatable organobentonite of 10g is dispersed in 1000g paraffin oil under ultrasound wave state, by emulsifying
Machine high shear agitation, the speed of high shear agitation is 2000r/min, and mixing time is 1h.
(3), during the Graphene of 2g surface modification adds 1000g paraffin oil to, high-speed stirred, the speed of high-speed stirred is
2000r/min, mixing time is 1h.
(4) joining in (2) by (3), high-speed stirred, the speed of high-speed stirred is 2000r/min, and mixing time is 1h.
(5) 985g ultra-high molecular weight polyethylene powder and 3g antioxidant powder are joined in (4), add 17kg simultaneously
Paraffin oil, is slowly warmed up to 250 degree, high-speed stirred, and the speed of high-speed stirred is 500r/min, to ultra-high molecular weight polyethylene powder
End is completely dissolved.
(6) gel spinning, uses frozen glue to the UHMWPE/ organosilicate clay fully dissolved/Graphene composite solution
Spin processes carries out spinning, and spinning temperature is 250 DEG C, prepares gained gelatine silk and passes through extraction, drawing-off, obtains the compound fibre of the present invention
Dimension.
Embodiment 3:
(1) during 5g Graphene joins the mixed solution of 250ml water and ethanol, the volume 1:9,800r/min of water and ethanol
Add 0.25g dodecyl triethoxysilane, 800r/min high-speed stirred 2h after high-speed stirred 0.5h, filter.Filter cake is 100
DEG C vacuum drying 3h after, comminution by gas stream.
(2) the inflatable organobentonite of 30g is dispersed in 3000g mineral oil under ultrasound wave state, by emulsifying
Machine high shear agitation, the speed of high shear agitation is 2000r/min, and mixing time is 1h.
(3), during the Graphene of 3g surface modification adds 1500g mineral oil to, high-speed stirred, the speed of high-speed stirred is
2000r/min, mixing time is 1h.
(4) joining in (2) by (3), high-speed stirred, the speed of high-speed stirred is 2000r/min, and mixing time is 1h.
(5) 964g ultra-high molecular weight polyethylene powder and 3g antioxidant powder are joined in (4), add simultaneously
14.5kg mineral oil, is slowly warmed up to 250 DEG C, high-speed stirred, and the speed of high-speed stirred is 500r/min, gathers to super high molecular weight
Ethylene powder is completely dissolved.
(6) gel spinning, uses frozen glue to the UHMWPE/ organosilicate clay fully dissolved/Graphene composite solution
Spin processes carries out spinning, and spinning temperature is 250 DEG C, prepares gained gelatine silk and passes through extraction, drawing-off, obtains the compound fibre of the present invention
Dimension.
Embodiment 4:
(1) during 5g Graphene joins the mixed solution of 250ml water and ethanol, the volume 1:9,800r/min of water and ethanol
Add 0.25g aminopropyl-aminoethyl trimethoxy silane, 800r/min high-speed stirred 2h after high-speed stirred 0.5h, filter.Filter cake
After 100 degree of vacuum drying 3h, comminution by gas stream.
(2) the inflatable organobentonite of 50g is dispersed in 5000g kerosene under ultrasound wave state, by mulser
High shear agitation, the speed of high shear agitation is 2000r/min, and mixing time is 1h.
(3), during the Graphene of 4g surface modification adds 2000g kerosene to, high-speed stirred, the speed of high-speed stirred is
2000r/min, mixing time is 1h.
(4) joining in (2) by (3), high-speed stirred, the speed of high-speed stirred is 2000r/min, and mixing time is 1h.
(5) 943g ultra-high molecular weight polyethylene powder and 3g antioxidant powder are joined in (4), add 12kg simultaneously
Kerosene, is slowly warmed up to 250 DEG C, high-speed stirred, and the speed of high-speed stirred is 500r/min, to ultra-high molecular weight polyethylene powder
It is completely dissolved.
(6) gel spinning, uses frozen glue to the UHMWPE/ organosilicate clay fully dissolved/Graphene composite solution
Spin processes carries out spinning, and spinning temperature is 250 DEG C, prepares gained gelatine silk and passes through extraction, drawing-off, obtains the compound fibre of the present invention
Dimension.
Embodiment 5:
(1) during 25g Graphene joins the mixed solution of 100ml water and ethanol, the volume 1:9,800r/ of water and ethanol
Add 0.5g dodecyltrimethoxysilane, 500r/min high-speed stirred 3h after min high-speed stirred 0.5h, filter.Filter cake exists
After 120 DEG C of vacuum drying 2h, comminution by gas stream.
(2) the inflatable organobentonite of 30g is dispersed in 3000g white oil under ultrasound wave state, by mulser
High shear agitation, the speed of high shear agitation is 3000r/min, and mixing time is 2h.
(3), during the Graphene of 4g surface modification adds 2000g white oil to, high-speed stirred, the speed of high-speed stirred is
3000r/min, mixing time is 1h.
(4) joining in (2) by (3), high-speed stirred, the speed of high-speed stirred is 2000r/min, and mixing time is 1h.
(5) 966g ultra-high molecular weight polyethylene powder and 3g antioxidant powder are joined in (4), add simultaneously
10.1kg white oil, is slowly warmed up to 280 DEG C, and high-speed stirred, the speed of high-speed stirred is 300r/min, to superhigh molecular weight polyethylene
Alkene powder is completely dissolved.
(6) gel spinning, uses frozen glue to the UHMWPE/ organosilicate clay fully dissolved/Graphene composite solution
Spin processes carries out spinning, and spinning temperature is 250 DEG C, prepares gained gelatine silk and passes through extraction, drawing-off, obtains the compound fibre of the present invention
Dimension.
Embodiment 6:
(1) during 5g Graphene joins the mixed solution of 250ml water and ethanol, the volume 1:9,800r/min of water and ethanol
Add 0.25g tetramethyl four ethylene cyclotetrasiloxane, 800r/min high-speed stirred 2h after high-speed stirred 0.5h, filter.Filter cake exists
After 100 degree of vacuum drying 3h, comminution by gas stream.
(2) the inflatable organobentonite of 100g is dispersed in 5000g white oil under ultrasound wave state, by mulser
High shear agitation, the speed of high shear agitation is 1000r/min, and mixing time is 3h.
(3), during the Graphene of 5g surface modification adds 5000g white oil to, high-speed stirred, the speed of high-speed stirred is
2000r/min, mixing time is 1h.
(4) joining in (2) by (3), high-speed stirred, the speed of high-speed stirred is 2000r/min, and mixing time is 1h.
(5) 899g ultra-high molecular weight polyethylene powder and 3g antioxidant powder are joined in (4), add 7kg simultaneously
White oil, is slowly warmed up to 240 DEG C, high-speed stirred, and the speed of high-speed stirred is 100r/min, to ultra-high molecular weight polyethylene powder
It is completely dissolved.
(6) gel spinning, uses frozen glue to the UHMWPE/ organosilicate clay fully dissolved/Graphene composite solution
Spin processes carries out spinning, and spinning temperature is 250 DEG C, prepares gained gelatine silk and passes through extraction, drawing-off, obtains the compound fibre of the present invention
Dimension.
Embodiment 7:
(1) during 5g Graphene joins the mixed solution of 250ml water and ethanol, the volume 1:9,800r/min of water and ethanol
Add 0.25g 18-amine., 800r/min high-speed stirred 2h after high-speed stirred 0.5h, filter.Filter cake is vacuum dried 3h at 100 degree
After, comminution by gas stream.
(2) the inflatable organobentonite of 1g is dispersed in 200g white oil under ultrasound wave state, high by mulser
Speed shear agitation, the speed of high shear agitation is 3500r/min, and mixing time is 1h.
(3), during the Graphene of 50g surface modification adds 10000g white oil to, high-speed stirred, the speed of high-speed stirred is
3000r/min, mixing time is 0.5h.
(4) joining in (2) by (3), high-speed stirred, the speed of high-speed stirred is 2000r/min, and mixing time is 1h.
(5) 943g ultra-high molecular weight polyethylene powder and 3g antioxidant powder are joined in (4), add 663g simultaneously
White oil, is slowly warmed up to 250 DEG C, high-speed stirred, and the speed of high-speed stirred is 500r/min, to ultra-high molecular weight polyethylene powder
It is completely dissolved.
(6) gel spinning, uses frozen glue to the UHMWPE/ organosilicate clay fully dissolved/Graphene composite solution
Spin processes carries out spinning, and spinning temperature is 250 DEG C, prepares gained gelatine silk and passes through extraction, drawing-off, obtains the compound fibre of the present invention
Dimension.
Composite fibre is made cloth or glove, tests its belt cutting-resisting property.Can by standard GB/T 24541-2009 or
Europe superscript EN388 tests, and according to European standard EN388, uses cut resistant testing machine, the cutting resistance of test precursor, is put by sample
On cut resistant testing machine platform, pad aluminium foil below and move horizontally, standby circular shear blade is placed on sample rotation
By opposite direction (180 °) rotation limit, the limit advance moved with sample, both directions are reverse, when sample is completely severed moment, circular
Blade contacts energising with padded aluminium foil, and now circuit notice enumerator cutting termination, during whole, enumerator is in all the time
In record；So sample cutting resistance data can be obtained, after test, cut resistant level is (to be by with the standard sample used
The plane silk floss of 200g/m2 is weaved cotton cloth) with under the conditions of cutting horizontal compared with relatively evaluate.Start test from standard sample, test sample
Carry out cutting test the most alternately with standard sample, after test sample carries out 3 times, last standard sample carries out the 4th test, and this is taken turns
Test just terminates.Evaluation of estimate can be calculated as the following formula and be referred to as cut resistant index (Index): N=(test sample standard sample before the test
The meter reading value of meter reading value+test sample standard sample after experiment) ÷ 2；Index=(read by the enumerator of test sample
Numerical value+N)/N assessment of levels press index (Index) classification:
| Index | Cut resistant grade |
| 2-2.5 | 1 |
| 2.5-5 | 2 |
| 5-10 | 3 |
| 10-20 | 4 |
| ＞ 20 | 5 |
Embodiment test result table
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although with reference to aforementioned reality
Executing example to be described in detail the present invention, for a person skilled in the art, it still can be to aforementioned each enforcement
Technical scheme described in example is modified, or wherein portion of techniques feature is carried out equivalent.All essences in the present invention
Within god and principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (10)
1. a cut resistant ultra-high molecular weight polyethylene composite fibre, it is characterised in that: by ultra-high molecular weight polyethylene and can be swollen
Swollen organosilicate clay, modified graphene, antioxidant are constituted, wherein,
Described inflatable silicate clay accounts for the 0.1%-10% of composite fibre gross mass, preferably 0.5%-5%, further preferably
3%；
Described modified graphene accounts for the 0.1%-5% of composite fibre gross mass, preferably 0.1%-0.5%, further preferably
0.4%.
Cut resistant ultra-high molecular weight polyethylene composite fibre the most according to claim 1, it is characterised in that: described inflatable
Organosilicate clay is one or more compositionss in organobentonite, organic rectorite or organic sepiolite；Preferably,
The particle diameter of described inflatable organosilicate clay is 0.1-50um, preferably 0.2-5um.
Cut resistant ultra-high molecular weight polyethylene composite fibre the most according to claim 1, it is characterised in that: described modified stone
Ink alkene is the Graphene of one or more the compositions surface modifications in silane coupler, organic amine,
Wherein, described silane coupler is preferably dodecyltrichlorosilane, dodecyltrimethoxysilane, dodecyl three
Ethoxysilane, tetramethyl four ethylene cyclotetrasiloxane, octamethylcy-clotetrasiloxane, aminopropyl triethoxysilane, aminopropyl
Trimethoxy silane, aminopropyl-aminoethyl trimethoxy silane, aminopropyl-aminoethyl triethoxysilane or aminoethyl ammonia second
Base aminopropyl trimethoxysilane；Described organic amine be preferably decyl amine, lauryl amine, cetylamine, 18-amine., 1,10-decamethylene diamine or
Distearyl amine；
It is further preferred that the Graphene that described modified graphene is dodecyltrimethoxysilane surface modification.
Cut resistant ultra-high molecular weight polyethylene composite fibre the most according to claim 3, it is characterised in that: described modified stone
Ink alkene is prepared as follows forming:
Graphene dispersion is in the mixed solution of water and ethanol, and Graphene and mixed solution mass ratio are 1:(25-100), preferably
1:(50-100), the volume ratio of water and ethanol is 1:9；Adding silane coupler, its addition is the 2-5% of Graphene quality,
500-2000r/min high-speed stirred 1-3h, filters；After filter cake is vacuum dried 2-4h at 80-120 DEG C, comminution by gas stream.
Cut resistant ultra-high molecular weight polyethylene composite fibre the most according to claim 1, it is characterised in that: described modified stone
The particle diameter of ink alkene is 0.1-20um, preferably 0.5-5um.
Cut resistant ultra-high molecular weight polyethylene composite fibre the most according to claim 1, it is characterised in that: described superelevation is divided
The molecular weight of sub-weight northylen is 1 × 106g/mol-8×106G/mol, preferably 3 × 106g/mol-5×106g/mol。
7. according to the preparation technology of the cut resistant ultra-high molecular weight polyethylene composite fibre described in any one of claim 1-6, its
It is characterised by: by the proportional quantity of each component in claim 1-6 any one composite fibre, comprise the steps:
1) inflatable organosilicate clay solution is prepared
By proportioning, joining in organic solvent by inflatable organosilicate clay, mulser high shear agitation exists to clay
Solvent is uniformly dispersed, is configured to the clay organic solvent solution that mass concentration is 0.5%-2%, the mass concentration of preferably 1%；
2) modified graphene solution is prepared
By proportioning, being added to by modified graphene in organic solvent, high-speed stirred is uniformly dispersed in a solvent to modified graphene,
It is configured to the Graphene organic solvent solution of mass concentration 0.1%-0.5%, the mass concentration of preferably 0.2%；
3) mixed at the beginning of liquid liquid
By step 2) gained modified graphene solution joins step 1) in gained inflatable organosilicate clay solution, at a high speed
Stirring makes modified graphene and inflatable organosilicate clay mix homogeneously；
4) UHMWPE/ inflatable organosilicate clay/Graphene composite solution is prepared
By proportioning, ultra-high molecular weight polyethylene powder and antioxidant powder are joined step 3) in gained mixed liquor, add simultaneously
Entering solvent so that ultra-high molecular weight polyethylene mass concentration is 5%-8%, the mass concentration of preferably 6% is slowly warmed up to 240-
280 DEG C, high-speed stirred is completely dissolved to ultra-high molecular weight polyethylene powder, prepares spinning solution；
5) gel spinning
Gel spinning method is used to carry out the UHMWPE/ inflatable organosilicate clay fully dissolved/Graphene composite solution
Spinning, spinning temperature is 240-280 DEG C, prepares gained gelatine silk and passes through extraction, drawing-off, obtains the composite fibre of the present invention.
The preparation technology of cut resistant superhigh molecular weight polyethylene fibers the most according to claim 7, it is characterised in that: respectively walk
Middle solvent for use is the solvent of solubilized ultra-high molecular weight polyethylene, preferred paraffinic oils, mineral oil, white oil or kerosene, optimum
Elect white oil as.
The preparation technology of cut resistant ultra-high molecular weight polyethylene composite fibre the most according to claim 7, it is characterised in that:
Described step 1) in, the speed of stirring is 1000-3500r/min, and mixing time is 1-3h；Preferably, the speed of stirring is
3000r/min, mixing time is 2h；
And/or, described step 2) in, the speed of stirring is 1000-3500r/min, and mixing time is 0.5-2h, it is preferred that stir
The speed mixed is 3000r/min, and mixing time is 1h；
And/or, described step 3) in, the speed of high-speed stirred is 1000-3000r/min, and mixing time is 0.5-2h；Preferably
, the speed of high-speed stirred is 2000r/min, and mixing time is 1h；
And/or, described step 4) in, the speed of high-speed stirred is 100-2000r/min；Preferably, temperature rises to 250 DEG C, speed
The speed of stirring is 300r/min.
The preparation technology of cut resistant ultra-high molecular weight polyethylene composite fibre the most according to claim 7, its feature exists
In: described step 5) in, described spinning temperature is 250 DEG C, and concentration of dope is 5%-8%.
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