CN107245225A - A kind of haloflex/superhigh molecular weight polyethylene fibers composite and preparation method thereof - Google Patents
A kind of haloflex/superhigh molecular weight polyethylene fibers composite and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to polymeric material field, and in particular to a kind of haloflex/superhigh molecular weight polyethylene fibers composite and preparation method thereof.The haloflex is periodicity haloflex, haloflex/superhigh molecular weight polyethylene fibers composite of the present invention, in the case where not changing haloflex chemical constitution, the aggregated structure of haloflex is adjusted by the way of superhigh molecular weight polyethylene fibers induce crystallization, realize the regulation and control to haloflex crystal structure, orthorhombic is regulated to from common three oblique crystalline substances, so that the effect for improving melting temperature and mechanical property is reached, and method is easy, be easy to get.
Description
Technical field
The present invention relates to polymeric material field, and in particular to a kind of haloflex/superhigh molecular weight polyethylene fibers
Composite and preparation method thereof.
Background technology
Polyethylene as the maximum kind of yield in commodity polymer, with nontoxic inexpensive, light weight, excellent moisture-proof,
The features such as good chemical stability, it is widely used in the fields such as food, automobile, chemical industry, is the important former material of national economy
Material.Nonpolar or polar group is generally introduced in polyethylene to reach the purpose of modified poly ethylene, such as linear low density polyethylene
Alkene, halo polyethylene etc..Haloflex has excellent weatherability, chemicals-resistant, ageing-resistant and fire-retardant etc. performance, gathers around it
There is very high commercial value.But it is due to that cl radical produces considerable influence to polyethylene backbone crystallization, especially when chloro mass contg
Bigger, the destruction to main chain order is then more serious, and its fusing point and mechanical property are also lower.The preparation chlorination generally used gathers
The mode of ethene is that by chlorination high density polyethylene (HDPE), the position of cl radical and content can not be controlled accurately in haloflex
System, causes the fusing point and mechanical property of haloflex relatively low, therefore seriously limits it to use larger range of.
Superhigh molecular weight polyethylene fibers are called high-strength high-modulus polyethylene fiber, are 1,000,000 by average relative molecular mass
Polyethylene spinning above is formed.There is ultralight, high specific strength due to superhigh molecular weight polyethylene fibers, it is high ratio modulus, superior
Energy absorption, preferably wear-resisting, corrosion-resistant, fast light etc. multiple excellent properties, in Aero-Space, national defense and military, peace
The fields such as full protection, ocean engineering, sports equipment, power communication, medical material and civilian netting are widely used.
There is superhigh molecular weight polyethylene fibers high molecular chain orientation to allow it as substrate induction common polythene or other
Epitaxial crystallization, the inducing action of orientation strand makes common polythene or other polymer molecular chains in super high molecular weight
Polyethylene fibre surface is axially orderly, be closely spaced, or even can promote the change of other polymer sheet crystal structures.
These unique properties allow superhigh molecular weight polyethylene fibers as a kind of new reinforcer, by preparing superelevation
The composite polyolefine material of molecular weight polyethylene fibre modification improves the hot property and mechanical performance of polymer.
The content of the invention
The problem of the invention aims to solve existing haloflex fusing point and relatively low mechanical property, there is provided one
Plant haloflex/superhigh molecular weight polyethylene fibers composite with high-melting-point and high intensity and preparation method thereof.
The present invention prepares periodicity haloflex using ad hoc approach first, chlorine in the periodicity haloflex
Position and content controllable precise of the group in main chain, thus can realize to the accurate of haloflex hot property and mechanical property
Regulation and control.In order to further improve the heat resistance and intensity of periodicity haloflex, the present invention utilizes ultra-high molecular weight polyethylene
The spy that the periodic structure of the highly oriented strand of fiber and the cell parameter of the chain direction of principal axis of periodicity haloflex match
Point, by specific processing technology induce haloflex grown nonparasitically upon another plant on superhigh molecular weight polyethylene fibers surface crystallization formation stretch
Chain crystal structure layer, haloflex matrix and superhigh molecular weight polyethylene fibers are effectively improved by such interfacial crystallization layer
Between interface binding power, so as to improve the transmission of load between haloflex matrix and superhigh molecular weight polyethylene fibers, make
It is standby to obtain high intensity, dystectic haloflex/superhigh molecular weight polyethylene fibers laminar composite.
As a result present inventor has found after in-depth study：By using periodicity haloflex and super
High molecular weight polyethylene fiber, can prepare high-melting-point and haloflex/superhigh molecular weight polyethylene fibers of high intensity
Composite, and this completes the present invention.
Concrete scheme is as follows：
A kind of haloflex/superhigh molecular weight polyethylene fibers composite, the haloflex is poly- for periodicity chlorination
Ethene, the formula of its constitutional repeating unit is as follows：
；
In the formula, X=4,6,7,9,10,14 or 18；
The number-average molecular weight of the haloflex is 8000~120000；
The mass ratio of the haloflex and superhigh molecular weight polyethylene fibers is 1000：8~100；
The composite, in means of differential scanning calorimetry measure, the crystalline fusion peak temperature determined with 10 DEG C/minute of the rate of heat addition
More than or equal to 100 DEG C；The composite, its tensile strength is more than or equal to 38MPa, and stretch modulus is more than or equal to 620MPa.
Preferably, in constitutional repeating unit formula, X can be one kind or several in 4,6,7,9,10,14,18
Kind.
Preferably, X is the one or more in 4,7,10,14.
Preferably, the number-average molecular weight of the haloflex is 15000~50000.
Preferably, the mass ratio of brominated polyethylene and superhigh molecular weight polyethylene fibers is 1000：15~40.Superelevation point
The fusing point rise and enhancing effect played when sub- weight polyethylene fiber content is too low are limited, and superhigh molecular weight polyethylene fibers contain
When measuring too high, adhesion is inadequate between superhigh molecular weight polyethylene fibers, therefore preferably above range.
Preferably 15~40 grams, when superhigh molecular weight polyethylene fibers content is too low, the fusing point rise and enhancing played are imitated
Really limited, during superhigh molecular weight polyethylene fibers too high levels, adhesion is inadequate between superhigh molecular weight polyethylene fibers, therefore
It is preferred that above range.
Superhigh molecular weight polyethylene fibers used in the present invention are prepared by gel spinning method, its a diameter of 3~40 μm,
It is preferred that the less superhigh molecular weight polyethylene fibers of diameter, the less superhigh molecular weight polyethylene fibers specific surface area of diameter is more
Greatly, the mechanical property enhancing of product becomes apparent under same amount, therefore preferably.
In haloflex/superhigh molecular weight polyethylene fibers composite of the present invention, determined in means of differential scanning calorimetry
In, the crystalline fusion peak temperature (fusing point) determined with 10 DEG C/minute of the rate of heat addition for 100 DEG C and more than, preferably 110 DEG C and with
On.
Haloflex/superhigh molecular weight polyethylene fibers composite of the present invention, the test of tensile strength be according to
National standard GB/T 1040.1-2006 are carried out, and its tensile strength is more than 38MPa, and stretch modulus is more than 620MPa, tensile strength
The upper limit is usually 160MPa, and the stretch modulus upper limit is 1.5GPa.
A kind of preparation method of haloflex/superhigh molecular weight polyethylene fibers composite, step includes：Will synthesis
Periodicity haloflex and ultra-high molecular weight polyethylene long fibre continuous uniform be added to online mixing injection molding apparatus
Middle injection molding obtains haloflex/superhigh molecular weight polyethylene fibers composite, wherein, material passes through injection molding machine nozzle
Temperature be 110~140 DEG C, injection pressure is 100~300MPa, and mold temperature is 30~60 DEG C, material in a mold cold
But speed is 4~40 DEG C/min.
Preferably, the synthetic route of the periodicity haloflex in the preparation method of above-mentioned composite is such as
Under：
（a）1~10 mol straight chain terminal alkene -1- alcohol is added to and fills 1~10mol carbon tetrabromides and 600~6000ml dichloros
In the reactor of methane, reactor is cooled to after 0 DEG C, is slowly added at 1~5mol triphenyl phosphorus, 0 DEG C stir 30~60 points
Clock, is then warmed to room temperature stirring 2 hours, after reaction terminates, separation product simultaneously removes solvent, obtains product A；
（b）Will（a）The 200-2000g of gained（1-10mol）Product A is added to equipped with 50-500 g magnesium chips and 1-5 L tetrahydrochysene furans
In the reactor muttered, reactor is cooled to after 0 DEG C, the 300-3000mL tetrahydrofurans containing 0.7-7 mol methyl formates are molten
Liquid is added in above-mentioned reactor, is flowed back 20-36 hours after being warmed to room temperature, reaction terminates, and adds 1M 1-5L hydrochloric acid solutions, extraction
After cleaning, remove solvent and be dried overnight, obtain white solid B；
（c）By step（b）200-2000g white solid B, be fitted into the reactor for filling 2-5L carbon tetrachloride solutions, add
0.8-3mol triphenyl phosphorus, then be stirred at room temperature 4-8 hours, reaction removes solvent after terminating, remove phosphorous oxide, obtain white
Solid C；
（d）By white solid C and Grubbs generation catalyst, with mol ratio 2000~10000：1 ratio mixing, 30~50
Polymerisation is vacuumized at DEG C 3 days, add Anaesthetie Ether terminating reaction, toluene stirring and dissolving is added afterwards, is then added to cold
Sour methanol solution in settle, filtration drying obtains unsaturated polymer D；
（e）Unsaturated polymer D is dissolved in ortho-xylene, added to Methyl benzenesulfonyl hydrazine（TSH）And tripropyl amine (TPA)（TPA）,
Wherein TSH and TPA and unsaturated polymer D mol ratio is 3~5：1 and 3~5:1, backflow is cooled to room temperature after 9 hours, plus
Enter into cold sour methanol solution sedimentation, filtration drying obtains periodicity haloflex.
Preferably, long fibre enters chopped fiber of the cutting on line into 5-50mm before kneading device.
Preferably, in step（d）In be additionally added reaction promoter aluminum diethylphosphinate, addition is per 10000g
1-4g is added in reactant.
Aluminum diethylphosphinate co-catalyst is added in the catalyzed polymerization process of the present invention, and former preparation chlorination is periodically
The method of polyethylene is compared, and the addition of appropriate aluminum diethylphosphinate reduces the activation temperature of catalyst, improves catalyst
Service efficiency, greatly reduction catalyst consumption, and enrich reaction type.
There is superhigh molecular weight polyethylene fibers itself excellent mechanical property can promote the enhancing of mechanical properties of polymer,
Interface interaction of the mechanical property of polymer composites also between filler and polymeric matrix is closely related simultaneously.In polymer
In composite system, because fiber has a very high chain rivet degree of orientation, fiber and polymeric matrix produce on the contact surface compared with
Strong interaction, can effectively facilitate matrix polymer strand and be piled into orderly aggregated structure.Crystallization of growing nonparasitically upon another plant belongs to
A kind of interfacial crystallization, because the matching relationship of lattice causes two kinds of materials of interface to be combined together, can effectively lift boundary
Face adhesion.According to crystallization theory of growing nonparasitically upon another plant, when the mismatch ratio of the Lattice Matching existed between macromolecule and substrate of growing nonparasitically upon another plant is less than 10%
When, macromolecule is only possible to produce crystallization of growing nonparasitically upon another plant in substrate surface, and mismatch ratio is lower（Matching degree is higher）Crystallization of growing nonparasitically upon another plant is easier.Profit
Crystallized with highly oriented superhigh molecular weight polyethylene fibers as nucleator inducing periodic haloflex, and due to superelevation
The structure and the cell parameter of periodicity haloflex of molecular weight polyethylene fibrous strands axial period match, super high molecular weight
The polyethylene fibre crystallization that can be grown nonparasitically upon another plant with inducing periodic haloflex on its surface forms the crystal structure of dense regular, so that
Weaken the destruction that cl radical is crystallized to polyethylene backbone.Therefore using superhigh molecular weight polyethylene fibers nucleating effect and grow nonparasitically upon another plant
Crystallization promotes periodicity haloflex to form orderly state of aggregation knot in superhigh molecular weight polyethylene fibers surface crystallization
Structure, can significantly improve the melting temperature and mechanical property of substitution polyethylene.
In above-mentioned composite preparation process, the temperature that material passes through injection molding machine nozzle is 110-140 DEG C, in this temperature model
Periodically haloflex good fluidity is enclosed, cooling rate is easily controlled after injection, ultra-high molecular weight polyethylene chopped fiber knot
Structure will not be destroyed；Injection pressure is 100-300MPa, and injection pressure is high, periodicity haloflex and superhigh molecular weight polyethylene
Alkene short fiber orientation degree is high, and advantages of good crystallization of growing nonparasitically upon another plant, Mechanical Properties of Products is good.
The mould preferred flat shape of injection machine, flat mould can make the scattered of promotion superhigh molecular weight polyethylene fibers and
The ratio of orientation, the orientation for promoting haloflex strand, product width and height is big, and superhigh molecular weight polyethylene fibers take
It is high to degree height, haloflex molecular chain orientation degree, be conducive to polymer fully to be connect with superhigh molecular weight polyethylene fibers
The raw crystallization of growing nonparasitically upon another plant of triggering, therefore preferably, the ratio of die width and height can be 10-500.
In addition, the cooldown rate of mold temperature and material in a mold is extremely important, the two conditions, which are directly affected, grows nonparasitically upon another plant
The effect of crystallization, mold temperature is 30-60 DEG C, and the cooldown rate of material in a mold is 4~40 DEG C/min.
Compared with prior art, positive beneficial effect is the present invention：
Haloflex/superhigh molecular weight polyethylene fibers composite of the present invention, is not changing haloflex chemistry knot
In the case of structure, the aggregated structure of haloflex is adjusted by the way of superhigh molecular weight polyethylene fibers induce crystallization,
The regulation and control to haloflex crystal structure are realized, orthorhombic is regulated to from common three oblique crystalline substances, so as to reach raising melting temperature
The effect of degree and mechanical property, and method is easy, be easy to get.
Brief description of the drawings
Fig. 1 is that periodicity haloflex/superhigh molecular weight polyethylene fibers that X is 7 in constitutional repeating unit formula are multiple
X is the differential scanning calorimetry of 7 periodicity haloflex in condensation material and common constitutional repeating unit formula（DSC）Curve；
Fig. 2 is periodicity haloflex/superhigh molecular weight polyethylene fibers composite wood that X is 7 in constitutional repeating unit formula
X is 7 periodicity haloflex and the wide-angle X- of superhigh molecular weight polyethylene fibers in material, common constitutional repeating unit formula
X ray diffration pattern x.
Embodiment
Explanation is further described to technical scheme below by specific embodiment, but the present invention is not limited to
The embodiment.If without specified otherwise, the raw material employed in embodiments of the invention is raw material commonly used in the art, real
The method employed in example is applied, is the conventional method of this area.
Embodiment 1：
X is the synthesis of 4 periodicity haloflex in constitutional repeating unit formula
（a）Alkene -1- the alcohol of 3 mol 5 is added in the reactor for filling 3mol carbon tetrabromides and 1500ml dichloromethane, will be anti-
Answer device to be cooled to after 0 DEG C, be slowly added to stir 45 minutes at 2mol triphenyl phosphorus, 0 DEG C, be then warmed to room temperature stirring 2 hours, instead
After should terminating, separation product simultaneously removes solvent, obtains product A；
（b）Will（a）The 400g products A of gained is added in the reactor equipped with 100 g magnesium chips and 2L tetrahydrofurans, by reactor
It is cooled to after 0 DEG C, the 1500mL tetrahydrofuran solutions containing 3 mol methyl formates are added in above-mentioned reactor, after being warmed to room temperature
Backflow 24 hours, reaction terminates, and adds 1M 2L hydrochloric acid solutions, after extraction cleaning, removes solvent and is dried overnight, obtain white
Solid B；
（c）By step（b）600g white solid B, be fitted into the reactor for filling 3L carbon tetrachloride solutions, add 2mol triphens
Base phosphorus, then be stirred at room temperature 6 hours, reaction removes solvent after terminating, remove phosphorous oxide, obtain white solid C；
（d）By white solid C and Grubbs generation catalyst, with mol ratio 7000：1 ratio is mixed, and is vacuumized at 40 DEG C poly-
Reaction 3 days is closed, Anaesthetie Ether terminating reaction is added, toluene stirring and dissolving is added afterwards, cold sour methanol solution is then added to
Middle sedimentation, filtration drying obtains unsaturated polymer D；
（e）Unsaturated polymer D is dissolved in ortho-xylene, added to Methyl benzenesulfonyl hydrazine（TSH）And tripropyl amine (TPA)（TPA）,
Wherein TSH and TPA and unsaturated polymer D mol ratio is 3.3：1 and 3.8:1, backflow is cooled to room temperature after 9 hours, adds
Settled into cold sour methanol solution, filtration drying obtains periodicity haloflex.
X is 4 in the periodicity haloflex prepared, constitutional repeating unit formula, and number-average molecular weight is 9992.
By 8 grams, a diameter of 40 μm of superhigh molecular weight polyethylene fibers and 1000 grams of constitutional repeating units prepared
X is added separately to knead in injection molding apparatus online for 4 periodicity haloflex in formula, and long fibre enters mixing and filled
Preceding cutting on line is put into 50mm chopped fiber, then injection molding obtains periodicity haloflex/ultra-high molecular weight polyethylene
Fibrous composite, wherein, the mould of injection machine is the ratio of the ratio 60 of flat, die length and height, width and height
Value 40, material is 110 DEG C, injection pressure 100MPa by the temperature of nozzle, and mold temperature is 30 DEG C, material in a mold cold
But speed is 40 DEG C/min.
Obtained periodicity haloflex/superhigh molecular weight polyethylene fibers composite, is surveyed in means of differential scanning calorimetry
In fixed, the crystalline fusion peak temperature using 10 DEG C/minute of firing rate measure is 100 DEG C, and its tensile strength is 38MPa, stretching die
Measure as 620MPa.
Embodiment 2：
On the basis of above-described embodiment 1, in step（d）In when white solid C and Grubbs generation catalyst is added, simultaneously
Reaction promoter aluminum diethylphosphinate is added, addition is 0.06g.The periodicity haloflex prepared, repetitive structure
X is 4 in unit formula, and number-average molecular weight is 19984.Obtained periodicity haloflex/superhigh molecular weight polyethylene fibers
Composite, in means of differential scanning calorimetry measure, the crystalline fusion peak temperature determined using 10 DEG C/minute of firing rate as 102 DEG C,
Its tensile strength is 43MPa, and stretch modulus is 680MPa.Understood with the contrast of embodiment 1, reaction promoter diethyl phosphinic acids are not added
The molecular weight for the periodicity haloflex that aluminium is obtained is 9992, and the periodicity chlorination for having added aluminum diethylphosphinate to obtain gathers
The molecular weight 19984 of ethene, molecular weight adds 9992, and the mechanical property of the composite prepared is higher.
Embodiment 3：
X is the synthesis of 7 periodicity haloflex in constitutional repeating unit formula
（a）Alkene -1- the alcohol of 3 mol 8 is added in the reactor for filling 3 mol carbon tetrabromides and 1500ml dichloromethane, will be anti-
Answer device to be cooled to after 0 DEG C, be slowly added to stir 50 minutes at 3 mol triphenyl phosphorus, 0 DEG C, be then warmed to room temperature stirring 2 hours,
After reaction terminates, separation product simultaneously removes solvent, obtains product A；
（b）Will（a）The 600g products A of gained is added in the reactor equipped with 100 g magnesium chips and 2 L tetrahydrofurans, will be reacted
Device is cooled to after 0 DEG C, and the 1500mL tetrahydrofuran solutions containing 3 mol methyl formates are added in above-mentioned reactor, are warmed to room temperature
Flow back 24 hours afterwards, reaction terminates, add 1M 2L hydrochloric acid solutions, after extraction cleaning, remove solvent and be dried overnight, obtain white
Color solid B；
（c）By step（b）600g white solid B, be fitted into the reactor for filling 3L carbon tetrachloride solutions, add 2 mol tri-
Phenyl phosphorus, then be stirred at room temperature 6 hours, reaction removes solvent after terminating, remove phosphorous oxide, obtain white solid C；
（d）By white solid C and Grubbs generation catalyst, with mol ratio 7000：1 ratio is mixed, and is vacuumized at 40 DEG C poly-
Reaction 3 days is closed, Anaesthetie Ether terminating reaction is added, toluene stirring and dissolving is added afterwards, cold sour methanol solution is then added to
Middle sedimentation, filtration drying obtains unsaturated polymer D；
（e）Unsaturated polymer D is dissolved in ortho-xylene, added to Methyl benzenesulfonyl hydrazine（TSH）And tripropyl amine (TPA)（TPA）,
Wherein TSH and TPA and unsaturated polymer D mol ratio is 3.5：1 and 3.5:1, backflow is cooled to room temperature after 9 hours, adds
Settled into cold sour methanol solution, filtration drying obtains periodicity haloflex.
X is 7 in the periodicity haloflex prepared, constitutional repeating unit formula, and number-average molecular weight is 9240.
By 30 grams, a diameter of 20 μm of superhigh molecular weight polyethylene fibers and 1000 grams of constitutional repeating units prepared
X is added separately to knead in injection molding apparatus online for 7 periodicity haloflex in formula, and long fibre enters mixing and filled
Preceding cutting on line is put into 20mm chopped fiber, then injection molding obtains periodicity haloflex/ultra-high molecular weight polyethylene
Fibrous composite, wherein, the mould of injection machine is the ratio of the ratio 60 of flat, die length and height, width and height
Value 40, material is 130 DEG C, injection pressure 200MPa by the temperature of nozzle, and mold temperature is 40 DEG C, material in a mold cold
But speed is 20 DEG C/min.
Obtained periodicity haloflex/superhigh molecular weight polyethylene fibers composite, is surveyed in means of differential scanning calorimetry
In fixed, the crystalline fusion peak temperature using 10 DEG C/minute of firing rate measure is 114 DEG C.Its tensile strength is 65MPa, stretching die
Measure as 750MPa.
Embodiment 4：
On the basis of above-described embodiment 3, in step（d）In when white solid C and Grubbs generation catalyst is added, simultaneously
Reaction promoter aluminum diethylphosphinate is added, addition is 0.12g.The periodicity haloflex prepared, repetitive structure
X is 7 in unit formula, and number-average molecular weight is 17835.Obtained periodicity haloflex/superhigh molecular weight polyethylene fibers
Composite, in means of differential scanning calorimetry measure, the crystalline fusion peak temperature using 10 DEG C/minute of firing rate measure is 123 DEG C.
Its tensile strength is 74MPa, and stretch modulus is 950MPa.Understood with the contrast of embodiment 3, reaction promoter diethyl phosphinic acids are not added
The molecular weight for the periodicity haloflex that aluminium is obtained is 9240, and the periodicity chlorination for having added aluminum diethylphosphinate to obtain gathers
The molecular weight 17835 of ethene, molecular weight adds 8595, and the mechanical property of the composite prepared is higher.
Embodiment 5：
X is the synthesis of 10 periodicity haloflex in constitutional repeating unit formula
（a）Alkene -1- the alcohol of 2 mol 10 is added in the reactor for filling 2mol carbon tetrabromides and 1200ml dichloromethane, will be anti-
Answer device to be cooled to after 0 DEG C, be slowly added to stir 30~60 minutes at 2mol triphenyl phosphorus, 0 DEG C, be then warmed to room temperature stirring 2 small
When, after reaction terminates, separation product simultaneously removes solvent, obtains product A；
（b）Will（a）The 400g products A of gained is added in the reactor equipped with 100 g magnesium chips and 2 L tetrahydrofurans, will be reacted
Device is cooled to after 0 DEG C, and the 600mL tetrahydrofuran solutions containing 1.4 mol methyl formates are added in above-mentioned reactor, are warmed to room temperature
Flow back 30 hours afterwards, reaction terminates, add 1M 2L hydrochloric acid solutions, after extraction cleaning, remove solvent and be dried overnight, obtain white
Color solid B；
（c）By step（b）300g white solid B, be fitted into the reactor for filling 3L carbon tetrachloride solutions, add 1.3mol tri-
Phenyl phosphorus, then be stirred at room temperature 8 hours, reaction removes solvent after terminating, remove phosphorous oxide, obtain white solid C；
（d）By white solid C and Grubbs generation catalyst, with mol ratio 6000：1 ratio is mixed, and is vacuumized at 50 DEG C poly-
Reaction 3 days is closed, is stopped after reaction, toluene stirring and dissolving is added, is then added in cold sour methanol solution and settles, crosses and is filtered dry
It is dry, obtain unsaturated polymer D；
（e）Unsaturated polymer D is dissolved in ortho-xylene, added to Methyl benzenesulfonyl hydrazine（TSH）And tripropyl amine (TPA)（TPA）,
Wherein TSH and TPA and unsaturated polymer D mol ratio is 3.3：1 and 4:1, backflow is cooled to room temperature after 9 hours, is added to
Settled in cold sour methanol solution, filtration drying obtains periodicity haloflex.
X is 10 in the periodicity haloflex prepared, constitutional repeating unit formula, and number-average molecular weight is 14203.
By 100 grams, the repetitive structure list that a diameter of 12 μm of superhigh molecular weight polyethylene fibers and 1000 grams are prepared
X is added separately to knead in injection molding apparatus online for 10 periodicity haloflex in first formula, and long fibre enters mixed
Refine device before cutting on line into 10mm chopped fiber, then injection molding obtain periodicity haloflex/super high molecular weight gather
Vinyl fiber composite, wherein, the mould of injection machine is the ratio 60 of flat, die length and height, width and height
Ratio 40, material is 120 DEG C, injection pressure 250MPa by the temperature of nozzle, and mold temperature is 50 DEG C, and material is in a mold
Cooldown rate be 8 DEG C/min.
Obtained periodicity haloflex/superhigh molecular weight polyethylene fibers composite, is surveyed in means of differential scanning calorimetry
In fixed, the crystalline fusion peak temperature using 10 DEG C/minute of firing rate measure is 124 DEG C.Its tensile strength is 85MPa, stretching die
Measure as 870MPa.
Embodiment 6：
On the basis of above-described embodiment 5, in step（d）In when white solid C and Grubbs generation catalyst is added, simultaneously
Reaction promoter aluminum diethylphosphinate is added, addition is 0.12g.The periodicity haloflex prepared, repetitive structure
X is 10 in unit formula, and number-average molecular weight is 22173.Obtained periodicity haloflex/superhigh molecular weight polyethylene fibers
Composite, in means of differential scanning calorimetry measure, the crystalline fusion peak temperature using 10 DEG C/minute of firing rate measure is 126 DEG C.
Its tensile strength is 95MPa, and stretch modulus is 1030MPa.Understood with the contrast of embodiment 5, reaction promoter diethyl time phosphine is not added
The molecular weight for the periodicity haloflex that sour aluminium is obtained is 14203, and the periodicity chlorine for having added aluminum diethylphosphinate to obtain
Change the molecular weight 22175 of polyethylene, molecular weight adds 7972, and the mechanical property of the composite prepared is higher.
Embodiment 7：
X is the synthesis of 14 periodicity haloflex in constitutional repeating unit formula
（a）Alkene -1- the alcohol of 2 mol 15 is added in the reactor for filling 2 mol carbon tetrabromides and 1200ml dichloromethane, will
Reactor is cooled to after 0 DEG C, is slowly added to stir 60 minutes at 2 mol triphenyl phosphorus, 0 DEG C, is then warmed to room temperature stirring 2 small
When, after reaction terminates, separation product simultaneously removes solvent, obtains product A；
（b）Will（a）The 400g products A of gained is added in the reactor equipped with 100 g magnesium chips and 3 L tetrahydrofurans, will be reacted
Device is cooled to after 0 DEG C, and the 2000mL tetrahydrofuran solutions containing 3 mol methyl formates are added in above-mentioned reactor, are warmed to room temperature
Flow back 36 hours afterwards, reaction terminates, add 1M 3 L hydrochloric acid solutions, after extraction cleaning, remove solvent and be dried overnight, obtain
White solid B；
（c）By step（b）600g white solid B, be fitted into the reactor for filling 3 L carbon tetrachloride solutions, add 2 mol tri-
Phenyl phosphorus, then be stirred at room temperature 8 hours, reaction removes solvent after terminating, remove phosphorous oxide, obtain white solid C；
（d）By white solid C and Grubbs generation catalyst, with mol ratio 8000：1 ratio mixing, and add 0.06g diethyls
Base phosphinic acids aluminium vacuumizes polymerisation 3 days as reaction promoter at 50 DEG C, adds Anaesthetie Ether terminating reaction, adds afterwards
Toluene stirring and dissolving, is then added in cold sour methanol solution and settles, and filtration drying obtains unsaturated polymer D；
（e）Unsaturated polymer D is dissolved in ortho-xylene, added to Methyl benzenesulfonyl hydrazine（TSH）And tripropyl amine (TPA)（TPA）,
Wherein TSH and TPA and unsaturated polymer D mol ratio is 3.3：1 and 4:1, backflow is cooled to room temperature after 9 hours, is added to
Settled in cold sour methanol solution, filtration drying obtains periodicity haloflex.
X is 14 in the periodicity haloflex prepared, constitutional repeating unit formula, and number-average molecular weight is 10488.
By 40 grams, a diameter of 3 μm of superhigh molecular weight polyethylene fibers and 1000 grams of constitutional repeating units prepared
X is added separately to knead injection molding in injection molding apparatus online and obtains the cycle for 14 periodicity haloflex in formula
Property haloflex/superhigh molecular weight polyethylene fibers composite, wherein, the mould of injection machine is flat, die length
With the ratio 60 of height, the ratio 40 of width and height, the temperature that material passes through nozzle is 110 DEG C, injection pressure 300MPa, mould
It is 60 DEG C to have temperature, and the cooldown rate of material in a mold is 4 DEG C/min.
Obtained periodicity haloflex/superhigh molecular weight polyethylene fibers composite, is surveyed in means of differential scanning calorimetry
In fixed, the crystalline fusion peak temperature using 10 DEG C/minute of firing rate measure is 128 DEG C.Its tensile strength is 115MPa, stretching die
Measure as 1230MPa.
Embodiment 8：
On the basis of above-described embodiment 7, in step（d）In when white solid C and Grubbs generation catalyst is added, simultaneously
Reaction promoter aluminum diethylphosphinate is added, addition is 0.24g.The periodicity haloflex prepared, repetitive structure
X is 14 in unit formula, and number-average molecular weight is 24963.Obtained periodicity haloflex/superhigh molecular weight polyethylene fibers
Composite, in means of differential scanning calorimetry measure, the crystalline fusion peak temperature using 10 DEG C/minute of firing rate measure is 129 DEG C.
Its tensile strength is 130MPa, and stretch modulus is 1450MPa.Understood with the contrast of embodiment 5, reaction promoter diethyl time phosphine is not added
The molecular weight for the periodicity haloflex that sour aluminium is obtained is 10488, and the periodicity chlorine for having added aluminum diethylphosphinate to obtain
Change the molecular weight 24963 of polyethylene, molecular weight adds 14475, and the mechanical property of the composite prepared is higher.
Comparative example 1
By 2 grams, the periodicity chlorination that a diameter of 20 μm of superhigh molecular weight polyethylene fibers and 1000 grams of embodiments 3 are prepared
Polyethylene, which is added separately to knead injection molding in injection molding apparatus online, obtains periodicity haloflex/super high molecular weight
Polyethylene fiber composites, wherein, the mould of injection machine is the ratio 60 of flat, die length and height, width and height
The ratio 40 of degree, the temperature that material passes through nozzle is 130 DEG C, injection pressure 200MPa, and mold temperature is 40 DEG C, and material is in mould
In cooldown rate be 10 DEG C/min.
Obtained periodicity haloflex/superhigh molecular weight polyethylene fibers composite, is surveyed in means of differential scanning calorimetry
In fixed, the crystalline fusion peak temperature using 10 DEG C/minute of firing rate measure is 97 DEG C, and its tensile strength is 29MPa, stretch modulus
For 430MPa.
The Comparative result of embodiment and comparative example is understood, appropriate superhigh molecular weight polyethylene fibers is added and passes through crystallization of growing nonparasitically upon another plant
The crystal structure of periodicity haloflex orthorhombic is changed over into from three oblique crystalline substances, composite fusing point and mechanical property are obtained
Significantly lifted.As shown in Figure 1, X gathers for 10 periodicity haloflex/super high molecular weight in constitutional repeating unit formula
Vinyl fiber composite fusing point reaches 126 DEG C, and the fusing point of periodicity haloflex is only 89 DEG C；As shown in Figure 2, weight
Periodicity haloflex/superhigh molecular weight polyethylene fibers composite, repetitive structures of the X for 10 in complex structure unit formula
X is 10 common periodicity haloflex and the wide-angle x-ray diffraction of superhigh molecular weight polyethylene fibers in unit formula
（WAXD）Figure, common periodicity haloflex is three tiltedly brilliant, and periodicity haloflex/superhigh molecular weight polyethylene fibers
Periodicity haloflex in composite is orthorhombic.
The present invention prepares periodicity haloflex using ad hoc approach first, cl radical in the periodicity haloflex
Position and content controllable precise in main chain, thus the accurate tune to haloflex hot property and mechanical property can be realized
Control.In order to further improve the heat resistance and intensity of periodicity haloflex, the present invention is fine using ultra-high molecular weight polyethylene
The characteristics of cell parameter for tieing up the periodic structure of highly oriented strand and the chain direction of principal axis of periodicity haloflex matches,
Haloflex crystallization of being grown nonparasitically upon another plant on superhigh molecular weight polyethylene fibers surface is induced to form extended chain by specific processing technology
Crystal structure layer, is effectively improved between haloflex matrix and superhigh molecular weight polyethylene fibers by such interfacial crystallization layer
Interface binding power, so as to improve the transmission of load between haloflex matrix and superhigh molecular weight polyethylene fibers, prepare
Obtain high intensity, dystectic haloflex/superhigh molecular weight polyethylene fibers laminar composite.
And on the reaction on basis, aluminum diethylphosphinate is added among haloflex preparation method as anti-
Auxiliary agent is answered, addition is to add 1-4g per in 10000g reactants, and catalyst is improved by adding aluminum diethylphosphinate
Service efficiency so that the haloflex molecular weight of preparation is higher, and enrich in reaction type, constitutional repeating unit formula
X is more preferably controlled.
Claims (10)
1. a kind of haloflex/superhigh molecular weight polyethylene fibers composite, it is characterised in that the haloflex is
Periodicity haloflex, the formula of its constitutional repeating unit is as follows：
；
In the formula, X=4,6,7,9,10,14 or 18；
The number-average molecular weight of the haloflex is 8000~120000；
The mass ratio of the haloflex and superhigh molecular weight polyethylene fibers is 1000：8~100；
The composite, in means of differential scanning calorimetry measure, the crystalline fusion peak temperature determined with 10 DEG C/minute of the rate of heat addition
More than or equal to 100 DEG C；The composite, its tensile strength is more than or equal to 38MPa, and stretch modulus is more than or equal to 620MPa.
2. a kind of haloflex/superhigh molecular weight polyethylene fibers composite according to claim 1, its feature exists
In, in the formula, X=4,7,10 or 14.
3. a kind of haloflex/superhigh molecular weight polyethylene fibers composite according to claim 1 or 2, it is special
Levy and be, the number-average molecular weight of the haloflex is 15000~50000.
4. a kind of haloflex/superhigh molecular weight polyethylene fibers composite according to claim 1 or 2, it is special
Levy and be, the mass ratio of the haloflex and superhigh molecular weight polyethylene fibers is 1000：15~40.
5. a kind of haloflex/superhigh molecular weight polyethylene fibers composite according to claim 1 or 2, it is special
Levy and be, a diameter of 3~40 μm of the superhigh molecular weight polyethylene fibers.
6. a kind of haloflex/superhigh molecular weight polyethylene fibers composite according to claim 1 or 2, it is special
Levy and be, the composite, in means of differential scanning calorimetry measure, the crystalline melting peak determined with 10 DEG C/minute of the rate of heat addition
Temperature is more than or equal to 110 DEG C.
7. a kind of system of haloflex/superhigh molecular weight polyethylene fibers composite as described in above-mentioned any claim
Preparation Method, it is characterised in that step includes：The periodicity haloflex of synthesis and ultra-high molecular weight polyethylene long fibre are connected
It is continuous to be even added to injection molding in online mixing injection molding apparatus and obtain haloflex/superhigh molecular weight polyethylene fibers
Composite, wherein, the temperature that material passes through injection molding machine nozzle is 110~140 DEG C, and injection pressure is 100~300MPa, mould
Temperature is 30~60 DEG C, and the cooldown rate of material in a mold is 4~40 DEG C/min.
8. a kind of preparation side of haloflex/superhigh molecular weight polyethylene fibers composite according to claim 7
Method, it is characterised in that the synthetic route of the haloflex is as follows：
（a）1~10 mol straight chain terminal alkene -1- alcohol is added to and fills 1~10mol carbon tetrabromides and 600~6000ml dichloros
In the reactor of methane, reactor is cooled to after 0 DEG C, is slowly added at 1~5mol triphenyl phosphorus, 0 DEG C stir 30~60 points
Clock, is then warmed to room temperature stirring 2 hours, after reaction terminates, separation product simultaneously removes solvent, obtains product A；
（b）Will（a）The 200-2000g of gained（1-10mol）Product A is added to equipped with 50-500 g magnesium chips and 1-5 L tetrahydrochysene furans
In the reactor muttered, reactor is cooled to after 0 DEG C, the 300-3000mL tetrahydrofurans containing 0.7-7 mol methyl formates are molten
Liquid is added in above-mentioned reactor, is flowed back 20-36 hours after being warmed to room temperature, reaction terminates, and adds 1M 1-5L hydrochloric acid solutions, extraction
After cleaning, remove solvent and be dried overnight, obtain white solid B；
（c）By step（b）200-2000g white solid B, be fitted into the reactor for filling 2-5L carbon tetrachloride solutions, add
0.8-3mol triphenyl phosphorus, then be stirred at room temperature 4-8 hours, reaction removes solvent after terminating, remove phosphorous oxide, obtain white
Solid C；
（d）By white solid C and Grubbs generation catalyst, with mol ratio 2000~10000：1 ratio mixing, 30~50 DEG C
Under vacuumize polymerisation 3 days, add Anaesthetie Ether terminating reaction, afterwards add toluene stirring and dissolving, be then added to cold
Settled in sour methanol solution, filtration drying obtains unsaturated polymer D；
（e）Unsaturated polymer D is dissolved in ortho-xylene, added to Methyl benzenesulfonyl hydrazine（TSH）And tripropyl amine (TPA)（TPA）,
Wherein TSH and TPA and unsaturated polymer D mol ratio is 3~5：1 and 3~5:1, backflow is cooled to room temperature after 9 hours, plus
Enter into cold sour methanol solution sedimentation, filtration drying obtains periodicity haloflex.
9. a kind of preparation side of haloflex/superhigh molecular weight polyethylene fibers composite according to claim 7
Method, it is characterised in that long fibre enters chopped fiber of the cutting on line into 5-50mm before kneading device.
10. a kind of preparation side of haloflex/superhigh molecular weight polyethylene fibers composite according to claim 8
Method, it is characterised in that in step（d）In be additionally added reaction promoter aluminum diethylphosphinate, addition is per 10000g reactants
Middle addition 1-4g.
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|---|---|---|---|---|
| CN101988266A (en) * | 2009-08-06 | 2011-03-23 | 中国科学院宁波材料技术与工程研究所 | Method for improving surface bonding strength of high molecular weight polyethylene (UHMWPE) fibre |
| CN202510863U (en) * | 2012-04-19 | 2012-10-31 | 邓全洪 | Flexible vent pipe with high-strength high-modulus polyethylene fiber fabric layer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101988266A (en) * | 2009-08-06 | 2011-03-23 | 中国科学院宁波材料技术与工程研究所 | Method for improving surface bonding strength of high molecular weight polyethylene (UHMWPE) fibre |
| CN202510863U (en) * | 2012-04-19 | 2012-10-31 | 邓全洪 | Flexible vent pipe with high-strength high-modulus polyethylene fiber fabric layer |
| CN104916363A (en) * | 2014-03-10 | 2015-09-16 | 佛山市顺德区北航先进技术产业基地有限公司 | Compound material core aluminum stranded wire and manufacturing method thereof |
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