CN102534838B - Ultra-high molecular weight polyethylene fiber spinning stock solution and preparation method thereof - Google Patents
Ultra-high molecular weight polyethylene fiber spinning stock solution and preparation method thereof Download PDFInfo
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Abstract
The invention provides an ultra-high molecular weight polyethylene fiber spinning stock solution which comprises the following components in percentage by weight: 10-15% of ultra-high molecular weight polyethylene, nucleating agent which accounts for 0.02-6 wt% of the ultra-high molecular weight polyethylene, and the balance of solvent. Compared with the prior art, the spinning stock solution provided by the invention contains the nucleating agent, which has the functions of enhancing the plasticity of the spinning stock solution and lowering the activation energy of the spinning stock solution slurry, thereby lowering the twisting density of ultra-high molecular weight polyethylene fiber macromolecules in the spinning stock solution. In addition, in the process of untwisting the spinning stock solution, the nucleating agent can be dispersed among the ultra-high molecular weight polyethylene macromolecular chain section as a nucleating core, thereby being beneficial to forming uniform two-dimensional nanocrystals. Thus, in the spinning formation process, the uniformity of the freshly formed filament crystal can be enhanced, thereby finally enhancing the performance of the ultra-high molecular weight polyethylene fiber.
Description
Technical field
The present invention relates to superhigh molecular weight polyethylene fibers, be specifically related to spinning solution of ultra-high molecular weight polyethylene fiber and preparation method thereof.
Background technology
Superhigh molecular weight polyethylene fibers (UHMWPE), also claims high-strength high-modulus polyethylene fiber, refers to that by the relative molecular weight polyethylene more than 1,000,000 is successively through high-performance fiber that spinning-extraction-be dried-ultra-drawing is made.Adopt the fibre reinforced composites made of superhigh molecular weight polyethylene fibers to have that quality is light, shock-resistant, dielectric properties advantages of higher, be widely used in aerospace field, defence field, marine site, weaponry field and daily industrial circle.
In the prior art, prepare superhigh molecular weight polyethylene fibers and conventionally use gel spinning technology, first this technology is invented by Dutch DSM N. V..In gel spinning technology, conventionally use the polyethylene of relative molecular weight more than 1,000,000 as raw material, using this raw material and the suitable swelling suspension obtaining of solvent as spinning solution, then this spinning solution is twined through the shearing of screw extruder, even mixed, solution, obtain nascent gel fiber through spinning pack extrusion molding again, then nascent gel fiber carried out to follow-up extraction, be dried and ultra-drawing obtains superhigh molecular weight polyethylene fibers.
The calculated results shows, the ultimate strength of UHMWPE fiber can reach 30 ± GPa, and modulus can reach 350GPa.In prior art, the laboratory product strength of UHMWPE fiber has reached 9GPa, and the strength and modulus of the UHMWPE fiber that still industrialization is at present produced is well below theoretical value, and if intensity is only 2.5～3.5GPa, modulus is only 90～110GPa.Along with the growth of related industry to high-strength high-modulus fibre demand, increasing scientific research personnel sets about research makes the strength and modulus of UHMWPE fiber to the close technique of its theoretical value.The result of study of warp shows, causes that the intensity of UHMWPE fiber prepared by gel spinning is a lot of far below the reason of its theoretical limit intensity, and wherein topmost reason is relevant with molecular structure and the crystal habit thereof of fiber.
In existing gel spinning technique, ultra-high molecular weight polyethylene spinning solution is after screw extruder obtains certain solution and twines, extrude and quenching formation frozen glue pre-oriented yarn by spinnerets, in this preorientation strand, keep the disentangled state of strand, in the process through extraction and super times of Multi-stage heat stretching, PE fiber macromolecular chain is fully stretched vertically, and degree of crystallinity and the degree of orientation be corresponding improve all; Meanwhile, the chain-folded lamellae in molecular structure transforms to extended chain, thereby obtains superhigh molecular weight polyethylene fibers high-strength, Gao Mo.
But the inventor is through research discovery, the crystallization between strand not only comes across in hot-stretch process.In fact, spinning liquid obtains nascent strand when shearing in screw rod and spraying quenching moulding by spinnerets time, between the macromolecular chain that partial solution twines, under orientation effect, first form the shish-kebab center line part with extended-chain crystal structure, this shish-kebab center line part can be used as nucleation and generates the chain-folded lamellae of some row, forms shish-kebab structure.Like this, in follow-up hot drafting process, the folded chain of strand opened gradually and stretching after, platelet is recrystallized in destroyed process, rhombic system Partial Conversion is more stable hexagonal crystal system, can be conducive to improve like this strength and modulus of superhigh molecular weight polyethylene fibers.
That is to say, if consider to improve the uniformity of crystallization in nascent strand, thereby contribute to make fiber after overheated drawing-off, make more shish-kebab rhombic system be converted into hexagonal crystal system and finally improve the performance of fiber.In prior art, the basic reason that superhigh molecular weight polyethylene fibers intensity is lower is that shish-kebab is not evenly continuous in the process forming, therefore make rhombic system be converted to the ratio of hexagonal crystal system too low, therefore the intensity of superhigh molecular weight polyethylene fibers improves limited.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of spinning solution of ultra-high molecular weight polyethylene fiber and preparation method thereof, compared with prior art, spinning solution provided by the invention can be conducive to form shish-kebab structure, thereby the superhigh molecular weight polyethylene fibers that uses this spinning solution to prepare has higher intensity.
In order to solve above technical problem, the invention provides a kind of spinning solution of ultra-high molecular weight polyethylene fiber, comprise in weight percent:
Ultra-high molecular weight polyethylene 10%～15%;
Nucleator, the percentage by weight that described nucleator accounts for described ultra-high molecular weight polyethylene is 0.02%～6%;
Balance solvent.
Preferably, also comprise antioxidant, the percentage by weight that described antioxidant accounts for the ultra-high molecular weight polyethylene total amount in described spinning solution is 0.1%～1%.
Preferably, also comprise surfactant, the percentage by weight that described surfactant accounts for the ultra-high molecular weight polyethylene total amount in spinning solution is 0.1%～0.5%.
Preferably, described nucleator comprises one or more in inorganic silicate nucleator, metal oxide nucleator, organic acid nucleator, acylate nucleator, polymer nucleator, D-sorbite or derivatives thereof nucleator, organic phosphate nucleating agent, tricarballylic acid type acid amides nucleator.
Preferably, described inorganic silicate nucleator is talcum powder.
Preferably, described metal oxide nucleator comprises titanium oxide, alkali metal oxide or alkaline earth oxide.
Preferably, described organic acid nucleator comprises 4-p t butylbenzoic acid, aliphatic acid or diphenyl acetic acid.
Preferably, described acylate nucleator comprises sodium succinate or Sodium Benzoate.
Preferably, described D-sorbite or derivatives thereof nucleator comprises dibenzylidene sorbitol, two (to methyl benzal) D-sorbite, two (to benzyl chloride fork) D-sorbite, 1,3-2,4 two Asias (4 methyl) benzyl-D-D-sorbite, 1,3,5-benzenetricarboxylic acid derivative.
Preferably, solvent in described ultra-high molecular weight polyethylene spinning solution be cycloalkane and alkane according to 85～90: the mixed solvent that 10～15 ratio is mixed to get, the carbon atom number of described cycloalkane is 25～50, and the carbon atom number of described alkane is 25～50
The present invention also provides a kind of preparation method of described spinning solution of ultra-high molecular weight polyethylene fiber, comprising:
Getting ratio that ultra-high molecular weight polyethylene lysate and ultra-high molecular weight polyethylene swelling solution are 0.42～2.85 according to weight ratio, to be mixed to get ultra-high molecular weight polyethylene weight content be 10%～15% spinning solution;
The content of the ultra-high molecular weight polyethylene in described ultra-high molecular weight polyethylene swelling solution is 10～50%;
The weight ratio of the ultra-high molecular weight polyethylene in the ultra-high molecular weight polyethylene in described ultra-high molecular weight polyethylene swelling solution and described ultra-high molecular weight polyethylene lysate is 2.5～70;
In described ultra-high molecular weight polyethylene lysate, have nucleator, the percentage by weight that described nucleator accounts for the ultra-high molecular weight polyethylene in described spinning solution of ultra-high molecular weight polyethylene fiber is 0.02%～5%.
Preferably, to account for the percentage by weight of the ultra-high molecular weight polyethylene in described ultra-high molecular weight polyethylene lysate be 0.8%～80% to described nucleator.
Preferably, in described ultra-high molecular weight polyethylene lysate, also comprise antioxidant, the percentage by weight that described antioxidant accounts for the ultra-high molecular weight polyethylene in described ultra-high molecular weight polyethylene lysate is 1%～8%.
Preferably, in described ultra-high molecular weight polyethylene swelling solution, also comprise surfactant.
Preferably, described ultra-high molecular weight polyethylene swelling solution is prepared as follows:
In first part of solvent, add ultra-high molecular weight polyethylene powder to stir;
In described first part of solvent, add second part of solvent and the first emulsified solvent to obtain the first mixture;
Described the first mixture is warming up to 90 DEG C～130 DEG C swelling ultra-high molecular weight polyethylene swelling solutions that obtain of insulation;
Described the first emulsified solvent is formed through Over emulsfication by the 3rd part of solvent and surfactant;
First part of solvent: second part of solvent: the 3rd part of solvent: the weight ratio of surfactant is 45～55: 45～55: 1～20: 0.05～0.1.
Preferably, the swellbility of described ultra-high molecular weight polyethylene swelling solution is 1～2.
Preferably, described ultra-high molecular weight polyethylene lysate is prepared as follows:
In the 4th part of solvent, add the second emulsified solvent, the 3rd emulsified solvent, the 5th part of stirring solvent evenly to obtain the second mixture, described the second mixture is warming up to 100 DEG C～190 DEG C stirrings and obtains ultra-high molecular weight polyethylene lysate;
Described the second emulsified solvent by the 6th part of solvent and ultra-high molecular weight polyethylene according to 1～5: 0.4～0.6 ratio emulsification forms;
Described the 3rd emulsified solvent is formed through Over emulsfication by the 7th portion of solvent, antioxidant and nucleator;
Described the 4th part of solvent: the 5th part of solvent: the 6th part of solvent: the weight ratio of the 7th part of solvent is 67～75: 15～25: 2～10: 2～4.
The invention provides a kind of spinning solution of ultra-high molecular weight polyethylene fiber, compared with prior art, in spinning solution provided by the invention, contain nucleator, the effect of nucleator is to increase the plasticity of spinning solution, reduce the activation energy of spinning solution slurry, twined density thereby reduced the macromolecular solution of the superhigh molecular weight polyethylene fibers in spinning solution.In addition, this spinning solution being carried out in the process that solution twines, nucleator can be used as nucleation core and is dispersed between ultra-high molecular weight polyethylene macromolecular chain segment, is conducive to form uniform two-dimensional nano crystalline substance; Like this, in the process of spray silk moulding, can improve the uniformity of nascent strand crystallization, thereby finally improve the performance of superhigh molecular weight polyethylene fibers.
Detailed description of the invention
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The invention provides a kind of spinning solution of ultra-high molecular weight polyethylene fiber, comprise in weight percent:
Ultra-high molecular weight polyethylene 10%～15%;
Nucleator, the percentage by weight that described nucleator accounts for described ultra-high molecular weight polyethylene is 0.02%～6%;
Balance solvent.
In spinning solution provided by the invention, the weight content of ultra-high molecular weight polyethylene is preferably 11%～14%, and more preferably 12～13%.The weight average molecular weight M of the ultra-high molecular weight polyethylene using in spinning solution of the present invention
wbe preferably 3～5 × 10
6, more preferably 3.5～4.5 × 10
6, the non-linear rate < 5% of ultra-high molecular weight polyethylene; The present invention preferably uses particle diameter to be the ultra-high molecular weight polyethylene powder of Gaussian distribution, and the particle diameter of described powder is preferably 60 order～200 orders.
According to the present invention, described nucleator comprises one or more in inorganic silicate nucleator, metal oxide nucleator, organic acid nucleator, acylate nucleator, polymer nucleator, D-sorbite or derivatives thereof nucleator, organic phosphate nucleating agent, tricarballylic acid type acid amides nucleator.
The present invention, the object lesson of described inorganic silicate nucleator can be talcum powder, but is not limited to this.Described metal oxide nucleator comprises titanium oxide, alkali metal oxide, as NaO, KO, RuO; Alkaline earth oxide is as MgO, CaO, BaO, but is not limited to this.The object lesson of described organic acid nucleator can be 4-p t butylbenzoic acid, aliphatic acid or diphenyl acetic acid, but is not limited to this.The object lesson of described acylate nucleator can be sodium succinate or Sodium Benzoate, but is not limited to this.The object lesson of described D-sorbite or derivatives thereof nucleator comprises dibenzylidene sorbitol, two (to methyl benzal) D-sorbite, two (to benzyl chloride fork) D-sorbite, 1,3-2,4 two Asias (4 methyl) benzyl-D-D-sorbite, 1,3,5-benzenetricarboxylic acid derivative, but be not limited to this.
According to the present invention, when the nucleator using is during for solid, preferably use particle diameter to be less than the nucleator of 200nm, more preferably use granularity to be less than the nucleator of 100nm, more preferably use granularity to be less than the nucleator of 50nm.The nucleator using during for liquid, preferably uses the nucleator being soluble in described spinning solution.
According to the present invention, in spinning solution, add after nucleator, nucleator can be realized plasticization and modification to spinning material, thereby has reduced the activity function of spinning slurry, thereby has reduced the ultra-high molecular weight polyethylene macromolecular entanglements density in spinning slurry.When under the shear action at screw extruder by this spinning solution, nucleator is scattered between the segment of ultra-high molecular weight polyethylene, can form uniform two-dimensional nano crystalline substance, in the process of spray silk, after suitable drawing-off, solution twines macromolecular chain increases percent crystallization in massecuite, makes the moulding of basic crystal formation more even, thereby is conducive to improve the final mechanical property of superhigh molecular weight polyethylene fibers.
In spinning solution provided by the invention, solvent is preferably cycloalkane: chain hydrocarbon isomers is according to 85～90: the mixture that 10～15 ratio is mixed to get, and the carbon atom number of described cycloalkane and alkane is preferably 25～50, and more preferably 30～40.Described solvent can use the solvent for ultra-high molecular weight polyethylene spinning solution well known to those skilled in the art, for example can use preferably 400 DEG C following without gaseous volatilization, initial boiling point preferably higher than 450 DEG C, density is preferably 0.84～0.87g/cm
3flash-point is preferably higher than the naphthenic oil of 260 DEG C, object lesson can be 5# white oil well known to those skilled in the art, 7# white oil, 10# white oil, 15# white oil, 22# white oil, 26# white oil, 32# white oil, 46# white oil, 68# white oil, 100# white oil, 150# white oil, but is not limited to this.
The present invention also provides a kind of preparation method of described spinning solution, comprises step:
Getting ratio that ultra-high molecular weight polyethylene lysate and ultra-high molecular weight polyethylene swelling solution are 0.42～2.85 according to weight ratio, to be mixed to get ultra-high molecular weight polyethylene weight content be 10%～15% spinning solution;
The weight content of the ultra-high molecular weight polyethylene in described ultra-high molecular weight polyethylene swelling solution is 10～50%;
The weight ratio of the ultra-high molecular weight polyethylene in the ultra-high molecular weight polyethylene in described ultra-high molecular weight polyethylene swelling solution and described ultra-high molecular weight polyethylene lysate is 2.5～70;
Described ultra-high molecular weight polyethylene lysate comprises nucleator, and the weight ratio that described nucleator accounts for described spinning solution is 0.1%～10%.
In spinning solution provided by the invention, can also comprise antioxidant, the percentage by weight that described antioxidant accounts for the ultra-high molecular weight polyethylene total amount in described spinning solution is 0.1%～1%, be preferably 0.1%～0.5%, preferably, the percentage by weight that described antioxidant accounts for the ultra-high molecular weight polyethylene in described ultra-high molecular weight polyethylene lysate is 1%～8%, more preferably 2%～7%, more preferably 4%～6%.Described antioxidant can be Hinered phenols antioxidant well known to those skilled in the art, arylamine kind antioxidant, object lesson can be 2, tri-grades of butyl-4-methylphenols of 6-, two (3, tri-grades of butyl-4-hydroxy phenyls of 5-) thioether, four (β (3, tri-grades of butyl-4-hydroxy phenyls of 5-) propionic acid) pentaerythritol ester etc., but be not limited to this.
In spinning solution provided by the invention, can also comprise surfactant, the percentage by weight that described surfactant accounts for the ultra-high molecular weight polyethylene total amount in spinning solution is 0.1%～0.5%.Described surfactant can be anion surfactant well known to those skilled in the art, cationic surfactant, non-ionic surface active agent, object lesson can be stearic acid, neopelex, quaternary ammonium compound, fatty glyceride, aliphatic acid sorb smooth (sapn), polysorbate (tween) etc., but is not limited to this.
According to the present invention, described ultra-high molecular weight polyethylene swelling solution refers to well known to those skilled in the art by after ultra-high molecular weight polyethylene and solvent, small solvent molecule between the large molecule of ultra-high molecular weight polyethylene, makes the suspension obtaining after the large molecule expansion of ultra-high molecular weight polyethylene through diffusion; Described ultra-high molecular weight polyethylene lysate refers to the solution obtaining in solvent that ultra-high molecular weight polyethylene is dissolved into well known to those skilled in the art.
According to the present invention, the weight content of the ultra-high molecular weight polyethylene in described ultra-high molecular weight polyethylene swelling solution is preferably 11%～49%, and more preferably 15%～40%, most preferably be 20%～35%.The weight content of the ultra-high molecular weight polyethylene in described ultra-high molecular weight polyethylene lysate is preferably 0.2%～5%, and more preferably 0.3%～2.5%, more preferably 0.8%～2%.
According to the present invention, when described ultra-high molecular weight polyethylene swelling solution and described ultra-high molecular weight polyethylene lysate mix and blend are prepared to spinning solution, the weight ratio of described ultra-high molecular weight polyethylene lysate and described ultra-high molecular weight polyethylene swelling solution is preferably 0.42-2.85, more preferably 1.0～2.5, more preferably 1.4～1.8.The weight ratio of the ultra-high molecular weight polyethylene in described swelling solution and described lysate is preferably 2.5～70, and more preferably 5～50, more preferably 10～30.For mixing time, be preferably 20min～120min, more preferably 45min～100min, most preferably is 60min～80min.
When described ultra-high molecular weight polyethylene swelling solution and described ultra-high molecular weight polyethylene lysate mix and blend are prepared to spinning solution, preferably adopt following steps:
First ultra-high molecular weight polyethylene swelling solution is stirred under normal temperature and pressure in mixing kettle, then described ultra-high molecular weight polyethylene swelling solution is warming up to the temperature higher than swelling solution phase separation temperature, be preferably higher than 8 DEG C～15 DEG C of phase separation temperatures, more preferably higher than 10 DEG C of phase separation temperatures.The phase transition temperature of ultra-high molecular weight polyethylene belongs to and well known to a person skilled in the art general knowledge, different and different according to molecular weight, greatly between 70 DEG C～90 DEG C.The present invention is warmed up to swelling solution after 65～85 DEG C, then obtains spinning solution to adding ultra-high molecular weight polyethylene lysate to be uniformly mixed in described swelling solution.
In the process of above-mentioned preparation mixing swelling solution and lysate, it is to reduce the viscosity of swelling solution that swelling solution is warming up to higher than the object of the temperature being separated, and increases the mobility of swelling solution.Then in above-mentioned whipping process, the effect of lysate is that swelling solution is played to plasticization, can improve preferably the larger situation of viscosity of spinning solution system, ensure that spinning solution has good mobility and wire vent continuity, avoid occurring lousiness, fracture of wire in follow-up spinning process.In addition, by add lysate in swelling solution, the ultra-high molecular weight polyethylene gel strand producing can also make gel spinning time contains appropriate entanglement, its objective is and can make to make the transmission of tension force in strand to carry out smoothly in follow-up drafting process, to reach the object of follow-up ultra-drawing, prevent fracture of wire.
According to the present invention, while preparing described ultra-high molecular weight polyethylene swelling solution, preferably use following steps:
In first part of solvent, add ultra-high molecular weight polyethylene powder to stir;
In described first part of solvent, add second part of solvent and the first emulsified solvent to obtain the first mixture;
Described the first mixture is warming up to 90 DEG C～130 DEG C, and preferably to 95 DEG C～120 DEG C, more preferably to 100 DEG C～110 DEG C, is incubated the swelling ultra-high molecular weight polyethylene swelling solution that obtains;
Described the first emulsified solvent is formed through Over emulsfication by the 3rd part of solvent and surfactant;
Described first part of solvent: second part of solvent: the 3rd part of solvent: surfactant is 45～55: 45～55 according to weight ratio: 1～20: 0.05～0.1, be preferably 45～55: 45～55: 2～10: 0.05～0.1, more preferably 50: 50: 4～8: 1.5～2.5: 0.05～0.1.
According to the present invention, described first part of emulsified solvent is preferably prepared as follows, antioxidant, surfactant are joined in described the 3rd part of solvent and carry out stirring and emulsifying, mixing speed is preferably 2500rpm (turning per minute)～3500rpm, be preferably 2750rpm～3250rpm, mixing time is preferably 20min～100min, more preferably 30min～80min, more preferably 40min～100min.
According to the present invention, described the first mixture is incubated when swelling, temperature retention time is adjusted according to swellbility, preferably makes the swellbility of described super high molecular weight reach 1～2, and more preferably 1.1～1.8, more preferably 1.2～1.6, then stop insulation.For temperature retention time, be preferably 30～100min, more preferably 40～90min, more preferably 50～80min.Swellbility η of the present invention calculates according to formula (I):
η=W
1/ W
2formula (I)
In formula (I), W
1implication be: get a ultra-high molecular weight polyethylene swelling solution, the gained of weighing after 20min suction filtration; W
2implication be: be W by the described parts by weight that obtain through suction filtration
1swollen materials with decahydronaphthalene carry out three times extraction 90 DEG C dry to constant weight weigh gained.
According to the present invention, while preparing described ultra-high molecular weight polyethylene lysate, preferably use following steps:
In the 4th emulsified solvent, add the second emulsified solvent, the 3rd emulsified solvent, the 5th part of stirring solvent evenly to obtain the second mixture, speed of agitator is preferably 2500rpm～3500rpm, more preferably 3000rpm, is then warmed up to described the second mixture 100 DEG C～190 DEG C stirrings and obtains ultra-high molecular weight polyethylene lysate.
Described the second emulsified solvent by the 6th part of solvent and ultra-high molecular weight polyethylene according to 1～5: 0.4～0.6 ratio emulsification forms;
Described the 3rd emulsified solvent is formed through Over emulsfication by the 7th portion of solvent, antioxidant and nucleator, described the 7th part of solvent preferably accounts for 2%～4% of solvent total amount in described ultra-high molecular weight polyethylene lysate by weight, in the present invention, described nucleator preferably accounts for 0.8%～80% of ultra-high molecular weight polyethylene total amount in described ultra-high molecular weight polyethylene lysate by weight, more preferably 0.8～56%, more preferably 0.8～24%.
According to the present invention, preparing in the process of ultra-high molecular weight polyethylene lysate, described the 4th part of solvent: described the 5th part of solvent: the 6th part of solvent: the 7th part of solvent is 67～75: 15～25 according to weight ratio: 2～10: 2～4, more preferably 67～75: 15～25: 3～8: 2～4, more preferably 67～75: 20: 4～6: 3.
According to the present invention, while preparing described the second emulsified solvent, described the 6th part of solvent and ultra-high molecular weight polyethylene can be divided into two parts uniformly and carry out respectively emulsification, emulsification times is preferably 10min～60min, be preferably 20min～50min, more preferably 30min～40min.
Described the second mixture is warmed up to 100 DEG C～190 DEG C stirrings to be obtained ultra-high molecular weight polyethylene lysate and preferably uses following steps: first described the second mixture is warming up to 100 DEG C～150 DEG C, preferably to 120 DEG C～140 DEG C carried out stirring at low speed, stirring at low speed speed is preferably 17rpm～25rpm, more preferably 18rpm～20rpm; The temperature that is stirred to the second mixture preferably reaches 140 DEG C～190 DEG C, more preferably reach 150 DEG C～180 DEG C, then rotating speed brought up to 35rpm～45rpm, more preferably brought up to 38rpm～42rpm and carry out high-speed stirred, be incubated again and obtain ultra-high molecular weight polyethylene lysate, temperature retention time is preferably 30min～100min, more preferably 40min～80min.
Preparing in the process of ultra-high molecular weight polyethylene lysate, the second mixture is first heated and carries out stirring at low speed, its objective is in the process of heating and stirring at low speed, ultra-high molecular weight polyethylene feed particles complete swelling also has major part to start to dissolve, the now entanglement between the high polymer macromolecular chain in ultra-high molecular weight polyethylene is eliminated substantially, makes nucleator can enter solution and twines and between strand, carry out preliminary dispersion.The temperature of stirring at low speed to the second mixture reaches 120 DEG C～190 DEG C, carries out high-speed stirred after preferably reaching 150 DEG C～180 DEG C, its objective is and promotes dissolving and the nucleator of ultra-high molecular weight polyethylene to disperse more uniformly.
According to the present invention, the superhigh molecular weight polyethylene fibers spinning solution of preparation can be prepared superhigh molecular weight polyethylene fibers according to gel spinning technology well known to those skilled in the art, object lesson can be: spinning solution is sent into double screw extruder and carry out solution and twine, the inlet temperature of double screw extruder is preferably 85 DEG C～120 DEG C, middle extrusion temperature is 240 DEG C～280 DEG C, and outlet temperature is 280 DEG C～320 DEG C.The optimal process of gel spinning is: the aperture of spinneret orifice is 0.6mm～5mm, and the draw ratio L/D of spinneret orifice is 6/1～30/1, and spinning solution rate of extrusion is 0.5m/min～10m/min; After extruding, spinneret draft ratio is controlled between 5～20 times, and preferably, between 6～15 times, spinning solution obtains frozen glue strand through the cooling and shaping of 0 DEG C～36 DEG C.
Obtain, after frozen glue strand, frozen glue strand being extracted, extractant is preferably hexane, heptane, toluene, chloromethanes, solvent naphtha, kerosene, more preferably kerosene.Then the strand after extraction is dried, baking temperature is preferably 40 DEG C～80 DEG C, then dry strand is applied to 30 times～130 times in the temperature range of 70 DEG C～160 DEG C, and preferably superhigh molecular weight polyethylene fibers is made in 40-60 hot drawing-off doubly.When described dried strand is carried out to hot drawing-off, that preferably described strand is carried out to two-stage at least just leads hot drawing-off doubly, and the temperature of the hot drawing-off of the first order is preferably 120 DEG C～160 DEG C, leads and is doubly preferably 2 times～10 times, more preferably 5 times～10 times; The temperature of the hot drawing-off in the second level is preferably 130 DEG C～160 DEG C, leads and is doubly preferably 2 times～10 times, more preferably 5 times～10 times.Carry out two-stage and just leading after hot drawing-off doubly, can also carry out to strand the negative drawing-off of one-level, negative drawing temperature is preferably 120 DEG C～140 DEG C, leads and is doubly preferably 0.91 times～0.99 times.
In the present invention, fibrous mechanical property is to test according to GB/T19975-2005.
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just as further illustrating the features and advantages of the present invention, instead of restriction to the claims in the present invention scope.
For better comparative effectiveness, in following embodiment and comparative example, use identical raw material, the weight average molecular weight M of ultra high molecular polyethylene used
wbe 4.2 × 10
6, powder size is 80 μ m～120 μ m, solvent for use 120# white oil.
Nucleator, antioxidant and the surfactant specification using in following examples and comparative example is as table 1:
The nucleator specification that table 1 embodiment of the present invention is used
Embodiment 1
Prepare superhigh molecular weight polyethylene fibers according to following operation:
Operation 1, preparing super molecular weight polyethylene swelling solution;
Operation 2, preparing super molecular weight polyethylene lysate;
Operation 3, preparing super molecular weight polyethylene spinning solution;
Operation 4, spinning.
Operation 1 specifically comprises the steps:
Step 11
Get first part of white oil of 50kg and stir being placed in swelling still, when stirring, evenly spray into the ultra-high molecular weight polyethylene powder of 30kg;
Step 12
Get the 3rd part of white oil of 4kg, then add 2 of 1.5kg, the neopelex surfactant of tri-grades of butyl-4-methylphenol antioxidant of 6-, 0.06kg carries out emulsification stirring and emulsifying and obtains the first emulsified solvent, and wherein mixing speed is 3000rpm, and emulsification times is 40min;
Step 13
To second part of white oil putting into the first emulsified solvent and 50kg in described swelling still, stirring is warming up to 105 DEG C, temperature retention time is 50min, obtains swellbility and be 1.23 ultra-high molecular weight polyethylene swelling solution, and in this swelling solution, the weight ratio of ultra-high molecular weight polyethylene is 22%.
First part of white oil in swelling solution: second part of white oil: the 3rd part of white oil is 52: 48: 4 by weight.
Operation 2 specifically comprises the steps:
Step 21
Get the ultra high molecular polyethylene powder of the 6th part of white oil of 4kg and 1.1kg, described the 6th part of white oil and polyethylene powders are divided into two parts uniformly and carry out emulsification and obtain the second emulsifying agent, emulsification times is 30min, and mixing speed when emulsification is 3000rpm;
Step 22
Get the 7th part of white oil of 3kg, add 2 of 0.04kg, the talcum powder of tri-grades of butyl-4-methylphenol antioxidant of 6-, 0.05kg carries out emulsification and obtains the 3rd emulsifying agent, and mixing speed when emulsification is 3000rpm, and emulsification times is 40min;
Step 23
The 4th part of white oil getting 67kg is placed in dissolution kettle and stirs, and then mixes to the 5th part of white oil putting into the second emulsifying agent, the 3rd emulsifying agent, 20kg in dissolution kettle;
Step 24
The compound that step 23 is obtained is warming up to 130 DEG C and stirs, and mixing speed is 19rpm;
Step 25
The compound of step 24 is heated up and reached after 160 DEG C, stir with the speed of 40rpm, then start insulation, temperature retention time is to obtain ultra-high molecular weight polyethylene lysate after 50min.
Operation 3 specifically comprises the steps:
Step 3
Get swelling solution stirring at normal temperature in swelling still prepared by operation 1, and then swelling solution is warmed up to 90 DEG C, obtain spinning solution of ultra-high molecular weight polyethylene fiber to dropping into lysate mix and blend 70min prepared by operation 2 in swelling solution again, wherein swelling solution and lysate weight ratio are 1: 1.1.
Operation 4 specifically comprises the steps:
Step 41
Spinning solution is sent into and in double screw extruder, carried out macromolecular solution and twine.Wherein, the inlet temperature of sending of double screw extruder is that 100 DEG C, medium temperature are that 260 DEG C, outlet temperature are 290 DEG C;
Step 42
Suspension twines, extrudes and make transparent frozen glue solution through the solution of double screw extruder.Frozen glue solution is extruded and entered temperature and make strand sizing obtain gel fiber as the tank that solidifies of 25 DEG C taking the plastic-blasting speed of 1m/min through measuring pump, the spinnerets (orifice diameter 1mm, draw ratio is that L/D is 10/1) with 400 holes;
Step 43
The gel fiber obtaining is adopted to kerosene extraction, then dry through the first order second level dry and 60 DEG C of 55 DEG C respectively;
Step 44
Dried gel fiber is carried out to the positive drawing-off of two-stage successively, and one-level is born drawing-off, and concrete technology is: first order drawing temperature is 100 DEG C, and leading is doubly 6.7 times; Second level drawing temperature is 120 DEG C, and leading is doubly 8.9 times; Third level drawing temperature is 130 DEG C, and leading is doubly 0.9 times.
The indices of spinning solution and the mechanical property of fiber the results are shown in table 4.
Embodiment 2-embodiment 9
Above-mentioned 8 enforcements technological parameter refer to table 2 and table 3, parameter unlisted in table 2 and table 3 is identical with embodiment 1.
The indices of spinning solution and the mechanical property of fiber the results are shown in table 4 and table 5.
Comparative example 1
Get the ultra-high molecular weight polyethylene of 7kg and 93kg white oil, add 2 of 1.5kg, the neopelex surfactant of tri-grades of butyl-4-methylphenol antioxidant of 6-, 0.014kg in first swelling still 65 DEG C stir 24 hours, then putting into 75 DEG C of second swelling stills stirs 12 hours, then putting into 110 DEG C of the 3rd swelling stills stirs 12 hours, the mixing speed of above-mentioned three swelling stills is 5rpm, finally force to be cooled to 70 DEG C, obtain solid content and be about 7% spinning solution.
Spinning technology parameter is identical with embodiment 1.
The indices of spinning solution and the mechanical property of fiber the results are shown in table 5.
Comparative example 2
According to the preparation technology of comparative example 1 prepare ultra-high molecular weight polyethylene content be 11% swelling solution as spinning solution, other parameter is identical with comparative example 1.
Spinning technology parameter is identical with embodiment 2.
The indices of spinning solution and the mechanical property of fiber the results are shown in table 5.
Comparative example 3
Preparation technology according to the spinning solution of embodiment 1 prepares spinning solution, is wherein with the difference of embodiment 1, does not add nucleator in this comparative example, and other processing step is identical with embodiment 1.
Spinning technique is identical with embodiment 9.
The indices of spinning solution and the mechanical property of fiber the results are shown in table 5.
The technological parameter of the spinning solution of table 2 embodiment 2-5
The technological parameter of the spinning solution of table 3 embodiment 6-9
The spinning solution index of table 4 embodiment 1-5 and the performance of fiber
The spinning solution index of table 5 embodiment 7-9, comparative example 1-3 and the performance of fiber
From the comparing result of table 4 and table 5, compared with not adding the spinning solution of nucleator, the superhigh molecular weight polyethylene fibers intensity that the spinning solution that uses the present invention to prepare is prepared under identical spinning condition obviously improves, and CV value is low, and stability of fiber is good.
Above spinning solution of ultra-high molecular weight polyethylene fiber provided by the present invention and preparation method thereof is described in detail.Applied specific case herein principle of the present invention and embodiment are set forth, the explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (15)
1. a spinning solution of ultra-high molecular weight polyethylene fiber, is characterized in that, comprises in weight percent:
Ultra-high molecular weight polyethylene 10%～15%;
Nucleator, the percentage by weight that described nucleator accounts for the ultra-high molecular weight polyethylene in described spinning solution of ultra-high molecular weight polyethylene fiber is 0.02%～5%;
Balance solvent, antioxidant and surfactant;
The preparation method of described spinning solution comprises:
The ratio that to get ultra-high molecular weight polyethylene lysate be 0.42～2.85 with ultra-high molecular weight polyethylene swelling solution according to weight ratio is mixed, and obtains spinning solution;
The content of the ultra-high molecular weight polyethylene in described ultra-high molecular weight polyethylene swelling solution is 10～50%;
The weight ratio of the ultra-high molecular weight polyethylene in the ultra-high molecular weight polyethylene in described ultra-high molecular weight polyethylene swelling solution and described ultra-high molecular weight polyethylene lysate is 2.5～70;
In described ultra-high molecular weight polyethylene lysate, there is nucleator;
Wherein, described ultra-high molecular weight polyethylene swelling solution is prepared as follows:
In first part of solvent, add ultra-high molecular weight polyethylene powder to stir;
In described first part of solvent, add second part of solvent and the first emulsified solvent to obtain the first mixture;
Described the first mixture is warming up to 90 DEG C～130 DEG C swelling ultra-high molecular weight polyethylene swelling solutions that obtain of insulation;
Described the first emulsified solvent is formed through Over emulsfication by the 3rd part of solvent and surfactant;
First part of solvent: second part of solvent: the 3rd part of solvent: the weight ratio of surfactant is 45～55:45～55:1～20:0.05～0.1;
Described ultra-high molecular weight polyethylene lysate is prepared as follows:
In the 4th part of solvent, add the second emulsified solvent, the 3rd emulsified solvent, the 5th part of stirring solvent evenly to obtain the second mixture, described the second mixture is warming up to 100 DEG C～190 DEG C stirrings and obtains ultra-high molecular weight polyethylene lysate;
Described the second emulsified solvent is formed according to the ratio emulsification of 1～5:0.4～0.6 by the 6th part of solvent and ultra-high molecular weight polyethylene;
Described the 3rd emulsified solvent is formed through Over emulsfication by the 7th portion of solvent, antioxidant and nucleator;
Described the 4th part of solvent: the 5th part of solvent: the 6th part of solvent: the weight ratio of the 7th part of solvent is 67～75:15～25:2～10:2～4.
2. spinning solution according to claim 1, is characterized in that, the percentage by weight that described antioxidant accounts for the ultra-high molecular weight polyethylene total amount in described spinning solution is 0.1%～1%.
3. spinning solution according to claim 1, is characterized in that, the percentage by weight that described surfactant accounts for the ultra-high molecular weight polyethylene total amount in spinning solution is 0.1%～0.5%.
4. according to the spinning solution described in claims 1 to 3 any one, it is characterized in that, described nucleator comprises one or more in inorganic silicate nucleator, metal oxide nucleator, organic acid nucleator, acylate nucleator, polymer nucleator, D-sorbite or derivatives thereof nucleator, organic phosphate nucleating agent, tricarballylic acid type acid amides nucleator.
5. spinning solution according to claim 4, is characterized in that, described inorganic silicate nucleator is talcum powder.
6. spinning solution according to claim 4, is characterized in that, described metal oxide nucleator comprises titanium oxide, alkali metal oxide or alkaline earth oxide.
7. spinning solution according to claim 4, is characterized in that, described organic acid nucleator comprises 4-p t butylbenzoic acid, aliphatic acid or diphenyl acetic acid.
8. spinning solution according to claim 4, is characterized in that, described acylate nucleator comprises sodium succinate or Sodium Benzoate.
9. spinning solution according to claim 4, it is characterized in that, described D-sorbite or derivatives thereof nucleator comprises dibenzylidene sorbitol, two (to methyl benzal) D-sorbite, two (to benzyl chloride fork) D-sorbite, 1,3-2,4 two Asias (4-methyl) benzyl-D-D-sorbite, 1,3,5-benzenetricarboxylic acid derivative.
10. according to the spinning solution described in claim 1～3,5～9 any one, it is characterized in that, solvent in described ultra-high molecular weight polyethylene spinning solution is the mixed solvent that cycloalkane and alkane are mixed to get according to the ratio of 85～90:10～15, the carbon atom number of described cycloalkane is 25～50, and the carbon atom number of described alkane is 25～50.
11. spinning solutions according to claim 4, it is characterized in that, solvent in described ultra-high molecular weight polyethylene spinning solution is the mixed solvent that cycloalkane and alkane are mixed to get according to the ratio of 85～90:10～15, the carbon atom number of described cycloalkane is 25～50, and the carbon atom number of described alkane is 25～50.
The preparation method of the spinning solution of ultra-high molecular weight polyethylene fiber described in 12. claim 1 to 11 any one, is characterized in that, comprising:
Getting ratio that ultra-high molecular weight polyethylene lysate and ultra-high molecular weight polyethylene swelling solution are 0.42～2.85 according to weight ratio, to be mixed to get ultra-high molecular weight polyethylene weight content be 10%～15% spinning solution;
The content of the ultra-high molecular weight polyethylene in described ultra-high molecular weight polyethylene swelling solution is 10～50%;
The weight ratio of the ultra-high molecular weight polyethylene in the ultra-high molecular weight polyethylene in described ultra-high molecular weight polyethylene swelling solution and described ultra-high molecular weight polyethylene lysate is 2.5～70;
In described ultra-high molecular weight polyethylene lysate, have nucleator, the percentage by weight that described nucleator accounts for the ultra-high molecular weight polyethylene in described spinning solution of ultra-high molecular weight polyethylene fiber is 0.02%～5%;
Wherein, described ultra-high molecular weight polyethylene swelling solution is prepared as follows:
In first part of solvent, add ultra-high molecular weight polyethylene powder to stir;
In described first part of solvent, add second part of solvent and the first emulsified solvent to obtain the first mixture;
Described the first mixture is warming up to 90 DEG C～130 DEG C swelling ultra-high molecular weight polyethylene swelling solutions that obtain of insulation;
Described the first emulsified solvent is formed through Over emulsfication by the 3rd part of solvent and surfactant;
First part of solvent: second part of solvent: the 3rd part of solvent: the weight ratio of surfactant is 45～55:45～55:1～20:0.05～0.1;
Described ultra-high molecular weight polyethylene lysate is prepared as follows:
In the 4th part of solvent, add the second emulsified solvent, the 3rd emulsified solvent, the 5th part of stirring solvent evenly to obtain the second mixture, described the second mixture is warming up to 100 DEG C～190 DEG C stirrings and obtains ultra-high molecular weight polyethylene lysate;
Described the second emulsified solvent is formed according to the ratio emulsification of 1～5:0.4～0.6 by the 6th part of solvent and ultra-high molecular weight polyethylene;
Described the 3rd emulsified solvent is formed through Over emulsfication by the 7th portion of solvent, antioxidant and nucleator;
Described the 4th part of solvent: the 5th part of solvent: the 6th part of solvent: the weight ratio of the 7th part of solvent is 67～75:15～25:2～10:2～4.
13. preparation methods according to claim 12, is characterized in that, the percentage by weight that described nucleator accounts for the ultra-high molecular weight polyethylene in described ultra-high molecular weight polyethylene lysate is 0.8%～80%.
14. preparation methods according to claim 13, is characterized in that, the percentage by weight that described antioxidant accounts for the ultra-high molecular weight polyethylene in described ultra-high molecular weight polyethylene lysate is 1%～8%.
15. preparation methods according to claim 14, is characterized in that, the swellbility of described ultra-high molecular weight polyethylene swelling solution is 1～2.
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| CN106555245B (en) * | 2015-09-24 | 2019-04-30 | 北京同益中特种纤维技术开发有限公司 | A kind of cut resistant ultra high molecular weight polyethylene fiber and its preparation method and application |
| CN111235668A (en) * | 2020-04-07 | 2020-06-05 | 江苏领誉纤维科技有限公司 | Method for preparing ultra-high molecular weight polyethylene fiber and fiber |
| CN112725916A (en) * | 2020-12-30 | 2021-04-30 | 长青藤高性能纤维材料有限公司 | White oil solvent suitable for UHMWPE fiber production process and preparation method thereof |
| CN113151912B (en) * | 2021-05-10 | 2022-09-13 | 浙江理工大学上虞工业技术研究院有限公司 | Ultra-high molecular weight polyethylene fiber and preparation method and application thereof |
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Address after: 100076 901 Workshop, No. 16 Zhonghe Street, Beijing Economic and Technological Development Zone Patentee after: Beijing Tong Yi Zhong new material Polytron Technologies Inc Address before: 101102 Beijing Daxing District Beijing Economic and Technological Development Zone No. 16 901 Factory Building Patentee before: Beijing Tongyizhong Specialty Fiber Technology & Development Co., Ltd. |