CN112281237B - High-modulus creep-resistant ultra-high molecular weight polyethylene fiber and preparation method thereof - Google Patents

High-modulus creep-resistant ultra-high molecular weight polyethylene fiber and preparation method thereof Download PDF

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CN112281237B
CN112281237B CN202011219644.1A CN202011219644A CN112281237B CN 112281237 B CN112281237 B CN 112281237B CN 202011219644 A CN202011219644 A CN 202011219644A CN 112281237 B CN112281237 B CN 112281237B
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molecular weight
weight polyethylene
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polyethylene fiber
fiber
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CN112281237A (en
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郭海军
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Beijing Fuwei New Material Technology Co ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/02—Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics
    • D07B1/025—Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics comprising high modulus, or high tenacity, polymer filaments or fibres, e.g. liquid-crystal polymers
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • D01F11/06—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/001—Treatment with visible light, infrared or ultraviolet, X-rays
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2201/00—Ropes or cables
    • D07B2201/20—Rope or cable components
    • D07B2201/2001—Wires or filaments
    • D07B2201/2009—Wires or filaments characterised by the materials used
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2205/00—Rope or cable materials
    • D07B2205/20—Organic high polymers
    • D07B2205/201—Polyolefins
    • D07B2205/2014—High performance polyolefins, e.g. Dyneema or Spectra

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)

Abstract

The invention relates to the technical field of fiber production, in particular to a high-modulus creep-resistant ultra-high molecular weight polyethylene fiber and a preparation method thereof. The fiber raw material comprises the following components: UHMWPE powder, an ultraviolet photosensitizer, a cross-linking agent, a silane coupling agent and a solvent; the mass ratio of the ultraviolet photosensitizer to the UHMWPE powder is 0.2-0.5% to 1; the mass ratio of the cross-linking agent to the UHMWPE powder is 0.1-1 percent to 1; the mass ratio of the silane coupling agent to the UHMWPE powder is 0.05-0.5%: 1; the mass ratio of the solvent to the UHMWPE powder is 1: 5-15%. The fiber provided by the invention can effectively control the UHMWPE macromolecular crosslinking area and the crosslinking point density, is suitable for dry-method and wet-method gel spinning processes, and the prepared ultrahigh molecular weight polyethylene fiber has high modulus and creep resistance. And after the fluorine-containing polymer is added into the raw materials, the creep resistance of the ultra-high molecular weight polyethylene fiber is further improved.

Description

High-modulus creep-resistant ultra-high molecular weight polyethylene fiber and preparation method thereof
Technical Field
The invention relates to the technical field of fiber production, in particular to a high-modulus creep-resistant ultrahigh molecular weight polyethylene fiber and a preparation method thereof.
Background
Polyethylene (UHMWPE) fibers of ultrahigh relative molecular mass, also known as high-strength high-modulus polyethylene fibers. Since the 70 s in the 20 th century, UHMWPE fibers have developed rapidly, and are called three high-performance fibers in the world together with aramid fibers and carbon fibers. The UHMWPE fiber is the fiber with the highest specific strength and specific modulus in the world at present, has lighter weight, and has excellent properties of good chemical stability, acid and alkali resistance, weather resistance, ultraviolet resistance, wear resistance, bending resistance, strain fatigue resistance, impact resistance and the like. Therefore, the UHMWPE fiber is widely applied to the fields of safety protection, national defense equipment, aerospace, marine fishery, sports equipment and the like.
However, the UHMWPE fiber is a nonpolar polyolefin fiber, the molecular chain structure of the fiber is a simple straight chain, no hydrogen bonding effect exists between molecules, and the van der waals force only has a dispersion force, the large molecular force is weak, and when the UHMWPE fiber is subjected to a long-term stress, the UHMWPE fiber is prone to continuous unrecoverable deformation and even finally to a creep behavior which leads to fracture, thereby largely limiting the application range of the fiber. Therefore, how to enhance the creep resistance of the UHMWPE fiber, thereby expanding the application field of the fiber and further realizing real industrialization has important significance.
At present, introducing a crosslinking structure into UHMWPE fibers is one of the effective methods for improving the creep resistance of UHMWPE fibers, and is also the focus of research in this field. The invention patent with publication number CN104695038A discloses a preparation method of heat-resistant creep-resistant supramolecular polyethylene constant-strength fiber, which is to add graphene, an initiator and a cross-linking agent into a supramolecular polyethylene matrix to combine physical cross-linking and chemical cross-linking. In the method, the graphene increases the density of physical crosslinking points of UHMWPE macromolecules, can improve the physical and mechanical properties of UHMWPE fibers to a certain extent, and simultaneously forms a crosslinked network structure through chemical crosslinking, thereby improving the creep resistance of the fibers. However, the addition of graphene in the method changes the fluid characteristics of the spinning melt, is not beneficial to subsequent spinning processing, and graphene does not improve the strength of the fiber and is a defect structure in the fiber structure. In addition, the density of crosslinking points is difficult to control in the chemical crosslinking process in the method, the mass of the crosslinked UHMWPE macromolecules is rapidly increased, the UHMWPE macromolecules are converted into a body structure from linear, and the stability is reduced due to overlarge internal stress in the subsequent orientation stretching process. Therefore, further improvements to the prior art are needed.
Disclosure of Invention
In view of the above, a need exists for a high-modulus creep-resistant ultrahigh molecular weight polyethylene fiber and a preparation method thereof, which can effectively control the macromolecular crosslinking region and the crosslinking point density of UHMWPE, and the prepared UHMWPE fiber has high modulus, creep resistance, tensile resistance and other properties, and is suitable for a subsequent gel spinning processing technology.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a high modulus creep-resistant ultra-high molecular weight polyethylene fiber, wherein the raw material of the ultra-high molecular weight polyethylene fiber comprises the following components: UHMWPE powder, an ultraviolet photosensitizer, a cross-linking agent, a silane coupling agent and a solvent; the mass ratio of the ultraviolet photosensitizer to the UHMWPE powder is 0.2-0.5% to 1; the mass ratio of the cross-linking agent to the UHMWPE powder is 0.1-1 percent to 1; the mass ratio of the silane coupling agent to the UHMWPE powder is 0.05-0.5%: 1; the mass ratio of the solvent to the UHMWPE powder is 1: 5-15%.
Furthermore, in the high-modulus creep-resistant ultrahigh molecular weight polyethylene fiber, the ultrahigh molecular weight polyethylene fiber raw material also comprises a fluorine-containing polymer, and the mass ratio of the fluorine-containing polymer to the UHMWPE powder is 0.05-0.2% to 1.
Further, when the raw material composition includes a fluorine-containing polymer, the amounts of the ultraviolet photosensitizer, the crosslinking agent and the silane coupling agent can be significantly reduced. The invention also provides a high-modulus creep-resistant ultrahigh molecular weight polyethylene fiber, wherein the raw material of the ultrahigh molecular weight polyethylene fiber comprises the following components: UHMWPE powder, an ultraviolet photosensitizer, a cross-linking agent, a silane coupling agent fluorine-containing polymer and a solvent; the mass ratio of the ultraviolet photosensitizer to the UHMWPE powder is 0.05-0.2% to 1; the mass ratio of the crosslinking agent to the UHMWPE powder is 0.1-0.5%: 1; the mass ratio of the silane coupling agent to the UHMWPE powder is 0.05-0.2%: 1; the mass ratio of the fluorine-containing polymer to the UHMWPE powder is 0.05-0.2% to 1; the mass ratio of the solvent to the UHMWPE powder is 1: 6% -12%.
Furthermore, in the high-modulus creep-resistant ultrahigh molecular weight polyethylene fiber, the ultrahigh molecular weight polyethylene fiber raw material also comprises other auxiliary agents.
Preferably, in the above high modulus creep-resistant ultrahigh molecular weight polyethylene fiber, the ultrahigh molecular weight polyethylene fiber raw material further comprises an antioxidant, including but not limited to one or more of antioxidant 1010, antioxidant B225, and vitamin E.
Further, in the above high modulus creep-resistant ultra-high molecular weight polyethylene fiber, the ultraviolet photosensitizer includes, but is not limited to, one or more of benzophenone and its derivatives, benzoyl peroxide, dicumyl peroxide, Irgacure 651.
Further, in the above high modulus creep resistant ultra high molecular weight polyethylene fiber, the crosslinking agent includes, but is not limited to, one or more of triallyl isocyanurate (TAIC), trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol triacrylate, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, ethoxylated bisphenol a diacrylate, diethylene glycol dimethacrylate, dipropylene glycol diacrylate, polyethylene glycol diacrylate.
Further, in the above high modulus creep-resistant ultrahigh molecular weight polyethylene fiber, the silane coupling agent includes, but is not limited to, one or more of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-tert-butylperoxysilane, vinyltris (β -methoxyethoxy) silane, Y- (methacryloyloxy) propyltrimethoxysilane.
Further, in the above high modulus creep-resistant ultrahigh molecular weight polyethylene fiber, the fluoropolymer is one or more of a copolymer of one or more fluoroolefins, and a copolymer of a fluoroolefin and another olefin.
Preferably, in the above high modulus creep-resistant ultrahigh molecular weight polyethylene fiber, the fluoropolymer is one or more of vinylidene fluoride, a binary copolymer of tetrafluoroethylene or hexafluoropropylene, vinylidene fluoride, a ternary copolymer of tetrafluoroethylene and hexafluoropropylene, vinylidene fluoride, a copolymer of tetrafluoroethylene or hexafluoropropylene and ethylene, vinylidene fluoride, and a copolymer of tetrafluoroethylene or hexafluoropropylene and propylene.
Furthermore, in the high-modulus creep-resistant ultrahigh molecular weight polyethylene fiber, the molecular weight of UHMWPE powder is 80-1000 ten thousand.
Preferably, in the high-modulus creep-resistant ultrahigh molecular weight polyethylene fiber, the molecular weight of the UHMWPE powder is 200-600 ten thousand.
In a second aspect, the present invention provides a wet process for preparing high modulus creep resistant ultra high molecular weight polyethylene fibers comprising the steps of:
(1) mixing and dissolving all components of the high-modulus creep-resistant ultra-high molecular weight polyethylene fiber raw material to form UHMWPE spinning solution;
(2) spinning by using a spinning machine;
(3) extracting with an extractant to obtain nascent fiber;
(4) carrying out ultraviolet radiation on the nascent fiber in a drying box; of ultraviolet lightThe wavelength is 200-300 nm; the intensity of the ultraviolet light is more than 500 mu W/cm 2 (ii) a The radiation time is 20 s-15 min.
Furthermore, in the wet process for preparing the high-modulus creep-resistant ultrahigh molecular weight polyethylene fiber, the solvent is one or more of mineral oil, kerosene and castor oil; the extracting agent used for extraction is one or more of dichloromethane, hydrocarbon cleaning agent, solvent gasoline, trifluoroethane, xylene and tetrachloroethylene.
Further, in the above wet process for preparing the high modulus creep-resistant ultra-high molecular weight polyethylene fiber, the lamp source of the ultraviolet light includes, but is not limited to, a high pressure mercury lamp, a low pressure mercury lamp, and an ultraviolet light generator.
Further, in the wet process for preparing the high-modulus creep-resistant ultrahigh molecular weight polyethylene fiber, the distance between the spinneret plate and the spinning coagulation bath is less than 15mm during the spinning in the step (2).
In a third aspect, the present invention provides a dry process for preparing high modulus, creep resistant ultra high molecular weight polyethylene fibers comprising the steps of:
mixing and dissolving all components of the high-modulus creep-resistant ultra-high molecular weight polyethylene fiber raw material to form UHMWPE spinning solution;
(II) spinning by using a spinning machine: the spinning solution extruded from the capillary holes of the spinning nozzle enters a spinning shaft to obtain nascent fiber;
thirdly, ultraviolet irradiation is carried out at the lower part of the spinning channel or after the spinning channel is discharged; the wavelength of the ultraviolet light is 200-300 nm; the ultraviolet light intensity is more than 3000 μ W/cm 2 (ii) a The radiation time is 5 s-30 s.
Furthermore, in the dry process for preparing the high-modulus creep-resistant ultrahigh molecular weight polyethylene fiber, the solvent is decalin.
Further, in the above dry process for preparing the high modulus creep-resistant ultra-high molecular weight polyethylene fiber, the lamp source of the ultraviolet light includes, but is not limited to, a high pressure mercury lamp, a low pressure mercury lamp, and an ultraviolet light generator.
Furthermore, in the dry process for preparing the high-modulus creep-resistant ultrahigh molecular weight polyethylene fiber, the filament number (dry state) is less than 100d under ultraviolet irradiation.
Preferably, in the above dry process for preparing high modulus creep-resistant ultra-high molecular weight polyethylene fiber, the filament number (dry state) is less than 50d under ultraviolet irradiation.
In a fourth aspect, the invention provides a high-modulus creep-resistant ultra-high molecular weight polyethylene fiber, which is obtained by performing 3-4-stage thermal stretching on a fiber subjected to ultraviolet radiation in the dry process or the wet process, wherein the stretching temperature is 110-150 ℃, and the total stretching ratio is 5-10 times.
The invention has the beneficial effects that:
(1) the raw materials of the high-modulus creep-resistant ultrahigh molecular weight polyethylene fiber provided by the invention comprise an ultraviolet photosensitizer, a cross-linking agent and a silane coupling agent. The ultraviolet photosensitizer is excited after absorbing ultraviolet rays to form free radicals, the free radicals capture hydrogen on UHMWPE macromolecules to form macromolecular free radicals, the macromolecular free radicals can be mutually coupled to generate crosslinking, and can also be transferred to molecules of a multifunctional crosslinking agent and a silane coupling agent to initiate crosslinking reaction, so that the density of a crosslinking area and a crosslinking point of the UHMWPE macromolecules is effectively controlled.
(2) The raw materials of the high-modulus creep-resistant ultra-high molecular weight polyethylene fiber provided by the invention also comprise the fluorine-containing polymer, and after the fluorine-containing polymer is introduced, the flow property of UHMWPE melt is effectively improved. Meanwhile, the crosslinking reaction initiated by ultraviolet light is mainly in the surface area of the material, and after the fluorine-containing polymer is introduced, the fluorine-containing polymer can 'promote' the photosensitizer, the crosslinking agent and the silane coupling agent to move to the surface area of the material in the processes of fiber production and stretching, so that the prepared ultra-high molecular weight polyethylene fiber not only has excellent performance, but also can obviously reduce the use amount of the photosensitizer, the crosslinking agent and the silane coupling agent, thereby saving the cost and being environment-friendly.
(3) The high-modulus creep-resistant ultrahigh molecular weight polyethylene fiber provided by the invention is simultaneously suitable for dry and wet gel spinning processes, and a proper preparation method can be selected according to actual production requirements.
(4) The ultra-high molecular weight polyethylene fiber prepared by the dry method and the wet method gel spinning process has high modulus and creep resistance. And after the fluorine-containing polymer is added into the raw materials, the creep resistance of the ultra-high molecular weight polyethylene fiber is further improved.
(5) The high-modulus creep-resistant UHMWPE fiber provided by the invention is suitable for the fields of impact-resistant protective materials with higher requirements on modulus and creep property, high-performance ropes, fishery ropes, and the like. Meanwhile, the UHMWPE fiber provided by the application has higher fiber hardness, is beneficial to improving the wear resistance, the cutting resistance and the heat-conducting property of the fiber, and is also suitable for application in the fields of wear-resistant materials, anti-cutting materials, heat-conducting fabrics and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be further clearly and completely described below with reference to the embodiments of the present invention. It should be noted that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Ultra-high molecular weight polyethylene fiber
The raw materials are as follows: 10 parts of UHMWPE powder (with a molecular weight of 420 ten thousand), 90 parts of mineral oil, 0.02 part of antioxidant 1010 and 0.04 part of benzophenone;
the preparation method comprises the following steps:
(1) mixing and dissolving all components of the high-modulus creep-resistant ultra-high molecular weight polyethylene fiber raw material to form UHMWPE spinning solution;
(2) spinning by using a spinning machine;
(3) extracting with dichloromethane to obtain nascent fiber;
(4) irradiating the nascent fiber with ultraviolet light in a drying oven at an ultraviolet intensity of 1500 μ W/cm 2 The irradiation time is 8.5 min; the ultraviolet wavelength is 200 nm;
(5) 4-level thermal stretching, the stretching temperature is 110-.
Example 2
The raw materials are as follows: 10 parts of UHMWPE powder (with a molecular weight of 420 ten thousand), 90 parts of mineral oil, 0.02 part of antioxidant 1010, 0.02 part of benzophenone, 0.015 part of benzoyl peroxide and 0.08 part of TAIC;
the preparation method comprises the following steps:
(1) mixing and dissolving all components of the high-modulus creep-resistant ultrahigh molecular weight polyethylene fiber raw material to form an UHMWPE spinning solution;
(2) spinning by using a spinning machine;
(3) extracting with dichloromethane to obtain nascent fiber;
(4) irradiating the nascent fiber with ultraviolet light in a drying oven at an ultraviolet intensity of 1500 μ W/cm 2 Irradiation time is 9 min; the ultraviolet wavelength is 200 nm;
(5) 4-level thermal stretching, the stretching temperature is 110-.
Example 3
The raw materials are as follows: 10 parts of UHMWPE powder (with a molecular weight of 420 ten thousand), 90 parts of mineral oil, 0.02 part of antioxidant 1010, 0.02 part of benzophenone, 0.015 part of benzoyl peroxide, 0.06 part of TAIC and 0.04 part of vinyl triethoxysilane;
the preparation method is the same as example 2.
Example 4
The raw materials are as follows: 7 parts of UHMWPE powder (with the molecular weight of 680 ten thousand), 93 parts of decalin, 0.02 part of antioxidant 1010, 0.03 part of benzophenone, 0.06 part of TAIC and 0.03 part of vinyltriethoxysilane;
the preparation method comprises the following steps:
mixing and dissolving all components of the high-modulus creep-resistant ultra-high molecular weight polyethylene fiber raw material to form UHMWPE spinning solution;
(II) spinning by using a spinning machine: the spinning solution extruded from the capillary holes of the spinning nozzle enters a spinning shaft to obtain nascent fiber;
thirdly, ultraviolet irradiation is carried out at the lower part of the spinning channel or after the spinning channel is discharged; the wavelength of the ultraviolet light is 200 nm; the intensity of the ultraviolet light is 4200μW/cm 2 (ii) a The irradiation time was 2 s.
And (IV) 4-stage thermal stretching, wherein the stretching temperature is 110-155 ℃, and the total stretching ratio is 5 times.
Example 5
The raw materials are as follows: 10 parts of UHMWPE powder (with a molecular weight of 420 ten thousand), 90 parts of mineral oil, 0.02 part of antioxidant 1010, 0.01 part of benzophenone, 0.02 part of TAIC, 0.01 part of vinyltriethoxysilane, 0.015 part of a copolymer of hexafluoropropylene and ethylene;
the preparation method comprises the following steps:
(1) mixing and dissolving all components of the high-modulus creep-resistant ultrahigh molecular weight polyethylene fiber raw material to form an UHMWPE spinning solution;
(2) spinning by using a spinning machine;
(3) extracting with dichloromethane to obtain nascent fiber;
(4) irradiating the nascent fiber with ultraviolet light in a drying oven at the ultraviolet light intensity of 1800 muW/cm 2 The irradiation time is 7.5 min; the ultraviolet wavelength is 200 nm;
(5) 4-level thermal stretching, the stretching temperature is 110-.
Comparative example 1
Ultra-high molecular weight polyethylene fiber
The raw materials are as follows: 10 parts of UHMWPE powder (with the molecular weight of 420 ten thousand), 90 parts of mineral oil and 0.02 part of antioxidant 1010;
the preparation method comprises the following steps:
(1) mixing and dissolving all components of the high-modulus creep-resistant ultrahigh molecular weight polyethylene fiber raw material to form an UHMWPE spinning solution;
(2) spinning by using a spinning machine;
(3) extracting with dichloromethane to obtain nascent fiber;
(4) and 4-stage hot stretching, wherein the stretching temperature is 110-155 ℃, and the total stretching magnification is 5 times.
Experimental data
The ultra-high molecular weight polyethylene fibers prepared in the above examples are respectively subjected to mechanical property tests with a test method of GBT 19975-.
TABLE 1
Figure BDA0002759095800000091
As can be seen from the data in Table 1, examples 1 to 5 all had better tensile break strength, higher Young's modulus and lower creep deformation than comparative example 1. Comparing example 2 with example 1, it can be seen that the fibers prepared by adding the cross-linking agent to the raw materials have higher Young's modulus and lower creep. It is understood from comparison of examples 2 and 3 that the Young's modulus is further improved and the creep amount is further reduced by adding a silane coupling agent to the raw materials. Comparing examples 3 and 4, it can be seen that the supramolecular polyethylene fiber prepared by the wet spinning process and the supramolecular polyethylene fiber prepared by the dry spinning process both have high modulus and low creep amount, which indicates that the supramolecular polyethylene fiber prepared by the invention can better control the degree of crosslinking and is suitable for subsequent oriented drawing. According to example 5, the daily creep amount of 20% breaking force is only 0.357%, which shows that the creep resistance of the fiber can be significantly improved by adding the fluoropolymer to the raw material.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (9)

1. The high-modulus creep-resistant ultrahigh molecular weight polyethylene fiber is characterized in that the raw material of the ultrahigh molecular weight polyethylene fiber comprises the following components: UHMWPE powder, an ultraviolet photosensitizer, a cross-linking agent, a silane coupling agent, a fluorine-containing polymer and a solvent; the mass ratio of the ultraviolet photosensitizer to the UHMWPE powder is 0.2-0.5% to 1; the mass ratio of the crosslinking agent to the UHMWPE powder is 0.1-1 percent to 1 percent; the mass ratio of the silane coupling agent to the UHMWPE powder is 0.05-0.5%: 1; the mass ratio of the fluorine-containing polymer to the UHMWPE powder is 0.05-0.2% to 1; the mass ratio of the solvent to the UHMWPE powder is 1: 5-15%.
2. The high-modulus creep-resistant ultrahigh molecular weight polyethylene fiber is characterized in that the raw material of the ultrahigh molecular weight polyethylene fiber comprises the following components: UHMWPE powder, an ultraviolet photosensitizer, a cross-linking agent, a silane coupling agent, a fluorine-containing polymer and a solvent; the mass ratio of the ultraviolet photosensitizer to the UHMWPE powder is 0.05-0.2% to 1; the mass ratio of the crosslinking agent to the UHMWPE powder is 0.1-0.5%: 1; the mass ratio of the silane coupling agent to the UHMWPE powder is 0.05-0.2%: 1; the mass ratio of the fluorine-containing polymer to the UHMWPE powder is 0.05-0.2% to 1; the mass ratio of the solvent to the UHMWPE powder is 1: 6% -12%.
3. The high modulus, creep-resistant ultrahigh molecular weight polyethylene fiber as claimed in claim 1 or 2, wherein the fluoropolymer is one or more of a copolymer of one or more fluoroolefins, a copolymer of a fluoroolefin with other olefins.
4. The high modulus creep-resistant ultra high molecular weight polyethylene fiber as claimed in claim 3, wherein said fluoropolymer is one or more of vinylidene fluoride, binary copolymer of tetrafluoroethylene or hexafluoropropylene, vinylidene fluoride, ternary copolymer of tetrafluoroethylene and hexafluoropropylene, vinylidene fluoride, copolymer of tetrafluoroethylene or hexafluoropropylene and ethylene, vinylidene fluoride, copolymer of tetrafluoroethylene or hexafluoropropylene and propylene.
5. The high modulus creep-resistant ultrahigh molecular weight polyethylene fiber according to claim 1, wherein the molecular weight of the UHMWPE powder is 80 to 1000 ten thousand.
6. A wet process for preparing high modulus creep resistant ultra high molecular weight polyethylene fibers comprising the steps of:
(1) mixing and dissolving the components of the high modulus creep-resistant ultrahigh molecular weight polyethylene fiber raw material according to any one of claims 1 to 5 to form an UHMWPE spinning solution;
(2) spinning by using a spinning machine;
(3) extracting with an extractant to obtain nascent fiber;
(4) carrying out ultraviolet radiation on the nascent fiber in a drying box; the wavelength of the ultraviolet light is 200-300 nm; the ultraviolet light intensity is more than 500 mu W/cm 2 (ii) a The radiation time is 20 s-15 min.
7. The wet process for preparing high modulus, creep resistant ultra high molecular weight polyethylene fiber according to claim 6, wherein the solvent used in step (1) is one or more of mineral oil, kerosene, castor oil; the extractant in the step (2) is one or more of dichloromethane, hydrocarbon cleaning agent, solvent gasoline, trifluoroethane, xylene and tetrachloroethylene.
8. A dry process for preparing high modulus creep resistant ultra high molecular weight polyethylene fibers comprising the steps of:
mixing and dissolving the components of the high-modulus creep-resistant ultrahigh molecular weight polyethylene fiber raw material according to any one of claims 1 to 5 to form an UHMWPE spinning solution;
(II) spinning by using a spinning machine: the spinning solution extruded from the capillary holes of the spinning nozzle enters a spinning shaft to obtain nascent fiber;
thirdly, ultraviolet irradiation is carried out at the lower part of the spinning channel or after the spinning channel is discharged; the wavelength of the ultraviolet light is 200-300 nm; the ultraviolet light intensity is more than 3000 μ W/cm 2 (ii) a The radiation time is 5 s-30 s.
9. A high-modulus creep-resistant ultra-high molecular weight polyethylene fiber is characterized in that the fiber subjected to ultraviolet radiation in any one of claims 6 to 8 is subjected to 3-4-stage thermal stretching, the stretching temperature is 110-150 ℃, and the total stretching ratio is 5-10 times.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2080824A1 (en) * 2006-11-08 2009-07-22 HU, Panpan A process for producing fiber of ultra high molecular weight polyethylene
CN104695038A (en) * 2015-03-04 2015-06-10 江苏神鹤科技发展有限公司 Heat-resisting creep-resisting ultra-high molecular weight polyethylene constant-strength fiber and preparation method thereof
CN109234850A (en) * 2018-08-06 2019-01-18 东华大学 Cross-linking modified ultra high molecular weight polyethylene fiber and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2080824A1 (en) * 2006-11-08 2009-07-22 HU, Panpan A process for producing fiber of ultra high molecular weight polyethylene
CN104695038A (en) * 2015-03-04 2015-06-10 江苏神鹤科技发展有限公司 Heat-resisting creep-resisting ultra-high molecular weight polyethylene constant-strength fiber and preparation method thereof
CN109234850A (en) * 2018-08-06 2019-01-18 东华大学 Cross-linking modified ultra high molecular weight polyethylene fiber and preparation method thereof

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