CN113502556A - High creep-resistant ultra-high molecular weight polyethylene fiber and preparation method thereof - Google Patents
High creep-resistant ultra-high molecular weight polyethylene fiber and preparation method thereof Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 112
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 title claims abstract description 76
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 45
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 43
- 239000000725 suspension Substances 0.000 claims abstract description 26
- 238000009987 spinning Methods 0.000 claims abstract description 18
- 238000004132 cross linking Methods 0.000 claims abstract description 14
- 239000012046 mixed solvent Substances 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 11
- 239000000498 cooling water Substances 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 235000015110 jellies Nutrition 0.000 claims abstract 3
- 239000008274 jelly Substances 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 44
- 208000012886 Vertigo Diseases 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 230000008961 swelling Effects 0.000 claims description 5
- 239000005662 Paraffin oil Substances 0.000 claims description 4
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical group CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000010894 electron beam technology Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 claims description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 3
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 claims description 3
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 3
- 239000003502 gasoline Substances 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- 230000005251 gamma ray Effects 0.000 claims description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims 1
- -1 freon Substances 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 6
- 230000005855 radiation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical group CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 4
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- 231100000987 absorbed dose Toxicity 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- 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
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- 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
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- 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
- D06M10/008—Treatment with radioactive elements or with neutrons, alpha, beta or gamma rays
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Abstract
本发明提供了一种高抗蠕变超高分子量聚乙烯纤维及其制备方法。该制备方法为：S1，将超高分子量聚乙烯粉料、混合溶剂、抗氧化剂和敏化剂按预定比例混合，搅拌处理得到均匀的混合悬浮液；S2，将混合悬浮液置于双螺杆挤出机进行纺丝处理后，再经过冷却水浴槽获得初生冻胶丝；将所述初生冻胶丝经由含抗氧化剂的混合萃取液萃取后再进行干燥处理，接着，经过多级热牵伸和多级烘箱获得纤维初产品；S3，辐照交联：将所述纤维初产品进行预定剂量的辐照处理，最后在氮气条件下进行退火处理，获得高抗蠕变超高分子量聚乙烯纤维。相比于常规超高分子量聚乙烯纤维，本发明制备的高抗蠕变超高分子量聚乙烯纤维的纤维蠕变伸长率下降50％及以上。
The invention provides a high creep-resistant ultra-high molecular weight polyethylene fiber and a preparation method thereof. The preparation method is as follows: S1, mixing ultra-high molecular weight polyethylene powder, mixed solvent, antioxidant and sensitizer in a predetermined proportion, and stirring to obtain a uniform mixed suspension; S2, placing the mixed suspension in a twin-screw extruder After spinning out of the machine, the primary jelly filaments are obtained through a cooling water bath; the nascent jelly filaments are extracted with a mixed extract containing antioxidants and then dried, and then subjected to multi-stage thermal drawing and multi-stage heat drawing. graded oven to obtain the initial fiber product; S3, radiation crosslinking: the initial fiber product is subjected to a predetermined dose of irradiation treatment, and finally annealed under nitrogen conditions to obtain high creep-resistant ultra-high molecular weight polyethylene fibers. Compared with conventional ultra-high molecular weight polyethylene fibers, the fiber creep elongation of the high-creep-resistant ultra-high molecular weight polyethylene fibers prepared by the present invention is reduced by 50% or more.
Description
Technical Field
The invention relates to the technical field of preparation of high molecular weight polyethylene fibers, in particular to a high creep-resistant ultrahigh molecular weight polyethylene fiber and a preparation method thereof.
Background
The UHMWPE fiber has many excellent performances as one of three high-performance fibers in the world, and can resist corrosion of chemicals such as strong acid, strong alkali and the like due to the characteristics of high specific strength, high specific modulus, excellent impact resistance and good wear resistance of the UHMWPE fiber, has high electromagnetic wave transmittance and lower friction coefficient than many materials, and has the characteristics of no water absorption, good biocompatibility and the like. Therefore, the UHMWPE fiber is widely applied to the fields of military protective materials, aerospace related materials, medical materials, radar antenna covers, anchor ropes for ships and the like.
Although UHMWPE fibers have many excellent properties, at the same time such materials have some drawbacks, such as poor heat resistance, poor creep resistance, poor composite adhesion, high melt viscosity, which results in difficult processing and shaping. Creep is one of the main problems of organic fibers, and due to poor creep resistance of material molecules and low Young modulus, intermolecular slippage can occur when the material molecules are stressed, so that the creep resistance of the fibers is poor; the creep properties of UHMWPE fibers greatly limit its use in the military and civilian industries.
At present, two methods are mainly used for improving the creep resistance of UHMWPE fibers, and the first method is to improve the degree of crystalline orientation in the preparation process of the UHMWPE fibers by adding nano particles in the process of preparing the UHMWPE fibers through hot drawing. This method improves creep resistance to some extent, but is not effective. With the second method, the creep resistance is improved by reducing the slippage between molecular chains by adding a crosslinking agent to induce crosslinking between the molecular chains within the fiber during spinning.
The invention patent with publication number CN105442100A provides an ultra-high molecular weight polyethylene fiber and a preparation method thereof. The preparation method comprises the steps of placing the ultra-high molecular weight polyethylene primary silk after solvent extraction into a modification solution containing a radiation-sensitive cross-linking agent for impregnation treatment; drying the dipped primary yarn, and drafting the primary yarn by multi-stage hot air; and irradiating the drafted fiber by using high-energy rays to obtain the irradiated and crosslinked ultrahigh molecular weight polyethylene fiber. However, the ultra-high molecular weight polyethylene fiber product has technical defects of fiber surface cross-linking, surface oxidation, non-uniform chemical structure, poor performance and the like.
In view of the above, there is a need for an improved high creep resistant ultra-high molecular weight polyethylene fiber and a method for preparing the same to solve the above problems.
Disclosure of Invention
The invention aims to provide a high creep-resistant ultra-high molecular weight polyethylene fiber and a preparation method thereof.
In order to achieve the above object, the present invention provides a method for preparing a high creep-resistant ultra-high molecular weight polyethylene fiber, comprising the steps of:
s1, preparing a mixed suspension: mixing the ultrahigh molecular weight polyethylene powder, the mixed solvent, the antioxidant and the sensitizer according to a predetermined ratio, and stirring for 8-20 hours to achieve sufficient swelling and uniform dispersion, so as to obtain a uniform mixed suspension;
s2, spinning and extracting: placing the mixed suspension obtained in the step S1 in a double-screw extruder for spinning treatment, and then passing through a cooling water bath to obtain primary gel filaments; extracting the primary gel silk by using a mixed extraction liquid consisting of an extracting agent and an antioxidant, drying, and then obtaining a fiber primary product by using a multi-stage hot drawing and a multi-stage oven;
s3, irradiation crosslinking: and (3) carrying out irradiation treatment with a preset dose on the fiber initial product, and finally carrying out annealing treatment under the condition of nitrogen to obtain the high creep-resistant ultrahigh molecular weight polyethylene fiber.
In a further improvement of the present invention, in step S2, the antioxidant in the mixed extract is tert-butylhydroquinone, dibutylhydroxytoluene, etc.; the extractant is two or more mixed liquids of Freon, dimethylbenzene, gasoline, acetone, trichlorotrifluoroethane and the like.
As a further improvement of the invention, in the mixed extract, the ratio of the antioxidant to the extractant is 1; 99-1: 20.
as a further improvement of the present invention, in step S1, the mixed solvent is a mixture of two or three of paraffin oil, white oil and mineral oil.
As a further improvement of the invention, in step S1, the ratio of the ultra-high molecular weight polyethylene powder, the mixed solvent, the antioxidant and the sensitizer in the mixed suspension is (5-25): (65-93); (1-5): (1-5).
As a further improvement of the present invention, in step S1, the sensitizer is one or more of trimethylolpropane trimethacrylate, triallyl isocyanurate and triallyl cyanurate.
As a further improvement of the invention, in step S3, the dose of the irradiation treatment is 10-200 kGy; the irradiation time is 1-48 h.
As a further improvement of the present invention, in step S3, the irradiation treatment is electron beam irradiation or reflected ray irradiation.
As a further improvement of the present invention, in step S2, the draft ratio is more than 40.
As a further improvement of the invention, the multistage drafting process has a draft ratio of 4-8, 2-5 and 2-5.
In order to achieve the aim, the invention also provides the high creep-resistant ultrahigh molecular weight polyethylene fiber prepared by the preparation method. Compared with the conventional ultrahigh molecular weight polyethylene fiber, the creep elongation of the high creep-resistant ultrahigh molecular weight polyethylene fiber is reduced by 50% or more.
The invention has the beneficial effects that:
1. the preparation method of the high creep-resistant ultra-high molecular weight polyethylene fiber provided by the invention adopts a two-step combined mode to respectively introduce the antioxidant in two processes of fiber preparation and fiber preparation, namely, the antioxidant is added for the first time in the process of preparing a spinning mixed suspension, and the antioxidant is introduced for the second time on the surface of a preformed fiber in the process of extracting a nascent gel yarn; the antioxidant is added into the spinning solution before preparation, mainly for preventing the oxidation caused by the contact with air in the spinning process; in the preparation, the antioxidant is added into the extraction liquid to prevent the fiber surface from being oxidized in the processes of super heat drawing and irradiation; therefore, the two steps of antioxidants are combined and cooperate, so that the antioxidants are uniformly dispersed on the surface and in the fiber, the antioxidant performance is obviously enhanced, the ultrahigh molecular weight polyethylene fiber primary product can be fully crosslinked in the air atmosphere in the irradiation process, and the oxidation phenomenon on the surface of the fiber is obviously reduced.
In the process of extracting the mixed solvent by adopting the mixed extraction liquid, the antioxidant is synchronously added into the mixed extraction liquid, and the extraction process can better form an antioxidant film on the surface of the fiber so as to prevent the oxidation reaction caused by the contact of the surface with oxygen in the processes of fiber hyperploid heat drawing and irradiation. The process is carried out in the continuous extraction process, and the antioxidant is directly introduced to the surface of the fiber which is most prone to oxidation reaction, so that the process difficulty is not increased, the process time is effectively shortened, and the technical defects that the conventional impregnation process consumes long time and increases the process difficulty are effectively overcome.
2. According to the preparation method of the high creep-resistant ultrahigh molecular weight polyethylene fiber provided by the invention, the UHMWPE powder can be fully swelled by adopting a method of mixing various solvents, and the spinning viscosity is reduced, so that the spinnability of the suspension is improved, and the spinning difficulty is reduced.
3. According to the preparation method of the high creep-resistant ultrahigh molecular weight polyethylene fiber, a sensitizer and an antioxidant are introduced in the swelling process of UHMWPE powder, and nascent precursor fibers containing the sensitizer are obtained; so that subsequent irradiation is performed for full crosslinking, and finally annealing treatment is performed, so that unreacted free radicals are effectively eliminated, and subsequent fiber storage at normal temperature and in an air environment is facilitated; therefore, the preparation process can be separated from the production line and the equipment is simplified.
Drawings
FIG. 1 is a flow chart of the preparation of the high creep-resistant ultra-high molecular weight polyethylene fiber provided by the present invention.
FIG. 2 is a cross-sectional view of a high creep-resistant UHMWPE fiber according to the present invention.
FIG. 3 is a graph showing tensile stress-strain curves of 50tex fiber bundles of the present invention at different absorbed dosages for examples 1, 6, 8 and comparative example 4.
FIG. 4 is a graph showing creep elongation versus time for 50tex fiber bundles of the present invention provided in examples 1, 6, 8 and comparative example 4 at different absorbent capacities.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the aspects of the present invention are shown in the drawings, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Referring to fig. 1, the present invention provides a method for preparing a high creep-resistant ultra-high molecular weight polyethylene fiber, comprising the following steps:
s1, preparing a mixed suspension: mixing the ultrahigh molecular weight polyethylene powder, the mixed solvent, the antioxidant and the sensitizer according to a predetermined ratio, and stirring for 8-20 hours to achieve sufficient swelling and uniform dispersion, so as to obtain a uniform mixed suspension;
s2, spinning and extracting: placing the mixed suspension obtained in the step S1 in a double-screw extruder for spinning treatment, and then passing through a cooling water bath to obtain primary gel filaments; extracting the primary gel silk by using a mixed extraction liquid consisting of an extracting agent and an antioxidant, drying, and then obtaining a fiber primary product by using a multi-stage hot drawing and a multi-stage oven;
s3, irradiation crosslinking: and (3) carrying out irradiation treatment with a preset dose on the fiber initial product, and finally carrying out annealing treatment under the condition of nitrogen to obtain the high creep-resistant ultrahigh molecular weight polyethylene fiber.
Preferably, in step S2, the antioxidant in the mixed extract is tert-butylhydroquinone, dibutylhydroxytoluene, or the like; the extractant is two or more mixed liquids of Freon, dimethylbenzene, gasoline, acetone, trichlorotrifluoroethane and the like.
Preferably, in the mixed extract, the ratio of the antioxidant to the extractant is 1; 99-1; 20.
preferably, in step S1, the mixed solvent is a mixture of two or three of paraffin oil, white oil and mineral oil.
Preferably, in step S1, the ratio of the ultra-high molecular weight polyethylene powder, the mixed solvent, the antioxidant and the sensitizer in the mixed suspension is (5-25): (65-93); (1-5): (1-5).
Preferably, in step S1, the sensitizer is one or more of trimethylolpropane trimethacrylate, triallyl isocyanurate and triallyl cyanurate.
Preferably, in the step S3, the irradiation treatment dose is 10 to 200 kGy; the irradiation time is 1-48 h.
Preferably, in step S3, the irradiation treatment is electron beam irradiation or gamma ray irradiation.
Preferably, in step S2, the draft ratio exceeds 40 times.
Preferably, the multistage drafting process is 4-8, 2-5 and 2-5 in draft ratio.
Example 1
The embodiment 1 of the invention provides a preparation method of a high creep-resistant ultrahigh molecular weight polyethylene fiber, which comprises the following steps:
s1, preparing a mixed suspension: mixing the ultrahigh molecular weight polyethylene powder, a mixed solvent, an antioxidant and a sensitizer by the weight ratio of 10; 87; 2; 1, stirring for 12 hours to achieve full swelling and uniform dispersion, and keeping the dynamic uniformity of the mixed solution to obtain uniform mixed suspension;
wherein the mixed solvent is a mixed solution of paraffin oil and white oil; the sensitizer is trimethylolpropane trimethacrylate; the antioxidant is tert-butyl hydroquinone.
S2, spinning and extracting: the mixed suspension obtained in the step S1 is subject to spinning treatment by a double-screw extruder, a spinneret plate and a spinning box (pre-drafting by 3-6 times), and then is subject to cooling water bath to obtain nascent gel silk; extracting the primary gel silk by using a mixed extraction liquid consisting of an extracting agent and an antioxidant, drying, and then obtaining a fiber primary product by using a multi-stage hot drawing and a multi-stage oven;
wherein in the mixed extract, the antioxidant is tert-butyl hydroquinone; the extracting agent is a mixed solution of freon and acetone; the ratio of the antioxidant to the extractant is 2; 98.
s3, irradiation crosslinking: carrying out electron beam irradiation treatment with the dosage of 50kGy on the fiber primary product, wherein the irradiation time is 10 h; and finally, annealing treatment is carried out under the condition of nitrogen, and the high creep-resistant ultrahigh molecular weight polyethylene fiber is obtained. The cross-linking process is shown in FIG. 2.
Through performance tests, compared with the conventional ultrahigh molecular weight polyethylene fiber, the creep elongation of the high creep-resistant ultrahigh molecular weight polyethylene fiber is reduced by 50%.
Comparative example 1
The difference from example 1 is that: no antioxidant was added to the extract of step S2, and the other steps were the same as in example 1 and are not repeated.
Comparative example 2
The difference from example 1 is that: no antioxidant was added to the suspension preparation process of step S1, and the other steps are the same as those in example 1 and are not repeated.
Comparative example 3
The difference from example 1 is that: and (5) adding no sensitizer in the preparation process of the suspension in the step S1, and after extraction treatment, carrying out impregnation treatment on a sensitizer solution.
Through performance tests, compared with the conventional ultrahigh molecular weight polyethylene fiber, the fiber creep elongation of the fiber prepared in the comparative example 3 is reduced by 35%.
Examples 2 to 5
The difference from example 1 is that: the proportions of antioxidant in the suspension of step S1 and of extractant and antioxidant in the extraction of step S2 were set differently, as shown in Table 1.
Table 1 shows the process parameter settings and monofilament fiber performance parameters of examples 1-5
The analysis was performed in conjunction with table 1:
the effect of the antioxidant ratio setting in the suspension on the fiber creep elongation or oxidation resistance of the high creep ultra high molecular weight polyethylene fiber is: the proportion of antioxidant in the suspension influences the degree of oxidation during the spinning of the fibres. Within a certain range, the higher the antioxidant ratio, the smaller the oxidation degree, which determines the chemical structure of the fiber, and the severe oxidation increases the creep elongation of the fiber.
In the mixed extract liquor, the proportion of the extracting agent and the antioxidant is set to have the following influence on the fiber creep elongation or the oxidation resistance of the high creep-resistant ultrahigh molecular weight polyethylene fiber: the proportion of antioxidant in the extract liquor determines the degree of oxidation of the surface of the fiber during the fiber over-drafting and irradiation processes. Within a certain range, the antioxidant ratio is high, the antioxidant effect is better, and the creep elongation of the final fiber is smaller.
Examples 6 to 8 and comparative example 4
The difference from example 1 is that: the proportions of the sensitizers in step S1 and the process parameters of the irradiation process in step S3 were set differently as shown in table 2.
Table 2 shows the process parameter settings and the performance parameters of the monofilament fibers in examples 1, 6 to 8 and comparative example 4
Analysis was performed in conjunction with table 2 and figures 3 to 4:
the influence of the proportion setting of the sensitizer on the fiber creep elongation of the high creep-resistant ultrahigh molecular weight polyethylene fiber is as follows: the proportion of sensitizer determines the degree of radiation crosslinking of the ultra-high molecular weight polyethylene fibers. Within a certain range, the higher the proportion of the sensitizer, the more obvious the internal crosslinking of the fiber, and the lower the creep elongation.
The influence of the technological parameters of the irradiation process on the creep elongation of the fiber of the high creep-resistant ultrahigh molecular weight polyethylene fiber is as follows: the process parameters of the irradiation process are related to the degree of internal crosslinking of the ultra-high molecular weight polyethylene fibers. Within a certain range, the higher the absorbed dose, the higher the crosslinking degree and the lower the creep elongation of the fiber when the irradiation time is fixed.
As can be seen from fig. 3, the tensile elongation of the radiation crosslinked ultra-high molecular weight polyethylene fiber prepared by the process is significantly reduced while the yield strength is maintained substantially unchanged.
As can be seen from fig. 4, the creep elongation of the radiation crosslinked ultra high molecular weight polyethylene fiber prepared by this process is significantly reduced and the creep resistance is enhanced under a constant load.
In conclusion, the invention provides a high creep-resistant ultra-high molecular weight polyethylene fiber and a preparation method thereof. The preparation method comprises the following steps: s1, mixing the ultra-high molecular weight polyethylene powder, the mixed solvent, the antioxidant and the sensitizer according to a predetermined proportion, and stirring to obtain a uniform mixed suspension; s2, placing the mixed suspension in a double-screw extruder for spinning treatment, and then passing through a cooling water bath tank to obtain primary gel filaments; extracting the nascent gel silk by using mixed extraction liquid containing antioxidant, drying, and then obtaining a fiber primary product by multi-stage hot drawing and multi-stage baking oven; s3, irradiation crosslinking: and (3) carrying out irradiation treatment with a preset dose on the fiber initial product, and finally carrying out annealing treatment under the condition of nitrogen to obtain the high creep-resistant ultrahigh molecular weight polyethylene fiber. Compared with the conventional ultrahigh molecular weight polyethylene fiber, the creep elongation of the high creep-resistant ultrahigh molecular weight polyethylene fiber prepared by the method is reduced by 50% or more.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
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| CN116180257A (en) * | 2023-04-04 | 2023-05-30 | 盐城优和博新材料有限公司 | A heat-resistant ultra-high molecular weight polyethylene composite fiber and its production method |
| CN116536786A (en) * | 2023-05-25 | 2023-08-04 | 山东新兴安全防护设备股份有限公司 | A kind of preparation method of ultrahigh molecular weight polyethylene fiber |
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| CN116536786A (en) * | 2023-05-25 | 2023-08-04 | 山东新兴安全防护设备股份有限公司 | A kind of preparation method of ultrahigh molecular weight polyethylene fiber |
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Inventor after: Wang Dong Inventor after: Yang Chenguang Inventor after: Shi Yunhu Inventor after: Wen Xin Inventor after: Wang Wenwen Inventor after: Wang Xiaojun Inventor before: Wang Dong Inventor before: Yang Chenguang Inventor before: Wen Xin Inventor before: Wang Wenwen Inventor before: Wang Xiaojun |
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Effective date of registration: 20230829 Address after: 430200 1 Sunshine Avenue, Jiangxia District, Wuhan, Hubei. Patentee after: Wuhan Textile University Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: SINOPEC YIZHENG CHEMICAL FIBRE Co.,Ltd. Address before: 430200 1 Sunshine Avenue, Jiangxia District, Wuhan, Hubei. Patentee before: Wuhan Textile University |