CN116334782A - Environment-friendly ultra-high molecular weight polyethylene fiber and preparation method thereof - Google Patents
Environment-friendly ultra-high molecular weight polyethylene fiber and preparation method thereof Download PDFInfo
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- CN116334782A CN116334782A CN202211725359.6A CN202211725359A CN116334782A CN 116334782 A CN116334782 A CN 116334782A CN 202211725359 A CN202211725359 A CN 202211725359A CN 116334782 A CN116334782 A CN 116334782A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to the technical field of polyethylene fibers, in particular to the field of IPCC08L23, and more particularly relates to an environment-friendly ultra-high molecular weight polyethylene fiber and a preparation method thereof. An environment-friendly ultra-high molecular weight polyethylene fiber, which comprises the following components: ultra-high molecular weight polyethylene, a catalytic degradation agent, a solvent and a lubricant. The weight ratio of the catalytic degradation agent to the ultra-high molecular weight polyethylene is (0.05-0.2): 1, the degradability of the polyolefin material can be improved while the mechanical strength is maintained; the weight ratio of the lubricant to the ultra-high molecular weight polyethylene is (0.1-0.3): 1, the degradability and mechanical strength of the polyolefin material can be further improved.
Description
Technical Field
The invention relates to the technical field of polyethylene fibers, in particular to the field of IPCC08L23, and more particularly relates to an environment-friendly ultra-high molecular weight polyethylene fiber and a preparation method thereof.
Background
The degradation of polyolefin plastics first occurs in a non-biological oxidation process, mainly photo-thermal oxidation, mechanochemical oxidation and the like, and oxygen in the air reacts with polyolefin under the actions of light, heat, machinery, chemistry and the like. The polyolefin gradually forms smaller molecular flakes, and functional groups with higher reactivity, such as carboxyl, hydroxyl, ester, aldehyde, alcohol and the like, change from hydrophobicity to hydrophilicity, so that the disintegrated polyolefin absorbs water and provides conditions for subsequent biodegradation; this is followed by a microbial degradation process, where microorganisms such as bacteria, fungi, algae use the oxidation products of the polymer chains as a carbon source, thereby forming carbon dioxide, water, bioorganic matter, etc. Commercial applications of degradable polyolefins have not been realized in a real sense, and the biggest problem is that the degradation efficiency is low, and particularly, polyolefin materials with ultra-high molecular weight are difficult to be thoroughly decomposed into final products such as carbon dioxide, water and the like in a short time; and meanwhile, the contradiction between the mechanical property and the degradation property of the polyolefin material is not easy to balance.
CN106519593a discloses a waste biomass-based degradation master batch, and a preparation method, application and application method thereof. The waste biomass-based degradation master batch is prepared from the following raw materials in parts by weight: 5-25 parts of waste biomass base, 5-15 parts of starch, 1-10 parts of mineral powder, 0.1-3 parts of ultraviolet light catalytic degradation agent, 0.1-2 parts of oxidation-assisted degradation agent and 10-45 parts of degradable resin. The degradation capability of plastics is improved to a certain extent, but the addition of ultraviolet light catalytic degradation agent small molecules can influence the mechanical properties of the material, and meanwhile, the weather resistance of the material is reduced.
Disclosure of Invention
The degradable blend is prepared by blending the catalytic degradation agent and the ultra-high molecular weight polyethylene, the catalytic degradation agent has good compatibility with the ultra-high molecular weight polyethylene, the mechanical strength of the ultra-high molecular weight polyethylene fiber is not damaged after the fiber is prepared, the ultra-high molecular weight polyethylene fiber is endowed with the degradability, and the ultra-high molecular weight polyethylene with both degradation and mechanical properties is realized.
In order to achieve the aim of the invention, the first aspect of the invention provides an environment-friendly ultra-high molecular weight polyethylene fiber, which comprises the following components: ultra-high molecular weight polyethylene, a catalytic degradation agent, a solvent and a lubricant.
Preferably, the ultra-high molecular weight polyethylene has a weight average molecular weight of 200 to 400 ten thousand.
Further preferably, the ultra-high molecular weight polyethylene has a weight average molecular weight of 250 to 300 ten thousand.
Still more preferably, the ultra-high molecular weight polyethylene has a weight average molecular weight of 260 ten thousand, which is self-produced by the present company.
The solvent comprises at least one of white oil, paraffin oil and decalin.
Preferably, the kinematic viscosity (40 ℃) of the solvent is from 20 to 45cSt.
Further preferably, the solvent comprises a paraffinic oil having a kinematic viscosity (40 ℃) of 29cSt, available from the flying petrochemical group.
The lubricant comprises at least one of stearic acid, oleic acid and polyethylene wax.
Preferably, the lubricant comprises stearic acid and oleic acid, and the weight ratio of the stearic acid to the oleic acid is 3: (1-2).
Further preferably, the lubricant comprises stearic acid and oleic acid, wherein the weight ratio of stearic acid to oleic acid is 3:1.
preferably, the stearic acid comprises stearic acid 1801, brand: indonesia; the oleic acid was purchased from Shandong Hongquan chemical technology Co.
The applicant found that the weight ratio of the catalytic degradation agent to the ultra-high molecular weight polyethylene is (0.05-0.2): 1, while maintaining mechanical strength, the degradability of the polyolefin material can be improved, and it is possible that functional groups such as amino groups and carboxyl groups in the molecular chain of the catalytic degradation agent improve the hydrophilicity of the material, and meanwhile, macromolecular substances in the catalytic degradation agent are close to the molecular weight of the high molecular weight polyethylene, so that entanglement among molecular chains is increased to a certain extent, and further research shows that the weight ratio of the lubricant to the ultra-high molecular weight polyethylene is (0.1-0.3): 1, the degradability and mechanical strength of the polyolefin material can be further improved, the polarity of the lubricant with a specific proportion is similar to that of the saturated fatty acid in the catalytic degradation agent, the miscibility of the system is promoted, and particularly, when the lubricant comprises stearic acid and oleic acid with a specific proportion, the polyolefin material is subjected to external force, the long side chain structure in the lubricant and the saturated fatty acid can generate certain slippage between macromolecular polyethylene chain segments to overcome deformation, so that the breaking elongation of the material is improved. Further researches show that the weight ratio of chitin to aldohexose in the catalytic degradation agent is 1: (0.5-1.2): when the polyolefin material is applied to the textile fabric through spinning in the range of 0.05-0.5, the addition amount of the catalytic degradation agent can be reduced while the high degradation performance is realized, and particularly when the polyolefin material is applied to the imitation silk fabric, the degradation performance is further improved due to the smaller fiber diameter.
Preferably, the weight ratio of the catalytic degradation agent to the ultra-high molecular weight polyethylene is (0.05-0.2): 1.
further preferably, the weight ratio of the catalytic degradation agent to the ultra-high molecular weight polyethylene is (0.06-0.1): 1.
still more preferably, the weight ratio of the catalytic degradation agent to the ultra-high molecular weight polyethylene is 0.08:1.
preferably, the weight ratio of the ultra-high molecular weight polyethylene to the solvent is (0.1-0.5): 1.
further preferably, the weight ratio of the ultra-high molecular weight polyethylene to the solvent is (0.1-0.3): 1.
still more preferably, the weight ratio of the ultra-high molecular weight polyethylene to the solvent is 0.15:1.
preferably, the weight ratio of the lubricant to the ultra-high molecular weight polyethylene is (0.1-0.4): 1.
further preferably, the weight ratio of the lubricant to the ultra-high molecular weight polyethylene is (0.1 to 0.3): 1.
still more preferably, the weight ratio of the lubricant to the ultra-high molecular weight polyethylene is 0.25:1.
preferably, the catalytic degradation agent is ECO (anaerobic plastic gnawing agent).
The preparation raw materials of the catalytic degradation agent comprise: polysaccharide, saturated fatty acid and silane coupling agent.
The polysaccharide comprises at least one of hyaluronic acid, heparin, inulin, cellulose, starch, chitin and aldohexose.
Preferably, the polysaccharide comprises chitin, aldohexose.
Further preferably, the chitin is purchased from Shandong Siyang Biotechnology Inc., and the aldohexose is purchased from Siam Dafeng Biotechnology Inc.
The saturated fatty acid comprises at least one of caprylic acid, capric acid, lauric acid, myristic acid and palmitic acid.
Preferably, the saturated fatty acids include palmitic acid (CAS: 57-10-3).
The silane coupling agent includes: one or more of gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane and gamma-aminopropyl trimethoxysilane.
Preferably, the silane coupling agent includes gamma-aminopropyl triethoxysilane (CAS: 919-30-2).
Preferably, the weight ratio of the silane coupling agent to the saturated fatty acid is 0.1 (1-2).
Further preferably, the weight ratio of the silane coupling agent to the saturated fatty acid is 0.1:1.
Preferably, the weight ratio of the chitin to the aldohexose is 1: (0.5-1.2): (0.05-0.5).
Further preferably, the weight ratio of the chitin to the aldohexose is 1: (0.5-1): (0.2-0.5).
Still more preferably, the weight ratio of chitin to aldohexose is 1:0.6:0.3.
the preparation method of the catalytic degradation agent comprises the following steps: sequentially adding polysaccharide, saturated fatty acid and silane coupling agent, and dispersing at high speed.
The second aspect of the invention provides a preparation method of an environment-friendly ultra-high molecular weight polyethylene fiber, which comprises the following steps:
s1, uniformly mixing ultra-high molecular weight polyethylene, a catalytic degradation agent, a solvent and a lubricant, continuously stirring at an elevated temperature, cooling for swelling, and standing to obtain a mixture 1;
s2, cooling the mixture 1, conveying the mixture into a double-screw extruder, and extruding and dissolving the mixture to obtain spinning solution;
s3, after spinning the spinning solution, cooling and shaping the spinning solution in a water bath to gel filaments, extracting, and sequentially stretching and thermally drawing.
Preferably, the solvent for extraction comprises n-hexane, ethylene glycol and isopropanol, and the weight ratio of n-hexane, ethylene glycol and isopropanol is 1: (0.1-0.4): (0.2-0.5).
Further preferably, the solvent for extraction comprises n-hexane, ethylene glycol and isopropanol, wherein the weight ratio of n-hexane, ethylene glycol and isopropanol is 3:1:1.
the spinning temperature is 200-235 ℃.
Preferably, the temperature of the spinning is 220 DEG C
The stretching temperature is 50-70 ℃, and the hot stretching temperature is 90-110 ℃.
Preferably, the temperature of the stretching is 60 ℃, and the temperature of the hot stretching is 100 ℃.
The stretching multiple is 6-8 times, and the hot stretching multiple is 6-10 times.
Preferably, the stretching is performed by 8 times, and the heat stretching is performed by 8 times.
The beneficial effects are that:
1. the weight ratio of the catalytic degradation agent to the ultra-high molecular weight polyethylene is (0.05-0.2): 1, the degradability of the polyolefin material can be improved while the mechanical strength is maintained.
2. The weight ratio of the lubricant to the ultra-high molecular weight polyethylene is (0.1-0.3): 1, the degradability and mechanical strength of the polyolefin material can be further improved.
3. The weight ratio of chitin to aldohexose to saturated fatty acid in the catalyst is 1: (0.5-1.2):
when (0.05-0.5), the polyolefin material is applied to the textile fabric through spinning, so that the catalyst has higher degradability and can reduce the addition amount of the catalyst.
Detailed Description
Example 1
An environment-friendly ultra-high molecular weight polyethylene fiber, which comprises the following components: ultra-high molecular weight polyethylene, a catalytic degradation agent, a solvent and a lubricant.
The parts by weight of the ultra-high molecular weight polyethylene are 10 parts.
The weight average molecular weight of the ultra-high molecular weight polyethylene is 260 ten thousand, and the ultra-high molecular weight polyethylene is self-produced by the company.
The solvent included paraffinic oil having a kinematic viscosity (40 ℃) of 29cSt, purchased from the flying petrochemical group.
The lubricant comprises stearic acid and oleic acid, wherein the weight ratio of the stearic acid to the oleic acid is 3:1.
the stearic acid includes stearic acid 1801, brand: indonesia; the oleic acid was purchased from Shandong Hongquan chemical technology Co.
The weight ratio of the catalytic degradation agent to the ultra-high molecular weight polyethylene is 0.08:1.
the weight ratio of the ultra-high molecular weight polyethylene to the solvent is 0.15:1.
the weight ratio of the lubricant to the ultra-high molecular weight polyethylene is 0.25:1.
the catalytic degradation agent is ECO (anaerobic plastic gnawing agent).
The preparation raw materials of the catalytic degradation agent comprise: polysaccharide, saturated fatty acid and silane coupling agent.
The parts by weight of the saturated fatty acid are 10 parts.
The polysaccharide comprises chitin, and aldohexose, wherein the chitin is purchased from Shandong Siyang biotechnology limited, and the aldohexose is purchased from Siam great harvest biotechnology limited.
The saturated fatty acids include palmitic acid (CAS: 57-10-3).
The silane coupling agent includes gamma-aminopropyl triethoxysilane (CAS: 919-30-2).
The weight ratio of the chitin to the aldohexose to the saturated fatty acid is 1:0.6:0.3.
the weight ratio of the silane coupling agent to the saturated fatty acid is 0.1:1.
The preparation method of the catalytic degradation agent comprises the following steps: sequentially adding polysaccharide, saturated fatty acid and silane coupling agent, and dispersing at high speed (2000 rpm) to obtain the final product.
The preparation method of the environment-friendly ultra-high molecular weight polyethylene fiber comprises the following steps:
s1, uniformly mixing ultra-high molecular weight polyethylene, a catalytic degradation agent, a solvent and a lubricant (1500 rpm,10 min), increasing the temperature to 140 ℃, continuously stirring for 3h, cooling to 105 ℃, swelling for 1h, and standing at 35 ℃ for 16h to obtain a mixture 1;
s2, cooling the mixture 1 to 30 ℃, conveying the mixture into a double-screw extruder, and extruding and dissolving to obtain spinning solution;
s3, after spinning the spinning solution, cooling and shaping the spinning solution to gel yarn in a water bath (25 ℃), extracting for 12 hours, sequentially stretching and thermally stretching, and finally heating for 3 minutes at 100 ℃.
The extracted solvent comprises n-hexane, ethylene glycol and isopropanol, wherein the weight ratio of the n-hexane to the ethylene glycol to the isopropanol is 3:1:1.
the temperature of the stretching was 60 ℃ and the temperature of the hot stretching was 100 ℃.
The stretching multiple is 8 times, and the heat stretching multiple is 8 times.
Example 2
The detailed description is the same as example 1; except that in example 2:
s1, uniformly mixing ultra-high molecular weight polyethylene, a catalytic degradation agent, a solvent and a lubricant (2500 rpm,15 min), raising the temperature to 140 ℃, continuously stirring for 3h, cooling to 110 ℃, swelling for 65min, and standing at 35 ℃ for 16h to obtain a mixture 1.
The weight ratio of the ultra-high molecular weight polyethylene to the solvent is 0.1:1.
the weight ratio of the lubricant to the ultra-high molecular weight polyethylene is 0.2:1.
example 3
The detailed description is the same as example 1; except that in example 3:
s1, uniformly mixing ultra-high molecular weight polyethylene, a catalytic degradation agent, a solvent and a lubricant (3000 rpm,12 min), increasing the temperature to 140 ℃, continuously stirring for 3h, cooling to 100 ℃, swelling for 70min, and standing at 35 ℃ for 16h to obtain a mixture 1.
The weight ratio of the ultra-high molecular weight polyethylene to the solvent is 0.3:1.
the weight ratio of the lubricant to the ultra-high molecular weight polyethylene is 0.4:1.
comparative example 1
The detailed description is the same as example 1; except that in comparative example 1: the weight ratio of the catalytic degradation agent to the ultra-high molecular weight polyethylene is 0.04:1.
comparative example 2
The detailed description is the same as example 1; except that in comparative example 2: the weight ratio of the catalytic degradation agent to the ultra-high molecular weight polyethylene is 0.25:1.
comparative example 3
The detailed description is the same as example 1; except that in comparative example 3: the weight ratio of chitin to aldohexose to saturated fatty acid in the catalyst is 1:0.4:0.6.
performance test method
The fibers obtained in examples 1-3 and comparative examples 1-3 were subjected to performance testing, and the test data are shown in Table 1.
1) The fiber breaking strength (cN/dtex) was measured with reference to GB/T19975-2005 method for testing tensile Property of high-strength fiber filaments.
2) Fiber density (g/cm) was tested with reference to ASTM D3800-99 (2010) standards 3 )。
3) Reference GB/T19277.1-2021 "determination of the final aerobic biological decomposition ability of materials under controlled composting conditions" part 1 of the method for determining released carbon dioxide: the polyethylene fiber was tested for 180-day degradation rate (%) under the provisions of the general method.
Performance test data
TABLE 1
Claims (10)
1. An environment-friendly ultra-high molecular weight polyethylene fiber is characterized by comprising the following components: ultra-high molecular weight polyethylene, a catalytic degradation agent, a solvent and a lubricant.
2. The environment-friendly ultra-high molecular weight polyethylene fiber according to claim 1, wherein the weight ratio of the catalytic degradation agent to the ultra-high molecular weight polyethylene is (0.05-0.2): 1.
3. the environmentally friendly ultra-high molecular weight polyethylene fiber according to claim 2, wherein the weight ratio of the ultra-high molecular weight polyethylene to the solvent is (0.1-0.5): 1.
4. an environmentally friendly ultra high molecular weight polyethylene fiber according to claim 3, wherein the weight ratio of the lubricant to ultra high molecular weight polyethylene is (0.1-0.4): 1.
5. the environment-friendly ultra-high molecular weight polyethylene fiber according to claim 1 or 4, wherein the preparation raw materials of the catalytic degradation agent comprise: polysaccharide, saturated fatty acid and silane coupling agent.
6. The environment-friendly ultra-high molecular weight polyethylene fiber according to claim 5, wherein the polysaccharide comprises chitin and aldohexose, and the weight ratio of the chitin to the aldohexose to the saturated fatty acid is 1:
(0.5-1.2)：(0.05-0.5)。
7. a method for preparing the environment-friendly ultra-high molecular weight polyethylene fiber according to any one of claims 1 to 6, comprising the steps of:
s1, uniformly mixing ultra-high molecular weight polyethylene, a catalytic degradation agent, a solvent and a lubricant, continuously stirring at an elevated temperature, cooling for swelling, and standing to obtain a mixture 1;
s2, cooling the mixture 1, conveying the mixture into a double-screw extruder, and extruding and dissolving the mixture to obtain spinning solution;
s3, after spinning the spinning solution, cooling and shaping the spinning solution in a water bath to gel filaments, extracting, and sequentially stretching and thermally drawing.
8. The method for preparing the environment-friendly ultra-high molecular weight polyethylene fiber according to claim 7, wherein the extracted solvent comprises n-hexane, ethylene glycol and isopropanol, and the weight ratio of n-hexane, ethylene glycol and isopropanol is 1: (0.1-0.4): (0.2-0.5).
9. The method for preparing environment-friendly ultra-high molecular weight polyethylene fiber according to claim 7, wherein the spinning temperature is 200-235 ℃.
10. The method for preparing environment-friendly ultra-high molecular weight polyethylene fiber according to claim 7, wherein the stretching temperature is 50-70 ℃, and the hot stretching temperature is 90-110 ℃.
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