CN114108112B - Polyethylene sheet - Google Patents
Polyethylene sheet Download PDFInfo
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- CN114108112B CN114108112B CN202011608393.6A CN202011608393A CN114108112B CN 114108112 B CN114108112 B CN 114108112B CN 202011608393 A CN202011608393 A CN 202011608393A CN 114108112 B CN114108112 B CN 114108112B
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- barium sulfate
- complexing agent
- tensile strength
- polyethylene sheet
- spinning
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/11—Flash-spinning
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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
-
- 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
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/007—Addition polymers
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention relates to a polyethylene sheet, which is characterized in that the aging rate delta S of the tensile strength is 0.10-0.30; Δs=1-S2/S1; s1 is the tensile strength of non-aged non-woven fabrics, and the unit is kN/m; s2 is the tensile strength of the non-woven fabric subjected to aging treatment, and the tensile strength is in kN/m; the aging treatment process conditions are as follows: irradiance of 60 + -2 w/m in the wavelength range of 300-400 nm 2 The black standard temperature is 65+/-2 ℃, the air temperature of the test bin is 38+/-3 ℃, the relative humidity is 50+/-10%, and the drying time is 1440 hours. The product of the invention still has good tensile strength after aging, thereby prolonging the service life of the product.
Description
[ field of technology ]
The invention relates to the technical field of flash spinning, in particular to a polyethylene sheet.
[ background Art ]
Flash spinning refers to a spinning process in which a high polymer solution is extruded at a high pressure above its solvent boiling point, and the solvent flash causes the polymer to cool and solidify to form fibers. Also known as solution flash spinning. It is required that the polymer and the solvent are not decomposed at a temperature not lower than the boiling point of the solvent, and the solvent is easily evaporated. The extruded solution trickles, causing the solvent to flash off when the pressure suddenly drops, solidifying the polymer into fibers, and then hot-pressing into a web. For example, linear polyethylene is prepared into solution in methylene dichloride, the solution is extruded under high pressure of 7Mpa, the methylene dichloride is flashed, and the polyethylene is solidified into superfine fiber nonwoven fabric. In 1955, dupont's researchers jimwite inadvertently discovered flash spinning, and the technology was studied by a deep person, and the next year patented. Then after further improvements to this technology, dupont registered the trademark Tyvek & reg for this product in 1965 and formally produced the product under this brand for commercial sale in 1967. Until now, tyvek has been a flash nonwoven market worldwide for decades over 30 years. For our country, this technology is still blank. Currently, professor Cheng Bowen of the university of Tianjin industry led its team to begin research on flash spun ultrafine fibers and their nonwoven products; the Xiamen works as a new material in combination with the university of Donghua and has also made some prospective studies on flash nonwoven fabrics.
US3081519a by dupont relates to a flash spinning process comprising: selecting a suitable solvent that is capable of solvent the polymer under autothermal or higher pressure conditions, but that is non-solvent to the polymer at or below its normal boiling point; dissolving a polymer suitable for flash spinning in the proper solvent in a high-temperature high-pressure chamber to form a uniform spinning solution; the solution is then extruded into a medium at low temperature and typically low pressure; due to the reduction of the spinning solution pressure, the single-phase solution formed in the high-temperature high-pressure chamber is changed into a two-phase dispersion solution, namely a solvent enrichment phase and a polymer enrichment dispersion phase; the two dispersion solutions are sprayed out through a spinneret under the pushing of pressure, and at this time, the solvent is rapidly volatilized due to the sudden release of the pressure, so-called flash evaporation, so that the sprayed polymer appears in the form of a tow.
The existing flash evaporation non-woven fabric has yellowing phenomenon after being used for a period of time, mainly due to irradiation and oxidation reaction of optical fibers in the environment, and the phenomenon of tensile strength reduction occurs along with the yellowing phenomenon.
[ invention ]
The invention aims to overcome the defects of the prior art and provides a polyethylene sheet.
The aim of the invention is realized by the following technical scheme:
a polyethylene sheet having a tensile strength aging rate DeltaS of 0.10 to 0.30;
△S＝1-S2/S1；
s1 is the tensile strength of non-aged non-woven fabrics, and the unit is kN/m;
s2 is the tensile strength of the non-woven fabric subjected to aging treatment, and the tensile strength is in kN/m;
the aging treatment process conditions are as follows: irradiance of 60 + -2 w/m in the wavelength range of 300-400 nm 2 The black standard temperature is 65+/-2 ℃, the air temperature of the test bin is 38+/-3 ℃, the relative humidity is 50+/-10%, and the drying time is 1440 hours.
The aging rate DeltaS of the tensile strength is 0.10-0.15.
The aging rate DeltaS of the tensile strength is 0.15-0.20.
The aging rate DeltaS of the tensile strength is 0.20-0.25.
The aging rate DeltaS of the tensile strength is 0.25-0.30.
A polyethylene sheet, wherein the aging rate DeltaF of the D65 fluorescent brightness is 0.05-0.20;
△F＝1-F2/F1
f1 is the D65 fluorescence brightness of the non-aged nonwoven fabric;
f2 is the D65 fluorescence brightness of the non-woven fabric after aging treatment;
the aging treatment process conditions are as follows: irradiance of 60 + -2 w/m in the wavelength range of 300-400 nm 2 Black standard temperature is 65+/-2 ℃ and test binThe air temperature was 38.+ -. 3 ℃, the relative humidity was 50.+ -. 10% and the drying time was 1440 hours.
The aging rate DeltaF of the D65 fluorescent brightness is 0.05-0.08.
The aging rate DeltaF of the D65 fluorescent brightness is 0.08-0.11.
The aging rate DeltaF of the D65 fluorescent brightness is 0.11-0.14.
The aging rate DeltaF of the D65 fluorescent brightness is 0.14-0.17.
The aging rate DeltaF of the D65 fluorescent brightness is 0.17-0.20.
A polyethylene sheet material comprises polyethylene and a complexing agent.
The mass fraction of the complexing agent in the polyethylene sheet is 0.1-0.3%.
The mass fraction of the complexing agent in the polyethylene sheet is 0.15-0.25%.
The complexing agent is modified barium sulfate and a complex of 1, 4-bis (2-cyano styryl) benzene.
The preparation method of the complexing agent comprises the following specific steps:
adding barium sulfate into an aqueous solution of isopropanol, adding a magnesium chloride solution, adsorbing on the surface of the barium sulfate to generate magnesium hydroxide precipitate, filtering, drying and calcining to obtain modified barium sulfate; dispersing modified barium sulfate in isopropanol water solution of diphenyl diethoxy silane, adding vinyl trimethoxy silane, treating at 45-60 ℃ for 15-25 minutes, filtering, and vacuum drying filter residues to obtain a barium sulfate physical brightening agent; and grinding and mixing the barium sulfate physical brightening agent and 1, 4-bis (2-cyano styryl) benzene to obtain the complexing agent.
The volume ratio of isopropanol to water in the aqueous solution of isopropanol was 1:1.
The mass fraction of the barium sulfate in the aqueous solution of the isopropanol is 2-10%.
The molar ratio of the barium sulfate to the magnesium chloride is 1:0.01-1:0.13.
The mass ratio of the modified barium sulfate to the diphenyl diethoxy silane is 1:1-1:3.5.
The mass ratio of the isopropanol to the diphenyldiethoxysilane is 1:0.04-1:0.25.
The mass ratio of the diphenyl diethoxy silane to the vinyl trimethoxy silane is 1:1-1:1.3.
The mass ratio of the barium sulfate physical brightening agent to the 1, 4-bis (2-cyano styryl) benzene is 1:1-1:1.3.
The calcination process is to rapidly raise the temperature at a temperature lower than 500 ℃ at a temperature raising rate of 30 ℃/min, and slowly raise the temperature at a temperature of 500-800 ℃ at a temperature raising rate of 8 ℃/min.
The CAS registration number of the 1, 4-bis (2-cyanostyryl) benzene is 13001-39-3, the molecular formula is C24H16N2, the molecular weight is 332.3972, the melting point is 230-234 ℃, the temperature must be lower than that of flash spinning, or the solvent can volatilize in the spinning process, so that the expected whitening effect is achieved, and the reason is that a high-melting-point reagent is selected; this is also the solvent choice made by the spin temperature characteristics of flash spinning. Meanwhile, good compatibility between the 1, 4-bis (2-cyanostyryl) benzene and the solvent for flash spinning must be considered; the compatibility with the spinning solvent is good, so that the complexing agent is uniformly dispersed in the polyethylene, and the whitening effect of the complexing agent is better exerted. This is one consideration in selecting 1, 4-bis (2-cyanostyryl) benzene.
Barium sulfate is used as a common brightening agent and mainly plays a role in physical brightening, but is used as an inorganic material, so that the dispersibility of the barium sulfate in a matrix is poor, the strength of the matrix is influenced, and the brightening effect is poor; the existing conventional method mainly adopts a coupling agent to modify a brightening agent to improve the compatibility with a matrix, but the whitening property is inevitably deteriorated due to the introduction of organic components, particularly silicon-containing materials; the 1, 4-bis (2-cyano styryl) benzene is used as an organic brightening agent, has a chemical brightening effect mainly, and achieves the chemical brightening effect through a large conjugated structure in molecules and groups on the conjugated structure, but is used as an organic molecule with low molecular weight, has weak bonding force with a matrix, and causes great strength loss to the matrix. According to the preparation method, diphenyl diethoxy silane is used as a coupling agent, and in order to have certain binding force with a matrix, the influence of a silicon-containing material on the molecules of the whitening agent is eliminated, magnesium ions with molecular chelation are introduced into the preparation process of the whitening agent, and the magnesium ions are introduced into the surface of the whitening agent, so that the influence of the coupling agent on the whitening agent is eliminated; meanwhile, the benzene ring structure introduced into the molecule of the whitening agent can be used as a large conjugated structure to have affinity with the 1, 4-bis (2-cyano styryl) benzene of the chemical whitening agent, so that the problem that the bonding force between the 1, 4-bis (2-cyano styryl) benzene and a matrix is weaker is avoided, the influence of the introduction of the whitening agent on the matrix strength is ensured, meanwhile, the introduction of the coupling agent containing the benzene ring structure can play a synergistic effect with the 1, 4-bis (2-cyano styryl) benzene of the chemical whitening agent, fully scattered light in the physical whitening agent is directly beaten to the chemical whitening of molecular level, electrons generated in the whitening process of the chemical whitening agent can be transmitted to the physical whitening agent, the purpose of enhancing the whitening effect is achieved by the absorption of the physical whitening agent, and the damage to the matrix material caused by single physical whitening agent or the whitening agent is avoided. The complexing agent plays a whitening function and is dispersed among fibers in the flash spinning process, so that the adhesive force among the fibers is increased, and the tensile strength of the sheet can be improved.
Compared with the prior art, the invention has the following positive effects:
after the flash evaporation non-woven fabric is used for a period of time, the tensile strength of the flash evaporation non-woven fabric is reduced while the brightness is maintained.
[ detailed description ] of the invention
The following provides a specific embodiment of a polyethylene sheet according to the invention.
Performance test and aging test
A D65 fluorescent brightness
Whiteness is the degree of whiteness from ideal, and also the degree of whiteness of the surface of a substance, expressed as a percentage of the white content. Brightness test is specifically described in GBT 7974-2013 for determination of blue diffuse reflectance factor D65 of paper, paperboard and pulp, and the test is performed according to the paper and paperboard method to determine D on the front side of the sample 65 Fluorescent brightness of F z The D65 fluorescence brightness of the back of the sample is measured to be F b Again, this definition: d65 fluorescence brightness f= (F) of sample z +F b )/2. D65 refers to fluorescence excited with a D65 light source, about ISO2470-1.
Two aging process
Ageing test referring to GB/T35256-2017 textile color fastness test artificial weathering exposure to filtered xenon arc radiation the test conditions for the ageing process of the present application are as follows: irradiance (w/m 2) with the wavelength in the range of 300-400 nanometers is 60+/-2, black standard temperature (DEG C) is 65+/-2, air temperature (DEG C) of a test bin is 38+/-3, relative humidity (%) is 50+/-10, and drying time is 1440 hours.
Three tensile strength
The tensile strength is the maximum tensile force which can be born before the breaking of a sample with unit width, the specific test is referred to a GBT 12914-2018 paper and paperboard tensile strength measuring constant-speed stretching method (20 mm/min), 10 samples are taken from the same sample, the width of the sample is 15 mm, the width direction of 5 samples is parallel to the production and processing direction of the sample, the width direction of the other 5 samples is perpendicular to the production and processing direction of the sample, the tensile strength of the sample is measured by adopting a tensile tester at 20mm/min, all the tensile forces are measured, the average tensile force of the sample is obtained, and the tensile strength is obtained by dividing the average tensile force by the width of the sample.
Example 1
A preparation method of a polyethylene sheet comprises the following specific steps:
(1) The spinning solution is prepared firstly and consists of a solvent and a polymer.
The solvent is 1,2, 3, 4-octafluorobutane.
The mass fraction of the polymer in the spinning solution is 12%.
The raw materials comprise polyethylene and complexing agent.
The mass fraction of the complexing agent in the polyethylene sheet is 0.1%.
The complexing agent is modified barium sulfate and a complex of 1, 4-bis (2-cyano styryl) benzene.
The preparation method of the complexing agent comprises the following specific steps:
adding barium sulfate into an aqueous solution of isopropanol, adding a magnesium chloride solution, adsorbing on the surface of the barium sulfate to generate magnesium hydroxide precipitate, filtering, drying and calcining to obtain modified barium sulfate; dispersing modified barium sulfate in isopropanol water solution of diphenyl diethoxy silane, adding vinyl trimethoxy silane, treating at 45-60 ℃ for 15-25 minutes, filtering, and vacuum drying filter residues to obtain a barium sulfate physical brightening agent; and grinding and mixing the barium sulfate physical brightening agent and 1, 4-bis (2-cyano styryl) benzene to obtain the complexing agent.
The volume ratio of isopropanol to water in the aqueous solution of isopropanol was 1:1.
The mass fraction of barium sulfate in the aqueous solution of isopropanol was 2.5%.
The molar ratio of barium sulfate to magnesium chloride was 1:0.015.
The mass ratio of the modified barium sulfate to the diphenyldiethoxysilane is 1:1.
The mass ratio of the isopropanol to the diphenyldiethoxysilane is 1:0.04.
The mass ratio of diphenyldiethoxysilane to vinyltrimethoxysilane is 1:1.
The mass ratio of the barium sulfate physical brightening agent to the 1, 4-bis (2-cyanostyryl) benzene is 1:1.
The CAS registration number of the 1, 4-bis (2-cyanostyryl) benzene is 13001-39-3, the molecular formula is C24H16N2, the molecular weight is 332.3972, the melting point is 230-234 ℃, the temperature must be lower than that of flash spinning, or the solvent can volatilize in the spinning process, so that the expected whitening effect is achieved, and the reason is that a high-melting-point reagent is selected; this is also the solvent choice made by the spin temperature characteristics of flash spinning. Meanwhile, good compatibility between the 1, 4-bis (2-cyanostyryl) benzene and the solvent for flash spinning must be considered; the compatibility with the spinning solvent is good, so that the complexing agent is uniformly dispersed in the polyethylene, and the whitening effect of the complexing agent is better exerted. This is one consideration in selecting 1, 4-bis (2-cyanostyryl) benzene.
(2) And (3) carrying out flash spinning at 145 ℃ to obtain flash fiber, forming a fiber web, and carrying out hot press molding on the fiber web by a roller at 110 ℃ to obtain the polyethylene sheet. Performance testing of the product as described for D65 fluorescence brightness (a D65 fluorescence brightness as described above), tensile strength (three tensile strengths as described above); testing data before aging, testing data after an aging test (the two aging processes) and respectively calculating the aging rate of D65 fluorescent brightness and the aging rate of tensile strength; specific test data are shown in table 1.
Example 2
A preparation method of a polyethylene sheet comprises the following specific steps:
(1) Preparing spinning solution, which consists of solvent and polymer,
the solvent is 1,2, 3, 4-octafluorobutane;
the mass fraction of the polymer in the spinning solution is 12.5%;
the raw materials comprise polyethylene and complexing agent;
the mass fraction of the complexing agent in the polyethylene sheet is 0.15%.
The complexing agent is modified barium sulfate and a complex of 1, 4-bis (2-cyano styryl) benzene.
The preparation method of the complexing agent comprises the following specific steps:
adding barium sulfate into an aqueous solution of isopropanol, adding a magnesium chloride solution, adsorbing on the surface of the barium sulfate to generate magnesium hydroxide precipitate, filtering, drying and calcining to obtain modified barium sulfate; dispersing modified barium sulfate in isopropanol water solution of diphenyl diethoxy silane, adding vinyl trimethoxy silane, treating at 45-60 ℃ for 15-25 minutes, filtering, and vacuum drying filter residues to obtain a barium sulfate physical brightening agent; and grinding and mixing the barium sulfate physical brightening agent and 1, 4-bis (2-cyano styryl) benzene to obtain the complexing agent.
The volume ratio of the isopropanol to the water in the aqueous solution of the isopropanol is 1:1;
the mass fraction of barium sulfate in the aqueous solution of isopropanol is 4%;
the molar ratio of the barium sulfate to the magnesium chloride is 1:0.05;
the mass ratio of the modified barium sulfate to the diphenyl diethoxysilane is 1:1.5;
the mass ratio of the isopropanol to the diphenyl diethoxysilane is 1:0.09;
the mass ratio of the diphenyl diethoxy silane to the vinyl trimethoxy silane is 1:1.05.
The mass ratio of the barium sulfate physical brightening agent to the 1, 4-bis (2-cyanostyryl) benzene is 1:1.15.
The CAS registration number of the 1, 4-bis (2-cyanostyryl) benzene is 13001-39-3, the molecular formula is C24H16N2, the molecular weight is 332.3972, the melting point is 230-234 ℃, the temperature must be lower than that of flash spinning, or the solvent can volatilize in the spinning process, so that the expected whitening effect is achieved, and the reason is that a high-melting-point reagent is selected; this is also the solvent choice made by the spin temperature characteristics of flash spinning. Meanwhile, good compatibility between the 1, 4-bis (2-cyanostyryl) benzene and the solvent for flash spinning must be considered; the compatibility with the spinning solvent is good, so that the complexing agent is uniformly dispersed in the polyethylene, and the whitening effect of the complexing agent is better exerted. This is one consideration in selecting 1, 4-bis (2-cyanostyryl) benzene.
(2) And (3) carrying out flash spinning at a spinning temperature of 150 ℃ to obtain flash fibers, forming a fiber web, and carrying out hot press molding on the fiber web by a roller at a hot press temperature of 115 ℃ to obtain the polyethylene sheet. Performance testing of the product as described for D65 fluorescence brightness (a D65 fluorescence brightness as described above), tensile strength (three tensile strengths as described above); testing data before aging, testing data after an aging test (the two aging processes) and respectively calculating the aging rate of D65 fluorescent brightness and the aging rate of tensile strength; specific test data are shown in table 1.
Example 3
A preparation method of a polyethylene sheet comprises the following specific steps:
(1) Preparing spinning solution, which consists of solvent and polymer,
the solvent is 1,2, 3, 4-octafluorobutane;
the mass fraction of the polymer in the spinning solution is 13%;
the raw materials comprise polyethylene and complexing agent;
the mass fraction of the complexing agent in the polyethylene sheet is 0.2%.
The complexing agent is modified barium sulfate and a complex of 1, 4-bis (2-cyano styryl) benzene.
The preparation method of the complexing agent comprises the following specific steps:
adding barium sulfate into an aqueous solution of isopropanol, adding a magnesium chloride solution, adsorbing on the surface of the barium sulfate to generate magnesium hydroxide precipitate, filtering, drying and calcining to obtain modified barium sulfate; dispersing modified barium sulfate in isopropanol water solution of diphenyl diethoxy silane, adding vinyl trimethoxy silane, treating at 45-60 ℃ for 15-25 minutes, filtering, and vacuum drying filter residues to obtain a barium sulfate physical brightening agent; and grinding and mixing the barium sulfate physical brightening agent and 1, 4-bis (2-cyano styryl) benzene to obtain the complexing agent.
The volume ratio of the isopropanol to the water in the aqueous solution of the isopropanol is 1:1;
the mass fraction of barium sulfate in the aqueous solution of isopropanol is 5%;
the molar ratio of the barium sulfate to the magnesium chloride is 1:0.1;
the mass ratio of the modified barium sulfate to the diphenyl diethoxysilane is 1:2;
the mass ratio of the isopropanol to the diphenyl diethoxysilane is 1:0.15;
the mass ratio of diphenyldiethoxysilane to vinyltrimethoxysilane was 1:1.2.
The mass ratio of the barium sulfate physical brightening agent to the 1, 4-bis (2-cyanostyryl) benzene is 1:1.2.
The CAS registration number of the 1, 4-bis (2-cyanostyryl) benzene is 13001-39-3, the molecular formula is C24H16N2, the molecular weight is 332.3972, the melting point is 230-234 ℃, the temperature must be lower than that of flash spinning, or the solvent can volatilize in the spinning process, so that the expected whitening effect is achieved, and the reason is that a high-melting-point reagent is selected; this is also the solvent choice made by the spin temperature characteristics of flash spinning. Meanwhile, good compatibility between the 1, 4-bis (2-cyanostyryl) benzene and the solvent for flash spinning must be considered; the compatibility with the spinning solvent is good, so that the complexing agent is uniformly dispersed in the polyethylene, and the whitening effect of the complexing agent is better exerted. This is one consideration in selecting 1, 4-bis (2-cyanostyryl) benzene.
(2) And (3) carrying out flash spinning at a spinning temperature of 150 ℃ to obtain flash fibers, forming a fiber web, and carrying out hot press molding on the fiber web by a roller at a hot press temperature of 120 ℃ to obtain the polyethylene sheet. Performance testing of the product as described for D65 fluorescence brightness (a D65 fluorescence brightness as described above), tensile strength (three tensile strengths as described above); testing data before aging, testing data after an aging test (the two aging processes) and respectively calculating the aging rate of D65 fluorescent brightness and the aging rate of tensile strength; specific test data are shown in table 1.
Example 4
A preparation method of a polyethylene sheet comprises the following specific steps:
(1) Preparing spinning solution, which consists of solvent and polymer,
the solvent is 1,2, 3, 4-octafluorobutane;
the mass fraction of the polymer in the spinning solution is 13.5%;
the raw materials comprise polyethylene and complexing agent;
the mass fraction of the complexing agent in the polyethylene sheet is 0.25%.
The complexing agent is modified barium sulfate and a complex of 1, 4-bis (2-cyano styryl) benzene.
The preparation method of the complexing agent comprises the following specific steps:
adding barium sulfate into an aqueous solution of isopropanol, adding a magnesium chloride solution, adsorbing on the surface of the barium sulfate to generate magnesium hydroxide precipitate, filtering, drying and calcining to obtain modified barium sulfate; dispersing modified barium sulfate in isopropanol water solution of diphenyl diethoxy silane, adding vinyl trimethoxy silane, treating at 45-60 ℃ for 15-25 minutes, filtering, and vacuum drying filter residues to obtain a barium sulfate physical brightening agent; and grinding and mixing the barium sulfate physical brightening agent and 1, 4-bis (2-cyano styryl) benzene to obtain the complexing agent.
The volume ratio of the isopropanol to the water in the aqueous solution of the isopropanol is 1:1;
the mass fraction of barium sulfate in the aqueous solution of isopropanol is 8%;
the molar ratio of the barium sulfate to the magnesium chloride is 1:0.11;
the mass ratio of the modified barium sulfate to the diphenyl diethoxysilane is 1:3;
the mass ratio of the isopropanol to the diphenyl diethoxysilane is 1:0.20;
the mass ratio of diphenyldiethoxysilane to vinyltrimethoxysilane was 1:1.25.
The mass ratio of the barium sulfate physical brightening agent to the 1, 4-bis (2-cyanostyryl) benzene is 1:1.25.
The CAS registration number of the 1, 4-bis (2-cyanostyryl) benzene is 13001-39-3, the molecular formula is C24H16N2, the molecular weight is 332.3972, the melting point is 230-234 ℃, the temperature must be lower than that of flash spinning, or the solvent can volatilize in the spinning process, so that the expected whitening effect is achieved, and the reason is that a high-melting-point reagent is selected; this is also the solvent choice made by the spin temperature characteristics of flash spinning. Meanwhile, good compatibility between the 1, 4-bis (2-cyanostyryl) benzene and the solvent for flash spinning must be considered; the compatibility with the spinning solvent is good, so that the complexing agent is uniformly dispersed in the polyethylene, and the whitening effect of the complexing agent is better exerted. This is one consideration in selecting 1, 4-bis (2-cyanostyryl) benzene.
(2) And (3) carrying out flash spinning at 160 ℃ to obtain flash-spun fibers, forming a fiber web, and carrying out hot press molding on the fiber web by a roller at 120 ℃ to obtain the polyethylene sheet. Performance testing of the product as described for D65 fluorescence brightness (a D65 fluorescence brightness as described above), tensile strength (three tensile strengths as described above); testing data before aging, testing data after an aging test (the two aging processes) and respectively calculating the aging rate of D65 fluorescent brightness and the aging rate of tensile strength; specific test data are shown in table 1.
Example 5
A preparation method of a polyethylene sheet comprises the following specific steps:
(1) Preparing spinning solution, which consists of solvent and polymer,
the solvent is 1,2, 3, 4-octafluorobutane;
the mass fraction of the polymer in the spinning solution is 14%;
the raw materials comprise polyethylene and complexing agent;
the mass fraction of the complexing agent in the polyethylene sheet is 0.3%.
The complexing agent is modified barium sulfate and a complex of 1, 4-bis (2-cyano styryl) benzene.
The preparation method of the complexing agent comprises the following specific steps:
adding barium sulfate into an aqueous solution of isopropanol, adding a magnesium chloride solution, adsorbing on the surface of the barium sulfate to generate magnesium hydroxide precipitate, filtering, drying and calcining to obtain modified barium sulfate; dispersing modified barium sulfate in isopropanol water solution of diphenyl diethoxy silane, adding vinyl trimethoxy silane, treating at 45-60 ℃ for 15-25 minutes, filtering, and vacuum drying filter residues to obtain a barium sulfate physical brightening agent; and grinding and mixing the barium sulfate physical brightening agent and 1, 4-bis (2-cyano styryl) benzene to obtain the complexing agent.
The volume ratio of the isopropanol to the water in the aqueous solution of the isopropanol is 1:1;
the mass fraction of barium sulfate in the aqueous solution of isopropanol is 10%;
the molar ratio of the barium sulfate to the magnesium chloride is 1:0.13;
the mass ratio of the modified barium sulfate to the diphenyl diethoxysilane is 1:3.5;
the mass ratio of the isopropanol to the diphenyl diethoxysilane is 1:0.25;
the mass ratio of diphenyldiethoxysilane to vinyltrimethoxysilane was 1:1.3.
The mass ratio of the barium sulfate physical brightening agent to the 1, 4-bis (2-cyanostyryl) benzene is 1:1.3.
The CAS registration number of the 1, 4-bis (2-cyanostyryl) benzene is 13001-39-3, the molecular formula is C24H16N2, the molecular weight is 332.3972, the melting point is 230-234 ℃, the temperature must be lower than that of flash spinning, or the solvent can volatilize in the spinning process, so that the expected whitening effect is achieved, and the reason is that a high-melting-point reagent is selected; this is also the solvent choice made by the spin temperature characteristics of flash spinning. Meanwhile, good compatibility between the 1, 4-bis (2-cyanostyryl) benzene and the solvent for flash spinning must be considered; the compatibility with the spinning solvent is good, so that the complexing agent is uniformly dispersed in the polyethylene, and the whitening effect of the complexing agent is better exerted. This is one consideration in selecting 1, 4-bis (2-cyanostyryl) benzene.
(2) And (3) carrying out flash spinning at 165 ℃ to obtain flash-spun fibers, forming a fiber web, and carrying out hot press molding on the fiber web by a roller at 125 ℃ to obtain the polyethylene sheet. Performance testing of the product as described for D65 fluorescence brightness (a D65 fluorescence brightness as described above), tensile strength (three tensile strengths as described above); testing data before aging, testing data after an aging test (the two aging processes) and respectively calculating the aging rate of D65 fluorescent brightness and the aging rate of tensile strength; specific test data are shown in table 1.
Comparative example 1
A preparation method of a polyethylene sheet comprises the following specific steps:
(1) Preparing spinning solution, which consists of solvent and polymer,
the solvent is 1,2, 3, 4-octafluorobutane;
the mass fraction of the polymer in the spinning solution is 13%;
the raw materials comprise polyethylene and complexing agent;
the mass fraction of the complexing agent in the polyethylene sheet is 0.2%.
The complexing agent is modified barium sulfate and a complex of 1, 4-bis (2-cyano styryl) benzene.
The preparation method of the complexing agent comprises the following specific steps:
adding barium sulfate into an aqueous solution of isopropanol, adding a magnesium chloride solution, adsorbing on the surface of the barium sulfate to generate magnesium hydroxide precipitate, filtering, drying and calcining to obtain modified barium sulfate; dispersing modified barium sulfate in isopropanol water solution of diphenyl diethoxy silane, adding vinyl trimethoxy silane, treating at 45-60 ℃ for 15-25 minutes, filtering, and vacuum drying filter residues to obtain a barium sulfate physical brightening agent; and grinding and mixing the barium sulfate physical brightening agent and 1, 4-bis (2-cyano styryl) benzene to obtain the complexing agent.
The volume ratio of the isopropanol to the water in the aqueous solution of the isopropanol is 1:1;
the mass fraction of barium sulfate in the aqueous solution of isopropanol is 5%;
the molar ratio of the barium sulfate to the magnesium chloride is 1:0.1;
the mass ratio of the modified barium sulfate to the diphenyl diethoxysilane is 1:2;
the mass ratio of the isopropanol to the diphenyl diethoxysilane is 1:0.15;
the mass ratio of diphenyldiethoxysilane to vinyltrimethoxysilane was 1:1.2.
The mass ratio of the barium sulfate physical brightening agent to the 1, 4-bis (2-cyanostyryl) benzene is 1:1.2.
(2) And (3) carrying out flash spinning at the spinning temperature of 135 ℃ to obtain flash fibers, forming a fiber web, and carrying out hot press molding on the fiber web by a roller at the hot press temperature of 100 ℃ to obtain the polyethylene sheet. Performance testing of the product as described for D65 fluorescence brightness (a D65 fluorescence brightness as described above), tensile strength (three tensile strengths as described above); testing data before aging, testing data after an aging test (the two aging processes) and respectively calculating the aging rate of D65 fluorescent brightness and the aging rate of tensile strength; specific test data are shown in table 1.
Comparative example 2
A preparation method of a polyethylene sheet comprises the following specific steps:
(1) Preparing spinning solution, which consists of solvent and polymer,
the solvent is 1,2, 3, 4-octafluorobutane;
the mass fraction of the polymer in the spinning solution is 13%;
the raw materials comprise polyethylene and complexing agent;
the mass fraction of the complexing agent in the polyethylene sheet is 0.05%.
The complexing agent is modified barium sulfate and a complex of 1, 4-bis (2-cyano styryl) benzene.
The preparation method of the complexing agent comprises the following specific steps:
adding barium sulfate into an aqueous solution of isopropanol, adding a magnesium chloride solution, adsorbing on the surface of the barium sulfate to generate magnesium hydroxide precipitate, filtering, drying and calcining to obtain modified barium sulfate; dispersing modified barium sulfate in isopropanol water solution of diphenyl diethoxy silane, adding vinyl trimethoxy silane, treating at 45-60 ℃ for 15-25 minutes, filtering, and vacuum drying filter residues to obtain a barium sulfate physical brightening agent; and grinding and mixing the barium sulfate physical brightening agent and 1, 4-bis (2-cyano styryl) benzene to obtain the complexing agent.
The volume ratio of the isopropanol to the water in the aqueous solution of the isopropanol is 1:1;
the mass fraction of barium sulfate in the aqueous solution of isopropanol is 5%;
the molar ratio of the barium sulfate to the magnesium chloride is 1:0.1;
the mass ratio of the modified barium sulfate to the diphenyl diethoxysilane is 1:2;
the mass ratio of the isopropanol to the diphenyl diethoxysilane is 1:0.15;
the mass ratio of diphenyldiethoxysilane to vinyltrimethoxysilane was 1:1.2.
The mass ratio of the barium sulfate physical brightening agent to the 1, 4-bis (2-cyanostyryl) benzene is 1:1.2.
(2) And (3) carrying out flash spinning at a spinning temperature of 150 ℃ to obtain flash fibers, forming a fiber web, and carrying out hot press molding on the fiber web by a roller at a hot press temperature of 120 ℃ to obtain the polyethylene sheet. Performance testing of the product as described for D65 fluorescence brightness (a D65 fluorescence brightness as described above), tensile strength (three tensile strengths as described above); testing data before aging, testing data after an aging test (the two aging processes) and respectively calculating the aging rate of D65 fluorescent brightness and the aging rate of tensile strength; specific test data are shown in table 1.
Comparative example 3
A preparation method of a polyethylene sheet comprises the following specific steps:
(1) Preparing spinning solution, which consists of solvent and polymer,
the solvent is 1,2, 3, 4-octafluorobutane;
the mass fraction of the polymer in the spinning solution is 13%;
the raw materials comprise polyethylene and complexing agent;
the mass fraction of the complexing agent in the polyethylene sheet is 0.2%.
The complexing agent is barium sulfate.
(2) And (3) carrying out flash spinning at a spinning temperature of 150 ℃ to obtain flash fibers, forming a fiber web, and carrying out hot press molding on the fiber web by a roller at a hot press temperature of 120 ℃ to obtain the polyethylene sheet. Performance testing of the product as described for D65 fluorescence brightness (a D65 fluorescence brightness as described above), tensile strength (three tensile strengths as described above); testing data before aging, testing data after an aging test (the two aging processes) and respectively calculating the aging rate of D65 fluorescent brightness and the aging rate of tensile strength; specific test data are shown in table 1.
Comparative example 4
A preparation method of a polyethylene sheet comprises the following specific steps:
(1) Preparing spinning solution, which consists of solvent and polymer,
the solvent is 1,2, 3, 4-octafluorobutane;
the mass fraction of the polymer in the spinning solution is 13%;
the raw materials comprise polyethylene and complexing agent;
the mass fraction of the complexing agent in the polyethylene sheet is 0.2%.
The complexing agent is 1, 4-bis (2-cyanostyryl) benzene.
(2) And (3) carrying out flash spinning at a spinning temperature of 150 ℃ to obtain flash fibers, forming a fiber web, and carrying out hot press molding on the fiber web by a roller at a hot press temperature of 120 ℃ to obtain the polyethylene sheet. Performance testing of the product as described for D65 fluorescence brightness (a D65 fluorescence brightness as described above), tensile strength (three tensile strengths as described above); testing data before aging, testing data after an aging test (the two aging processes) and respectively calculating the aging rate of D65 fluorescent brightness and the aging rate of tensile strength; specific test data are shown in table 1.
Comparative example 5
A preparation method of a polyethylene sheet comprises the following specific steps:
(1) Preparing spinning solution, which consists of solvent and polymer;
the solvent is 1,2, 3, 4-octafluorobutane;
the mass fraction of the polymer in the spinning solution is 13%;
the raw materials comprise polyethylene and complexing agent;
the mass fraction of the complexing agent in the polyethylene sheet is 0.2%.
The complexing agent is barium sulfate and 1, 4-bis (2-cyano styryl) benzene.
(2) And (3) carrying out flash spinning at a spinning temperature of 150 ℃ to obtain flash fibers, forming a fiber web, and carrying out hot press molding on the fiber web by a roller at a hot press temperature of 120 ℃ to obtain the polyethylene sheet. Performance testing of the product as described for D65 fluorescence brightness (a D65 fluorescence brightness as described above), tensile strength (three tensile strengths as described above); testing data before aging, testing data after an aging test (the two aging processes) and respectively calculating the aging rate of D65 fluorescent brightness and the aging rate of tensile strength; specific test data are shown in table 1.
Table 1 product performance test data sheet
| Aging rate of D65 fluorescent luminance | Aging rate of tensile Strength | |
| Example 1 | 0.189 | 0.287 |
| Example 2 | 0.158 | 0.252 |
| Example 3 | 0.102 | 0.213 |
| Example 4 | 0.067 | 0.187 |
| Example 5 | 0.055 | 0.125 |
| Comparative example 1 | 0.401 | 0.368 |
| Comparative example 2 | 0.387 | 0.401 |
| Comparative example 3 | 0.302 | 0.353 |
| Comparative example 4 | 0.263 | 0.332 |
| Comparative example 5 | 0.283 | 0.346 |
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the concept of the present invention, and are intended to be within the scope of the present invention.
Claims (2)
1. A polyethylene sheet, characterized in that the aging rate Δs of the tensile strength is 0.10 to 0.30;
△S=1-S2/S1；
s1 is the tensile strength of the unaged sheet, in kN/m;
s2 is the tensile strength of the sheet after aging treatment, and the unit is kN/m;
the aging treatment process conditions are as follows: irradiance of 60+ -2 w/m in the wavelength range of 300-400 nm 2 The black standard temperature is 65+/-2 ℃, the air temperature of the test bin is 38+/-3 ℃, the relative humidity is 50+/-10%, and the drying time is 1440 hours;
the preparation method of the polyethylene sheet comprises the following specific steps:
(1) Preparing spinning solution, which consists of solvent and polymer;
the solvent is 1,2, 3, 4-octafluorobutane;
a polyethylene sheet material comprising polyethylene and a complexing agent;
the mass fraction of the complexing agent in the polyethylene sheet is 0.1-0.3%;
the complexing agent is modified barium sulfate and a compound of 1, 4-bis (2-cyano styryl) benzene;
the preparation method of the complexing agent comprises the following specific steps:
adding barium sulfate into an aqueous solution of isopropanol, adding a magnesium chloride solution, adsorbing on the surface of the barium sulfate to generate magnesium hydroxide precipitate, filtering, drying and calcining to obtain modified barium sulfate; dispersing modified barium sulfate in isopropanol water solution of diphenyl diethoxy silane, adding vinyl trimethoxy silane, treating at 45-60 ℃ for 15-25 minutes, filtering, and vacuum drying filter residues to obtain a barium sulfate physical brightening agent; grinding and mixing the barium sulfate physical brightening agent and 1, 4-bis (2-cyano styryl) benzene to obtain a complexing agent;
(2) And (3) carrying out flash spinning on the spinning solution to obtain flash fibers, forming a fiber web, and carrying out hot press forming on the fiber web by a roller, wherein the hot press temperature is 110 ℃ or 115 ℃ or 120 ℃, so as to obtain the polyethylene sheet.
2. A polyethylene sheet according to claim 1, wherein the mass fraction of complexing agent in the polyethylene sheet is between 0.15 and 0.25%.
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