CN108570172B - ultrahigh molecular weight polyolefin swelling substance containing high boiling point solvent, and preparation method and application thereof - Google Patents

ultrahigh molecular weight polyolefin swelling substance containing high boiling point solvent, and preparation method and application thereof Download PDF

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CN108570172B
CN108570172B CN201710150873.4A CN201710150873A CN108570172B CN 108570172 B CN108570172 B CN 108570172B CN 201710150873 A CN201710150873 A CN 201710150873A CN 108570172 B CN108570172 B CN 108570172B
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molecular weight
boiling point
point solvent
ultrahigh molecular
polyolefin
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CN108570172A (en
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李化毅
张瑜
刘金凤
李倩
徐坚
孙同兵
朱才镇
赵宁
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Institute of Chemistry CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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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  • General Chemical & Material Sciences (AREA)
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  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

The invention provides ultrahigh molecular weight polyolefin swellables containing high boiling point solvent, a preparation method and application thereof, wherein the method comprises the following steps of 1) mixing ultrahigh molecular weight polyolefin resin, high boiling point solvent, low boiling point solvent and an antioxidant system to obtain a mixed material, 2) heating the mixed material in the step 1), cooling the system temperature to room temperature after the polyolefin resin is completely dissolved, 3) removing the low boiling point solvent through reduced pressure distillation to obtain the ultrahigh molecular weight polyolefin swellables containing the high boiling point solvent, wherein the weight percentage of the ultrahigh molecular weight polyolefin in the ultrahigh molecular weight polyolefin swellables is less than or equal to 100 wt%, the dissolution speed of the ultrahigh molecular weight polyolefin swellables is accelerated and the dissolution is uniform.

Description

ultrahigh molecular weight polyolefin swelling substance containing high boiling point solvent, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of polyolefin, and particularly relates to ultrahigh molecular weight polyolefin swelling substances containing high-boiling-point solvents, and a preparation method and application thereof.
Background
The ultra-high molecular weight polyolefin has the excellent characteristics of strong impact resistance, abrasion resistance, anti-adhesion capability and the like, and is widely applied to the fields of sports, spinning, mining, buildings and the like by , particularly, the ultra-high molecular weight polyethylene is thermoplastic engineering plastics with linear molecular chain segments and excellent comprehensive performance, the ultra-high molecular weight polyethylene fibers are high-strength fibers and wide in application, and are particularly suitable for preparing bulletproof clothes, the ultra-high molecular weight polyethylene fibers are prepared by a jelly spinning method, the method is that the ultra-high molecular weight polyethylene is dissolved to form gel at first and then is subjected to wet spinning to prepare the fibers, however, because the ultra-high molecular weight polyethylene has large molecular weight, the dissolution is very difficult, two adverse effects are easily caused, namely, , the dissolution time of the ultra-high molecular weight polyethylene is long, the ultra-high molecular weight polyethylene is easily degraded, and secondly, the.
Therefore, it is necessary to develop methods that can shorten the dissolution time and ensure that the properties of the ultrahigh molecular weight polyolefin are not reduced, so that the ultrahigh molecular weight polyolefin has better processability and more -range application prospects.
Disclosure of Invention
In order to solve the above problems, the present invention aims to provide kinds of ultrahigh molecular weight polyolefin swellables containing high boiling point solvent, and a preparation method and applications thereof.
Another objects of the present invention are to provide a method for preparing polyolefin fibers, wherein the swelling material of the ultrahigh molecular weight polyolefin containing the high boiling point solvent is used as a raw material.
The purpose of the invention is realized by the following technical scheme:
A process for preparing a swollen ultrahigh molecular weight polyolefin containing a high boiling point solvent, said process comprising the steps of:
1) mixing the ultrahigh molecular weight polyolefin resin, the high boiling point solvent, the low boiling point solvent and the antioxidant system to obtain a mixed material;
2) heating the mixed material in the step 1), and cooling the system temperature to room temperature after the polyolefin resin is completely dissolved;
3) then, removing the low-boiling point solvent by reduced pressure distillation to obtain an ultrahigh molecular weight polyolefin swelling material containing a high-boiling point solvent;
the weight percentage of the ultrahigh molecular weight polyolefin in the mixed material is more than 0 and less than or equal to 45 wt%.
According to the invention, the weight percentage of the ultrahigh molecular weight polyolefin in the mixed material is more than 0 and less than or equal to 30 wt%, preferably more than 0 and less than or equal to 20 wt%.
According to the invention, in step 1), said ultra-high molecular weight polyolefin is selected from ultra-high molecular weight polyethylene and its copolymers, its melting point is greater than 120 ℃, the weight average molecular weight is greater than 100 ten million grams/mole; or selected from ultra high molecular weight polypropylene and copolymers thereof, having a melting point greater than 150 ℃ and a weight average molecular weight greater than 80 micrograms/mole.
According to the invention, in step 1), the high-boiling solvent is selected from at least of straight-chain alkanes and cycloalkanes with boiling points greater than 200 ℃ and mixtures thereof (such as white oil), decahydronaphthalene, dichlorobenzene, trichlorobenzene, 1,1, 1-trichloroethane, preferably white oil.
According to the invention, in step 1), the low-boiling solvent is selected from or more of straight-chain alkane and cycloalkane with boiling point not more than 150 ℃ and the mixture thereof, toluene, xylene, trimethylbenzene, ethylbenzene and cumene, preferably toluene, xylene or the mixture of the two.
According to the invention, in step 1), the antioxidant system comprises (1) th primary antioxidant selected from or more of hindered phenols, (2) secondary antioxidant selected from or more of phosphites or thioesters, and (3) second primary antioxidant selected from or more of aminic antioxidants.
The mass charge ratio of the components in the system is primary antioxidant, 10-25 wt% of secondary antioxidant and 50-80 wt% of secondary primary antioxidant, 10-25 wt%, and the sum of the mass percentages of the components in the system is 100%.
According to the invention, in the step 1), the content of the antioxidant system in the mixture is more than 0 and less than or equal to 5 wt%, preferably more than 0 and less than or equal to 2.5 wt%, and more preferably more than 0 and less than or equal to 1 wt%, and the step is preferably 0.05 to 0.5 wt%, for example 0.1 to 0.3 wt%.
According to the invention, in the step 1), the mass ratio of the high boiling point solvent to the low boiling point solvent is 1 (1-50), preferably 1 (2-20), and more preferably 1 (3-10).
According to the invention, in the step 2), the heating temperature is 100-200 ℃, and the heating time is 20-180 min; preferably, the heating temperature is 130-190 ℃, and the heating time is 30-120 min.
According to the invention, in the step 3), the reduced pressure distillation temperature is 50-100 ℃, and the pressure is-0.2-0.01 MPa; for example, the temperature of the reduced pressure distillation is 85 ℃ and the pressure is-0.1 MPa.
According to the invention, in the step 3), the ultrahigh molecular weight polyolefin swelling material containing the high boiling point solvent is subjected to vacuum drying treatment; the temperature of the vacuum drying is 40-80 ℃, and the time is 6-18 h; for example, the temperature of the vacuum drying is 60 ℃ and the time is 12 h.
In the present invention, the purpose of the vacuum drying is to remove as much as possible the low boiling point solvent in the ultrahigh molecular weight polyolefin swollen product containing the high boiling point solvent to obtain a mixture containing only the high boiling point solvent, the antioxidant system and the polyolefin.
According to the present invention, filtration steps may be further included before the vacuum distillation operation in step 3), and the purpose of the filtration step is to remove part of the solvent in the system.
According to the invention, in step 3), the high boiling point solvent is contained in the obtained ultrahigh molecular weight polyolefin swollen matter containing the high boiling point solvent, and the content of the ultrahigh molecular weight polyolefin in the ultrahigh molecular weight polyolefin swollen matter containing the high boiling point solvent is more than 0 and less than or equal to 70 wt%, preferably more than 0 and less than or equal to 50 wt%.
The invention also provides ultrahigh molecular weight polyolefin swellers containing high boiling point solvent prepared by the above preparation method, which comprises:
a) the weight percentage of the ultrahigh molecular weight polyolefin is more than 0 and less than 100wt percent, preferably more than 0 and less than or equal to 50wt percent;
b) an antioxidant system, the weight percentage is more than 0 and less than or equal to 5wt percent, preferably more than 0 and less than or equal to 1.0wt percent;
c) the weight percentage of the high-boiling point solvent is more than 0 and less than 100wt percent, and preferably more than 0 and less than or equal to 50wt percent.
The invention also provides a preparation method of polyolefin fibers, wherein the ultrahigh molecular weight polyolefin swelling material containing the high boiling point solvent is used as a raw material.
According to the invention, the method comprises the following steps:
1) dissolving the ultrahigh molecular weight polyolefin swelling material containing the high boiling point solvent to form gel;
2) and obtaining the polyolefin fiber through wet spinning.
Preferably, the polyolefin is selected from the group consisting of ultra high molecular weight polyethylene and copolymers thereof, having a melting point greater than 120 ℃ and a weight average molecular weight greater than 100 micrograms/mole; or selected from ultra high molecular weight polypropylene and copolymers thereof, having a melting point greater than 150 ℃ and a weight average molecular weight greater than 80 micrograms/mole.
The invention also provides application of the ultrahigh molecular weight polyolefin swelling material containing the high boiling point solvent, which can be used for preparing polyolefin fibers and the like.
The invention has the beneficial effects that:
the invention provides ultrahigh molecular weight polyolefin swellables containing high boiling point solvent, a preparation method and application thereof, wherein the weight percentage of the ultrahigh molecular weight polyolefin in the ultrahigh molecular weight polyolefin swellables containing high boiling point solvent is less than 100 wt% (preferably less than or equal to 50 wt%), the ultrahigh molecular weight polyolefin swellables containing high boiling point solvent have the advantages of high dissolution speed and uniform dissolution, and are beneficial to preparing polyolefin fibers through wet spinning.
Detailed Description
As described above, the present invention provides methods for preparing an ultrahigh molecular weight polyolefin swellable mass containing a high boiling point solvent, the method comprising the steps of:
1) mixing the ultrahigh molecular weight polyolefin resin, the high boiling point solvent, the low boiling point solvent and the antioxidant system to obtain a mixed material;
2) heating the mixed material in the step 1), and cooling the system temperature to room temperature after the polyolefin resin is completely dissolved;
3) then, removing the low-boiling point solvent by reduced pressure distillation to obtain an ultrahigh molecular weight polyolefin swelling material containing a high-boiling point solvent;
the weight percentage of the ultrahigh molecular weight polyolefin in the mixed material is more than 0 and less than or equal to 45 wt%.
In preferred embodiments, filtration steps can be further included before the vacuum distillation operation in step 3), and the purpose of the filtration steps is to remove part of the solvent in the system.
In the antioxidant system of the present invention, the hindered phenol is selected from the group consisting of 2, 4-di-tert-butylphenol, 2, 6-di-tert-butylphenol, 2,4, 6-tri-tert-butylphenol, pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, triethylene glycol-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 4 '-thiobis (6-tert-butyl-3-methylphenol), isooctyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) bis (3, -diethylhexyl) acrylate, and a combination of two or more.
Preferably, the hindered phenol is selected from 2, 6-di-tert-butyl-4-methylphenol.
The phosphite ester is selected from or more than two of trinonyl phosphite, tris [2, 4-di-tert-butylphenyl ] phosphite, bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite, bis (2-methyl-4, 6-bis (1,1 '-dimethylethyl) phenol) ethyl phosphate, tetrakis (2, 4-di-tert-butyl octaalkoxy-4, 4-biphenyl) phosphate, tetrakis (2, 4-di-tert-butylphenyl-4, 4' -biphenyl) bisphosphate, 2 '-ethylidene bis (4, 6-di-tert-butylphenyl) fluorophosphite, carbyl-4, 4' -diiso-ylidene-aliphatic alcohol-phosphate, diphenyl isodecyl phosphite, triethyl phosphite, tributyl phosphite and trioctyl phosphite.
Preferably, the phosphite is selected from the group consisting of trinonyl phosphite.
The thioester is selected from the group consisting of didodecyl thiodipropionate, dioctadecyl thiodipropionate, ditetradecyl thiodipropionate and kinds or a mixture of two or more of thiodipropionate.
The amine antioxidant is selected from kinds or a mixture of two or more kinds of hydroxylamine, N ' -diaryl-p-phenylenediamine, N ' -diaryl butyl-p-phenylenediamine, N-aryl-N ' -alkyl-p-phenylenediamine (such as N-phenyl-N ' -cyclohexyl-p-phenylenediamine, N-phenyl-N ' -isopropyl-p-phenylenediamine, N-phenyl-N ' -isohexyl-p-phenylenediamine, N-phenyl-N-sec-butyl-p-phenylenediamine), 3, 5-diethyl-toluene-diamine, N-phenyl-2-naphthylamine, N-phenyl-1-naphthylamine, N ' -dialkyl-p-phenylenediamine (such as N, N ' -di-sec-butyl-p-phenylenediamine, N ' -bis (1, 4-dimethylpentyl) -p-phenylenediamine), dialkyl diphenylamine (such as diisooctyl diphenylamine, dinonyl diphenylamine), diaminotoluene derivatives, and 1, 8-diaminonaphthalene derivatives.
Preferably, the amine antioxidant is selected from N, N' -di-sec-butyl-p-phenylenediamine.
The invention is further illustrated at in conjunction with specific examples, it being understood that these examples are intended only to illustrate the invention and not to limit the scope of the invention.
In this example, the melting point of the selected ultra-high molecular weight polyethylene was 140 ℃ and the weight average molecular weight was greater than 80 micrograms/mole.
In this example, the melting point of the selected ultra-high molecular weight polypropylene was 180 ℃ and the weight average molecular weight was greater than 100 million g/mole.
In the embodiment, the selected antioxidant system is selected from 25 wt% of hindered phenol 2, 6-di-tert-butyl-4-methylphenol as a main antioxidant, 50 wt% of phosphite ester or thioester tritonyl phosphite as an auxiliary antioxidant, and 25 wt% of amine antioxidants 2, 6-di-tert-butyl-4-methylphenol as a main antioxidant.
Example 1 ultra high molecular weight polyethylene swell containing high boiling point solvent (high and low boiling point solvents in a mass ratio of 1:9)
Mixing white oil and toluene uniformly according to the mass ratio of 1:9, namely taking 8g of white oil and 72g of toluene. Adding 2g of ultra-high molecular weight polyethylene and an antioxidant system with the mass of 0.25 percent of the whole system into the mixed solvent; refluxing and dissolving at 140 ℃, completely dissolving the ultrahigh molecular weight polyethylene after about 45min, and cooling the system to room temperature; filtering to remove part of the solvent, removing the low boiling point solvent by reduced pressure distillation (at 80 ℃ and under the condition of-0.1 MPa), and vacuum drying (at 60 ℃ and for 12h) to obtain the ultrahigh molecular weight polyethylene swelling material containing the high boiling point solvent, wherein the total mass of the swelling material is about 5 g.
Wherein the content of the ultra-high molecular weight polyethylene in the ultra-high molecular weight polyethylene swollen product containing the high boiling point solvent prepared in example 1 was 40 wt%. The ultra-high molecular weight polyethylene swell containing high boiling point solvent has a melting temperature of 119.76 ℃ and a crystallization temperature of 104.46 ℃.
1g of the ultrahigh-molecular-weight polyethylene swollen product containing the high-boiling-point solvent prepared in example 1 was dissolved in 10g of white oil, and the solution was dissolved by heating at 140 ℃ for about 30 minutes, whereby the ultrahigh-molecular-weight polyethylene swollen product containing the high-boiling-point solvent was dissolved in the white oil.
Example 2 ultra high molecular weight polyethylene swell containing high boiling point solvent (high and low boiling point solvents in a mass ratio of 1:7)
Mixing white oil and toluene at a mass ratio of 1:7, namely taking 10g of white oil and 70g of toluene. Adding 2g of ultra-high molecular weight polyethylene and an antioxidant system with the mass of 0.25 wt% of the whole system into the mixed solvent; refluxing and dissolving at 140 ℃, completely dissolving the ultrahigh molecular weight polyethylene after about 45min, and cooling the system to room temperature; filtering to remove part of the solvent, removing the low boiling point solvent by reduced pressure distillation (at 80 ℃ and under the condition of-0.1 MPa), and vacuum drying (at 60 ℃ and for 12h) to obtain the ultrahigh molecular weight polyethylene swelling material containing the high boiling point solvent, wherein the total mass of the swelling material is about 5 g.
Wherein the content of the ultra-high molecular weight polyethylene in the ultra-high molecular weight polyethylene swollen product containing the high boiling point solvent prepared in example 2 was 40 wt%. The ultra-high molecular weight polyethylene swelling material containing the high-boiling point solvent has the melting temperature of 121.37 ℃ and the crystallization temperature of 105.65 ℃.
1g of the ultrahigh-molecular-weight polyethylene swollen product containing the high-boiling-point solvent prepared in example 2 was dissolved in 10g of white oil, and the solution was dissolved by heating at 140 ℃ for about 30 minutes, whereby the ultrahigh-molecular-weight polyethylene swollen product containing the high-boiling-point solvent was dissolved in the white oil.
Example 3 ultra high molecular weight polyethylene swell containing high boiling point solvent (high and low boiling point solvents in a mass ratio of 1:5)
The white oil and the toluene are uniformly mixed according to the mass ratio of 1:5, namely 14g of white oil and 70g of toluene are taken. Adding 2g of ultra-high molecular weight polyethylene and an antioxidant system with the mass of 0.25 wt% of the whole system into the mixed solvent; refluxing and dissolving at 140 ℃, completely dissolving the ultrahigh molecular weight polyethylene after about 45min, and cooling the system to room temperature; filtering to remove part of the solvent, removing the low boiling point solvent by reduced pressure distillation (at 80 ℃ and under the condition of-0.1 MPa), and vacuum drying (at 60 ℃ and for 12h) to obtain the ultrahigh molecular weight polyethylene swelling material containing the high boiling point solvent, wherein the total mass of the ultrahigh molecular weight polyethylene swelling material is about 8 g.
Wherein the content of the ultra-high molecular weight polyethylene in the ultra-high molecular weight polyethylene swollen product containing the high boiling point solvent prepared in example 3 was 25 wt%. The ultra-high molecular weight polyethylene swelling material containing the high-boiling point solvent has the melting temperature of 119.19 ℃ and the crystallization temperature of 103.73 ℃.
1g of the ultrahigh-molecular-weight polyethylene swollen product containing the high-boiling-point solvent prepared in example 3 was dissolved in 10g of white oil, and the solution was dissolved by heating at 140 ℃ for about 20 minutes, whereby the ultrahigh-molecular-weight polyethylene swollen product containing the high-boiling-point solvent was dissolved in the white oil.
Example 4 swelling Material of ultra-high molecular weight Polypropylene containing high boiling solvent (high and low boiling solvents in a mass ratio of 1:9)
The preparation method of the ultrahigh molecular weight polypropylene swollen matter containing the high boiling point solvent is the same as that of example 1, except that the ultrahigh molecular weight polyethylene is replaced by the ultrahigh molecular weight polypropylene, and the reflux dissolution at 140 ℃ is replaced by the reflux dissolution at 180 ℃.
Wherein the content of the ultrahigh molecular weight polypropylene in the ultrahigh molecular weight polypropylene swollen product containing the high boiling point solvent prepared in example 4 was 40% by weight.
1g of the dried ultrahigh molecular weight polypropylene swollen product containing the high boiling point solvent prepared in example 4 was dissolved in 10g of white oil, and the solution was heated at 180 ℃ for about 30 minutes to dissolve the ultrahigh molecular weight polypropylene swollen product containing the high boiling point solvent in the white oil.
Example 5 swelling Material of ultra-high molecular weight Polypropylene containing high boiling solvent (high and low boiling solvents in a mass ratio of 1:7)
The preparation method of the ultrahigh molecular weight polypropylene swelling material containing the high boiling point solvent is the same as that of example 2, except that the ultrahigh molecular weight polyethylene is replaced by the ultrahigh molecular weight polypropylene, and the reflux dissolution at 140 ℃ is replaced by the reflux dissolution at 180 ℃.
Wherein the content of the ultrahigh molecular weight polypropylene in the ultrahigh molecular weight polypropylene swollen product containing the high boiling point solvent prepared in example 5 was 40% by weight.
1g of the dried ultrahigh molecular weight polypropylene swollen product containing the high boiling point solvent prepared in example 5 was dissolved in 10g of white oil, and the solution was heated at 180 ℃ for about 30 minutes to dissolve the ultrahigh molecular weight polypropylene swollen product containing the high boiling point solvent in the white oil.
Example 6 swelling Material of ultra-high molecular weight Polypropylene containing high boiling solvent (high and low boiling solvents in a mass ratio of 1:5)
The preparation method of the ultrahigh molecular weight polypropylene swollen matter containing the high boiling point solvent is the same as that of example 3, except that the ultrahigh molecular weight polyethylene is replaced by the ultrahigh molecular weight polypropylene, and the reflux dissolution at 140 ℃ is replaced by the reflux dissolution at 180 ℃.
Wherein the content of the ultrahigh molecular weight polypropylene in the ultrahigh molecular weight polypropylene swollen product containing the high boiling point solvent prepared in example 6 was 25% by weight.
1g of the dried ultrahigh molecular weight polypropylene swollen product containing the high boiling point solvent prepared in example 6 was dissolved in 10g of white oil, and the solution was heated at 180 ℃ for about 20 minutes to dissolve the ultrahigh molecular weight polypropylene swollen product containing the high boiling point solvent in the white oil.
Comparative example 1
2g of ultra-high molecular weight polyethylene is directly dissolved in 30g of white oil, stirred at the temperature of 140 ℃, and after 3 hours, the ultra-high molecular weight polyethylene is dissolved in the white oil.
Comparative example 2
2g of ultrahigh molecular weight polypropylene is directly dissolved in 30g of white oil, stirred at 180 ℃, and after 3 hours, the ultrahigh molecular weight polypropylene is dissolved in the white oil.
Comparative example 3
Mixing white oil and toluene uniformly according to the mass ratio of 1:9, namely taking 8g of white oil and 72g of toluene. Adding 2g of ultra-high molecular weight polyethylene and an antioxidant system with the mass of 0.25 percent of the whole system into the mixed solvent; stirring uniformly, distilling at 85 ℃, removing low-boiling point solvent, and vacuum drying (60 ℃, drying for 12h) to obtain a solid-liquid mixture of white oil and polyethylene, wherein the mass percentage of the polyethylene is 20 wt%.
1g of the solid-liquid mixture of the white oil prepared in comparative example 3 and polyethylene was dissolved in 10g of the white oil, and the mixture was dissolved by heating at 140 ℃ for about 100 minutes to dissolve the polyethylene in the white oil.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (21)

  1. A process for preparing ultrahigh molecular weight polyolefin swellables containing high boiling point solvents, characterized in that said process comprises the steps of:
    1) mixing ultrahigh molecular weight polyolefin resin, a high boiling point solvent, a low boiling point solvent and an antioxidant system to obtain a mixed material, wherein the mass percentage of the ultrahigh molecular weight polyolefin in the mixed material is more than 0 and less than or equal to 45 wt%, the mass percentage of the antioxidant system in the mixed material is more than 0 and less than or equal to 5 wt%, the high boiling point solvent is at least selected from straight chain alkane and cycloalkane with the boiling point of more than 200 ℃ and a mixture thereof, and trichlorobenzene, the low boiling point solvent is or more selected from straight chain alkane and cycloalkane with the boiling point of not more than 150 ℃ and a mixture thereof, toluene, xylene and ethylbenzene, and the mass ratio of the high boiling point solvent to the low boiling point solvent is 1 (1-50);
    2) heating the mixed material in the step 1), and cooling the system temperature to room temperature after the polyolefin resin is completely dissolved;
    3) then, removing the low-boiling point solvent by reduced pressure distillation to obtain an ultrahigh molecular weight polyolefin swelling material containing a high-boiling point solvent; the weight percentage of the ultrahigh molecular weight polyolefin in the ultrahigh molecular weight polyolefin swelling material containing the high boiling point solvent is more than 0 and less than or equal to 50 wt%, the weight percentage of the antioxidant system is more than 0 and less than or equal to 5 wt%, the weight percentage of the high boiling point solvent is more than 0 and less than 100 wt%, and the sum of the weight percentages of all the components is 100 wt%.
  2. 2. The method according to claim 1, wherein the content of the ultrahigh molecular weight polyolefin in the mixture is greater than 0 and equal to or less than 30 wt%.
  3. 3. The method according to claim 2, wherein the weight percentage of the ultrahigh molecular weight polyolefin in the mixed material is greater than 0 and less than or equal to 20 wt%.
  4. 4. The method of claim 1, wherein in step 1), the ultra-high molecular weight polyolefin is selected from the group consisting of ultra-high molecular weight polyethylene and copolymers thereof, having a melting point of greater than 120 ℃ and a weight average molecular weight of greater than 100 micrograms/mole; or selected from ultra high molecular weight polypropylene and copolymers thereof, having a melting point greater than 150 ℃ and a weight average molecular weight greater than 80 micrograms/mole.
  5. 5. The method according to claim 1, wherein in step 1), the high-boiling solvent is at least selected from white oil and trichlorobenzene.
  6. 6. The method of claim 5, wherein the high boiling point solvent is selected from white oils.
  7. 7. The method according to claim 1, wherein in step 1), the low boiling solvent is selected from toluene, xylene or a mixture of the two.
  8. 8. The method according to claim 1, wherein in step 1), the antioxidant system comprises (1) th primary antioxidant selected from or more of hindered phenols, (2) secondary antioxidant selected from or more of phosphites or thioesters, and (3) second primary antioxidant selected from or more of aminic antioxidants;
    the antioxidant system comprises th main antioxidant, 10-25 wt% of auxiliary antioxidant and 50-80 wt% of second main antioxidant, wherein the mass ratio of the components in the antioxidant system is 10-25 wt%, and the sum of the mass percentages of the components in the system is 100%.
  9. 9. The preparation method of claim 1, wherein in the step 1), the content of the antioxidant system in the mixture is greater than 0 and less than or equal to 2.5 wt%, or greater than 0 and less than or equal to 1 wt%, or 0.05 to 0.5 wt%, or 0.1 to 0.3 wt%.
  10. 10. The preparation method according to claim 1, wherein in the step 1), the mass ratio of the high boiling point solvent to the low boiling point solvent is 1 (2-20), or 1 (3-10).
  11. 11. The method according to any of claims 1-10, wherein the heating temperature in step 2) is 100-200 ℃ and the heating time is 20-180 min.
  12. 12. The method according to claim 11, wherein the heating temperature is 130 to 190 ℃ and the heating time is 30 to 120 min.
  13. 13. The method according to any of claims 1-10, wherein the vacuum distillation temperature in step 3) is 50-100 ℃, and the pressure is-0.1-0.01 MPa.
  14. 14. The method according to claim 13, wherein the reduced pressure distillation is carried out at a temperature of 85 ℃ and a pressure of-0.1 MPa.
  15. 15. The method according to any of claims 1-10, wherein in step 3), the swollen product of ultrahigh molecular weight polyolefin containing high boiling point solvent is further subjected to vacuum drying at 40-80 ℃ for 6-18 h.
  16. 16. The method according to any of of claim 1 to 10, wherein filtration steps are further included before the vacuum distillation operation in step 3), and the purpose of the filtration steps is to remove a part of the solvent in the system.
  17. 17, ultra-high molecular weight polyolefin swellables containing high boiling point solvent prepared by the method of any of claims 1-16, wherein the swellables contain:
    a) the weight percentage of the ultrahigh molecular weight polyolefin is more than 0 and less than or equal to 50 wt%;
    b) an antioxidant system, the weight percentage is more than 0 and less than or equal to 5 wt%;
    c) a high boiling point solvent, the weight percentage is more than 0 and less than 100 wt%;
    wherein the sum of the weight percentages of the components is 100 wt%.
  18. 18. The ultrahigh molecular weight polyolefin swell according to claim 17 wherein the weight percentage of antioxidant system in the swell is greater than 0 and equal to or less than 1.0 wt%.
  19. A process for preparing polyolefin fibers from polyolefin fibers of 19, , wherein the process comprises starting from a swollen ultrahigh molecular weight polyolefin of any of claims 1 to 16 or of claim 17 or 18 containing a high boiling solvent.
  20. 20. The method for preparing according to claim 19, characterized in that it comprises the following steps:
    1) dissolving the ultrahigh molecular weight polyolefin swelling material containing the high boiling point solvent to form gel;
    2) and obtaining the polyolefin fiber through wet spinning.
  21. 21. Use of an ultrahigh molecular weight polyolefin swell containing high boiling point solvent as prepared according to any of claims in claims 1 to 16 or as described in claim 17 or 18 for the preparation of polyolefin fibres.
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CN1332812A (en) * 1998-10-28 2002-01-23 Dsm有限公司 Highly oriented polyolefin fibre

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