CN112301452A - Preparation method of photochromic ultrahigh molecular weight polyethylene fiber - Google Patents
Preparation method of photochromic ultrahigh molecular weight polyethylene fiber Download PDFInfo
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- CN112301452A CN112301452A CN202011216633.8A CN202011216633A CN112301452A CN 112301452 A CN112301452 A CN 112301452A CN 202011216633 A CN202011216633 A CN 202011216633A CN 112301452 A CN112301452 A CN 112301452A
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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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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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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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Abstract
The invention relates to a preparation method of photochromic ultrahigh molecular weight polyethylene fibers, which comprises the following steps: 1) mixing a photochromic matrix, a formaldehyde solution and water, adjusting the pH value to 7.6-8.2, standing after complete dissolution, adding a sodium dodecyl sulfate solution, and stirring to obtain a prepolymer solution; 2) performing encapsulation reaction, mixing the prepolymer solution and the polyvinyl alcohol solution, adjusting the pH value to 6-6.4, stirring, adjusting the pH value to 4-4.4, heating to 75-85 ℃, preserving heat, washing with water after the reaction is finished, and drying to obtain photochromic microcapsules; 3) the preparation method comprises the steps of mixing and swelling the ultra-high molecular weight polyethylene solution and the photochromic microcapsules, keeping the temperature at 35-75 ℃ to form a spinning fluid, extruding, extracting and stretching to obtain the photochromic ultra-high molecular weight polyethylene fiber, wherein the photochromic ultra-high molecular weight polyethylene fiber has a stable structure and good quality, can be photochromic for 1 ten thousand times, is sensitive to light and has the identification precision of 10 mm.
Description
Technical Field
The invention belongs to the technical field of ultra-high molecular weight polyethylene fibers, and particularly relates to a preparation method of photochromic ultra-high molecular weight polyethylene fibers.
Background
In more than 100 years after the advent of photochromic materials and technology, photochromic materials are receiving more and more attention due to the characteristic that the photochromic materials can generate color change after being excited by a light source, and are being applied to the fields of intelligent anti-counterfeiting, information storage, textiles, daily necessities, characteristic photosensitive materials and the like. However, if the photochromic material is directly exposed to natural environments such as visible light for a long time, it is easily affected by the environment such as temperature, pH, oxygen, etc., and finally, the photochromic performance is deteriorated or unstable, or even lost.
In patent CN101225296A, lifepo guang ling et al used in situ polymerization to encapsulate photochromic compound solution in melamine-formaldehyde resin to prepare photochromic microcapsules, which isolated the photochromic material from the external environment, effectively protected the photochromic material and also achieved permanent solidification of the photochromic material. However, the organic solvents adopted by the organic solvents are benzene, ethanol, toluene, tetrachloroethylene or carbon tetrachloride and the like with low boiling point and strong toxicity, which are easy to cause harm to human bodies or environment and limit the application of the organic solvents to a certain extent. More importantly, the capsule with the single core-shell structure wrapping the liquid capsule core has poor mechanical property and thermal stability, so that the application of the capsule in the field of polymer processing is limited. Zhanyan et al prepared a photochromic microcapsule with double-layer wall in patent CN102886233A, which firstly encapsulated photochromic materials with vinyl monomers for the first time, and then encapsulated the photochromic materials with etherified amino resin for the second time on the surface by an in-situ polymerization method, and finally obtained the double-shell microcapsule with double-layer coating structure. The method still has the defects of poor thermal stability and mechanical property in the patent CN101225296A, and also needs a complex double-layer coating process, which is not beneficial to large-scale production.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of photochromic ultrahigh molecular weight polyethylene fibers, which has stable structure and good quality, can photochromically reach 10000 times, is sensitive to light and has the identification precision of 10 mm.
The invention relates to a preparation method of photochromic ultrahigh molecular weight polyethylene fiber, which comprises the following steps:
1) preparation of prepolymer solution
Mixing a photochromic matrix, a formaldehyde solution and water, adjusting the pH value to 7.6-8.2, standing for a period of time after the photochromic matrix is completely dissolved, adding a sodium dodecyl sulfate solution, and stirring to obtain a prepolymer solution;
the photochromic matrix is a color-changing material, the formaldehyde solution is favorable for dissolving the photochromic matrix, and the sodium dodecyl sulfate is used as an anionic surfactant and is favorable for the next reaction of the photochromic matrix.
2) Encapsulation reactions
Mixing the prepolymer solution and the polyvinyl alcohol solution, adjusting the pH value to 6-6.4, stirring, adjusting the pH value to 4-4.4, heating to 75-85 ℃, preserving heat, washing with water after the reaction is finished, and drying to obtain photochromic microcapsules;
the prepolymer solution is the main body of the reaction, and the polyvinyl alcohol solution is the key for influencing the appearance and the particle size distribution of the photochromic capsules.
3) Preparation of photochromic ultrahigh molecular weight polyethylene fiber
Mixing the ultrahigh molecular weight polyethylene solution and the photochromic microcapsules, swelling, keeping the temperature at 35-75 ℃ to form spinning fluid, extruding, extracting and stretching to obtain the photochromic ultrahigh molecular weight polyethylene fiber.
In the step 1), the photochromic matrix is one or more of spiropyran compounds, spirooxazine compounds, dithizone compounds and phenoxy naphthonaphthonaphthoquinone compounds.
In the step 1), after the pH value is adjusted to 7.6-8.2, standing for a period of time, heating to 70 ℃, and preserving heat to completely dissolve the photochromic matrix.
In the step 1), the weight concentration of the sodium dodecyl sulfate solution is 15-18%.
In the step 1), the weight ratio of the photochromic matrix to the formaldehyde solution is 3-7: 100.
the weight concentration of the polyvinyl alcohol solution in the step 2) is 12-15%.
The volume ratio of the prepolymer solution to the polyvinyl alcohol solution in step 2) is 4: 1.
And the step of washing in the step 2) is that the product after the reaction is finished sequentially passes through two washing tanks, the temperature of the first water bath tank is 50-55 ℃, the temperature of the second water bath tank is 40-45 ℃, and the retention time is 5 minutes.
The weight concentration of the ultra-high molecular weight polyethylene solution is 15.8-18.9%.
The weight ratio of the ultra-high molecular weight polyethylene solution to the photochromic microcapsules is (45-65): 1.
The beneficial effect of the invention is that,
(1) the photochromic polyethylene prepared by the method has stable structure and good performance.
(2) The photochromic ultrahigh molecular weight polyethylene fiber prepared by the method is sensitive to light, the identification precision is 10mm, and the identification precision is improved by 10% compared with that of the traditional process.
(3) The photochromic ultrahigh molecular weight polyethylene fiber prepared by the method has good quality and can be photochromic for 10000 times.
Detailed Description
Example 1
A preparation method of photochromic ultrahigh molecular weight polyethylene fiber comprises the following steps:
preparation of photochromic microcapsules
(1) Preparation of prepolymer solution
Weighing a certain mass of photochromic matrix (one of spiropyrans, spirooxazines, dithizones and phenoxy naphthoquinones), weighing a certain volume of formaldehyde solution, adding a certain volume of deionized water (the volume ratio of the formaldehyde solution to the deionized water is 1:2, and the concentration of the formaldehyde solution is 30% -40%), adding the mixture into a reaction kettle, adjusting the pH value of the reaction system to 7.6-8.2 by using an alkaline solution, and stirring and mixing. Standing for 1-1.5 hours, heating to 70 ℃ within 15 minutes, keeping the temperature for reaction for 2-2.5 hours to completely dissolve the photochromic matrix, standing for 1-1.2 hours, adding a sodium dodecyl sulfate solution with a certain volume and concentration, and stirring for a certain time to obtain a prepolymer solution. (the volume ratio of the formaldehyde solution to the deionized water: sodium dodecyl sulfate is 1:2: 1.6; the concentration of the formaldehyde solution is 30% -40%, the concentration of the sodium dodecyl sulfate solution is 15% -18%, and the stirring speed is more than or equal to 1000 rpm).
(2) Encapsulation reactions
Adding PVA solution with certain concentration and volume as dispersant (the concentration is 12-15%, the volume is one fourth of the prepolymer solution), adjusting the pH of the reaction system to 6.0-6.4 by using acid substances, mechanically stirring at a certain rotation speed for a certain time (the rotation speed is 1200-1600rpm, the time is 30-40 minutes) at room temperature, adjusting the pH value of the reaction system to 4.0-4.4, heating the reaction system to 75-85 ℃, and carrying out heat preservation reaction for 2.5-3 hours. After the reaction is finished, the sample is washed twice through a first water bath and a second water bath (the temperature of the first water bath is 50-55 ℃, the temperature of the second water bath is 40-45 ℃, the retention time is 5 minutes), and the sample is taken out of the water bath and dried to obtain the photochromic microcapsule.
Secondly, photochromic ultra-high molecular weight polyethylene fiber and preparation thereof:
preparing an ultra-high molecular weight polyethylene solution according to a conventional method, mixing the ultra-high molecular weight polyethylene solution and photochromic microcapsules in a swelling kettle according to a mass ratio of 65: 1-45: 1, continuously stirring, heating to 35-75 ℃, and keeping the temperature for 1-1.2 hours to form a spinning fluid, wherein the mass percentage of the ultra-high molecular weight polyethylene is 15.8-18.9%; spinning fluid is injected into the jelly precursor obtained by the double-screw extruder from the blanking kettle; and then the ultrahigh molecular weight polyethylene fiber with photochromic effect is prepared through the processes of extraction, super-drawing and the like.
Example 2
A preparation method of photochromic ultrahigh molecular weight polyethylene fiber comprises the following steps:
preparation of photochromic microcapsules
(1) Preparation of prepolymer solution
Weighing a certain mass of photochromic matrix (spiropyran), weighing a certain volume of formaldehyde solution, adding a certain volume of deionized water (the volume ratio of the formaldehyde solution to the deionized water is 1:2, the concentration of the formaldehyde solution is 30%), adding the mixture into a reaction kettle, adjusting the pH value of a reaction system to 8 by using an alkaline solution (sodium hydroxide solution), and stirring and mixing. Standing for 1 hour, heating to 70 ℃ within 15 minutes, keeping the temperature for reaction for 2.5 hours, completely dissolving the photochromic matrix, standing for 1 hour, adding a sodium dodecyl sulfate solution with a certain volume and concentration, and stirring for a certain time to obtain a prepolymer solution. (the volume ratio of the formaldehyde solution to the deionized water: sodium dodecyl sulfate is 1:2: 1.6; the concentration of the formaldehyde solution is 30%, the weight concentration of the sodium dodecyl sulfate solution is 15-18%, and the stirring speed is more than or equal to 1000 rpm).
(2) Encapsulation reactions
Adding PVA solution with certain concentration and volume into the prepared prepolymer solution as a dispersing agent (the weight concentration is 12 percent, and the volume is one fourth of the prepolymer solution), adjusting the pH value of a reaction system to be 6.0-6.4 by using an acidic substance (hydrochloric acid solution), mechanically stirring for a certain time (the rotating speed is 1200rpm, the time is 40 minutes) at a certain rotating speed under the condition of room temperature, adjusting the pH value of the reaction system to be 4.0-4.4, simultaneously heating the reaction system to 75-85 ℃, and preserving the temperature for reaction for 3 hours. After the reaction is finished, the sample is washed twice through a first water bath and a second water bath (the temperature of the first water bath is 55 ℃, the temperature of the second water bath is 40 ℃, the retention time is 5 minutes), and the sample is taken out of the water bath and dried to obtain the photochromic microcapsules.
Secondly, photochromic ultra-high molecular weight polyethylene fiber and preparation thereof:
preparing an ultra-high molecular weight polyethylene solution according to a conventional method, mixing the ultra-high molecular weight polyethylene solution and photochromic microcapsules in a swelling kettle according to the mass ratio of 50:1, continuously stirring, heating to 50 ℃, and preserving heat for 1.2 hours to form a spinning fluid, wherein the mass percentage of the ultra-high molecular weight polyethylene is 18%; spinning fluid is injected into the jelly precursor obtained by the double-screw extruder from the blanking kettle; and then the ultrahigh molecular weight polyethylene fiber with photochromic effect is prepared through the processes of extraction, super-drawing and the like.
Comparative example 1
Compared with the example 2, the difference lies in that:
(1) preparation of prepolymer solution
The difference is that in comparative example 1, the spiropyran, the formaldehyde solution, the deionized water and the sodium dodecyl sulfate solution are directly mixed, the pH value is adjusted to 8, the temperature is kept for 2.5 hours at the temperature of 70 ℃, the mixture is kept still for 1 hour, and a prepolymer solution is obtained, wherein the contents and the concentrations of the spiropyran, the formaldehyde solution, the deionized water and the sodium dodecyl sulfate solution are the same as those in example 2.
The other steps are the same as in example 2.
Comparative example 2
Comparative example 2 differs from example 2 in that:
(2) encapsulation reaction, comparative example 2 comprises the steps of:
adding PVA solution with certain concentration and volume into the prepared prepolymer solution as a dispersing agent (the weight concentration is 12 percent, and the volume is one fourth of the prepolymer solution), adjusting the pH of the reaction system to 4.0-4.4 by using an acidic substance (hydrochloric acid solution), heating the reaction system to 75-85 ℃, and carrying out heat preservation reaction for 3 hours. After the reaction is finished, the sample is washed twice through a water bath (the temperature of the water bath is 50 ℃, the retention time is 10 minutes), and the sample is taken out of the water bath and dried to obtain the photochromic microcapsule.
The other steps are the same as in example 2.
Experimental example 1
Placing the ultra-high molecular weight polyethylene fiber with photochromic effect prepared under different process conditions in an oven, drying at 60-70 ℃, measuring the mass of the fiber at certain intervals, reducing the mass of a sample along with the prolonging of the drying time, and obtaining the weight loss rate through the mass change before and after drying. The weight loss ratio of example 2 is 8-10%, the weight loss ratio of comparative example 1 is 20-25%, and the weight loss ratio of comparative example 2 is 22-28%, which proves that the structure of example 2 is stable.
Placing the ultra-high molecular weight polyethylene fiber with photochromic effect prepared under different process conditions in a darkroom, arranging a light source, and shielding the fiber and the light source by using light shielding plates with different aperture sizes, wherein the experiment proves that: the ultra-high molecular weight polyethylene fiber with photochromic effect prepared in example 2 can change color when the pore size is 2mm, the pore size of the fiber prepared in comparative example 1 is 10mm, and the pore size of the fiber prepared in comparative example 1 is 20 mm.
The photochromic times experiment was performed under the condition that a light shielding plate of 20mm was repeatedly opened, the photochromic times of the ultra-high molecular weight polyethylene fiber having the photochromic effect obtained in example 2 were more than 1 ten thousand times, the photochromic times of the fiber obtained in comparative example 1 were 5 thousand times, and the photochromic times of the fiber obtained in comparative example 2 were 8 thousand times.
Claims (10)
1. A preparation method of photochromic ultrahigh molecular weight polyethylene fibers is characterized by comprising the following steps:
1) preparation of prepolymer solution
Mixing a photochromic matrix, a formaldehyde solution and water, adjusting the pH value to 7.6-8.2, standing for a period of time after the photochromic matrix is completely dissolved, adding a sodium dodecyl sulfate solution, and stirring to obtain a prepolymer solution;
2) encapsulation reactions
Mixing the prepolymer solution and the polyvinyl alcohol solution, adjusting the pH value to 6-6.4, stirring, adjusting the pH value to 4-4.4, heating to 75-85 ℃, preserving heat, washing with water after the reaction is finished, and drying to obtain photochromic microcapsules;
3) preparation of photochromic ultrahigh molecular weight polyethylene fiber
Mixing the ultrahigh molecular weight polyethylene solution and the photochromic microcapsules, swelling, keeping the temperature at 35-75 ℃ to form spinning fluid, extruding, extracting and stretching to obtain the photochromic ultrahigh molecular weight polyethylene fiber.
2. The method of claim 1, wherein the photochromic ultrahigh molecular weight polyethylene fiber is prepared by using one or more compounds selected from the group consisting of spiropyrans, spirooxazines, dithizones and phenoxynaphthacenequinone as the photochromic matrix in step 1).
3. The method for preparing photochromic ultrahigh molecular weight polyethylene fiber according to claim 1 or 2, wherein in the step 1), after adjusting the pH to 7.6 to 8.2, the fiber is left for a while, heated to 70 ℃, and kept warm to completely dissolve the photochromic matrix.
4. The method for preparing photochromic ultrahigh molecular weight polyethylene fiber according to claim 1 or 2, wherein the weight concentration of the sodium lauryl sulfate solution in the step 1) is 15 to 18%.
5. The method for preparing photochromic ultrahigh molecular weight polyethylene fiber according to claim 1 or 2, wherein in the step 1), the weight ratio of the photochromic matrix to the formaldehyde solution is 3-7: 100.
6. the method of preparing photochromic ultra-high molecular weight polyethylene fiber according to claim 1, wherein the concentration of the polyvinyl alcohol solution in the step 2) is 12-15% by weight.
7. The method of preparing photochromic ultra-high molecular weight polyethylene fiber according to claim 1 or 6, wherein the volume ratio of the prepolymer solution to the polyvinyl alcohol solution in the step 2) is 4: 1.
8. The method for preparing photochromic ultra-high molecular weight polyethylene fibers according to claim 1 or 6, wherein the step of washing in the step 2) is to pass the product after the reaction through two washing tanks in sequence, the temperature of the first water bath is 50-55 ℃, the temperature of the second water bath is 40-45 ℃, and the retention time is 5 minutes.
9. The method of preparing a photochromic ultra-high molecular weight polyethylene fiber according to claim 1, wherein the weight concentration of the ultra-high molecular weight polyethylene solution is 15.8 to 18.9%.
10. The method for preparing photochromic ultrahigh molecular weight polyethylene fiber according to claim 1 or 9, wherein the weight ratio of the ultrahigh molecular weight polyethylene solution to the photochromic microcapsules is (45-65): 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113293452A (en) * | 2021-03-15 | 2021-08-24 | 浙江千禧龙纤特种纤维股份有限公司 | Ultra-high molecular weight polyethylene fiber cable, cable material and preparation method thereof |
| CN117904742A (en) * | 2024-03-19 | 2024-04-19 | 苏州宝丽迪材料科技股份有限公司 | Photochromic polyvinyl alcohol fiber and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101225296A (en) * | 2008-02-01 | 2008-07-23 | 北京服装学院 | Method for preparing photochromic micro-encapsulation |
| CN108589351A (en) * | 2018-04-18 | 2018-09-28 | 江苏工程职业技术学院 | A kind of production method of the photochromic cable of high-strength and high-modulus weight northylen |
| CN110904523A (en) * | 2019-11-26 | 2020-03-24 | 湖南中泰特种装备有限责任公司 | Phase-change thermoregulation microcapsule ultra-high molecular weight polyethylene fiber and preparation method thereof |
-
2020
- 2020-11-04 CN CN202011216633.8A patent/CN112301452A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225296A (en) * | 2008-02-01 | 2008-07-23 | 北京服装学院 | Method for preparing photochromic micro-encapsulation |
| CN108589351A (en) * | 2018-04-18 | 2018-09-28 | 江苏工程职业技术学院 | A kind of production method of the photochromic cable of high-strength and high-modulus weight northylen |
| CN110904523A (en) * | 2019-11-26 | 2020-03-24 | 湖南中泰特种装备有限责任公司 | Phase-change thermoregulation microcapsule ultra-high molecular weight polyethylene fiber and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113293452A (en) * | 2021-03-15 | 2021-08-24 | 浙江千禧龙纤特种纤维股份有限公司 | Ultra-high molecular weight polyethylene fiber cable, cable material and preparation method thereof |
| CN113293452B (en) * | 2021-03-15 | 2022-06-03 | 浙江千禧龙纤特种纤维股份有限公司 | Ultra-high molecular weight polyethylene fiber cable, cable material and preparation method thereof |
| CN117904742A (en) * | 2024-03-19 | 2024-04-19 | 苏州宝丽迪材料科技股份有限公司 | Photochromic polyvinyl alcohol fiber and preparation method thereof |
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Application publication date: 20210202 |