CN111154100A - Preparation method of high-elasticity and high-heat-resistance polyimide - Google Patents
Preparation method of high-elasticity and high-heat-resistance polyimide Download PDFInfo
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- CN111154100A CN111154100A CN202010016508.6A CN202010016508A CN111154100A CN 111154100 A CN111154100 A CN 111154100A CN 202010016508 A CN202010016508 A CN 202010016508A CN 111154100 A CN111154100 A CN 111154100A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The invention discloses a preparation method of high-elasticity and high-heat-resistance polyimide, which comprises the following steps: firstly, preparing cage octa (gamma-aminopropyl) silsesquioxane by taking gamma-aminopropyl triethoxysilane as a raw material, completely dissolving the cage octa (gamma-aminopropyl) silsesquioxane and a polar solution in a three-neck flask, sequentially adding diamine and dianhydride to obtain yellow uniform viscous liquid, coating the liquid on a glass plate, placing the glass plate in a vacuum oven and a muffle furnace, taking out the glass plate, and sequentially carrying out constant-temperature water bath, cooling and demoulding to finally obtain the modified polyimide. The invention has the advantages of simple process flow in the whole process, low cost and important industrial significance, and the modified polyimide has excellent mechanical property and thermodynamic stability.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation method of high-elasticity and high-heat-resistance polyimide.
Background
Polyimide is one of organic polymer materials with the best comprehensive performance. The polyimide has good heat resistance because the structure contains a large number of benzene rings, heterocyclic rings and imine structures, is the wire enamel variety with the highest heat resistance grade at present, and has the heat resistance gradeUp to 240 grade, polyimide is in N2Thermal decomposition temperature t of medium loss 5% by weightd 5About 560 to 580 ℃. However, with the development of industrial technology, higher requirements are also put on materials, and polyimide has a strong structure rigidity, so that the elasticity is not good, and the elongation is only about 6%.
Silsesquioxane is a substance containing RSiO1.5 (O: Si: l.5: 1 in molecule) structure, R substituent is hydrogen, alkyl, alkenyl, aryl, arylene and derivative groups thereof, and silsesquioxane can be divided into random structure, ladder structure, cage structure and semi-cage structure according to different structures, wherein silsesquioxane compounds of cage structure and semi-cage structure are called POSS, and POSS has great advantages in the aspects of improving heat resistance, mechanical property, size stability and the like of materials; in order to improve the elasticity of polyimide and further enhance the heat resistance of the polyimide, the invention introduces cage octa (gamma-aminopropyl) silsesquioxane (POSS-NH)2) The polyimide is modified.
Disclosure of Invention
The invention aims to solve the problems and designs a preparation method of high-elasticity and high-heat-resistance polyimide.
The technical scheme of the invention is that the preparation method of the high-elasticity and high-heat-resistance polyimide is to introduce cage octa (gamma-aminopropyl) silsesquioxane to modify the polyimide and is realized by the following steps:
s1, preparing the cage octa (gamma-aminopropyl) silsesquioxane: adding deionized water, propanol, acetonitrile and tetrabutylammonium hydroxide aqueous solution into a three-neck flask provided with a mechanical stirring and condensing tube, fully mixing, adding gamma-aminopropyltriethoxysilane into the mixed solution for reaction, adding tetrahydrofuran after the reaction is finished, and sequentially filtering, washing and drying to obtain a white solid product, namely the cage octa (gamma-aminopropyl) silsesquioxane, when a large amount of white solid is separated out;
s2, preparing the cage octa (gamma-aminopropyl) silsesquioxane modified polyimide: grinding the cage octa (gamma-aminopropyl) silsesquioxane prepared in the step S2, weighing a proper amount of ground cage octa (gamma-aminopropyl) silsesquioxane, placing the cage octa (gamma-aminopropyl) silsesquioxane in a dry three-necked bottle with a thermometer, adding a polar solvent, stirring for dissolving, heating to 90 ℃, adding diamine after the cage octa (gamma-aminopropyl) silsesquioxane is completely dissolved, fully stirring, dissolving and mixing the diamine and the cage octa (gamma-aminopropyl) silsesquioxane, adding a proper amount of dianhydride for reacting to obtain yellow uniform viscous liquid, uniformly coating the obtained liquid on a clean and dry glass plate by using an automatic coating dryer, coating a wet film by using a scraper, placing the glass plate in a vacuum oven after the coating is finished, setting the temperature of the vacuum oven for reacting, taking out the glass plate after the reaction is finished, placing the glass plate in a muffle furnace, and setting the temperature of the muffle furnace, reacting, cooling to room temperature after the reaction is finished, fully cooling, taking out the glass plate, and sequentially carrying out constant-temperature water bath, cooling and demoulding to finally obtain the polyimide film.
As a further description of the present invention, the specific process after the γ -aminopropyltriethoxysilane is added in S1 is as follows: slowly dropwise adding gamma-aminopropyltriethoxysilane into the mixed solution, heating to 50 ℃ for reaction, preferably reacting for 24 hours, cooling to room temperature after the reaction is finished, adding cold tetrahydrofuran, filtering the obtained white solid until a large amount of white solid is separated out, washing the filtered white solid for three times by using the cold tetrahydrofuran, and drying for 36 hours at the temperature of 80 ℃ in vacuum after the washing is finished to obtain the white solid product.
As a further illustration of the invention, the setting of the temperature of the vacuum oven in S2 includes four stages, the temperature range is preferably 120-180 ℃, the pressure range is preferably-0.09 MPa-0 MPa, and the reaction time of each stage is preferably 2 hours.
As a further description of the present invention, the setting of the muffle furnace temperature in S2 includes three stages, the temperature range is preferably 210 ℃ to 300 ℃, and the reaction time in each stage is preferably 1 hour.
And preferably adding the dianhydride into the S2 by 3-4 times, cooling to room temperature after the dianhydride is added, and reacting to obtain yellow uniform viscous liquid, wherein the reaction time is preferably 24 hours.
As a further explanation of the present invention, the temperature of the thermostatic waterbath in S2 is preferably 90 ℃.
As a further illustration of the present invention, the weight ratio of the gamma-aminopropyltriethoxysilane in the whole system in the S1 step is preferably 10% -80%; the amount of the cage octa-poly (gamma-aminopropyl) silsesquioxane weighed in the S2 accounts for preferably 0.1-20% of the mass fraction of the diamine.
As a further illustration of the present invention, the diamine may be replaced with a dianhydride and the dianhydride may be replaced with a diamine in the S2.
As a further illustration of the present invention, the diamine comprises one or more of 4,4 '-diaminodiphenyl ether, 4' -diaminodiphenylmethane, 4 '-diaminodiphenyl sulfide, 4' -diaminodiphenyl sulfone; the dianhydride comprises one or more of pyromellitic dianhydride, 3,3',4,4' -biphenyl tetracarboxylic dianhydride, 2,3,3',4' -biphenyl tetracarboxylic dianhydride, 2,3', 3-biphenyl tetracarboxylic dianhydride and 2, 3-naphthalene dianhydride; the polar solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, tetrahydrofuran and acetonitrile.
The preparation method has the beneficial effects that 1, gamma-aminopropyltriethoxysilane is used as a raw material to synthesize cage octa (gamma-aminopropyl) silsesquioxane, then a polyamic acid solution is prepared, and then the polyimide modified by the cage octa (gamma-aminopropyl) silsesquioxane is prepared by fully performing imidization reaction in a vacuum oven and fully performing imidization reaction in a muffle furnace in sequence; the whole process is simple in process flow, low in cost and important in industrialization.
2. The unique cage structure of the cage octa (gamma-aminopropyl) silsesquioxane has excellent mechanical property and thermodynamic stability, and the cage octa (gamma-aminopropyl) silsesquioxane is introduced into a synthetic raw material of a polyimide precursor, so that the comprehensive mechanical property of the polyimide can be improved, and the elastic property and the heat resistance of the polyimide are improved.
Detailed Description
Because polyimide is the enameled wire variety with the highest heat-resisting grade at present, the heat-resisting grade can reach 240 grades, and the polyimide is N2Thermal decomposition temperature t of medium loss 5% by weightd 5About 560 to 580 ℃. However, the polyimide has a strong structure rigidity, so that the elasticity is not good, and the elongation is only about 6 percent, so that the invention introduces cage octa (gamma-aminopropyl) silsesquioxane (POSS-NH is used in the following description)2Expressed) to obtain a highly elastic, highly heat-resistant polyimide.
The invention provides a preparation method of high-elasticity and high-heat-resistance polyimide, which comprises the following steps:
S1.POSS-NH2the preparation of (1): adding deionized water, propanol, acetonitrile and tetrabutylammonium hydroxide aqueous solution into a three-neck flask provided with a mechanical stirring and condensing tube, fully mixing, slowly dropwise adding gamma-aminopropyltriethoxysilane into the mixed solution, heating to 50 ℃ for reaction for 24 hours, cooling to room temperature after the reaction is finished, adding cold tetrahydrofuran, filtering the precipitated white solid until a large amount of white solid is precipitated, washing the white solid obtained after filtration for three times with the cold tetrahydrofuran, and drying at 80 ℃ in vacuum for 36 hours after the washing is finished to obtain a white solid product, namely POSS-NH2Wherein the weight ratio of the gamma-aminopropyl triethoxysilane in the whole system is preferably 10-80%.
S2.POSS-NH2Preparation of modified polyimide: POSS-NH prepared in S12Grinding, and weighing a proper amount of ground POSS-NH2Placing in a dry three-necked bottle with a thermometer, adding polar solvent, stirring for dissolving, heating to 90 deg.C, adding diamine (or dianhydride) after completely dissolving, and mixing diamine (or dianhydride) and POSS-NH2Fully stirring, dissolving and mixing, adding a proper amount of dianhydride (or diamine) for 3-4 times to react, cooling to room temperature after the dianhydride (or diamine) is added, continuing to react for 24 hours to obtain yellow uniform viscous liquid, uniformly coating the obtained liquid on a clean and dry glass plate by using an automatic coating dryer, coating a wet film by using a scraper, and quickly coating the film after the film is coatedTaking down a scraper, putting the glass plate into a vacuum oven, setting the temperature of the vacuum oven at the same time, adopting a step-type heating method and dividing the glass plate into four stages, wherein the first stage is to react for 2 hours under the conditions of 90 ℃ and normal pressure, the second stage is to react for 2 hours under the conditions of 120 ℃ and-0.03 Mpa, the third stage is to react for 2 hours under the conditions of 150 ℃ and-0.06 Mpa, the fourth stage is to react for 2 hours under the conditions of 180 ℃ and-0.09 Mpa, the imidization reaction is fully carried out in the vacuum oven, after the reaction is finished, turning off the power supply of the oven, taking out the glass plate and quickly putting the glass plate into a muffle furnace, setting the temperature of the muffle furnace and dividing the glass plate into three stages, the first stage is to react for 1 hour under the condition of 210 ℃, the second stage is to react for 1 hour under the condition of 250 ℃, the third stage is to react for 1 hour under the condition of, cooling to room temperature after the reaction is finished, fully cooling, taking out the glass plate, placing the glass plate in a constant-temperature water bath at 90 ℃ for heating, taking out the glass plate for cooling for demoulding, and finally obtaining the product which is subjected to POSS-NH2Modified polyimide membranes, wherein POSS-NH2The amount of the diamine accounts for 0.1 to 20 percent of the mass fraction of the diamine.
The invention will now be further illustrated by reference to the following examples:
example 1. weighing an appropriate amount of diamine and baking at 90 ℃ in a vacuum oven for 4.5 hours, then weighing an appropriate amount of dianhydride and baking at 150 ℃ in a vacuum oven for 6.5 hours, taking out and putting in a drying dish after baking is finished and cooling to room temperature for standby application, putting a three-necked bottle with a thermometer in a circulating water bath, adding 2184g of N, N-dimethylacetamide, stirring, simultaneously adding 200g of 4,4 '-diaminodiphenyl ether when stirring is started, dissolving the 4,4' -diaminodiphenyl ether, adding 216g of pyromellitic dianhydride by 3 times, reacting for 3 hours after the pyromellitic dianhydride is added, obtaining a light yellow uniform viscous liquid, namely a polyimide precursor polyamic acid solution, and then obtaining a polyimide film.
Example 2.
S1.POSS-NH2The preparation of (1): a three-necked flask equipped with mechanical stirring and condenser was charged with 8.1g deionized water, 3.6g propanol, 0.9g acetonitrile, and 0.2g aqueous tetrabutylammonium hydroxideAfter fully mixing, slowly dropwise adding 2g of gamma-aminopropyltriethoxysilane into the mixed solution, heating to 50 ℃ for reacting for 24 hours, cooling to room temperature after the reaction is finished, adding cold tetrahydrofuran, filtering the separated white solid after a large amount of white solid is separated out, washing the white solid obtained after filtration for three times by using the cold tetrahydrofuran, and drying for 36 hours at the vacuum temperature of 80 ℃ after the washing is finished to obtain a white solid product, namely POSS-NH2。
S2.POSS-NH2Preparation of modified polyimide: POSS-NH prepared in S12Grinding, and weighing a proper amount of ground POSS-NH2Placing in a dry three-necked bottle with a thermometer, adding 2184g of N, N-dimethylacetamide, stirring for dissolving, heating to 90 deg.C, adding 200g of 4,4 '-diaminodiphenyl ether after completely dissolving, and mixing 4,4' -diaminodiphenyl ether and POSS-NH2Fully stirring, dissolving and mixing, adding 216g of pyromellitic dianhydride for 3 times for reaction, cooling to room temperature after the pyromellitic dianhydride is added, continuing the reaction for 24 hours to obtain yellow uniform viscous liquid, uniformly coating the obtained liquid on a clean and dry glass plate by using an automatic coating dryer, coating a wet film by using a scraper, quickly taking down the scraper after the coating is finished, putting the glass plate into a vacuum oven, setting the temperature of the vacuum oven, adopting a step-type heating method and dividing the temperature into four stages, wherein the first stage is to react for 2 hours at 90 ℃ and normal pressure, the second stage is to react for 2 hours at 120 ℃ and-0.03 MPa, the third stage is to react for 2 hours at 150 ℃ and-0.06 MPa, the fourth stage is to react for 2 hours at 180 ℃ and-0.09 MPa, and fully performing imidization reaction in the vacuum oven, turning off the power supply of the oven after the reaction is finished, taking out the glass plate and quickly putting the glass plate into a muffle furnace, setting the temperature of the muffle furnace and dividing the temperature into three stages, wherein the first stage is to react for 1 hour at 210 ℃, the second stage is to react for 1 hour at 250 ℃, the third stage is to react for 1 hour at 300 ℃, the imidization reaction is fully carried out in the muffle furnace, the temperature is reduced to room temperature after the reaction is finished, the glass plate is taken out and put into a constant-temperature water bath at 90 ℃ to be heated after being fully cooled, and then the glass plate is taken out to be cooled and taken offMembrane, finally obtaining POSS-NH2A modified polyimide film.
Example 3.
In example 2, 2g of gamma-aminopropyltriethoxysilane was slowly dropped instead of 10g of gamma-aminopropyltriethoxysilane, and the other procedure was the same as in example 2.
Example 4.
In example 2, 2g of gamma-aminopropyltriethoxysilane was slowly dropped instead of 20g of gamma-aminopropyltriethoxysilane, and the other process was the same as in example 2.
Table 1 process recipe in each example
The polyimide films prepared in the examples were subjected to the performance test, and the test results are shown in the following table 2:
table 2 results of performance test of each example
It can be seen from Table 2 that the reaction proceeds via POSS-NH2The comprehensive performance of the modified polyimide is higher than that of the common polyimide; along with the increase of the content of the gamma-aminopropyltriethoxysilane, the 5 percent weight loss thermal decomposition temperature is greatly improved compared with the common polyimide, wherein the 5 percent weight loss thermal decomposition temperature in the example 3 is higher by 620 ℃, which shows that the temperature is improved by POSS-NH2The heat resistance of the modified polyimide is further enhanced; from the elastic modulus and elongation, it can be seen that the polymer passes through POSS-NH2The modified polyimide also showed an improvement in elastic properties, with an elongation of up to 11% higher in example 3, indicating the passage of POSS-NH2The modified polyimide has excellent mechanical properties.
The technical solutions described above only represent the preferred technical solutions of the present invention, and some possible modifications to some parts of the technical solutions by those skilled in the art all represent the principles of the present invention, and fall within the protection scope of the present invention.
Claims (9)
1. A preparation method of high-elasticity and high-heat-resistance polyimide is characterized in that cage octa (gamma-aminopropyl) silsesquioxane is introduced to modify the polyimide and is realized by the following steps:
s1, preparing the cage octa (gamma-aminopropyl) silsesquioxane: adding deionized water, propanol, acetonitrile and tetrabutylammonium hydroxide aqueous solution into a three-neck flask provided with a mechanical stirring and condensing tube, fully mixing, adding gamma-aminopropyltriethoxysilane into the mixed solution for reaction, adding tetrahydrofuran after the reaction is finished, and sequentially filtering, washing and drying to obtain a white solid product, namely the cage octa (gamma-aminopropyl) silsesquioxane, when a large amount of white solid is separated out;
s2, preparing the cage octa (gamma-aminopropyl) silsesquioxane modified polyimide: grinding the cage octa (gamma-aminopropyl) silsesquioxane prepared in the step S2, weighing a proper amount of ground cage octa (gamma-aminopropyl) silsesquioxane, placing the cage octa (gamma-aminopropyl) silsesquioxane in a dry three-necked bottle with a thermometer, adding a polar solvent, stirring for dissolving, heating to 90 ℃, adding diamine after the cage octa (gamma-aminopropyl) silsesquioxane is completely dissolved, fully stirring, dissolving and mixing the diamine and the cage octa (gamma-aminopropyl) silsesquioxane, adding a proper amount of dianhydride for reacting to obtain yellow uniform viscous liquid, uniformly coating the obtained liquid on a clean and dry glass plate by using an automatic coating dryer, coating a wet film by using a scraper, placing the glass plate in a vacuum oven after the coating is finished, setting the temperature of the vacuum oven for reacting, taking out the glass plate after the reaction is finished, placing the glass plate in a muffle furnace, and setting the temperature of the muffle furnace, reacting, cooling to room temperature after the reaction is finished, fully cooling, taking out the glass plate, and sequentially carrying out constant-temperature water bath, cooling and demoulding to finally obtain the polyimide film.
2. The method for preparing high-elasticity and high-heat-resistance polyimide according to claim 1, wherein the specific process after the gamma-aminopropyltriethoxysilane is added into the S1 is as follows: slowly dropwise adding gamma-aminopropyltriethoxysilane into the mixed solution, heating to 50 ℃ for reaction, preferably reacting for 24 hours, cooling to room temperature after the reaction is finished, adding cold tetrahydrofuran, filtering the obtained white solid until a large amount of white solid is separated out, washing the filtered white solid for three times by using the cold tetrahydrofuran, and drying for 36 hours at the temperature of 80 ℃ in vacuum after the washing is finished to obtain the white solid product.
3. The method of claim 1, wherein the setting of the vacuum oven temperature in S2 includes four stages, the temperature range is preferably 120 ℃ to 180 ℃, the pressure range is preferably-0.09 Mpa to 0Mpa, and the reaction time in each stage is preferably 2 hours.
4. The method for preparing high-elastic and high-heat-resistant polyimide according to claim 1, wherein the muffle furnace temperature is set in S2 to include three stages, the temperature range is preferably 210 ℃ to 300 ℃, and the reaction time in each stage is preferably 1 hour.
5. The method for preparing high-elasticity and high-heat-resistance polyimide according to claim 1, wherein the dianhydride is added to S2 preferably in 3-4 times, and the dianhydride is cooled to room temperature after being added to react to obtain yellow uniform viscous liquid, wherein the reaction time is preferably 24 hours.
6. The method for preparing highly elastic and highly heat resistant polyimide according to claim 1, wherein the temperature of the thermostatic water bath in S2 is preferably 90 ℃.
7. The method for preparing high-elastic and high-heat-resistant polyimide according to claim 1, wherein the gamma-aminopropyltriethoxysilane is preferably 10-80% by weight of the whole system in the step S1; the amount of the cage octa-poly (gamma-aminopropyl) silsesquioxane weighed in the S2 accounts for preferably 0.1-20% of the mass fraction of the diamine.
8. The method of claim 1, wherein the diamine is replaced with dianhydride and the dianhydride is replaced with diamine in S2.
9. The method of claim 1, wherein the diamine comprises one or more of 4,4 '-diaminodiphenyl ether, 4' -diaminodiphenylmethane, 4 '-diaminodiphenyl sulfide, and 4,4' -diaminodiphenyl sulfone; the dianhydride comprises one or more of pyromellitic dianhydride, 3,3',4,4' -biphenyl tetracarboxylic dianhydride, 2,3,3',4' -biphenyl tetracarboxylic dianhydride, 2,3', 3-biphenyl tetracarboxylic dianhydride and 2, 3-naphthalene dianhydride; the polar solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, tetrahydrofuran and acetonitrile.
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Cited By (2)
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| CN113777702A (en) * | 2021-09-06 | 2021-12-10 | 中国建筑材料科学研究总院有限公司 | Method and device for binding optical fiber filaments after arranging boards |
| CN113963848A (en) * | 2021-10-25 | 2022-01-21 | 广东远光电缆实业有限公司 | Preparation process of light high-flexibility wear-resistant cable for mobile power generation vehicle |
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| CN102731809A (en) * | 2012-06-04 | 2012-10-17 | 西北工业大学 | Preparation method of atomic oxygen-resistant polyimide hybrid films containing POSS (polyhedral oligomeric silsesquioxanes) structures |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113777702A (en) * | 2021-09-06 | 2021-12-10 | 中国建筑材料科学研究总院有限公司 | Method and device for binding optical fiber filaments after arranging boards |
| CN113777702B (en) * | 2021-09-06 | 2023-11-03 | 中国建筑材料科学研究总院有限公司 | Method and device for binding optical fiber after plate arrangement |
| CN113963848A (en) * | 2021-10-25 | 2022-01-21 | 广东远光电缆实业有限公司 | Preparation process of light high-flexibility wear-resistant cable for mobile power generation vehicle |
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Application publication date: 20200515 |