CN103145985A - Preparation of polyimide resin and application in high-temperature-resistant optical fiber coatings thereof - Google Patents
Preparation of polyimide resin and application in high-temperature-resistant optical fiber coatings thereof Download PDFInfo
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- CN103145985A CN103145985A CN2012105231431A CN201210523143A CN103145985A CN 103145985 A CN103145985 A CN 103145985A CN 2012105231431 A CN2012105231431 A CN 2012105231431A CN 201210523143 A CN201210523143 A CN 201210523143A CN 103145985 A CN103145985 A CN 103145985A
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Abstract
The invention discloses preparation of polyimide resin and an application in high-temperature-resistant optical fiber coatings thereof. The preparation of the polyimide resin comprises the following steps that (1) tetracarboxylic acid dianhydride compounds and diamine compounds are adopted as raw materials to react in solvents under the temperature of 40DEG C-60DEG C, the reaction is not terminated until an acid value decreases to a theoretical value, and polyimide acid intermediates after anhydride ring opening are obtained, wherein the molar ratio between the tetracarboxylic acid dianhydride compounds and the diamine compounds is 0.50-1.5 :1; (2) the polyimide acid intermediates which are obtained from step (1) are dehydrated and cyclized under the temperature of 200 DEG C-500DEG C for 10s-10min, and are placed in a drying oven, after the surfaces of the polyimide acid intermediates are dry, under the temperature of 100 DEG C-400DEG C for 2h-6h to remove solvents and form a film.
Description
Technical field
The present invention relates to a kind of high temperature resistant polyimide resin; In addition, the invention still further relates to its preparation method and the application in optical fiber coatings.
Background technology
Society, optical fiber industry is just growing to the requirement of high-temperature resistant coating, and this high-temperature resistant optical fiber coating can be applicable to the fields such as automobile, flying body, medical science or some military affairs.At present, the preparation of optical fiber coatings is divided into thermofixation and the large class of ultraviolet light polymerization two by the difference of mechanism of polymerization.UV curing optical fiber coating system generally is comprised of oligopolymer, activity diluting monomer, light trigger and various additives etc.Wherein oligopolymer is the main body of UV curing optical fiber coating, and its performance has determined the salient features of coating basically.And the UV curing optical fiber coating that usually adopts the oligopolymer such as epoxy acrylic and urethane acrylate to prepare can only use at low temperatures, can not meet the requirement of optical fiber resistance to elevated temperatures far away.Based on the requirement to the high-temperature resistant optical fiber resin, we design and have prepared the polyimide resin of the heat resistance that has excellent mechanical property and give prominence to, and use it in high-temperature resistant optical fiber coating.
Polyimide is a base polymer that contains imide ring on main chain, is one of organic polymer material of over-all properties the best.Owing to containing aromatic nucleus on main chain, as the matrix resin of coating, have excellent mechanical property and outstanding heat resistance.At present, the polyimide type high-temperature resistant coating is mainly solvent type, is about to improve deliquescent polyimide and is dissolved in (as DMF) in polar solvent, coats device surface, the drying film-forming.When this cured film was used under 300 ℃ of envrionment temperatures, it is stable that molecular structure keeps, and mechanical property is substantially constant, effectively guarantees the stability of Optical Fiber Transmission information.Simultaneously, by use raw material and processing condition are designed and optimize, gained cured film resistance toheat can reach more than 400 ℃.Therefore, the polyimide coating material has application prospect preferably in the high-temperature resistant optical fiber paint field.
Summary of the invention
The shortcoming that the UV curing optical fiber coating of preparing for oligopolymer such as existing epoxy acrylic and urethane acrylates can only use at low temperatures, technical problem to be solved by this invention is to provide a kind of polyimide resin of the heat resistance that has excellent mechanical property and give prominence to, and proposes Preparation Method And The Use.
For this reason, the present invention proposes following technical scheme:
A kind of preparation method of polyimide resin said method comprising the steps of:
(1) take tetracarboxylic dianhydride's compounds and diamine compounds as raw material, react in solvent under 40～60 ℃, drop to theoretical acid number to acid number, termination reaction, obtain the polyimide acid intermediate after the acid anhydrides open loop, wherein the mol ratio of tetracarboxylic dianhydride's compounds and diamine compounds is (0.50～1.5): 1;
(2) the polyimide acid intermediate that step (1) is obtained at 200 ~ 500 ℃, under 10s ~ 10min, is dehydrated into ring, after surface drying, then places 2 ~ 6h desolventizing, film forming in 100 ~ 400 ℃ of baking ovens.
Wherein: the solvent described in step (1) is a kind of in DMF, N, N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone; Described solvent load accounts for 10～70% of reaction system total mass; Described tetracarboxylic dianhydride's compounds is selected from: all benzene dianhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic dianhydride, 4, at least a in 4'-Biphenyl Ether dianhydride, the equal benzoic anhydride of phenylate diamines, ketone acid anhydride and hexafluorodianhydride; Described diamine compounds is selected from: 4,4'-Biphenyl Ether diamines, 4,4'-diaminobenzophenone, 4, at least a in 4'-diaminodiphenylmethane, hexanediamine, hexafluoro diamines.
Preferably, in step of the present invention (1), take tetracarboxylic dianhydride's compounds as raw material reaction, comprising add above-mentioned tetracarboxylic dianhydride's compounds in solvent, feed way is batch charging.
Preferably, after the film forming described in step (2), method are the quick surface drying of first high temperature, more slightly change into film with the thorough solvent Perfect Ring of removing of long period under low temperature.
The present invention also comprises, the polyimide resin for preparing with preparation method of the present invention.
Polyimide resin of the present invention is tested its mechanical property, degree of cure and weightless performance, and its high-temperature stability is carried out long-term follow.Thereby estimate its use properties.Below be performance test:
Mechanical property:
Mechanical property with universal mechanical tester test cured film comprises specific modulus, elongation at break and breaking tenacity.Result is as shown in the table.The mechanical property of the polyimide resin cured film that five embodiment of the present invention make all can satisfy the performance requriements of present commercial optical fiber coatings.
Thermogravimetic analysis (TGA)
Get the cured film of embodiment one, with thermal gravimetric analyzer, it is tested, the results are shown in Figure 1.As seen from Figure 1, the polyimide resin that embodiment one makes has slight weightlessness since 400 ℃, has obviously weightless during to 600 ℃.Therefore, in this material, molecular structure has good high temperature stability performance.
Mechanical property high temperature is followed the tracks of
The cured film that embodiment one, embodiment two and embodiment three are made is positioned in high temperature oven (400 ℃), regularly follows the tracks of its mechanical property changing conditions, and result as shown in Figure 2.As can see from Figure 2, the cured film modulus that embodiment one, two and three makes in time accumulation, there is no considerable change.Explanation thus, this mechanical property of materials high-temperature stability is better, can use for a long time in hot environment.
By the analysis to the mechanical property of materials of the present invention and thermostability, prove that this material has good mechanical property, chemical stability and thermostability, can be used for the high-temperature resistant optical fiber paint field fully.
Polyimide resin of the present invention, stable performance under hot conditions, thin film-forming method satisfies the requirement of drawing optical fibers coating processes, can be applied to the high-temperature resistant optical fiber coating material.Optical fiber and the optical cable produced after being applied by it can satisfy the service requirements under hot environment.
Therefore, the present invention also comprises, the polyimide resin for preparing with preparation method of the present invention can be used for the coating of optical fiber or optical cable as coating.
Description of drawings
The cured film of Fig. 1 embodiment one tests to it hot weightless picture that obtains with thermal gravimetric analyzer
The cured film that Fig. 2 embodiment one, embodiment two and embodiment three make is positioned in high temperature oven (400 ℃), regularly follows the tracks of its mechanical property and changes the modulus time plot that obtains.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.These embodiment are interpreted as only being used for explanation the present invention and are not used in restriction protection scope of the present invention.After the content of having read the present invention's record, those skilled in the art can make various changes or modifications the present invention, and these equivalences change and modification falls into claim limited range of the present invention equally.
Embodiment one
In the 1000ML four-necked bottle of agitator, prolong, thermometer is housed, under room temperature, add 97.12g
4,4`-diaminodiphenyl oxide and 481.08g N, N-N,N-DIMETHYLACETAMIDE, 40 ℃ of heated and stirred after diamines dissolves fully, add the 109.06g pyromellitic dianhydride in batches.Measure acid number according to the GB2895-82 method.Until acid number termination reaction when dropping to theoretical acid number.Obtain 687.26g polyimide acid intermediate.
The polyimide acid intermediate is coated on quartz glass plate with blade applicator, first is positioned over 10min in 200 ℃ of baking ovens, make its Procuring.And then be placed on placement 2H in 400 ℃ of red lines, reach deep layer and solidify.
Embodiment two
In the 1000ML four-necked bottle of agitator, prolong, thermometer is housed, under room temperature, add 97.12g 4,4`-diaminodiphenyl oxide and 481.08g N-Methyl pyrrolidone, 60 ℃ of heated and stirred after diamines dissolves fully, add the 109.06g pyromellitic dianhydride in batches.Measure acid number according to the GB2895-82 method.Until acid number termination reaction when dropping to theoretical acid number.Obtain 687.26g polyimide acid intermediate.
The polyimide acid intermediate is coated on quartz glass plate with blade applicator, first is positioned over 10s in 500 ℃ of baking ovens, make its Procuring.And then be placed on placement 6H in 100 ℃ of red lines, reach deep layer and solidify.
Embodiment three
In the 1000ML four-necked bottle of agitator, prolong, thermometer is housed, under room temperature, add 97.12g
4,4`-diaminodiphenyl oxide and 481.08g N-Methyl pyrrolidone, 60 ℃ of heated and stirred after diamines dissolves fully, add the 105.79g pyromellitic dianhydride in batches.Measure acid number according to the GB2895-82 method.Until acid number termination reaction when dropping to theoretical acid number.Obtain 683.98g polyimide acid intermediate.
The polyimide acid intermediate is coated on quartz glass plate with blade applicator, first is positioned over 10s in 500 ℃ of baking ovens, make its Procuring.And then be placed on placement 6H in 100 ℃ of red lines, reach deep layer and solidify.
Embodiment four
In the 1000ML four-necked bottle of agitator, prolong, thermometer is housed, under room temperature, add 67.01g
4,4`-diaminodiphenyl oxide and 415.98g N, N-N,N-DIMETHYLACETAMIDE, 40 ℃ of heated and stirred after diamines dissolves fully, add the 109.06g pyromellitic dianhydride in batches.Measure acid number according to the GB2895-82 method.Until acid number termination reaction when dropping to theoretical acid number.Obtain 592.05g polyimide acid intermediate.
The polyimide acid intermediate is coated on quartz glass plate with blade applicator, first is positioned over 10min in 200 ℃ of baking ovens, make its Procuring.And then be placed on placement 2H in 400 ℃ of red lines, reach deep layer and solidify.
Embodiment five
In the 1000ML four-necked bottle of agitator, prolong, thermometer is housed, under room temperature, add 150.03g
4,4`-diaminodiphenyl oxide and 28.78g N, N-N,N-DIMETHYLACETAMIDE, 40 ℃ of heated and stirred after diamines dissolves fully, add the 109.06g pyromellitic dianhydride in batches.Measure acid number according to the GB2895-82 method.Until acid number termination reaction when dropping to theoretical acid number.Obtain 287.88g polyimide acid intermediate.
The polyimide acid intermediate is coated on quartz glass plate with blade applicator, first is positioned over 10min in 200 ℃ of baking ovens, make its Procuring.And then be placed on placement 2H in 400 ℃ of red lines, reach deep layer and solidify.
Embodiment six
In the 1000ML four-necked bottle of agitator, prolong, thermometer is housed, under room temperature, add 201.68g
4,4`-diaminodiphenyl oxide and 34.29g N, dinethylformamide, 40 ℃ of heated and stirred after diamines dissolves fully, add the 109.06g pyromellitic dianhydride in batches.Measure acid number according to the GB2895-82 method.Until acid number termination reaction when dropping to theoretical acid number.Obtain 345.03g polyimide acid intermediate.
The polyimide acid intermediate is coated on quartz glass plate with blade applicator, first is positioned over 10min in 200 ℃ of baking ovens, make its Procuring.And then be placed on placement 2H in 400 ℃ of red lines, reach deep layer and solidify.
Embodiment seven
In the 1000ML four-necked bottle of agitator, prolong, thermometer is housed, under room temperature, add 97.12g
4,4`-diaminodiphenyl oxide and 481.08g N, dinethylformamide, 40 ℃ of heated and stirred after diamines dissolves fully, add the 109.06g pyromellitic dianhydride in batches.Measure acid number according to the GB2895-82 method.Until acid number termination reaction when dropping to theoretical acid number.Obtain 687.26g polyimide acid intermediate.
The polyimide acid intermediate is coated on quartz glass plate with blade applicator, first is positioned over 10min in 200 ℃ of baking ovens, make its Procuring.And then be placed on placement 2H in 400 ℃ of red lines, reach deep layer and solidify.
Embodiment eight
In the 1000ML four-necked bottle of agitator, prolong, thermometer is housed, under room temperature, add 72.45g
4,4`-diaminobenzophenone and 421.56g N, dinethylformamide, 40 ℃ of heated and stirred after diamines dissolves fully, add 110.01g4 in batches, 4'-Biphenyl Ether dianhydride.Measure acid number according to the GB2895-82 method.Until acid number termination reaction when dropping to theoretical acid number.Obtain 604.02g polyimide acid intermediate.
The polyimide acid intermediate is coated on quartz glass plate with blade applicator, first is positioned over 10min in 200 ℃ of baking ovens, make its Procuring.And then be placed on placement 2H in 400 ℃ of red lines, reach deep layer and solidify.
Embodiment nine
In the 1000ML four-necked bottle of agitator, prolong, thermometer is housed, under room temperature, add 70.25g 4,4'-diaminodiphenylmethane and 421.56g N, dinethylformamide, 40 ℃ of heated and stirred after diamines dissolves fully, add the 124.51g benzophenone tetracarboxylic dianhydride in batches.Measure acid number according to the GB2895-82 method.Until acid number termination reaction when dropping to theoretical acid number.Obtain 616.32g polyimide acid intermediate.
The polyimide acid intermediate is coated on quartz glass plate with blade applicator, first is positioned over 10min in 200 ℃ of baking ovens, make its Procuring.And then be placed on placement 2H in 400 ℃ of red lines, reach deep layer and solidify.
Embodiment ten
In the 1000ML four-necked bottle of agitator, prolong, thermometer is housed, under room temperature, add 50.20g hexanediamine and 421.56g N-Methyl pyrrolidone, 40 ℃ of heated and stirred after diamines dissolves fully, add the equal benzoic anhydride of 136.80g phenylate diamines in batches.Measure acid number according to the GB2895-82 method.Until acid number termination reaction when dropping to theoretical acid number.Obtain 421.56g polyimide acid intermediate.
The polyimide acid intermediate is coated on quartz glass plate with blade applicator, first is positioned over 10min in 200 ℃ of baking ovens, make its Procuring.And then be placed on placement 2H in 400 ℃ of red lines, reach deep layer and solidify.
Embodiment 11
In the 1000ML four-necked bottle of agitator, prolong, thermometer is housed, under room temperature, add 72.45g4,4`-diaminobenzophenone and 400.39g N-Methyl pyrrolidone, 40 ℃ of heated and stirred after diamines dissolves fully, add 124.51g ketone acid anhydride in batches.Measure acid number according to the GB2895-82 method.Until acid number termination reaction when dropping to theoretical acid number.Obtain 597.35g polyimide acid intermediate.
The polyimide acid intermediate is coated on quartz glass plate with blade applicator, first is positioned over 10min in 200 ℃ of baking ovens, make its Procuring.And then be placed on placement 2H in 400 ℃ of red lines, reach deep layer and solidify.
Embodiment 12
In the 1000ML four-necked bottle of agitator, prolong, thermometer is housed, under room temperature, add 75.56g hexafluoro diamines and 400.39g N-Methyl pyrrolidone, 40 ℃ of heated and stirred after diamines dissolves fully, add the 90.08g hexafluorodianhydride in batches.Measure acid number according to the GB2895-82 method.Until acid number termination reaction when dropping to theoretical acid number.Obtain 566.03g polyimide acid intermediate.
The polyimide acid intermediate is coated on quartz glass plate with blade applicator, first is positioned over 10min in 200 ℃ of baking ovens, make its Procuring.And then be placed on placement 2H in 400 ℃ of red lines, reach deep layer and solidify.
Claims (10)
1. the preparation method of a polyimide resin, is characterized in that, comprises the following steps:
(1) take tetracarboxylic dianhydride's compounds and diamine compounds as raw material, react in solvent under 40～60 ℃, drop to theoretical acid number to acid number, termination reaction, obtain the polyimide acid intermediate after the acid anhydrides open loop, wherein the mol ratio of tetracarboxylic dianhydride's compounds and diamine compounds is 0.50～1.5:1;
(2) the polyimide acid intermediate that step (1) is obtained at 200 ~ 500 ℃, under 10s ~ 10min, is dehydrated into ring, after surface drying, then places 2 ~ 6h desolventizing, film forming in 100 ~ 400 ℃ of baking ovens.
2. preparation method according to claim 1 is characterized in that: wherein the solvent described in step (1) is a kind of in DMF, N, N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone; Described solvent load accounts for 10～70% of reaction system total mass.
3. preparation method according to claim 1, it is characterized in that: wherein the tetracarboxylic dianhydride's compounds described in step (1) is selected from: all benzene dianhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic dianhydride, 4, at least a in 4'-Biphenyl Ether dianhydride, the equal benzoic anhydride of phenylate diamines, ketone acid anhydride and hexafluorodianhydride.
4. preparation method according to claim 1, it is characterized in that: wherein the diamine compounds described in step (1) is selected from: 4,4'-Biphenyl Ether diamines, 4,4'-diaminobenzophenone, 4, at least a in 4'-diaminodiphenylmethane, hexanediamine, hexafluoro diamines.
5. preparation method according to claim 1 is characterized in that: wherein in step (1) take tetracarboxylic dianhydride's compounds as raw material reaction, comprise the step that adds above-mentioned tetracarboxylic dianhydride's compounds in the solvent, feed way is batch charging.
6. preparation method according to claim 1 is characterized in that: the film forming described in step (2) wherein, and after method is the quick surface drying of first high temperature, more slightly thoroughly removes the solvent Perfect Ring with the long period under low temperature and change into film.
7. the polyimide resin that in claim 1～6, the described preparation method of any one prepares.
8. the application of polyimide resin claimed in claim 7 in optical fiber or optical cable coating.
9. application claimed in claim 8, is characterized in that, the optical fiber of producing after applying still keeps good transmission performance under higher use temperature, can satisfy the hot environment service requirements.
10. application claimed in claim 8, is characterized in that, the optical cable of producing after applying still keeps good transmission performance under higher use temperature, can satisfy the hot environment service requirements.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111153597A (en) * | 2019-12-26 | 2020-05-15 | 中天科技光纤有限公司 | Optical fiber |
| CN115159866A (en) * | 2022-06-28 | 2022-10-11 | 南京玻璃纤维研究设计院有限公司 | Glass fiber impregnating compound suitable for PPS resin and preparation method thereof |
| CN115236797A (en) * | 2022-08-12 | 2022-10-25 | 武汉理工大学 | High-temperature-resistant weak-fiber grating array and preparation method thereof |
| CN115254061A (en) * | 2022-08-15 | 2022-11-01 | 齐齐哈尔大学 | Preparation method of ultrahigh cross-linked porous organic polymer iodine adsorbent |
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| CN1654518A (en) * | 2005-01-31 | 2005-08-17 | 南京工业大学 | Preparation method of polyimide film for flexible printed circuit board |
| CN1786052A (en) * | 2004-12-07 | 2006-06-14 | 长春人造树脂厂股份有限公司 | Preparation method of polyimide |
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| CN1410471A (en) * | 2002-11-22 | 2003-04-16 | 中国科学院长春应用化学研究所 | Preparation method of polyether imide flexible printed circuit substrate material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111153597A (en) * | 2019-12-26 | 2020-05-15 | 中天科技光纤有限公司 | Optical fiber |
| CN115159866A (en) * | 2022-06-28 | 2022-10-11 | 南京玻璃纤维研究设计院有限公司 | Glass fiber impregnating compound suitable for PPS resin and preparation method thereof |
| CN115159866B (en) * | 2022-06-28 | 2023-09-08 | 南京玻璃纤维研究设计院有限公司 | Glass fiber impregnating compound suitable for PPS resin and preparation method thereof |
| CN115236797A (en) * | 2022-08-12 | 2022-10-25 | 武汉理工大学 | High-temperature-resistant weak-fiber grating array and preparation method thereof |
| CN115236797B (en) * | 2022-08-12 | 2024-04-16 | 武汉理工大学 | High-temperature-resistant weak fiber grating array and preparation method thereof |
| CN115254061A (en) * | 2022-08-15 | 2022-11-01 | 齐齐哈尔大学 | Preparation method of ultrahigh cross-linked porous organic polymer iodine adsorbent |
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Application publication date: 20130612 |