CN105401251B - A kind of preparation method of the high ortho position molybdenum phenolic fibre of resistance to ablation - Google Patents
A kind of preparation method of the high ortho position molybdenum phenolic fibre of resistance to ablation Download PDFInfo
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- CN105401251B CN105401251B CN201510781947.5A CN201510781947A CN105401251B CN 105401251 B CN105401251 B CN 105401251B CN 201510781947 A CN201510781947 A CN 201510781947A CN 105401251 B CN105401251 B CN 105401251B
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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
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
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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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention discloses a kind of preparation method of the resistance to high ortho position molybdenum phenolic fibre of ablation, mixed phenols compound and formaldehyde, add a certain amount of catalyst Titanium Citrate, 0.5 ~ 2.9h of boiling reaction afterwards according to a certain percentage；Diluting concentrated sulfuric acid is added, continues to react 30min ~ 50min；The 3h of decompression dehydration 0.5, adds the molybdic acid of mass ratio 6 18% and is modified reaction, constant temperature seethes with excitement 2 hours when temperature reaches 90 97 DEG C；Decompression dehydration, 110 DEG C are warming up to resin, stop dehydration；By resin in 120 170 DEG C of melt spinnings；As-spun fibre is put into the solidify liquid configured, 95 DEG C are progressively warming up to since room temperature, room temperature is naturally cooled to after constant temperature；Then progressively heat up heat cure under condition of nitrogen gas.The fibre strength of high ortho position molybdenum phenolic fibre is 3 34cN/dtex, and modulus is 40 400 cN/dtex, the degree of cross linking 30 38%.
Description
Technical field
The invention belongs to the preparation field of the extraordinary fiber of resistance to ablation, more particularly to a kind of high ortho position molybdenum phenolic fibre of resistance to ablation
Preparation method.
Background technology
Common phenolic aldehyde can be used for a long time below 150 DEG C, but just occur obvious oxidative phenomena more than this temperature.And with
Pyrolysis, carbonization phenomenon occur successively for the rise of temperature, phenolic aldehyde.To improve the heat resistance of phenolic fibre, generally using chemical method
Resin is modified, such as by the phenolic hydroxyl group etherificate of phenolic fibre, esterification, heavy metal chelating [Wang Hongbin, Dang Jiangmin, Ren Rui
Deng synthetic fiber industry, 2012,35 (2), 12-15, USPat 4851279].Common phenolic aldehyde is improved by these methods
Heat resistance, extends the use scope of phenolic fibre.The electron-withdrawing energy of B-O bases can also be used simultaneously, improve the electricity on phenyl ring
The activity of methylene, improves the heat endurance of phenolic aldehyde on sub- enrichment state, reduction phenolic fibre.Boron element pair is introduced in phenolic aldehyde
It, which is modified, causes traditional thermosetting phenolic resin various aspects of performance to be improved [CN102443181B], achieves good
Effect.
Molybdenum phenol-formaldehyde resin modified has more superior resistance to ablation than traditional phenol-formaldehyde resin modified, heat resistance, instantaneous resistance to high
Warm nature and mechanical property, are concentrated mainly on the fields of space technology such as rocket, guided missile, spacecraft as the excellent material of resistance to ablation
Material, automobile brake sheet etc..But molybdenum modified phenolic has no application in fibre modification, also had no in the modification of high ortho phenolic fiber
Report.Simultaneously because the limitation of phenolic resin chemical constitution, the improvement of thermoplastic phenolic fibre property is mostly on single performance
Improve, and other performances decline, it is difficult to which the multinomial performance of phenolic fibre is greatly improved on the original basis.
The content of the invention
To solve the problem of above-mentioned prior art is present, it is an object of the invention to provide a kind of resistance to high ortho position molybdenum phenol of ablation
The preparation method of aldehyde fiber.
There are spinning properties for phenolic fibre in the prior art poor, often need with the co-blended spinning such as PVA or PA, obtain
Fibrous mechanical property it is poor, heat resistance is not enough, ablation resistance shortcoming, is difficult to prolonged application in special dimension.The present invention is proposed
High ortho position Mo-phenolic resin, and spinning are synthesized by gentle method, it is excellent to have obtained ablation resistance by two-stage cure, resistance to
The high ortho position molybdenum phenolic fibre that high-temperature behavior, mechanical property are greatly improved.
To reach above-mentioned purpose, the technical scheme is that：
A kind of preparation method of the high ortho position molybdenum phenolic fibre of resistance to ablation, comprises the following steps：
（1）Mixed phenols compound and formaldehyde, add a certain amount of catalyst Titanium Citrate afterwards according to a certain percentage, boiling
React 0.5 ~ 2.9h；Above-mentioned phenolic compound is any one in phenol, paracresol, xylenol；
（2）Diluting concentrated sulfuric acid is added, continues to react 30min ~ 50min；
（3）Decompression dehydration 0.5-3h, resin temperature reaches 90-97 DEG C；
（4）Add mass ratio and be modified reaction for phenolic compound amount 6-18% molybdic acid, constant temperature seethes with excitement 2 hours；
（5）Decompression dehydration, until resin temperature rises to 100-130 DEG C of discharging, obtains molecular weight for 5000-30000Da, O/
P（Ortho para position ratio）It is worth for 4-8, the high ortho position molybdic acid phenolic resin that 140 DEG C of viscosity are 9-30.5cP；
（6）By resin in 120-170 DEG C of melt spinning；
（7）As-spun fibre is put into the solidify liquid configured, 95 DEG C is progressively warming up to since room temperature, constant temperature 0-2 is small
When, then naturally cool to room temperature；
（8）Filament after the solidification of two steps solidifies a step takes out cleaning and dried, and vacuum drying oven is put into afterwards, is set
Temperature is 50 DEG C and vacuumized 2 hours, is passed through nitrogen, is progressively warming up to 240 DEG C, naturally cools to room temperature after being kept for 0-2 hours, obtains
To high ortho position molybdenum phenolic fibre.
Further, in the step one, the mol ratio of phenolic compound and formaldehyde is 1:0.8-0.9, phenolic compound
It is 50 with Titanium Citrate mass ratio:0.5-2, reaction is carried out in three-necked flask.
Further, in the step 2, the 0.1-0.5ml concentrated sulfuric acids are added per 100g phenolic compounds.
Further, in the step 7, solidify liquid uses the ﹪ of formaldehyde mass fraction 18, the water of hydrochloric acid mass fraction 12%
Solution.
Further, in the step 7, the heating rate since room temperature is：Rise 1-6 DEG C within every 2 minutes.
Further, in the step 8, the heating rate for being warming up to 240 DEG C is：Rise 12-20 DEG C within every 2 minutes.
Beneficial effects of the present invention are：The present invention is compared with prior art from Titanium Citrate as catalyst, and molybdenum is modified,
With reaction rate is fast, simple and easy to apply, resin ortho para position ratio（O/P）Value is high, melt is uniform, viscosity is low, under the conditions of HMW
It is easy to spinning, spinning properties are good, solidification rate is fast, the degree of cross linking is high, by increasing Mo-O keys in high ortho position phenolic aldehyde molecule, due to
Mo-O is located on main chain, adds the energy to failure of phenolic aldehyde molecule, improves compliance, so that high ortho position molybdenum phenolic fibre
Ablation resistance, heat endurance, mechanical property and anti-flammability are obtained for raising, on the one hand improve fiber heat endurance,
Anti-flammability and ablation resistance, on the other hand solve high ortho phenolic fiber fragility greatly, the relatively low shortcoming of intensity has obtained comprehensive
Close the high ortho position molybdenum phenolic fibre of excellent performance.
The fibre strength of high ortho position molybdenum phenolic fibre is 3-34cN/dtex, and modulus is 40-400 cN/dtex, the degree of cross linking
30-38%, heat decomposition temperature reaches that the carbon left under 350 DEG C or so, 1000 DEG C of nitrogen atmospheres is up to 60-78%, limited oxygen index
For 36-43, so as to obtain that mechanical property, ablation resistance are excellent, the high ortho position molybdenum phenolic aldehyde that heat resistance, anti-flammability are improved is fine
Dimension.
Brief description of the drawings
Fig. 1 is the hot property of the high step cured fiber of ortho position molybdenum phenolic aldehyde two of 18% molybdic acid content.
Embodiment
Technical solution of the present invention is described in further detail with reference to the accompanying drawings and detailed description：
Embodiment 1
According to 1:0.85 mixed in molar ratio phenol（100g）With formaldehyde（73.3g）, the catalysis of 1g Titanium Citrates is added afterwards
Agent, boiling reaction 0.5h；Add diluting concentrated sulfuric acid（The concentrated sulfuric acid is 0.1ml）, continue to react 50min；Decompression dehydration 3h, resin temperature
Degree reaches 97 DEG C；Add quality and be modified reaction for 6g molybdic acid, constant temperature seethes with excitement 2 hours；Decompression dehydration, when resin temperature liter
To 100 DEG C of dischargings, molecular weight is obtained for 25000Da, O/P（Ortho para position ratio）It is worth for 4.8, the height neighbour that 140 DEG C of viscosity are 20.5cP
Position molybdic acid phenolic resin；
As-spun fibre is put into the solidify liquid configured by resin in 120 DEG C of melt spinnings（The ﹪ of formaldehyde mass fraction 18, salt
The aqueous solution of sour mass fraction 12%）In, progressively heated up since room temperature（Rise 1 DEG C within every 2 minutes）Rise to 95 DEG C, constant temperature 0 hour,
Then room temperature is naturally cooled to；
After silk after one step is solidified is cleaned and dried after taking out, vacuum drying oven is put into, sets temperature to be 50 DEG C and takes out true
It is empty 2 hours, nitrogen is passed through, is progressively heated up（Rise 12 DEG C within every 2 minutes）To 240 DEG C, room temperature is naturally cooled to after being kept for 0 hour, is obtained
To high ortho position molybdenum phenolic fibre.
The fibre strength of 6% high ortho position molybdenum phenolic fibre is 4cN/dtex, and modulus is 40 cN/dtex, the degree of cross linking 35%, heat
Decomposition temperature reaches that the carbon left under 290 DEG C, 1000 DEG C of nitrogen atmospheres is 62%, and limited oxygen index is 36.
Embodiment 2
According to 1:0.8 mixed in molar ratio phenol（100g）With formaldehyde（69.0g）, the catalysis of 4g Titanium Citrates is added afterwards
Agent, boiling reaction 2.9h；Add diluting concentrated sulfuric acid（The concentrated sulfuric acid is 0.5ml）, continue to react 30min；Decompression dehydration 0.5h, resin
Temperature reaches 90 DEG C；Add quality and be modified reaction for 18g molybdic acid, constant temperature seethes with excitement 2 hours；Decompression dehydration, when resin temperature
Degree rises to 109 DEG C of dischargings, obtains molecular weight for 5000Da, O/P（Ortho para position ratio）It is worth for 7.8, the height that 140 DEG C of viscosity are 9.5cP
Ortho position molybdic acid phenolic resin；
As-spun fibre is put into the solidify liquid configured by resin in 140 DEG C of melt spinnings（The ﹪ of formaldehyde mass fraction 18, salt
The aqueous solution of sour mass fraction 12%）In, progressively heated up since room temperature（Rise 6 DEG C within every 2 minutes）Rise to 95 DEG C, constant temperature 2 hours,
Then room temperature is naturally cooled to；
After silk after one step is solidified is cleaned and dried after taking out, vacuum drying oven is put into, sets temperature to be 50 DEG C and takes out true
It is empty 2 hours, nitrogen is passed through, is progressively heated up（Rise 20 DEG C within every 2 minutes）To 240 DEG C, room temperature is naturally cooled to after being kept for 2 hours, is obtained
To high ortho position molybdenum phenolic fibre.
The fibre strength of 18% high ortho position molybdenum phenolic fibre be 32cN/dtex, modulus be 380 cN/dtex, the degree of cross linking 36%,
Heat decomposition temperature reaches that the carbon left under 350 DEG C, 1000 DEG C of nitrogen atmospheres is 70%, and limited oxygen index is 42.It is as shown in Figure 1
The hot property of the 18% high step cured fiber of ortho position molybdenum phenolic aldehyde two.
Embodiment 3
The high ortho position molybdenum phenolic fibre of the gained of embodiment 2 is with phenolic resin according to 4:6 mass ratio, which be combined, obtains height
Ortho position molybdenum phenolic fibre/phenolic resin composite, the heat conductivity be 0.39W/m*K, linear ablative rate for-
0.010mm/s, oxy-acetylene flame mass ablative rate is 0.0213g/s, and density is 1.31g/cm3, it is residual under 1000 DEG C of nitrogen atmospheres
Charcoal amount is 75%, and limited oxygen index is 40.As a result show that the composite material interface is well combined, ablation resistance is excellent, with phenolic aldehyde
Resin is improved than thermal insulation, heat resistance and anti-flammability, and cooperative effect is obvious.
Embodiment 4
The fiber of the gained of embodiment 2 is made into 140g/m2, thickness 0.31mm plain cloth, limited oxygen index is 43,280
Carbonized after DEG C oxidation in nitrogen, 850 DEG C of steam activations obtain specific surface area 2280m2/ g active carbon fibre fabric, hole
Footpath 3.1nm, extension at break 3.9%, iodine absorption number is 2600mg/g.
Embodiment 5
According to 1:0.9 mixed in molar ratio phenol（100g）With formaldehyde（77.6g）, the catalysis of 3g Titanium Citrates is added afterwards
Agent, boiling reaction 1.5h；Add diluting concentrated sulfuric acid（The concentrated sulfuric acid is 0.3ml）, continue to react 40min；Decompression dehydration 2h, resin temperature
Degree reaches 95 DEG C；Add quality and be modified reaction for 10g molybdic acid, constant temperature seethes with excitement 2 hours；Decompression dehydration, works as resin temperature
130 DEG C of dischargings are risen to, molecular weight are obtained for 26000Da, O/P（Ortho para position ratio）It is worth for 6.7, the height neighbour that 140 DEG C of viscosity are 25cP
Position molybdic acid phenolic resin；
As-spun fibre is put into the solidify liquid configured by resin in 170 DEG C of melt spinnings（The ﹪ of formaldehyde mass fraction 18, salt
The aqueous solution of sour mass fraction 12%）In, progressively heated up since room temperature（Rise 4 DEG C within every 2 minutes）Rise to 95 DEG C, constant temperature 1 hour,
Then room temperature is naturally cooled to；
After silk after one step is solidified is cleaned and dried after taking out, vacuum drying oven is put into, sets temperature to be 50 DEG C and takes out true
It is empty 2 hours, nitrogen is passed through, is progressively heated up（Rise 16 DEG C within every 2 minutes）To 240 DEG C, room temperature is naturally cooled to after being kept for 1 hour, is obtained
To high ortho position molybdenum phenolic fibre.
The fibre strength of 10% high ortho position molybdenum phenolic fibre be 28cN/dtex, modulus be 200 cN/dtex, the degree of cross linking 34%,
Heat decomposition temperature reaches that the carbon left under 350 DEG C, 1000 DEG C of nitrogen atmospheres is 78%, and limited oxygen index is 43.
Embodiment 6
According to 1:0.85 mixed in molar ratio phenol（100g）With formaldehyde（73.3g）, the catalysis of 2g Titanium Citrates is added afterwards
Agent, boiling reaction 2h；Add diluting concentrated sulfuric acid（The concentrated sulfuric acid is 0.4ml）, continue to react 50min；Decompression dehydration 2.8h, resin temperature
Degree reaches 97 DEG C；Add quality and be modified reaction for 14g molybdic acid, constant temperature seethes with excitement 2 hours；Decompression dehydration, works as resin temperature
128 DEG C of dischargings are risen to, molecular weight are obtained for 23000Da, O/P（Ortho para position ratio）It is worth for 4.5, the height that 150 DEG C of viscosity are 22.5cP
Ortho position molybdic acid phenolic resin；
As-spun fibre is put into the solidify liquid configured by resin in 170 DEG C of melt spinnings（The ﹪ of formaldehyde mass fraction 18, salt
The aqueous solution of sour mass fraction 12%）In, progressively heated up since room temperature（Rise 3 DEG C within every 2 minutes）Rise to 95 DEG C, constant temperature 2 hours,
Then room temperature is naturally cooled to；
After silk after one step is solidified is cleaned and dried after taking out, vacuum drying oven is put into, sets temperature to be 50 DEG C and takes out true
It is empty 2 hours, nitrogen is passed through, is progressively heated up（Rise 14 DEG C within every 2 minutes）To 240 DEG C, room temperature is naturally cooled to after being kept for 0 hour, is obtained
To high ortho position molybdenum phenolic fibre.
The fibre strength of 14% high ortho position molybdenum phenolic fibre be 4.4cN/dtex, modulus be 42 cN/dtex, the degree of cross linking 39%,
Heat decomposition temperature reaches that the carbon left under 310 DEG C, 1000 DEG C of nitrogen atmospheres is 67%, and limited oxygen index is 38.
Embodiment 7
According to 1:0.9 mixed in molar ratio paracresol（100g）With formaldehyde（67.5g）, the catalysis of 3g Titanium Citrates is added afterwards
Agent, boiling reaction 1.5h；Add diluting concentrated sulfuric acid（The concentrated sulfuric acid is 0.3ml）, continue to react 40min；Decompression dehydration 2h, resin temperature
Degree reaches 95 DEG C；Add quality and be modified reaction for 10g molybdic acid, constant temperature seethes with excitement 2 hours；Decompression dehydration, works as resin temperature
130 DEG C of dischargings are risen to, molecular weight are obtained for 23000Da, O/P（Ortho para position ratio）It is worth for 5.7, the height neighbour that 140 DEG C of viscosity are 27cP
Position molybdic acid phenolic resin；
As-spun fibre is put into the solidify liquid configured by resin in 170 DEG C of melt spinnings（The ﹪ of formaldehyde mass fraction 18, salt
The aqueous solution of sour mass fraction 12%）In, progressively heated up since room temperature（Rise 1 DEG C within every 2 minutes）Rise to 95 DEG C, constant temperature 2 hours,
Then room temperature is naturally cooled to；
After silk after one step is solidified is cleaned and dried after taking out, vacuum drying oven is put into, sets temperature to be 50 DEG C and takes out true
It is empty 2 hours, nitrogen is passed through, is progressively heated up（Rise 12 DEG C within every 2 minutes）To 240 DEG C, room temperature is naturally cooled to after being kept for 0 hour, is obtained
To high ortho position molybdenum phenolic fibre.
The fibre strength of 10% high ortho position molybdenum phenolic fibre be 24cN/dtex, modulus be 32 cN/dtex, the degree of cross linking 31%,
Heat decomposition temperature reaches that the carbon left under 320 DEG C, 1000 DEG C of nitrogen atmospheres is 71%, and limited oxygen index is 42.
Embodiment 8
According to 1:0.85 mixed in molar ratio xylenol（100g）With formaldehyde（66.4g）, 2g Titanium Citrates are added afterwards urges
Agent, boiling reaction 2h；Add diluting concentrated sulfuric acid（The concentrated sulfuric acid is 0.4ml）, continue to react 40min；Decompression dehydration 2.5h, resin
Temperature reaches 97 DEG C；Add quality and be modified reaction for 14g molybdic acid, constant temperature seethes with excitement 2 hours；Decompression dehydration, when resin temperature
Degree rises to 128 DEG C of dischargings, obtains molecular weight for 25000Da, O/P（Ortho para position ratio）It is worth for 4.7,150 DEG C of viscosity are 21.5cP's
High ortho position molybdic acid phenolic resin；
As-spun fibre is put into the solidify liquid configured by resin in 170 DEG C of melt spinnings（The ﹪ of formaldehyde mass fraction 18, salt
The aqueous solution of sour mass fraction 12%）In, progressively heated up since room temperature（Rise 1 DEG C within every 2 minutes）Rise to 95 DEG C, constant temperature 2 hours,
Then room temperature is naturally cooled to；
After silk after one step is solidified is cleaned and dried after taking out, vacuum drying oven is put into, sets temperature to be 50 DEG C and takes out true
It is empty 2 hours, nitrogen is passed through, is progressively heated up（Rise 12 DEG C within every 2 minutes）To 240 DEG C, room temperature is naturally cooled to after being kept for 0 hour, is obtained
To high ortho position molybdenum phenolic fibre.
The fibre strength of 14% high ortho position molybdenum phenolic fibre be 4.1cN/dtex, modulus be 62 cN/dtex, the degree of cross linking 49%,
Heat decomposition temperature reaches that the carbon left under 332 DEG C, 1000 DEG C of nitrogen atmospheres is 68%, and limited oxygen index is 36.
Claims (4)
1. a kind of preparation method of the high ortho position molybdenum phenolic fibre of resistance to ablation, it is characterised in that comprise the following steps：
（1）Phenolic compound is mixed with formaldehyde, Titanium Citrate, 0.5 ~ 2.9h of boiling reaction, the phenols chemical combination is then added
Thing is any one in phenol, paracresol, xylenol, and the ratio between amount of material of the phenolic compound and formaldehyde is 1:0.8-
0.9, the mass ratio of phenolic compound and Titanium Citrate is 50:0.5-2；
（2）The concentrated sulfuric acid is added, the 0.1-0.5ml concentrated sulfuric acids are added per 100g phenolic compounds, continues to react 30min ~ 50min；
（3）Decompression dehydration 0.5-3h, resin temperature reaches 90-97 DEG C；
（4）Molybdic acid is added, the addition quality of the molybdic acid is the 6-18% of phenolic compound quality, and constant temperature seethes with excitement 2 hours；
（5）Decompression dehydration, until resin temperature rises to 100-130 DEG C of discharging, obtains high ortho position molybdic acid phenolic resin；
（6）By high ortho position molybdic acid phenolic resin melt spinning under the conditions of 120-170 DEG C, as-spun fibre is obtained；
（7）As-spun fibre is put into the solidify liquid configured, is progressively warming up to 95 DEG C since room temperature, constant temperature 0-2 hours, so
After naturally cool to room temperature, obtain filament；
（8）Filament is taken out and cleans and dries, vacuum drying oven is put into afterwards, sets temperature to be 50 DEG C and vacuumizes 2 hours, be passed through
Nitrogen, is progressively warming up to 240 DEG C, naturally cools to room temperature after being kept for 0-2 hours, obtains high ortho position molybdenum phenolic fibre.
2. the preparation method of the high ortho position molybdenum phenolic fibre of resistance to ablation according to claim 1, it is characterised in that：The step
（7）Middle solidify liquid is the mixed liquor for the hydrochloric acid that the formaldehyde and mass fraction that mass fraction is 18% are 12%.
3. the preparation method of the high ortho position molybdenum phenolic fibre of resistance to ablation according to claim 1, it is characterised in that：The step
（7）Middle heating rate is to rise 1-7 DEG C in every 2 minutes.
4. the preparation method of the high ortho position molybdenum phenolic fibre of resistance to ablation according to claim 1, it is characterised in that：The step
（8）Middle heating rate is to rise 12-20 DEG C in every 2 minutes.
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| CN107815742B (en) * | 2017-11-10 | 2020-05-01 | 中国科学院山西煤炭化学研究所 | Solidification method of thermosetting phenolic resin protofilament |
| CN108823798B (en) * | 2018-07-27 | 2020-08-07 | 中原工学院 | Preparation method of phenyl molybdate modified high-ortho thermosetting phenolic-based hollow nano gradient activated carbon fiber membrane |
| CN109056101B (en) * | 2018-07-27 | 2021-01-26 | 中原工学院 | Method for preparing molybdic acid modified high-molecular-weight high-ortho thermosetting phenolic fiber through wet spinning |
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| CN101289768A (en) * | 2008-06-13 | 2008-10-22 | 陕西师范大学 | Method for preparing boronphenolic fibre |
| CN103060941A (en) * | 2013-01-15 | 2013-04-24 | 中原工学院 | Preparation method of high molecular weight phenolic fiber |
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| CN101289768A (en) * | 2008-06-13 | 2008-10-22 | 陕西师范大学 | Method for preparing boronphenolic fibre |
| CN103060941A (en) * | 2013-01-15 | 2013-04-24 | 中原工学院 | Preparation method of high molecular weight phenolic fiber |
| CN103409841A (en) * | 2013-07-30 | 2013-11-27 | 中原工学院 | Preparation method of boric acid modified high-ortho phenolic fiber |
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