CN103046154A - Preparation method of dual-catalytic phenolic aldehyde fibers - Google Patents
Preparation method of dual-catalytic phenolic aldehyde fibers Download PDFInfo
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- CN103046154A CN103046154A CN2013100135945A CN201310013594A CN103046154A CN 103046154 A CN103046154 A CN 103046154A CN 2013100135945 A CN2013100135945 A CN 2013100135945A CN 201310013594 A CN201310013594 A CN 201310013594A CN 103046154 A CN103046154 A CN 103046154A
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Abstract
The invention relates to a preparation method of dual-catalytic phenolic aldehyde fibers, which is characterized by comprising the following steps: (1) adding weak acid salt of divalent metal into phenolic compounds and aldehyde compounds to prepare a spinnable phenolic aldehyde resin; (2) carrying out melt spinning on the spinnable phenolic aldehyde resin at 120-200 DEG C to prepare phenolic aldehyde fiber fibrils; and (3) curing and crosslinking the phenolic aldehyde fibers fibrils in a curing liquid at 10-95 DEG C for 2-300 minutes to prepre the phenolic aldehyde fibers. The invention has the advantages of cheap and accessible raw materials, low condition requirements for reaction and sufficient synthetic reaction. The prepared phenolic resin with high molecular weight (2000-50000) and high ortho rate (50-95%) has the advantages of simple structure, high spinning speed, small fiber diameter and excellent spinning property. The curing and crosslinking speed of the fibrils is high, the diameter of the prepared fibers can be controlled at 2-13 micrometers, the tensile strength is 150-700 MPa, the elastic modulus can reach 2900 MPa, and the elongation at break can reach 10-20%.
Description
Technical field
The invention belongs to the preparation field of organic fiber, particularly a kind of by two high ortho position phenolic aldehyde that catalyze and synthesize, melt spinning, curing cross-linked obtain the method for high-performance pnenolic aldehyde fiber.
Background technology
In the world wide, the output of phenolic resins is about 4,000,000 tons, and the Year's consumption of domestic phenolic resins has reached 700,000 tons, and constantly studies the frontier of expansion phenolic aldehyde always.Nowadays phenolic aldehyde has been widely used in the fields such as wood bonding, moulding compound, casting mould material, refractory material, rubber for tire, friction material, grinding tool abrasive material, electronic package material, dipping laminated material, fibre reinforced composites, phenolic foam.Along with progress of research, synthetic to become more meticulous, controlledization development, the molecular structure control of synthetic phenolic aldehyde is gradually deeply.By initial A, B, the C b stage resin b of being divided into, to the appearance of high adjacent position phenolic resin, grasped gradually obtaining that structure is clear and definite, molecular weight is controlled, viscosity is low, the method for the high adjacent position phenolic resin of quick solidifying.Nowadays the fields such as rubber mass, injection molding material, plastic packaging material are widened in the application of high adjacent position phenolic resin gradually.
With respect to the output of phenolic resins megaton, the global output of phenolic fibre only is about 1500 tons, and domestic especially without industrialization product.Only rose in 2000, Chinese Academy of Sciences's Shanxi coalification has begun to carry out development [the C.L. Liu of phenolic fibre, Q.G. Guo, J.L. Shi. A Study on Crosslinking of Phenolic Fibers[J]. Materials Chemistry and Physics, 2005,90,315 – 321], and then Shaanxi Normal University [Dong Wensheng, Liu Chunling, Yin Yonggang. the preparation method of phenolic resin fiber of high molecular weight [P]. number of patent application, 200810150043,2008], University Of Tianjin [Guo Jinhai, Shandong, Ye Jianzhong. fiber number and pre-oxidation treatment are on the impact [J] of phenolic fibre performance. New Chemical Materials, 2010 (4), 74-76] etc. unit prepare phenolic resins by diverse ways, and prepared phenolic fibre, but the research scale is generally less; The phenolic fibre production in the whole world is monopolized by Kynol on the other hand, and correlative study is less, and this has all caused making slow progress of phenolic fibre.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of pair of catalysis phenolic fibre.Under normal pressure, the reactant liquor of phenol and aldehyde is synthetic resin under two catalysis of divalent metal salt of weak acid and hydrochloric acid, and decompression dehydration, melt spinning prepare high ortho position phenolic aldehyde fibril, and curing cross-linked then prepares the high ortho position phenolic fibre of different aggregated structures.The method provides the method for the excellent phenolic fibre of a kind of processability.
Technical scheme of the present invention is: the preparation method of a kind of pair of catalysis phenolic fibre, and its step is as follows:
(1) in phenolic compound and aldehyde compound, adds the reaction of divalent metal salt of weak acid, described phenolic compound is 1.5 ~ 1:1 with the ratio of the amount of substance of aldehyde compound, under 80 ~ 110 ℃ of conditions, react 0.1h ~ 10h, and then the dropping mass fraction is 37% concentrated hydrochloric acid reaction, the molar ratio of described aldehyde compound and divalent metal salt of weak acid, hydrochloric acid is 1:0.001 ~ 0.09:0.001 ~ 0.1, continue reaction, time is 0.1h ~ 10h, 50 ~ 100 ℃ of lower decompression dehydration 0.5 ~ 5h make spinnability phenolic resins;
(2) with spinnability phenolic resins melt spinning under 120 ~ 200 ℃ condition, make the phenolic fibre fibril;
(3) with phenolic fibre curing cross-linked in consolidation liquid, temperature is 10 ~ 95 ℃, and the time is 2 ~ 300min, makes phenolic fibre.
Phenolic compound is phenol or p-cresol in the described step (1), described aldehyde compound be formaldehyde, acetaldehyde, with the paraformaldehyde of formaldehyde Isoequivalent weight, with the metaformaldehyde of formaldehyde Isoequivalent weight, with the para-acetaldehyde of formaldehyde Isoequivalent weight, described divalent metal salt of weak acid is calcium oxalate, zinc acetate or calcium acetate.
In phenolic compound and aldehyde compound, add the reaction of divalent metal salt of weak acid in the described step (1), under 80 ~ 110 ℃ of conditions, react 2 ~ 6h, and then drip the reaction of 37% concentrated hydrochloric acid, continue reaction, time is 0.4 ~ 5h, 50 ~ 100 ℃ of lower decompression dehydration 0.5 ~ 5h, make spinnability phenolic resins, described phenolic compound is 1.25 ~ 1.05 with the ratio of the amount of substance of aldehyde compound, and the molar ratio of described aldehyde compound and divalent metal salt of weak acid, hydrochloric acid is 1:0.005 ~ 0.04:0.02 ~ 0.08.
Described consolidation liquid is that water, mass fraction are 37% concentrated hydrochloric acid and the mixture of aldehyde, and water, hydrochloric acid are 1:0.03 ~ 0.14:0.03 ~ 0.14 with the ratio of the amount of substance of aldehyde, and described aldehyde is formaldehyde or acetaldehyde.
Described consolidation liquid is that water, mass fraction are 98% the concentrated sulfuric acid and the mixture of aldehyde, and water, sulfuric acid are 1:0.015 ~ 0.07:0.03 ~ 0.14 with the ratio of the amount of substance of aldehyde, and described aldehyde is formaldehyde or acetaldehyde.
Described consolidation liquid is that water, mass fraction are 85% SPA and the mixture of aldehyde, and water, phosphoric acid are 1:0.01 ~ 0.05:0.03 ~ 0.14 with the ratio of the amount of substance of aldehyde, and described aldehyde is formaldehyde or acetaldehyde.
The present invention has the following advantages: raw material is cheap and easy to get, and the reaction requirement condition is low, and synthetic reaction is abundant.Obtain molecular weight and be 2000 ~ 50000 high molecular, 50 ~ 95% high adjacent position phenolic resin, simple in structure, spinning speed is fast, fibre diameter is little, and spinning properties is outstanding.The curing cross-linked speed of precursor is fast, and the fibre diameter of preparation can be controlled in 2 ~ 13 microns, and TENSILE STRENGTH 150-700MPa, elastic modelling quantity can arrive 2900MPa, and elongation at break can reach 10 ~ 20% simultaneously.
The specific embodiment
Embodiment 1
Weighing phenol 94g, 37% formaldehyde 54g(amount of substance is respectively 1mol, 0.67mol) pour in the there-necked flask, electric stirring, and to wherein adding zinc acetate (6.7 * 10
-4Mol), be warming up to boiling, add hydrochloric acid (6.7 * 10 behind the reaction 10h
-4Mol), behind the back flow reaction 0.1h, heat filtering and at 50 ℃ of lower decompression dehydration 5h, the high molecular high adjacent position phenolic resin that makes, molecular weight are 50000, ortho position accounting 95%.120 ℃ of precursor curing cross-linked 300min in 10 ℃ coagulating bath (water: hydrochloric acid: the amount of substance of formaldehyde is 1:0.03:0.03) that lower melt spinning obtains make the high ortho position of crosslinked high molecular phenolic fibre.
Embodiment 2
Weighing phenol 94g, 37% formaldehyde 81g(amount of substance is 1mol) pour in the there-necked flask, electric stirring, and to wherein adding zinc acetate (0.09mol), be warming up to boiling, add hydrochloric acid (0.1mol) behind the reaction 0.1h, behind the back flow reaction 10h, heat filtering and at 70 ℃ of lower decompression dehydration 3.5h, the high molecular high adjacent position phenolic resin that makes, molecular weight is 2000, ortho position accounting 95%.200 ℃ of precursor curing cross-linked 2min in 95 ℃ coagulating bath (water: sulfuric acid: the amount of substance of formaldehyde is 1:0.07:0.03) that lower melt spinning obtains make the high ortho position of crosslinked high molecular phenolic fibre.
Embodiment 3
Weighing p-cresol 108g, 37% formaldehyde 54g(amount of substance is respectively 1mol, 0.67mol) pour in the there-necked flask, electric stirring, and to wherein adding calcium acetate (6.7 * 10
-4Mol), be warming up to 80 ℃, reaction adds hydrochloric acid (0.067mol) behind the 10h, behind the back flow reaction 0.1h, and heat filtering and at 60 ℃ of lower decompression dehydration 5h, the high molecular high adjacent position phenolic resin that makes, molecular weight are 50000, ortho position accounting 50%.120 ℃ of precursor curing cross-linked 300min in 10 ℃ coagulating bath (water: phosphoric acid: the amount of substance of acetaldehyde is 1:0.01:0.03) that lower melt spinning obtains make the high ortho position of crosslinked high molecular phenolic fibre.
Embodiment 4
Weighing phenol 94g, 40% acetaldehyde 110g(amount of substance is 1mol) pour in the there-necked flask, electric stirring, and to wherein adding calcium oxalate (0.09mol), be warming up to boiling, add hydrochloric acid (1 * 10 behind the reaction 0.1h
-3Mol), behind the back flow reaction 10h, heat filtering and at 70 ℃ of lower decompression dehydration 0.5h, the high molecular high adjacent position phenolic resin that makes, molecular weight are 2000, ortho position accounting 50%.200 ℃ of precursor curing cross-linked 10min in 95 ℃ coagulating bath (water: ammonia: the amount of substance of formaldehyde is 1:0.14:0.14) that lower melt spinning obtains make the high ortho position of crosslinked high molecular phenolic fibre.
Embodiment 5
Weighing phenol 94g, 37% formaldehyde 69g(amount of substance is respectively 1mol, 0.85mol) pour in the there-necked flask electric stirring into, and to wherein adding zinc acetate (0.012mol), be warming up to boiling, add hydrochloric acid (0.04mol) behind the reaction 4h, behind the back flow reaction 0.9h, heat filtering and at 50 ℃ of lower decompression dehydration 5h, the high molecular high adjacent position phenolic resin that makes, molecular weight are 50000, ortho position accounting 95%.150 ℃ of precursor curing cross-linked 40min in 70 ℃ coagulating bath (water: hydrochloric acid: the amount of substance of formaldehyde is 1:0.03:0.03) that lower melt spinning obtains make the high ortho position of crosslinked high molecular phenolic fibre.
Embodiment 6
Weighing phenol 94g, 37% formaldehyde 69g(amount of substance is respectively 1mol, 0.85mol) pour in the there-necked flask electric stirring into, and to wherein adding zinc acetate (0.02mol), be warming up to boiling, add hydrochloric acid (0.035mol) behind the reaction 3.5h, behind the back flow reaction 0.5h, heat filtering and at 70 ℃ of lower decompression dehydration 3.5h, the high molecular high adjacent position phenolic resin that makes, molecular weight are 2500, ortho position accounting 95%.130 ℃ of precursor curing cross-linked 29min in 65 ℃ coagulating bath (water: sulfuric acid: the amount of substance of formaldehyde is 1:0.07:0.03) that lower melt spinning obtains make the high ortho position of crosslinked high molecular phenolic fibre.
Embodiment 7
Weighing p-cresol 108g, 37% formaldehyde 69g(amount of substance is respectively 1mol, 0.85mol) pour in the there-necked flask electric stirring into, and to wherein adding calcium acetate (0.01mol), be warming up to 97 ℃, add hydrochloric acid (0.04mol) behind the reaction 5h, behind the back flow reaction 0.9h, heat filtering and at 60 ℃ of lower decompression dehydration 5h, the high molecular high adjacent position phenolic resin that makes, molecular weight are 50000, ortho position accounting 70%.150 ℃ of precursor curing cross-linked 50min in 65 ℃ coagulating bath (water: phosphoric acid: the amount of substance of acetaldehyde is 1:0.01:0.03) that lower melt spinning obtains make the high ortho position of crosslinked high molecular phenolic fibre.
Embodiment 8
Weighing phenol 94g, 40% acetaldehyde 93.5g(amount of substance is respectively 1mol, 0.85mol) pour in the there-necked flask electric stirring into, and to wherein adding calcium oxalate (0.03mol), be warming up to boiling, add hydrochloric acid (0.045mol) behind the reaction 4h, behind the back flow reaction 0.8h, heat filtering and at 70 ℃ of lower decompression dehydration 0.5h, the high molecular high adjacent position phenolic resin that makes, molecular weight are 2000, ortho position accounting 60%.140 ℃ of precursor curing cross-linked 40min in 65 ℃ coagulating bath (water: ammonia: the amount of substance of formaldehyde is 1:0.14:0.14) that lower melt spinning obtains make the high ortho position of crosslinked high molecular phenolic fibre.
Claims (6)
1. the preparation method of two catalysis phenolic fibres is characterized in that its step is as follows:
(1) in phenolic compound and aldehyde compound, adds the reaction of divalent metal salt of weak acid, described phenolic compound is 1.5 ~ 1:1 with the ratio of the amount of substance of aldehyde compound, under 80 ~ 110 ℃ of conditions, react 0.1h ~ 10h, and then the dropping mass fraction is 37% concentrated hydrochloric acid reaction, the molar ratio of described aldehyde compound and divalent metal salt of weak acid, hydrochloric acid is 1:0.001 ~ 0.09:0.001 ~ 0.1, continue reaction, time is 0.1h ~ 10h, 50 ~ 100 ℃ of lower decompression dehydration 0.5 ~ 5h make spinnability phenolic resins;
(2) with spinnability phenolic resins melt spinning under 120 ~ 200 ℃ condition, make the phenolic fibre fibril;
(3) with phenolic fibre curing cross-linked in consolidation liquid, temperature is 10 ~ 95 ℃, and the time is 2 ~ 300min, makes phenolic fibre.
2. the preparation method of according to claim 1 pair of catalysis phenolic fibre, it is characterized in that: phenolic compound is phenol or p-cresol in the described step (1), described aldehyde compound be formaldehyde, acetaldehyde, with the paraformaldehyde of formaldehyde Isoequivalent weight, with the metaformaldehyde of formaldehyde Isoequivalent weight, with the para-acetaldehyde of formaldehyde Isoequivalent weight, described divalent metal salt of weak acid is calcium oxalate, zinc acetate or calcium acetate.
3. the preparation method of according to claim 1 pair of catalysis phenolic fibre, it is characterized in that: in phenolic compound and aldehyde compound, add the reaction of divalent metal salt of weak acid in the described step (1), under 80 ~ 110 ℃ of conditions, react 2 ~ 6h, and then drip the reaction of 37% concentrated hydrochloric acid, continue reaction, time is 0.4 ~ 5h, 50 ~ 100 ℃ of lower decompression dehydration 0.5 ~ 5h, make spinnability phenolic resins, described phenolic compound is 1.25 ~ 1.05 with the ratio of the amount of substance of aldehyde compound, described aldehyde compound and divalent metal salt of weak acid, the molar ratio of hydrochloric acid is 1:0.005 ~ 0.04:0.02 ~ 0.08.
4. the preparation method of a kind of pair of catalysis phenolic fibre according to claim 1, it is characterized in that: described consolidation liquid is that water, mass fraction are 37% concentrated hydrochloric acid and the mixture of aldehyde, water, hydrochloric acid are 1:0.03 ~ 0.14:0.03 ~ 0.14 with the ratio of the amount of substance of aldehyde, and described aldehyde is formaldehyde or acetaldehyde.
5. the preparation method of a kind of pair of catalysis phenolic fibre according to claim 1, it is characterized in that: described consolidation liquid is that water, mass fraction are 98% the concentrated sulfuric acid and the mixture of aldehyde, water, sulfuric acid are 1:0.015 ~ 0.07:0.03 ~ 0.14 with the ratio of the amount of substance of aldehyde, and described aldehyde is formaldehyde or acetaldehyde.
6. the preparation method of a kind of pair of catalysis phenolic fibre according to claim 1, it is characterized in that: described consolidation liquid is that water, mass fraction are 85% SPA and the mixture of aldehyde, water, phosphoric acid are 1:0.01 ~ 0.05:0.03 ~ 0.14 with the ratio of the amount of substance of aldehyde, and described aldehyde is formaldehyde or acetaldehyde.
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| CN104109911A (en) * | 2014-07-02 | 2014-10-22 | 陕西省石油化工研究设计院 | Preparation method for maleimide-modified phenolic fiber |
| CN108950720A (en) * | 2018-07-27 | 2018-12-07 | 中原工学院 | A method of the modified high ortho phenolic fiber of phenyl-borate is prepared by wet spinning |
| CN109081338A (en) * | 2018-07-27 | 2018-12-25 | 中原工学院 | A kind of preparation method of the high hollow nanometer gradient activated carbon fiber film of ortho position boron modification thermosetting phenolic base |
| CN109208116A (en) * | 2018-07-27 | 2019-01-15 | 中原工学院 | A method of high ortho position thermosetting phenolic fiber is prepared using wet spinning |
| CN113215668A (en) * | 2021-04-16 | 2021-08-06 | 山西钢科碳材料有限公司 | Polyacrylonitrile nascent fiber, polyacrylonitrile fiber and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109208116A (en) * | 2018-07-27 | 2019-01-15 | 中原工学院 | A method of high ortho position thermosetting phenolic fiber is prepared using wet spinning |
| CN109208116B (en) * | 2018-07-27 | 2021-03-16 | 中原工学院 | Method for preparing high-ortho thermosetting phenolic fiber by adopting wet spinning |
| CN113215668A (en) * | 2021-04-16 | 2021-08-06 | 山西钢科碳材料有限公司 | Polyacrylonitrile nascent fiber, polyacrylonitrile fiber and preparation method thereof |
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Application publication date: 20130417 |