CN101289767A - Method for preparing phenolic resin fiber of high molecular weight - Google Patents
Method for preparing phenolic resin fiber of high molecular weight Download PDFInfo
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Abstract
The invention relates to a method for preparing high molecular weight phenolic resin fibers, comprising the following processing steps of: mixture making, chemical reaction, preparation of phenolic resins, preparation of nascent fibers, preparation of solidifying liquid, solidification reaction, and washing and drying. The method adopts phenol and aldehyde as raw materials which are prepared into the high molecular weight phenolic resins under the condition of high temperature and high pressure; after melt-spinning, the solidification reaction is performed in the solidifying liquid and the high molecular weight phenolic resin fibers are prepared. The method has the advantages of short reaction time, high curing degree and so on; the high molecular weight phenolic resin fibers prepared by adoption of the method have high mechanical strength via test and are characterized by antiflamming, flame resistance, heat insulation, corrosion resistance and so on; the materials can be used as heat-insulating, insulating and corrosion resistant materials of an aerial aerocraft, as materials of fireproof and corrosion resistant clothes and also as materials of an acid and corrosion resistant filter, and are also raw materials of special fibers such as carbon fibers, graphite fibers, active carbon fibers, ion exchangers and so on.
Description
Technical field
The invention belongs to macromolecule phenolic fiber material technology field, relate to the preparation method of highly cross-linkedization phenolic fiber particularly.
Background technology
Phenolic fibre is owing to have flame proof, anti-combustion, thermal insulation and characteristic such as anti-corrosion, can be used for adiabatic in space travel, national defence and the aircraft industry, insulation and resistant material, also can be used as fire prevention, anticorrosion is obeyed and acidproof, corrosion-resistant filtering material.Be again the primary raw materials of special fibres such as charcoal fiber, graphite fibre, active carbon fibre peacekeeping ion-exchange simultaneously.
The patent No. is 3714111 United States Patent (USP), discloses the preparation method of phenolic fibre, and this method, and then is solidified in hydrochloric acid and formaldehyde baths and made through the fusion method spinning by novolac resin.In the method, as-spun fibre will just can be warming up to the curing reaction of finishing phenolic fibre under 100 ℃, time consumption and energy consumption through the reaction of several hrs down at 40 ℃ and 60 ℃.
Existing phenolic resins preparation method, select for use formaldehyde and excessive phenol under the strong acid catalytic action, the ortho position of formaldehyde and phenol or contraposition generation addition reaction obtain a hydroxymethylphenol, this intermediate product is reset rapidly, with the unreacted hydrogen atom generation in ortho position dehydration condensation on another phenol molecule, connect with the methine bridging, form the linear pattern novolac resin.Phenolic resins molecular weight with this method preparation is low, has only 500～1000g/mol, degree of branching height.In curing reaction,
+CH
2OH need overcome the sterically hindered reaction position that just can diffuse to, and solidification rate is slow, and can not make all reaction positions that the addition polycondensation reaction takes place, and the cured fiber crosslinking degree is low, and intensity is low.The employing high molecular weight phenolic resin is a persursor material, the drawback that can avoid commercial phenolic resins to bring.
The patent No. is 4299947, denomination of invention is the preparation of " high molecular weight phenolic resin ", adopt divalent metal salt to make the ortho position inducing catalyst, but easy gel in the phenol formaldehyde condensation process, free phenol content height, and containing metal impurity in the resin influences the anti-ablation heat-proof quality of goods.
Summary of the invention
Technical problem to be solved by this invention is to overcome above-mentioned phenolic resins preparation method's shortcoming, provide a kind of product not containing metal hetero atom, intensity height, have the preparation method of the phenolic fiber of anti-ablation heat-proof quality.
Solving the problems of the technologies described above the technical scheme that is adopted is that it comprises the steps:
1, batching
With phenol or m-cresol and aldehyde compound is 1: 0.5～0.9 to join in the autoclave in molar ratio.
Above-mentioned aldehyde compound be formaldehyde or acetaldehyde or with the paraformaldehyde of quality such as formaldehyde or with the metaformaldehyde of quality such as formaldehyde, paraformaldehyde is that the degree of polymerization is 8～100 low molecular weight polyformaldehyde, rich Dihua worker Co., Ltd produces by Tianjin.
2, chemical reaction
Reactant is warming up to 120～240 ℃ under stirring, pressure is 2.0～7.0MPa, isothermal reaction 30～140 minutes.
3, preparation phenolic resins
After reaction finishes, product is put into vacuum drying chamber, 120～220 ℃ of dryings 1～9 hour, controlled pressure-0.05～-0.09MPa, be prepared into phenolic resins.
4, preparation as-spun fibre
High molecular weight phenolic resin is put into the melt spinning device spinning, and the concrete grammar of melt spinning is that 3714111 the disclosed preparation method of United States Patent (USP) is prepared into as-spun fibre according to the patent No..
5, preparation consolidation liquid
Water intaking, acid, aldehyde compound are mixed with consolidation liquid, and water is 1: 0.03～0.15: 0.03～0.15 with the mol ratio of acid, aldehyde compound;
Above-mentioned aldehyde compound be formaldehyde or acetaldehyde or with the paraformaldehyde of quality such as formaldehyde or with the metaformaldehyde of quality such as formaldehyde; Above-mentioned acid is hydrochloric acid or sulfuric acid or oxalic acid or phosphoric acid, promptly uses 1 mole hydrochloride or 1/2 mol sulfuric acid or 1/2 mole of oxalic acid or 1/3 mole of phosphoric acid.
6, curing reaction
As-spun fibre is put into consolidation liquid, and the mass ratio of consolidation liquid and as-spun fibre is 100: 5～40, is warming up to 60～100 ℃, isothermal reaction 0.5～4.5 hour.
7, flushing is dry
After reaction finishes, fiber is taken out, use deionized water rinsing 3～5 times, air dry is prepared into phenolic resin fiber of high molecular weight.
8, test
The fracture strength of phenolic resin fiber of high molecular weight adopts the dynamic viscoelasticity spectrum instrument to test according to " synthetic staple ultimate strength and extension at break experimental technique " GB/T 14337-93.
In proportioning process step 1 of the present invention, the preferred molar ratio of phenol or m-cresol and aldehyde compound is 1: 0.5～0.8.In chemical reaction process step 2 of the present invention, reactant preferably is warming up to 150～240 ℃, pressure under stirring be 3.0～7.0MPa, isothermal reaction 50～100 minutes.In preparation phenolic aldehyde resin art step 3 of the present invention, product is put into vacuum drying chamber, preferred 150～200 ℃ of dryings 3～8 hours, controlled pressure-0.06～-0.08MPa.In preparation consolidation liquid processing step 5 of the present invention, water is 1: 0.06～0.12: 0.06～0.12 with the preferred molar ratio of acid, aldehyde compound, described acid is hydrochloric acid or sulfuric acid or oxalic acid or phosphoric acid, promptly uses 1 mole hydrochloride or 1/2 mol sulfuric acid or 1/2 mole of oxalic acid or 1/3 mole of phosphoric acid.In curing reaction processing step 6 of the present invention, consolidation liquid is 100: 10～30 with the preferred mass ratio of as-spun fibre, be warming up to 80～100 ℃, isothermal reaction 1.5～4 hours.
In proportioning process step 1 of the present invention, the best of phenol or m-cresol and aldehyde compound is 1: 0.7 in molar ratio.In chemical reaction process step 2 of the present invention, reactant optimum temperature rise to 210 ℃, pressure under stirring are 6.0MPa, isothermal reaction 50 minutes.In preparation phenolic aldehyde resin art step 3 of the present invention, product is put into vacuum drying chamber, best 180 ℃ of dryings 5 hours, controlled pressure are at-0.07MPa.In preparation consolidation liquid processing step 5 of the present invention, water is 1: 0.09: 0.09 with the optimum mole ratio of acid, aldehyde compound, described acid is hydrochloric acid or sulfuric acid or oxalic acid or phosphoric acid, promptly uses 1 mole hydrochloride or 1/2 mol sulfuric acid or 1/2 mole of oxalic acid or 1/3 mole of phosphoric acid.In curing reaction processing step 6 of the present invention, the optimum quality ratio of consolidation liquid and as-spun fibre is 100: 20, is warming up to 100 ℃, isothermal reaction 2.5 hours.
It is raw material that the present invention adopts phenol and aldehyde, under high-temperature and high-pressure conditions, be prepared into high molecular weight phenolic resin, through the melting spinning, in consolidation liquid, be cured reaction, be prepared into phenolic resin fiber of high molecular weight, it is short that the present invention has the reaction time, the state of cure advantages of higher, the phenolic resin fiber of high molecular weight of employing the present invention preparation is the mechanical strength height after tested, has flame proof, anti-combustion, characteristic such as adiabatic and anti-corrosion, this material, can be used for the thermal insulation of space flight and aviation aircraft, insulation and resistant material, also can be used for fire prevention, the material of anticorrosion clothes also can be used for acidproof, the material of corrosion-resistant filter also is the charcoal fiber, graphite fibre, the raw material of special fibres such as active carbon fibre peacekeeping ion-exchanger.
The specific embodiment
The present invention is described in more detail below in conjunction with embodiment, but the invention is not restricted to these embodiment.
Embodiment 1
With 0.5 mole of m-cresol is that example is prepared into high-ortho novolac resin used other raw material and preparation method and comprises the steps:
1, batching
Get m-cresol 54g and paraformaldehyde 10.5g joins in the autoclave, promptly the mol ratio of m-cresol and paraformaldehyde formaldehyde identical in quality is 1: 0.7, and paraformaldehyde is that the degree of polymerization is 8～100 low molecular weight polyformaldehyde.
2, chemical reaction
Reactant is warming up to 210 ℃ under stirring, pressure is 6.0MPa, isothermal reaction 50 minutes.
3, preparation phenolic resins
After reaction finishes, product is put into vacuum drying chamber, 180 ℃ of dryings 5 hours, controlled pressure are prepared into phenolic resins at-0.07MPa.
Prepared one-tenth phenolic resins adopts gel permeation chromatography, measure phenolic resins molecular weight and distribution thereof down at 30 ℃, molecular weight is 48200, splitter is that (RT 1.0 for Aquapak A-440, RT 2.0, RT 5.0), the flow rate of solvents tetrahydrofurane is 1.0ml/min, standard specimen is that (molecular weight is 474～205000g/mo1) to monodisperse polystyrene.
4, preparation as-spun fibre
High molecular weight phenolic resin is put into the melt spinning device spinning, and the concrete grammar of melt spinning is that 3714111 the disclosed preparation method of United States Patent (USP) is prepared into as-spun fibre according to the patent No..
5, preparation consolidation liquid
Water intaking 100g, mass concentration are that 30% hydrochloric acid 117.65g, mass concentration are that 40% acetaldehyde 88.24g is mixed with consolidation liquid according to a conventional method, and promptly the mass ratio of water, hydrochloric acid, acetaldehyde is 100: 15: 15.
5, curing reaction
Get as-spun fibre 20g and put into consolidation liquid 100g, average rate heated up 2.5 hours to 100 ℃ and is cured reaction.
6, flushing is dry
After reaction finishes, fiber is taken out, use deionized water rinsing 3～5 times, air dry is prepared into phenolic resin fiber of high molecular weight.
7, test
The fracture strength of phenolic resin fiber of high molecular weight adopts the dynamic viscoelasticity spectrum instrument to test according to " synthetic staple ultimate strength and extension at break experimental technique " GB/T 14337-93, and fracture strength is 223MPa.
Embodiment 2
With 0.5 mole of m-cresol is that example is prepared into high-ortho novolac resin used other raw material and preparation method and comprises the steps:
In proportioning process step 1, get m-cresol 54g and paraformaldehyde 13.51g, promptly the mol ratio of m-cresol and paraformaldehyde formaldehyde identical in quality is 1: 0.9.In chemical reaction process step 2, reactant is warming up to 210 ℃ under stirring, pressure is 2.0 MPa, isothermal reaction 50 minutes.In preparation phenolic aldehyde resin art step 3, reaction is put into vacuum drying chamber with product after finishing, 180 ℃ of dryings 5 hours, and controlled pressure is prepared into phenolic resins at-0.07MPa.The mensuration of the molecular weight of phenolic resins is identical with embodiment 1, is prepared into the molecule amount and is 14000 phenolic resins.Other step is identical with embodiment 1, be prepared into phenolic resin fiber of high molecular weight, the fracture strength of prepared phenolic resin fiber of high molecular weight adopts the dynamic viscoelasticity spectrum instrument to test according to " synthetic staple ultimate strength and extension at break experimental technique " GB/T 14337-93, and fracture strength is 155MPa.
Embodiment 3
With 0.5 mole of m-cresol is that example is prepared into high-ortho novolac resin used other raw material and preparation method and comprises the steps:
In proportioning process step 1, get m-cresol 54g and paraformaldehyde 7.51g, promptly the mol ratio of m-cresol and paraformaldehyde formaldehyde identical in quality is 1: 0.5.In chemical reaction process step 2, reactant is warming up to 210 ℃ under stirring, pressure is 6.0 MPa, isothermal reaction 50 minutes.In preparation phenolic aldehyde resin art step 3, reaction is put into vacuum drying chamber with product after finishing, 180 ℃ of dryings 5 hours, and controlled pressure is prepared into phenolic resins at-0.07MPa.The mensuration of the molecular weight of phenolic resins is identical with embodiment 1 with the calculating of adjacency pair position ratio, is prepared into the molecule amount and is 8900 phenolic resins.Other step is identical with embodiment 1, be prepared into phenolic resin fiber of high molecular weight, the fracture strength of prepared phenolic resin fiber of high molecular weight adopts the dynamic viscoelasticity spectrum instrument to test according to " synthetic staple ultimate strength and extension at break experimental technique " GB/T 14337-93, and fracture strength is 170MPa.
Embodiment 4
With 0.5 mole of phenol is that example is prepared into high-ortho novolac resin used other raw material and preparation method and comprises the steps:
In proportioning process step 1, get phenol 47g and mass concentration and be 37% formaldehyde 28.41g, promptly the mol ratio of phenol and formaldehyde is 1: 0.70, joins in the autoclave.In chemical reaction process step 2, reactant is warming up to 210 ℃ under stirring, pressure is 2.0MPa, isothermal reaction 50 minutes.In preparation phenolic aldehyde resin art step 3, reaction is put into vacuum drying chamber with product after finishing, 180 ℃ of dryings 5 hours, and controlled pressure is prepared into phenolic resins at-0.07MPa.The mensuration of the molecular weight of phenolic resins is identical with embodiment 1, is prepared into the molecule amount and is 1780 phenolic resins.Other step is identical with embodiment 1, be prepared into phenolic resin fiber of high molecular weight, the fracture strength of prepared phenolic resin fiber of high molecular weight adopts the dynamic viscoelasticity spectrum instrument to test according to " synthetic staple ultimate strength and extension at break experimental technique " GB/T 14337-93, and fracture strength is 156MPa.
Embodiment 5
With 0.5 mole of phenol is that example is prepared into high-ortho novolac resin used other raw material and preparation method and comprises the steps:
In proportioning process step 1, get phenol 47g and mass concentration and be 37% formaldehyde 28.41g, promptly phenol and the mol ratio of formaldehyde are to mix at 1: 0.70, join in the autoclave.In chemical reaction process step 2, reactant is warming up to 210 ℃ under stirring, pressure is 7.0MPa, isothermal reaction 50 minutes.In preparation phenolic aldehyde resin art step 3, reaction is put into vacuum drying chamber with product after finishing, 180 ℃ of dryings 5 hours, and controlled pressure is prepared into phenolic resins at-0.07MPa.The mensuration of the molecular weight of phenolic resins is identical with embodiment 1, is prepared into the molecule amount and is 36400 phenolic resins.Other step is identical with embodiment 1, be prepared into phenolic resin fiber of high molecular weight, the fracture strength of prepared phenolic resin fiber of high molecular weight adopts the dynamic viscoelasticity spectrum instrument to test according to " synthetic staple ultimate strength and extension at break experimental technique " GB/T 14337-93, and fracture strength is 150MPa.
Embodiment 6
With 0.5 mole of m-cresol is that example is prepared into high-ortho novolac resin used other raw material and preparation method and comprises the steps:
In proportioning process step 1, get m-cresol 54g and mass concentration and be 37% formaldehyde 28.41g, promptly m-cresol and the mol ratio of formaldehyde are to mix at 1: 0.70, join in the autoclave.In chemical reaction process step 2, reactant is warming up to 120 ℃ under stirring, pressure is 6.0MPa, isothermal reaction 50 minutes.In preparation phenolic aldehyde resin art step 3, reaction is put into vacuum drying chamber with product after finishing, 180 ℃ of dryings 5 hours, and controlled pressure is prepared into phenolic resins at-0.07MPa.The mensuration of the molecular weight of phenolic resins is identical with embodiment 1, is prepared into the molecule amount and is 16400 phenolic resins.Other step is identical with embodiment 1, be prepared into phenolic resin fiber of high molecular weight, the fracture strength of prepared phenolic resin fiber of high molecular weight adopts the dynamic viscoelasticity spectrum instrument to test according to " synthetic staple ultimate strength and extension at break experimental technique " GB/T 14337-93, and fracture strength is 150MPa.
Embodiment 7
With 0.5 mole of m-cresol is that example is prepared into high-ortho novolac resin used other raw material and preparation method and comprises the steps:
In proportioning process step 1, get m-cresol 54g and mass concentration and be 37% formaldehyde 28.41g, promptly m-cresol and the mol ratio of formaldehyde are to mix at 1: 0.70, join in the autoclave.In chemical reaction process step 2, reactant is warming up to 240 ℃ under stirring, pressure is 6.0MPa, isothermal reaction 50 minutes.In preparation phenolic aldehyde resin art step 3, reaction is put into vacuum drying chamber with product after finishing, 180 ℃ of dryings 5 hours, and controlled pressure is prepared into phenolic resins at-0.07MPa.The mensuration embodiment 1 of the molecular weight of phenolic resins is identical, is prepared into the molecule amount and is 35340 phenolic resins.Other step is identical with embodiment 1, be prepared into phenolic resin fiber of high molecular weight, the fracture strength of prepared phenolic resin fiber of high molecular weight adopts the dynamic viscoelasticity spectrum instrument to test according to " synthetic staple ultimate strength and extension at break experimental technique " GB/T 14337-93, and fracture strength is 160MPa.
Embodiment 8
With 0.5 mole of phenol is that example is prepared into high-ortho novolac resin used other raw material and preparation method and comprises the steps:
In proportioning process step 1, get phenol 47g and paraformaldehyde 10.51g, promptly the mol ratio of phenol and paraformaldehyde formaldehyde identical in quality is to mix at 1: 0.70, joins in the autoclave.In chemical reaction process step 2, reactant is warming up to 210 ℃ under stirring, pressure is 6.0MPa, isothermal reaction 30 minutes.In preparation phenolic aldehyde resin art step 3, reaction is put into vacuum drying chamber with product after finishing, 180 ℃ of dryings 5 hours, and controlled pressure is prepared into phenolic resins at-0.07MPa.The mensuration of the molecular weight of phenolic resins is identical with embodiment 1, is prepared into the molecule amount and is 27460 phenolic resins.Other step is identical with embodiment 1, be prepared into phenolic resin fiber of high molecular weight, the fracture strength of prepared phenolic resin fiber of high molecular weight adopts the dynamic viscoelasticity spectrum instrument to test according to " synthetic staple ultimate strength and extension at break experimental technique " GB/T 14337-93, and fracture strength is 179MPa.
Embodiment 9
With 0.5 mole of phenol is that example is prepared into high-ortho novolac resin used other raw material and preparation method and comprises the steps:
In proportioning process step 1, get phenol 47g and paraformaldehyde 10.51g, promptly the mol ratio of phenol and paraformaldehyde formaldehyde identical in quality is to mix at 1: 0.70, joins in the autoclave.In chemical reaction process step 2, reactant is warming up to 210 ℃ under stirring, pressure is 6.0MPa, isothermal reaction 140 minutes.In preparation phenolic aldehyde resin art step 3, reaction is put into vacuum drying chamber with product after finishing, 180 ℃ of dryings 5 hours, and controlled pressure is prepared into phenolic resins at-0.07MPa.The mensuration of the molecular weight of phenolic resins is identical with embodiment 1, is prepared into the molecule amount and is 25700 phenolic resins.Other step is identical with embodiment 1, be prepared into phenolic resin fiber of high molecular weight, the fracture strength of prepared phenolic resin fiber of high molecular weight adopts the dynamic viscoelasticity spectrum instrument to test according to " synthetic staple ultimate strength and extension at break experimental technique " GB/T 14337-93, and fracture strength is 162MPa.
Embodiment 10
With 0.5 mole of m-cresol is that example is prepared into high-ortho novolac resin used other raw material and preparation method and comprises the steps:
Formaldehyde in above embodiment 4～7 is replaced with acetaldehyde, and the consumption of acetaldehyde is identical with the molar weight of formaldehyde, and the also available metaformaldehyde of used formaldehyde is replaced, the consumption of metaformaldehyde and formaldehyde identical in quality.Other processing step is identical with respective embodiments, is prepared into phenolic resin fiber of high molecular weight.
Embodiment 11
With 0.5 mole of phenol is that example is prepared into phenolic resin fiber of high molecular weight used other raw material and preparation method and comprises the steps:
In proportioning process step 1, get phenol 47g and paraformaldehyde 10.51g, promptly the mol ratio of phenol and paraformaldehyde formaldehyde identical in quality is to mix at 1: 0.70, joins in the autoclave.In chemical reaction process step 2, reactant is warming up to 210 ℃ under stirring, pressure is 6.0MPa, isothermal reaction 50 minutes.In preparation phenolic aldehyde resin art step 3, reaction is put into vacuum drying chamber with product after finishing, 180 ℃ of dryings 5 hours, and controlled pressure is prepared into phenolic resins at-0.07MPa.The mensuration of the molecular weight of phenolic resins is identical with embodiment 1, is prepared into the molecule amount and is 53000 phenolic resins.
High molecular weight phenolic resin is through melt spinning, make as-spun fibre, water 100g, oxalic acid 7.5g, paraformaldehyde 15g, paraformaldehyde is that the degree of polymerization is 8～100 low molecular weight polyformaldehyde, be mixed with consolidation liquid according to a conventional method, promptly water, oxalic acid, with the mol ratio of paraformaldehyde formaldehyde identical in quality be 1: 0.015: 0.09, get as-spun fibre 40g and put into consolidation liquid 100g, average rate heated up 2.5 hours to 100 ℃ and is cured reaction, was prepared into phenolic fiber.The fracture strength of prepared phenolic resin fiber of high molecular weight adopts the dynamic viscoelasticity spectrum instrument to test according to " synthetic staple ultimate strength and extension at break experimental technique " GB/T 14337-93, and fracture strength is 189MPa.
Embodiment 12
With 0.5 mole of phenol is that example is prepared into phenolic resin fiber of high molecular weight used other raw material and preparation method and comprises the steps:
In the present embodiment, used raw material and the processing step of preparation as-spun fibre is identical with embodiment 11.Water 100g, oxalic acid 37.5g, paraformaldehyde 15g, be mixed with consolidation liquid according to a conventional method, be water, oxalic acid, with the mol ratio of paraformaldehyde formaldehyde identical in quality be 1: 0.075: 0.09, get as-spun fibre 40g and put into consolidation liquid 100g, average rate heated up 2.5 hours to 100 ℃ and is cured reaction, was prepared into phenolic fiber.The fracture strength of prepared phenolic resin fiber of high molecular weight adopts the dynamic viscoelasticity spectrum instrument to test according to " synthetic staple ultimate strength and extension at break experimental technique " GB/T 14337-93, and fracture strength is 175MPa.
Embodiment 13
With 0.5 mole of phenol is that example is prepared into phenolic resin fiber of high molecular weight used other raw material and preparation method and comprises the steps:
In the present embodiment, used raw material and the processing step of preparation as-spun fibre is identical with embodiment 11.Water intaking 100g, oxalic acid 15g, paraformaldehyde 5g are mixed with consolidation liquid according to a conventional method, the mol ratio that is water and oxalic acid, paraformaldehyde formaldehyde identical in quality is 1: 0.045: 0.03, get as-spun fibre 40g and put into consolidation liquid 100g, average rate heated up 2.5 hours to 100 ℃ and is cured reaction, was prepared into phenolic fiber.The fracture strength of prepared phenolic resin fiber of high molecular weight adopts the dynamic viscoelasticity spectrum instrument to test according to " synthetic staple ultimate strength and extension at break experimental technique " GB/T 14337-93, and fracture strength is 185MPa.
Embodiment 14
With 0.5 mole of phenol is that example is prepared into phenolic resin fiber of high molecular weight used other raw material and preparation method and comprises the steps:
In the present embodiment, used raw material and the processing step of preparation as-spun fibre is identical with embodiment 11.Water intaking 100g, oxalic acid 15g, paraformaldehyde 25g are mixed with consolidation liquid according to a conventional method, the mol ratio that is water and oxalic acid, paraformaldehyde formaldehyde identical in quality is 1: 0.045: 0.15, get as-spun fibre 40g and put into consolidation liquid 100g, average rate heated up 2.5 hours to 100 ℃ and is cured reaction, was prepared into phenolic fiber.The fracture strength of prepared phenolic resin fiber of high molecular weight adopts the dynamic viscoelasticity spectrum instrument to test according to " synthetic staple ultimate strength and extension at break experimental technique " GB/T 14337-93, and fracture strength is 178MPa.
Embodiment 15
In above embodiment 1～14, in preparation consolidation liquid processing step 5, used oxalic acid or hydrochloric acid are replaced with sulfuric acid, and promptly 1 mole hydrochloride is replaced with 1/2 mol sulfuric acid, and 1 mole of oxalic acid is replaced with 1 mol sulfuric acid.Other processing step is identical with respective embodiments.
Promptly use 1 mole hydrochloride or 1/2 mol sulfuric acid or 1/2 mole of oxalic acid or 1/3 mole of phosphoric acid.
Embodiment 16
In above embodiment 1～14, in preparation consolidation liquid processing step 5, used oxalic acid or hydrochloric acid are replaced with phosphoric acid, and promptly 1 mole hydrochloride is replaced with 1/3 mole of phosphoric acid, and 1 mole of oxalic acid is replaced with 2/3 mole of phosphoric acid.Other processing step is identical with respective embodiments.
Embodiment 17
With 0.5 mole of phenol is that example is prepared into phenolic resin fiber of high molecular weight used other raw material and preparation method and comprises the steps:
In the present embodiment, used raw material and the processing step of preparation as-spun fibre is identical with embodiment 11.Water intaking 31.88g, mass concentration are that 30% hydrochloric acid 60.83g, mass concentration are that 37% formaldehyde 40.54g is mixed with consolidation liquid according to a conventional method, the mol ratio that is water and hydrochloric acid, formaldehyde is 1: 0.09: 0.09, get as-spun fibre 5g and put into consolidation liquid 100g, average rate heated up 2.5 hours to 100 ℃ and is cured reaction, was prepared into phenolic fiber.The fracture strength of prepared phenolic resin fiber of high molecular weight adopts the dynamic viscoelasticity spectrum instrument to test according to " synthetic staple ultimate strength and extension at break experimental technique " GB/T 14337-93, and fracture strength is 213MPa.
In order to determine the processing step of the best of the present invention, the inventor has carried out a large amount of laboratory study tests, and various test situation are as follows:
Experiment material: phenol, C
6H
5OH, molecular weight 94.11 is analyzed purely, and Tianjin good fortune chemical reagent in morning factory produces; M-cresol, C
7H
8O, molecular weight 108.14 is analyzed purely, and Chemical Reagent Co., Ltd., Sinopharm Group produces; Formaldehyde, HCHO, molecular weight 30.03 is analyzed purely, is the formalin of content＞37%, and chemical reagent factory in Xi'an produces; Paraformaldehyde, (HCHO) n, molecular weight (30.03) n analyzes purely, and the rich Dihua worker Co., Ltd in Tianjin produces; Acetaldehyde, CH
3CHO, molecular weight 44.05 is analyzed purely, is the formalin of content＞40%, and Chemical Reagent Co., Ltd., Sinopharm Group produces.
Laboratory apparatus: the softening point test device, the SYD-2806E type, Guangzhou is built mechanical ﹠ electronic equipment corporation, Ltd admittedly and is produced; Gel permeation chromatography, model are GPC-717/1515/2414, are produced by U.S. Waters company, measure phenolic resins molecular weight and distribution thereof down at 30 ℃, splitter is that (RT 1.0, and RT 2.0 for Aquapak A-440, RT 5.0), flow rate 1.0ml minute of solvents tetrahydrofurane (THF)
-1, standard specimen is that (its molecular weight is 474～205000g/mol) to monodisperse polystyrene; Superconduction Fourier numeralization nuclear magnetic resonance spectrometer, model is Avance 300MHZ, is produced by Bruker company; Vacuum drying chamber, model are DZF-6050, and one permanent Science and Technology Ltd. produces by Shanghai; Autoclave, model are PCF0075-20 type (subsidiary K type thermocouple, SCB3111 type pressure transmitter and paddle), are produced by upright automatic control equipment research institute of high and new technology industrial development zone, Yantai section; Dynamic viscoelasticity spectrum instrument, model are Q800DMA, are produced by U.S. TA company.
The present invention compared with prior art has following advantage:
(1) containing metal impurity not in the high molecular weight phenolic resin.
(2) lack fiber crosslinking degree height, intensity height hardening time.
(3) goods have good anti-ablation heat-proof quality.
In order to determine The optimum reaction conditions of the present invention, the inventor has carried out a large amount of laboratory study tests, and various test situation are as follows:
1, preparation phenolic resins proportioning raw materials determines
Get m-cresol 54g and paraformaldehyde 7.51～13.51g, be m-cresol with the mol ratio of paraformaldehyde formaldehyde identical in quality be to mix in 1: 0.50～1: 0.90, place the autoclave that paddle and thermocouple are housed, be warming up to 210 ℃ of isothermal reactions 50 minutes, keep-uping pressure is 4.0～7.0MPa.After reaction finishes, product is put into 180 ℃ of vacuumizes of vacuum drying chamber 5 hours, controlled pressure is made high molecular weight phenolic resin at-0.07MPa.Adopt gel permeation chromatography, measure phenolic resins molecular weight and distribution thereof down at 30 ℃, splitter is that (RT 1.0 for Aquapak A-440, RT 2.0, RT 5.0), the flow rate 1.0ml/min of solvents tetrahydrofurane, standard specimen are that molecular weight is 474～205000g/mol monodisperse polystyrene, and test result sees Table 1.
High molecular weight phenolic resin is through melt spinning, make as-spun fibre, water intaking 34.92g, mass concentration are that 30% hydrochloric acid 60.83g, mass concentration are that 40% acetaldehyde 37.5g is mixed with consolidation liquid according to a conventional method, the mol ratio that is water and hydrochloric acid, acetaldehyde is 1: 0.09: 0.09, get as-spun fibre 20g and put into consolidation liquid 100g, average rate heated up 2.5 hours to 100 ℃ and is cured reaction, was prepared into phenolic fiber.The fracture strength of phenolic fiber adopts the dynamic viscoelasticity spectrum instrument to test according to " synthetic staple ultimate strength and extension at break experimental technique " GB/T14337-93.Test result sees Table 1.
The different phenol formaldehyde ratios of table 1 are to the phenolic fiber Effect on Performance
| Phenol formaldehyde ratio | 1∶0.50 | 1∶0.60 | 1∶0.65 | 1∶0.70 | 1∶0.75 | 1∶0.80 | 1∶0.90 |
| Molecular weight (Mn) | 8900 | 17400 | 29520 | 48200 | 44200 | 33900 | 14000 |
| Fracture strength (MPa) | 170 | 203 | 205 | 223 | 198 | 162 | 155 |
By table 1 as seen, the mol ratio of m-cresol and paraformaldehyde is 1: 0.65～0.75 o'clock, prepared phenolic fiber better performances.It is 1: 0.65～0.75 that the present invention selects phenol formaldehyde ratio, and best phenol formaldehyde ratio is 1: 0.70.
2, reaction pressure determines
Get phenol 47g and mass concentration and be 37% formaldehyde 28.41g, promptly phenol and the mol ratio of formaldehyde are to mix at 1: 0.70, react in the autoclave that stirring arm and thermocouple are housed.Be warming up to 210 ℃ of isothermal reactions 50 minutes, Pressure control 2.0,3.0,4.0,5.0,6.0,7.0,8.0,9.0,10.5MPa carries out chemical reaction respectively.Reaction finishes, and product is put into 180 ℃ of vacuumizes of vacuum drying chamber 5 hours, and controlled pressure is made high molecular weight phenolic resin at-0.07MPa.The used tester of the molecular weight of high molecular weight phenolic resin is identical with experiment 1 with method of testing.Test result sees Table 2.
High molecular weight phenolic resin is through melt spinning, make as-spun fibre, water 49.96g, mass concentration are that 50% sulfuric acid 49g, mass concentration are that 37% formaldehyde 40.54g is mixed with consolidation liquid according to a conventional method, the mol ratio that is water, sulfuric acid, formaldehyde is 1: 0.045: 0.09, get as-spun fibre 30g and put into consolidation liquid 100g, average rate heated up 2.5 hours to 100 ℃ and is cured reaction, was prepared into phenolic fiber.The fracture strength of phenolic resin fiber of high molecular weight is tested by the using method of instrument with the dynamic viscoelasticity spectrum instrument.Test result sees Table 2
Table 2 differential responses pressure is to the phenolic fiber Effect on Performance
| Pressure Pa | 2.0 | 3.0 | 4.0 | 5.0 | 6.0 | 7.0 | 8.0 | 9.0 | 10.5 |
| Molecular weight (Mw) | 1780 | 3900 | 17200 | 34500 | 48000 | 36400 | 23600 | 18500 | - |
| Intensity (MPa) | 156 | 170 | 186 | 198 | 220 | 150 | Become fine poor | Become fine poor | - |
By table 2 as seen, under the situation that only changes reaction pressure, when pressure during at 2.0～7.0MPa, prepared phenolic fiber better performances.Choice reaction pressure of the present invention is 2.0～7.0MP, and wherein optimum response pressure is 6.0MPa.
3, reaction temperature determines
Get m-cresol 54g and mass concentration and be 37% formaldehyde 28.41g, promptly m-cresol and the mol ratio of formaldehyde are to mix at 1: 0.70, react in the autoclave that stirring arm and thermocouple are housed.Isothermal reaction is 50 minutes when being warming up to 120～270 ℃, and pressure remains between 4.0～7.0MPa.Reaction finishes, and product is put into 180 ℃ of vacuumizes of vacuum drying chamber 5 hours, and controlled pressure is made high adjacent position phenolic resin at-0.07MPa.The used tester of the molecular weight of high molecular weight phenolic resin is identical with experiment 1 with method of testing.Test result sees Table 3.
High molecular weight phenolic resin is through melt spinning, make as-spun fibre, water 74.46g, oxalic acid 22.51g, mass concentration are that 37% formaldehyde 40.54g is mixed with consolidation liquid according to a conventional method, the mol ratio that is water, oxalic acid, formaldehyde is 1: 0.045: 0.09, get as-spun fibre 30g and put into consolidation liquid 100g, average rate heated up 2.5 hours to 100 ℃ and is cured reaction, was prepared into phenolic fiber.The fracture strength of phenolic resin fiber of high molecular weight is tested by the using method of instrument with the dynamic viscoelasticity spectrum instrument.
Test result sees Table 3
Table 3 differential responses temperature is to the performance impact of phenolic fiber
| Reaction temperature (℃) | 120 | 150 | 180 | 210 | 240 | 270 |
| Molecular weight (Mn) | 16400 | 18770 | 36320 | 48140 | 35340 | - |
| Fibre strength (MPa) | 150 | 182 | 218 | 198 | 160 |
By table 3 as seen, in the test that only changes reaction temperature, when reaction temperature is 120～240 ℃, prepared phenolic fiber better performances.Choice reaction temperature of the present invention is 120～240 ℃, and wherein best is answered temperature is 210 ℃.
4, the reaction time determines
Get phenol 47g and paraformaldehyde 10.51g, promptly the mol ratio of phenol and paraformaldehyde formaldehyde identical in quality is to mix at 1: 0.70, reacts in the autoclave that stirring arm and thermocouple are housed.Constant temperature was 30～140 minutes when reaction temperature rose to 210 ℃, and pressure remains on 6.0MPa.Reaction finishes, and product is put into 180 ℃ of vacuumizes of vacuum drying chamber 5 hours, and controlled pressure is made phenolic resins at-0.07MPa.The used tester of the molecular weight of phenolic resins is identical with experiment 1 with method of testing.Test result sees Table 4.
Phenolic resins is through melt spinning, make as-spun fibre, water 75.5g, mass concentration are that 40% phosphatase 24 0.83g, paraformaldehyde 15g are mixed with consolidation liquid according to a conventional method, the mol ratio that is water, phosphoric acid, paraformaldehyde formaldehyde identical in quality is 1: 0.03: 0.09, get as-spun fibre 30g and put into consolidation liquid 100g, average rate heated up 2.5 hours to 100 ℃ and is cured reaction, was prepared into phenolic fiber.The fracture strength of phenolic resin fiber of high molecular weight is tested by the using method of instrument with the dynamic viscoelasticity spectrum instrument.
Test result sees Table 4
The table 4 differential responses time is to the performance impact of phenolic fiber
| Reaction time (Min) | 30 | 50 | 80 | 100 | 120 | 140 |
| Molecular weight (Mn) | 27460 | 53000 | 43450 | 38500 | 33400 | 25700 |
| Intensity (MPa) | 179 | 234 | 225 | 203 | 185 | 162 |
By table 4 as seen, in the test that only changes the reaction time, the reaction time is when being 30～140 minutes, prepared phenolic fiber better performances.The choice reaction time of the present invention is 30～140 minutes, and wherein the best is 50 minutes between sending out at once.
5, the determining of sour proportioning in the consolidation liquid
In above experiment 4, constant temperature was 50 minutes when reaction temperature rose to 210 ℃, and used raw material and other processing step are identical with experiment 4, and being prepared into the molecule amount is 53000 phenolic resins, and phenolic resins is made as-spun fibre through melt spinning.Water intaking 100g, oxalic acid 7.5～37.5g, paraformaldehyde 15g, paraformaldehyde is that the degree of polymerization is 8～100 low molecular weight polyformaldehyde, be mixed with consolidation liquid according to a conventional method, the mol ratio that is water, oxalic acid, paraformaldehyde formaldehyde identical in quality is 1: 0.015～0.075: 0.09, get as-spun fibre 40g and put into consolidation liquid 100g, average rate heated up 2.5 hours to 100 ℃ and is cured reaction, was prepared into phenolic fiber.The fracture strength of phenolic resin fiber of high molecular weight is tested by the using method of instrument with the dynamic viscoelasticity spectrum instrument.Test result sees Table 5.
Sour proportioning is to the performance impact of phenolic fiber in table 5 consolidation liquid
| Proportioning (mol ratio) | 0.015 | 0.03 | 0.045 | 0.06 | 0.075 |
| Intensity (MPa) | 189 | 213 | 225 | 204 | 175 |
By table 5 as seen, when the mass ratio of consolidation liquid and as-spun fibre is 100: 40, the mol ratio of water and oxalic acid, paraformaldehyde is 1: 0.015～0.075: 0.09 o'clock in the consolidation liquid, and the intensity of fiber is higher, and wherein the optimum quality ratio of water and oxalic acid, formaldehyde is 1: 0.045: 0.09.
6, the determining of aldehyde compound proportioning in the consolidation liquid
Make as-spun fibre by the method shown in the experiment 5.Water intaking 100g, oxalic acid 15g, paraformaldehyde 5～25g are mixed with consolidation liquid according to a conventional method, the mol ratio that is water and oxalic acid, paraformaldehyde formaldehyde identical in quality is 1: 0.045: 0.03～0.15, get as-spun fibre 40g and put into consolidation liquid 100g, average rate heated up 2.5 hours to 100 ℃ and is cured reaction, was prepared into phenolic fiber.The fracture strength of phenolic resin fiber of high molecular weight is tested by the using method of instrument with the dynamic viscoelasticity spectrum instrument.Test result sees Table 6.
The proportioning of aldehyde compound is to the performance impact of phenolic fiber in table 6 consolidation liquid
| Aldehyde compound proportioning (mole) | 0.03 | 0.06 | 0.09 | 0.12 | 0.15 |
| Intensity MPa | 185 | 210 | 225 | 208 | 178 |
By table 6 as seen, the intensity of fiber is higher when the mol ratio of water in the consolidation liquid and oxalic acid, paraformaldehyde formaldehyde identical in quality is 1: 0.045: 0.03～0.15, and wherein the optimum mole ratio of water and oxalic acid, paraformaldehyde formaldehyde identical in quality is 1: 0.045: 0.09.
7, the determining of fibre furnish in the consolidation liquid
Make as-spun fibre by the method shown in the experiment 5.Water intaking 31.88g, mass concentration are that 30% hydrochloric acid 60.83g, mass concentration are that 37% formaldehyde 40.54g is mixed with consolidation liquid according to a conventional method, the mol ratio that is water and hydrochloric acid, formaldehyde is 1: 0.09: 0.09, get as-spun fibre 5～40g and put into consolidation liquid 100g, average rate heated up 2.5 hours to 100 ℃ and is cured reaction, was prepared into phenolic fiber.The fracture strength of phenolic resin fiber of high molecular weight is tested by the using method of instrument with the dynamic viscoelasticity spectrum instrument.Test result sees Table 7.
Table 7 consolidation liquid and birth fibre furnish are to the phenolic fiber Effect on Performance
| The proportioning of fiber and consolidation liquid (wt%) | 5 | 10 | 20 | 30 | 40 |
| Intensity (MPa) | 213 | 226 | 232 | 225 | 200 |
By table 7 as seen, consolidation liquid is 100: 5～40 o'clock with the fiber quality ratio, and the intensity of fiber is higher, and it is 100: 5～40 that the present invention selects consolidation liquid and quality of fiber ratio, and wherein consolidation liquid and fiber optimum quality ratio are 100: 20.
Claims (3)
1, a kind of preparation method of phenolic resin fiber of high molecular weight is characterized in that it comprises the steps:
(1) batching
With phenol or m-cresol and aldehyde compound is 1: 0.5～0.9 to join in the autoclave in molar ratio;
Above-mentioned aldehyde compound be formaldehyde or acetaldehyde or with the paraformaldehyde of quality such as formaldehyde or with the metaformaldehyde of quality such as formaldehyde, paraformaldehyde is that the degree of polymerization is 8～100 low molecular weight polyformaldehyde;
(2) chemical reaction
Reactant is warming up to 120～240 ℃ under stirring, pressure is 2.0～7.0MPa, isothermal reaction 30～140 minutes;
(3) preparation phenolic resins
After reaction finishes, product is put into vacuum drying chamber, 120～220 ℃ of dryings 1～9 hour, controlled pressure-0.05～-0.09MPa, be prepared into phenolic resins;
(4) preparation as-spun fibre
High molecular weight phenolic resin is put into the melt spinning device spinning, and the concrete grammar of melt spinning is that 3714111 the disclosed preparation method of United States Patent (USP) is prepared into as-spun fibre according to the patent No.;
(5) preparation consolidation liquid
Water intaking, acid, aldehyde compound are mixed with consolidation liquid, and water is 1: 0.03～0.15: 0.03～0.15 with the mol ratio of acid, aldehyde compound;
Above-mentioned aldehyde compound be formaldehyde or acetaldehyde or with the paraformaldehyde of quality such as formaldehyde or with the metaformaldehyde of quality such as formaldehyde; Above-mentioned acid is hydrochloric acid or sulfuric acid or oxalic acid or phosphoric acid, promptly uses 1 mole hydrochloride or 1/2 mol sulfuric acid or 1/2 mole of oxalic acid or 1/3 mole of phosphoric acid;
(6) curing reaction
As-spun fibre is put into consolidation liquid, and the mass ratio of consolidation liquid and as-spun fibre is 100: 5～40, is warming up to 60～100 ℃, isothermal reaction 0.5～4.5 hour;
(7) flushing is dry
After reaction finishes, fiber is taken out, use deionized water rinsing 3～5 times, air dry is prepared into phenolic resin fiber of high molecular weight.
2, according to the preparation method of the described phenolic resin fiber of high molecular weight of claim 1, it is characterized in that: in proportioning process step (1), wherein the mol ratio of phenol or m-cresol and aldehyde compound is 1: 0.5～0.8; In chemical reaction process step (2), reactant wherein is warming up to 150～240 ℃, pressure under stirring be 3.0～7.0MPa, isothermal reaction 50～100 minutes; In preparation phenolic aldehyde resin art step (3), product is put into vacuum drying chamber, wherein 150～200 ℃ of dryings 3～8 hours, controlled pressure-0.06～-0.08MPa; In preparation consolidation liquid processing step (5), wherein water is 1: 0.06～0.12: 0.06～0.12 with the mol ratio of acid, aldehyde compound, described acid is hydrochloric acid or sulfuric acid or oxalic acid or phosphoric acid, promptly uses 1 mole hydrochloride or 1/2 mol sulfuric acid or 1/2 mole of oxalic acid or 1/3 mole of phosphoric acid; In curing reaction processing step (6), wherein the mass ratio of consolidation liquid and as-spun fibre is 100: 10～30, was warming up to 80～100 ℃, isothermal reaction 1.5～4 hours.
3, according to the preparation method of the described phenolic resin fiber of high molecular weight of claim 1, it is characterized in that: in proportioning process step (1), wherein phenol or m-cresol and aldehyde compound is 1: 0.7 in molar ratio; In chemical reaction process step (2), reactant wherein is warming up to 210 ℃, pressure under stirring be 6.0MPa, isothermal reaction 50 minutes; In preparation phenolic aldehyde resin art step (3), product is put into vacuum drying chamber, wherein 180 ℃ of dryings 5 hours, controlled pressure are at-0.07MPa; In preparation consolidation liquid processing step (5), wherein water is 1: 0.09: 0.09 with the mol ratio of acid, aldehyde compound, described acid is hydrochloric acid or sulfuric acid or oxalic acid or phosphoric acid, promptly uses 1 mole hydrochloride or 1/2 mol sulfuric acid or 1/2 mole of oxalic acid or 1/3 mole of phosphoric acid; In this curing reaction processing step (6), wherein the mass ratio of consolidation liquid and as-spun fibre is 100: 20, was warming up to 100 ℃, isothermal reaction 2.5 hours.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101709516B (en) * | 2009-11-26 | 2011-08-17 | 陕西师范大学 | Method for preparing toughening agent modified phenolic fiber |
| CN103046154A (en) * | 2013-01-15 | 2013-04-17 | 中原工学院 | Preparation method of dual-catalytic phenolic aldehyde fibers |
| CN103060941A (en) * | 2013-01-15 | 2013-04-24 | 中原工学院 | Preparation method of high molecular weight phenolic fiber |
| CN105332081A (en) * | 2015-11-16 | 2016-02-17 | 中原工学院 | Preparing method for ablation-resistant high-ortho phenolic fibers |
| CN109913960A (en) * | 2019-03-14 | 2019-06-21 | 唐山开滦化工科技有限公司 | A kind of low orientated high preparation method for stretching polyformaldehyde as-spun fibre |
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2008
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101709516B (en) * | 2009-11-26 | 2011-08-17 | 陕西师范大学 | Method for preparing toughening agent modified phenolic fiber |
| CN103046154A (en) * | 2013-01-15 | 2013-04-17 | 中原工学院 | Preparation method of dual-catalytic phenolic aldehyde fibers |
| CN103060941A (en) * | 2013-01-15 | 2013-04-24 | 中原工学院 | Preparation method of high molecular weight phenolic fiber |
| CN105332081A (en) * | 2015-11-16 | 2016-02-17 | 中原工学院 | Preparing method for ablation-resistant high-ortho phenolic fibers |
| CN105332081B (en) * | 2015-11-16 | 2017-09-15 | 中原工学院 | A kind of preparation method of the high ortho position boronphenolic fibre of resistance to ablation |
| CN109913960A (en) * | 2019-03-14 | 2019-06-21 | 唐山开滦化工科技有限公司 | A kind of low orientated high preparation method for stretching polyformaldehyde as-spun fibre |
| CN109913960B (en) * | 2019-03-14 | 2020-05-22 | 唐山开滦化工科技有限公司 | Preparation method of low-orientation high-stretch polyformaldehyde nascent fiber |
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