CN107237009A - A kind of environment-friendly type refractory fibre and preparation method thereof - Google Patents
A kind of environment-friendly type refractory fibre and preparation method thereof Download PDFInfo
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- CN107237009A CN107237009A CN201710526864.0A CN201710526864A CN107237009A CN 107237009 A CN107237009 A CN 107237009A CN 201710526864 A CN201710526864 A CN 201710526864A CN 107237009 A CN107237009 A CN 107237009A
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- refractory fibre
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- friendly type
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- type refractory
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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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a kind of environment-friendly type refractory fibre and preparation method thereof, the environment-friendly type refractory fibre is made up of the raw material of following parts by weight：65~75 parts of aluminum oxide, 30~50 parts of magnesia, 10~15 parts of titanium dioxide, 4~8 parts of yttria and antistatic 12.2~14.3 parts of combined binder.The present invention adds the antistatic combined binder containing formaldehyde catching agent in formula system, can reduce content of free aldehyde in refractory fibre so that refractory fibre more environmental protection and with antistatic property；Preparation technology is simple, and parameter is easily controllable, expands application field, increases the performance of enterprises.
Description
Technical field
The present invention relates to refractory fibre technical field, more particularly to a kind of environment-friendly type refractory fibre with antistatic behaviour and
Its preparation method.
Background technology
Refractory fibre is soft, elasticity is good, or preferably encapsulant, due to insulation, anti-oxidant, oil resistant and water-fast
Performance, easy construction, therefore be widely used in fields such as metallurgy, building materials, oil, chemical industry, ship, electric power, space flight.Aluminum oxide is fine
Dimension removes that high intensity, high-modulus, thermal conductivity with general ceramic fibre are small, thermal coefficient of expansion is low, chemical resistance of concrete ability, extraordinary
Heat resistance, high-temperature oxidation the advantages of outside, also with cost of material is relatively low, simple production process the features such as, with higher
Cost performance and commercial value, be widely used in industrial, military, civilian field of compound material.Control alumina fibre production
Different process process, can obtain heterogeneity and the high-performance fiber product suitable for different application.At present, alumina setter is fine
Dimension uses phenolic resin binder, and it has the harmful substances such as free phenol, free aldehyde, and pitch used can give out at high temperature
The toxic smog of yellow, execution conditions are severe, the health of serious infringement workman.In addition, the research of alumina setter fiber is main
The research of heat resistance is concentrated on, but electrostatic interaction is easily produced based on fiber properties, in use easy adsorption cotton
Bits, debris, it is not easy to clean, interference is produced, the potential safety hazard used can be also produced.
" a kind of preparation method of hollow aluminum fiber " is disclosed in Chinese patent literature, its notification number is
CN106350899A, the invention is impregnated in aluminum salt solution by the use of hollow bombax cotton as carrier and obtains presoma,
Hollow aluminum fiber is made after high-temperature calcination, fiber prepared by this method has density low, and degree of hollowness is high, and heat-insulating property is good
The features such as.But, the invention is not directed to the contaminative of alumina setter fiber and the research of antistatic property.
The content of the invention
The present invention in order to overcome existing alumina setter fiber contamination environment, without antistatic behaviour the problem of there is provided
A kind of environment-friendly type refractory fibre with antistatic behaviour.
Simple, the preparation method of the easily controllable environment-friendly type refractory fibre of parameter present invention also offers a kind of technique.
To achieve these goals, the present invention uses following technical scheme：
A kind of environment-friendly type refractory fibre, the environment-friendly type refractory fibre is made up of the raw material of following parts by weight：Aluminum oxide 65~75
Part, 30~50 parts of magnesia, 10~15 parts of titanium dioxide, 4~8 parts of yttria and antistatic combined binder 12.2~
14.3 parts.
The refractory fibre Main Ingredients and Appearance of the present invention is aluminum oxide, and cost is low, and heat resistance is high.It is exhausted as Ultralight high temperature
One of hot material, has light, heat-insulated effect, due to the good chemical resistance of aluminum oxide as production refractory fibre
Can, the feature of environmental protection and recycling property of refractory fibre can be increased.Titanium dioxide is added in raw material, the effect of catalysis can be played, can
To be acted synergistically with aluminum oxide, the effect of toughness reinforcing is played, in addition, titanium dioxide has preferable ultraviolet masking action,
Used in refractory fibre as sun-screening agent and antioxidant, the service life of refractory fibre can be extended.Yttria can be with
It is used as fluorescence additive so that the refractory fibre of preparation has fluorescent characteristic.
Preferably, the antistatic combined binder is made up of the raw material of following parts by weight：7~8 parts of phenolic resin, nothing
0.15~0.2 part of 5~6 parts of water-ethanol, formaldehyde catching agent 0.05~0.15 and antistatic additive.
Preferably, the formaldehyde catching agent has following formula：R-NH2, R is selected from-OH ,-CH2-CH2-SO3H ,-CH2(COOH)
With-CH (COOH) (CH2CH2CONH2) in one or more.
Use the compound for containing primary amine group as formaldehyde catching agent in the antistatic combined binder of the present invention, its is anti-
The principle is answered to be：Under acid condition, the carbonyl of free aldehyde is at 45~60 DEG C in the primary amine group and phenolic resin in formaldehyde catching agent
Under the conditions of can occur nucleophilic addition generation RNHCH2OH, the structural stability is very poor, can generate RNH=with rapid dehydration
CH2, and condensation reaction occurs from each other, form polymeric crosslinker.On the one hand the reaction can dissociate in reduction system aldehyde
Content, on the other hand can generate network-like polymeric crosslinker, its can be improved heat-resisting to phenolic resin modified toughness reinforcing
Performance and caking property.-CH(COOH)(CH2CH2CONH2) be amino acid formula, the present invention in amino acid be selected from different bright ammonia
Acid, glutamine, alanine, valine, lysine, arginine, histidine, methionine, threonine, glycine, serine, half
Cystine, and its salt.
Preferably, the antistatic additive is PEO, polyether ester amides, in carboxyl betaine graft inter polymer
It is one or more of.
Selected PEO of the invention, polyether ester amides and carboxyl betaine graft inter polymer are that macromolecule is permanent
Type antistatic additive, belongs to hydrophilic polymer, and its action principle is as follows：After itself and phenolic resin macromolecule matrix are blended, a side
Face is stronger due to the locomitivity of its strand, intermolecular to be easy to proton to move, and generation is conducted and discharged by ionic conduction
Electrostatic charge；On the other hand, antistatic effect is embodied by its special dispersing morphology.Research shows：Macromolecule is permanent
Type antistatic additive is mainly distributed in article topsheet in fine stratiform or tendon shape, constitutes electric conductivity top layer, and in core
It is in almost spherical distribution, is formed so-called " core shell structure ", and electrostatic charge is leaked as path.Because macromolecule permanent type resists
Electrostatic agent is to reach antistatic effect to reduce material volume resistivity, water absorbent surface is not exclusively relied on, so by environment
Humidity influence does not almost have, and macromolecule permanent antistatic agent will be added in the bonding agent of the present invention, enables to bonding agent to have
There is stable antistatic effect, security performance is high.
A kind of preparation method of environment-friendly type refractory fibre, comprises the following steps：
(1) weigh raw material for standby according to said ratio, by aluminum oxide, magnesia, titanium dioxide and yttria in 200~
Blending progress is crushed and obtains major ingredient after 1~2h of insulation at 400 DEG C；
(2) antistatic combined binder is slowly added into major ingredient, the mixture after being well mixed, which is put into melting furnace, to be added
Hot to 1500~1800 DEG C obtain fused solution；
(3) impurity in filtering fused solution, filtrate flows into uninterruptedly to stir in 1800~1950 DEG C of stirred autoclave and spun
Silk liquid；(4) spinning solution is flowed out from discharging opening, is sprayed into pore of the spinning head through spinning head, and spinning solution quickly consolidated by cooling
Body fiber, is collected by condensers and obtains environment-friendly type refractory fibre.
Antistatic combined binder is added in the major ingredient after crushing, reaction can be sufficiently mixed so that refractory fibre has
There is antistatic property, it is to avoid cause security incident due to producing electrostatic in use.
Preferably, the particle diameter of major ingredient described in step (1) is 150~240 mesh.
The present invention uses the raw material of 150~240 mesh, results in faster melting rate, on the one hand can improve whole
The production efficiency of technique, the obtained refractory fibre of another aspect has metastable characteristic.
Preferably, the centrifugal speed of spinning head is 2~30,000 revs/min in step (4), the aperture of pore is 0.1~0.3
Millimeter.
Preferably, a diameter of 25~30 microns of environment-friendly type refractory fibre described in step (4), length is 70~260 millis
Rice.
The present invention has the advantages that：
(1) content of free aldehyde in refractory fibre can be reduced by adding the antistatic combined binder containing formaldehyde catching agent so that resistance to
Fiery fiber more environmental protection and with antistatic property；
(2) preparation technology is simple, and parameter is easily controllable, expands application field, increases the performance of enterprises.
Embodiment
Below by specific embodiment, technical scheme is described in further detail.
In the present invention, if not refering in particular to, all devices and raw material are commercially available or the industry is conventional, following
Method in embodiment, is this area conventional method unless otherwise instructed.
Embodiment 1
It is stand-by that antistatic combined binder is prepared according to following proportioning：Phenolic resin 7g, absolute ethyl alcohol 5g, 0.05g H2N-
CH2-CH2-SO3H and PEO 0.15g；
(1) aluminum oxide 65g, magnesia 30g, titanium dioxide 10g and yttria 4g are weighed at 200 DEG C according to following proportioning
Blending carries out crushing the major ingredient for obtaining that particle diameter is 150 mesh after insulation 1h；
(2) the antistatic combined binders of 12.2g are slowly added into major ingredient, the mixture after being well mixed puts into melting furnace
In be heated to 1500 DEG C and obtain fused solution；
(3) impurity in filtering fused solution, filtrate, which flows into uninterruptedly to stir in 1800 DEG C of stirred autoclave, obtains spinning solution；
(4) spinning solution flows out from discharging opening, is sprayed into pore of the spinning head through spinning head, and the centrifugal speed of spinning head is 20,000
Rev/min, the aperture of pore is 0.1 millimeter.Quickly cooling obtains solid fiber to spinning solution, is collected and is put down by condensers
A diameter of 25 microns, length is 70 millimeters of environment-friendly type refractory fibre.
Embodiment 2
It is stand-by that antistatic combined binder is prepared according to following proportioning：Phenolic resin 8g, absolute ethyl alcohol 6g, 0.1g NH2OH, gathers
Polyetheresteramide 0.1g and 0.1g carboxyl betaine graft inter polymer；
(1) aluminum oxide 75g, magnesia 50g, titanium dioxide 15g and yttria 8g are weighed at 400 DEG C according to following proportioning
Blending carries out crushing the major ingredient for obtaining that particle diameter is 240 mesh after insulation 2h；
(2) the antistatic combined binders of 14.3g are slowly added into major ingredient, the mixture after being well mixed puts into melting furnace
In be heated to 1500 DEG C and obtain fused solution；
(3) impurity in filtering fused solution, filtrate, which flows into uninterruptedly to stir in 1950 DEG C of stirred autoclave, obtains spinning solution；
(4) spinning solution flows out from discharging opening, is sprayed into pore of the spinning head through spinning head, and the centrifugal speed of spinning head is 30,000
Rev/min, the aperture of pore is 0.3 millimeter.Quickly cooling obtains solid fiber to spinning solution, is collected and is put down by condensers
A diameter of 30 microns, length is 260 millimeters of environment-friendly type refractory fibre.
Embodiment 3
It is stand-by that antistatic combined binder is prepared according to following proportioning：Phenolic resin 7.5g, absolute ethyl alcohol 5.5g, 0.03g's
NH2OH and 0.07g H2N-CH2(COOH), carboxyl betaine graft inter polymer 0.18g；
(1) aluminum oxide 70g, magnesia 40g, titanium dioxide 12g and yttria 6g are weighed at 300 DEG C according to following proportioning
Blending carries out crushing the major ingredient for obtaining that particle diameter is 200 mesh after insulation 1.5h；
(2) the antistatic combined binders of 13.28g are slowly added into major ingredient, the mixture after being well mixed, which is put into, to be melted
1500 DEG C are heated in stove and obtains fused solution；
(3) impurity in filtering fused solution, filtrate, which flows into uninterruptedly to stir in 1900 DEG C of stirred autoclave, obtains spinning solution；
(4) spinning solution flows out from discharging opening, is sprayed into pore of the spinning head through spinning head, and the centrifugal speed of spinning head is 2.5
Ten thousand revs/min, the aperture of pore is 0.2 millimeter.Quickly cooling obtains solid fiber to spinning solution, is collected and obtained by condensers
Average diameter is 38 microns, and length is 160 millimeters of environment-friendly type refractory fibre.
Comparative example
Comparative example uses commercial alumina refractory fibre.
To environment-friendly type refractory fibre made from embodiment 1-3 and the physical and chemical index of the commercial alumina refractory fibre of comparative example
Detected, as a result as shown in table 1.
The physical and chemical index result of table 1.
| Physical and chemical index | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example |
| Free aldehyde, wt% | 0.3 | 0.2 | 0.5 | 5 |
| Heat resistance, DEG C | 2345 | 2350 | 2380 | 2005 |
| The Electrostatic Absorption of cotton chip | Nothing | Nothing | Nothing | Have |
As can be seen from Table 1, by adding the combined binder of the formaldehyde catching agent containing primary amine group and antistatic additive to passing
The refractory fibre of system is modified, obtained environment-friendly type refractory fibre relative to commercial alumina refractory fibre heat resistance more
Height, and greatly reduce the content of free aldehyde, more environmental protection.It is obtained by adding antistatic additive in formula system
Refractory fibre has stable anti-static ability, and security performance is high.
The present invention, which adds the antistatic combined binder containing formaldehyde catching agent, can reduce content of free aldehyde in refractory fibre,
So that refractory fibre more environmental protection and with antistatic property；Preparation technology is simple, and parameter is easily controllable, expands application neck
Domain, increases the performance of enterprises.
Claims (8)
1. a kind of environment-friendly type refractory fibre, it is characterised in that the environment-friendly type refractory fibre is made up of the raw material of following parts by weight：
65~75 parts of aluminum oxide, 30~50 parts of magnesia, 10~15 parts of titanium dioxide, 4~8 parts of yttria and antistatic composite junction
12.2~14.3 parts of mixture.
2. a kind of environment-friendly type refractory fibre according to claim 1, it is characterised in that the antistatic combined binder by
The raw material of following parts by weight is made：7~8 parts of phenolic resin, 5~6 parts of absolute ethyl alcohol, formaldehyde catching agent 0.05~0.15 and anti-quiet
Electric 0.15~0.2 part of agent.
3. a kind of environment-friendly type refractory fibre according to claim 2, it is characterised in that under the formaldehyde catching agent has
Formula：R-NH2, R is selected from-OH ,-CH2-CH2-SO3H ,-CH2And-CH (COOH) (CH (COOH)2CH2CONH2) in one kind or several
Kind.
4. a kind of environment-friendly type refractory fibre according to claim 2, it is characterised in that the antistatic additive is polycyclic oxygen second
One or more in alkane, polyether ester amides, carboxyl betaine graft inter polymer.
5. a kind of preparation method of environment-friendly type refractory fibre as claimed in claim 4, it is characterised in that comprise the following steps：
(1) weigh raw material for standby according to said ratio, by aluminum oxide, magnesia, titanium dioxide and yttria in 200~
Blending progress is crushed and obtains major ingredient after 1~2h of insulation at 400 DEG C；
(2) antistatic combined binder is slowly added into major ingredient, the mixture after being well mixed, which is put into melting furnace, to be added
Hot to 1500~1800 DEG C obtain fused solution；
(3) impurity in filtering fused solution, filtrate flows into uninterruptedly to stir in 1800~1950 DEG C of stirred autoclave and spun
Silk liquid；
(4) spinning solution flows out from discharging opening, is sprayed into pore of the spinning head through spinning head, and quickly cooling obtains solid to spinning solution
Fiber, is collected by condensers and obtains environment-friendly type refractory fibre.
6. a kind of preparation method of environment-friendly type refractory fibre according to claim 5, it is characterised in that institute in step (1)
The particle diameter for stating major ingredient is 150~240 mesh.
7. the preparation method of a kind of environment-friendly type refractory fibre according to claim 5 or 6, it is characterised in that in step (4)
The centrifugal speed of spinning head is 2~30,000 revs/min, and the aperture of pore is 0.1~0.3 millimeter.
8. the preparation method of a kind of environment-friendly type refractory fibre according to claim 5 or 6, it is characterised in that in step (4)
A diameter of 25~30 microns of the environment-friendly type refractory fibre, length is 70~260 millimeters.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710526864.0A CN107237009A (en) | 2017-06-30 | 2017-06-30 | A kind of environment-friendly type refractory fibre and preparation method thereof |
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| CN201710526864.0A CN107237009A (en) | 2017-06-30 | 2017-06-30 | A kind of environment-friendly type refractory fibre and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108085782A (en) * | 2017-11-30 | 2018-05-29 | 长兴科创科技咨询有限公司 | A kind of novel environment friendly alumina setter fiber and preparation method thereof |
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| CN101622195A (en) * | 2006-09-29 | 2010-01-06 | 阿克伦大学 | Metal oxide fibers and nanofibers, method for making same, and uses thereof |
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| CN103282395A (en) * | 2010-10-01 | 2013-09-04 | 迪纳化学公司 | Low free formaldehyde phenolic resins for abrasive products |
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| CN106435835A (en) * | 2016-08-30 | 2017-02-22 | 江苏南山冶金机械制造有限公司 | Preparing method of refractory fiber used for high-temperature furnace roller |
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2017
- 2017-06-30 CN CN201710526864.0A patent/CN107237009A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101263090A (en) * | 2006-05-19 | 2008-09-10 | 维克托·F·凯伯 | Composition and method for producing continuous basalt fibers |
| CN101622195A (en) * | 2006-09-29 | 2010-01-06 | 阿克伦大学 | Metal oxide fibers and nanofibers, method for making same, and uses thereof |
| CN101945829A (en) * | 2007-12-28 | 2011-01-12 | 3M创新有限公司 | Methods of making ceramic fibers and beads |
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| CN108085782A (en) * | 2017-11-30 | 2018-05-29 | 长兴科创科技咨询有限公司 | A kind of novel environment friendly alumina setter fiber and preparation method thereof |
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Application publication date: 20171010 |