CN101565491B - Thermoplastic liquid phenolic resin and preparation method thereof - Google Patents
Thermoplastic liquid phenolic resin and preparation method thereof Download PDFInfo
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- CN101565491B CN101565491B CN2008100111831A CN200810011183A CN101565491B CN 101565491 B CN101565491 B CN 101565491B CN 2008100111831 A CN2008100111831 A CN 2008100111831A CN 200810011183 A CN200810011183 A CN 200810011183A CN 101565491 B CN101565491 B CN 101565491B
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Abstract
The present invention relates to a preparation method of thermoplastic liquid phenolic resin used in fireproof materials. The method comprises the following steps: the well prepared phenol, formaldehyde and oxalic acid are pumped into a reaction vessel under vacuum according to a certain parts by weight, an emptying valve is turned on, the reaction is carried out when the temperature is raised to 90-110 DEG C under the action of stirring and the reaction time is 50-80 min; the emptying valve is turned off, the vacuum is opened, a steam valve is turned on for heating and temperature rising, the degree of vacuum is kept between minus 0.5 and minus 0.8 MPa, the dehydration is carried out when the steam pressure is 4 to 6 MPa, no water exists after one hour, the temperature of the material is about 105 DEG C at the moment and the dehydration is finished; the thylene glycol well prepared in advance is added in according to a certain parts by weight, the temperature is reduced to about 60 DEG C after even mixing and then the material is put in a clean galvanized iron drum and packaged to obtain the finished product. The content of the free phenol is reduced to 3 percent below, and the serious pollution and the serious harm to the human body generated during the manufacturing process and the using process of the magnesia carbon brick are also greatly reduced in proportion; the wettability is good, the quality of the finished product is basically ensured and the pot life of the half finished product is prolonged by dozens of times.
Description
Technical field
The invention belongs to the phenolic resin binder technical field, specifically a kind of used for refractory material thermoplastic liquid phenolic resin and production method thereof.
Background technology
As everyone knows, have purposes widely as the resol of macromolecular material industrial, wherein at the magnesia carbon brick of one of important refractory materials of smelting iron and steel industry, resol is to be used to produce the obligato wedding agent of magnesia carbon brick.
In decades, domestic magnesia carbon brick is produced used resol and is continued to use the heat curing-type liquid phenolic resin always.But the heat curing-type liquid phenolic resin exists the higher and product of free phenol content and work in-process and meets that heat easily becomes sticky, the shortcoming of hardening.And in resin transportation, preservation and production process, it is inevitable meeting heat.
1, to the pollution damage of environment and human body
Phenol is one of main raw material(s) of resol.Phenolic compound can suck and per os enter number of ways such as digestive tube and enters in the body through Mucocutaneous contact, respiratory tract.Phenol toxicity maximum in phenolic compound, and its chemical structural formula is firm can be along with factors vary such as oxidation, sunlight, times and decompose.There is the intensive corrosive nature human body contact back to tissues such as skin, mucous membranes.Nervus centralis or damage liver, renal function can be suppressed, leukemia and sterile etc. can be caused.It is one of main and serious pollutent that environment (comprising water, air and cured article) is polluted.
Tradition resol free phenol content generally accounts for more than 10% in finished product.Because the restriction of production technique, this part free phenol can't be participated in reaction, generate product, because the existence of free phenol, comparatively seriously influence and restricting the quality product of resol on the one hand, also seriously caused the pollution of time several operations on the other hand, environment and human body have been caused serious threat and infringement., after compression moulding, enter in the drying kiln drying course as magnesia carbon brick, can produce a large amount of phenol gas evolution, present strong aromatic hydrocarbon and pungent smell.Atmosphere pollution and threaten human health seriously.
2, the instability of product and work in-process performance
Heat-reactive phenolic resin is owing to be subjected to the restriction of the intrinsic physical and chemical performance of resin itself, and it begins polymer volatilization retrogradation to occur, the situation generation of hardening gradually when surpassing more than 50 ℃ when surpassing 35 ℃.Resin for some time before compression moulding, will be subjected to the restriction of temperature on the one hand, and be subjected to the restriction of time on the other hand again after work in-process are made in stirring with magnesia.
Be subjected to aspect the temperature effect: resin and magnesia owing to stir the effect of friction, often will make to be stirred thing and to generate high temperature more than 45 ℃ in the mix process.Such temperature must have a negative impact to the quality of resin, and it is aging to be commonly called as resin.
Aspect time effects: often produce a large amount of work in-process mixed materials owing to equipment failure maintenance, work in-process brick lack reasons such as limit arrisdefect, tailing.These work in-process mixed materials can not be made finished bricks in case surpass 10 hours, will all scrap.And the yield rate of magnesia carbon brick had only about 90% in the past, and for a brick field of producing several ten thousand tons of bricks per year, this part loses every year all between hundreds of thousands of unit.
So the deficiency on these performances of liquid thermoset resol is comparatively seriously restricting the development of refractories industry traditionally, comparatively seriously formed to the pollution of environment and to people's healthy infringement.Because China is one of main host country of the resources of magnesia in the world, also be maximum in the world Iron and Steel Production state, we can say that China is the largest production state and the export State of magnesia carbon brick.Liquid thermoset resol seems particularly important to the restriction of cost with to environment and human pollution in the production of magnesium carbon.Change early and reverse this phenomenon and seem particularly urgent.
Summary of the invention
The objective of the invention is: a kind of used for refractory material thermoplastic liquid phenolic resin and production method thereof that free phenol content improves physical and chemical performance that reduce is provided.
The object of the present invention is achieved like this: its producer is: with ready phenol, formaldehyde, oxalic acid or hydrochloric acid according to the following number of weight ratio with vacuum with in its suction jacketed type reactor, open blow-off valve, under agitation be warming up to 90～110 ℃ and begin reaction, the reaction times is 50～80 minutes; Close blow-off valve, open vacuum, open the steam valve heat temperature raising, keep vacuum tightness-0.5～-0.8Mp, vapour pressure is dewatered at 4～6Mp, about 1 hour, no longer include water and deviate from, this moment temperature of charge about 105 ℃, dehydration finishes;
Add ethylene glycol, glycerol, mixed alcohol or the polyvalent alcohol of getting ready in advance by following parts by weight, be cooled to behind the mixing about 60 ℃, put into and be finished product after clean zinc-plated bucket is packed;
Chemical ingredients that the present invention contains and ratio of weight and number are: content is 10 parts of phenol more than 95%, 6.5～7.2 parts in technical grade formaldehyde, with 0.1～0.20 part of the hydrochloric acid of two times of water-reducible oxalic acid or 30%～35%, ethylene glycol, glycerol, mix 5.0～6.0 parts of alcohol or polyvalent alcohols.
The content of phenol raw material of the present invention is preferably and is equal to or greater than 99%.
The present invention is in when dehydration, keeps vacuum tightness to carry out under 4Mp in-0.58Mp, vapour pressure.
Advantage of the present invention is:
1, environmental protection
The free phenol content of new type resin by 10% of conventional resins be reduced to＜3%.The reduction significantly of free phenol, the grievous injury that the severe contamination that produces in manufacturing processed and in the use for magnesia carbon brick reaches human body also is in proportion reduction significantly.For reducing pollutant emission and alleviating the infringement of human body significant.
2, obviously improve the wettability and the moisture retention of the semi-product material in the brickmaking process
Wettability and moisture retention are two very important indexs in the brickmaking production process, also are crucial indexs.
Have a look wettability earlier.In the batch mixing process, because the durothermic raising of this resin is significant in actual production.The heat that produces in the spice process no longer produces any influence and aging to resin quality, makes resin keep good wetting regime, makes itself and material can reach a perfect proportioning state.Resin extensively is evenly dispersed in the brick material.Changed in the past the situation that the on-the-spot graphite at batch mixing flies upward, illustrated graphite this be difficult to wetting brick material also can be well and resin-bonded.The powder that black in finished product, no longer occurs with the surface of hand touch brick.Proved absolutely that resin combines fully with material, the not existence of free siccative, and this slight change has illustrated very crucial problem.To produce far-reaching influence to the raising of quality product.
Have a look moisture retention again.With the work in-process behind the new type resin spice, at normal temperatures can be at 168 hours with its activity of interior maintenance.And the resin semi-product material activity of mixing system can only be kept about 10 hours in the past.And this variation is to influence on the product cost or all significant on improving the quality of products.
At first be to influence on the product cost.
(1), overtime work in-process causing because of equipment failure deposit, no longer produce and scrap.
(2), 10% finished product scrap rate can realize reclaiming, brickmaking no longer produces and scraps again.
(3), tailing, land material, class back residue material etc. and no longer produce and scrap.
(4), disregard the factor of stating of counting in, the magnesia carbon brick that drops into new type resin production is compared on raw materials cost with the magnesia carbon brick that drops into conventional resins production and is remained basically stable.
Next is on quality product.
A, since its wettability good, make the mix of semi-product material be in optimum regime, and make the quality of finished product can access basic assurance.Both guaranteed that the magnesia carbon brick void content reduced, density improves, intensity increases, the neat smooth surface of outward appearance corner angle, made the national standard and the export standard that reach and surpass magnesia carbon brick that it can be stable.
B, because after using new type resin, active phase tens times the raising of its work in-process, can allow the ageing mixture of semi-product material, and can guarantee that the ageing mixture of certain hour is the prerequisite that can make the high quality magnesia carbon brick, this can not imagine in the use of liquid-solid property resol.This ageing mixture is just as awake face, " having only the good face of waking up just can make the such high quality flour products of ultra-fine hand-pulled noodles ".
To be described in further detail the present invention by example below, but following example only is the present invention's example wherein, the rights protection scope of not representing the present invention and being limited, the scope of the present invention is as the criterion with claims.
Embodiment
Example 1
1, reaction:
Earlier be that 99% phenol 600kg, content are 36.5% formaldehyde 400kg, it are pumped in the reactor that strap clamp overlaps by vacuum with the water-reducible oxalic acid 6kg of duple with the content of getting ready, open blow-off valve, start and stir slowly intensification of beginning, near temperature of charge reaches 100 ℃, begin reaction.Too fierce as reaction, can in chuck, feed water coolant, so that reaction relaxes; Become turbid after 10 minutes, keep the material temperature to continue reaction about 1 hour for 100 ℃, reaction finishes, and begins dehydration.
2, dehydration:
Close blow-off valve, open vacuum, open the steam valve heat temperature raising.Keep vacuum tightness about-0.6Mp, vapour pressure is dewatered about 4Mp.About 1 hour, no longer include water and deviate from, temperature of charge is about 105 ℃ at this moment, and dehydration finishes.
Add the ethylene glycol 310kg that gets ready in advance under stirring again, be cooled to about 60 ℃, produce the liquid phenolic resin finished product of about 1000kg, put into clean zinc-plated bucket then and pack.
Example 2
1, reaction:
Earlier be that 95% commercial-grade phenol 600kg, content are that 36.5% technical grade formaldehyde 430kg, 30% hydrochloric acid 6kg are pumped into it in reactor of strap clamp cover by vacuum with the content of getting ready, open blow-off valve, start and stir slowly intensification of beginning, near temperature of charge reaches 100 ℃, begin reaction.Too fierce as reaction, can in chuck, feed water coolant, so that reaction relaxes; Become turbid after 10 minutes, keep the material temperature to continue reaction about 1 hour for 100 ℃, reaction finishes, and begins dehydration.
2, dehydration:
Close blow-off valve, open vacuum, open the steam valve heat temperature raising.Keep vacuum tightness about-0.6Mp, vapour pressure is dewatered about 4Mp.About 1 hour, no longer include water and deviate from, temperature of charge is about 105 ℃ at this moment, and dehydration finishes.
Add the mixed pure 350kg that gets ready in advance under stirring again, be cooled to about 60 ℃, produce the liquid phenolic resin finished product of about 1030kg, put into clean zinc-plated bucket then and pack.
A few days ago, finished product of the present invention is by having carried out application test in producers such as Yongji, Yingkou wheat lattice novel refractory company, English refractory materials company limited of Shenyang section, the prosperous refractory materials of Beijing rising sun company limiteds.Through the repeatedly actual big experiment that feeds intake of producing of many families, all obtained the ideal effect.The product inner quality obviously improves, the product appearance quality is neatly smooth, the work in-process waste material substantially no longer produces, production place dust raising phenomenon is greatly taken on a new look, the pungent smell of brickmaking production scene and drying kiln volatile phenol obviously reduces, and the user has given height and positive evaluation.
Claims (5)
1. used for refractory material thermoplastic liquid phenolic resin, it is characterized in that: chemical ingredients that contains and ratio of weight and number are: content is 10 parts of phenol more than 95%, 6.5～7.2 parts in technical grade formaldehyde, with 0.1～0.20 part of the hydrochloric acid of two times of water-reducible oxalic acid or 30%～35%, ethylene glycol, glycerol, mix 5.0～6.0 parts of alcohol or polyvalent alcohols.
2. used for refractory material thermoplastic liquid phenolic resin according to claim 1 is characterized in that: the content of phenol is for being equal to or greater than 99%.
3. the production method of a used for refractory material thermoplastic liquid phenolic resin, its producer is: with ready phenol, formaldehyde, oxalic acid or hydrochloric acid according to the following number of weight ratio with vacuum with in its suction jacketed type reactor, open blow-off valve, under agitation be warming up to 90～110 ℃ and begin reaction, the reaction times is 50～80 minutes; Close blow-off valve, open vacuum, open the steam valve heat temperature raising, keep vacuum tightness-0.5～-0.8MPa, vapour pressure is dewatered at 4～6MPa, about 1 hour, no longer include water and deviate from, this moment temperature of charge about 105 ℃, dehydration finishes;
Add ethylene glycol, glycerol, mixed alcohol or the polyvalent alcohol of getting ready in advance by following parts by weight, be cooled to behind the mixing about 60 ℃, put into and be finished product after clean zinc-plated bucket is packed;
Content is 10 parts of phenol more than 95%, and 6.5～7.2 parts in technical grade formaldehyde with 0.1～0.20 part of the hydrochloric acid of two times of water-reducible oxalic acid or 30%～35%, ethylene glycol, glycerol, mixes 5.0～6.0 parts of alcohol or polyvalent alcohols.
4. the production method of used for refractory material thermoplastic liquid phenolic resin according to claim 3 is characterized in that: the content of phenol is for being equal to or greater than 99%.
5. the production method of used for refractory material thermoplastic liquid phenolic resin according to claim 3 is characterized in that: during dehydration, keep vacuum tightness to carry out under 4MPa in-0.58MPa, vapour pressure.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008100111831A CN101565491B (en) | 2008-04-25 | 2008-04-25 | Thermoplastic liquid phenolic resin and preparation method thereof |
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| CN2008100111831A CN101565491B (en) | 2008-04-25 | 2008-04-25 | Thermoplastic liquid phenolic resin and preparation method thereof |
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| CN101565491B true CN101565491B (en) | 2011-06-08 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103319671B (en) * | 2013-07-24 | 2016-01-13 | 山东圣泉新材料股份有限公司 | The preparation method of phenolic resin for refractory material |
| CN108148161A (en) * | 2018-01-24 | 2018-06-12 | 山东永汇新材料股份有限公司 | The method that flushing-free exempts from addition drop phenol agent synthetic thermoplastic phenolic resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045778A (en) * | 2006-09-15 | 2007-10-03 | 中国科学院山西煤炭化学研究所 | Preparation method of boron modified phenolic resin |
| CN101062969A (en) * | 2006-12-07 | 2007-10-31 | 沈阳化工学院 | Pnenolic aldehyde type adsorption resin and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045778A (en) * | 2006-09-15 | 2007-10-03 | 中国科学院山西煤炭化学研究所 | Preparation method of boron modified phenolic resin |
| CN101062969A (en) * | 2006-12-07 | 2007-10-31 | 沈阳化工学院 | Pnenolic aldehyde type adsorption resin and preparation method thereof |
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