CN103597001A - Method for manufacturing urea-modified novolac phenol resin, urea-modified novolac phenol resin obtained thereby, and resin-coated sand obtained using same - Google Patents
Method for manufacturing urea-modified novolac phenol resin, urea-modified novolac phenol resin obtained thereby, and resin-coated sand obtained using same Download PDFInfo
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- CN103597001A CN103597001A CN201280029176.9A CN201280029176A CN103597001A CN 103597001 A CN103597001 A CN 103597001A CN 201280029176 A CN201280029176 A CN 201280029176A CN 103597001 A CN103597001 A CN 103597001A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
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Abstract
Provided are a method that can stably manufacture a urea-modified novolac phenol resin that is easy to handle and has low viscosity and a method that can effectively manufacture a novolac phenol resin modified by a large amount of urea. A resin obtained by this method and resin-coated sand that can actualize excellent casting properties using this resin are also provided. In the production of a urea-modified novolac phenol resin by cocondensing a phenolic compound, aldehydes, and urea or methylol urea, urea or methylol urea is added in small amounts continuously or intermittently to the reaction system while allowing the reaction of the phenolic compound and aldehydes to proceed, and the phenolic compound and the aldehydes are cocondensed sequentially.
Description
Technical field
The present invention relates to the manufacture method of urea-modified phenolic varnish type resol and the urea-modified phenolic varnish type resol being obtained by the method and the coated sand obtaining with it, especially, relate generally to suitable matrix material or phenolic varnish type resol coated with resin, urea-modified as coated sand, and effective manufacture method, the coated sand that uses in addition this phenolic varnish type resol to obtain.
Background technology
All the time, on the specific effect that can give at nitrogen compound, the basis of function, for industrial reasons such as costs, with modifications such as urea, trimeric cyanamides resol used more and more widely.Especially, when manufacturing modified phenolic resins, urea is compared with phenol, has the advantages such as speed of response flame retardant resistance fast and gained modified resin improves, and therefore at numerous industrial circles, is used widely.
Yet about urea-modified resol, known have when manufacturing resol type phenol resin, adds urea to make it react to obtain the gimmick of urea-modified resol type phenol resin in phenol and formaldehyde.For example, a clear example having recorded the method in TOHKEMY 2009-84382 communique.Yet the urea-modified resol type phenol resin about so obtaining, not only has hygroscopic problem, and the caused crackle of condensation water producing while being shaped is, the smell that the generation of formaldehyde causes etc. also become problem, is difficult in practical use.
On the other hand, in the situation that the phenolic varnish type resol that makes phenolic compound and formaldehyde reaction manufacture under acidic conditions, make to exist in reaction system urea, make urea and above-mentioned phenolic compound, when formaldehyde one reacts to manufacture cocondensation resin, the cocondensation reaction of these three kinds of compositions cannot be carried out smoothly, especially, as urea with respect to the ratio of the total amount of the phenolic compound being used and urea be 10 % by weight above, increase the consumption of urea, while attempting to manufacture the urea-modified phenolic varnish type resol of using urea high modification, because phenolic compound is different with respect to the speed of response of formaldehyde with urea, therefore can cause urea separately and the polymerization (condensation) of formaldehyde, cause gelation, the manufacture of target cocondensation resin itself all can become difficulty.In addition, in this reaction, suppose to allow to carry out resinifying, the viscosity of its resinifying product also can rise, and is difficult to bring into play the desirable properties of the urea-modified resin of gained.
In addition, in Japanese kokai publication sho 58-37020 communique, clearly recorded the technology of using urea in the manufacturing process of phenolic varnish type resol, but its main purpose is only: after formaldehyde finishes with reacting of phenol, in its reaction product, add urea, make to remain in unreacted formaldehyde and the urea reaction in generated phenolic varnish type resol, suppress thus the smell that formaldehyde causes.In this Japanese kokai publication sho 58-37020 communique, for for obtaining the effective way of urea-modified phenolic varnish type resol, do not record completely.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2009-84382 communique
Patent documentation 2: Japanese kokai publication sho 58-37020 communique
Summary of the invention
the problem that invention will solve
At this, the present invention be take above-mentioned situation and is made as background, its problem that will solve is to provide can stablize method operation easy to manufacture, that have low viscous urea-modified phenolic varnish type resol, and be to provide can high efficiency manufacture through the gimmick of a large amount of urea-modified phenolic varnish type resol, and then be also to provide the coated sand that can bring into play excellent mould characteristic.
for the scheme of dealing with problems
Then, for the present invention, for the problem that addresses the above problem or hold according to the record of specification sheets integral body, accompanying drawing, following cited variety of way can suitable enforcement, and in addition, each mode of the following stated also can adopt when combining arbitrarily.In addition, technical scheme of the present invention and even technical characterictic are not limited to the scheme of the following stated completely, be interpreted as record based on specification sheets integral body and wherein disclosed technical conceive can be cognitive scheme.
(1) a kind of manufacture method of urea-modified phenolic varnish type resol, it is characterized in that, make phenolic compound, when aldehydes and urea or the urea-modified phenolic varnish type resol of the incompatible manufacture of methylolurea cocondensation, make aforementioned phenolic compound contact with aforementioned aldehydes their reaction is carried out on one side, in reaction system, little by little add aforementioned urea or methylolurea continuously or discontinuously on one side, the consumption of estimating until be reached for aforementioned cocondensation, make added urea or methylolurea carry out cocondensation with aforementioned phenolic compound and aforementioned aldehydes successively.
(2) according to the manufacture method of urea-modified phenolic varnish type resol aforementioned schemes (1) Suo Shu, wherein, aforementioned urea or methylolurea add in reaction system under the form of the aqueous solution or suspension.
(3) according to the manufacture method of the urea-modified phenolic varnish type resol described in aforementioned schemes (1) or (2), wherein, aforementioned urea or methylolurea are added continuously in reaction system with a certain proportion of interpolation speed.
(4) according to the manufacture method of the urea-modified phenolic varnish type resol described in aforementioned schemes (1) or (2), wherein, the interpolation of the interruption of aforementioned urea or methylolurea separates certain intervals, with a certain amount of, implements at every turn.
(5), according to the manufacture method of the urea-modified phenolic varnish type resol described in any one in aforementioned schemes (1)～(4), wherein, aforementioned urea or methylolurea are solid.
(6) according to the manufacture method of the urea-modified phenolic varnish type resol described in any one in aforementioned schemes (1)～(5), wherein, make after aforementioned phenolic compound and aforementioned aldehydes carry out initial condensation, to start its initial condenses to add aforementioned urea or methylolurea.
(7) according to the manufacture method of urea-modified phenolic varnish type resol aforementioned schemes (6) Suo Shu, when the consumption of estimating for aforementioned cocondensation of the amount of residual aldehydes and aforementioned urea or methylolurea equates in aforementioned initial condenses, start to add this urea or methylolurea.
(8) a phenolic varnish type resol, it is to obtain by the manufacture method described in any one in aforementioned schemes (1)～(7).
(9) a phenolic varnish type resol, is characterized in that, it is by making phenolic compound, aldehydes and urea or the incompatible manufacture of methylolurea cocondensation.
(10) according to urea-modified phenolic varnish type resol aforementioned schemes (9) Suo Shu, it is characterized in that, it is by making phenolic compound, aldehydes and urea or the incompatible manufacture of methylolurea cocondensation, and its caloric receptivity of following pyrolysis is 5～200J/g.
(11) according to aforementioned schemes (9) or (10) described urea-modified phenolic varnish type resol, it is characterized in that, it is by making phenolic compound, aldehydes and urea or the incompatible manufacture of methylolurea cocondensation, when utilizing differential scanning calorimeter mensuration to follow the caloric receptivity of pyrolysis, in the scope of 280 ℃～400 ℃, there is endotherm(ic)peak.
(12) according to the urea-modified phenolic varnish type resol described in any one in aforementioned schemes (9)～(11), it is characterized in that the mol ratio of phenolic compound (P), aldehydes (F) and urea or methylolurea (U): be F/(P+U) 0.50～0.75.
(13) according to the urea-modified phenolic varnish type resol described in any one in aforementioned schemes (9)～(12), it is characterized in that, using cone-and-plate viscometer is 500～4500mPas at 160 ℃ of melt viscosities that record.
(14) according to the urea-modified phenolic varnish type resol described in any one in aforementioned schemes (9)～(13), it is characterized in that, weight-average molecular weight (Mw) is 550～2500.
(15) according to the urea-modified phenolic varnish type resol described in any one in aforementioned schemes (9)～(14), it is characterized in that urea or methylolurea (U) the urea-modified rate to phenolic compound (P): be U/(U+P) 5～50%.
(16), it is characterized in that, its urea-modified phenolic varnish type resol coating resistivity against fire particle that uses the manufacture method described in any one in aforementioned schemes (1)～(7) to obtain forms.
(17), it is characterized in that, it uses urea-modified phenolic varnish type resol coating resistivity against fire particle described in any one in aforementioned schemes (9)～(15) to form.
the effect of invention
Manufacture method for this foundation urea-modified phenolic varnish type resol of the present invention, for obtaining the reaction system of phenolic compound and the aldehydes of phenolic varnish type resol, with the urea of their cocondensation or methylolurea be not quickly or disposable interpolation, but little by little add continuously or discontinuously in batches, supply with the consumption of estimating until be reached for cocondensation, therefore can effectively form more low viscous urea-modified novolac resin, thus, manufacture at this resin, operation becomes on easy basis, can also advantageously give play to the characteristic of urea-modified phenolic varnish type resol.
And, by adopting this gimmick with small proportion portion-wise addition urea or methylolurea, can make the cocondensation stable reaction of phenolic compound, aldehydes and urea or methylolurea carry out, thus, can increase the final feed rate (cocondensation resultant) of this urea or methylolurea, thereby can effectively obtain through a large amount of urea-modified phenolic varnish type resol.
On the other hand, to in the reaction system of phenolic compound and aldehydes quickly or when it is reacted the disposable supply total amount that will carry out the urea of cocondensation or the consumption of methylolurea, reaction heat significantly increases, the temperature of reaction system sharply rises, cause thus the independent polymerization of hydrolysis, urea (condensation) of urea, thereby cause the gelation of following molecular weight to rise, in addition, the steady qualityization of the urea-modified phenolic varnish type resol of gained is impaired, form the very high reaction product of viscosity, have the practical problem of being unable to undergo.
In addition, the urea-modified phenolic varnish type resol so obtaining according to the present invention has and the proportional caloric receptivity of its nitrogenous rate, there is the feature that flame retardant resistance is high, and then, by this urea-modified resin as the matrix material of resistivity against fire particle or coated sand that coated with resin forms can show can be practical mould strength, and can contribute to mould characteristic, such as improvement of the bad problem of cast(ing) surface such as shrinkage cavities, the improvement of the collapsibility of mould etc.
Accompanying drawing explanation
Fig. 1 is the chart of measurement result that infrared rays (IR) absorption spectrum of the urea-modified phenolic varnish type resol obtaining in embodiment 3, embodiment 4 and comparative example 3 is shown.
Fig. 2 is the DSC curve of measurement result that the caloric receptivity of the urea-modified phenolic varnish type resol obtaining in embodiment 3, embodiment 4 and comparative example 3 is shown.
Embodiment
Yet, the phenolic compound of one of raw material of the urea-modified phenolic varnish type resol of manufacturing according to the present invention as formation, except phenol itself, also can list such as alkylphenols such as cresols, xylenol, butylphenol, nonylphenols, the polyphenol such as Resorcinol, Bisphenol F, dihydroxyphenyl propane, and their the known materials such as mixture, these phenolic compounds can be used separately or appropriately combined use.
Particularly, as alkylphenol, can use: ortho-cresol, meta-cresol, p-cresol, phlorol, m-ethylphenol, p-ethyl phenol, 2, 3-xylenol, 3, 5-xylenol, 2, 5-xylenol, 3, 4-xylenol, 2-propylphenol, 2-isopropyl-phenol, 3-propylphenol, 3-isopropyl-phenol, 4-isopropyl-phenol, 4-propylphenol, 2-sec-butyl phenol, 2-TBP, 3-sec-butyl phenol, 3-tert.-butyl phenol, 4-sec-butyl phenol, 4-TBP, 2-cyclohexylphenol, 3-cyclohexylphenol, 4-cyclohexylphenol, 2-nonylphenol, 3-nonylphenol, 4-nonylphenol, 2-dodecyl phenol, 3-dodecyl phenol, 4-dodecyl phenol, 2-octadecyl phenol, 3-octadecyl phenol, 4-octadecyl phenol, 2-sec.-propyl-5-methylphenol, 2-tert-butyl-4-methyl-Phenol, 3 methy 6 tert butyl phenol, 2, 3, 5-pseudocuminol, 2, 3, 5-triethyl phenol etc.
In addition, in the present invention, as phenolic compound, also can adopt all the time for the manufacture of the known various materials of resol, can list such as known materials such as various polyatomic phenols, bisphenols, many condensed ring phenols, phenols purifying residues.
In addition, as the aldehydes forming according to other raw materials urea-modified phenolic varnish type resol of the present invention, that react with above-mentioned phenolic compound, suitable choice for use such as the known various compounds such as formaldehyde, formalin, paraformaldehyde, trioxymethylene, acetaldehyde, paraldehyde, propionic aldehyde.This aldehydes and above-mentioned phenolic compound are same, can use separately also and can be used in combination of two or more.
And then, when making above-mentioned phenolic compound react to manufacture the resol of phenolic varnish type with aldehydes, can use known various acid catalyst all the time.Except organic acid, the mineral acids such as suitable use such as oxalic acid, hydrochloric acid, sulfuric acid, toxilic acid, phosphoric acid are as catalyzer, can also use the compounds such as the divalent metal salts such as zinc oxide, zinc chloride, zinc acetate, plumbic acetate, zinc borate, magnesium oxide, oxide compound.It should be noted that, consumption about this acid catalyst, according to the kind of catalyzer, in known amount ranges, suitably select, and generally with respect to the total amount of phenolic compound and urea or methylolurea, can adopt 0.01～10 quality % left and right, be preferably the ratio about 0.1～1 quality %.
Then, the present invention by making to exist as ternary urea or methylolurea in the reaction system based on acid catalyst of above-mentioned phenolic compound and aldehydes, make this three mutually carry out condensation reaction, thereby manufacture novolac resin, urea-modified phenolic varnish type resol as cocondensation mould assembly, as methylolurea used herein, have: monomethylol urea, dimethylolurea, trimethylol urea, tatramethylol urea.In addition, as this ternary urea, methylolurea, can under the form of the aqueous solution, suspension or solid, add in reaction system, but while dropping into solid in reaction process, existence is caused the anxiety of speed of response reduction by the melting heat of this solid, therefore in the present invention, it is desirable to drop into reaction system under the form of the aqueous solution, suspension.In addition, in the 3rd composition, urea is generally used under the form of the aqueous solution, and methylolurea cannot be completely water-soluble and use with the form of suspension, or use with the form of solid.
In addition, for phenolic compound (P), aldehydes (F) and the urea or the methylolurea (U) that use in order to obtain this urea-modified phenolic varnish type resol, count in molar ratio, with following ratio, make this three reaction: F/P is generally 0.40～2.00, is preferably 0.50～1.95, and F/(P+U) value (mol ratio) be generally 0.40～0.80, be preferably 0.50～0.75.In addition, this F/P, F/(P+U) value when excessive, because increasing viscosity rise, the fusing point followed, the molecular weight of the urea-modified phenolic varnish type resol of target rises, cause being difficult to use in the target purposes such as coated sand, in addition according to circumstances can initiated gel, produce the anxiety of the manufacture change difficulty of resin itself.And these F/P, F/(P+U) value when too small, the molecular weight of the urea-modified phenolic varnish type resol of target reduces, thereupon, melting point depression, gel time is elongated, causes being difficult to use in the problem of the purposes such as coated sand.
And then, in the relation of phenolic compound and urea or methylolurea, when very few as the consumption of ternary urea or methylolurea, urea-modified rate reduces, be difficult to give full play to the heat-absorbing action as the urea-modified phenolic varnish type resol of gained feature, in addition, when the resin as in the purposes such as coated sand, be difficult to fully assist the inhibition of cast(ing) surface bad (shrinkage cavity etc.), the improvement of collapsibility, therefore, generally, under quality criteria, urea or methylolurea (U) can be adjusted to ratios more than 5 quality % with respect to phenolic compound (P) and the ratio of the total amount of urea or methylolurea (U).In addition, here, the consumption of methylolurea is used it to form urea amount used.And the consumption of urea or methylolurea is when increase, the characteristic of the urea-modified phenolic varnish type resol of gained weakens, demonstrate the characteristic as urea resin, therefore, generally, urea or methylolurea can be adjusted to below 80 quality % with respect to the usage rate of the total mass of phenolic compound and urea or methylolurea, are preferably below 50 quality %.The urea, methylolurea Shi ， Tough, water tolerance, the thermotolerance that use to surpass the ratio of this upper limit reduce, and hardness, fragility rise, and are difficult to the resin as coated sand etc.
Here, the present invention making above-mentioned three compositions, be that phenolic compound, aldehydes and urea or methylolurea are while reacting to manufacture the urea-modified novolac resin of cocondensation mould assembly, to in the reaction system of phenolic compound and aldehydes little by little (slowly) interpolation as ternary urea or methylolurea, the consumption of estimating until be reached for cocondensation, makes added urea or methylolurea carry out cocondensation with phenolic compound and aldehydes successively.
Then, by so will carrying out the urea of cocondensation or the consumption of methylolurea in batches, little by little add in reaction system along with the carrying out of reaction, can effectively suppress or stop sharply generation, the temperature of reaction of the condensation reaction heat of phenolic compound under an acidic catalyst and aldehydes, the neutralization heat while adding urea or methylolurea to rise, therefore, by suppressing the hydrolysis of urea, methylolurea, make the time of reaction soln in slightly acidic region keep longlyer, can advantageously promote phenol to react with the cocondensation of urea or methylolurea.
Here, urea, the aqueous solution of methylolurea is the weakly alkaline of pH=7.5 left and right, and then, when its aqueous solution is heated to 100 ℃ of above temperature, urea is hydrolyzed, produce ammonia, thereby pH value rises, therefore the temperature of reaction in reaction system and pH value are studied, found that, in the present invention, interpolation from urea or methylolurea was started till the time that interpolation finishes, conventionally it is desirable to, adopt the pH value of reaction system to become neutral region (left and right, pH=7～8) before from acidic region (below pH=4), be preferably while becoming pH=7.5, and then, as it, add the time length, it is desirable to, about 1.5～2 hours from interpolation starts finish to add.
In addition, in the present invention, the interpolation of a little of urea, methylolurea is carried out with continuous or discontinuous manner, for its continuous adding mode, can advantageously adopt with a certain proportion of interpolation speed (with certain speed by a certain amount of) to the mode of adding in reaction system, in addition, in the interruption addition manner of urea, methylolurea, it is desirable to, separate certain intervals, at every turn with a certain amount of enforcement.In addition, in the interruption addition manner of this devices spaced apart, for example set every 10 minutes equal times, drop into a certain amount of, or, when the consumption of urea, methylolurea is few, also can adopts it is progressively added drop-wise to mode in reaction system etc.
Yet, urea and phenol are with their the reacting of hydroxy methyl derivant, the cocondensation of preferential initiation and urea due to the hydroxymethyl of phenol, in addition, pH dependency about reaction medium, under solutions of weak acidity, preferential and the urea reaction of hydroxymethyl, under strong acidic condition or under alkaline condition, can cause the independent polymerization of urea, it is the condensation reaction of urea and aldehyde, therefore in the present invention, it is desirable to, make after phenolic compound and aldehydes carry out initial condensation, start the initial condenses of gained to add urea or methylolurea, make this urea, methylolurea and phenolic compound and aldehydes be cocondensation effectively.
Especially, in the situation that the use molar weight of the aldehydes using in cocondensation reaction is more than the use molar weight as ternary urea or methylolurea, when this pass ties up to and also keeps in reaction system, easily bring out the increase of molecular weight of the novolac resin of generation, viscosity rise, therefore in the present invention, it is desirable to, first, make phenolic compound and aldehydes carry out initial condensation, then, the amount of residual unreacted aldehydes in the initial condenses of gained (mole) while equating with the input amount of urea or methylolurea (the use molar weight of estimating for copolymerization), start to add this urea or methylolurea.
In addition, after initial condensation for this phenolic compound and aldehydes, add the time point of urea or methylolurea, in advance under the existence of the acid catalyst of the regulation of specified amount, make phenolic compound (P) and aldehydes (F) in accordance with regulations mol ratio carry out condensation reaction, measure in time the aldehyde amount of residual (unreacted), to obtain the residual aldehyde rate of gained (y) and reaction times relation (x) such as relational expressions such as exponential approximation formulas, thereby can then use this relational expression to calculate the time opening of cocondensation reaction, in other words, calculate the interpolation time opening of urea or methylolurea.
For example, in the condensation reaction of phenol and formalin, as acid catalyst, use 0.5 quality %(with respect to phenol) oxalic acid, with various mol ratios (F/P=0.65,0.69,0.84,1.00,1.23,1.54), react, measure residual formalin amount, obtain thus as described in Table 1, residual formalin rate (y) and reaction times exponential approximation formula (x).Then, by income index approximate expression, can easily calculate in the reaction of A～F of following table 1, reach with the amount of urea (mole) the reacting the time opening of the formalin amount (residual formalin rate) of equivalent (h).
It should be noted that, the calculation method of this reaction time opening (h) carries out according to the following steps.That is, first, with following formula, calculate residual formalin rate (y), then, y by the approximate expression of the following table 1 of residual formalin rate (y) substitution of gained, calculates corresponding x, can easily obtain thus the reaction time opening (h) that the cocondensation of urea or methylolurea is started.
The amount of substance of residual formalin rate (y)=urea (mole) amount of substance of ÷ formalin (mole) * 100
[table 1]
In addition, the cocondensation compound that the urea-modified phenolic varnish type resol obtaining according to this gimmick of the present invention is urea derivative and phenolic compound, for its reaction mechanism, can be explained as follows.That is, first, under acidic conditions, the condensation reaction generation hydroxymethyl phenol by phenolic compound and aldehydes, in the starting stage, forms the reaction product of the lower molecular weight of hydroxymethyl phenol and phenol.Then, interpolation time point according to the rules, with regulation ratio, urea, methylolurea are little by little dropped into reaction system, the rising of inhibited reaction temperature thus, and suppress the hydrolysis of urea, methylolurea, make the pH of reaction system increase gently simultaneously, and in slightly acidic region, preferential initiation hydroxymethyl phenol reacts with urea, thereby can form the cocondensation compound of target.
Then, because the urea-modified phenolic varnish type resol so obtaining is more low viscous resin, so its processing ease, can be advantageously used in various uses, in addition, owing to carrying out modification with a large amount of urea, therefore rate nitrogenous with it proportionally, in the region of 350～365 ℃, there is strong heat-absorbing action, and flame retardant resistance raising, can be advantageously used in various uses thus.
In addition, for above-mentioned urea-modified phenolic varnish type resol, also can in its manufacturing processed or after it is manufactured, add, mix compound, resin arbitrarily, for example epoxy resin, melamine resin, urea-formaldehyde resin, xylene resin, vinyl acetate resin, polyamide resin, trimeric cyanamide compounds, epoxy compounds, cashew nut wet goods, or it is reacted and use with the form of various modified novolac type resol.
Then, what so obtain can be for various uses according to its characteristic according to urea-modified phenolic varnish type resol of the present invention, especially, for the present invention, suitable as mould matrix material or the coated with resin with coated sand.
In addition, when using this foundation urea-modified phenolic varnish type phenolic resin-made molding resins precoated sand of the present invention, for example, according to known various gimmicks, hot sand hybrid system (heating sand mixture method, ホ ッ ト マ ー リ Application グ method) etc., adopt the surperficial gimmick with this urea-modified phenolic varnish type resol coating regulation resistivity against fire particle.Now, consumption as urea-modified phenolic varnish type resol, with respect to resistivity against fire particle 100 mass parts, reaching the ratio of 0.4～5 about mass parts, preferably to reach ratio and the compounding of resistivity against fire particle of 0.5～4 mass parts left and right, the surface of coating resistivity against fire particle.
It should be noted that, as using resistivity against fire particle here, also can use known various material, can be natural particle, can be also artificial particle, is not particularly limited.Can list such as: quartz sand, olivine sand, zircon sand, chromite sand, aluminum oxide sand, ferrochrome are that slag, ferronickel are that slag, converter slag, mullite are artificial particle (such as the trade(brand)name " CERABEADS " that can buy from ITOCHU CERATECH CORP. etc.), their reclaimed sand etc., can use wherein a kind of or be used in combination of two or more.
And, use the coated sand so obtain to carry out mould that moulding forms in using its casting process, can effectively suppress the bad generation of the cast(ing) surfaces such as shrinkage cavity, and aspect the collapsibility of the mould after casting, also bring into play advantageous feature.
Embodiment
Below provide several embodiments of the invention and further illustrate the present invention, but the present invention is not subject to any restriction of the record of this embodiment, this is self-evident.In addition, the present invention is interpreted as except following examples, so except above-mentioned specific descriptions, can also be in the situation that not departing from purport of the present invention, the knowledge based on those skilled in the art is carried out various changes, modification, improvement etc.It should be noted that, F shown below, P and U are used separately as the shorthand notation of formalin, phenol and urea.
The manufacture of the novolac resin of the urea-modified rate 5% of-embodiment 1-[mol ratio (F/(P+U))=0.60]
First, in the there-necked flask of 3000ml that possesses thermometer, vacuum stirring device and prolong, hold phenol 1200g(12.77mol) and formalin 47% aqueous solution 527g(8.26mol) and as the oxalic acid 6.3g(0.07mol of catalyzer) afterwards, limit is uniformly mixed, limit will slowly be warming up to reflux temperature (98～105 ℃) in reaction vessel, then heated and stirred is 22 minutes, carries out thus initial condensation reaction.
Then, with respect to the initial condensation reaction thing of this gained, to add complete mode with 120 minutes, drip the urea 60g(1.00mol that is dissolved in advance distilled water 90ml), then heated and stirred is approximately 60 minutes, further reacts.Then, after this utilizes the reaction of heated and stirred, the pH of reaction soln becomes 7, confirm to have consumed formalin, then limit is uniformly mixed, heating and concentrating under reduced pressure are carried out until the temperature of reaction solution (liquid temperature) reaches 180 ℃ of left and right in limit, obtain thus the urea-modified novolac resin (urea-modified phenolic varnish type resol) of yellow transparent solid.
The novolac resin of the urea-modified rate 9% of-embodiment 2-[mol ratio (F/(P+U))=0.60] synthetic
First, in the there-necked flask of 3000ml that possesses thermometer, vacuum stirring device and prolong, hold phenol 1200g(12.77mol) and formalin 47% aqueous solution 566g(8.86mol) and as the oxalic acid 3.8g(0.04mol of catalyzer) afterwards, limit is uniformly mixed, limit will slowly be warming up to reflux temperature (98～105 ℃) in reaction vessel, then heated and stirred is 22 minutes, carries out thus initial condensation reaction.
Then,, with respect to the initial condensation reaction thing of this gained, to add complete mode with 120 minutes, drip the urea 120g(2.00mol that is dissolved in advance distilled water 180ml) afterwards, heated and stirred 60 minutes, further reacts.Then, after this utilizes the reaction of heated and stirred, the pH of reaction soln becomes 7, confirm to have consumed formalin, then limit is uniformly mixed, heating and concentrating under reduced pressure are carried out until the temperature of reaction solution (liquid temperature) reaches 180 ℃ of left and right in limit, obtain thus the urea-modified novolac resin of yellow transparent solid.
The novolac resin of the urea-modified rate 20% of-embodiment 3-[mol ratio (F/(P+U))=0.60] synthetic
First, in the there-necked flask of 3000ml that possesses thermometer, vacuum stirring device and prolong, hold phenol 960g(10.21mol) and formalin 47% aqueous solution 544g(8.53mol) and as the oxalic acid 6.0g(0.07mol of catalyzer) afterwards, limit is uniformly mixed, limit will slowly be warming up to reflux temperature (98～105 ℃) in reaction vessel, then heated and stirred is 22 minutes, carries out thus initial condensation reaction.
Then,, with respect to the initial condensation reaction thing of this gained, to add complete mode with 120 minutes, drip the urea 240g(4.00mol that is dissolved in advance distilled water 360ml) afterwards, heated and stirred 60 minutes, further reacts.Then, after this utilizes the reaction of heated and stirred, the pH of reaction soln becomes 7, confirm to have consumed formalin, then limit is uniformly mixed, heating and concentrating under reduced pressure are carried out until the temperature of reaction solution (liquid temperature) reaches 180 ℃ of left and right in limit, obtain thus the urea-modified novolac resin of yellow transparent solid.
The novolac resin of the urea-modified rate 30% of-embodiment 4-[mol ratio (F/(P+U))=0.60] synthetic
First, in the there-necked flask of 3000ml that possesses thermometer, vacuum stirring device and prolong, hold phenol 840g(8.94mol) and formalin 47% aqueous solution 572g(8.96mol) and as the oxalic acid 6.0g(0.07mol of catalyzer) afterwards, limit is uniformly mixed, limit will slowly be warming up to reflux temperature (98～105 ℃) in reaction vessel, then heated and stirred is 30 minutes, carries out thus initial condensation reaction.
Then,, with respect to the initial condensation reaction thing of this gained, to add complete mode with 120 minutes, drip the urea 360g(6.00mol that is dissolved in advance distilled water 540ml) afterwards, heated and stirred 60 minutes, further reacts.Then, after this utilizes the reaction of heated and stirred, the pH of reaction soln becomes 7, confirm to have consumed formalin, then limit is uniformly mixed, heating and concentrating under reduced pressure are carried out until the temperature of reaction solution (liquid temperature) reaches 180 ℃ of left and right in limit, obtain thus the urea-modified novolac resin of yellow transparent solid.
The novolac resin of the urea-modified rate 40% of-embodiment 5-[mol ratio (F/(P+U))=0.60] synthetic
First, in the there-necked flask of 3000ml that possesses thermometer, vacuum stirring device and prolong, hold phenol 720g(7.66mol) and formalin 47% aqueous solution 599g(9.39mol) and as the oxalic acid 6.0g(0.07mol of catalyzer) afterwards, limit is uniformly mixed, limit will slowly be warming up to reflux temperature (98～105 ℃) in reaction vessel, then heated and stirred is 32 minutes, carries out thus initial condensation reaction.
Then,, with respect to the initial condensation reaction thing of this gained, to add complete mode with 120 minutes, drip the urea 480g(7.99mol that is dissolved in advance distilled water 720ml) afterwards, heated and stirred 60 minutes, further reacts.Then, after this utilizes the reaction of heated and stirred, the pH of reaction soln becomes 7, confirm to have consumed formalin, then limit is uniformly mixed, heating and concentrating under reduced pressure are carried out until the temperature of reaction solution (liquid temperature) reaches 180 ℃ of left and right in limit, obtain thus the urea-modified novolac resin of yellow transparent solid.
The novolac resin of the urea-modified rate 50% of-embodiment 6-[mol ratio (F/(P+U))=0.60] synthetic
First, in the there-necked flask of 3000ml that possesses thermometer, vacuum stirring device and prolong, hold phenol 600g(6.38mol) and formalin 47% aqueous solution 627g(9.82mol) and as the oxalic acid 6.0g(0.07mol of catalyzer) afterwards, limit is uniformly mixed, and limit will slowly be warming up to reflux temperature (98～105 ℃) in reaction vessel.Then, after this heats up, to add complete mode with 120 minutes, drip the urea 600g(9.96mol that is dissolved in advance distilled water 900ml), then heated and stirred is 60 minutes, reacts.Then, after this utilizes the reaction of heated and stirred, the pH of reaction soln becomes 7, confirms to have consumed formalin.Then, limit is uniformly mixed, and heating and concentrating under reduced pressure are carried out until the temperature of reaction solution (liquid temperature) reaches 180 ℃ of left and right in limit, obtain thus the urea-modified novolac resin of yellow transparent solid.It should be noted that, in the present embodiment, the many 0.14mol of consumption of the amount ratio formalin of the urea of input, are therefore different from the various embodiments described above, do not implement initial condensation reaction.
The novolac resin of the urea-modified rate 5% of-embodiment 7-[mol ratio (F/(P+U))=0.60] synthetic
First, in the there-necked flask of 3000ml that possesses thermometer, vacuum stirring device and prolong, hold phenol 1200g(12.77mol) and formalin 47% aqueous solution 527g(8.26mol) and as the oxalic acid 6.3g(0.07mol of catalyzer) afterwards, limit is uniformly mixed, and limit will slowly be warming up to reflux temperature (98～105 ℃) in reaction vessel.Then, to add complete mode with 120 minutes, drip the urea 60g(1.00mol that is dissolved in advance distilled water 90ml) afterwards, heated and stirred 60 minutes, reacts.Then, after this utilizes the reaction of heated and stirred, the pH of reaction soln becomes 7, confirms to have consumed formalin.Then, limit is uniformly mixed, and heating and concentrating under reduced pressure are carried out until the temperature of reaction solution (liquid temperature) reaches 180 ℃ of left and right in limit, obtain thus the urea-modified novolac resin of yellow transparent solid.
The novolac resin of the urea-modified rate 30% of-embodiment 8-[mol ratio (F/(P+U))=0.70] synthetic
First, in the there-necked flask of 3000ml that possesses thermometer, vacuum stirring device and prolong, hold phenol 840g(8.94mol) and formalin 47% aqueous solution 667g(10.5mol) and as the oxalic acid 6.0g(0.07mol of catalyzer) afterwards, limit is uniformly mixed, limit will slowly be warming up to reflux temperature (98～105 ℃) in reaction vessel, then heated and stirred is 88 minutes, carries out thus initial condensation reaction.
Then,, with respect to the initial condensation reaction thing of this gained, to add complete mode with 120 minutes, drip the urea 360g(6.00mol that is dissolved in advance distilled water 540ml) afterwards, heated and stirred 60 minutes, further reacts.Then, after this utilizes the reaction of heated and stirred, the pH of reaction soln becomes 7, confirm to have consumed formalin, then limit is uniformly mixed, heating and concentrating under reduced pressure are carried out until the temperature of reaction solution (liquid temperature) reaches 180 ℃ of left and right in limit, obtain thus the urea-modified novolac resin of yellow transparent solid.
The novolac resin of the urea-modified rate 30% of-embodiment 9-[mol ratio (F/(P+U))=0.50] synthetic
First, in the there-necked flask of 3000ml that possesses thermometer, vacuum stirring device and prolong, hold phenol 840g(8.94mol) and formalin 47% aqueous solution 476g(7.5mol) and as the oxalic acid 6.0g(0.07mol of catalyzer) afterwards, limit is uniformly mixed, limit will slowly be warming up to reflux temperature (98～105 ℃) in reaction vessel, then heated and stirred is 10 minutes, carries out thus initial condensation reaction.
Then,, with respect to the initial condensation reaction thing of this gained, to add complete mode with 120 minutes, drip the urea 360g(6.00mol that is dissolved in advance distilled water 540ml) afterwards, heated and stirred 60 minutes, further reacts.Then, after this utilizes the reaction of heated and stirred, the pH of reaction soln becomes 7, confirm to have consumed formalin, then limit is uniformly mixed, heating and concentrating under reduced pressure are carried out until the temperature of reaction solution (liquid temperature) reaches 180 ℃ of left and right in limit, obtain thus the urea-modified novolac resin of yellow transparent solid.
The novolac resin of-embodiment 10-monomethylol urea degree of modification 20% [mol ratio (F/(P+U))=0.60] synthetic
First, in the flask of 1000ml, hold urea 240g(4.00mol), distilled water 240ml and formalin 47% aqueous solution 255g(4.00mol), add NaOH until pH=9～10 make its reaction, obtain being thus suspended in the monomethylol urea of the form in solution.Then, the suspension of this gained monomethylol urea is moved to separating funnel.
Then, possessing thermometer, vacuum stirring device and prolong, also be equipped with in the four-hole boiling flask of 3000ml of the separating funnel that accommodates above-mentioned methylolurea suspension and hold phenol 960g(10.21mol) and formalin 47% aqueous solution 289g(4.52mol), and as the oxalic acid 6.0g(0.07mol of catalyzer) afterwards, limit is uniformly mixed, limit will slowly be warming up to reflux temperature (98～105 ℃) in reaction vessel, then to add complete mode after separating funnel drips monomethylol urea suspension with 120 minutes, heated and stirred 60 minutes, react thus.Then, after this utilizes the reaction of heated and stirred, the pH of reaction soln becomes 7, confirms to have consumed formalin.Then, limit is uniformly mixed, and heating and concentrating under reduced pressure are carried out until the temperature of reaction solution (liquid temperature) reaches 180 ℃ of left and right in limit, obtain thus the urea-modified novolac resin of yellow transparent solid.
The novolac resin of-embodiment 11-monomethylol urea degree of modification 30% [mol ratio (F/(P+U))=0.50] synthetic
First, in the flask of 1000ml, hold urea 360g(6.00mol), distilled water 540ml and formalin 47% aqueous solution 382g(6.00mol), add NaOH until pH=9～10, make its reaction, obtain being thus suspended in the monomethylol urea of the white solid of the form in solution.Then, this gained monomethylol urea suspension is moved to separating funnel, for the condensation reaction of phenol.
Then, possessing thermometer, vacuum stirring device and prolong, also be equipped with in the four-hole boiling flask of 3000ml of the separating funnel that accommodates above-mentioned methylolurea suspension and hold phenol 840g(8.94mol) and formalin 47% aqueous solution 96g(1.51mol), and as the oxalic acid 6.0g(0.07mol of catalyzer) afterwards, limit is uniformly mixed, limit will slowly be warming up to reflux temperature (98～105 ℃) in reaction vessel, then to add complete mode after separating funnel drips monomethylol urea suspension with 120 minutes, heated and stirred 60 minutes, react thus.Then, after this utilizes the reaction of heated and stirred, the pH of reaction soln becomes 7, confirms to have consumed formalin.Then, limit is uniformly mixed, and carries out heating and concentrating under reduced pressure until the temperature of reaction solution (liquid temperature) reaches 180 ℃ of left and right, obtains thus the urea-modified novolac resin of yellow transparent solid.
The novolac resin of-embodiment 12-monomethylol urea degree of modification 30% [mol ratio (F/(P+U))=0.60] synthetic
First, in the flask of 1000ml, hold urea 360g(6.00mol), distilled water 360ml and formalin 47% aqueous solution 382g(6.00mol), add NaOH until pH=9～10 make its reaction, obtain being thus suspended in the monomethylol urea of the form in solution.Then, the suspension of this gained monomethylol urea is moved to separating funnel.
Then, possessing thermometer, vacuum stirring device and prolong, also be equipped with in the four-hole boiling flask of 3000ml of the separating funnel that accommodates above-mentioned methylolurea suspension and hold phenol 840g(8.94mol) and formalin 47% aqueous solution 190g(2.97mol), and as the oxalic acid 6.0g(0.07mol of catalyzer) afterwards, limit is uniformly mixed, limit will slowly be warming up to reflux temperature (98～105 ℃) in reaction vessel, then to add complete mode after separating funnel drips monomethylol urea suspension with 120 minutes, heated and stirred 60 minutes, react thus.Then, after this utilizes the reaction of heated and stirred, the pH of reaction soln becomes 7, confirms to have consumed formalin.Then, limit is uniformly mixed, and heating and concentrating under reduced pressure are carried out until the temperature of reaction solution (liquid temperature) reaches 180 ℃ of left and right in limit, obtain thus the urea-modified novolac resin of yellow transparent solid.
The novolac resin of-embodiment 13-dimethylolurea degree of modification 20% [mol ratio (F/(P+U))=0.50] synthetic
First, in the flask of 1000ml, hold urea 240g(4.00mol), distilled water 360ml and formalin 47% aqueous solution 453g(7.10mol), add NaOH until pH=9～10 make its reaction, obtain thus the dimethylolurea suspended substance of white solid.
Then, in the there-necked flask of 3000ml that possesses thermometer, vacuum stirring device and prolong, hold phenol 960g(10.21mol) and as the oxalic acid 6.0g(0.07mol of catalyzer) afterwards, limit is uniformly mixed, limit will slowly be warming up to reflux temperature (98～105 ℃) in reaction vessel, then with the interval of 10 minutes with within 120 minutes, drop into by a certain percentage dimethylolurea suspended substance obtained above in batches.And then heated and stirred 60 minutes, reacts thus.Then, after this reaction, the pH of reaction soln becomes 7, confirms to have consumed formalin.Then, limit is uniformly mixed, and heating and concentrating under reduced pressure are carried out until the temperature of reaction solution (liquid temperature) reaches 180 ℃ of left and right in limit, obtain thus the urea-modified novolac resin of yellow transparent solid.
The novolac resin of-embodiment 14-dimethylolurea degree of modification 20% [mol ratio (F/(P+U))=0.60] synthetic
First, in the flask of 1000ml, hold urea 240g(4.00mol), distilled water 360ml and formalin 47% aqueous solution 544g(8.53mol), add NaOH until pH=9～10 make its reaction, obtain thus the dimethylolurea suspended substance of white solid.
Then, in the there-necked flask of 3000ml that possesses thermometer, vacuum stirring device and prolong, hold phenol 960g(10.21mol) and as the oxalic acid 6.0g(0.07mol of catalyzer) afterwards, limit is uniformly mixed, limit will slowly be warming up to reflux temperature (98～105 ℃) in reaction vessel, then with the interval of 10 minutes with within 120 minutes, drop into by a certain percentage dimethylolurea suspended substance obtained above in batches.And then heated and stirred 60 minutes, reacts thus.Then, after this reaction, the pH of reaction soln becomes 7, confirms to have consumed formalin.Then, limit is uniformly mixed, and heating and concentrating under reduced pressure are carried out until the temperature of reaction solution (liquid temperature) reaches 180 ℃ of left and right in limit, obtain thus the urea-modified novolac resin of yellow transparent solid.
Urea-modified 30% the novolac resin of-comparative example 1-based on the disposable input of urea [mol ratio (F/(P+U))=0.60] synthetic
The urea 90g(1.50mol that holds the 120ml that is dissolved in advance distilled water in the there-necked flask of 500ml that possesses thermometer, vacuum stirring device and prolong), phenol 210g(2.13mol) and formalin 47% aqueous solution 139g(2.18mol) and as the oxalic acid 1.5g(0.02mol of catalyzer) afterwards, limit is uniformly mixed, limit will slowly be warming up to reflux temperature (98～105 ℃) in reaction vessel, further heated and stirred is approximately 240 minutes, carries out thus condensation reaction.Then, after this reaction, while being uniformly mixed, under heating and concentrating under reduced pressure, in 150 ℃ of left and right of temperature (liquid temperature) of reaction solution, there is gelation, solidified.
The novolac resin of-comparative example 2-monomethylol urea modification 6% [mol ratio (F/(P+U))=0.68] synthetic
In the flask of 500ml that possesses thermometer, vacuum stirring device and prolong, first hold urea 12g(0.20mol) and formalin 47% aqueous solution 23g(0.36mol), at 50 ℃ after heated and stirred 150 minutes, hold phenol 188g(2.00mol) and as the oxalic acid 0.94g(0.01mol of catalyzer), limit is uniformly mixed, limit will slowly be warming up to reflux temperature (98～105 ℃) in reaction vessel, then stir 60 minutes, make its reaction.And then, add formalin 47% aqueous solution 73g(1.14mol) and oxalic acid 0.6g(6.00mmol), return stirring 120 minutes, reacts.Then, after this reaction, limit is uniformly mixed, and heat and concentrating under reduced pressure on limit, and result, in about 150 ℃ generation gelations of temperature (liquid temperature) of reaction solution, is solidified.
Synthesizing of-comparative example 3-novolac resin [mol ratio (F/P)=0.60]
In the there-necked flask of 3000ml that possesses thermometer, vacuum stirring device and prolong, hold phenol 1200g(12.77mol) and formalin 47% aqueous solution 490g(7.68mol) and as the oxalic acid 3.6g(0.04mol of catalyzer) afterwards, limit is uniformly mixed, limit will slowly be warming up to reflux temperature (98～105 ℃) in reaction vessel, further heated and stirred is approximately 240 minutes, carries out thus condensation reaction.Then, after this reaction, limit is uniformly mixed, and heating and concentrating under reduced pressure are carried out until the temperature of reaction solution (liquid temperature) reaches 180 ℃ of left and right in limit, obtain thus the resol of the phenolic varnish type of yellow transparent solid.
[evaluating characteristics 1]
For various urea-modified novolac resin compositions obtained above, according to following measuring method, measure respectively various physical property.And acquired results is shown in to following table 2 and table 3 in the lump.
-mensuration of weight-average molecular weight (Mw), number-average molecular weight (Mn), unreacting phenol amount-
For the weight-average molecular weight (Mw) of urea-modified novolac resin composition and the mensuration of number-average molecular weight (Mn), obtain the molecular weight of the phenol conversion recording by gel permeation chromatography (GPC) method.In addition, determinator is used GPC determinator (TOSOH Co., Ltd's manufacture, trade(brand)name: HLC8320GPC), and chromatographic column is used mixing polystyrene gel chromatographic column (TOSOH Co., Ltd's manufacture, trade(brand)name: G1000HXL, G2000JXL).In addition, meanwhile, by this GPC method, obtain unreacting phenol amount.
-mensuration of nitrogenous rate-
The nitrogenous rate of each urea-modified novolac resin is obtained by Kjeldahl determination.
-mensuration of length of flow, gelation time, fusing point-
The length of flow of each urea-modified novolac resin, gelation time and fusing point are measured according to JIS K6910.
-mensuration of viscosity-
By using cone-and-plate viscometer, (East Asia Industrial Co., Ltd manufactures the viscosity of each urea-modified novolac resin, trade(brand)name: CV1S), take 0.15g sample, at temperature of heating plate: measure its melt viscosity at 160 ℃.
-calorimetric measurement-
Utilize being determined as follows of the caloric receptivity of following pyrolysis of each urea-modified novolac resin of differential scanning calorimeter (DSC) to carry out.
; the trade(brand)name of using Rigaku Corporation to manufacture as differential scanning calorimeter: DSC8230; 5.00mg powdered sample is mixed with 0.75mg vulkacit H; under nitrogen atmosphere; with 5 ℃/min, from 25 ℃, be warming up to 500 ℃ of endothermic curves (DSC curve) that obtain following decomposition; mensuration, from the temperature of the heat absorption summit of this DSC curve observation, recepts the caloric in addition and calculates according to above-mentioned DSC curve.Although the DSC curve now recording becomes the heat of the longitudinal axis, follow the temperature of transverse axis to rise and the curve of rising but heat was once declining because of heat absorption in specific temperature range curve, the apex portion of the curve that this heat is declined is as endotherm(ic)peak (referring to the curve of the embodiment 3 of Fig. 2 and 300 ℃～400 ℃ of scopes of embodiment 4).
[table 2]
[table 3]
The structure elucidation of [evaluating characteristics 2] urea-modified novolac resin
The bonding mode of the methene key in-urea-modified novolac resin and neighbour/to the mensuration of (o/p) bonding ratio-
For the bonding mode of the methene key in each urea-modified novolac resin and the mensuration of o/p bonding ratio, use the nuclear magnetic resonance device (U.S.: Varian Inc. manufactures; INOVA400), measure 13C-NMR(100MHz, solvent: deuterated pyridine-d5), obtain [o, o-phenol-CH
2-phenol] key, [o, p-phenol-CH
2-phenol] key, [p, p-phenol-CH
2-phenol] key, [o-phenol-CH
2-NHCO-] key, [p-phenol-CH
2-NHCO-] key, [NH-CH
2-NH-] key there is density, calculate bonding ratio separately.In addition, the resin using in this mensuration is the resin of embodiment 4, embodiment 11 and embodiment 14.The results are shown in following table 4.
[table 4]
-mensuration of infrared rays (IR) absorption spectrum-
For the mensuration of infrared rays (IR) spectrum of each urea-modified novolac resin, (JASCO company manufactures to use infrared spectrophotometry device; FT/IR-4200) carry out, confirm the characteristic absorption band (1450cm of NH key
-1), CH
2characteristic absorption band (1300～the 1400cm of key
-1), the characteristic absorption band (1700cm of C=O key
-1) existence.Wherein, especially by the existence of C=O key, can learn and form urea-modified novolac resin.In addition, the resin using in this mensuration is the resin of embodiment 3, embodiment 4 and comparative example 3.And, the results are shown in Fig. 1.
In addition, for the urea-modified phenolic varnish type resin obtaining in embodiment 3, embodiment 4 and comparative example 3, use differential scanning calorimeter (DSC) to obtain the DSC curve of following pyrolysis of each urea-modified novolac resin, the results are shown in Fig. 2.
According to the structure elucidation of above-mentioned urea-modified novolac resin, while one example being shown for, foundation urea-modified phenolic varnish type resol of the present invention that phenolic compound, aldehydes and urea or methylolurea cocondensation are manufactured by making, it is the represented material of following general formula (1).In addition, in formula, m represents the integer of 0～20 left and right.
[Chemical formula 1]
Then, use the various urea-modified novolac resin so obtaining, according to following gimmick, manufacture coated sand (RCS) (sample 1～15) for outer casing mold respectively.
-manufacture of sample 1～15 and evaluation thereof-
To experiment, by input in high-speed mixer, be preheated to the resistivity against fire particle (flatterysand of 150～180 ℃, Off ラ タ リ ー) each resin 140g(2.0%/resistivity against fire particle of 7000g and embodiment 1～14 or comparative example 3), in mixing 60 seconds in mixing machine, thus each urea-modified novolac resin melting is coated on to resistivity against fire particle surface.Then, to adding the vulkacit H 21g(15.0%/resin as solidifying agent in mixing machine) be dissolved in water coolant: the vulkacit H aqueous solution forming 105g(1.5%/resistivity against fire particle), after air-cooled, add calcium stearate 7g(0.1%/resistivity against fire particle), obtain thus various RCS(samples 1～15).For this gained sample 1～15, according to following test method(s), carry out the mensuration of its characteristic.The results are shown in following table 5.
[evaluating characteristics 3]
-mensuration of fusion point-
The various outer casing mold RCS that use above-mentioned manufacture, measure respectively according to JACT method.
-mensuration of mould strength-
Use the various outer casing mold RCS of above-mentioned manufacture, according to JIS-K-6910, make respectively JIS formula test film (width: 10mm * thickness: 10mm * length: 60mm, calcination condition: 250 ℃ * 60 seconds), then for this gained JIS formula test film (below also referred to as test film or TP), intensity (MPa) while catching a cold according to JACT test method(s): SM-1 mensuration, evaluates as mould strength.
[table 5]
Known according to the result of above-mentioned table 2～table 5, when using urea or methylolurea to carry out that cocondensation is incompatible obtains urea-modified novolac resin (urea-modified phenolic varnish type resol), as comparative example 1～2 in the total amount of the consumption of initial disposable input urea or methylolurea, can there is gelation, cannot form good resin, and as according to embodiments of the invention 1～14, by little by little adding urea or methylolurea with a certain proportion of interpolation speed, can obtain convenience excellence, there is low viscous urea-modified novolac resin.
In addition, known according to the result of embodiment 1 grade, by making phenol first react (initial condensation reaction) with formalin, little by little drop into again afterwards urea, can further advantageously reduce the viscosity of resin thus.Particularly, the amount of the amount by the urea adding and residual unreacted formalin starts to drop into urea while reaching roughly the same molar weight, can be conducive to realize the stable lowering viscousity of urea-modified novolac resin.
And then, can also easily understand, by making mol ratio (F/(P+U)) in the scope of 0.5～0.7 left and right, the urea-modified novolac resin of manufacturing objective well.In addition, this mol ratio surpasses at 0.8 o'clock, and the viscosity of resin is too high, so the upper limit of mol ratio it is desirable to till 0.8, and the scope of preferred mol ratio thinks 0.50～0.75.
In addition, according to urea-modified phenolic varnish type resol of the present invention, the urea-modified rate (U/(U+P) to phenolic compound (P) at urea or methylolurea (U)) be in the scope of 5～50% left and right time, can advantageously manufacture.Especially, known according to table 5, to obtain for urea-modified rate is set in to 5～30% scope urea-modified phenolic varnish type resol, by being used it to manufacture coated sand (RCS) for outer casing mold, and with gained RCS mfg. moulding die, can obtain having the mould of high mould strength.Here, urea-modified rate is obtained by quality criteria, and, when using methylolurea, use its urea amount (quality) synthetic used as U value, thereby obtain urea-modified rate.
In addition, for foundation urea-modified phenolic varnish type resol of the present invention, [phenol-CH
2-NHCO-] bond number accounts for [phenol-CH
2-NHCO-] bond number, [NH-CH
2-NH-] bond number and [phenol-CH
2-phenol] average ratio of summation of bond number is 25～35% left and right, has and the proportional caloric receptivity of nitrogenous rate, confirmed that flame retardant resistance is high.And then more than the caloric receptivity of this resin is preferably 5J/g, 5～200J/g more preferably, thus, by its heat-absorbing action, can suppress shrinkage cavity, cast(ing) surface bad etc.Moreover according to the embodiment shown in table 2,3, can obtain weight-average molecular weight (Mw) is that 550～2500 left and right, cone-plate viscosity are the material of 500～4500mPas left and right, has also confirmed in the lump thus processing ease.And, investigate this urea-modified phenolic varnish type resol when the application of mould purposes, knownly can also show the mould strength that can use.
Claims (17)
1. a manufacture method for urea-modified phenolic varnish type resol, is characterized in that,
When making phenolic compound, aldehydes and urea or the urea-modified phenolic varnish type resol of the incompatible manufacture of methylolurea cocondensation,
Make described phenolic compound contact with described aldehydes their reaction is carried out on one side, in reaction system, little by little add described urea or methylolurea continuously or discontinuously on one side, the consumption of estimating until be reached for described cocondensation, makes added urea or methylolurea carry out cocondensation with described phenolic compound and described aldehydes successively.
2. the manufacture method of urea-modified phenolic varnish type resol according to claim 1, wherein, described urea or methylolurea add in reaction system under the form of the aqueous solution or suspension.
3. the manufacture method of urea-modified phenolic varnish type resol according to claim 1 and 2, wherein, described urea or methylolurea are added continuously in reaction system with a certain proportion of interpolation speed.
4. the manufacture method of urea-modified phenolic varnish type resol according to claim 1 and 2, wherein, the interpolation of the interruption of described urea or methylolurea separates certain intervals, with a certain amount of, implements at every turn.
5. according to the manufacture method of the urea-modified phenolic varnish type resol described in any one in claim 1～4, wherein, described urea or methylolurea are solid.
6. according to the manufacture method of the urea-modified phenolic varnish type resol described in any one in claim 1～5, wherein, make after described phenolic compound and described aldehydes carry out initial condensation, to start its initial condenses to add described urea or methylolurea.
7. the manufacture method of urea-modified phenolic varnish type resol according to claim 6, wherein, when the consumption of estimating for described cocondensation of the amount of residual aldehydes and described urea or methylolurea equates in described initial condenses, start to add this urea or methylolurea.
8. a urea-modified phenolic varnish type resol, it is to obtain by the manufacture method described in any one in claim 1～7.
9. a urea-modified phenolic varnish type resol, is characterized in that, it is by making phenolic compound, aldehydes and urea or the incompatible manufacture of methylolurea cocondensation.
10. urea-modified phenolic varnish type resol according to claim 9, is characterized in that, it is by making phenolic compound, aldehydes and urea or the incompatible manufacture of methylolurea cocondensation, and its caloric receptivity of following pyrolysis is 5～200J/g.
11. according to the urea-modified phenolic varnish type resol described in claim 9 or 10, it is characterized in that, it is by making phenolic compound, aldehydes and urea or the incompatible manufacture of methylolurea cocondensation, when utilizing differential scanning calorimeter mensuration to follow the caloric receptivity of pyrolysis, in the scope of 280 ℃～400 ℃, there is endotherm(ic)peak.
12. according to the urea-modified phenolic varnish type resol described in any one in claim 9～11, it is characterized in that the mol ratio of phenolic compound (P), aldehydes (F) and urea or methylolurea (U): be F/(P+U) 0.50～0.75.
13. according to the urea-modified phenolic varnish type resol described in any one in claim 9～12, it is characterized in that, the melt viscosity that uses cone-and-plate viscometer to record at 160 ℃ is 500～4500mPas.
14. according to the urea-modified phenolic varnish type resol described in any one in claim 9～13, it is characterized in that, weight-average molecular weight (Mw) is 550～2500.
15. according to the urea-modified phenolic varnish type resol described in any one in claim 9～14, it is characterized in that urea or methylolurea (U) the urea-modified rate to phenolic compound (P): be U/(U+P) 5～50%.
16. 1 kinds of coated sands, is characterized in that, it uses the urea-modified phenolic varnish type resol the coating resistivity against fire particle that by the manufacture method described in any one in claim 1～7, are obtained to form.
17. 1 kinds of coated sands, is characterized in that, its right to use requires urea-modified phenolic varnish type resol the coating resistivity against fire particle described in any one in 9～15 to form.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011132053 | 2011-06-14 | ||
| JP2011-132053 | 2011-06-14 | ||
| PCT/JP2012/065068 WO2012173129A1 (en) | 2011-06-14 | 2012-06-13 | Method for manufacturing urea-modified novolac phenol resin, urea-modified novolac phenol resin obtained thereby, and resin-coated sand obtained using same |
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| Publication Number | Publication Date |
|---|---|
| CN103597001A true CN103597001A (en) | 2014-02-19 |
| CN103597001B CN103597001B (en) | 2016-04-06 |
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| CN201280029176.9A Active CN103597001B (en) | 2011-06-14 | 2012-06-13 | The manufacture method of urea-modified novolak phenolics and the urea-modified novolak phenolics obtained by the method and the coated sand obtained with it |
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| JP (1) | JP5938037B2 (en) |
| CN (1) | CN103597001B (en) |
| WO (1) | WO2012173129A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103848950A (en) * | 2014-03-06 | 2014-06-11 | 山东海冠化工科技有限公司 | Method for modifying phenolic resin by adopting methylolurea and method for preparing foam by utilizing modified phenolic resin |
| CN104841862A (en) * | 2015-05-07 | 2015-08-19 | 马鞍山市恒毅机械制造有限公司 | Casting high-strength and high-temperature-resistant precoated sand and preparation method thereof |
| CN106883800A (en) * | 2017-03-31 | 2017-06-23 | 中国林业科学研究院木材工业研究所 | A kind of Resin adhesive and preparation method thereof |
| CN107151299A (en) * | 2017-07-12 | 2017-09-12 | 河北科技大学 | It is a kind of for delicate fragrance type phenol-formaldehyde resin modified of sand casting and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384886A (en) * | 2015-11-19 | 2016-03-09 | 滕州市华海新型保温材料有限公司 | Phenolic-aldehyde based novel composite material for ventilation systems of railway transportation hubs and preparation method thereof |
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- 2012-06-13 WO PCT/JP2012/065068 patent/WO2012173129A1/en active Application Filing
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| CN101291967A (en) * | 2005-10-27 | 2008-10-22 | 旭有机材工业株式会社 | Novolak type phenol resin for shell molding, method of producing the same and resin-coated sand |
| CN101974140A (en) * | 2010-10-15 | 2011-02-16 | 山东圣泉化工股份有限公司 | Preparation method for phenolic resin |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103848950A (en) * | 2014-03-06 | 2014-06-11 | 山东海冠化工科技有限公司 | Method for modifying phenolic resin by adopting methylolurea and method for preparing foam by utilizing modified phenolic resin |
| CN104841862A (en) * | 2015-05-07 | 2015-08-19 | 马鞍山市恒毅机械制造有限公司 | Casting high-strength and high-temperature-resistant precoated sand and preparation method thereof |
| CN106883800A (en) * | 2017-03-31 | 2017-06-23 | 中国林业科学研究院木材工业研究所 | A kind of Resin adhesive and preparation method thereof |
| CN107151299A (en) * | 2017-07-12 | 2017-09-12 | 河北科技大学 | It is a kind of for delicate fragrance type phenol-formaldehyde resin modified of sand casting and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN103597001B (en) | 2016-04-06 |
| JPWO2012173129A1 (en) | 2015-02-23 |
| JP5938037B2 (en) | 2016-06-22 |
| WO2012173129A1 (en) | 2012-12-20 |
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