CN102977297B - Polyphenyleneoxide phenol formaldehyde resin and preparation method thereof, and phenol-urea-alkane resin and applications thereof - Google Patents
Polyphenyleneoxide phenol formaldehyde resin and preparation method thereof, and phenol-urea-alkane resin and applications thereof Download PDFInfo
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- CN102977297B CN102977297B CN201210246360.0A CN201210246360A CN102977297B CN 102977297 B CN102977297 B CN 102977297B CN 201210246360 A CN201210246360 A CN 201210246360A CN 102977297 B CN102977297 B CN 102977297B
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Abstract
The present invention discloses a polyphenyleneoxide phenol formaldehyde resin and a preparation method thereof, and a phenol-urea-alkane resin and applications thereof. The method comprises the following steps that: (1) in the presence of an acid catalyst, furfural residue contacts a fatty alcohol and/or an epoxy compound so as to liquefy the furfural residue, and the resulting liquefied product and a dioxane aqueous solution are mixed and separated to obtain a first solid phase product and a first liquid phase product; (2) in the presence of an acid catalyst, the first solid phase product in the step (1) contacts a phenol compound so as to liquefy the first solid phase product, and the resulting liquefied product and a dioxane aqueous solution are mixed and separated to obtain a second solid phase product and a second liquid phase product; and (3) under a polymerization condition, the first liquid phase product contacts the second liquid phase product. With the method, the furfural residue adopted as waste is effectively utilized, a new method for polyphenyleneoxide phenol formaldehyde resin preparation is developed, cost is reduced, and a sand core model prepared by the phenol-urea-alkane resin has good mechanical strength.
Description
Technical field
The present invention relates to a kind of polyphenylene oxide resol and preparation method thereof and phenol urethane resin and application thereof.
Background technology
At present, China has more than 200 to overlap furfural production device, and industrial scale is generally 1000-3000 ton/year.China's furfural overall throughput exceedes 200,000 tons/year, approximately more than 10 ten thousand tons of actual annual production.China's furfural production ability accounts for 50% left and right of world's overall throughput, has very important status in international furfural market.
Furfural is generally produced as raw material taking the tankage of the agricultural byproducts such as corn cob, corn stalk, Wheat Straw, straw, rice husk, cotton seed hulls and bagasse, and the residual solids of extracting after furfural is exactly furfural dregs.China's furfural production Raw expense accounts for the more than 1/3 of product cost, according to measuring and calculating, the furfural mill of producing 1000 tons per year can produce 10000-12000 ton furfural dregs every year, in described furfural dregs, contain a large amount of organic matters, this part furfural dregs major part is burnt as waste, and the acid that contains 7 % by weight left and right in furfural dregs produces heavy corrosion to boiler plant, so directly burning uneconomical.Meanwhile, more than by raw material, after furfural boiling, the cellulignin contents on dry basis in residue still reaches 60 % by weight, so it is one of effective way of increasing economic efficiency that these residues are fully utilized.
Summary of the invention
The object of the present invention is to provide the method for utilizing a kind of and the diverse furfural dregs of prior art, that is, prepare the method for polyphenylene oxide resol taking furfural dregs as raw material, and a kind of phenol urethane resin and application thereof.
The present inventor finds, by furfural dregs is contacted and is liquefied with fatty alcohol and/or epoxy compounds, and from liquefied product, isolate the first solid product and the first liquid product, the first solid product is continued to contact and liquefy with phenolic compound, and from liquefied product, isolate second solid phase product and second liquid phase product, and under polymeric reaction condition, the first liquid product is contacted and can prepare polyphenylene oxide resol with second liquid phase product, and utilize polyphenylene oxide resol provided by the invention to prepare sand core for casting model sizing agent, it is phenol urethane resin, can make core model there is higher physical strength, and reduce preparation cost, thereby complete the present invention.
The invention provides a kind of preparation method of polyphenylene oxide resol, wherein, the method comprises the steps:
(1) under the existence of acid catalyst, furfural dregs is contacted with fatty alcohol and/or epoxy compounds, make furfural dregs liquefaction, and by the liquefied product obtaining and dioxane aqueous solution, and separation obtains the first solid product and the first liquid product;
(2) under the existence of acid catalyst, the first solid product of step (1) is contacted with phenolic compound, make the first solid product liquefaction, and by the liquefied product obtaining and dioxane aqueous solution, and separation obtains second solid phase product and second liquid phase product;
(3), under polymeric reaction condition, the first liquid product is contacted with second liquid phase product.
The present invention also provides a kind of polyphenylene oxide resol being prepared by method provided by the invention.
The present invention also provides a kind of phenol urethane resin, and this phenol urethane resin contains components I, compositionⅱ and the solidifying agent independently deposited respectively, and described components I is polyphenylene oxide resol, and described compositionⅱ is isocyanate resin, and described solidifying agent is that amine is solidifying agent; Wherein, described components I contains polyphenylene oxide resol provided by the invention.
The present invention also provides a kind of described phenol urethane resin in the application of preparing in foundry sand core model.
The recycling method of furfural dregs provided by the invention is by being used furfural dregs to contact with fatty alcohol and/or epoxy compounds as raw material, make furfural dregs liquefaction, and from liquefied product, isolate solid product and again contact with phenolic compound, make described solid product liquefaction, and under polymeric reaction condition, liquid product contact after twice liquefaction is carried out to polyreaction and obtain polyphenylene oxide resol, make to have obtained effective utilization as the furfural dregs of waste on the one hand, on the other hand also for a kind of new method has been opened up in the preparation of polyphenylene oxide resol.The more important thing is, utilize the polyphenylene oxide resol preparation being prepared by method of the present invention to obtain foundry sand core model sizing agent, i.e. phenol urethane resin, for the preparation of core model there is good physical strength.Particularly, in the time that the content of polyphenylene oxide resol of the present invention is the 5-50 % by weight of the components I gross weight in the phenol urethane resin while preparing core model, not only can significantly improve the physical strength of described core model, can also greatly reduce manufacturing cost.
Other features and advantages of the present invention are described in detail the embodiment part subsequently.
Embodiment
According to the present invention, the preparation method of described polyphenylene oxide resol comprises the steps:
(1) under the existence of acid catalyst, furfural dregs is contacted with fatty alcohol and/or epoxy compounds, make furfural dregs liquefaction, and by the liquefied product obtaining and dioxane aqueous solution, and separation obtains the first solid product and the first liquid product;
(2) under the existence of acid catalyst, the first solid product of step (1) is contacted with phenolic compound, make the first solid product liquefaction, and by the liquefied product obtaining and dioxane aqueous solution, and separation obtains second solid phase product and second liquid phase product;
(3), under polymeric reaction condition, the first liquid product is contacted with second liquid phase product.
According to the present invention, in step (1), with respect to 100 weight part furfural dregs, total consumption of fatty alcohol and epoxy compounds can be 150-600 weight part, and the consumption of acid catalyst can be the 0.05-3 % by weight of the total mass of fatty alcohol and epoxy compounds; Under preferable case, with respect to 100 weight part furfural dregs, total consumption of fatty alcohol and epoxy compounds is 200-300 weight part, and the consumption of acid catalyst is the 0.5-1.5 % by weight of the total mass of fatty alcohol and epoxy compounds.
It should be noted that, wherein, total consumption of described fatty alcohol and epoxy compounds or the total mass of fatty alcohol and epoxy compounds refer to, in the time using fatty alcohol and epoxy compounds simultaneously, described total consumption or total mass refer to total consumption or the total mass of fatty alcohol and epoxy compounds, in the time of a kind of in independent use fatty alcohol and epoxy compounds, described total consumption or total mass refer to consumption or the quality of fatty alcohol or epoxy compounds.
According to the present invention, described fatty alcohol and epoxy compounds can be hydroxy-containing compounds and the epoxy compoundss of the various furfural dregs that can liquefy, for example, described fatty alcohol can be one or more in 2-10, hydroxyl value be 2-3 aliphatic polyol and polyether glycol for carbonatoms.Particularly, described fatty alcohol can be selected from one or more in ethylene glycol, glycerol, polyoxyethylene glycol (as Macrogol 200, poly(oxyethylene glycol) 400, Polyethylene Glycol-600 etc.); Described epoxy compounds can be oxyethane and/or propylene oxide.
According to the present invention, in step (2), with respect to 100 weight part the first solid products, the consumption of phenolic compound can be 150-600 weight part, and the consumption of acid catalyst can be the 0.05-3 % by weight of phenolic compound quality.Under preferable case, with respect to 100 weight part the first solid products, the consumption of phenolic compound is 200-300 weight part, and the consumption of acid catalyst is the 1-2 % by weight of phenolic compound quality.
According to the present invention, described phenolic compound can be the phenolic compound of various first solid products that can liquefy, for example, described phenolic compound can be selected from one or more in phenol, Ortho Cresol, m-cresol, p-cresol, pyrocatechol, Resorcinol, Resorcinol, pyrogallol, Phloroglucinol, hydroxyquinol, naphthyl alcohol, 2-Naphthol, dihydroxyphenyl propane and Bisphenol F.
According to the present invention, in step (1) and step (2), the described dioxane aqueous solution can dissolve furfural dregs liquefied product and the first solid phase liquefied product respectively, other solid impurities can not be dissolved in wherein, therefore, can make to be dissolved with the water-soluble liquid phase and the layering of solid residue phase of liquefied product by stratification, and the aqueous solution that is dissolved with liquefied product is separated out.Wherein, concentration and the consumption of the described dioxane aqueous solution are not particularly limited, as long as energy liquefacttus product completely, under preferable case, in step (1), the weight ratio of the dioxane aqueous solution and furfural dregs liquefied product is 2-100:1, more preferably 4-10:1; In step (2), the weight ratio of the dioxane aqueous solution and the first solid product liquefied product is 2-100:1, more preferably 4-10:1; The mass percent concentration of the described dioxane aqueous solution can be 20-80%, more preferably 40-60% conventionally.
According to the present invention, in above-mentioned reaction, that is, in step (1) and step (2), react in the liquefaction process of furfural dregs and the first solid product effect of catalyzer of described acid catalyst.Described acid catalyst can be the conventional various middle strong acid using in described liquefaction process, for example, can be selected from one or more in phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, Phenylsulfonic acid and phenylformic acid, the preferred acid catalyst of the present invention is the aqueous sulfuric acid that sulfuric acid content is not less than 75 % by weight, and more preferably sulfuric acid content is not less than the vitriol oil of 95 % by weight.
According to the present invention, in step (1), condition and mode to described contact are not particularly limited, for example, the condition of described contact can comprise the temperature of contact and the pressure of the time contacting and contact, and the temperature of described contact can be 110-180 DEG C, is preferably 130-150 DEG C; The time of contact can be 20-120 minute, is preferably 50-90 minute; The pressure of contact can be 0-0.42 MPa, is preferably 0.2-0.4 MPa.Under normal pressure, reaction preferably will be carried out reflux, to reclaim light constituent.
According to the present invention, in step (2), condition and mode to described contact are not particularly limited, for example, described contacted condition can comprise the temperature of contact and the pressure of the time contacting and contact, and the temperature of described contact can be 100-180 DEG C, is preferably 130-150 DEG C; The time of contact can be 10-120 minute, is preferably 50-90 minute; The pressure of contact can be 0-0.42 MPa, is preferably 0.2-0.42 MPa.Under normal pressure, reaction preferably will be carried out reflux, to reclaim light constituent.
The present invention is not particularly limited the type of heating in when contact, can be that common heating heats up, and also microwave heating heats up.Further preferred described contact is carried out in closed environment, by making the pressure of contact reach the slightly malleation of preferred 0.2-0.42 MPa in closed environment, can further improve like this yield, liquefied fraction and Reaction time shorten, and simple to operate.
According to the present invention, before the method is also included in the first liquid product is contacted with second liquid phase product, the step of removing the dioxane aqueous solution in the first liquid product and second liquid phase product.Described method of removing the dioxane aqueous solution can adopt the method for well known to a person skilled in the art to carry out, for example, can adopt rotary evaporation in vacuo to slough the method for the aqueous solution of dioxane, concrete operations condition is conventionally known to one of skill in the art, here repeats no more.
According to the present invention, in step (3), the condition of described polyreaction can comprise polymeric reaction temperature and pressure, and for example, described polymeric reaction temperature can be-180 DEG C of room temperatures (as 20 DEG C), is preferably 130-150 DEG C; Polymerization pressure can be 0-0.4MPa, is preferably 0.1-0.3MPa; The weight ratio of the first liquid phase and second liquid phase can be 0.5-5:1, is preferably 1-2:1.
According to the present invention, furfural is generally produced as raw material taking the tankage of the agricultural byproducts such as corn cob, corn stalk, Wheat Straw, straw, rice husk, cotton seed hulls and bagasse, and the residual solids of extracting after furfural is exactly furfural dregs.The composition of described furfural dregs is conventionally known to one of skill in the art, for example, wherein, content of cellulose is generally the 30-45 % by weight of furfural dregs gross weight, hemicellulose level is generally the 4-12 % by weight of furfural dregs gross weight, and the content of xylogen is generally the 19-30 % by weight of furfural dregs gross weight.
The present invention also provides the polyphenylene oxide preparing according to the method described in the present invention resol.
The present invention also provides a kind of phenol urethane resin, and this phenol urethane resin contains components I, compositionⅱ and the solidifying agent independently deposited respectively, and described components I is polyphenylene oxide resol, and described compositionⅱ is isocyanate resin, and described solidifying agent is that amine is solidifying agent; Wherein, described components I contains polyphenylene oxide resol provided by the invention.
According to the present invention, the present inventor is surprised to find that, adopt polyphenylene oxide resol provided by the invention to replace commercially available polyphenylene oxide resol in part components I, just can there is very excellent physical strength at the core model that described phenol urethane resin is obtained during for the preparation of core model, and significantly reduce the cost of components I polyphenylene oxide resol.Polyphenylene oxide resol of the present invention can be the 2-100 % by weight of components I gross weight.Under preferable case, considering cost and effect, described polyphenylene oxide resol provided by the invention is the 2-60 % by weight of components I gross weight, more preferably 5-50 % by weight.
The present invention also provides a kind of described phenol urethane resin in the application of preparing in foundry sand core model.Described foundry sand core model is that silica sand and phenol urethane resin mixing after fixing moulding are obtained, wherein, described phenol urethane resin plays the effect of sizing agent, for example: the mixture that silica sand, components I, compositionⅱ and solidifying agent are mixed to get is through solidifying and moulding.
It should be noted that, in prior art, described components I and compositionⅱ all can be commercially available, and the present invention just adopts polyphenylene oxide resol provided by the invention to replace the polyphenylene oxide resol being purchased in some or all of replacement components I, condition to silica sand, compositionⅱ and solidifying agent and curing molding, the method for moulding are all not particularly limited, and can be concrete substance classes known in the field, content and condition.For example, the total content of described components I and compositionⅱ is the 0.5-4 % by weight of silica sand weight, and the weight ratio of described components I and compositionⅱ is 1:0.8-1.0; The content of described solidifying agent is the 2-4 % by weight of the gross weight of components I and compositionⅱ.Described compositionⅱ can be PAPI and/or MDI.Described solidifying agent is that amine is solidifying agent, for example triethylamine.Described curing temperature can be-130 DEG C of room temperatures (as 20 DEG C), and the curing time can be 5 seconds-30 minutes.Wherein, the method for moulding can be carried out appropriate selection according to the shape of core model and purposes, is here not particularly limited, for example, the temperature of moulding can be-130 DEG C of room temperatures (as 20 DEG C), and the time of compacting can be 5 seconds-30 minutes, and the pressure of compacting can be 0-4MPa.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, also can carry out arbitrary combination between various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Below will describe the present invention by embodiment.
In following embodiment, the utilization ratio of furfural dregs is calculated according to the following equation:
Weigh the quality of second solid phase product, calculate it and account for the quality percentage composition Y of furfural dregs raw material, the value of 100%-Y is furfural dregs utilization ratio.
Embodiment 1
The present embodiment is for illustrating the preparation of polyphenylene oxide resol.
(1) by 100 grams of furfural dregs (content of cellulose 31.08 % by weight, hemicellulose level 4.59 % by weight, content of lignin 28.29 % by weight), 200 grams of ethylene glycol, 6 gram mass percentage concentrations are that the aqueous sulfuric acid of 95 % by weight joins in 2 liters of closed reactors that agitator and temperature controller are housed, energising heating after sealing, make the temperature in reactor remain on 140 DEG C, pressure remains under 0.4 MPa liquefaction reaction 60 minutes, then by the aqueous solution of this liquefied product and dioxane, (aqueous solution of dioxane and the mass ratio of liquefied product are 4:1, the mass percent concentration of the dioxane aqueous solution is 50%) mix, dissolve to remove solid residue wherein, and carry out solid-liquid separation, obtain the first solid product and the first liquid product, and rotary evaporation in vacuo is sloughed the aqueous solution of the dioxane in the first liquid product,
(2) by 10 gram of first solid product, 20 grams of phenol, 0.6 gram mass percentage concentration is that the aqueous sulfuric acid of 95 % by weight joins in 2 liters of closed reactors that agitator and temperature controller are housed, energising heating after sealing, make the temperature in reactor remain on 150 DEG C, pressure remains under 0.4 MPa liquefaction reaction 60 minutes, then by the aqueous solution of this liquefied product and dioxane, (aqueous solution of dioxane and the mass ratio of liquefied product are 4:1, the mass percent concentration of the dioxane aqueous solution is 50%) mix, dissolve to remove solid residue wherein, and carry out solid-liquid separation, obtain second solid phase product and second liquid phase product, and rotary evaporation in vacuo is sloughed the aqueous solution of the dioxane in second liquid phase product,
(3) under 140 DEG C, 0.2MPa pressure, the first liquid product is contacted and carries out polyreaction with second liquid phase product (weight ratio of the two is 1:1), obtain polyphenylene oxide resol (contain phenol, furfural dregs in raw material and contain the phenmethyl ether compound that part furfural derivatives and degraded form), the utilization ratio of furfural dregs is 95%.Product is characterized with infrared spectroscopy, result shows, at 1500cm
-1near there is the charateristic avsorption band of phenyl ring, at 1000cm
-1-1400cm
-1there is the absorption peak of ehter bond, at 3300cm
-1near there is the absorption peak of phenolic hydroxyl group, and at 1730cm
-1near occurred illustrating the absorption peak of aldehyde radical and generated polyphenylene oxide resol.
Embodiment 2
The present embodiment is for illustrating the preparation of polyphenylene oxide resol.
(1) by 100 grams of furfural dregs (content of cellulose 31.08 % by weight, hemicellulose level 4.59 % by weight, content of lignin 28.29 % by weight), 300 grams of glycerol, 9 gram mass percentage concentrations are that the aqueous sulfuric acid of 95 % by weight joins in 2 liters of closed reactors that agitator and temperature controller are housed, energising heating after sealing, make the temperature in reactor remain on 150 DEG C, pressure remains under 0.3 MPa liquefaction reaction 50 minutes, then by the aqueous solution of this liquefied product and dioxane, (aqueous solution of dioxane and the mass ratio of liquefied product are 10:1, the mass percent concentration of the dioxane aqueous solution is 50%) mix, dissolve to remove solid residue wherein, and carry out solid-liquid separation, obtain the first solid product and the first liquid product, and rotary evaporation in vacuo is sloughed the aqueous solution of the dioxane in the first liquid product,
(2) by 10 gram of first solid product, 30 grams of p-cresols, 0.75 gram mass percentage concentration is that the aqueous sulfuric acid of 95 % by weight joins in 2 liters of closed reactors that agitator and temperature controller are housed, energising heating after sealing, make the temperature in reactor remain on 140 DEG C, pressure remains under 0.3 MPa liquefaction reaction 50 minutes, then by the aqueous solution of this liquefied product and dioxane, (aqueous solution of dioxane and the mass ratio of liquefied product are 10:1, the mass percent concentration of the dioxane aqueous solution is 50%) mix, dissolve to remove solid residue wherein, and carry out solid-liquid separation, obtain second solid phase product and second liquid phase product, and rotary evaporation in vacuo is sloughed the aqueous solution of the dioxane in second liquid phase product,
(3) under 130 DEG C, 0.1MPa pressure, the first liquid product is contacted and carries out polyreaction with second liquid phase product (weight ratio of the two is 1.5:1), obtain polyphenylene oxide resol (contain phenol, furfural dregs in raw material and contain the phenmethyl ether compound that part furfural derivatives and degraded form), the utilization ratio of furfural dregs is 90%.Product is characterized with infrared spectroscopy, result shows, at 1500cm
-1near there is the charateristic avsorption band of phenyl ring, at 1000cm
-1-1400cm
-1there is the absorption peak of ehter bond, at 3300cm
-1near there is the absorption peak of phenolic hydroxyl group, and at 1730cm
-1near occurred illustrating the absorption peak of aldehyde radical and generated polyphenylene oxide resol.
Embodiment 3
The present embodiment is for illustrating the preparation of polyphenylene oxide resol.
(1) by 100 grams of furfural dregs (content of cellulose 31.08 % by weight, hemicellulose level 4.59 % by weight, content of lignin 28.29 % by weight), 250 grams of propylene oxide, 5.3 gram mass percentage concentrations are 95 % by weight aqueous sulfuric acid mixes, dissolve to remove solid residue wherein, and carry out solid-liquid separation, obtain second solid phase product and second liquid phase product; And rotary evaporation in vacuo is sloughed the aqueous solution of the dioxane in second liquid phase product;
(2) by 10 gram of first solid product, 20 grams of phenol, 0.6 gram mass percentage concentration is that the aqueous sulfuric acid of 95 % by weight joins in 2 liters of closed reactors that agitator and temperature controller are housed, energising heating after sealing, make the temperature in reactor remain on 150 DEG C, pressure remains under 0.4 MPa liquefaction reaction 60 minutes, then by the aqueous solution of this liquefied product and dioxane, (aqueous solution of dioxane and the mass ratio of liquefied product are 4:1, the mass percent concentration of the dioxane aqueous solution is 50%) mix, dissolve to remove solid residue wherein, and carry out solid-liquid separation, obtain second solid phase product and second liquid phase product, and rotary evaporation in vacuo is sloughed the aqueous solution of the dioxane in second liquid phase product,
(3) under 150 DEG C, 0.3MPa pressure, the first liquid product is contacted and carries out polyreaction with second liquid phase product (weight ratio of the two is 2:1), obtain polyphenylene oxide resol (contain phenol, furfural dregs in raw material and contain the phenmethyl ether compound that part furfural derivatives and degraded form), the utilization ratio of furfural dregs is 83%.Product is characterized with infrared spectroscopy, result shows, at 1500cm
-1near there is the charateristic avsorption band of phenyl ring, at 1000cm
-1-1400cm
-1there is the absorption peak of ehter bond, at 3300cm
-1near there is the absorption peak of phenolic hydroxyl group, and at 1730cm
-1near occurred illustrating the absorption peak of aldehyde radical and generated polyphenylene oxide resol.
Embodiment 4
The present embodiment is for illustrating the preparation of polyphenylene oxide resol.
(1) by 100 grams of furfural dregs (content of cellulose 31.08 % by weight, hemicellulose level 4.59 % by weight, content of lignin 28.29 % by weight), 150 grams of oxyethane, 7.5 gram mass percentage concentrations are that the aqueous hydrochloric acid of 37 % by weight joins in 2 liters of closed reactors that agitator and temperature controller are housed, energising heating after sealing, make the temperature in reactor remain on 110 DEG C, pressure remains under 0.1 MPa liquefaction reaction 20 minutes, then by the aqueous solution of this liquefied product and dioxane, (aqueous solution of dioxane and the mass ratio of liquefied product are 2:1, the mass percent concentration of the dioxane aqueous solution is 50%) mix, dissolve to remove solid residue wherein, and carry out solid-liquid separation, obtain the first solid product and the first liquid product, and rotary evaporation in vacuo is sloughed the aqueous solution of the dioxane in the first liquid product,
(2) by 10 gram of first solid product, 15 grams of pyrogallols, 0.45 gram mass percentage concentration is that the aqueous hydrochloric acid of 37 % by weight joins in 2 liters of closed reactors that agitator and temperature controller are housed, energising heating after sealing, make the temperature in reactor remain on 140 DEG C, pressure remains under 0.1 MPa liquefaction reaction 40 minutes, then by the aqueous solution of this liquefied product and dioxane, (aqueous solution of dioxane and the mass ratio of liquefied product are 2:1, the mass percent concentration of the dioxane aqueous solution is 50%) mix, dissolve to remove solid residue wherein, and carry out solid-liquid separation, obtain second solid phase product and second liquid phase product, and rotary evaporation in vacuo is sloughed the aqueous solution of the dioxane in second liquid phase product,
(3) under 20 DEG C, 0.4MPa pressure, the first liquid product is contacted and carries out polyreaction with second liquid phase product (weight ratio of the two is 0.5:1), obtain polyphenylene oxide resol (contain phenol, furfural dregs in raw material and contain the phenmethyl ether compound that part furfural derivatives and degraded form), the utilization ratio of furfural dregs is 60%.Product is characterized with infrared spectroscopy, result shows, at 1500cm
-1near there is the charateristic avsorption band of phenyl ring, at 1000cm
-1-1400cm
-1there is the absorption peak of ehter bond, at 3300cm
-1near there is the absorption peak of phenolic hydroxyl group, and at 1730cm
-1near occurred illustrating the absorption peak of aldehyde radical and generated polyphenylene oxide resol.
Embodiment 5
The present embodiment is for illustrating the preparation of polyphenylene oxide resol.
(1) by 100 grams of furfural dregs (content of cellulose 31.08 % by weight, hemicellulose level 4.59 % by weight, content of lignin 28.29 % by weight), 300 grams of polyoxyethylene glycol, 9 grams of phenylformic acid solids join in 2 liters of closed reactors that agitator and temperature controller are housed, energising heating after sealing, make the temperature in reactor remain on 180 DEG C, pressure remains under 0.01 MPa liquefaction reaction 120 minutes, then by the aqueous solution of this liquefied product and dioxane, (aqueous solution of dioxane and the mass ratio of liquefied product are 100:1, the mass percent concentration of the dioxane aqueous solution is 50%) mix, dissolve to remove solid residue wherein, and carry out solid-liquid separation, obtain the first solid product and the first liquid product, and rotary evaporation in vacuo is sloughed the aqueous solution of the dioxane in the first liquid product,
(2) by 10 gram of first solid product, 60 grams of Bisphenol F, 1.8 grams of phenylformic acid solids join in 2 liters of closed reactors that agitator and temperature controller are housed, energising heating after sealing, make the temperature in reactor remain on 180 DEG C, pressure remains under 0.01 MPa liquefaction reaction 120 minutes, then by the aqueous solution of this liquefied product and dioxane, (aqueous solution of dioxane and the mass ratio of liquefied product are 100:1, the mass percent concentration of the dioxane aqueous solution is 60%) mix, dissolve to remove solid residue wherein, and carry out solid-liquid separation, obtain second solid phase product and second liquid phase product, and rotary evaporation in vacuo is sloughed the aqueous solution of the dioxane in second liquid phase product,
(3) under 180 DEG C, 0.01MPa pressure, the first liquid product is contacted and carries out polyreaction with second liquid phase product (weight ratio of the two is 1:1), obtain polyphenylene oxide resol (contain bis-phenol, furfural dregs in raw material and contain the phenmethyl ether compound that part furfural derivatives and degraded form), the utilization ratio of furfural dregs is 75%.Product is characterized with infrared spectroscopy, result shows, at 1500cm
-1near there is the charateristic avsorption band of phenyl ring, at 1000cm
-1-1400cm
-1there is the absorption peak of ehter bond, at 3300cm
-1near there is the absorption peak of phenolic hydroxyl group, and at 1730cm
-1near occurred illustrating the absorption peak of aldehyde radical and generated polyphenylene oxide resol.
EXPERIMENTAL EXAMPLE 1
By the polyphenylene oxide resol being prepared by furfural dregs by embodiment 1 and commercially available polyphenylene oxide resol (purchased from Ya Shilan (Changzhou) Chemical Co., Ltd., the trade mark is sent general I-1600) after blending as components I (described in embodiment 1, polyphenylene oxide resol is 50 % by weight of components I gross weight), its physical and chemical index is as shown in table 1 below.
By components I and compositionⅱ (MDI, be purchased from Yantai Wan Hua company, isocyanic acid content 30.03 % by weight) mix with silica sand, the method of mixing is: first by silica sand and components I mixing 1min, add again compositionⅱ mixing 2min, wherein, the weight ratio of components I and compositionⅱ is 55:45, and the gross weight of components I and compositionⅱ accounts for 2 % by weight of silica sand weight; The coremaking of shaking out after mixing, 0.2MPa blowing down solidifying agent triethylamine (1 ton of sand needs 0.45Kg triethylamine) (solidifying agent be components I and compositionⅱ gross weight 2.25%), the process performance index of the core model of measuring with the GB GB/T 24413-2009 of phenol urethane resin according to casting is as shown in table 2 below.
Table 1
| Index | Performance |
| Outward appearance | Brown liquid |
| Density (20 DEG C, g/cm 3） | 1.103 |
| Viscosity (20 DEG C, mPa.s) | 290 |
| Free formaldehyde content, % by weight | 0.48 |
Table 2
| Index | Performance |
| 24 hours tensile strength, MPa | 1.93 |
| Gas forming amount (ml/g) | 12.9 |
Note: described tensile strength refers to the tensile strength of core model.
EXPERIMENTAL EXAMPLE 2
By the polyphenylene oxide resol being prepared by furfural dregs by embodiment 2 and commercially available polyphenylene oxide resol (purchased from Ya Shilan (Changzhou) Chemical Co., Ltd., the trade mark is sent general I-1600) after blending as components I (described in embodiment 2, polyphenylene oxide resol is 20 % by weight of components I gross weight), its physical and chemical index is as shown in table 3 below.
By components I and compositionⅱ (MDI, be purchased from Yantai Wan Hua company, isocyanic acid content 30.03 % by weight) mix with silica sand, the method of mixing is: first by silica sand and components I mixing 1min, add again compositionⅱ mixing 2min, wherein, the weight ratio of components I and compositionⅱ is 55:45, and the gross weight of components I and compositionⅱ accounts for 2 % by weight of silica sand weight; The coremaking of shaking out after mixing, at 0.2MPa blowing down triethylamine, (1 ton of sand needs 0.45Kg triethylamine) (solidifying agent be components I and compositionⅱ gross weight 2.25%) according to the GB GB/T 24413-2009 of casting phenol urethane resin measure core model process performance index as shown in table 4 below.
Table 3
| Index | Performance |
| Outward appearance | Faint yellow |
| Density (20 DEG C, g/cm 3） | 1.091 |
| Viscosity (20 DEG C, mPa.s) | 280 |
| Free formaldehyde content, % by weight | 0.39 |
Table 4
| Index | Performance |
| 24 hours tensile strength, MPa | 1.98 |
| Gas forming amount (ml/g) | 12.3 |
Note: described tensile strength refers to the tensile strength of core model.
EXPERIMENTAL EXAMPLE 3
By the polyphenylene oxide resol being prepared by furfural dregs by embodiment 3 and commercially available polyphenylene oxide resol (purchased from Ya Shilan (Changzhou) Chemical Co., Ltd., the trade mark is sent general I-1600) after blending as components I (described in embodiment 3, polyphenylene oxide resol is 40 % by weight of components I gross weight), its physical and chemical index is as shown in table 5 below.
By components I and compositionⅱ (MDI, be purchased from Yantai Wan Hua company, isocyanic acid content 30.03 % by weight) mix with silica sand, the method of mixing is: first by silica sand and components I mixing 1min, add again compositionⅱ mixing 2min, wherein, the weight ratio of components I and compositionⅱ is 55:45, and the gross weight of components I and compositionⅱ accounts for 2 % by weight of silica sand weight; The coremaking of shaking out after mixing, at 0.2MPa blowing down triethylamine, (1 ton of sand needs 0.45Kg triethylamine) (solidifying agent be components I and compositionⅱ gross weight 2.25%), according to casting with the GB GB/T 24413-2009 of phenol urethane resin measure core model process performance index as shown in table 6 below.
Table 5
| Index | Performance |
| Outward appearance | Deep yellow |
| Density (20 DEG C, g/cm 3） | 0.959 |
| Viscosity (20 DEG C, mPa.s) | 270 |
| Free formaldehyde content, % by weight | 0.45 |
Table 6
| Index | Performance |
| 24 hours tensile strength, MPa | 1.90 |
| Gas forming amount (ml/g) | 13.4 |
Note: described tensile strength refers to the tensile strength of core model.
EXPERIMENTAL EXAMPLE 4
By the polyphenylene oxide resol being prepared by furfural dregs by embodiment 4 and commercially available polyphenylene oxide resol (purchased from Ya Shilan (Changzhou) Chemical Co., Ltd., the trade mark is sent general I-1600) after blending as components I (described in embodiment 4, polyphenylene oxide resol is 20 % by weight of components I gross weight), its physical and chemical index is as shown in table 7 below.
By components I and compositionⅱ (PAPI, be purchased from Yantai Wan Hua company, isocyanic acid content 31 % by weight) mix with silica sand, the method of mixing is: first by silica sand and components I mixing 1min, add again compositionⅱ mixing 2min, wherein, the weight ratio of components I and compositionⅱ is 50:50, and the gross weight of components I and compositionⅱ accounts for 2 % by weight of silica sand weight; The coremaking of shaking out after mixing, at 0.2MPa blowing down triethylamine, (1 ton of sand needs 0.45Kg triethylamine) (solidifying agent be components I and compositionⅱ gross weight 3%), according to casting with the GB GB/T 24413-2009 of phenol urethane resin measure core model process performance index as shown in table 8 below.
Table 7
| Index | Performance |
| Outward appearance | Faint yellow |
| Density (20 DEG C, g/cm 3） | 0.982 |
| Viscosity (20 DEG C, mPa.s) | 260 |
| Free formaldehyde content, % by weight | 0.35 |
Table 8
| Index | Performance |
| 24 hours tensile strength, MPa | 1.85 |
| Gas forming amount (ml/g) | 13.0 |
Note: described tensile strength refers to the tensile strength of core model.
EXPERIMENTAL EXAMPLE 5
By the polyphenylene oxide resol being prepared by furfural dregs by embodiment 5 and commercially available polyphenylene oxide resol (purchased from Ya Shilan (Changzhou) Chemical Co., Ltd., the trade mark is sent general I-1600) after blending as components I (described in embodiment 5, polyphenylene oxide resol is 30 % by weight of components I gross weight), its physical and chemical index is as shown in table 9 below.
By components I and compositionⅱ (PAPI, be purchased from Yantai Wan Hua company, isocyanic acid content 31 % by weight) mix with silica sand, the method of mixing is: first by silica sand and components I mixing 1min, add again compositionⅱ mixing 2min, wherein, the weight ratio of components I and compositionⅱ is 60:40, and the gross weight of components I and compositionⅱ accounts for 4 % by weight of silica sand weight; The coremaking of shaking out after mixing, at 0.2MPa blowing down triethylamine, (1 ton of sand needs 0.45Kg triethylamine) (solidifying agent be components I and compositionⅱ gross weight 4%), according to casting with the GB GB/T 24413-2009 of phenol urethane resin measure core model process performance index as shown in table 10 below.
Table 9
| Index | Performance |
| Outward appearance | Deep yellow |
| Density (20 DEG C, g/cm 3） | 0.973 |
| Viscosity (20 DEG C, mPa.s) | 300 |
| Free formaldehyde content, % by weight | 0.43 |
Table 10
| Index | Performance |
| 24 hours tensile strength, MPa | 1.82 |
| Gas forming amount (ml/g) | 13.5 |
Note: described tensile strength refers to the tensile strength of core model.
Result by embodiment of the present invention 1-5 and EXPERIMENTAL EXAMPLE 1-5 is known, and the present invention is utilized effectively waste material furfural dregs, has opened up a kind of novel method, and reduced cost for preparing polyphenylene oxide resol.In addition the core model of being prepared by phenol urethane resin of the present invention, has good physical strength.
Claims (15)
1. a preparation method for polyphenylene oxide resol, is characterized in that, the method comprises the steps:
(1) under the existence of acid catalyst, furfural dregs is contacted with fatty alcohol and/or epoxy compounds, make furfural dregs liquefaction, and by the liquefied product obtaining and dioxane aqueous solution, and separation obtains the first solid product and the first liquid product;
(2) under the existence of acid catalyst, the first solid product of step (1) is contacted with phenolic compound, make the first solid product liquefaction, and by the liquefied product obtaining and dioxane aqueous solution, and separation obtains second solid phase product and second liquid phase product;
(3), under polymeric reaction condition, the first liquid product is contacted with second liquid phase product.
2. method according to claim 1, wherein, in step (1), with respect to 100 weight part furfural dregs, total consumption of fatty alcohol and epoxy compounds is 150-600 weight part, and the consumption of acid catalyst is the 0.05-3 % by weight of the total mass of fatty alcohol and epoxy compounds.
3. method according to claim 1 and 2, wherein, described fatty alcohol is that carbonatoms is one or more in 2-10, hydroxyl value be 2-3 aliphatic polyol and polyether glycol; Described epoxy compounds is that carbonatoms is the oxirane of 2-5.
4. method according to claim 1, wherein, in step (1), the weight ratio of the dioxane aqueous solution and liquefied product is 2-100:1; The mass percent concentration of the described dioxane aqueous solution is 20-80%.
5. according to the method described in right 1, wherein, in step (2), with respect to 100 weight part the first solid products, the consumption of phenolic compound is 150-600 weight part, and the consumption of acid catalyst is the 0.05-3 % by weight of phenolic compound quality.
6. method according to claim 1 or 5, wherein, described phenolic compound is selected from one or more in phenol, Ortho Cresol, m-cresol, p-cresol, pyrocatechol, Resorcinol, Resorcinol, pyrogallol, Phloroglucinol, hydroxyquinol, naphthyl alcohol, 2-Naphthol, dihydroxyphenyl propane and Bisphenol F.
7. method according to claim 1, wherein, in step (2), the weight ratio of the dioxane aqueous solution and liquefied product is 2-100:1; The mass percent concentration of the described dioxane aqueous solution is 20-80%.
8. according to the method described in claim 1,2 or 5, wherein, described acid catalyst is selected from one or more in phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, Phenylsulfonic acid and phenylformic acid.
9. method according to claim 1, wherein, in step (1), the condition of described contact comprises that the temperature of contact is 110-180 DEG C, and the time of contact is 20-120 minute, and the pressure of contact is 0-0.42 MPa.
10. method according to claim 1, wherein, in step (2), the condition of described contact comprises that the temperature of contact is 100-180 DEG C, and the time of contact is 10-120 minute, and the pressure of contact is 0-0.42 MPa.
11. methods according to claim 1, wherein, before the method is also included in the first liquid product is contacted with second liquid phase product, the step of removing the dioxane aqueous solution in the first liquid product and second liquid phase product.
12. according to the method described in claim 1 or 11, and wherein, in step (3), polymeric reaction condition comprises that temperature of reaction is 20-180 DEG C, and pressure is 0-0.4MPa, and the weight ratio of the first liquid phase and second liquid phase is 0.5-5:1.
13. 1 kinds of phenol urethane resins, this phenol urethane resin contains components I, compositionⅱ and the solidifying agent independently deposited respectively, and described components I is polyphenylene oxide resol, and described compositionⅱ is isocyanate resin, and described solidifying agent is that amine is solidifying agent; It is characterized in that, described components I contains the polyphenylene oxide resol being prepared by the method described in any one in claim 1-12.
14. phenol urethane resins according to claim 13, wherein, the content of the polyphenylene oxide resol being prepared by the method described in any one in claim 1-12 is the 2-100 % by weight of components I gross weight.
Phenol urethane resin described in 15. claims 13 or 14 is in the application of preparing in foundry sand core model.
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Citations (3)
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|---|---|---|---|---|
| US4546124A (en) * | 1984-10-12 | 1985-10-08 | Acme Resin Corporation | Polyurethane binder compositions |
| CN101058664A (en) * | 2007-06-05 | 2007-10-24 | 苏州市兴业铸造材料有限公司 | Method of increasing cold box resin high-temperature behavior |
| CN101524737A (en) * | 2009-04-10 | 2009-09-09 | 苏州市兴业铸造材料有限公司 | Phenol urethane cold core box bond for nonferrous casting and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4546124A (en) * | 1984-10-12 | 1985-10-08 | Acme Resin Corporation | Polyurethane binder compositions |
| CN101058664A (en) * | 2007-06-05 | 2007-10-24 | 苏州市兴业铸造材料有限公司 | Method of increasing cold box resin high-temperature behavior |
| CN101524737A (en) * | 2009-04-10 | 2009-09-09 | 苏州市兴业铸造材料有限公司 | Phenol urethane cold core box bond for nonferrous casting and preparation method thereof |
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| FranciliB.Oliveiraetal..Phenol–FurfuralResinstoElaborateCompositesReinforcedwithSisalFibers––MolecularAnalysisofResinandPropertiesofComposites .《Journal of Applied Polymer Science》.2008 |
| Phenol–Furfural Resins to Elaborate Composites Reinforced with Sisal Fibers––Molecular Analysis of Resin and Properties of Composites,;Francili B. Oliveira et al.;《Journal of Applied Polymer Science》;20080506;第109卷;第2291–2303页 * |
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| 黄仁和等.铸造用聚氨酯苯醚型酚醛树脂合成工艺研究.《铸造》.2008,第57卷(第1期),8-11. |
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