CN117106145A - A kind of phenolic resin and preparation method thereof - Google Patents
A kind of phenolic resin and preparation method thereof Download PDFInfo
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- CN117106145A CN117106145A CN202311206454.XA CN202311206454A CN117106145A CN 117106145 A CN117106145 A CN 117106145A CN 202311206454 A CN202311206454 A CN 202311206454A CN 117106145 A CN117106145 A CN 117106145A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09J161/14—Modified phenol-aldehyde condensates
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Abstract
The invention relates to the technical field of adhesives, and discloses a phenolic resin which comprises the following raw materials in parts by weight: 45-60 parts of phenol, 100-150 parts of formaldehyde, 2-10 parts of catalyst, 2-8 parts of urea and 5-15 parts of water; the preparation method of the phenolic resin comprises the following steps: adding phenol and formaldehyde into a reactor, stirring and mixing, and measuring the refractive index; adding a catalyst into a reactor, stirring and dissolving, and carrying out polymerization under the heating condition to obtain a polycondensation product; and regulating the pH value of the polycondensation product, and then adding urea, and stirring until the urea is completely dissolved to obtain the phenolic resin. The phenolic resin adhesive prepared by the invention meets the performance requirement standard of the adhesive in the preparation process of rock wool in the factory, has good adhesive performance and moderate curing time, and has the contents of free phenol and free formaldehyde which are obviously lower than the market binder standard, excellent product performance and high yield.
Description
Technical Field
The invention relates to the technical field of adhesive preparation, in particular to phenolic resin and a preparation method thereof.
Background
With the development of rock wool products, the research on phenolic resin adhesives for producing rock wool heat insulation materials is also continuous and intensive. In the past, the research on rock wool resin is tightly combined with the performance requirement and the production process of rock wool products, and along with the increasing maturity of rock wool production equipment, the research on the cooperation among various elements in the production process is increasingly prominent.
Rock wool has excellent heat insulation performance and is widely applied to the field of building heat preservation as a heat preservation material. The binder phenolic resin used for rock wool production has the advantages of higher mechanical strength, good heat resistance, flame resistance, low toxicity, low smoke generation and the like, can be blended with other polymers, realizes high performance and is widely applied to various fields of national economy. The polycondensation reaction of phenols and aldehydes can be carried out under a pressurized or depressurized condition, which accelerates the polycondensation reaction, reduces the catalyst amount and can obtain a higher quality product, but the method is not widely used because of special equipment and difficult operation control, and the depressurization method prolongs the reaction time, but does not actually improve the resin properties.
It is therefore a matter of urgent need to be solved by those skilled in the art how to provide a method which is easy to control the conditions and can produce high quality phenolic resins.
Disclosure of Invention
In view of the above, the invention provides a phenolic resin and a preparation method thereof, which are used for solving the problems of low production efficiency, poor quality and complex operation of the phenolic resin binder used in the existing rock wool production.
In order to solve the technical problems, the invention adopts the following technical scheme:
in one aspect of the invention, a phenolic resin is provided, which comprises the following raw materials in parts by weight: 45-60 parts of phenol, 100-150 parts of formaldehyde, 2-10 parts of catalyst, 2-8 parts of urea and 5-15 parts of water.
Preferably, the phenolic resin further comprises 1-5 parts of a dilute acid solution, wherein the dilute acid solution is any one of dilute sulfuric acid, dilute hydrochloric acid and dilute nitric acid.
Preferably, in the phenolic resin, the catalyst comprises any one or more of potassium hydroxide, sodium hydroxide, barium hydroxide, calcium oxide and magnesium oxide.
In another aspect of the present invention, there is provided a method for preparing a phenolic resin, comprising the steps of:
(1) Adding phenol and formaldehyde into a reactor, stirring and mixing, and measuring the refractive index;
(2) Adding a catalyst into a reactor, stirring and dissolving, and carrying out polymerization under the heating condition to obtain a polycondensation product;
(3) And regulating the pH value of the polycondensation product, and then adding urea, and stirring until the urea is completely dissolved to obtain the phenolic resin.
Preferably, in the above preparation method of phenolic resin, the step (1) specifically includes:
adding phenol water solution and formaldehyde into a reactor, stirring for 5-10min, sampling, measuring and adjusting the refractive index to a first preset value;
tap water is continuously added into the reaction kettle, the mixture is stirred for 5 to 10 minutes, then sampling measurement is carried out, and the refractive index is regulated to a second preset value.
Preferably, in the above method for preparing phenolic resin, the first preset value is 1.4200 ±0.0030; if the sampling measured value is higher than the first preset value, adjusting the refractive index to the first preset value by adding formaldehyde; if the sampling measured value is lower than the first preset value, adjusting the refractive index to the first preset value by adding phenol;
further, the second preset value is 1.4158 +/-0.0030; if the sampling measured value is higher than the second preset value, adding water to adjust the refractive index to the second preset value; and if the sampling measurement value is lower than the second preset value, adjusting the refractive index to the second preset value by adding phenol.
Preferably, in the above method for preparing phenolic resin, the heating condition in the step (2) is specifically: heating the temperature of the reactor to 45-55 ℃ at a speed of 1-5 ℃/min, and preserving heat for 40-80min; then heating to 65-75 ℃ at a speed of 3-6 ℃/min, and reacting to an end point at 65-75 ℃.
Preferably, in the above method for producing a phenolic resin, the method for determining the reaction end point is as follows: taking a measurement sample from the reactor, cooling to below 25 ℃, adding hydrochloric acid solution, and judging the reaction as a reaction end point if milky turbidity appears in 30 seconds;
further, the volume ratio of the assay sample to the hydrochloric acid solution is (2-3): (15-50), and the concentration of the hydrochloric acid solution is 1mol/L.
Preferably, in the above method for producing a phenol resin, after the polymerization reaction reaches the end, the reaction is stopped by cooling the reactor to 25 ℃ or lower.
Preferably, in the above method for producing a phenolic resin, the pH of the polycondensation product is adjusted to 7.5 to 8.0 by a dilute acid solution in step (3);
further, the stirring time is 20-40min.
The invention provides a phenolic resin and a preparation method thereof, which has the beneficial effects that compared with the prior art:
the phenolic resin adhesive prepared by the invention meets the performance requirement standard of the adhesive in the preparation process of rock wool in the factory, has good adhesive performance and moderate curing time, and has the contents of free phenol and free formaldehyde which are obviously lower than the market binder standard, excellent product performance and high yield.
The reaction condition is easy to control, the reaction condition can be judged by detecting the refractive index of the solution to determine the time for entering the subsequent reaction, and the performance of the phenolic resin can be more stable; in addition, the catalyst is added for gradual heating and staged reaction, so that the viscosity, the curing performance and the like of the phenolic resin can be effectively ensured to meet the standard requirements, the free phenol content and the free aldehyde content in the phenolic resin are effectively reduced, and the utilization rate of raw materials is improved.
Detailed Description
Embodiments of the present invention are described in detail below, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The following examples are illustrative only and are not to be construed as limiting the invention. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In one aspect of the invention, the invention provides a phenolic resin.
According to the embodiment of the invention, the phenolic resin comprises the following raw materials in parts by weight: 45-60 parts of phenol, 100-150 parts of formaldehyde, 2-10 parts of catalyst, 2-8 parts of urea and 5-15 parts of water.
Further, the phenolic resin comprises the following raw materials in parts by weight: 52 parts of phenol, 127 parts of formaldehyde, 6 parts of catalyst, 5 parts of urea and 10 parts of water; or the phenolic resin comprises the following raw materials in parts by weight: 45 parts of phenol, 100 parts of formaldehyde, 2 parts of catalyst, 2 parts of urea and 5 parts of water; or phenolic resin, which comprises the following raw materials in parts by weight: 60 parts of phenol, 150 parts of formaldehyde, 10 parts of catalyst, 8 parts of urea and 15 parts of water.
In some embodiments of the invention, the phenolic resin further comprises 1-5 parts of a diluted acid solution, and the diluted acid solution is any one of diluted sulfuric acid, diluted hydrochloric acid and diluted nitric acid, and the pH value of the polycondensation product is adjusted by adding the diluted acid solution, wherein the diluted acid solution is preferably a diluted sulfuric acid solution with the volume percentage of 37%.
In some embodiments of the present invention, the catalyst comprises any one or more of potassium hydroxide, sodium hydroxide, barium hydroxide, calcium oxide and magnesium oxide, preferably barium hydroxide octahydrate, and the polymerization reaction of phenol and formaldehyde can be accelerated by adding the catalyst, and the activity of molecular weight, hardness and the like of a polycondensation product can be enhanced.
In another aspect of the invention, a method of preparing a phenolic resin is provided.
According to an embodiment of the invention, the preparation method of the phenolic resin comprises the following steps:
and S100, adding phenol and formaldehyde into a reactor, stirring and mixing, and measuring the refractive index.
In the step, firstly adding phenol water solution and formaldehyde into a reactor, stirring for 5-10min, sampling, measuring and adjusting the refractive index to a first preset value; then adding tap water into the reaction kettle, stirring for 5-10min, sampling, measuring and adjusting the refractive index to a second preset value.
In some embodiments of the invention, the first preset value is 1.4200 ±0.0030, preferably 1.4200 ±0.0010; if the sampling measured value is higher than the first preset value, reducing the refractive index to the first preset value by adding formaldehyde; if the sampling measured value is lower than the first preset value, the refractive index is increased to the first preset value by adding phenol;
in some embodiments of the invention, the second preset value is 1.4158 ±0.0030, preferably 1.4158 ±0.0010; if the sampling measured value is higher than the second preset value, adding water to adjust the refractive index to the second preset value; and if the sampling measurement value is lower than the second preset value, adjusting the refractive index to the second preset value by adding phenol.
The invention can detect the reaction progress by detecting the refractive index of the reaction solution in the reaction process, flexibly control the reaction progress, ensure that the reaction reaches the requirement and enhance the stability of the quality of the phenolic resin product.
And S200, adding a catalyst into the reactor, stirring and dissolving, and carrying out polymerization under the heating condition to obtain a polycondensation product.
In this step, by adding a catalyst, the reaction speed can be increased, the reaction temperature can be reduced, and the selectivity of the reaction can be improved. Wherein the stirring dissolution time is 5-20min, so that the catalytic performance and the reaction speed of the catalyst can be further accelerated.
In some embodiments of the invention, the heating conditions are specifically: heating the temperature of the reactor to 45-55 ℃ at a speed of 1-5 ℃/min, and preserving heat for 40-80min; then heating to 65-75 ℃ at a speed of 3-6 ℃/min, and reacting to an end point at 65-75 ℃.
In the heating catalytic reaction process, the reaction is carried out respectively at different temperatures through staged temperature rising, so that the polycondensation reaction is carried out more thoroughly, the phenolic resin product has more stable structure, higher hardness and better cohesiveness, and the contents of free phenol and free aldehyde can be effectively reduced.
Further, the method for determining the reaction end point is as follows: taking a measurement sample from a reactor, cooling to below 25 ℃, adding hydrochloric acid solution, and judging as a reaction end point if milky turbidity appears in 30 seconds, wherein the volume ratio of the measurement sample to the hydrochloric acid solution is (2-3): (15-50), and the concentration of the hydrochloric acid solution is 1mol/L.
In general, the reaction reaches the end after 2 to 3 hours at 65 to 75 ℃. Sampling from the reactor to the container when the reaction time reaches 60min at 65-75 ℃, cooling the container to below 25 ℃ through flowing water, then adding hydrochloric acid solution, if milky turbid matters appear in 30s, indicating that the polymerization reaction end point reaches, otherwise, continuing sampling detection after a certain time interval until the reaction end point is reached, and stopping sampling; it should be noted that the sampling interval is shortened with the increase of the reaction time, so as to avoid excessive reaction.
In some embodiments of the invention, after the polymerization reaction reaches the end point, the reaction is stopped by cooling the reactor below 25 ℃ to prevent further condensation.
And S300, regulating the pH value of the polycondensation product, and then adding urea, and stirring until the urea is completely dissolved, thus obtaining the phenolic resin.
In this step, the pH of the polycondensation product is adjusted to 7.5 to 8.0 by means of a dilute acid solution, by adjusting the pH of the polycondensation product. The molecular weight of the resin can be increased, the molecular chain crosslinking is more compact, and the hardness and the heat resistance of the phenolic resin are improved.
In some embodiments of the invention, the urea is added and stirred for 20-40 minutes to achieve complete dissolution. The urea can be added as formaldehyde eliminator, the curing temperature of the phenolic resin and the free aldehyde content in the product are obviously reduced, the adhesive strength, the curing speed and the storage stability of the phenolic resin can be effectively improved, in addition, the phenolic resin added with urea contains active group hydroxymethyl, and the phenolic ring and the hydroxymethyl urea are mainly connected through methylene bonds, so that the flame retardant property of the phenolic resin is improved.
S400, placing phenolic resin liquid into a resin storage tank for storage, controlling the storage temperature to be lower than 25 ℃, checking the phenolic resin according to an enterprise internal control standard, and after the phenolic resin is checked to be qualified, using the phenolic resin
In yet another aspect of the present invention, a rock wool comprising the phenolic resin is provided, whereby the rock wool has all of the features and advantages of the phenolic resin described above and is not described in detail herein. In general, the rock wool has the characteristics of excellent mechanical properties, heat resistance, weather resistance, flame retardance and excellent mechanical properties.
The invention is illustrated below by means of specific examples, which are given for illustrative purposes only and do not limit the scope of the invention in any way, as will be understood by those skilled in the art. In addition, in the examples below, reagents and equipment used are commercially available unless otherwise specified. If in the following examples specific treatment conditions and treatment methods are not explicitly described, the treatment may be performed using conditions and methods well known in the art.
Example 1
The embodiment provides phenolic resin, which comprises the following raw materials in parts by weight: 52 parts of phenol, 127 parts of formaldehyde, 6 parts of barium hydroxide octahydrate, 5 parts of urea, 8 parts of water and 2 parts of 37% sulfuric acid solution.
The preparation method of the phenolic resin comprises the following steps:
(1) Adding phenol water solution and formaldehyde into a reactor, stirring for 8min, sampling, measuring and adjusting the refractive index to 1.4200, and allowing the deviation to be +/-0.0030; then adding tap water into the reaction kettle, stirring for 8min, sampling, measuring and adjusting the refractive index to 1.4158, wherein the allowable deviation is +/-0.0030;
(2) Adding barium hydroxide octahydrate into a reactor, stirring and dissolving for 15min, then heating the temperature of the reactor to 50 ℃ at the speed of 3 ℃/min, preserving heat for 60min, continuously heating to 70 ℃ at the speed of 5 ℃/min, and reacting at 70 ℃ to the end point to obtain a polycondensation product;
(3) Regulating the pH value of the polycondensation product to 7.5-8.0, adding urea, and stirring for 30min until the urea is completely dissolved to obtain phenolic resin;
(4) And (3) placing the phenolic resin liquid into a resin storage tank for storage, controlling the storage temperature to be lower than 25 ℃, and checking the phenolic resin according to the enterprise internal control standard, wherein the phenolic resin can be used after the phenolic resin is checked to be qualified.
Example 2
The embodiment provides phenolic resin, which comprises the following raw materials in parts by weight: 45 parts of phenol, 100 parts of formaldehyde, 2 parts of sodium hydroxide, 2 parts of urea, 5 parts of water and 1 part of 37% dilute sulfuric acid solution.
The preparation method of the phenolic resin comprises the following steps:
(1) Adding phenol water solution and formaldehyde into a reactor, stirring for 5min, sampling, measuring and adjusting the refractive index to 1.4200, and allowing the deviation to be +/-0.0030; then adding tap water into the reaction kettle, stirring for 5min, sampling, measuring and adjusting the refractive index to 1.4158, wherein the allowable deviation is +/-0.0030;
(2) Adding sodium hydroxide into a reactor, stirring and dissolving for 5min, then heating the temperature of the reactor to 45 ℃ at the speed of 1 ℃/min, preserving heat for 80min, continuously heating to 65 ℃ at the speed of 3 ℃/min, and reacting at 65 ℃ to the end point to obtain a polycondensation product;
(3) Regulating the pH value of the polycondensation product to 7.5-8.0, then adding urea, and stirring for 40min until the urea is completely dissolved, thus obtaining phenolic resin;
(4) And (3) placing the phenolic resin liquid into a resin storage tank for storage, controlling the storage temperature to be lower than 25 ℃, and checking the phenolic resin according to the enterprise internal control standard, wherein the phenolic resin can be used after the phenolic resin is checked to be qualified.
Example 3
The embodiment provides phenolic resin, which comprises the following raw materials in parts by weight: 60 parts of phenol, 150 parts of formaldehyde, 10 parts of potassium hydroxide, 8 parts of urea, 15 parts of water and 5 parts of 37% dilute sulfuric acid solution.
The preparation method of the phenolic resin comprises the following steps:
(1) Adding phenol water solution and formaldehyde into a reactor, stirring for 10min, sampling, measuring and adjusting the refractive index to 1.4200, and allowing the deviation to be +/-0.0030; then adding tap water into the reaction kettle, stirring for 10min, sampling, measuring and adjusting the refractive index to 1.4158, wherein the allowable deviation is +/-0.0030;
(2) Adding potassium hydroxide into a reactor, stirring and dissolving for 20min, then heating the temperature of the reactor to 55 ℃ at the speed of 5 ℃/min, preserving heat for 40min, continuously heating to 75 ℃ at the speed of 6 ℃/min, and reacting at 75 ℃ to the end point to obtain a polycondensation product;
(3) Regulating the pH value of the polycondensation product to 7.5-8.0, then adding urea, and stirring for 20min until the urea is completely dissolved, thus obtaining phenolic resin;
(4) And (3) placing the phenolic resin liquid into a resin storage tank for storage, controlling the storage temperature to be lower than 25 ℃, and checking the phenolic resin according to the enterprise internal control standard, wherein the phenolic resin can be used after the phenolic resin is checked to be qualified.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that urea is added in an amount of 1 part.
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that urea is added in an amount of 10 parts.
Comparative example 3
Comparative example 3 is substantially the same as example 1, differing only in step (1):
(1) Adding phenol water solution, formaldehyde and tap water into a reactor, and stirring for 16min.
Comparative example 4
Comparative example 4 is substantially the same as example 1, except that step (2) is different:
(2) Adding a catalyst into a reactor, stirring and dissolving for 15min, then heating the temperature of the reactor to 70 ℃ at a speed of 5 ℃/min, and reacting at 70 ℃ to the end point to obtain a polycondensation product.
Comparative example 5
Comparative example 5 is substantially the same as example 1, except that step (2) is different:
(2) Adding a catalyst into a reactor, stirring and dissolving for 15min, then heating the temperature of the reactor to 40 ℃ at the speed of 3 ℃/min, preserving heat for 60min, continuously heating to 70 ℃ at the speed of 5 ℃/min, and reacting at 70 ℃ to the end point to obtain a polycondensation product.
Comparative example 6
Comparative example 6 is substantially the same as example 1, except that step (2) is different:
(2) Adding a catalyst into a reactor, stirring and dissolving for 15min, then heating the temperature of the reactor to 50 ℃ at the speed of 3 ℃/min, preserving heat for 30min, continuously heating to 70 ℃ at the speed of 5 ℃/min, and reacting at 70 ℃ to the end point to obtain a polycondensation product.
Comparative example 7
The comparative example provides a phenolic resin which comprises the following raw materials in parts by weight: 52 parts of phenol, 127 parts of formaldehyde, 6 parts of barium hydroxide octahydrate, 5 parts of urea, 8 parts of water and 2 parts of 37% sulfuric acid solution.
(1) Adding phenol water solution, formaldehyde and barium hydroxide octahydrate into a reactor simultaneously, stirring and mixing, heating the reactor to 50 ℃ at the speed of 3 ℃/min, preserving heat for 60min, continuously heating to 70 ℃ at the speed of 5 ℃/min, and reacting at 70 ℃ to the end point to obtain a polycondensation product;
(2) Regulating the pH value of the polycondensation product to 7.5-8.0, adding urea, and stirring for 30min until the urea is completely dissolved to obtain phenolic resin;
(3) And (3) placing the phenolic resin liquid into a resin storage tank for storage, controlling the storage temperature to be lower than 25 ℃, and checking the phenolic resin according to the enterprise internal control standard, wherein the phenolic resin can be used after the phenolic resin is checked to be qualified.
Product performance verification
In order to verify the physical and chemical properties of the phenolic resin adhesives of examples 1 to 3 and comparative examples 1 to 7, the solid content, water solubility, viscosity, curing time, free phenol content, free aldehyde content, water resistance and the like were measured, respectively, and the measurement results are shown in Table 1.
TABLE 1
As shown in Table 1, the phenolic resin adhesive prepared by the invention meets the performance requirement standard of the adhesive in the preparation process of rock wool in the factory, has good adhesive performance and moderate curing time, and the free phenol and free formaldehyde contents are obviously lower than the market binder standard, so that the product performance is excellent and the yield is high.
As is clear from examples 1 and comparative examples 1 to 2, the addition amount of urea in the present invention has a large influence on the free aldehyde content and viscosity of the phenolic resin, and the proper urea addition amount can also improve the stability and flame retardant property of the phenolic resin, if the urea addition amount is too small, the free aldehyde content in the phenolic resin will be significantly improved, the use requirement of rock wool cannot be met, the viscosity, curing time, solid content and the like can not be met, the yield of the phenolic resin is low, and when the urea addition amount is too large, each performance index meets the use requirement, but based on the cost consideration, the urea addition amount is preferably 2 to 8 parts.
As is clear from examples 1 and 3, the refractive index measurement of the phenolic resin product during mixing and stirring of formaldehyde and phenol has a great influence on the refractive index of the phenolic resin product, and the content of free phenol and free aldehyde can reach the use standard if the refractive index is not monitored, but the content is obviously higher than that of example 1, and the raw material utilization rate is lower.
As can be seen from example 1 and comparative examples 4 to 6, the staged heating reaction after adding the catalyst in the invention has larger influence on the solid content, curing time, viscosity, free phenol content and free aldehyde content of the phenolic resin, and can not meet the requirements of rock wool production in the factory, so that the heating reaction condition after adding the catalyst in the preparation process of the phenolic resin is required to be strictly controlled, and the yield is improved while the performances of the phenolic resin are improved.
As can be seen from examples 1 and 7, comparative example 7 is a one pot process for preparing a phenolic resin, which has a solid content, refractive index, and curing time as compared with the process for preparing a phenolic resin of the present invention. The viscosity and the like can not meet the standard requirements, and the yield is low, so that the method for firstly mixing formaldehyde and phenol and then adding the catalyst can obviously improve various performances of the phenolic resin.
In the description of the present specification, reference to the terms "one embodiment," "another embodiment," "yet another embodiment," "some embodiments," "other embodiments," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction. In addition, it should be noted that, in this specification, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. The phenolic resin is characterized by comprising the following raw materials in parts by weight: 45-60 parts of phenol, 100-150 parts of formaldehyde, 2-10 parts of catalyst, 2-8 parts of urea and 5-15 parts of water.
2. The phenolic resin of claim 1, further comprising 1-5 parts of a dilute acid solution, wherein the dilute acid solution is any one of dilute sulfuric acid, dilute hydrochloric acid, and dilute nitric acid.
3. The phenolic resin of claim 1, wherein the catalyst comprises any one or more of potassium hydroxide, sodium hydroxide, barium hydroxide, calcium oxide, magnesium oxide.
4. A process for the preparation of a phenolic resin as claimed in any one of claims 1 to 3, comprising the steps of:
(1) Adding phenol and formaldehyde into a reactor, stirring and mixing, and measuring the refractive index;
(2) Adding a catalyst into a reactor, stirring and dissolving, and carrying out polymerization under the heating condition to obtain a polycondensation product;
(3) And regulating the pH value of the polycondensation product, and then adding urea, and stirring until the urea is completely dissolved to obtain the phenolic resin.
5. The method of producing phenolic resin according to claim 4, wherein step (1) is specifically:
adding phenol water solution and formaldehyde into a reactor, stirring for 5-10min, sampling, measuring and adjusting the refractive index to a first preset value;
tap water is continuously added into the reaction kettle, the mixture is stirred for 5 to 10 minutes, then sampling measurement is carried out, and the refractive index is regulated to a second preset value.
6. The method of producing a phenolic resin according to claim 5, wherein the first preset value is 1.4200 ±0.0030; if the sampling measured value is higher than the first preset value, adjusting the refractive index to the first preset value by adding formaldehyde; if the sampling measured value is lower than the first preset value, adjusting the refractive index to the first preset value by adding phenol;
and/or the second preset value is 1.4158 +/-0.0030; if the sampling measured value is higher than the second preset value, adding water to adjust the refractive index to the second preset value; and if the sampling measurement value is lower than the second preset value, adjusting the refractive index to the second preset value by adding phenol.
7. The method of producing a phenolic resin according to claim 4, wherein the heating conditions in step (2) are specifically:
heating the temperature of the reactor to 45-55 ℃ at a speed of 1-5 ℃/min, and preserving heat for 40-80min; then heating to 65-75 ℃ at a speed of 3-6 ℃/min, and reacting to an end point at 65-75 ℃.
8. The method for producing a phenol resin according to claim 7, wherein the method for determining the reaction end point is as follows: taking a measurement sample from the reactor, cooling to below 25 ℃, adding hydrochloric acid solution, and judging the reaction as a reaction end point if milky turbidity appears in 30 seconds;
and/or the volume ratio of the assay to the hydrochloric acid solution is (2-3): (15-50), and the concentration of the hydrochloric acid solution is 1mol/L.
9. The method for producing a phenol resin according to claim 8, wherein when the polymerization reaction reaches the end, the reaction is stopped by cooling the reactor to 25 ℃ or lower.
10. The method of producing a phenolic resin according to claim 4, wherein the pH of the polycondensation product is adjusted to 7.5 to 8.0 by a dilute acid solution in step (3);
and/or the stirring time is 20-40min.
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| CN121554627A (en) * | 2026-01-23 | 2026-02-24 | 成都博高合成材料有限公司 | End point control method for polymerization reaction of hydroxy acrylic resin and application thereof |
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| CN110092878A (en) * | 2019-05-06 | 2019-08-06 | 西北永新涂料有限公司 | The preparation method of aqueous rock wool glue phenolic resin |
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| SU852884A1 (en) * | 1979-12-18 | 1981-08-07 | Всесоюзный Научно-Исследовательскийинститут Теплоизоляционных И Акусти-Ческих Строительных Материалов И Из-Делий | Method of preparing phenolformaldehyde resins for making mineral wool articles |
| US4757108A (en) * | 1986-06-18 | 1988-07-12 | Borden, Inc. | Water soluble phenolic resole-urea composition |
| CN101177471A (en) * | 2007-12-12 | 2008-05-14 | 谢建军 | Method for producing phenol resin |
| CN105601859A (en) * | 2016-01-19 | 2016-05-25 | 宜兴市宇球保温材料有限公司 | Water-soluble phenol-formaldehyde resin glue for rock wool and preparation method thereof |
| CN110092878A (en) * | 2019-05-06 | 2019-08-06 | 西北永新涂料有限公司 | The preparation method of aqueous rock wool glue phenolic resin |
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| CN121554627A (en) * | 2026-01-23 | 2026-02-24 | 成都博高合成材料有限公司 | End point control method for polymerization reaction of hydroxy acrylic resin and application thereof |
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