CN111978497B - Preparation method, product and application of semi-solid thermosetting phenolic resin - Google Patents
Preparation method, product and application of semi-solid thermosetting phenolic resin Download PDFInfo
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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
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
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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
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
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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
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
- C08G8/22—Resorcinol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
Abstract
The application relates to a preparation method, a product and application of a semi-solid thermosetting phenolic resin, wherein the preparation method comprises the following steps: 1) adding phenol, paraformaldehyde and an alkali catalyst into a reaction kettle, heating, stirring and heating to 60-70 ℃, adding a first batch of resorcinol, heating to 70-80 ℃, starting to dropwise add an aldehyde aqueous solution, and carrying out a first-stage constant-temperature reaction; 2) cooling to 60-70 ℃, adding a second batch of resorcinol and paraformaldehyde, heating to 75-80 ℃, and continuing to perform constant-temperature reaction; 3) after the aldehyde aqueous solution in the step 1) is completely dripped, heating to 80-105 ℃ for second-stage constant-temperature reaction. The preparation method regulates and controls the reaction trend of phenols and aldehydes by sectional temperature control, the obtained thermosetting phenolic resin can be cured without overhigh temperature, has short curing time, high curing speed and certain fluidity, and can be used as the adhesive of phenolic molding plastic required by special industries such as precise electric appliances, instruments and meters.
Description
Technical Field
The application relates to the field of phenolic resin synthesis, in particular to a preparation method, a product and application of a semi-solid thermosetting phenolic resin.
Background
The traditional phenolic moulding plastic manufacturing process adopts a two-step method, and most of the phenolic moulding plastic needs to be added with a curing agent. The two-step process is to refine and form the phenolic moulding plastic by using thermoplastic phenolic resin as a binder and adding inorganic or organic fillers, curing agents, curing accelerators, lubricants, colorants, plasticizers and the like.
However, since the phenol novolac resin contains no or very little methylol groups, it is only melted upon heating and does not cure. Therefore, the curing of phenolic molding compounds generally requires the addition of hexamethylenetetramine, i.e., urotropin, as a curing agent. On heating, hexamethylenetetramine decomposes to release small amounts of ammonia, most of which volatilizes at high temperature, but still remains in the form of free ammonia in the part, which is slowly released during use of the part.
In general, the trace ammonia gas does not affect the use of the parts, but in the industry of electronic instruments and meters, phenolic molding compounds are often used as structural bodies of instruments and meters, and the structural bodies generally have metal components and electrical contacts, so that even if the ammonia gas is in a small amount, the metal components and the electrical contacts are corroded after long-time contact, the safety and the reliability of the instruments and meters are seriously affected, and the service life of the instruments and meters is greatly reduced. The use of the common phenolic moulding plastic in the industries of manufacturing precise electric appliances, instruments and the like is limited, so that the development of the ammonia-free phenolic moulding plastic can meet the special requirements of special industries.
Disclosure of Invention
Therefore, it is necessary to provide a method for preparing a semi-solid thermosetting phenolic resin aiming at the technical problem that phenolic resin and hexamethylenetetramine are required to be added in the preparation of the existing phenolic moulding compound.
The technical scheme provided by the invention is as follows:
a preparation method of a semi-solid thermosetting phenolic resin comprises the following steps:
1) adding phenol, paraformaldehyde and an alkali catalyst into a reaction kettle, heating, stirring and heating to 60-70 ℃, adding a first batch of resorcinol, heating to 70-80 ℃, starting to dropwise add an aldehyde aqueous solution, and carrying out a first-stage constant-temperature reaction;
2) cooling to 60-70 ℃, adding a second batch of resorcinol and paraformaldehyde, heating to 75-80 ℃, and continuing to perform constant-temperature reaction;
3) after the aldehyde aqueous solution in the step 1) is completely dripped, heating to 80-105 ℃ for second-stage constant-temperature reaction.
In the invention, the reaction trend of phenols and aldehydes is regulated and controlled by sectional temperature control, and the phenolic reaction process can be divided into two steps of addition reaction and polycondensation reaction. Wherein, the addition reaction means that when the aldehyde phenol is reacted, ortho-position and para-position of phenolic hydroxyl group are substituted to generate a plurality of hydroxymethyl phenols, and a mixture of monohydric phenol alcohol and polyhydric phenol alcohol is formed. The polycondensation reaction mainly refers to the polycondensation reaction of hydroxymethyl compounds, namely monohydric phenol alcohol, polyhydric phenol alcohol or dimer and the like are subjected to continuous polycondensation reaction under certain conditions, so that the relative molecular weight of the resin is continuously increased, and a network structure is gradually formed to obtain the thermosetting resin.
Several alternatives are provided below, but not as an additional limitation to the above general solution, but merely as a further addition or preference, each alternative being combinable individually for the above general solution or among several alternatives without technical or logical contradictions.
Preferably, the alkali catalyst is selected from one or more of ammonia water, triethylamine, barium hydroxide and metal oxide.
Preferably, the alkali catalyst is a composite alkali catalyst, and comprises ammonia water and magnesium oxide.
Preferably, the phenol in the step 1) is one or more selected from phenol, m-cresol, cardanol, resorcinol, bisphenol A and p-cresol.
Preferably, the aqueous aldehyde solution in the step 1) is an aqueous formaldehyde solution.
Preferably, the reaction time of the first-stage isothermal reaction in the step 1) is 1-1.5 h.
Preferably, the reaction time of the isothermal reaction in the step 2) is 0.5-1 h.
Preferably, the reaction time of the second-stage isothermal reaction in the step 3) is 1-3 h.
Preferably, the preparation method of the semi-solid thermosetting phenolic resin comprises the following steps:
1) adding 530-550 g of phenol, 5-6 g of paraformaldehyde and an alkali catalyst into a reaction kettle, heating, stirring and heating to 60-70 ℃, adding a first batch of 25-35 g of resorcinol, heating to 70-80 ℃, starting to dropwise add 590-600 g of formaldehyde solution, and carrying out a first-stage constant-temperature reaction; the mass fraction of the formaldehyde aqueous solution is 35-40 wt%;
2) cooling to 60-70 ℃, adding a second batch of 25-35 g of resorcinol and 5-6 g of paraformaldehyde, heating to 75-80 ℃, and continuing to perform constant-temperature reaction;
3) after the aldehyde aqueous solution in the step 1) is completely dripped, heating to 80-105 ℃ for second-stage constant-temperature reaction.
Preferably, the preparation method of the semi-solid thermosetting phenolic resin comprises the following steps:
1) adding 530-550 g of phenol, 5-6 g of paraformaldehyde and 35-60 g of ammonia water solution into a reaction kettle, heating and stirring to raise the temperature to 60-70 ℃, adding a first batch of 25-35 g of resorcinol, raising the temperature to 70-80 ℃, starting to dropwise add 590-600 g of formaldehyde water solution, and carrying out a first-stage constant-temperature reaction; the mass fraction of the formaldehyde aqueous solution is 35-40 wt%;
2) cooling to 60-70 ℃, adding a second batch of 25-35 g of resorcinol and 5-6 g of paraformaldehyde, heating to 75-80 ℃, and continuing to perform constant-temperature reaction;
3) after the aldehyde aqueous solution in the step 1) is completely dripped, heating to 80-105 ℃ for second-stage constant-temperature reaction.
Preferably, the preparation method of the semi-solid thermosetting phenolic resin comprises the following steps:
1) adding 530-550 g of phenol, 5-6 g of paraformaldehyde, 35-50 g of ammonia water solution and 10-12 g of magnesium oxide into a reaction kettle, heating and stirring to raise the temperature to 60-70 ℃, adding a first batch of 25-35 g of resorcinol, raising the temperature to 70-80 ℃, starting to dropwise add 590-600 g of formaldehyde water solution, and carrying out a first-stage constant-temperature reaction; the mass fraction of the formaldehyde aqueous solution is 35-40 wt%;
2) cooling to 60-70 ℃, adding a second batch of 25-35 g of resorcinol and 5-6 g of paraformaldehyde, heating to 75-80 ℃, and continuing to perform constant-temperature reaction;
3) after the aldehyde aqueous solution in the step 1) is completely dripped, heating to 80-105 ℃ for second-stage constant-temperature reaction.
The invention also provides the semi-solid thermosetting phenolic resin prepared by the preparation method.
The invention also provides application of the semi-solid thermosetting phenolic resin in preparation of low-temperature curing phenolic molding plastic.
The invention has the following beneficial effects:
(1) the phenolic resin obtained by the preparation method is thermosetting phenolic resin, does not need to add a curing agent urotropine, can be self-cured without overhigh temperature, and has small damage to the service life and the performance of a product.
(2) The thermosetting phenolic resin obtained by the preparation method is in a thermosetting state or a semi-solid state, is more convenient to transport, transfer and store than a liquid state, has high transport efficiency, and is convenient for process blending and processing molding.
(3) The preparation method regulates and controls the reaction trend of phenols and aldehydes by sectional temperature control, the obtained thermosetting phenolic resin can be cured without overhigh temperature, has short curing time, high curing speed and certain fluidity, and can be used as the adhesive of phenolic molding plastic required by special industries such as precise electric appliances, instruments and meters.
Detailed Description
For the convenience of understanding, the present invention will be described below by way of examples. It will be understood by those skilled in the art that the examples are merely for the purpose of further illustrating the invention and should not be taken as limiting the invention in any way, as many variations and modifications of the invention are possible without departing from the scope of the invention and are intended to be covered thereby.
Example 1
(1) 540 g of phenol, 5.78g of paraformaldehyde and 35.36g of ammonia water solution are sequentially added into a reaction kettle provided with a stirrer, a thermometer, a vacuum meter, a condensing and refluxing device and a heating and cooling device, wherein the paraformaldehyde not only participates in the reaction and plays a role of a curing agent to a certain extent, a small amount of paraformaldehyde is added to be beneficial to reducing the curing temperature, the curing efficiency is improved, the curing time is shortened, and excessive addition is not beneficial to reaction control and cost increase. Heating and stirring to uniformly mix the raw materials, adding a first batch of 30g of resorcinol when the temperature rises to 65 ℃, slowly raising the temperature, starting to dropwise add 594g of 37 wt% of formaldehyde aqueous solution when the temperature rises to 73-78 ℃, carrying out a first-stage reaction, wherein the first-stage reaction mainly comprises small molecule addition reaction, the constant-temperature reaction time is 1.0-1.5 hours, cooling to 65 ℃, adding a second batch of 30g of resorcinol and 5.78g of paraformaldehyde, raising the temperature to 75-78 ℃, continuing the constant-temperature reaction for 0.5-1.0 hours, and adopting the dropwise adding form of the formaldehyde aqueous solution to mainly carry out the addition reaction in the stage to form a mixture of monohydric phenol alcohol and polyhydric phenol alcohol. As the formaldehyde content increases, a small portion of the polycondensation reaction occurs while the addition reaction occurs.
(2) After the formaldehyde aqueous solution is completely dripped, the temperature is raised to 85 ℃ for the second stage reaction, and in the stage, the monohydric phenol alcohol and the polyhydric phenol alcohol are continuously subjected to polycondensation reaction under the conditions of heating and alkalinity, so that the relative molecular mass of the resin is increased, and a cross-linked network is formed. And (3) carrying out constant-temperature reaction for 1.5-2.5 hours, and dehydrating to obtain the phenolic resin.
Example 2
(1) 540 g of phenol, 5.78g of paraformaldehyde and 35.36g of ammonia solution are sequentially added into a reaction kettle provided with a stirrer, a thermometer, a vacuum meter, a condensing and refluxing device and a heating and cooling device, the mixture is heated and stirred, the temperature is slowly raised, a first batch of 30g of resorcinol is added when the temperature is raised to 65 ℃, the temperature is slowly raised to 73-78 ℃, 594g of 37 wt% formalin is dropwise added for a first-stage reaction, the reaction in the stage is mainly a small molecule addition reaction, the constant-temperature reaction time is 1.0-1.5 hours, a second batch of 30g of resorcinol and 5.78g of paraformaldehyde are added after the temperature is lowered to 65 ℃, the temperature is raised to 75-78 ℃, and the constant-temperature reaction is continued for 0.5-1.0 hour.
(2) After the formaldehyde aqueous solution is completely dripped, the temperature is raised to 90 ℃ for the second stage reaction, and in the stage, the monohydric phenol alcohol and the polyhydric phenol alcohol are continuously subjected to polycondensation reaction under the conditions of heating and alkalinity, so that the relative molecular mass of the resin is increased, and a cross-linked network is formed. And (3) carrying out constant-temperature reaction for 1.5-2.5 hours, and dehydrating to obtain the phenolic resin.
Example 3
(1) 540 g of phenol, 5.78g of paraformaldehyde and 46.67g of ammonia water solution are sequentially added into a reaction kettle provided with a stirrer, a thermometer, a vacuum meter, a condensing and refluxing device and a heating and cooling device, the mixture is heated and stirred, the temperature is slowly increased, a first batch of 30g of resorcinol is added when the temperature is increased to 65 ℃, the temperature is slowly increased to 73-78 ℃, 594g of 37 wt% formalin is dropwise added for a first-stage reaction, the reaction in the stage is mainly a small molecule addition reaction, the constant-temperature reaction time is 1.0-1.5 hours, a second batch of 30g of resorcinol and 5.78g of paraformaldehyde are added after the temperature is reduced to 65 ℃, the temperature is increased to 75-78 ℃, and the constant-temperature reaction is continued for 0.5-1.0 hour.
(2) After the formaldehyde aqueous solution is completely dripped, the temperature is raised to 90 ℃ for the second stage reaction, and in the stage, the monohydric phenol alcohol and the polyhydric phenol alcohol are continuously subjected to polycondensation reaction under the conditions of heating and alkalinity, so that the relative molecular mass of the resin is increased, and a cross-linked network is formed. And (3) carrying out constant-temperature reaction for 1.5-2.5 hours, and dehydrating to obtain the phenolic resin.
Example 4
(1) 540 g of phenol, 5.78g of paraformaldehyde and 52.33g of ammonia solution are sequentially added into a reaction kettle provided with a stirrer, a thermometer, a vacuum meter, a condensing and refluxing device and a heating and cooling device, the mixture is heated and stirred, the temperature is slowly increased, the first 30g of resorcinol is added when the temperature is increased to 65 ℃, the temperature is slowly increased to 73-78 ℃, 594g of 37 wt% formaldehyde aqueous solution is dropwise added to carry out the first stage reaction, the reaction in the stage mainly comprises small molecule addition reaction, the constant temperature reaction time is 1.0-1.5 hours, the second 30g of resorcinol and 5.78g of paraformaldehyde are added after the temperature is reduced to 65 ℃, the temperature is increased to 75-78 ℃, and the constant temperature reaction is continued for 0.5-1.0 hour.
(2) After the formaldehyde aqueous solution is completely dripped, the temperature is raised to 90 ℃ for the second stage reaction, and in the stage, the monohydric phenol alcohol and the polyhydric phenol alcohol are continuously subjected to polycondensation reaction under the conditions of heating and alkalinity, so that the relative molecular mass of the resin is increased, and a cross-linked network is formed. And (3) carrying out constant-temperature reaction for 1.5-2.5 hours, and dehydrating to obtain the phenolic resin.
Example 5
(1) 540 g of phenol, 5.78g of paraformaldehyde and 56.57g of ammonia solution are sequentially added into a reaction kettle provided with a stirrer, a thermometer, a vacuum meter, a condensing and refluxing device and a heating and cooling device, the mixture is heated and stirred, the temperature is slowly raised, a first batch of 30g of resorcinol is added when the temperature is raised to 65 ℃, the temperature is slowly raised to 73-78 ℃, 594g of 37 wt% formaldehyde aqueous solution is dropwise added to carry out a first-stage reaction, the reaction in the stage is mainly small molecule addition reaction, the constant-temperature reaction time is 1.0-1.5 hours, a second batch of 30g of resorcinol and 5.78g of paraformaldehyde are added after the temperature is lowered to 65 ℃, the temperature is raised to 75-78 ℃, and the constant-temperature reaction is continued for 0.5-1.0 hour.
(2) After the formaldehyde aqueous solution is completely dripped, the temperature is raised to 90 ℃ for the second stage reaction, and in the stage, the monohydric phenol alcohol and the polyhydric phenol alcohol are continuously subjected to polycondensation reaction under the conditions of heating and alkalinity, so that the relative molecular mass of the resin is increased, and a cross-linked network is formed. And (3) carrying out constant-temperature reaction for 1.5-2.5 hours, and dehydrating to obtain the phenolic resin.
Example 6
(1) 540 g of phenol, 5.78g of paraformaldehyde and 11.88g of magnesium oxide powder are sequentially added into a reaction kettle provided with a stirrer, a thermometer, a vacuum meter, a condensing and refluxing device and a heating and cooling device, the mixture is heated and stirred, the temperature is slowly increased, a first batch of 30g of resorcinol is added when the temperature is increased to 65 ℃, the temperature is slowly increased to 73-78 ℃, 594g of 37 wt% formalin is dropwise added for a first-stage reaction, the reaction in the stage is mainly a small molecule addition reaction, the constant-temperature reaction time is 1.0-1.5 hours, a second batch of 30g of resorcinol and 5.78g of paraformaldehyde are added after the temperature is reduced to 65 ℃, the temperature is increased to 75-78 ℃, and the constant-temperature reaction is continued for 0.5-1.0 hour.
(2) After the formaldehyde aqueous solution is completely dripped, the temperature is raised to 90 ℃ for the second stage reaction, and in the stage, the monohydric phenol alcohol and the polyhydric phenol alcohol are continuously subjected to polycondensation reaction under the conditions of heating and alkalinity, so that the relative molecular mass of the resin is increased, and a cross-linked network is formed. And (3) carrying out constant-temperature reaction for 1.5-2.5 hours, and dehydrating to obtain the phenolic resin.
Example 7
(1) 540 g of phenol, 5.78g of paraformaldehyde and 35.36g of ammonia water solution are sequentially added into a reaction kettle provided with a stirrer, a thermometer, a vacuum meter, a condensing and refluxing device and a heating and cooling device, 11.88g of magnesium oxide powder is added after stirring for 5 minutes, heating and stirring are carried out, the temperature is slowly increased, a first batch of 30g of resorcinol is added when the temperature is increased to 65 ℃, the temperature is slowly increased to 73-78 ℃, 594g of 37 wt% formaldehyde water solution is dropwise added to carry out a first-stage reaction, the first-stage reaction mainly comprises a micromolecule addition reaction, the constant-temperature reaction time is 1.0-1.5 hours, after the temperature is reduced to 65 ℃, a second batch of 30g of resorcinol and 5.78g of paraformaldehyde are added, the temperature is increased to 75-78 ℃, and the constant-temperature reaction is continued for 0.5-1.0 hour.
(2) After the formaldehyde is completely dripped, the temperature is raised to 90 ℃ for the second stage reaction, and in the stage, the monohydric phenol alcohol and the polyhydric phenol alcohol are continuously subjected to polycondensation reaction under the conditions of heating and alkalinity, so that the relative molecular mass of the resin is increased, and a cross-linked network is formed. And (3) carrying out constant-temperature reaction for 1.5-2.5 hours, and dehydrating to obtain the phenolic resin.
Example 8
(1) 540 g of phenol, 5.78g of paraformaldehyde and 46.67g of ammonia water solution are sequentially added into a reaction kettle provided with a stirrer, a thermometer, a vacuum meter, a condensing and refluxing device and a heating and cooling device, 11.88g of magnesium oxide powder is added after stirring for 5 minutes, heating and stirring are carried out, the temperature is slowly increased, a first batch of 30g of resorcinol is added when the temperature is increased to 65 ℃, the temperature is slowly increased to 73-78 ℃, 594g of 37 wt% formaldehyde water solution is dropwise added to carry out a first-stage reaction, the first-stage reaction mainly comprises a micromolecule addition reaction, the constant-temperature reaction time is 1.0-1.5 hours, after the temperature is reduced to 65 ℃, a second batch of 30g of resorcinol and 5.78g of paraformaldehyde are added, the temperature is increased to 75-78 ℃, and the constant-temperature reaction is continued for 0.5-1.0 hour.
(2) After the formaldehyde is completely dripped, the temperature is raised to 90 ℃ for the second stage reaction, and in the stage, the monohydric phenol alcohol and the polyhydric phenol alcohol are continuously subjected to polycondensation reaction under the conditions of heating and alkalinity, so that the relative molecular mass of the resin is increased, and a cross-linked network is formed. And (3) carrying out constant-temperature reaction for 1.5-2.5 hours, and dehydrating to obtain the phenolic resin.
Comparative example 1
PF-8203 solid thermoplastic resin for phenolic molding compound is commercially available.
Comparative example 2
(1) 570 g of phenol and 35.36g of ammonia water solution are sequentially added into a reaction kettle provided with a stirrer, a thermometer, a vacuum meter, a condensing and refluxing device and a heating and cooling device, the mixture is heated and stirred, the temperature is slowly raised, 625g of 37 wt% formaldehyde water solution is dropwise added into the mixture when the temperature is raised to 73-78 ℃ to carry out a first-stage reaction, the first-stage reaction is mainly a small molecule addition reaction, and the constant-temperature reaction time is 1.5-2 hours.
(2) After the formaldehyde aqueous solution is completely dripped, the temperature is raised to 85 ℃ for the second stage reaction, and in the stage, the monohydric phenol alcohol and the polyhydric phenol alcohol are continuously subjected to polycondensation reaction under the conditions of heating and alkalinity, so that the relative molecular mass of the resin is increased, and a cross-linked network is formed. And (3) carrying out constant-temperature reaction for 1.5-2.5 hours, and dehydrating to obtain the phenolic resin.
Comparative example 3
(1) 540 g of phenol and 35.36g of ammonia water solution are sequentially added into a reaction kettle provided with a stirrer, a thermometer, a vacuum meter, a condensing and refluxing device and a heating and cooling device, the mixture is heated and stirred, the temperature is slowly raised, 60g of resorcinol is added when the temperature is raised to 65 ℃, the temperature is slowly raised, the mixture is heated and stirred when the temperature is raised to 73-78 ℃, 625g of 37 wt% formaldehyde water solution is dropwise added into the mixture to carry out a first-stage reaction, the first-stage reaction is mainly a micromolecule addition reaction, and the constant temperature reaction time is 1.5-2 hours.
(2) After the formaldehyde aqueous solution is completely dripped, the temperature is raised to 85 ℃ for the second stage reaction, and in the stage, the monohydric phenol alcohol and the polyhydric phenol alcohol are continuously subjected to polycondensation reaction under the conditions of heating and alkalinity, so that the relative molecular mass of the resin is increased, and a cross-linked network is formed. And (3) carrying out constant-temperature reaction for 1.5-2.5 hours, and dehydrating to obtain the phenolic resin.
Basic performance test:
the test is carried out by adopting a ring and ball method, and the basic performances of the examples 1-8 and the comparative examples 1-3 are shown in the table 1:
TABLE 1 basic Performance test results
| Serial number | Softening point/. degree.C | Solids content/% | Residual carbon rate/%) |
| Example 1 | 60.5 | 93.53 | 54.23 |
| Example 2 | 65.0 | 92.87 | 54.45 |
| Example 3 | 62.0 | 93.52 | 55.34 |
| Example 4 | 62.25 | 93.63 | 54.55 |
| Example 5 | 65.25 | 92.39 | 54.7 |
| Example 6 | 57.5 | 93.68 | 56.24 |
| Example 7 | 56.25 | 93.55 | 55.88 |
| Example 8 | 56.5 | 92.97 | 55.82 |
| Comparative example 1 | 103.0 | 98.33 | 51.64 |
| Comparative example 2 | 65.5 | 90.76 | 51.51 |
| Comparative example 3 | 67.0 | 92.67 | 52.55 |
According to the test data, the phenolic resin and the preparation method thereof provided by the invention have the advantages of low softening point, high curing speed, high carbon residue rate, good fluidity during molding and processing, and are beneficial to processing and molding.
Claims (3)
1. The preparation method of the semi-solid thermosetting phenolic resin is characterized by comprising the following steps:
1) adding 530-550 g of phenol, 5-6 g of paraformaldehyde, 35.36-46.67 g of ammonia water solution and 10-12 g of magnesium oxide into a reaction kettle, heating, stirring and heating to 60-70 ℃, adding a first batch of 25-35 g of resorcinol, heating to 70-80 ℃, starting to dropwise add 590-600 g of formaldehyde water solution, and carrying out a first-stage constant-temperature reaction; the mass fraction of the formaldehyde aqueous solution is 35-40 wt%; the reaction time of the first-stage constant-temperature reaction is 1-1.5 h;
2) cooling to 60-70 ℃, adding a second batch of 25-35 g of resorcinol and 5-6 g of paraformaldehyde, heating to 75-80 ℃, and continuing constant-temperature reaction for 0.5-1 h;
3) after the aldehyde aqueous solution in the step 1) is completely dripped, heating to 80-105 ℃ for second-stage constant-temperature reaction, wherein the reaction time of the second-stage constant-temperature reaction is 1-3 h.
2. A semi-solid thermosetting phenol-formaldehyde resin prepared by the method of claim 1.
3. Use of a semi-solid thermosetting phenolic resin according to claim 2 in the preparation of a low temperature cured phenolic moulding compound.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61174214A (en) * | 1985-01-29 | 1986-08-05 | Sumitomo Deyurezu Kk | Production of phenolic resin |
| CN101597364A (en) * | 2009-06-30 | 2009-12-09 | 陕西师范大学 | The synthetic method of thermosetting phenol-formaldehyde resin in solid at normal temperature |
| CN102219883A (en) * | 2011-05-15 | 2011-10-19 | 山东莱芜润达化工有限公司 | Production method of solid-thermosetting phenolic resin |
| CN102585125A (en) * | 2012-02-17 | 2012-07-18 | 广州三则电子材料有限公司 | Method for preparing thermoset phenolic resin and method for preparing conductive slurry |
| CN102936322A (en) * | 2012-12-12 | 2013-02-20 | 江苏锋芒复合材料科技集团有限公司 | Thermosetting phenolic resin preparation method without wastewater discharge |
| CN103897125A (en) * | 2014-03-31 | 2014-07-02 | 山东圣泉化工股份有限公司 | Method for preparing thermosetting phenol resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4385470B2 (en) * | 1999-07-08 | 2009-12-16 | 住友ベークライト株式会社 | Synthesis method of phenolic resin |
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| JPS61174214A (en) * | 1985-01-29 | 1986-08-05 | Sumitomo Deyurezu Kk | Production of phenolic resin |
| CN101597364A (en) * | 2009-06-30 | 2009-12-09 | 陕西师范大学 | The synthetic method of thermosetting phenol-formaldehyde resin in solid at normal temperature |
| CN102219883A (en) * | 2011-05-15 | 2011-10-19 | 山东莱芜润达化工有限公司 | Production method of solid-thermosetting phenolic resin |
| CN102585125A (en) * | 2012-02-17 | 2012-07-18 | 广州三则电子材料有限公司 | Method for preparing thermoset phenolic resin and method for preparing conductive slurry |
| CN102936322A (en) * | 2012-12-12 | 2013-02-20 | 江苏锋芒复合材料科技集团有限公司 | Thermosetting phenolic resin preparation method without wastewater discharge |
| CN103897125A (en) * | 2014-03-31 | 2014-07-02 | 山东圣泉化工股份有限公司 | Method for preparing thermosetting phenol resin |
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