CN113045720B - Meta-xylene resin, preparation method thereof and insulating paint - Google Patents

Meta-xylene resin, preparation method thereof and insulating paint Download PDF

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CN113045720B
CN113045720B CN201911372898.4A CN201911372898A CN113045720B CN 113045720 B CN113045720 B CN 113045720B CN 201911372898 A CN201911372898 A CN 201911372898A CN 113045720 B CN113045720 B CN 113045720B
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xylene
resin
catalyst
sulfonic acid
paraformaldehyde
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CN113045720A (en
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唐磊
刘翠华
李枝芳
张瑜
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Shandong Shengquan New Material Co Ltd
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    • 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
    • C08G10/00—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only
    • C08G10/02—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only of aldehydes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/18—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or their halogen derivatives only
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints

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Abstract

The disclosure provides a m-xylene resin, a preparation method thereof and an insulating varnish. Wherein, the m-xylene resin is prepared by the polycondensation of raw materials including m-xylene and paraformaldehyde under the action of a catalyst; wherein the catalyst comprises an organic sulfonic acid catalyst; the oxygen content of the m-xylene resin is 3-10%, the viscosity is 200-4000 MPa.s, and the solid content is more than or equal to 90%; preferably, the oxygen content of the m-xylene resin is 4-9%, and the solid content is more than or equal to 94%. The method for preparing the m-xylene resin is simple, and the prepared m-xylene resin has moderate viscosity, low oxygen content, high resin yield, excellent insulating paint performance, smooth coating surface and no air bubbles.

Description

Meta-xylene resin, preparation method thereof and insulating paint
Technical Field
The disclosure belongs to the technical field of polymer preparation, and particularly relates to m-xylene resin for insulating paint, a preparation method of the m-xylene resin and insulating paint prepared from the m-xylene resin.
Background
In the preparation of xylene formaldehyde resin, sulfuric acid is generally used as a catalyst, and xylene and liquid formaldehyde are generally mixed for reaction. The mixed xylene contains about 40 percent of meta-xylene, in order to improve the conversion rate of the xylene, a large amount of concentrated sulfuric acid is needed to be used in the production process of the xylene, the reaction activity of formaldehyde and the xylene is enhanced under the condition of strong acid, the oxygen content of xylene resin prepared by the traditional process is 9 to 12 percent, and the viscosity of the resin is more than 20000 MPa.s.
The existing process method for preparing the xylene formaldehyde resin uses perchloric acid as a catalyst, the softening point of the xylene resin prepared by the process is at 110-200 ℃, the resin is solid, and the application is limited in normal-temperature mixing of other materials.
The existing m-xylene resin uses m-xylene and formaldehyde to carry out polycondensation reaction, and uses methanesulfonic acid as a catalyst, so that the resin with the oxygen content of 9-11% and the resin viscosity of less than or equal to 60MPa.s can be obtained, but the aim of reducing the active groups of the resin is not achieved.
Disclosure of Invention
In view of the defects of the prior art, one of the purposes of the present disclosure is to provide a meta-xylene resin, which is prepared by performing polycondensation reaction on raw materials comprising meta-xylene and paraformaldehyde under the action of a catalyst; wherein the catalyst comprises an organic sulfonic acid catalyst; the oxygen content of the m-xylene resin is 3-10%, the viscosity is 200-4000 MPa.s, and the solid content is more than or equal to 90%; preferably, the oxygen content of the m-xylene resin is 4-9%, and the solid content is more than or equal to 94%.
In some embodiments of the present disclosure, the organic sulfonic acid catalyst comprises one or more of toluene sulfonic acid, methyl sulfonic acid, benzene sulfonic acid.
In some embodiments of the present disclosure, the catalyst further comprises a phase transfer catalyst.
In some embodiments of the present disclosure, the phase transfer catalyst comprises one or more of tetrabutylammonium bromide, dodecyltrimethylammonium chloride, polyethers, quaternary phosphonium salts.
Further, the present disclosure also provides a method for preparing the above-mentioned metaxylene, comprising:
carrying out polycondensation reaction on raw materials comprising the m-xylene and the paraformaldehyde for 4-10 h at the temperature of 80-110 ℃ under the action of the catalyst; the catalyst comprises an organic sulfonic acid catalyst;
standing and layering after the polycondensation reaction is finished, and taking an upper-layer product;
adding calcium oxide and water into the upper-layer product to perform a neutralization reaction to obtain a resin clear solution;
and carrying out reduced pressure concentration on the resin clear liquid to obtain the m-xylene resin.
In some embodiments of the present disclosure, the catalyst further comprises a phase transfer catalyst; carrying out polycondensation reaction on the raw materials comprising the m-xylene and the paraformaldehyde at the temperature of 80-110 ℃ for 4-10 h under the action of the catalyst, wherein the polycondensation reaction comprises the following steps:
and carrying out polycondensation reaction on the raw materials comprising the m-xylene and the paraformaldehyde for 5-8 h at the temperature of 80-110 ℃ under the action of the organic sulfonic acid catalyst and the phase transfer catalyst.
In some embodiments of the present disclosure, the molar ratio of the meta-xylene to the paraformaldehyde is 1: (1-2), the dosage of the organic sulfonic acid catalyst is 5% -30% of the dosage of the m-xylene, the dosage of the phase transfer catalyst is 0-0.5% of the dosage of the m-xylene, the concentration of the paraformaldehyde is 90% -98%, and the concentration of the organic sulfonic acid catalyst is 50% -95%.
In some embodiments of the present disclosure, the molar ratio of meta-xylene to paraformaldehyde is 1: (1.2-1.8), the dosage of the organic sulfonic acid catalyst is 10-20% of the dosage of the m-xylene, the dosage of the phase transfer catalyst is 0-0.3% of the dosage of the m-xylene, and the concentration of the organic sulfonic acid catalyst is 50-80%.
In some embodiments of the present disclosure, the method further comprises:
and (3) separating, concentrating and recovering the lower-layer catalyst obtained by standing and layering after the polycondensation reaction is finished.
In addition, the present disclosure also provides an insulating varnish comprising the above-mentioned m-xylene.
The method for preparing the m-xylene resin is simple, the reaction activity time of the prepared m-xylene resin and epoxy is controlled to be 15-40 minutes, the subsequent insulating paint production process can be controlled, and time is not wasted. In addition, the m-xylene resin disclosed by the invention is moderate in viscosity, low in oxygen content and high in resin yield, can be used for preparing automobile electrophoresis insulating paint, anticorrosion insulating paint and the like, is excellent in insulating paint performance, and the coating surface of an insulating paint product is smooth and free of bubbles.
Additional aspects and advantages of the disclosure will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the disclosure.
Detailed Description
The technical solutions of the present disclosure will be described below clearly and completely with reference to embodiments, and it should be apparent that the described embodiments are some, but not all embodiments of the present disclosure. All other embodiments, which can be derived by a person skilled in the art from the embodiments disclosed herein without making any creative effort, shall fall within the protection scope of the present disclosure.
The terms "including" and "having," as well as any variations thereof, of the present disclosure are intended to cover non-exclusive inclusions. For example, a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to only those steps or elements listed, but may alternatively include other steps or elements not listed, or inherent to such process, method, article, or apparatus.
Reference in the present disclosure to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the present disclosure. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. One skilled in the art will explicitly and implicitly appreciate that the embodiments described in this disclosure can be combined with other embodiments.
In addition, the process conditions taken in the following examples are all exemplary, and the applicable ranges are shown in the foregoing summary, and for the process parameters not particularly noted, the conventional techniques can be referred to. The detection methods used in the following examples are all conventional in the industry. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. All reagents or instruments are conventional products which are not indicated by the manufacturer and are commercially available.
The disclosure firstly provides a m-xylene resin, which is prepared by carrying out polycondensation reaction on m-xylene and paraformaldehyde under the action of an organic sulfonic acid catalyst; wherein the oxygen content of the m-xylene resin is 4-9%, the viscosity is 200-4000 MPa.s, and the solid content is more than or equal to 94%.
The paraformaldehyde disclosed by the disclosure refers to solid formaldehyde, and the molecular weight of the solid formaldehyde is the same as that of the formaldehyde.
The organic sulfonic acid catalyst is used as a catalyst for the polycondensation reaction, and the catalyst is strong non-oxidizing acid, so that the oxidation of resin in the reaction process can be reduced, and the chroma of the resin is lower. Optionally, the organic sulfonic acid catalyst comprises one or more of toluene sulfonic acid, methyl sulfonic acid, benzene sulfonic acid.
The meta-xylene resin prepared by the method disclosed by the invention is relatively low in oxygen content, moderate in viscosity and mild in reactivity. Alternatively, m-xylene resin is used to react with epoxy resin to make an insulating varnish. The viscosity of the insulating paint is directly influenced by the viscosity of the m-xylene resin, the viscosity of the insulating paint is small and uneven due to too low viscosity, and the viscosity of the insulating paint is large, thick and poor in leveling property due to the large viscosity of the m-xylene resin. The reaction activity is influenced by the oxygen content of the m-xylene, the higher the oxygen content is, the higher the reaction activity of the m-xylene resin and the epoxy resin is, in the coating process of the insulating paint, a solvent in the insulating paint cannot be fully volatilized, if the reaction speed is higher than the volatilization speed of the solvent, the solvent is coated in the insulating paint, and the insulating paint can generate the foaming problem; if the oxygen content is too low, the reaction crosslinking degree of the m-xylene resin and the epoxy resin is low, and the effect cannot be achieved, and the oxygen content of the m-xylene resin used must be controlled within a certain range.
In the method, because the oxygen content of the m-xylene resin is moderate, the reaction process is mild in the process of preparing the insulating paint by reacting with the epoxy resin, and the solvent is thoroughly volatilized in the coating process, so that the foaming problem caused by the high-viscosity high-activity resin can be avoided.
The m-xylene resin provided by the disclosure can also be prepared by performing polycondensation reaction on m-xylene and paraformaldehyde under the action of an organic sulfonic acid catalyst and a phase transfer catalyst.
In the disclosure, the phase transfer catalyst is a cocatalyst of the polycondensation reaction, the preparation reaction of the m-xylene resin belongs to the heterogeneous reaction, and the addition of the phase transfer catalyst can accelerate the heterogeneous reaction rate and is beneficial to the improvement of the resin yield. Optionally, the phase transfer catalyst comprises one or more of tetrabutylammonium bromide, dodecyltrimethylammonium chloride, polyether, and quaternary phosphonium salt.
The present disclosure further provides a method of preparing the above-described metaxylene resin, comprising the steps of:
(1) under the action of organic sulfonic acid catalyst, m-xylene and paraformaldehyde are subjected to polycondensation reaction at 80-110 ℃ for 4-10 h.
Wherein, the mol ratio of the m-xylene to the paraformaldehyde can be selected from 1: (1-2), more preferably 1: (1.2-1.8). The molar ratio of meta-xylene to paraformaldehyde of the present disclosure affects the oxygen content of the final product.
Wherein, the amount of the organic sulfonic acid catalyst is 5-30% of the amount of the m-xylene, and preferably 10-20%.
Wherein, the concentration of the organic sulfonic acid catalyst is 50 to 95 percent. The dosage and concentration of the catalyst affect the viscosity of the resin, the dosage of the catalyst is more, the concentration is higher, the viscosity of the resin is higher, and conversely, the viscosity of the resin is lower.
Wherein, the concentration of the paraformaldehyde can be 90-98%.
In the disclosure, the adding mode of each raw material is not limited, and the raw materials can be added all at one time or fed for multiple times in batches, and the adding mode is set according to the actual situation.
(2) And standing for layering after the polycondensation reaction is finished, and taking an upper-layer product.
And standing for layering to obtain an upper product which is a resin layer and a lower product which is a catalyst layer.
(3) And adding calcium oxide and water into the upper-layer product to perform a neutralization reaction to obtain a resin clear solution.
In the present disclosure, the amount of calcium oxide added is not particularly limited as long as the material is neutralized to neutrality, and the amount of water used is also not particularly limited as long as the neutralized product is washed away.
(4) And concentrating the resin clear solution under reduced pressure to obtain the m-xylene resin.
And carrying out reduced pressure concentration under the vacuum condition, and removing m-xylene to obtain the m-xylene resin.
The preparation method provided by the disclosure is very simple and is very easy to industrialize.
The present disclosure provides another method for preparing the above-mentioned m-xylene resin, comprising the steps of:
(1) carrying out polycondensation reaction on m-xylene and paraformaldehyde at the temperature of 80-110 ℃ for 4-10 h under the action of an organic sulfonic acid catalyst and a phase transfer catalyst.
Wherein, the molar ratio of the m-xylene to the paraformaldehyde, the dosage of the organic sulfonic acid catalyst, the concentration of the organic sulfonic acid catalyst and the concentration range of the paraformaldehyde are consistent with the previous description, and are not repeated herein.
The amount of the phase transfer catalyst can be 0-0.5% of the amount of the m-xylene, and preferably, the amount of the phase transfer catalyst is 0-0.3% of the amount of the m-xylene.
(2) And standing for layering after the polycondensation reaction is finished, and taking an upper-layer product.
After standing and layering, the upper product is a resin layer, and the lower product is a catalyst layer.
(3) And adding calcium oxide and water into the upper-layer product to perform a neutralization reaction to obtain a resin clear solution.
The amounts of calcium oxide and water added are the same as before and are not described further herein.
(4) And concentrating the resin clear solution under reduced pressure to obtain the m-xylene resin.
And carrying out reduced pressure concentration under the vacuum condition, and removing m-xylene to obtain the m-xylene resin.
(5) And (3) separating, concentrating and recovering the lower-layer catalyst obtained by standing and layering after the polycondensation reaction is finished.
The present disclosure further provides an insulating varnish prepared from the above-described m-xylene resin. The insulating paint disclosed by the invention has excellent performance, and the coating surface of an insulating paint product is smooth and free of bubbles.
In the present disclosure, the testing method of the resin index is as follows:
measurement of oxygen content:
the method comprises the following operation steps: respectively weighing 50g of m-xylene resin, 50g of phenol (accurate to 0.02g), 100ml of toluene and 1ml of p-toluenesulfonic acid ethanol solution, placing the m-xylene resin, the phenol, the toluene and the p-toluenesulfonic acid ethanol solution into a three-necked bottle with a water separator, slowly heating to 100 ℃, separating water in the water separator, and weighing the total amount W of the separated water when the supernatant becomes clear.
Calculation of oxygen content: x ═ (16/18) × 2 × W
In the formula: x represents oxygen content; 16/18 is the oxygen content in water; 2 is a coefficient; w: quality of distilled water.
Solid content test:
accurately weighing 2 g-2.2 g of sample (accurately to 0.0001g), placing the sample in an aluminum foil box with the bottom diameter of 40mm, placing the sample in an oven with the temperature of 105 +/-1 ℃, drying for 1 hour, taking out and placing the sample in a dryer to cool to room temperature.
Calculation of solid content: solid content W 1 /W 0 ×100％
In the formula: w 1 Represents the mass of the sample after baking; w 0 Is the original sample mass
Measurement of viscosity:
the samples were directly placed in a viscosity cup of a rotational viscometer at 25 ℃ and tested 2 times, and the average value of the test results was the rotational viscosity of the resin at 25 ℃.
Testing of the reaction time with epoxy:
10g of sample is added into 10g of epoxy 828, 0.05g of imidazole is added, and after uniform stirring, 0.5g of mixed sample is placed in a gel tester to test the gel time at 180 ℃.
Calculation of resin yield:
yield is resin weight/m-xylene weight
And (3) testing the apparent performance of the prepared insulating paint:
a20 g sample was added to 100g epoxy 828, and 0.05g imidazole and 50g butanone were added to react at 120 ℃ for 60 minutes, followed by cooling to 40 ℃ or lower. The prepared material was coated to a paint film thickness of 2mm and placed in an oven at 150 ℃ for 30 minutes, with 10 replicates per sample. After curing, the surface of the paint film coated with the paint film is foamed to be N, and the surface which is not foamed to be Y.
Color intensity
Measured according to GBT22295-2008 transparent liquid color measurement method (Gardner color).
Preparation of meta-xylene resin
Example 1
318g of m-xylene, 97.8g of paraformaldehyde (with the concentration of 92 percent) and 47g of p-toluenesulfonic acid (prepared into an aqueous solution with the acid concentration of 80 percent) are added into a reaction bottle with a condenser, then the temperature is raised to 100 ℃, and the reflux reaction is carried out for 6 hours. The reaction mixture was allowed to stand for separation, and after the upper resin layer was neutralized with 150g of water and 3g of calcium oxide, the upper resin clear solution was concentrated under reduced pressure to obtain 254g of m-xylene resin. The lower catalyst layer was separated, concentrated and recovered.
The oxygen content, viscosity, solid content, reaction time with epoxy and resin yield of the obtained m-xylene resin were measured, and see table 1 for details.
Example 2
318g of m-xylene, 195.6g of paraformaldehyde (with the concentration of 92 percent) and 47g of p-toluenesulfonic acid (prepared into an aqueous solution with the acid concentration of 80 percent) are added into a reaction bottle with a condenser, then the temperature is raised to 100 ℃, and the reflux reaction is carried out for 6 hours. The reaction mixture was allowed to stand for separation, and after the upper resin layer was neutralized with 150g of water and 3g of calcium oxide, the upper resin clear solution was concentrated under reduced pressure to obtain 286g of m-xylene resin. The lower catalyst layer was separated, concentrated and recovered.
The oxygen content, viscosity, solid content, reaction time with epoxy and resin yield of the obtained m-xylene resin were measured, and see table 1 for details.
Example 3
318g of m-xylene, 146.7g of paraformaldehyde (the concentration of 92 percent) and 47g of p-toluenesulfonic acid (prepared into an aqueous solution with the acid concentration of 80 percent) are added into a reaction bottle with a condenser, then the temperature is raised to 100 ℃, and the reflux reaction is carried out for 6 hours. The reaction mixture was allowed to stand for layer separation, and after the upper resin layer was neutralized with 150g of water and 3g of calcium oxide, the upper resin clear solution was concentrated under reduced pressure to obtain 267g of m-xylene resin. The lower catalyst layer was separated, concentrated and recovered.
The oxygen content, viscosity, solid content, reaction time with epoxy and resin yield of the obtained m-xylene resin were measured, and see table 1 for details.
Example 4
318g of m-xylene, 146.7g of paraformaldehyde (the concentration of 92 percent) and 15.9g of p-toluenesulfonic acid (prepared into an aqueous solution with the acid concentration of 80 percent) are added into a reaction bottle with a condenser, then the temperature is raised to 95 ℃, and the reflux reaction is carried out for 6 hours. The reaction mixture was allowed to stand for separation, and after the upper resin layer was neutralized with 150g of water and 3g of calcium oxide, the upper resin clear solution was concentrated under reduced pressure to obtain 235.3g of m-xylene resin. The lower catalyst layer was separated, concentrated and recovered.
The oxygen content, viscosity, solid content, reaction time with epoxy and resin yield of the obtained m-xylene resin were measured, and see table 1 for details.
Example 5
318g of m-xylene, 146.7g of paraformaldehyde (the concentration of 92 percent) and 95.4g of p-toluenesulfonic acid (prepared into an aqueous solution with the acid concentration of 80 percent) are added into a reaction bottle with a condenser, then the temperature is raised to 100 ℃, and the reflux reaction is carried out for 3 hours. The reaction mixture was allowed to stand for separation, and after the upper resin layer was neutralized with 150g of water and 3g of calcium oxide, the upper resin clear solution was concentrated under reduced pressure to obtain 283g of m-xylene resin. The lower catalyst layer was separated, concentrated and recovered.
The oxygen content, viscosity, solid content, reaction time with epoxy and resin yield of the obtained m-xylene resin were measured, and see table 1 for details.
Example 6
318g of m-xylene, 146.7g of paraformaldehyde (the concentration is 92 percent) and 48g of p-toluenesulfonic acid (prepared into an aqueous solution with the acid concentration of 50 percent) are added into a reaction bottle with a condenser, and then the temperature is raised to 100 ℃ for reaction. The reaction was refluxed for 11 hours. The reaction mixture was allowed to stand for separation, and after the upper resin layer was neutralized with 150g of water and 3g of calcium oxide, the upper resin clear solution was concentrated under reduced pressure to obtain 223g of a m-xylene resin. The lower catalyst layer was separated, concentrated and recovered.
The oxygen content, viscosity, solid content, reaction time with epoxy and resin yield of the obtained m-xylene resin were measured, and see table 1 for details.
Example 7
318g of m-xylene, 146.7g of paraformaldehyde (the concentration of 92 percent) and 48g of p-toluenesulfonic acid (prepared into an aqueous solution with the acid concentration of 95 percent) are added into a reaction bottle with a condenser, then the temperature is raised to 100 ℃, and the reflux reaction is carried out for 4 hours. The reaction mixture was allowed to stand for separation, and after the upper resin layer was neutralized with 150g of water and 3g of calcium oxide, the upper resin clear solution was concentrated under reduced pressure to obtain 264g of a m-xylene resin. The lower catalyst layer was separated, concentrated and recovered.
The oxygen content, viscosity, solid content, reaction time with epoxy and resin yield of the obtained m-xylene resin were measured, and see table 1 for details.
Example 8
318g of m-xylene, 146.7g of paraformaldehyde (the concentration of 92 percent), 48g of p-toluenesulfonic acid (prepared into an aqueous solution with the acid concentration of 50 percent) and 0.3g of tetrabutylammonium bromide are added into a reaction bottle with a condenser, then the temperature is raised to 100 ℃, and the reflux reaction is carried out for 11 hours. The reaction mixture was allowed to stand for layer separation, and after the upper resin layer was neutralized with 150g of water and 3g of calcium oxide, the upper resin clear solution was concentrated under reduced pressure to obtain 257.6g of m-xylene resin. The lower catalyst layer was separated, concentrated and recovered.
The oxygen content, viscosity, solid content, reaction time with epoxy and resin yield of the obtained m-xylene resin were measured, and see table 1 for details.
Example 9
318g of m-xylene, 146.7g of paraformaldehyde (the concentration of which is 92 percent), 15.9g of p-toluenesulfonic acid (prepared into an aqueous solution with the acid concentration of 80 percent) and dodecyl trimethyl ammonium chloride are added into a reaction bottle with a condenser, and then the temperature is raised to 95 ℃ for reflux reaction for 6 hours. The reaction mixture was allowed to stand for layer separation, and after the upper resin layer was neutralized with 150g of water and 3g of calcium oxide, the upper resin clear solution was concentrated under reduced pressure to obtain 267g of m-xylene resin. The lower catalyst layer was separated, concentrated and recovered.
The oxygen content, viscosity, solid content, reaction time with epoxy and resin yield of the obtained m-xylene resin were measured, and see table 1 for details.
Comparative example 1
318g of mixed xylene, 243g of formaldehyde (concentration: 37%) and 84g of sulfuric acid (concentration: 98%) were put into a reaction flask equipped with a condenser, and then heated to 100 ℃ to conduct a reflux reaction for 10 hours. The reaction mixture was allowed to stand for separation, and after the upper resin layer was neutralized with 150g of water and 3g of calcium oxide, the upper resin clear solution was concentrated under reduced pressure to obtain 159g of a m-xylene resin. The lower catalyst layer was separated, concentrated and recovered.
The oxygen content, viscosity, solid content, reaction time with epoxy and resin yield of the obtained m-xylene resin were measured, and see table 1 for details.
Comparative example 2
318g of m-xylene, 215.2g of paraformaldehyde (the concentration of 92 percent) and 47.7g of p-toluenesulfonic acid (prepared into an aqueous solution with the acid concentration of 80 percent) are added into a reaction bottle with a condenser, then the temperature is raised to 95 ℃, and the reflux reaction is carried out for 8 hours. The reaction mixture was allowed to stand for separation, and after the upper resin layer was neutralized with 150g of water and 3g of calcium oxide, the upper resin clear solution was concentrated under reduced pressure to obtain 295.7g of m-xylene resin. The lower catalyst layer was separated, concentrated and recovered.
The oxygen content, viscosity, solid content, reaction time with epoxy and resin yield of the obtained m-xylene resin were measured, and see table 1 for details.
Comparative example 3
318g of m-xylene, 146.7g of paraformaldehyde (the concentration of 92 percent) and 127.2g of p-toluenesulfonic acid (prepared into an aqueous solution with the acid concentration of 80 percent) are added into a reaction bottle with a condenser, and then the temperature is raised to 95 ℃ for reaction. The reaction was refluxed for 5 hours. The reaction mixture was allowed to stand for separation, and after the upper resin layer was neutralized with 150g of water and 3g of calcium oxide, the upper resin clear solution was concentrated under reduced pressure to obtain 295.7g of m-xylene resin. The lower catalyst layer was separated, concentrated and recovered.
The oxygen content, viscosity, solid content, reaction time with epoxy and resin yield of the obtained m-xylene resin were measured, and see table 1 for details.
Figure BDA0002339586780000121
Figure BDA0002339586780000131
From examples 1 to 3, it is understood that when the same organic sulfonic acid catalyst is used, the oxygen content, viscosity, solid content and resin yield increase with the increase of the molar ratio of m-xylene to paraformaldehyde and the reaction activity time with epoxy decreases with the increase of the molar ratio of m-xylene to paraformaldehyde with a constant amount and concentration of the organic sulfonic acid catalyst.
From examples 3 to 5, it is understood that when the same organic sulfonic acid is used, the higher the amount of the organic sulfonic acid catalyst used, the higher the oxygen content, the viscosity, the solid content, the resin yield and the color when the concentration of the organic sulfonic acid is constant and the molar ratio of m-xylene to paraformaldehyde is constant.
From examples 6 to 7, it is understood that when the same type of organic sulfonic acid is used, the higher the concentration of the organic sulfonic acid is, the higher the viscosity, the time of the reaction with epoxy, the resin yield and the chromaticity are, and the lower the oxygen content and the solid content are, the higher the organic sulfonic acid is, the organic sulfonic acid is used in a fixed amount, and the molar ratio of m-xylene to paraformaldehyde is fixed.
It is understood from examples 6 and 8, and examples 4 and 9 that the resin yield of the m-xylene resin obtained by adding the phase transfer catalyst can be improved by about 10%.
As can be seen from example 1 and comparative example 1, the meta-xylene resin obtained by using sulfuric acid as a catalyst has high oxygen content, very high viscosity (25400MPa.s), reaction activity time with epoxy is only 8 minutes, subsequent insulating paint production process is not easy to control, resin yield is only 50%, and the surface of a tested paint film is foamed, while the meta-xylene resin provided by the disclosure has low oxygen content, moderate viscosity, reaction activity time with epoxy is 35 minutes, and resin yield is also 80%.
From example 1 and comparative example 2, it can be seen that when the molar ratio of metaxylene to paraformaldehyde is higher than 1: 2, the obtained metaxylene resin has a high oxygen content (9.5%), a reaction time with epoxy of only 12 minutes, and the tested paint film surface is foamed.
It is understood from example 3 and comparative example 3 that when the amount of the organosulfonic acid catalyst is more than 30%, the resulting m-xylene resin has a high viscosity (5620MPa. s) and a relatively long reaction time with epoxy (45 minutes).
In conclusion, the method for preparing the m-xylene resin is simple, the reaction activity time of the prepared m-xylene resin and epoxy is controlled to be 15-40 minutes, the subsequent insulating paint production process can be controlled, and time is not wasted. In addition, the m-xylene resin disclosed by the invention is moderate in viscosity, low in oxygen content and high in resin yield, can be used for preparing automobile electrophoresis insulating paint, anticorrosion insulating paint and the like, is excellent in insulating paint performance, and the coating surface of an insulating paint product is smooth and free of bubbles.
It should be understood that the above examples are only for clearly illustrating the present disclosure, and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention as herein taught are within the scope of the present disclosure.

Claims (11)

1. The m-xylene resin is characterized by being prepared by carrying out polycondensation reaction on raw materials comprising m-xylene and paraformaldehyde under the action of a catalyst; wherein the catalyst comprises an organosulfonic acid catalyst; the m-xylene resin has an oxygen content of 3-10%, a viscosity of 200-4000 mPa.s, and a solid content of more than or equal to 90%; the molar ratio of the m-xylene to the paraformaldehyde is 1: (1-2), the dosage of the organic sulfonic acid catalyst is 5% -30% of the dosage of the m-xylene, the concentration of the paraformaldehyde is 90% -98%, and the concentration of the organic sulfonic acid catalyst is 50% -95%.
2. The metaxylene resin of claim 1, wherein the organic sulfonic acid catalyst comprises one or more of toluene sulfonic acid, methyl sulfonic acid, and benzene sulfonic acid.
3. The metaxylene resin of claim 1, wherein the catalyst further comprises a phase transfer catalyst.
4. The metaxylene resin of claim 3, wherein the phase transfer catalyst comprises one or more of tetrabutylammonium bromide, dodecyltrimethylammonium chloride, polyethers, quaternary phosphonium salts.
5. The metaxylene resin as claimed in claim 1, wherein the metaxylene resin has an oxygen content of 4-9% and a solid content of 94% or more.
6. A method for preparing the m-xylene resin according to any one of claims 1 to 5, comprising:
carrying out polycondensation reaction on raw materials comprising the m-xylene and the paraformaldehyde at the temperature of 80-110 ℃ for 4-10 h under the action of the catalyst; the catalyst comprises an organic sulfonic acid catalyst;
standing and layering after the polycondensation reaction is finished, and taking an upper-layer product;
adding calcium oxide and water into the upper-layer product to perform a neutralization reaction to obtain a resin clear solution;
and carrying out reduced pressure concentration on the resin clear liquid to obtain the m-xylene resin.
7. The method of claim 6, wherein the catalyst further comprises a phase transfer catalyst; carrying out polycondensation reaction on the raw materials comprising the m-xylene and the paraformaldehyde at the temperature of 80-110 ℃ for 4-10 h under the action of the catalyst, wherein the polycondensation reaction comprises the following steps:
and carrying out polycondensation reaction on the raw materials comprising the m-xylene and the paraformaldehyde at the temperature of 80-110 ℃ for 5-8 h under the action of the organic sulfonic acid catalyst and the phase transfer catalyst.
8. The method according to claim 7, wherein the amount of the phase transfer catalyst is 0 to 0.5% of the amount of the meta-xylene.
9. The method of claim 7, wherein the molar ratio of meta-xylene to paraformaldehyde is from 1: (1.2-1.8), the dosage of the organic sulfonic acid catalyst is 10% -20% of the dosage of the m-xylene, the dosage of the phase transfer catalyst is 0-0.3% of the dosage of the m-xylene, and the concentration of the organic sulfonic acid catalyst is 50% -80%.
10. The method of claim 6, further comprising:
and (3) separating, concentrating and recovering the lower-layer catalyst obtained by standing and layering after the polycondensation reaction is finished.
11. An insulating varnish characterized by comprising the m-xylene resin according to any one of claims 1 to 5.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4082728A (en) * 1976-08-23 1978-04-04 The Standard Oil Company Xylene-formaldehyde resin compositions and process
CN102643400A (en) * 2012-05-03 2012-08-22 上海忠诚精细化工科技有限公司 Meta-xylene formaldehyde resin and producing method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1192543A (en) * 1997-09-25 1999-04-06 Mitsubishi Gas Chem Co Inc Aromatic hydrocarbon/formaldehyde resin

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4082728A (en) * 1976-08-23 1978-04-04 The Standard Oil Company Xylene-formaldehyde resin compositions and process
CN102643400A (en) * 2012-05-03 2012-08-22 上海忠诚精细化工科技有限公司 Meta-xylene formaldehyde resin and producing method thereof

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