WO2022098075A1

WO2022098075A1 - Method for preparing phenolic novolac resin

Info

Publication number: WO2022098075A1
Application number: PCT/KR2021/015763
Authority: WO
Inventors: 김원준; 김혜현; 박동경
Original assignee: 송원산업 주식회사
Priority date: 2020-11-06
Filing date: 2021-11-03
Publication date: 2022-05-12
Also published as: TW202219095A; CN116390962A; JP2023548088A; TWI813054B; KR102497115B1; KR20220061592A

Abstract

Disclosed is a method for preparing a phenolic novolac resin. A method for preparing a phenolic novolac resin according to an embodiment of the present invention is directed to a reaction in the absence of an acid catalyst, the method comprising the steps of: adding 4,4'-bis(chloromethyl)-1,1-biphenyl and phenolic compounds to prepare a mixture solution; subjecting the mixture solution to reaction at 40-180°C for 1-10 hours; and evaporating and removing the reaction solvent and residual materials and solidifying the reaction product.

Description

Novolak-type phenolic resin manufacturing method

The present invention relates to a method for producing a novolak-type phenol resin, and more particularly, to a novolac-type phenol resin that suppresses the reaction of by-products such as ether series or halogen alkyl and minimizes loss of hydroxyl groups during the reaction process. it's about how

Novolac-type phenolic resin (Phenolic Novolac Resin) is widely used in adhesives, molding materials, paints, photoresist materials, epoxy resin raw materials, etc. due to excellent heat resistance and moisture resistance.

In particular, as a curing agent such as an epoxy resin, it is widely used in electrical and electronic fields such as semiconductor encapsulants and insulating materials for printed wiring boards.

Conventional novolak-type phenolic resin is synthesized by adding 4,4'-bis(chloromethyl)-1,1-biphenyl and phenol to an organic solvent or an alcohol-based solvent and then reacting in the presence of an acid catalyst. synthesized

However, when an organic solvent is used in the reaction process, there is a problem in that the gram equivalent of hydroxyl (the reciprocal of the number of OH per unit g) value is high due to a side reaction in which ether-based by-products are generated.

An increase in the hydroxyl equivalent weight means a decrease in the number of hydroxyl groups per unit molecule. It causes a problem that the physical and chemical properties of the product may be deteriorated.

In addition, when an alcohol-based solvent such as methanol, ethanol, or isopropyl alcohol is used, an acid catalyst and alcohol react to produce an alkyl halide, and the alkyl halide reacts with a reactant phenol to produce various by-products such as alkylphenol. will form The formation of by-products not only lowers the yield of the final product, but also causes additional problems in the recovery and reuse of phenol as a reactant.

Accordingly, there has been a need for a new manufacturing method capable of producing a novolak-type phenolic resin of excellent quality while suppressing side reactions that form various types of by-products.

The present invention has been devised to solve the above-described problems, and an object of the present invention is to provide a high-quality novolak-type phenol resin prepared by suppressing side reactions causing by-products and a method for producing the same.

The problems of the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

In the novolak-type phenol resin manufacturing method according to an embodiment of the present invention for achieving the above object, 4,4'-bis(chloromethyl)-1,1-bi is dissolved in water as a reaction solvent in the absence of an acid catalyst. It includes the steps of preparing a mixed solution by adding phenyl and phenol compounds, reacting the mixed solution at 40 to 180° C. for 1 to 10 hours, and evaporating the reaction solvent and residual material to solidify the reactant.

According to an embodiment of the present invention, the method may further include discharging all or part of the hydrogen chloride generated in the reaction process in a state of dissolving it in water, which is the reaction solvent.

According to an embodiment of the present invention, the preparing of the mixed solution comprises adding 10 wt% to 500w% of water based on the weight of 4,4'-bis(chloromethyl)-1,1-biphenyl. may include steps.

According to an embodiment of the present invention, the method may further include adding 1.5 to 5 mol-equivalent of a phenolic compound to the 4,4'-bis(chloromethyl)-1,1-biphenyl.

According to an embodiment of the present invention, the novolak-type phenolic resin is represented by the following formula (I).

(I)

The novolak-type phenolic resin composition according to another embodiment of the present invention includes a compound represented by the following formula (I) having a hydroxyl equivalent of 200 to 235 g/eq and a softening point of 86 to 92°C.

(I)

According to an embodiment of the present invention, the content of the compound represented by the following formula (II) or the compound represented by the formula (III) may be less than 0.5 wt% based on the weight of the novolak-type phenol resin composition.

(II)

(III)

According to an embodiment of the present invention, the compound represented by the formula (II) or the compound represented by the formula (III) may not be included.

According to the method for producing the above-described novolak-type phenolic resin, it is possible to achieve the effect that a high-purity novolak-type phenolic resin can be manufactured by suppressing the production of by-products such as ether-based or alkylphenol.

In addition, the effect of being able to produce a novolak-type phenol resin in which the gram equivalent of hydroxyl meets the target level can be achieved.

Effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description of the claims.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the accompanying drawings are only described to more easily disclose the contents of the present invention, and those of ordinary skill in the art can easily understand that the scope of the present invention is not limited to the scope of the accompanying drawings. you will know

And, in describing the embodiment of the present invention, the same name and the same reference numerals are used for components having the same function, but substantially not completely the same as the components of the prior art.

In addition, the terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It should be understood that this does not preclude the existence or addition of numbers, steps, operations, components, parts, or combinations thereof.

The compound represented by Formula 1 may be obtained by condensation reaction of 4,4'-bis(chloromethyl)-1,1-biphenyl with a phenol compound.

Here, the phenol compound may be any one of phenol, o-cresol, m-cresol, p-cresol, catechol, hydroquinone, resorcinol, pyrogallol, and a-naphthol. Preferably, the phenolic compound is phenol.

When phenol is used as the phenol compound, the amount of phenol used is 1.5 to 5 mol-equivalent based on 4,4'-bis(chloromethyl)-1,1-biphenyl. Preferably, 2 to 4.5 mol-equivalents are used.

Meanwhile, water is used as the reaction solvent in the manufacturing method according to an embodiment of the present invention. Specifically, water as a reaction solvent is introduced into the reactor simultaneously or sequentially with the 4,4'-bis(chloromethyl)-1,1-biphenyl and phenol compounds.

Water as a reaction solvent is 10wt% to 300w%, preferably 30wt% to 200w%, more preferably 50wt% to 100w% based on the weight of 4,4'-bis(chloromethyl)-1,1-biphenyl is used

When water is used as the reaction solvent, it is possible to achieve the effect of increasing the yield of products by suppressing the formation of by-products such as ether series, halogen alkyl compounds or di-alkyl ether compounds without accompanying loss of hydroxyl groups. .

In addition, even without a large-capacity scrubber device for collecting gaseous HCl that is inevitably generated in the reaction process, it is possible to achieve the effect of dissolving all or part of HCL in water in the reaction solvent to be discharged.

In addition, since it is possible to suppress the reaction of the phenolic compound input as a reaction material with other compounds during the reaction process, the effect of facilitating the recovery and reuse of the phenolic compound can be achieved.

After introducing the above-described reaction material and reaction solvent to the reactor, the reaction temperature is set to 40 ~ 180 ℃ under atmospheric conditions. Preferably the reaction temperature is 90 ~ 110 ℃. In addition, the reaction time is 1 to 10 hours.

When the temperature inside the reactor reaches 90 ~ 110 ℃ under the above conditions, hydrogen chloride gas is generated. Hydrogen chloride gas may be dissolved in water as a reaction solvent and discharged to the outside.

When the reaction is completed, an organic solvent is added to the reactor to extract organic matter. As the organic solvent for extracting the organic material, methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, and the like may be used. Preferably toluene is used.

Additionally, water and phenol, which are reaction solvents, are evaporated and removed using a fractionation tube, and various foreign substances are removed through filtration. When the distillation is complete, the product is cooled and solidified.

The hydroxyl equivalent (reciprocal of the number of OH per unit g) of the novolak-type phenol resin represented by Formula 1 obtained through the above-described process is 200 to 235 g/eq. Preferably it is 225-235 g/eq.

The hydroxyl equivalent measurement method is as follows.

Potentiometer: Metrohm 888titrando

Electrode: metrohm 6.0229.100 Solvotrode

First, a solution was prepared by mixing 7.8 ml of acetic anhydride and 35 ml of pyridine, and 5 ml of the mixed solution was mixed with 1 g of the sample and reacted at 160 ° C for 1 hour. Then, after adding 1 to 1.5 ml of distilled water, the reaction was further carried out for 15 minutes or more, followed by cooling.

Next, THF and acetone were added to dilute, and potentiometric titration was performed for the sample solution and the blank using 0.5N-KOH (EtOH) solution, respectively.

The hydroxyl equivalent was calculated by substituting the values of the measured blank and the sample solution into the following equation.

28.05 * (B-V) * F / sample amount [g] = OH value [KOH mg/g]

Here, B = the measured value of the blank solution, and V is the measured value of the sample solution.

Hydroxyl equivalent [g/eq]=26110 / OH value [KOH mg/g]

On the other hand, the softening point of the novolak-type phenol resin represented by the formula (1) is 86 ~ 92 ℃.

The softening point was measured using Metler Toledo's model name DP70. First, the sample to be measured was melted at 140° C. to 160° C., then filled in a cup provided in the measuring device, and then the surface was flattened. A cover was put on the upper part of the cup, and a glass tube was inserted into the lower part to be fixed to the carrier, and then the measurement was started with the carrier inserted into the measuring device.

After inserting the sample into the measuring device, the initial temperature is set at 60°C and held for 10 seconds, heated at a rate of 2°C/min. The temperature was determined as the softening point.

In addition, the content of the compound represented by Formula 2 or Formula 3 included in the novolak-type phenolic resin composition synthesized through the above-described process is less than 0.5 wt% based on the total weight of the novolak-type phenolic resin composition. Preferably less than 0.3 wt %. More preferably, the novolak-type phenolic resin composition does not substantially include a compound represented by the following Chemical Formula 2 or Chemical Formula 3.

The content of by-products represented by Chemical Formulas 2 and 3 was measured through Gel Permeation Chromatograph (GPC) analysis.

Column: Shoedex KF-801, 802, 803

Detector: water company 2414RI

Pump: water company 1515

Auto sampler: water company 2707

Mobile phase: THF (GPC grade) 1ml/min

The mobile phase THF (GPC grade) was set at 1 ml/min, and after operating the GPC, THF was flowed sufficiently to stabilize it. Thereafter, 0.05 g of the sample was dissolved in THF to prepare a sample solution.

Each 50 μl of blank THF and sample solution was injected and each analysis was performed. After integrating so that the base line is horizontal for all peaks, it is divided vertically based on the Valley of each peak. In the measured sample analysis result, a common peak was excluded by contrast with the blank, and the area% of each peak was written.

Hereinafter, although this invention is demonstrated more concretely, this invention is not limited to the following example.

[Example 1]

Based on 4,4'-bis(chloromethyl)-1,1-biphenyl, 2.3 molar-equivalent of phenol was added to the reactor. Water was used as the reaction solvent. As water, 50 wt% of 4,4'-bis(chloromethyl)-1,1-biphenyl was used.

Then, after raising the temperature of the reactor to 80 ~ 110 ℃, the hydrochloric acid gas generated as the reaction proceeds was discharged to the outside of the reactor to be collected in water or sodium hydroxide solution.

After the reaction was continued for 3 hours, when the reaction was completed, toluene, an organic solvent, was added, and acid wastewater was removed through oil-water layer separation. Then, water as a reaction solvent, hydrochloric acid as a by-product, toluene as an extraction solvent, and residual phenol were removed through distillation. Upon completion of the distillation, the final product was cooled to obtain a novolak-type phenolic resin composition containing the compound represented by Chemical Formula 1.

The compound represented by Formula 2 or Formula 3 contained in the novolak-type phenol resin composition obtained through the above-described process was not detected.

In addition, the hydroxyl equivalent of the novolak-type phenol resin represented by Formula 1 was 227 g/eq, and the softening point was measured to be 91.6°C.

[Example 2]

2.5 molar-equivalent of phenol based on 4,4'-bis(chloromethyl)-1,1-biphenyl was introduced into the reactor. Water was used as the reaction solvent. As for water, 100 wt% of 4,4'-bis(chloromethyl)-1,1-biphenyl was used.

It was confirmed that the compound represented by Formula 2 or Formula 3 contained in the novolak-type phenol resin composition obtained through the above-described process was 0.06 wt%.

In addition, the hydroxyl equivalent of the novolak-type phenol resin was 227 g/eq, and the softening point was measured to be 89.1°C.

[Comparative Example 1]

Hydrochloric acid diluted to a concentration of 35% and 2.1 molar equivalents of phenol based on 4,4'-bis(chloromethyl)-1,1-biphenyl was added to the reactor. Toluene was used as the reaction solvent. 100 wt% of 4,4'-bis(chloromethyl)-1,1-biphenyl was used for water, and 0.8 wt% of hydrochloric acid was used.

Thereafter, the temperature of the reactor was raised to 110-115° C. to reflux toluene, and hydrochloric acid gas generated as the reaction progressed was discharged to the outside of the reactor to be collected in water or sodium hydroxide solution.

After the reaction was continued for 8 hours, when the reaction was completed, toluene, a reaction solvent, and hydrochloric acid and residual phenol as a catalyst and by-products were removed through distillation. Upon completion of the distillation, the final product was cooled to obtain a novolak-type phenolic resin composition represented by Chemical Formula 1.

It was confirmed that the compound represented by Formula 2 or Formula 3 contained in the novolak-type phenol resin composition obtained through the above-described process was 4.55 wt%.

In addition, the hydroxyl equivalent of the novolak-type phenol resin represented by Chemical Formula 1 was 244 g/eq, and the softening point was measured to be 85.9°C.

As described above, preferred embodiments according to the present invention have been reviewed, and the fact that the present invention can be embodied in other specific forms without departing from the spirit or scope of the present invention in addition to the above-described embodiments is one of ordinary skill in the art. It is obvious to them. Therefore, the above-described embodiments are to be regarded as illustrative rather than restrictive, and accordingly, the present invention is not limited to the above description, but may be modified within the scope of the appended claims and their equivalents.

Claims

preparing a mixed solution of 4,4'-bis(chloromethyl)-1,1-biphenyl and a phenol compound by reaction in the absence of an acid catalyst;

reacting the mixed solution at 40 to 180° C. for 1 to 10 hours; and

A method for producing a novolak-type phenolic resin comprising the steps of evaporating the reaction solvent and residual material and solidifying the reactant.
The method of claim 1,

The method for producing a novolak-type phenolic resin further comprising discharging all or part of the hydrogen chloride generated in the reaction process in a state of dissolving it in water, which is the reaction solvent.
The method of claim 1,

The step of preparing the mixed solution,

A method for producing a novolak-type phenolic resin comprising the step of adding 10 wt% to 500 wt% of water based on the weight of the 4,4'-bis(chloromethyl)-1,1-biphenyl.
4. The method of claim 3,

The method for producing a novolak-type phenolic resin further comprising the step of adding 1.5 to 5 mol-equivalent of a phenol compound to the 4,4'-bis(chloromethyl)-1,1-biphenyl.
5. The method according to any one of claims 1 to 4,

The novolak-type phenolic resin is a method for producing a novolak-type phenolic resin represented by the following formula (I).

(I)
A novolak-type phenolic resin composition comprising a compound represented by the following formula (I) having a hydroxyl equivalent weight of 200 to 235 g/eq and a softening point of 86 to 92 °C.

(I)
A novolak-type phenolic resin composition in which the content of the compound represented by the following formula (II) or the compound represented by the formula (III) is less than 0.5 wt% based on the weight of the novolak-type phenolic resin composition.

(II)

(III)
8. The method of claim 7,

A novolak-type phenolic resin composition that does not contain the compound represented by the formula (II) or the compound represented by the formula (III).