CN116390962A - Preparation method of novolac resin - Google Patents
Preparation method of novolac resin Download PDFInfo
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- CN116390962A CN116390962A CN202180075048.7A CN202180075048A CN116390962A CN 116390962 A CN116390962 A CN 116390962A CN 202180075048 A CN202180075048 A CN 202180075048A CN 116390962 A CN116390962 A CN 116390962A
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- novolac resin
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- chloromethyl
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- 229920003986 novolac Polymers 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 20
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical group C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 150000002989 phenols Chemical class 0.000 claims abstract description 8
- 239000000376 reactant Substances 0.000 claims abstract description 5
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 239000011342 resin composition Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 6
- -1 phenol compound Chemical class 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 20
- 239000006227 byproduct Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000012488 sample solution Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000012467 final product Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 150000001350 alkyl halides Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of novolac resin. According to one embodiment of the invention, a method for preparing a novolac resin includes: preparing a mixed solution of 4,4' -bis (chloromethyl) -1, 1-biphenyl and a phenolic compound by a reaction in the presence of an acid-free catalyst; a step of reacting the mixed solution at 40-180 ℃ for 1-10 hours; and evaporating to remove the reaction solvent and the residues to solidify the reactant.
Description
Technical Field
The invention relates to a preparation method of a novolac resin, in particular to a preparation method of a novolac resin, which can inhibit the reaction of byproducts such as ethers or haloalkanes and minimize the loss of hydroxyl in the reaction process.
Background
Phenolic novolak resin (Phenolic Novolac Resin) is widely used as an adhesive, a molding material, a paint, a photoresist material, an epoxy resin raw material, and the like because of its excellent heat resistance, moisture resistance, and the like.
In particular, as a curing agent for epoxy resins and the like, it is widely used in the fields of electronics and electric such as semiconductor packaging materials and insulating materials for printed wiring boards.
The existing method for synthesizing the novolac resin comprises the following steps: the synthesis is carried out by adding 4,4' -bis (chloromethyl) -1, 1-biphenyl and phenol (phenol) to an organic solvent or an alcohol solvent, and then reacting them in the presence of an acid catalyst.
However, when an organic solvent is used in the reaction process, there is a problem that the value of g equivalent (reciprocal of the number of OH groups per unit (g)) of hydroxyl groups becomes high due to side reactions that generate ether by-products.
A higher hydroxyl group g equivalent (hydroxyl equivalent weight) means that the number of hydroxyl groups per molecule decreases, at which time the reduction of the epoxidizable moiety eventually leads to a decrease in the crosslink density of the polymer after curing of the product, thereby causing a problem of decreasing the physicochemical properties of the product.
In addition, when an alcohol solvent such as methanol, ethanol, or isopropanol is used, an alkyl halide is formed by the reaction between an acid catalyst and an alcohol, and the alkyl halide reacts with phenol as a reactant to form various by-products such as alkylphenol. The formation of by-products not only reduces the yield of the final product but also causes additional problems in recovering phenol as a reactant and reusing it.
Accordingly, there is a need for a new preparation method that can prepare a high quality novolac resin while suppressing side reactions that form various byproducts.
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made to overcome the above-mentioned problems occurring in the prior art, and an object thereof is to provide a high-quality novolac resin which is prepared in such a manner that side reactions that generate by-products are suppressed, and a method for preparing the same.
The object of the present invention is not limited to the above-described problems, but other problems not mentioned can be clearly understood by those skilled in the art from the following description.
Means for solving the problems
To achieve the object, a method for preparing a novolac resin according to an embodiment of the invention includes: a step of preparing a mixed solution by adding 4,4' -bis (chloromethyl) -1, 1-biphenyl and phenol (phenol) compounds to water as a reaction solvent in the absence of an acid catalyst; a step of reacting the mixed solution at 40-180 ℃ for 1-10 hours; and evaporating and removing the reaction solvent and residues to solidify the reactants.
According to an embodiment of the present invention, it may further include: and discharging all or part of the hydrogen chloride generated during the reaction in a state of being dissolved in water as the reaction solvent.
According to an embodiment of the present invention, the step of preparing the mixed solution may include: a step of adding 10 to 500wt% of water with respect to the weight of the 4,4' -bis (chloromethyl) -1, 1-biphenyl.
According to an embodiment of the present invention, it may further include: a step of adding 1.5 to 5mol equivalent of a phenolic compound to the 4,4' -bis (chloromethyl) -1, 1-biphenyl.
According to one embodiment of the present invention, the novolac resin is represented by the following formula (I):
a novolac resin composition according to another embodiment of the invention comprises a compound represented by the following chemical formula (I) with a hydroxyl equivalent weight of 200 to 235g/eq and a softening point of 86 to 92℃:
according to an embodiment of the present invention, the content of the compound represented by the following chemical formula (II) or the compound represented by the chemical formula (III) may be less than 0.5wt%, relative to the novolac resin composition:
according to an embodiment of the present invention, the compound represented by the following chemical formula (II) or the compound represented by the chemical formula (III) may not be included.
Effects of the invention
The following technical effects can be obtained according to the present invention.
According to the method for producing a novolac resin, a novolac resin with high purity can be produced by suppressing the formation of byproducts such as ethers or alkylphenols (alkylphenols).
In addition, phenolic novolak resins having g-equivalents of hydroxyl groups that meet target levels can be prepared according to the present invention.
The effects of the present invention are not limited to those described, and those skilled in the art can clearly understand other effects not mentioned through other descriptions recited in the claims.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. Those skilled in the art to which the invention pertains will appreciate that the drawings are only for better illustration of the invention and are not limiting of the invention.
Note that in describing the embodiments of the present invention, elements having the same functions are given the same names, but are not exactly the same as elements in the related art.
In addition, the terminology used in the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Where the context does not clearly indicate the contrary, singular references include plural meanings. In this application, the terms "comprises" and "comprising," and the like, mean that there is a feature, number, step, action, structure, component, or combination thereof described in the specification, and that the presence or additional possibility of one or more other features, numbers, steps, actions, structures, components, or combination thereof is not pre-excluded.
The compound represented by chemical formula 1 can be obtained by condensing 4,4' -bis (chloromethyl) -1, 1-biphenyl and a phenolic compound:
[ chemical formula 1]
The phenolic compound may be any 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 phenolic compound, the amount of phenol used is 1.5 to 5mol equivalent based on 4,4' -bis (chloromethyl) -1, 1-biphenyl. Preferably, 2 to 4.5mol equivalent is used.
In addition, in the production method according to an embodiment of the present invention, water is used as the reaction solvent. Specifically, water as a reaction solvent is fed to the reactor together with 4,4' -bis (chloromethyl) -1, 1-biphenyl or sequentially with the phenol compound.
The water used as the reaction solvent is 10 to 300 wt%, preferably 30 to 200 wt%, more preferably 50 to 100wt%, based on the weight of 4,4' -bis (chloromethyl) -1, 1-biphenyl.
When water is used as the reaction solvent, the following effects can be achieved: the method can prevent the loss of hydroxyl, inhibit the generation of byproducts such as ethers, halogenated alkyl compounds or dialkyl ether compounds, and the like, thereby improving the yield of products.
In addition, the following effects can be obtained: even if a large capacity scrubber device (scrubber device) for capturing HCl in a gas phase inevitably generated during the reaction is not provided, all or part of HCl may be dissolved in water as a reaction solvent and discharged.
In addition, the following effects can be obtained: the reaction of the phenol compound added as a reactive substance with other compounds during the reaction can be suppressed, and the phenol compound can be easily recovered and reused.
After the reaction substance and the reaction solvent are charged into the reactor, the reaction temperature is set to 40 to 180 ℃ under normal pressure. Preferably, the reaction temperature is from 90 to 110 ℃. The reaction time is 1 to 10 hours.
Under these conditions, if the temperature inside the reactor reaches 90 to 110 ℃, hydrogen chloride gas will be generated. The hydrogen chloride gas is dissolved in water as a reaction solvent and discharged to the outside.
After the reaction, an organic solvent is charged into the reactor to extract an organic substance. As the organic solvent for extracting the organic substance, methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, etc. can be used. Preferably toluene is used.
In addition, water, phenol, and the like as reaction solvents are removed by evaporation using a shunt tube, and various foreign substances are removed by filtration. After all distillation is completed, the product is cooled to solidify.
The hydroxyl equivalent (reciprocal of the number of OH in unit g) of the novolac resin represented by chemical formula 1 obtained by the process is 200 to 235g/eq. Preferably, it may be 225 to 235g/eq.
The hydroxyl equivalent weight measurement method is as follows:
potential difference measuring instrument: 888titrando device of Universal (Metrohm) company
An electrode: 6.0229.100 Solvotride apparatus from Metrohm company
First, 7.8ml of acetic anhydride and 35ml of pyridine were mixed to prepare a solution, and 5ml of the mixed solution was mixed with 1g of a sample and reacted at 160℃for 1 hour. After that, 1 to 1.5ml of distilled water was added thereto, and the reaction was further carried out for 15 minutes or longer, followed by cooling.
Subsequently, THF and acetone were added to dilute the sample solution, and each of the sample solution and a Blank (Blank) was titrated by potential difference with a 0.5N-KOH (EtOH) solution.
The hydroxyl equivalent was calculated by substituting the values of the Blank (Blank) and the sample solution measured into the following formula.
28.05 (B-V) F/sample amount [ g ] =oh value [ KOH mg/g ]
Wherein B is the measurement value of Blank group (Blank) solution, and V is the measurement value of sample solution.
Hydroxyl equivalent [ g/eq ] = 26110/OH value [ KOH mg/g ]
The novolac resin represented by chemical formula 1 has a softening point of 86 to 92 ℃.
The softening point was measured using a DP70 model device from Metler Toledo. Firstly, after a sample to be measured is melted to 140 to 160 ℃, a cup provided in a measuring device is filled and the surface of the cup is leveled. After the upper part of the cup is covered with the lid and the lower part is inserted into the glass tube, thereby being fixed to a carrier (carrier), measurement is started in a state where the carrier is put into the measuring device.
After the sample was put into the measuring apparatus, the initial temperature was set to 60℃and maintained for 10 seconds, and then the sample was heated at a rate of 2℃per minute, and the temperature at which the sample in the cup softened and flowed down and reached the final position by gravity was determined as the softening point.
In addition, the content of the compound represented by chemical formula 2 or chemical formula 3 contained in the novolac resin composition synthesized by the process is less than 0.5wt% with respect to the total novolac resin composition weight. Preferably less than 0.3wt%. More preferably, the novolac resin composition contains substantially no compound represented by the following chemical formula 2 or chemical formula 3:
[ chemical formula 2]
[ chemical formula 3]
The content of the by-products represented by chemical formula 2 and chemical formula 3 was measured by GPC (gel permeation chromatography, gel Permeation Chromatograph) analysis.
Chromatographic column: KF-801, 802, 803 from Shoedex Corp
The detecting instrument comprises: 2414RI of Water company
And (3) a pump: 1515 from water company
Automatic sample injector: 2707 of Water company
Mobile phase: THF (GPC grade) 1ml/min
The mobile phase THF (GPC grade) was set at 1ml/min, and after starting GPC, THF was allowed to sufficiently flow and stabilized. Thereafter, 0.05g of the sample was dissolved in THF to prepare a sample solution.
A blank was injected separately for analysis with THF (Blank THF) and 50l of sample solution. All peaks were integrated to level the baseline (base line) and then separated vertically based on the peak Valley (Valley) of each peak. In the measured analysis results of the samples, the Area percentage (Area%) of each peak was recorded excluding the peak common to the Blank control.
Hereinafter, the present invention will be described more specifically, but the present invention is not limited to the following examples.
Example 1
2.3mol equivalents of phenol, based on 4,4' -bis (chloromethyl) -1, 1-biphenyl, were charged to the reactor. The reaction solvent used was water. 50% by weight of water, based on 4,4' -bis (chloromethyl) -1, 1-biphenyl, are used.
After that, after the temperature of the reactor is raised to 80 to 110 ℃, hydrochloric acid gas generated as the reaction proceeds is discharged to the outside of the reactor to be trapped by water or sodium hydroxide solution.
After the reaction was completed, toluene was added as an organic solvent, and the acid wastewater was separated by an oil-water layer. In addition, water as a reaction solvent, hydrochloric acid as a by-product, toluene as an extraction solvent, and remaining phenol were removed by distillation. After the distillation is completed, the final product is cooled to obtain a novolac resin composition including the compound represented by chemical formula 1.
In the novolac resin composition obtained by the process, the compound represented by chemical formula 2 or chemical formula 3 is not detected.
In addition, the hydroxyl equivalent of the novolac resin represented by chemical formula 1 was 227g/eq, and the softening point was 91.6 ℃.
Example 2
2.5mol equivalents of phenol, based on 4,4' -bis (chloromethyl) -1, 1-biphenyl, were charged to the reactor. The reaction solvent used was water. Water was used in an amount of 100% by weight, based on 4,4' -bis (chloromethyl) -1, 1-biphenyl.
After that, after the temperature of the reactor is raised to 80 to 110 ℃, hydrochloric acid gas generated as the reaction proceeds is discharged to the outside of the reactor to be trapped by water or sodium hydroxide solution.
After the reaction was completed, toluene was added as an organic solvent, and the acid wastewater was separated by an oil-water layer. In addition, water as a reaction solvent, hydrochloric acid as a by-product, toluene as an extraction solvent, and remaining phenol were removed by distillation. After the distillation is completed, the final product is cooled to obtain a novolac resin composition including the compound represented by chemical formula 1.
In the novolac resin composition obtained by the process, the compound represented by chemical formula 2 or chemical formula 3 was detected to be contained at 0.06wt%.
In addition, the hydroxyl equivalent weight of the novolac resin was 227g/eq, and the softening point was 89.1 ℃.
Comparative example 1
2.1mol equivalents of phenol and hydrochloric acid diluted to a concentration of 35% based on 4,4' -bis (chloromethyl) -1, 1-biphenyl were fed into the reactor. Toluene was used as the reaction solvent. Based on 4,4' -bis (chloromethyl) -1, 1-biphenyl, 100% by weight of water and 0.8% by weight of hydrochloric acid were used.
Thereafter, the temperature of the reactor was increased to 110 to 115 ℃ to reflux toluene, whereby hydrochloric acid gas generated as the reaction proceeded was discharged to the outside of the reactor to be trapped by water or sodium hydroxide solution.
After the reaction was completed for 8 hours, toluene and catalyst as a reaction solvent, hydrochloric acid as a by-product, and remaining phenol were removed by distillation. After the distillation is completed, the final product is cooled to obtain a novolac resin composition represented by chemical formula 1.
In the novolac resin composition obtained by the process, the compound represented by chemical formula 2 or chemical formula 3 contained was detected to be 4.55wt%.
In addition, the hydroxyl equivalent of the novolac resin represented by chemical formula 1 was 244g/eq, and the softening point was 85.9 ℃.
While the preferred embodiments according to the present invention have been described above, it will be understood by those skilled in the art that the present invention may be embodied in various other forms without departing from the spirit or scope of the present invention, in addition to the embodiments described above. Accordingly, the above-described embodiments are provided to illustrate the present invention and not to limit the present invention, i.e., the present invention is not limited to the above-described embodiments, but may be modified within the scope of the appended claims and equivalents thereof.
Claims (8)
1. A method for preparing a novolac resin, comprising:
preparing a mixed solution of 4,4' -bis (chloromethyl) -1, 1-biphenyl and a phenol compound by a reaction in the presence of an acid-free catalyst;
a step of reacting the mixed solution at 40-180 ℃ for 1-10 hours; the method comprises the steps of,
evaporating to remove the reaction solvent and residues to solidify the reactant.
2. The method for producing a novolak resin according to claim 1, wherein,
further comprises: and discharging all or part of the hydrogen chloride generated during the reaction in a state of being dissolved in water as the reaction solvent.
3. The method for producing a novolak resin according to claim 1, wherein,
the step of preparing the mixed solution includes:
a step of adding 10 to 500wt% of water with respect to the weight of the 4,4' -bis (chloromethyl) -1, 1-biphenyl.
4. A process for preparing a novolak resin according to claim 3, wherein,
further comprises: a step of adding 1.5 to 5mol equivalent of a phenolic compound to the 4,4' -bis (chloromethyl) -1, 1-biphenyl.
5. The method for producing a novolak resin according to any of claims 1-4, wherein,
the novolac resin is represented by the following chemical formula (I):
6. a novolac resin composition, characterized in that,
the novolac resin composition comprises a compound represented by the following chemical formula (I) with a hydroxyl equivalent of 200-235 g/eq and a softening point of 86-92℃:
7. a novolac resin composition, characterized in that,
the content of the compound represented by the following chemical formula (II) or the compound represented by the chemical formula (III) is less than 0.5% by weight relative to the novolac resin composition:
8. the method for producing a novolak resin according to claim 7, wherein,
the compound represented by the formula (II) or the compound represented by the formula (III) is not contained.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2020-0147726 | 2020-11-06 | ||
| KR1020200147726A KR102497115B1 (en) | 2020-11-06 | 2020-11-06 | Phenolin novolac resin and process for production thereof |
| PCT/KR2021/015763 WO2022098075A1 (en) | 2020-11-06 | 2021-11-03 | Method for preparing phenolic novolac resin |
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| CN116390962A true CN116390962A (en) | 2023-07-04 |
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| JP (1) | JP2023548088A (en) |
| KR (1) | KR102497115B1 (en) |
| CN (1) | CN116390962A (en) |
| TW (1) | TWI813054B (en) |
| WO (1) | WO2022098075A1 (en) |
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| CN117887016A (en) * | 2024-01-15 | 2024-04-16 | 同宇新材料(广东)股份有限公司 | Polybiphenyl phenolic resin and preparation method and application thereof |
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| JP4082481B2 (en) * | 1999-08-25 | 2008-04-30 | 日本化薬株式会社 | Phenol resin, epoxy resin, thermosetting resin composition, and resin production method |
| US6723801B2 (en) * | 2000-10-05 | 2004-04-20 | Nippon Kayaku Kabushiki Kaisha | Polyphenol resin, process for its production, epoxy resin composition and its use |
| JP4104107B2 (en) * | 2000-10-05 | 2008-06-18 | 日本化薬株式会社 | Epoxy resin composition and use thereof |
| JP2003105049A (en) * | 2001-10-01 | 2003-04-09 | Nippon Kayaku Co Ltd | Method for manufacturing polyphenol resin |
| JP2003261746A (en) * | 2002-03-11 | 2003-09-19 | Kyocera Chemical Corp | Resin composition for sealing and sealed electronic device |
| TWI415911B (en) * | 2005-07-13 | 2013-11-21 | Ube Industries | Biphenylene cross-linked phenol novolac resin and the use thereof |
| JP5536384B2 (en) * | 2009-07-15 | 2014-07-02 | リグナイト株式会社 | Process for producing modified phenolic resin, phenolic resin composition, refractory composition, resin-coated sand for molding, molding material, nonwoven fabric, cured product, carbide, activated carbon |
| CN111051374B (en) * | 2017-09-11 | 2023-02-28 | Ｕｂｅ株式会社 | Phenolic resin composition for photoresist and photoresist composition |
| CN110051374A (en) * | 2018-03-15 | 2019-07-26 | 滨松光子医疗科技(廊坊)有限公司 | The gamma camera being made into novel TlBr detector |
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| CN117887016A (en) * | 2024-01-15 | 2024-04-16 | 同宇新材料(广东)股份有限公司 | Polybiphenyl phenolic resin and preparation method and application thereof |
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| Publication number | Publication date |
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| JP2023548088A (en) | 2023-11-15 |
| WO2022098075A1 (en) | 2022-05-12 |
| TWI813054B (en) | 2023-08-21 |
| KR20220061592A (en) | 2022-05-13 |
| TW202219095A (en) | 2022-05-16 |
| KR102497115B1 (en) | 2023-02-07 |
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