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WO2018139074A1 - Résine phénolique de type novolaque, composition de résine et procédé de production de résine phénolique de type novolaque - Google Patents

Résine phénolique de type novolaque, composition de résine et procédé de production de résine phénolique de type novolaque Download PDF

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Publication number
WO2018139074A1
WO2018139074A1 PCT/JP2017/044286 JP2017044286W WO2018139074A1 WO 2018139074 A1 WO2018139074 A1 WO 2018139074A1 JP 2017044286 W JP2017044286 W JP 2017044286W WO 2018139074 A1 WO2018139074 A1 WO 2018139074A1
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Prior art keywords
lignin
mass
acid
parts
novolac type
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PCT/JP2017/044286
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English (en)
Japanese (ja)
Inventor
康典 大橋
霖 周
麻衣子 山本
勇希 谷口
木村　肇
大塚　恵子
松本　明博
Original Assignee
ハリマ化成株式会社
地方独立行政法人大阪産業技術研究所
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Publication of WO2018139074A1 publication Critical patent/WO2018139074A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
    • 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
    • C08L61/14—Modified phenol-aldehyde condensates

Definitions

  • the present invention relates to a novolac type phenol resin, a resin composition, and a method for producing a novolac type phenol resin. More specifically, the present invention relates to a novolac type phenol resin, a resin composition containing the novolac type phenol resin, and the novolac type phenol. The present invention relates to a method for producing a resin.
  • thermosetting resins have been widely used in various industrial fields such as electric parts, automobile parts, building materials, and daily necessities.
  • novolac type phenolic resins are widely used as molding materials because they are excellent in electrical insulation, heat resistance, mechanical properties, moldability, and the like.
  • the novolac type phenol resin can be obtained by reacting phenols and aldehydes in the presence of an acid catalyst.
  • an acid catalyst On the other hand, in recent years, from the viewpoint of protecting the global environment, etc., it has been required to reduce the amount of petroleum resources used, and the use of plant-derived raw materials instead of petroleum resources has been studied.
  • lignin As such a plant-derived raw material, lignin has attracted attention. Specifically, as a novolac type phenol resin obtained using lignin, for example, lignin, phenol or a phenol derivative, and aldehydes, A lignin-modified novolac type phenolic resin obtained by reacting in the presence of an organic acid has been proposed. (See Patent Document 1 below).
  • Patent Document 1 describes that as lignin, craft lignin obtained from raw materials such as wood and grassy materials, lignin sulfonic acid and the like can be used without limitation.
  • lignin sulfonic acid and the like can be used.
  • the reactivity with phenol and aldehydes is inferior, and the productivity (resin yield, production rate, etc.) of the lignin-modified novolac type phenol resin is inferior.
  • An object of the present invention is to provide a novolak type phenol resin excellent in productivity, a resin composition containing the novolac type phenol resin, and a method for producing the novolac type phenol resin.
  • the present invention [1] is a reaction product of a lignin having an aliphatic hydroxyl group in the molecule, a phenol, and an aldehyde under an acid catalyst, and the content of the aliphatic hydroxyl group in the lignin is:
  • a novolac-type phenol resin is contained in an amount of 0.5% by mass or more and 7.0% by mass or less based on the total amount of the lignin.
  • the present invention [2] includes the novolak type phenol resin according to the above [1], which is a reaction product of a lignin-phenol composition containing the reaction product of the lignin and the phenols and the aldehyde. It is out.
  • the present invention includes the novolac phenol resin according to the above [1] or [2], wherein the lignin is a lignin modified with acetic acid.
  • the present invention [4] includes a resin composition containing the novolac type phenol resin according to any one of the above [1] to [3].
  • the present invention [5] includes a step of reacting a lignin having an aliphatic hydroxyl group in the molecule, a phenol, and an aldehyde in the presence of an acid catalyst, wherein the content of the aliphatic hydroxyl group in the lignin is as described above.
  • the novolak-type phenolic resin and resin composition of the present invention are excellent in productivity (resin yield, production rate, etc.) because lignin having an aliphatic hydroxyl group in the molecule at a predetermined ratio is used as a raw material.
  • a novolac type phenol resin of the present invention can be obtained with high productivity.
  • the novolac type phenol resin of the present invention can be obtained by reacting lignin having an aliphatic hydroxyl group (described later) in the molecule, phenols and aldehydes in the presence of an acid catalyst. That is, the novolak type phenol resin of the present invention is a reaction product of lignin having an aliphatic hydroxyl group (described later) in the molecule, phenols, and aldehydes.
  • Lignin is a high molecular phenolic compound having a basic skeleton such as guaiacyl lignin (G type), syringyl lignin (S type), p-hydroxyphenyl lignin (H type) and the like.
  • lignin is classified according to, for example, the type of plant used as a raw material, and specific examples include woody plant-derived lignin and herbaceous plant-derived lignin.
  • woody plant-derived lignin examples include coniferous lignin contained in conifers (eg, cedar), for example, broadleaf lignin contained in broadleaf trees. Such woody plant-derived lignin does not contain lignin having H-type basic skeleton, for example, conifer lignin has G-type basic skeleton, and hardwood lignin has G-type and S-type basic skeleton. Yes.
  • Examples of the herbaceous plant-derived lignin include, for example, rice-based lignin contained in Gramineae plants, and more specifically, wheat straw lignin contained in wheat straw, rice straw lignin contained in rice straw, and corn. Examples include corn lignin and bamboo lignin contained in bamboo. Such herbaceous plant-derived lignin has all of H-type, G-type and S-type as the basic skeleton.
  • lignins can be used alone or in combination of two or more.
  • the lignin is preferably a herbaceous plant-derived lignin, more preferably a herbaceous plant-derived lignin derived from straw, or a herbaceous plant-derived lignin derived from corn.
  • lignin from the viewpoint of reactivity, it is preferable to contain an H-type basic skeleton in a proportion of 3% by mass or more, more preferably 9% by mass or more, and still more preferably 14% by mass or more. It is done.
  • Such lignin is contained in waste liquid (black liquor) discharged when pulp is produced from a plant by a known method such as an alkali method (soda method), a sulfurous acid method, or a kraft method. More specifically, the waste liquid (black liquor) discharged in the alkali method contains alkali lignin, and the waste liquid (black liquor) discharged in the sulfurous acid method contains sulfite lignin. The discharged waste liquid (black liquor) contains kraft lignin.
  • examples of lignin include acid-modified lignin obtained by modifying lignin with an acid (such as a carboxylic acid), and explosion lignin obtained by treating a plant with an explosion method.
  • an acid such as a carboxylic acid
  • explosion lignin obtained by treating a plant with an explosion method.
  • the lignin is preferably an acid-modified lignin, more preferably a carboxylic acid-modified lignin.
  • examples of the carboxylic acid include a carboxylic acid having one carboxy group (hereinafter, sometimes referred to as a monofunctional carboxylic acid).
  • Functional carboxylic acid unsaturated aliphatic monofunctional carboxylic acid, aromatic monofunctional carboxylic acid and the like can be mentioned.
  • saturated aliphatic monofunctional carboxylic acid examples include acetic acid, propionic acid, butyric acid, lauric acid and the like.
  • Examples of the unsaturated aliphatic monofunctional carboxylic acid include acrylic acid, methacrylic acid, and linoleic acid.
  • aromatic monofunctional carboxylic acid examples include benzoic acid, 2-phenoxybenzoic acid, and 4-methylbenzoic acid.
  • carboxylic acids can be used alone or in combination of two or more.
  • the carboxylic acid is preferably a saturated aliphatic monofunctional carboxylic acid, more preferably acetic acid (in other words, lignin modified with acetic acid is used as lignin). If the carboxylic acid is used, a carboxylic acid-modified lignin can be easily obtained, and the carboxylic acid-modified lignin obtained has a relatively high solubility in an organic solvent and has a melting temperature as described later. Since it is relatively low temperature (about 100 to 200 ° C.), it is excellent in handleability.
  • the carboxylic acid can be prepared as an aqueous solution.
  • the concentration of the carboxylic acid aqueous solution is not particularly limited and is set as appropriate.
  • the production method of the carboxylic acid-modified lignin is not particularly limited, and can conform to a known method.
  • a plant material for example, a conifer, a broadleaf tree, a gramineous plant, etc.
  • a carboxylic acid preferably acetic acid
  • a carboxylic acid-modified lignin can be obtained as a pulp waste liquid by modifying with a carboxylic acid.
  • the cooking method is not particularly limited.
  • a plant material that is a raw material for lignin is mixed with a carboxylic acid and an inorganic acid (for example, hydrochloric acid, sulfuric acid, etc.) and reacted.
  • an inorganic acid for example, hydrochloric acid, sulfuric acid, etc.
  • the mixing ratio of the carboxylic acid is such that the carboxylic acid (100% conversion) is, for example, 500 parts by mass or more, preferably 900 parts by mass or more, for example, 30000 with respect to 100 parts by mass of the plant material that is the raw material for lignin. It is 1 part by mass or less, preferably 15000 parts by mass or less.
  • the blending ratio of the inorganic acid is, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more with respect to 100 parts by mass of the plant material that is the raw material for lignin. For example, it is 10 parts by mass or less, preferably 5 parts by mass or less.
  • the reaction temperature is, for example, 30 ° C. or more, preferably 50 ° C. or more, for example, 400 ° C. or less, preferably 250 ° C. or less.
  • the reaction time is, for example, 0.5 hours or more, preferably 1 hour or more, for example, 20 hours or less, preferably 10 hours or less.
  • the pulp is separated by a known separation method such as filtration, and the filtrate (pulp waste liquid) is recovered.
  • the unreacted carboxylic acid is known using, for example, a rotary evaporator, vacuum distillation or the like. It is removed (distilled off) by the method. Thereafter, a large excess of water is added to precipitate the carboxylic acid-modified lignin, followed by filtration to recover the carboxylic acid-modified lignin as a solid content.
  • the method for obtaining the carboxylic acid-modified lignin is not limited to the above.
  • lignin not modified with carboxylic acid for example, the above alkaline lignin, the above sulfite lignin, the above kraft lignin, etc. (hereinafter referred to as unmodified lignin)
  • a carboxylic acid can be used to modify an aliphatic hydroxyl group (described later) of lignin with a carboxylic acid to obtain a carboxylic acid-modified lignin.
  • the native lignin is preferably powdered native lignin.
  • the average particle size of the powdered unmodified lignin is, for example, 0.1 ⁇ m or more, preferably 5 ⁇ m or more, for example, 1000 ⁇ m or less, preferably 500 ⁇ m or less.
  • the average particle diameter is in the above range, aggregation of the unmodified lignin can be suppressed and the unmodified lignin can be favorably dispersed in the carboxylic acid.
  • the powdered unmodified lignin can be obtained by drying and pulverizing the lump unmodified lignin by a known method, or a commercially available product can be used.
  • unmodified lignin and carboxylic acid for example, unmodified lignin, carboxylic acid and inorganic acid (for example, hydrochloric acid, sulfuric acid, etc.) are mixed and reacted.
  • unmodified lignin, carboxylic acid and inorganic acid for example, hydrochloric acid, sulfuric acid, etc.
  • the mixing ratio of the carboxylic acid is, for example, 300 parts by mass or more, preferably 500 parts by mass or more, for example, 15000 parts by mass or less, based on 100 parts by mass of the unmodified lignin. Preferably, it is 10000 parts by mass or less.
  • the blending ratio of the inorganic acid is such that the inorganic acid (100% conversion) is, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more with respect to 100 parts by mass of the unmodified lignin. 10 parts by mass or less, preferably 5 parts by mass or less.
  • the reaction temperature is, for example, 30 ° C. or more, preferably 50 ° C. or more, for example, 400 ° C. or less, preferably 250 ° C. or less.
  • the reaction time is, for example, 0.5 hours or more, preferably 1 hour or more, for example, 20 hours or less, preferably 10 hours or less.
  • Such carboxylic acid-modified lignin is excellent in handleability.
  • lignin that has not been modified with carboxylic acid has relatively low solubility in organic solvents and does not melt, so that it may be inferior in handleability depending on the application.
  • lignin modified with carboxylic acid as described above is an organic solvent (for example, esters such as methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone).
  • esters such as methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone
  • aliphatic alcohols such as methanol, for example, phenols such as phenol, cresol, bisphenol A, for example, ethers such as diethyl ether, tetrahydrofuran and dioxane, such as methyl cellosolve acetate, ethyl cellosolve acetate, methylcarbyl Tall acetate, ethyl carbitol acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybuty Glycol ether esters such as acetate and ethyl-3-ethoxypropionate, for example, nitriles such as acetonitrile, others, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexa Since it is relatively soluble in polar solvents such as methylphosphonilamide
  • the carboxylic acid-modified lignin can also be used as a solution of the above organic solvent.
  • the concentration of the carboxylic acid-modified lignin in the solution is, for example, 10% by mass or more, and preferably 30% by mass or more.
  • the average particle size of the carboxylic acid-modified lignin is, for example, 0.1 ⁇ m or more, preferably 5 ⁇ m or more, for example, 2 cm or less, preferably 1 cm or less.
  • the carboxylic acid-modified lignin is obtained as a mixture of a component (soluble component) that can be dissolved by the organic solvent (preferably ethyl acetate) and a component that cannot be dissolved by the organic solvent (insoluble component).
  • soluble component preferably ethyl acetate
  • insoluble component a component that cannot be dissolved by the organic solvent
  • a mixture of a soluble component and an insoluble component (referred to as crude carboxylic acid-modified lignin) can be used as the carboxylic acid-modified lignin.
  • the carboxylic acid-modified lignin is preferably a soluble component.
  • the extraction conditions are appropriately set according to the organic solvent used and the physical properties of the crude carboxylic acid-modified lignin.
  • lignin (such as unmodified lignin and carboxylic acid-modified lignin) has an aliphatic hydroxyl group in the molecule.
  • An aliphatic hydroxyl group is a hydroxyl group that is not directly bonded to an aromatic ring but directly bonded to an aliphatic hydrocarbon, and is distinguished from a hydroxyl group directly bonded to an aromatic ring (aromatic hydroxyl group (phenolic hydroxyl group)).
  • the content of the aliphatic hydroxyl group of lignin is 0.5% by mass or more, preferably 3.0% by mass or more, and 7.0% by mass or less, preferably 5.5% by mass with respect to the total amount of lignin. % Or less.
  • the lignin containing an aliphatic hydroxyl group in the above range is preferably a carboxylic acid-modified lignin derived from a herbaceous plant, more preferably an acetic acid-modified lignin derived from a herbaceous plant.
  • Phenols are phenols and derivatives thereof such as phenol, and further, for example, o-cresol, p-cresol, p-ter-butylphenol, p-phenylphenol, p-cumylphenol, p-nonylphenol, Examples include 2,4- or 2,6-xylenol, m-cresol, resorcinol, 3,5-xylenol, bisphenol A, dihydroxydiphenylmethane, and the like. Further, for example, halogenated phenols substituted with halogen such as chlorine and bromine can be mentioned. These phenols can be used alone or in combination of two or more.
  • Phenols are preferably phenol.
  • aldehydes examples include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde (n-butyraldehyde, isobutyraldehyde), furfural, glyoxal, benzaldehyde, trioxane, tetraoxane and the like. Moreover, a part of aldehyde may be substituted with furfuryl alcohol or the like. These aldehydes can be used alone or in combination of two or more.
  • aldehydes include formaldehyde and paraformaldehyde.
  • aldehydes can be used as an aqueous solution, for example.
  • the concentration of aldehydes is, for example, 10% by mass or more, preferably 20% by mass or more, for example, 99% by mass or less, preferably 95% by mass or less.
  • ketones can be blended with aldehydes.
  • ketones examples include acetone, methyl ethyl ketone, diethyl ketone, acetophenone, diphenyl ketone, and the like. These ketones can be used alone or in combination of two or more.
  • the blending ratio of the ketones is, for example, 0.01 parts by mass or more, preferably 1 part by mass or more with respect to 100 parts by mass of the aldehydes based on the solid content. 200 parts by mass or less, preferably 100 parts by mass or less.
  • the mixing ratio of the phenols is, for example, 30 parts by mass or more, preferably 50 parts by mass or more, more preferably 100 parts by mass or more, for example, 1000 parts by mass with respect to 100 parts by mass of lignin.
  • it is preferably 500 parts by mass or less, and more preferably 350 parts by mass or less.
  • the blending ratio of aldehydes is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, for example, 35 parts by mass or less, preferably 30 parts by mass or less, relative to 100 parts by mass of phenols. is there.
  • the blending ratio of aldehydes is, for example, 1.5 parts by mass or more, preferably 3 parts by mass or more, for example, 350 parts by mass or less, preferably 300 parts by mass or less, with respect to 100 parts by mass of lignin. It is.
  • the blending ratio of each component is within the above range, various physical properties (electrical insulation, mechanical properties, heat resistance, water resistance, etc.) can be improved.
  • Examples of the acid catalyst include organic acids and inorganic acids.
  • organic acid examples include sulfonic acid compounds such as methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, cumenesulfonic acid, dinonylnaphthalene monosulfonic acid, dinonylnaphthalenedisulfonic acid, for example, trimethyl phosphate, Examples thereof include phosphate esters having an alkyl group having 1 to 18 carbon atoms such as triethyl phosphate, monobutyl phosphate, dibutyl phosphate, tributyl phosphate, trioctyl phosphate, and the like, for example, formic acid, acetic acid, oxalic acid and the like.
  • sulfonic acid compounds such as methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, cumenesulfonic acid, dinonylna
  • inorganic acids examples include phosphoric acid, hydrochloric acid, sulfuric acid, and nitric acid.
  • These acid catalysts can be used alone or in combination of two or more.
  • the acid catalyst is preferably an organic acid, more preferably oxalic acid.
  • the mixing ratio of the acid catalyst is, for example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more, for example, 10 parts by mass or less, preferably 100 parts by mass with respect to 100 parts by mass of phenols. 7 parts by mass or less.
  • the timing of addition of the acid catalyst is not particularly limited, and may be added in advance to at least one of lignin, phenols, and aldehydes, and added at the same time when lignin, phenols, and aldehydes are blended. Further, it may be added after blending lignin, phenols and aldehydes.
  • the reaction temperature is, for example, 50 ° C. or higher, preferably 80 ° C. or higher, for example, 200 ° C. or lower, preferably 180 ° C. or lower.
  • the reaction time is, for example, 1 hour or more, preferably 2 hours or more, for example, 20 hours or less, preferably 15 hours or less.
  • a novolac type phenol resin is obtained as a reaction product of lignin, phenols and aldehydes.
  • a novolac-type phenol resin is obtained by the reaction of phenols and aldehydes in the presence of an acid catalyst, and the novolac-type phenol resin is modified with lignin.
  • a novolak-type phenol resin modified with lignin (hereinafter sometimes referred to as a lignin-modified novolak-type phenol resin) is obtained.
  • lignin and phenols are reacted to prepare a lignin-phenol composition containing a reaction product of lignin and phenols, and then the lignin-phenol composition and aldehyde React with a kind.
  • the phenols are blended in an excess equivalent amount with respect to lignin.
  • the blending ratio of phenols is, for example, 30 parts by mass or more, preferably 100 parts by mass of lignin. 50 parts by mass or more, for example, 1000 parts by mass or less, preferably 500 parts by mass or less.
  • the mixing ratio of the acid catalyst is, for example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more, for example, 10 parts by mass or less, preferably 5 parts by mass with respect to 100 parts by mass of the phenols. It is as follows.
  • the timing of addition of the acid catalyst is not particularly limited, and may be added in advance to at least one of lignin and phenols, or may be added simultaneously with the blending of lignin and phenols. It may be added after blending lignin and phenols.
  • the reaction temperature is, for example, 60 ° C. or higher, preferably 80 ° C. or higher, for example, 250 ° C. or lower, preferably 200 ° C. or lower.
  • the reaction time is, for example, 0.5 hours or more, preferably 1 hour or more, for example, 10 hours or less, preferably 5 hours or less.
  • This reaction modifies lignin with phenols. Specifically, an aliphatic hydroxyl group in the lignin molecule (in the case where the lignin is a carboxylic acid-modified lignin, an aliphatic hydroxyl group modified with a carboxylic acid and an aliphatic hydroxyl group remaining unmodified with a carboxylic acid are included. .) Is replaced by phenols.
  • the lignin-phenol composition obtained by the above reaction contains a reaction product of lignin and phenols (lignin modified with phenols) and free phenols.
  • the lignin-phenol composition obtained as described above (that is, lignin modified with phenols and free phenols) is reacted with aldehydes.
  • the blending ratio of aldehydes is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, with respect to 100 parts by mass of phenols (phenols used as a raw material in the above reaction). , 35 parts by mass or less, preferably 30 parts by mass or less.
  • the above acid catalyst can be added at an appropriate ratio, if necessary.
  • the reaction temperature is, for example, 50 ° C. or higher, preferably 80 ° C. or higher, for example, 200 ° C. or lower, preferably 180 ° C. or lower.
  • the reaction time is, for example, 1 hour or more, preferably 2 hours or more, for example, 20 hours or less, preferably 15 hours or less.
  • the above lignin-phenol composition reacts with aldehydes to obtain a novolak-type phenol resin modified with lignin (lignin-modified novolak-type phenol resin).
  • unreacted raw materials unreacted phenols, etc.
  • acid catalyst can be removed by a known method such as distillation, if necessary.
  • Such a novolak type phenolic resin (that is, lignin-modified novolak type phenolic resin) uses lignin having an aliphatic hydroxyl group in the molecule at a predetermined ratio as a raw material, so that productivity (resin yield, production rate, etc.) is improved. Excellent.
  • a molded product excellent in various physical properties electrical insulation, mechanical properties, heat resistance, water resistance, etc. can be obtained.
  • the novolac type phenol resin can be obtained with good productivity (resin yield, production rate, etc.).
  • the resin composition of this invention contains said novolak-type phenol resin as an essential component.
  • the resin composition can contain a phenol resin curing agent, if necessary.
  • the phenol resin curing agent is not particularly limited, and a known curing agent can be used. Specifically, for example, hexamethylenetetramine, methylolmelamine, methylolurea, phenol novolac and the like can be mentioned.
  • phenolic resin curing agents can be used alone or in combination of two or more.
  • the blending ratio of the phenol resin curing agent is appropriately set according to the purpose and application.
  • the resin composition can further contain an additive.
  • additives added to the resin composition examples include known additives added to the resin composition, known additives such as fillers (wood flour, pulp, glass fibers, etc.), colorants, plasticizers, stabilizers, release agents ( Metal soap such as zinc stearate).
  • additives can be used alone or in combination of two or more.
  • the content of the additive is appropriately set according to the purpose and application within a range that does not impair the excellent effects of the present invention.
  • the blending ratio is, for example, 10 parts by mass or more, preferably 20 parts by mass or more with respect to 100 parts by mass of the resin composition. 500 parts by mass or less, preferably 300 parts by mass or less.
  • the additive may be added in advance to at least one of lignin, phenols, and aldehydes, or may be added at the same time when lignin, phenols, and aldehydes are blended, and lignin, phenol It may be added after blending of aldehydes and aldehydes, or may be added directly to their reaction products.
  • the resin composition thus obtained contains the above-described novolak-type phenol resin (that is, lignin-modified novolak-type phenol resin), and thus has excellent productivity and various physical properties.
  • Such a resin composition is suitably used for the production of a molded product.
  • the above resin composition is molded by a known thermosetting resin molding method such as transfer molding or compression molding.
  • a known thermosetting resin molding method such as transfer molding or compression molding.
  • the molded product obtained can be widely used in various industrial fields such as electric parts, automobile parts, building materials, and daily necessities.
  • Resin yield (%) [mass of obtained novolac-type phenol resin] ⁇ [total mass of charged raw materials] ⁇ 100 ⁇ Manufacture of lignin >> Production Example 1 (Lignin Acetate) 100 parts by mass of corn stover was mixed with 1000 parts by mass of 95% by mass acetic acid and 3 parts by mass of sulfuric acid, and reacted for 4 hours under reflux. After the reaction, the pulp was removed by filtration, and the pulp waste liquid was recovered. Next, after removing acetic acid in the pulp waste liquid using a rotary evaporator and concentrating until the volume becomes 1/10, 10 times the amount of the concentrated liquid (mass basis) is added and filtered, Acetic acid-modified lignin was obtained as a solid content.
  • the content of aliphatic hydroxyl groups in acetic acid-modified lignin was 5.1% by mass.
  • the content of aliphatic hydroxyl group in alkali lignin was 3.1% by mass.
  • Example 1 493.5 g of phenol was put in a flask and heated to about 50 ° C. to liquefy the phenol, and then 150 g of lignin acetate obtained in Production Example 1 was added.
  • the yield of novolac type phenolic resin was 74.9%.
  • Examples 2 to 4 and Comparative Example 1 A novolac type phenolic resin and a resin composition were obtained in the same manner as in Example 1 except that the formulation shown in Table 1 was used.
  • Example 2 the alkaline lignin obtained in Production Example 2 was used in place of acetic acid lignin.
  • Example 3 kraft lignin (manufactured by SIGMA-ALDRICH, aliphatic hydroxyl group content 4.4 mass%) was used instead of acetic acid lignin.
  • Example 4 493.5 g of phenol was put in a flask and heated to about 50 ° C. to liquefy the phenol, and then 150 g of acetic acid-modified lignin obtained in Production Example 1 was added.
  • the yield of novolac type phenolic resin was 69.7%.
  • Example 5 A novolac type phenolic resin and a resin composition were obtained in the same manner as in Example 4 except that the formulation shown in Table 2 was used.
  • Example 5 alkaline lignin obtained in Production Example 2 was used in place of acetic acid lignin.
  • Comparative Example 2 846 g of phenol, 13.02 g of oxalic acid (acid catalyst) and 172.5 g of paraformaldehyde were placed in a flask and reacted at 95 ° C. for 2.5 hours. Next, the temperature was raised to 110 ° C. at 0.5 ° C./min and reacted at 110 ° C. for 1.5 hours. Next, the temperature was raised to 120 ° C. at 0.5 ° C./min and reacted at 120 ° C. for 2 hours.
  • the yield of novolac type phenolic resin was 60.1%.
  • Glass transition temperature (Tg) The solid dynamic viscoelasticity was measured using Rhegel-E4000 (manufactured by UBM) (frequency 1 Hz, temperature rising rate 2 ° C./min). And the peak temperature of the obtained tan-delta curve was calculated
  • volume resistivity (electrical insulation) According to JIS K6911 (1995 edition), volume resistivity ( ⁇ ⁇ cm) was measured using HP4339A (manufactured by Agilent Technologies).
  • the production method of the novolac type phenolic resin, the resin composition and the novolac type phenolic resin of the present invention can be widely used in various industrial fields such as electric parts, automobile parts, building materials and daily necessities.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

Cette résine phénolique de type novolaque est un produit de réaction qui est obtenu par réaction d'une lignine qui présente un groupe hydroxyle aliphatique dans chaque molécule, d'un phénol et d'un aldéhyde en présence d'un catalyseur acide ; et le rapport de la teneur en groupe hydroxyle aliphatique dans la lignine est de 0,5 % en masse à 7,0 % en masse (valeurs extrêmes comprises) par rapport à la masse totale de la lignine.
PCT/JP2017/044286 2017-01-24 2017-12-11 Résine phénolique de type novolaque, composition de résine et procédé de production de résine phénolique de type novolaque WO2018139074A1 (fr)

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US20190233570A1 (en) * 2018-01-26 2019-08-01 Hexion Inc. Manufacture of novolacs and resoles using lignin
JP2020050814A (ja) * 2018-09-28 2020-04-02 住友ベークライト株式会社 フェノール変性リグニン樹脂を含む樹脂材料、それを用いたフェノール変性リグニン樹脂組成物および構造体
CN113728053A (zh) * 2018-12-27 2021-11-30 苏扎诺有限公司 酚醛清漆型酚醛树脂、所述酚醛树脂的合成方法及其用途

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WO2016098667A1 (fr) * 2014-12-16 2016-06-23 ハリマ化成株式会社 Feuille imprégnée, feuille stratifiée et composition de résine
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JP2014024933A (ja) * 2012-07-26 2014-02-06 Hitachi Chemical Co Ltd リグニンを用いた自己硬化型樹脂
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JP2020050814A (ja) * 2018-09-28 2020-04-02 住友ベークライト株式会社 フェノール変性リグニン樹脂を含む樹脂材料、それを用いたフェノール変性リグニン樹脂組成物および構造体
CN113728053A (zh) * 2018-12-27 2021-11-30 苏扎诺有限公司 酚醛清漆型酚醛树脂、所述酚醛树脂的合成方法及其用途
EP3904459A4 (fr) * 2018-12-27 2022-09-07 Suzano S.A. Résines phénoliques de type novolaque, procédé de synthèse desdites résines phénoliques et utilisation de celles-ci

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