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WO2018150708A1 - Procédé de fabrication de dérivé de biomasse, résine phénol modifié par biomasse ainsi que procédé de fabrication de celle-ci, procédé de fabrication de composition de résine phénol modifié par biomasse - Google Patents

Procédé de fabrication de dérivé de biomasse, résine phénol modifié par biomasse ainsi que procédé de fabrication de celle-ci, procédé de fabrication de composition de résine phénol modifié par biomasse Download PDF

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Publication number
WO2018150708A1
WO2018150708A1 PCT/JP2017/045128 JP2017045128W WO2018150708A1 WO 2018150708 A1 WO2018150708 A1 WO 2018150708A1 JP 2017045128 W JP2017045128 W JP 2017045128W WO 2018150708 A1 WO2018150708 A1 WO 2018150708A1
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Prior art keywords
biomass
producing
phenolic resin
modified phenolic
modified
Prior art date
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Ceased
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PCT/JP2017/045128
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English (en)
Japanese (ja)
Inventor
直幸 原田
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Sumitomo Bakelite Co Ltd
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Sumitomo Bakelite Co Ltd
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Priority to JP2018526732A priority Critical patent/JPWO2018150708A1/ja
Publication of WO2018150708A1 publication Critical patent/WO2018150708A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • 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
    • C08G8/28—Chemically modified polycondensates
    • C08G8/34—Chemically modified polycondensates by natural resins or resin acids, e.g. rosin

Definitions

  • the present invention relates to a method for producing a biomass derivative, a method for producing a biomass-modified phenol resin, a method for producing a biomass-modified phenol resin composition, and a biomass-modified phenol resin.
  • Examples of the technique relating to the method for producing the modified phenolic resin include the technique described in Patent Document 1. According to this document, cashew oil and sulfuric acid are added and reacted at 200 ° C. for 10 hours to obtain a cashew oil self-polymerized product, and then phenol, formalin and sulfuric acid are added thereto and reacted at 100 ° C. for 5 hours. After that, ammonia water was added, the temperature was raised to 180 ° C., and vacuum distillation was started to obtain a cashew oil-modified phenol resin suitable as a rubber composition for a tire (Patent Document 1). Example 1).
  • a method for producing a biomass-modified phenolic resin comprising a step of obtaining a biomass-modified phenolic resin by reacting the biomass derivative, phenols and aldehydes obtained by the method for producing a biomass derivative.
  • a method for producing a biomass-modified phenol resin composition comprising a step of mixing a biomass-modified phenol resin obtained by the method for producing a biomass-modified phenol resin and a curing agent.
  • the unsaturated carbon chain-containing phenols derived from plant raw materials have a structural unit directly bonded through the unsaturated carbon chain,
  • the ratio of peaks derived from alkyl chain unsaturated bonds (peaks of 4.5 to 6.0 ppm) in the 1 H-NMR spectrum are peaks derived from hydrogen bonded to carbon atoms (peaks of 0.2 to 7.5 ppm).
  • the biomass-modified phenolic resin is 2% or less of the total integrated value.
  • a biomass derivative, a biomass-modified phenol resin, a method for producing a biomass-modified phenol resin composition, and a biomass-modified phenol resin capable of realizing a cured product having excellent heat resistance, mechanical strength, and flexibility are provided.
  • the method for producing a biomass derivative according to the present embodiment includes a self-polymerization step of self-polymerizing unsaturated carbon chain-containing phenols derived from plant raw materials to obtain a copolymer, and adding phenols to double bonds of unsaturated carbon chains in the copolymer. And an addition reaction step of causing an addition reaction.
  • the method for producing a biomass-modified phenolic resin of the present embodiment can include a step of obtaining a biomass-modified phenolic resin by reacting the obtained biomass derivative, phenols and aldehydes.
  • the self-polymerization step can increase the copolymer derived from plant raw materials (hereinafter sometimes referred to as biomass) to increase the structure having flexibility. Furthermore, by the addition reaction step, phenols can be added to the copolymer, and the copolymers can be bonded to each other via the phenol. Thereby, in the biomass derivative, the reactive group at the time of resinification can be increased due to the added phenols, and the copolymer having a flexible structure increases via the phenols, so that the flexibility is increased. The strength and heat resistance can be improved by increasing the crosslinking density.
  • unsaturated carbon chain-containing phenols derived from plant raw materials are obtained by heat-treating unsaturated carbon chain-containing phenols derived from plant raw materials in a container in the presence of an acidic catalyst. Can be self-polymerized to obtain a copolymer. Thereby, the structure derived from the biomass which has a softness
  • phenols, aldehydes and phenol resins are not included.
  • the acidic catalyst used in the self-polymerization step is not particularly limited, and examples thereof include organic carboxylic acids such as oxalic acid and acetic acid, organic sulfonic acids such as benzenesulfonic acid, paratoluenesulfonic acid, and methanesulfonic acid, hydrochloric acid, sulfuric acid, and the like.
  • organic carboxylic acids such as oxalic acid and acetic acid
  • organic sulfonic acids such as benzenesulfonic acid, paratoluenesulfonic acid, and methanesulfonic acid, hydrochloric acid, sulfuric acid, and the like.
  • An inorganic acid etc. are mentioned.
  • organic sulfonic acids such as paratoluenesulfonic acid and inorganic acids such as sulfuric acid can be used.
  • the reaction temperature in the self-polymerization step can be appropriately selected depending on the plant raw material, but may be, for example, 130 ° C. to 200 ° C., preferably 140 ° C. to 180 ° C. (hereinafter, “ ⁇ ” Unless otherwise stated, it includes the upper and lower limits).
  • the reaction time in the self-polymerization step is not particularly limited and may be appropriately determined according to the reaction conditions. For example, it may be 1 to 8 hours.
  • the plant raw material is not particularly limited as long as it is an unsaturated carbon chain-containing phenol, but for example, plant-derived non-organic compounds such as cinnamic acid, cinnamaldehyde, caffeic acid, ferulic acid, coumaric acid, and derivatives thereof.
  • plant-derived non-organic compounds such as cinnamic acid, cinnamaldehyde, caffeic acid, ferulic acid, coumaric acid, and derivatives thereof.
  • Saturated carboxylic acids plant-derived phenolic hydroxyl groups such as cashew nut shell liquid (cashew oil) such as cardanol, curdle, methyl curdal and anacardic acid, urushi extracts such as urushiol, laccol and thiol, and purified products thereof
  • unsaturated alkyl group-containing phenols These may be used alone or in combination of two or more.
  • the biomass modification rate in the biomass-modified phenol resin can be increased, and the heat resistance of the cured product can be improved.
  • phenolic hydroxyl group and unsaturated alkyl group-containing phenols it is possible to realize a biomass-modified phenolic resin that is excellent in reactivity while having a high biomass introduction rate.
  • a molded product composed of a cured product of a biomass-modified phenol resin can be excellent in heat resistance.
  • plant raw materials containing cashew oil can be used from the viewpoint of cost.
  • the cashew oil is an oily liquid contained in cashew nut shells, and contains anacardic acid, cardol, 2-methylcardol, cardanol and the like.
  • the cashew oil can include one or more selected from the group consisting of cardanol, cardol, and 2-methylcardol.
  • a purified product of cashew oil such as cardanol may also be used. These may be used alone or in combination of two or more.
  • the phenolic hydroxyl group and unsaturated alkyl group-containing phenols can include, for example, a phenol compound represented by the following general formula (1). These may be used alone or in combination of two or more.
  • R represents a linear unsaturated hydrocarbon group having 10 or more carbon atoms.
  • the hydrogen atom bonded to the benzene ring having a phenolic hydroxyl group may be substituted with a substituent.
  • R may be any of the ortho, meta, and para positions, and may be one or more, two or more, or three or more.
  • R represents a straight chain unsaturated hydrocarbon group having 10 or more carbon atoms, preferably a straight chain unsaturated hydrocarbon group having 10 to 20 carbon atoms, and a straight chain chain having 12 to 20 carbon atoms.
  • An unsaturated hydrocarbon group is preferred, and a straight chain unsaturated hydrocarbon group having 12 to 18 carbon atoms is more preferred.
  • the straight-chain unsaturated hydrocarbon group only needs to have one or more double bonds, and may have two or three.
  • the substituent that replaces the hydrogen atom bonded to the benzene ring having a phenolic hydroxyl group is not particularly limited, and examples thereof include an acetyl group, a methyl group, and a hydroxyl group.
  • phenol compound represented by the above (1) examples include 3-dodecenylphenol, 3-tridecenylphenol, 3-pentadecenylphenol, 5-tridecenylresorcinol, 5- Pentadecenyl resorcinol, cardanol, which is a phenol having a linear unsaturated hydrocarbon group having 15 carbon atoms in the meta position, cardol having a linear unsaturated hydrocarbon group having 15 carbon atoms in the meta position and a hydroxyl group, in the meta position Examples thereof include a linear unsaturated hydrocarbon group having 15 carbon atoms, a hydroxyl group, and 2-methylcardol, which is a phenol having a methyl group in the ortho position.
  • the obtained copolymer may be, for example, a monomer derived from biomass, a dimer, a trimer, a tetramer, or a pentamer or more.
  • the copolymer may contain these alone or in combination.
  • the abundance ratio of each monomer in the copolymer can be measured by GPC, for example.
  • the content ratio of the copolymer component of the dimer or higher is, for example, 40% by mass or higher, preferably 50%. It is at least mass%, more preferably at least 60 mass%.
  • the addition reaction step is performed by, for example, subjecting the obtained copolymer and phenols in a vessel to a double bond of an unsaturated carbon chain in the copolymer by heat treatment in the presence of an acidic catalyst.
  • Biomass derivatives can be obtained by addition reaction of the above.
  • the monomer when the biomass-derived monomer remains in the self-polymerization step, the monomer can also react in the addition reaction step, so the ratio of the copolymer pentamer or higher component in the obtained biomass derivative Can be increased.
  • the content ratio of the copolymer component of the dimer or higher is, for example, 45% by mass or more, preferably 55% by mass. % Or more, and more preferably 65% by mass or more.
  • the content ratio of the copolymer component of the pentamer or higher after the addition reaction step is 1.1 times or more with respect to the content ratio of the copolymer component of the pentamer or higher after the self-polymerization step and before the addition reaction step, for example. Preferably, it is 1.2 times or more, more preferably 1.3 times or more.
  • phenols can be added to the copolymer, and the copolymers can be bonded to each other via the phenol.
  • the reactive group at the time of resinification can be increased due to the added phenols, and the copolymer having a flexible structure becomes larger via the phenols, so that the flexibility is increased.
  • the strength and heat resistance can be improved by increasing the crosslinking density.
  • the acidic catalyst exemplified in the self-polymerization step can be used.
  • the reaction temperature in the addition reaction step can be appropriately selected depending on the plant raw material, but may be, for example, 140 ° C. to 200 ° C., and preferably 160 ° C. to 180 ° C.
  • the reaction time in the addition reaction step is not particularly limited and may be appropriately determined according to the reaction conditions. For example, the reaction time may be 2 to 8 hours.
  • the self-polymerization step and the addition reaction step may be continuously performed using, for example, the same kind of acidic catalyst.
  • the acidic catalyst may be neutralized and removed as necessary, or the acidic catalyst may remain in the biomass derivative as it is.
  • excess unreacted phenols may be removed thereafter, or unreacted phenols may remain in the biomass derivative.
  • the number of phenol rings may be mononuclear, dinuclear or trinuclear, and the number of phenolic hydroxyl groups may be one or two or more. Examples of the phenols are not particularly limited.
  • phenol cresols such as orthocresol, metacresol, and paracresol
  • 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6 -Xylenol such as xylenol, 3,5-xylenol; 2,3,5-trimethylphenol, 2-ethylphenol, 4-ethylphenol, 2-isopropylphenol, 4-isopropylphenol, n-butylphenol, isobutylphenol, tert- Alkylphenols such as butylphenol, hexylphenol, octylphenol, nonylphenol, phenylphenol, benzylphenol, cumylphenol, allylphenol; naphtho such as 1-naphthol and 2-naphthol Halogenated phenols such as fluorophenol, chlorophenol, bromophenol and iodophenol, monohydric phenol substitutes such as p
  • the step of obtaining the biomass-modified phenol resin can include a step of reacting the obtained biomass derivative, phenols and aldehydes.
  • denaturation phenol resin which a biomass derivative, phenols, and aldehydes react can be obtained.
  • the step of obtaining a reaction solution can be performed under acidic conditions.
  • a known acidic catalyst such as an organic acid or an inorganic acid can be used.
  • the step of obtaining a reaction solution can be performed under alkaline conditions.
  • an alkaline catalyst can be used.
  • a method for producing a novolac type phenol resin will be described. Among these, from the viewpoint of strength, a novolac-type biomass-modified phenol resin can be used.
  • aldehydes used for the process of obtaining the said biomass modified phenol resin
  • formaldehyde such as formalin and paraformaldehyde
  • Trioxane acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal N-butyraldehyde, caproaldehyde, allyl aldehyde, benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde and the like.
  • formaldehyde such as formalin and paraformaldehyde
  • Trioxane acetaldehyde
  • propionaldehyde polyoxymethylene
  • chloral hexamethylenetetramine
  • furfural glyoxal N-butyralde
  • aldehydes may be used alone or in combination of two or more.
  • aldehydes can contain formaldehyde or acetaldehyde, and formalin or paraformaldehyde can be used from the viewpoint of productivity and low cost.
  • the phenols described in the addition reaction step can be used. These may be used alone or in combination of two or more.
  • the phenols used in each step may be the same or different.
  • the acidic catalyst used when synthesizing the novolac-type biomass-modified phenolic resin is not particularly limited.
  • acids such as oxalic acid, hydrochloric acid, sulfuric acid, diethylsulfuric acid, paratoluenesulfonic acid, and metals such as zinc acetate
  • metals such as zinc acetate
  • salts examples thereof include salts, and these can be used alone or in combination of two or more.
  • it does not specifically limit as the usage-amount of an acidic catalyst It can be 0.1 mass% or more and 10 mass% or less with respect to the biomass modified phenol resin whole.
  • reaction solvent in the present embodiment water may be used, but an organic solvent may be used.
  • organic solvent a non-aqueous solvent can be used using a non-polar solvent.
  • organic solvents include, for example, alcohols, ketones, aromatics, alcohols include methanol, ethanol, propyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, glycerin, etc., and ketones include Acetone, methyl ethyl ketone and the like, and aromatics include toluene, xylene and the like. These may be used alone or in combination of two or more.
  • the reaction temperature may be, for example, 40 ° C. to 120 ° C., preferably 60 ° C. to 110 ° C.
  • limiting in particular in reaction time What is necessary is just to determine suitably according to the kind of starting material, compounding molar ratio, the usage-amount and kind of a catalyst, and reaction conditions.
  • reaction solution containing a biomass-modified phenol resin can be obtained.
  • a neutralization step for neutralizing the reaction solution may be performed.
  • a dehydration step may be further performed.
  • vacuum dehydration may be used, but normal pressure dehydration may be used.
  • the degree of vacuum at the time of dehydration under reduced pressure may be, for example, 110 torr or less, and more preferably 80 torr or less.
  • the dehydration time can be shortened, and a stable biomass-modified phenol resin with little variation in resin characteristics can be obtained.
  • moisture content in biomass modified phenol resin can be made into 5 weight% or less by such a spin-drying
  • the novolac-type biomass-modified phenol resin can be recovered.
  • the biomass-modified phenolic resin obtained by the method for producing a biomass-modified phenolic resin of this embodiment will be described.
  • the biomass-modified phenolic resin of this embodiment can be solid at room temperature of 25 ° C.
  • the biomass-modified phenol resin of the present embodiment can have a structural unit in which unsaturated carbon chain-containing phenols derived from plant raw materials are directly bonded via the unsaturated carbon chain.
  • This direct bond can have, for example, a structure in which unsaturated double bonds in an unsaturated carbon chain react with each other and phenolic phenol rings derived from biomass are chemically cross-linked via each other's carbon chain.
  • An example of the biomass-modified phenol resin of the present embodiment can have a structural unit in which biomass-derived phenols are directly bonded to each other via a crosslinking group having 10 or more carbon atoms.
  • This bridging group can have a structure in which the unsaturated carbon chain derived from biomass is directly bonded to a terminal or an internal double bond.
  • the unsaturated carbon chain may be, for example, an unsaturated alkyl group, preferably a straight chain unsaturated hydrocarbon group having 10 or more carbon atoms.
  • the ratio of peaks derived from alkyl chain unsaturated bonds (peaks of 4.5 to 6.0 ppm) in the 1 H-NMR spectrum is, for example, hydrogen bonded to carbon atoms.
  • the upper limit of the total integrated value of peaks derived from (peaks of 0.2 to 7.5 ppm) is 2.0% or less, preferably 1.5% or less, more preferably 1.0% or less More preferably, it is 0.9% or less.
  • the lower limit value of the total integrated value is not particularly limited, but may be, for example, 0% or more, 0.15% or more, or 0.2% or more.
  • the ratio of the peak derived from the alkyl chain unsaturated bond can be controlled.
  • performing the addition reaction step by appropriately selecting the type of catalyst, reaction temperature, type of biomass, etc., is in the numerical range of the ratio of the peak derived from the alkyl chain unsaturated bond. It is mentioned as an element.
  • the modification rate of the biomass-modified phenolic resin of this embodiment may be, for example, 1% to 99%, 5% to 80%, or 10% to 60%.
  • the modification rate can be controlled by appropriately adjusting the ratio of the charged amount of the biomass derivative.
  • the heat resistance, mechanical strength, and flexibility of the obtained cured product can be improved.
  • the biomass-modified phenolic resin of the present embodiment can have a reduced presence rate of double bonds of biomass-derived unsaturated carbon chains as compared with the case where the addition reaction step is not performed.
  • stability over time can be improved about biomass modification phenol resin stored at normal temperature etc.
  • the detailed mechanism is not clear, there is a risk that the remaining double bond reacts during storage, thickening or increasing the molecular weight, and the properties of the cured product may be deteriorated. It is considered that such a phenomenon can be suppressed and stability over time can be improved.
  • the biomass-modified phenolic resin composition of the present embodiment can contain the biomass-modified phenolic resin and a curing agent.
  • the curing agent examples include hexamethylenetetramine and resol type phenol resin.
  • hexamethylenetetramine can be used from the viewpoint of the heat resistance of the cured product and the biomass content.
  • the biomass-modified phenol resin composition of this embodiment can contain various fillers, for example.
  • the filler is not particularly limited.
  • inorganic powder fillers such as magnesium hydroxide, aluminum hydroxide, wollastonite and metal powder, and reinforcing fibers such as glass fiber, carbon fiber, aramid fiber, nylon fiber and metal fiber. These may be used alone or in combination of two or more.
  • the biomass-modified phenolic resin composition of the present embodiment further includes additives such as a colorant, a mold release agent, a curing catalyst, a curing aid, a coupling agent, a low stress agent, a flame retardant, and a solvent as necessary. Can be included.
  • the method for producing a biomass-modified phenolic resin composition of the present embodiment can include a step of mixing the biomass-modified phenolic resin obtained by the above-described method for producing a biomass-modified phenolic resin and a curing agent.
  • a blend is mixed at a predetermined blending ratio, melt-kneaded using a kneader such as a heating roll, a kneader, or a twin-screw extruder, and then cooled, ground, or granulated.
  • a kneader such as a heating roll, a kneader, or a twin-screw extruder
  • the above biomass-modified phenolic resin composition can be obtained by a method of mixing the above blend as it is or adding a solvent or the like to the above blend and using a dry or wet mixer.
  • a cured product (molded body) of a biomass-modified phenol resin can be obtained by molding such a biomass-modified phenol resin composition into a normal molding method such as compression molding, transfer molding, injection molding or the like.
  • the cured product (molded product) of the biomass-modified phenolic resin of the present embodiment has the same heat resistance as an existing phenolic resin and is excellent in durability at high temperatures, and can be used for various applications. It can be applied to a wide range of uses such as moldings for automobiles, general-purpose machines, household appliances and peripheral devices thereof, grinding stones, tires, molding materials, epoxy curing agents, and the like.
  • a method for producing a biomass derivative according to claim 1 A method for producing a biomass derivative, wherein the plant material contains cashew oil. 3.
  • a method for producing a biomass derivative according to claim 1 A method for producing a biomass derivative, wherein the cashew oil contains one or more selected from the group consisting of cardanol, cardol, and 2-methylcardol. 4). 1.
  • a method for producing a biomass-modified phenol resin comprising a step of obtaining a biomass-modified phenol resin by reacting a biomass derivative obtained by the method for producing a biomass derivative according to any one of the above, phenols and aldehydes. 5). 4).
  • a method for producing a biomass-modified phenolic resin according to claim 1 The method for producing a biomass-modified phenolic resin, wherein the biomass-modified phenolic resin is solid at room temperature of 25 ° C. 6). 4). Or 5.
  • a method for producing a biomass-modified phenolic resin according to claim 1 The step of obtaining the biomass-modified phenol resin is a method for producing a biomass-modified phenol resin, which is performed under acidic conditions. 7). 4).
  • a method for producing a biomass-modified phenolic resin according to any one of The step of obtaining the biomass-modified phenol resin is a method for producing a biomass-modified phenol resin, including a step of removing the unreacted phenols. 8). 4).
  • To 7. A method for producing a biomass-modified phenolic resin according to any one of A method for producing a biomass-modified phenolic resin, wherein the aldehyde contains formaldehyde or acetaldehyde. 9. 1. To 8.
  • a method for producing a biomass-modified phenolic resin composition comprising a step of mixing a biomass-modified phenolic resin obtained by the method for producing a biomass-modified phenolic resin according to any one of the above and a curing agent. 11.
  • the unsaturated carbon chain-containing phenols derived from plant raw materials have a structural unit directly bonded through the unsaturated carbon chain,
  • the ratio of peaks derived from alkyl chain unsaturated bonds (peaks of 4.5 to 6.0 ppm) in the 1 H-NMR spectrum are peaks derived from hydrogen bonded to carbon atoms (peaks of 0.2 to 7.5 ppm).
  • Biomass-modified phenolic resin that is 2% or less of the total integrated value.
  • this biomass derivative a was found to have had a residual unsaturated double bond decreased by adding phenol to the unsaturated double bond derived from cashew oil. It was found that the content ratio of the copolymer component of the monomer or higher was increased to 72% by mass, and that the component of the pentamer was increased by 1.4 times in terms of the mass ratio compared to before the phenol addition reaction. 1000 parts of phenol, 838 parts of 37% formalin aqueous solution and 5 parts of 96% concentrated sulfuric acid were added to 1041 parts of the obtained biomass derivative a and reacted at 100 ° C. for 2 hours.
  • biomass-modified phenol resin B the biomass content is 20%, and the ratio of the peak derived from the alkyl chain unsaturated bond hydrogen determined from NMR is the integrated value of the peak derived from hydrogen bonded to the carbon atom. It was 0.5% with respect to the total.
  • biomass-modified phenolic resin C the biomass content is 10%, and the ratio of the peak derived from the alkyl chain unsaturated bond hydrogen determined from NMR is the integrated value of the peak derived from hydrogen bonded to the carbon atom. It was 0.7% with respect to the sum total.
  • the temperature was raised to 180 ° C., vacuum distillation was started, and when it reached 0.9 kPa, distillation was performed for 3 hours while blowing water vapor to obtain 1160 parts of a biomass-modified phenol resin D1160.
  • the biomass content is 25%
  • the ratio of the peak derived from the alkyl chain unsaturated bond hydrogen determined from NMR is the integrated value of the peak derived from hydrogen bonded to the carbon atom. It was 2.9% based on the total.
  • biomass-modified phenol resin E the biomass content is 59%, and the ratio of the peak derived from the alkyl chain unsaturated bond hydrogen obtained from NMR is the integrated value of the peak derived from hydrogen bonded to the carbon atom. It was 0.1% with respect to the total.
  • biomass-modified phenolic resin F1333 parts the biomass content is 38%, and the ratio of the peak derived from the alkyl chain unsaturated bond hydrogen determined by NMR is the integrated value of the peak derived from hydrogen bonded to the carbon atom. It was 2.2% with respect to the total.
  • the biomass content is 38%
  • the ratio of the peak derived from the alkyl chain unsaturated bond hydrogen determined by NMR is the integrated value of the peak derived from hydrogen bonded to the carbon atom. It was 0.1% with respect to the total.
  • the biomass-modified phenol resins A to G of Examples 1 to 3 and Comparative Examples 1 to 4 and the unmodified phenol resin H of Comparative Example 5 were evaluated in the following manner.
  • “Bending strength” and “flexural modulus” of the obtained cured product were measured at a room temperature of 25 ° C. or 250 ° C. in accordance with JIS K 6911 “Bending test method of hard plastic”.
  • the bending strength measured at room temperature of 25 ° C. is expressed as “25 ° C. bending strength”
  • the bending strength measured at 250 ° C. is expressed as “250 ° C. bending strength”
  • the bending elastic modulus measured at room temperature of 25 ° C. is expressed as “25 ° C.
  • the bending elastic modulus measured at 250 ° C. is expressed as “250 ° C. bending elastic modulus”.
  • the heat resistance is based on the following evaluation criteria for the bending strength ratio of “250 ° C. bending strength” to “25 ° C. bending strength” to “25 ° C. bending strength” of the obtained cured product. Based on the evaluation. The results are shown in Table 1. ⁇ : 0.66 or more ⁇ : 0.62 or more to less than 0.66 ⁇ : 0.58 or more to less than 0.62 ⁇ : less than 0.58
  • the cured products of Examples 1 to 3 are superior in flexibility and low elasticity because the flexural modulus at room temperature of 25 ° C. is lower than the cured products of Comparative Examples 1, 3, 4, and 5. I understood. Further, the cured products of Examples 1 to 3 are superior in strength because both the bending strength at room temperature of 25 ° C. and the bending strength at 250 ° C. are higher than those of Comparative Examples 1 to 3 and 4. I understood that. In addition, the cured products of Examples 1 to 3 are superior in heat resistance to the cured products of Comparative Examples 1 to 3 and 4 from the result of the bending strength ratio of 250 ° C. bending strength to 25 ° C. bending strength. I understood. The cured product (molded product) of the biomass-modified phenolic resin using the biomass derivatives of Examples 1 to 3 has the same high heat resistance as the existing phenolic resin, and has excellent flexibility and low elastic modulus. It can be suitably used for various applications.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

Le procédé de fabrication de dérivé de biomasse de l'invention inclut : une étape d'auto-polymérisation au cours de laquelle un copolymère est obtenu par auto-polymérisation de phénols comprenant une chaîne de carbone insaturé dérivé de matières premières végétales ; et une étape de réaction d'addition au cours de laquelle les phénols sont mis en réaction d'addition avec une double liaison de la chaîne de carbone insaturé contenue dans le copolymère.
PCT/JP2017/045128 2017-02-15 2017-12-15 Procédé de fabrication de dérivé de biomasse, résine phénol modifié par biomasse ainsi que procédé de fabrication de celle-ci, procédé de fabrication de composition de résine phénol modifié par biomasse Ceased WO2018150708A1 (fr)

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JPS52138595A (en) * 1976-05-15 1977-11-18 Matsushita Electric Works Ltd Preparation of modified phenolic resins
JP2002212250A (ja) * 2001-01-19 2002-07-31 Nisshoku Sukenekutadei Kagaku Kk カシュー油変性フェノール樹脂、その製造方法およびその用途
JP2007269843A (ja) * 2006-03-30 2007-10-18 Dainippon Ink & Chem Inc カシュー油変性固形フェノール樹脂の製造方法とゴム組成物
JP2013023633A (ja) * 2011-07-25 2013-02-04 Gun Ei Chem Ind Co Ltd 固形レゾール型バイオマスフェノール樹脂およびゴム組成物
JP2013177524A (ja) * 2012-02-29 2013-09-09 Sumitomo Bakelite Co Ltd バイオマス誘導体、バイオマス誘導体組成物及びバイオマス誘導体硬化物
JP2013209439A (ja) * 2012-03-30 2013-10-10 Sumitomo Bakelite Co Ltd バイオマス変性フェノール樹脂の製造方法、バイオマス変性フェノール樹脂、バイオマス変性フェノール樹脂組成物及びバイオマス変性フェノール樹脂硬化物
WO2017068866A1 (fr) * 2015-10-21 2017-04-27 住友ベークライト株式会社 Résine résol phénolique liquide, son procédé de préparation, et article

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52138595A (en) * 1976-05-15 1977-11-18 Matsushita Electric Works Ltd Preparation of modified phenolic resins
JP2002212250A (ja) * 2001-01-19 2002-07-31 Nisshoku Sukenekutadei Kagaku Kk カシュー油変性フェノール樹脂、その製造方法およびその用途
JP2007269843A (ja) * 2006-03-30 2007-10-18 Dainippon Ink & Chem Inc カシュー油変性固形フェノール樹脂の製造方法とゴム組成物
JP2013023633A (ja) * 2011-07-25 2013-02-04 Gun Ei Chem Ind Co Ltd 固形レゾール型バイオマスフェノール樹脂およびゴム組成物
JP2013177524A (ja) * 2012-02-29 2013-09-09 Sumitomo Bakelite Co Ltd バイオマス誘導体、バイオマス誘導体組成物及びバイオマス誘導体硬化物
JP2013209439A (ja) * 2012-03-30 2013-10-10 Sumitomo Bakelite Co Ltd バイオマス変性フェノール樹脂の製造方法、バイオマス変性フェノール樹脂、バイオマス変性フェノール樹脂組成物及びバイオマス変性フェノール樹脂硬化物
WO2017068866A1 (fr) * 2015-10-21 2017-04-27 住友ベークライト株式会社 Résine résol phénolique liquide, son procédé de préparation, et article

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