WO2018150708A1 - Method for producing biomass derivative, method for producing biomass-modified phenolic resin, method for producing biomass-modified phenolic resin composition, and biomass-modified phenolic resin - Google Patents

Abstract

This method for producing a biomass derivative includes a self-polymerization step for self-polymerizing unsaturated carbon chain-containing phenols derived from plant materials to obtain a copolymer, and an addition reaction step in which the phenols are subjected to an addition reaction to the double bonds of the unsaturated carbon chains in the copolymer.

Description

Method for producing biomass derivative, method for producing biomass-modified phenolic resin, method for producing biomass-modified phenolic resin composition, and biomass-modified phenolic resin

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).

JP 2007-269843 A

However, as a result of examination by the present inventors, the cured product obtained using the cashew oil-modified phenol resin described in the above literature has room for improvement in terms of heat resistance and mechanical strength.

As a result of examining the cured product of the biomass-modified phenolic resin with a focus on the balance of heat resistance, mechanical strength, and flexibility, the following has been found.
First, when phenols having a flexible skeleton derived from plant raw materials are used to modify ordinary phenol resins, the flexibility can be increased slightly compared to ordinary phenol resins, but the flexibility is still insufficient. It turned out to be.
Therefore, if a normal phenol resin is modified by using a copolymer obtained by self-polymerizing phenols derived from plant raw materials in advance, a cured product having excellent flexibility can be obtained, but on the other hand, mechanical strength and heat resistance are low. It turned out to be reduced.
Based on these findings, further research has been conducted to modify ordinary phenolic resins using the above-mentioned copolymers, and to add phenols to unsaturated carbon chain double bonds remaining in the copolymers. By reducing the double bonds of unsaturated carbon chains, it is possible to improve heat resistance, mechanical strength, and flexibility in the obtained biomass derivative and a cured product of biomass-modified phenol resin using the same. The present inventors have found that this can be done and have completed the present invention.

According to the present invention,
A self-polymerization step of self-polymerizing unsaturated carbon chain-containing phenols derived from plant materials to obtain a copolymer;
And an addition reaction step of adding a phenol to an unsaturated carbon chain double bond in the copolymer.

Also according to the invention,
There is provided 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.

Also according to the invention,
There is provided 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.

Also according to the invention,
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.

According to the present invention, 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.

In addition, 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.

According to this embodiment, 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.

According to this embodiment, by using a biomass derivative and a biomass-modified phenol resin using the biomass derivative, heat resistance, mechanical strength and flexibility can be improved in the cured product.

Hereinafter, each process of the manufacturing method of the biomass derivative of this embodiment and the biomass modification | denaturation phenol resin using the same is demonstrated.

First, in the self-polymerization step, for example, 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 | flexibility can be increased. In the container during the self-polymerization step, 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. An inorganic acid etc. are mentioned. Among these, 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. 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 And unsaturated alkyl group-containing phenols; These may be used alone or in combination of two or more.

In this embodiment, by using unsaturated carbon chain-containing phenols as plant raw materials, the biomass modification rate in the biomass-modified phenol resin can be increased, and the heat resistance of the cured product can be improved. Moreover, by using 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. In addition, unlike other animal and vegetable oils and fats, since there is no easily decomposable functional group such as an ester group, a molded product composed of a cured product of a biomass-modified phenol resin can be excellent in heat resistance.

In the self-polymerization step, 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. Among these, 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.

In formula (1), R represents a linear unsaturated hydrocarbon group having 10 or more carbon atoms. However, the hydrogen atom bonded to the benzene ring having a phenolic hydroxyl group may be substituted with a substituent. Further, R may be any of the ortho, meta, and para positions, and may be one or more, two or more, or three or more.
In the above formula (1), 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. When the number of carbon atoms of the linear unsaturated hydrocarbon group is not more than the upper limit of the above range, dilution with an organic solvent is facilitated. On the other hand, when the number of carbon atoms of the linear unsaturated hydrocarbon group is equal to or more than the lower limit, flexibility is easily improved. 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.

Specific examples of the phenol compound represented by the above (1) 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. Moreover, the abundance ratio of each monomer in the copolymer can be measured by GPC, for example.

Further, when the mass ratio is calculated based on the area ratio obtained by GPC measurement after the self-polymerization step, 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%.

Subsequently, 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. Thereby, in the copolymer in which monomers derived from biomass are polymerized, double bonds of unsaturated carbon chains remaining in the copolymer can be reduced.

In addition, 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.

When the mass ratio is calculated based on the area ratio obtained by GPC measurement after the addition reaction step, 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.
Further, 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.

By such an 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 becomes larger via the phenols, so that the flexibility is increased. The strength and heat resistance can be improved by increasing the crosslinking density.

In the addition reaction step, for example, the acidic catalyst exemplified in the self-polymerization step can be used. In addition, 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.

In the method for producing a biomass derivative of the present embodiment, the self-polymerization step and the addition reaction step may be continuously performed using, for example, the same kind of acidic catalyst.
In the method for producing a biomass derivative, the acidic catalyst may be neutralized and removed as necessary, or the acidic catalyst may remain in the biomass derivative as it is. Moreover, according to the product form after processing, excess unreacted phenols may be removed thereafter, or unreacted phenols may remain in the biomass derivative.

As the phenols used in the addition reaction step, for example, 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. For example, 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-phenylphenol, aminophenol, nitrophenol, dinitrophenol and trinitrophenol; resorcin, alkylresorcin, pyrogallol, And polyhydric phenols such as catechol, alkylcatechol, hydroquinone, alkylhydroquinone, phloroglucin, bisphenol A, bisphenol F, bisphenol S, dihydroxynaphthalene and naphthalene. These may be used alone or in combination of two or more. Among these, the phenols can include one or more selected from the group consisting of phenol, cresol, xylenol and alkylphenol, and phenol can be used from an inexpensive viewpoint.

Subsequently, the step of obtaining the biomass-modified phenol resin can include a step of reacting the obtained biomass derivative, phenols and aldehydes. Thereby, the reaction solution containing the biomass modification | denaturation phenol resin which a biomass derivative, phenols, and aldehydes react can be obtained.

In this embodiment, from the viewpoint of producing a novolak-type biomass-modified phenol resin, the step of obtaining a reaction solution can be performed under acidic conditions. In this case, a known acidic catalyst such as an organic acid or an inorganic acid can be used. On the other hand, from the viewpoint of producing a resole-type biomass-modified phenol resin, the step of obtaining a reaction solution can be performed under alkaline conditions. In this case, an alkaline catalyst can be used. Here, as an example, 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.

Although it does not specifically limit as aldehydes used for the process of obtaining the said biomass modified phenol resin, For example, 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. These aldehydes may be used alone or in combination of two or more. Among these, aldehydes can contain formaldehyde or acetaldehyde, and formalin or paraformaldehyde can be used from the viewpoint of productivity and low cost.

As the phenols used in the step of obtaining the biomass-modified phenol resin, 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. For example, acids such as oxalic acid, hydrochloric acid, sulfuric acid, diethylsulfuric acid, paratoluenesulfonic acid, and metals such as zinc acetate Examples thereof include salts, and these can be used alone or in combination of two or more. Although 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.

As the reaction solvent in the present embodiment, water may be used, but an organic solvent may be used. As the organic solvent, a non-aqueous solvent can be used using a non-polar solvent. Examples of 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. In addition, there is no restriction | 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.

As described above, a reaction solution containing a biomass-modified phenol resin can be obtained.

In the present embodiment, a neutralization step for neutralizing the reaction solution may be performed.
Further, a dehydration step may be further performed. As a dehydration method, 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. Thereby, the dehydration time can be shortened, and a stable biomass-modified phenol resin with little variation in resin characteristics can be obtained. Moreover, the water | moisture content in biomass modified phenol resin can be made into 5 weight% or less by such a spin-drying | dehydration process. Water can be sufficiently removed by these methods. However, in order to further remove water, it may be combined with a step of using a known water removing device such as a vacuum dryer or a thin film evaporator.
Moreover, you may add the process of removing an unreacted monomer (for example, unreacted phenols) by a de-monomer process after said reaction as needed.

As described above, 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.

Moreover, 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.

In the biomass-modified phenol resin of the present embodiment, 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.

In this embodiment, for example, by appropriately selecting the type and blending amount of each component contained in the biomass-modified phenol resin, the method for preparing the biomass-modified phenol resin, etc., the ratio of the peak derived from the alkyl chain unsaturated bond Can be controlled. Among these, for example, 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%. For example, the modification rate can be controlled by appropriately adjusting the ratio of the charged amount of the biomass derivative.

As a result of investigation by the present inventor, when the above addition reaction step is not performed, many double bonds remain in the copolymer, and the crosslink density is lowered because the reaction cannot be effectively performed. It has been found that the heat resistance is reduced.
Moreover, when the said self-polymerization process is not performed, since the part derived from the biomass which has a flexible structure is small, it turned out that the softness | flexibility of hardened | cured material becomes low.

On the other hand, by using the biomass-modified phenol resin of the present embodiment, as described above, the heat resistance, mechanical strength, and flexibility of the obtained cured product can be improved.

In addition, 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. Thereby, stability over time can be improved about biomass modification phenol resin stored at normal temperature etc. Although 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.

Next, the biomass-modified phenol resin composition of this embodiment will be described.

The biomass-modified phenolic resin composition of the present embodiment can contain the biomass-modified phenolic resin and a curing agent.

Examples of the curing agent include hexamethylenetetramine and resol type phenol resin. Among these, 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. For example, silica, alumina, magnesia, carbon, silicon carbide, boron nitride, aluminum nitride, silicon nitride, calcium carbonate, barium carbonate, calcium sulfate, barium sulfate, clay, talc, mica And 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. As a specific example, first, 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. Alternatively, 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.

As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.
Hereinafter, examples of the reference form will be added.
1. A self-polymerization step of self-polymerizing unsaturated carbon chain-containing phenols derived from plant materials to obtain a copolymer;
An addition reaction step of adding a phenol to an unsaturated carbon chain double bond in the copolymer.
2. 1. 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. 2. 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. To 3. 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). To 6. 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 according to any one of
A method for producing a biomass-modified phenolic resin, wherein the phenols include one or more selected from the group consisting of phenol, cresol, xylenol and alkylphenol.
10. 4). To 9. 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.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the description of these examples.

(Preparation of biomass-modified phenolic resin of Example 1)
5 parts of 96% concentrated sulfuric acid was added to 1000 parts of cashew oil (manufactured by Tohoku Chemical Co., Ltd., LB-7000), and reacted at 160 ° C. for 5 hours. When the mass ratio was calculated based on the area ratio obtained by the GPC measurement, the content ratio of the copolymer component of the dimer or higher was 65% by mass. Further, NMR revealed that there existed copolymer components in which unsaturated alkyl groups of cashew oil-derived monomers were directly bonded to each other.
Thereafter, 400 parts of phenol was added and reacted at 180 ° C. for 5 hours to obtain a biomass derivative a. From the results of NMR and GPC measurements, 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. Subsequently, dehydration was performed by atmospheric distillation until the temperature of the reaction mixture reached 130 ° C. Thereafter, 3 parts of calcium hydroxide was added and vacuum distillation was performed until the temperature of the reaction mixture reached 170 ° C. in order to remove unreacted phenol. Subsequently, steam was blown in at 0.9 kPa, and unreacted phenol was removed by distillation by steam distillation to obtain 1800 parts of a biomass-modified phenol resin A.
In the obtained biomass-modified phenol resin A, the biomass content is 40%, 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 0.6% with respect to the sum total.

(Preparation of biomass-modified phenolic resin of Example 2)
5 parts of 96% concentrated sulfuric acid was added to 1000 parts of cashew oil (manufactured by Tohoku Chemical Co., Ltd., LB-7000), and reacted at 160 ° C. for 5 hours. Thereafter, 400 parts of phenol was added and reacted at 180 ° C. for 5 hours to obtain a biomass derivative a.
1000 parts of phenol, 720 parts of 37% formalin aqueous solution and 5 parts of 96% concentrated sulfuric acid were added to 359 parts of the obtained biomass derivative a, and reacted at 100 ° C. for 2 hours. Subsequently, dehydration was performed by atmospheric distillation until the temperature of the reaction mixture reached 130 ° C. Thereafter, 3 parts of calcium hydroxide was added and vacuum distillation was performed until the temperature of the reaction mixture reached 170 ° C. in order to remove unreacted phenol. Subsequently, steam was blown in with 0.9 kPa, and unreacted phenol was distilled off by steam distillation to obtain 1230 parts of biomass-modified phenol resin B.
In the obtained 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.

(Preparation of biomass-modified phenolic resin of Example 3)
5 parts of 96% concentrated sulfuric acid was added to 1000 parts of cashew oil (manufactured by Tohoku Chemical Co., Ltd., LB-7000), and reacted at 160 ° C. for 5 hours. Thereafter, 400 parts of phenol was added and reacted at 180 ° C. for 5 hours to obtain a biomass derivative a.
To 155 parts of the obtained biomass derivative a, 1000 parts of phenol, 683 parts of 37% formalin aqueous solution and 5 parts of 96% concentrated sulfuric acid were added and reacted at 100 ° C. for 30 minutes. Subsequently, dehydration was performed by atmospheric distillation until the temperature of the reaction mixture reached 130 ° C. Thereafter, 3 parts of calcium hydroxide was added and vacuum distillation was performed until the temperature of the reaction mixture reached 170 ° C. in order to remove unreacted phenol. Subsequently, steam was blown in at 0.9 kPa, and unreacted phenol was distilled off by steam distillation to obtain 1080 parts of biomass-modified phenolic resin C.
In the obtained biomass-modified phenol 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.

(Production of biomass-modified phenolic resin of Comparative Example 1)
1.5 parts of 96% concentrated sulfuric acid was added to 300 parts of cashew oil (LB-7000, manufactured by Tohoku Chemical Co., Ltd.), and reacted at 200 ° C. for 10 hours. The temperature was lowered to 50 ° C., 1000 parts of phenol, 571 parts of 37% formalin and 5 parts of sulfuric acid were added and reacted at 100 ° C. for 5 hours, and then 4.5 parts of 25% aqueous ammonia was added. 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.
In the obtained biomass-modified phenol resin D, the biomass content is 25%, 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 2.9% based on the total.

(Production of biomass-modified phenolic resin of Comparative Example 2)
500 parts of phenol and 500 parts of cashew oil (LB-7000, manufactured by Tohoku Chemical Co., Ltd.) were mixed, 30 parts of 96% concentrated sulfuric acid was added, and the reaction was carried out at 150 ° C. for 3 hours to obtain a reaction product. 106 parts of 37% formalin aqueous solution was mixed with 1000 parts of the obtained reaction product, 10 parts of oxalic acid was added as a catalyst, and the mixture was reacted at 100 ° C. for 2 hours. Subsequently, dehydration was performed by atmospheric distillation until the temperature of the reaction mixture reached 130 ° C. Thereafter, vacuum distillation was performed until the temperature of the reaction mixture reached 170 ° C. in order to remove unreacted phenol. Subsequently, steam was blown in at 0.9 kPa, and unreacted phenol was removed by distillation by steam distillation to obtain E830 parts of a biomass-modified phenol resin.
In the obtained 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.

(Production of biomass-modified phenolic resin of Comparative Example 3)
1000 parts of phenol, 500 parts of cashew oil (manufactured by Tohoku Chemical Co., Ltd., LB-7000) and 600 parts of 37% formalin aqueous solution were mixed, 20 parts of 96% concentrated sulfuric acid was added as a catalyst, and the mixture was reacted at 100 ° C. for 2 hours. Subsequently, dehydration was performed by atmospheric distillation until the temperature of the reaction mixture reached 130 ° C. Thereafter, vacuum distillation was performed until the temperature of the reaction mixture reached 170 ° C. in order to remove unreacted phenol. Subsequently, steam was blown in at 0.9 kPa, and unreacted phenol was distilled off by steam distillation to obtain biomass-modified phenolic resin F1333 parts.
In the obtained biomass-modified phenol resin F, 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.

(Preparation of biomass modified phenolic resin of Comparative Example 4)
1000 parts of phenol and 600 parts of a 37% formalin aqueous solution were mixed, 20 parts of 96% concentrated sulfuric acid was added as a catalyst, and the mixture was reacted at 100 ° C. for 2 hours. Subsequently, dehydration was performed by atmospheric distillation until the temperature of the reaction mixture reached 130 ° C. Thereafter, 500 parts of cashew oil (LB-7000, manufactured by Tohoku Chemical Co., Ltd.) was added, and vacuum distillation was performed until the temperature of the reaction mixture reached 170 ° C. Thereafter, an additional aging reaction was carried out at 230 ° C. for 20 hours to obtain biomass modified phenolic resin G1320 parts.
In the obtained biomass-modified phenol resin G, 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 0.1% with respect to the total.

(Preparation of unmodified phenol resin of Comparative Example 5)
1000 parts of phenol and 690 parts of 37% formalin aqueous solution were mixed, 10 parts of oxalic acid was added as a catalyst, and the mixture was reacted at 100 ° C. for 2 hours. Subsequently, dehydration was performed by atmospheric distillation until the temperature of the reaction mixture reached 130 ° C. Thereafter, in order to remove the unreacted phenol, the reaction product was further reduced in pressure to 0.9 kPa, and heated until the temperature of the reaction mixture reached 170 ° C., followed by distillation under reduced pressure. Subsequently, steam was blown in with 0.9 kPa, and unreacted phenol was distilled off by steam distillation to obtain H933 parts of unmodified phenol resin.

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.

10 parts of hexamethylenetetramine (hexamine) as a curing agent was added to each of the obtained biomass-modified phenol resins A to G or 100 parts of the unmodified phenol resin H, and mixed using a lab plast mill. The mixture was molded at 175 ° C. and a pressure of 10 MPa to obtain a cured product.

“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”.
Hereinafter, 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”, and 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”.

In Table 1, the case where the biomass-modified phenol resin was obtained is indicated in the column “modified”, the case where the biomass-modified phenol resin was not obtained is indicated as ×, and the case where the “self-polymerization step” or the “addition reaction step” was performed The case where the test was not carried out was indicated as x.

(Heat-resistant)
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 Δ: 0.58 or more to less than 0.62 ×: less than 0.58

(Strength)
The strength was evaluated based on the following evaluation criteria for “25 ° C. bending strength” of the obtained cured product. The results are shown in Table 1.
◎: 100 MPa or more ○: 95 MPa or more to less than 100 MPa Δ: 90 MPa or more to less than 95 MPa x: less than 90 MPa

(Flexibility)
The flexibility was evaluated on the “25 ° C. flexural modulus” of the obtained cured product based on the following evaluation criteria. The results are shown in Table 1.
A: Less than 2.0 GPa: 2.0 GPa or more and less than 3.0 GPa Δ: 3.0 GPa or more and less than 4.0 GPa x: 4.0 GPa or more

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.

This application claims priority based on Japanese Patent Application No. 2017-025755 filed on Feb. 15, 2017, the entire disclosure of which is incorporated herein.

Claims (18)

A self-polymerization step of self-polymerizing unsaturated carbon chain-containing phenols derived from plant materials to obtain a copolymer;
An addition reaction step of adding a phenol to an unsaturated carbon chain double bond in the copolymer. A method for producing a biomass derivative according to claim 1,
The said self-polymerization process is a manufacturing method of a biomass derivative including the process of heat-processing the unsaturated carbon chain containing phenols derived from the said plant raw material in a container. A method for producing a biomass derivative according to claim 2,
The method for producing a biomass derivative, wherein the container in the self-polymerization step does not contain any of phenols, aldehydes, and phenol resins. A method for producing a biomass derivative according to claim 2 or 3,
The method for producing a biomass derivative, wherein the heat treatment during the self-polymerization step is performed under acidic conditions. A method for producing a biomass derivative according to any one of claims 1 to 4,
The said addition reaction process is a manufacturing method of a biomass derivative including the process of heat-processing the said copolymer and the said phenols in a container. A method for producing a biomass derivative according to claim 5,
The method for producing a biomass derivative, wherein the heat treatment in the addition reaction step is performed under acidic conditions. A method for producing a biomass derivative according to any one of claims 1 to 6,
A method for producing a biomass derivative, wherein the plant material contains cashew oil. A method for producing a biomass derivative according to claim 7,
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. A method for producing a biomass derivative according to any one of claims 1 to 8,
A method for producing a biomass derivative, wherein the phenols include one or more selected from the group consisting of phenol, cresol, xylenol and alkylphenol. A biomass-modified phenolic resin comprising a step of obtaining a biomass-modified phenolic resin by reacting a biomass derivative obtained by the method for producing a biomass derivative according to any one of claims 1 to 9, a phenol and an aldehyde. Manufacturing method. A method for producing a biomass-modified phenolic resin according to claim 10,
The method for producing a biomass-modified phenolic resin, wherein the biomass-modified phenolic resin is solid at room temperature of 25 ° C. A method for producing a biomass-modified phenolic resin according to claim 10 or 11,
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. A method for producing a biomass-modified phenolic resin according to any one of claims 10 to 12,
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. A method for producing a biomass-modified phenolic resin according to any one of claims 10 to 13,
A method for producing a biomass-modified phenolic resin, wherein the aldehyde contains formaldehyde or acetaldehyde. A method for producing a biomass-modified phenolic resin according to any one of claims 10 to 14,
A method for producing a biomass-modified phenolic resin, wherein the phenols include one or more selected from the group consisting of phenol, cresol, xylenol and alkylphenol. 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 claims 10 to 15 and a curing agent. . A method for producing a biomass-modified phenolic resin composition according to claim 16,
A method for producing a biomass-modified phenol resin composition, wherein a filler is further mixed in the mixing step. 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 2.0% or less of the total integrated value.