JP5915331B2 - Method for producing biomass-modified phenolic resin, biomass-modified phenolic resin, biomass-modified phenolic resin composition, and biomass-modified phenolic resin cured product - Google Patents

Description

  The present invention relates to a method for producing a biomass-modified phenol resin, a biomass-modified phenol resin, a biomass-modified phenol resin composition, and a cured biomass-modified phenol resin. In particular, a method for producing a biomass-modified phenol resin having heat resistance equivalent to that of an existing phenol resin and having excellent flexibility and low elastic modulus, biomass-modified phenol resin, biomass-modified phenol resin composition, and biomass-modified phenol resin It relates to a cured product.

  At present, synthetic resins are widely used in various fields because of their excellent properties. On the other hand, since most synthetic resins are made from petroleum, coal, and natural gas, which are fossil resources, the need for fossil resources is increasing from the viewpoint of resource depletion and global warming. In recent years, synthetic resins using biomass derived from animals and plants as a raw material have been studied, and their practical application has been progressing with polylactic acid as a representative. On the other hand, many of these biomass-derived resins are thermoplastic resins, which are inferior in durability, particularly heat resistance, and so far, applicable items have been limited.

  An example of a biomass-derived synthetic resin having a relatively high heat resistance is a thermosetting oil-modified phenol resin. In particular, cashew oil-modified phenolic resin is an aromatic compound having a phenolic hydroxyl group, so it is incorporated into the resin skeleton when cured and exhibits higher heat resistance than other biomass-derived synthetic resins. (For example, Patent Documents 1, 2, 3, and 4). However, when compared with synthetic resins obtained using petroleum-derived raw materials such as unmodified phenolic resins that are not modified with biomass such as oil, the heat resistance of the oil-modified phenolic resins deteriorates as the biomass content increases. Tended to be. Therefore, although there are many parts that can be applied as compared with thermoplastic biomass resins, the range of application has been limited mainly due to durability problems in the use of existing synthetic resins that require high heat resistance. In addition, there is an increasing demand to increase the biomass content mainly due to environmental considerations, but the biomass content is reduced by having a complex structure of biomass raw materials derived from biological metabolic systems, particularly unsaturated bonds. When it is increased, gelation due to self-polymerization is likely to occur during synthesis, and it has been difficult to industrially obtain a resin having a high biomass content.

  Examples of a method for obtaining a resin or derivative having a high biomass content include a method for obtaining a biomass derivative by adding phenols to a drying oil obtained from vegetable oil or the like (for example, Patent Documents 5 and 6). On the other hand, the heat resistance is poor compared to the unmodified phenol resin, and there is a problem that the durability at high temperature is inferior, so that the range of use is limited, such as being only partially added to the synthetic resin. Further, these resins have a problem that it is difficult to obtain a molded product because they have a low softening point and are difficult to handle.

JP 2007-2032 A JP 2002-212250 A JP 2000-44642 A JP 2007-269843 A Japanese Patent Laid-Open No. 53-36504 JP-A-5-320294

  The present invention is a biomass-modified phenolic resin having heat resistance equivalent to that of an existing phenolic resin and having excellent flexibility and low elastic modulus, and a biomass-modified phenolic resin composition obtained by using the same and a cured product thereof It provides things.

Such an object is achieved by the following present inventions (1) to (8).
(1) A biomass-modified phenolic resin obtained using a biomass (a) containing an alkyl chain unsaturated bond, a phenol (b), and an aldehyde source (d), wherein the biomass (a ) is an aromatic compound, wherein the biomass containing the alkyl chain unsaturated bond (a) the derived structure 50 mass% or more, in a proportion of 95 wt% or less, wherein in the IH-NMR spectra alkyl chain unsaturated The proportion of peaks derived from bonding (peaks of 4.5 to 6.0 ppm) is 1% of the total integrated value of peaks derived from hydrogen bonded to carbon atoms (0.2 to 7.5 ppm peak). A biomass-modified phenol resin having a softening point of 60 ° C. or higher .
( 2 ) The phenol (b) contains at least one selected from phenol, cresol, resorcin, catechol, hydroquinone, pyrogallol, phloroglucinol, and a saturated alkylphenol having 2 to 9 alkyl chain carbon atoms (1) The biomass-modified phenol resin described in 1.
( 3 ) The biomass-modified phenol resin according to any one of (1) and (2) , wherein the biomass (a) containing the alkyl chain unsaturated bond is a biomass-derived unsaturated alkylphenol containing a phenolic hydroxyl group.
( 4 ) The biomass-derived unsaturated alkylphenol is at least one selected from cashew nut shell liquid, urushi extract, cardanol, curdle, methyl curdal, anacardic acid, urushiol, laccol, thiol, and purified products thereof. The biomass-modified phenolic resin according to (3) , comprising:
( 5 ) In any one of (1) to (4) , the aldehyde source (d) contains at least one selected from formaldehyde, paraformaldehyde, trioxane, acetaldehyde, paraaldehyde, glyoxal, and hexamethylenetetramine. The biomass-modified phenolic resin described.
( 6 ) A biomass-modified phenolic resin composition comprising the biomass-modified phenolic resin according to any one of (1) to (5) and a curing agent (e).
( 7 ) The biomass-modified phenolic resin composition according to (6) , wherein the curing agent (e) contains at least one selected from hexamethylenetetramine and a resol type phenolic resin.
( 8 ) A biomass-modified phenolic resin cured product obtained by heating and curing the biomass-modified phenolic resin composition according to (6) or (7) .
( 9 ) (I) A step of adding a phenol (b) to a biomass (a) containing an alkyl chain unsaturated bond to obtain a biomass derivative (c), and (II) the obtained biomass derivative (c) and phenol A step (IIa) of reacting the class (b) with the aldehyde source (d), or a step (IIb) of reacting the obtained biomass derivative (c) with the aldehyde source (d);
A method for producing a biomass-modified phenolic resin, comprising:

  According to the present invention, it is possible to obtain a biomass-modified phenolic resin having heat resistance equivalent to that of an existing phenolic resin and having excellent flexibility and low elastic modulus even though the biomass content is high. In addition, despite the high biomass content, it is possible to obtain a biomass-modified phenolic resin composition and a cured product thereof that are difficult to undergo thermal decomposition and that can be widely used for parts that require heat resistance.

First, the biomass-modified phenolic resin of the present invention will be described. The biomass-modified phenolic resin of the present invention is a biomass-modified phenolic resin obtained using a biomass (a) containing an alkyl chain unsaturated bond, a phenol (b), and an aldehyde source (d), and comprising an alkyl chain unsaturated bond The biomass (a) containing is an aromatic compound and contains a structure derived from the biomass (a) containing an alkyl chain unsaturated bond in a proportion of 50% by mass or more and 95% by mass or less. As a method for measuring the content of the structure derived from biomass (a) containing an alkyl chain unsaturated bond, a method for quantifying the amount of ¹⁴ C derived from biomass (a) containing an alkyl chain unsaturated bond by isotope analysis Although it can be used, the mass of the biomass (a) containing the alkyl chain unsaturated bond used may be simply calculated by dividing the mass of the obtained biomass-modified phenol resin. By setting the content ratio of the structure derived from the biomass (a) containing an alkyl chain unsaturated bond within the above range, the reactivity with a curing agent such as hexamethylenetetramine and a resol type phenol resin is good and good after curing molding. A cured resin having heat resistance can be obtained. When the content rate of the structure derived from the biomass (a) containing an alkyl chain unsaturated bond is less than the lower limit, it may not be possible to meet the demand for the biomass content rate from the environmental aspect. When the content of the structure derived from biomass (a) containing an alkyl chain unsaturated bond is higher than the above upper limit, biomass modification having good reactivity with a curing agent such as hexamethylenetetramine and resol type phenol resin It is difficult to obtain a phenol resin, and gelation may occur during the reaction, and a cured resin product may not be obtained.

Moreover, it is preferable that the biomass modified phenolic resin of this invention has few alkyl chain unsaturated bonds derived from biomass (a) containing an alkyl chain unsaturated bond in resin. The amount of the alkyl chain unsaturation, ^{1 H-NMR} spectrum can be determined by a peak derived from an alkyl chain unsaturated bond hydrogen in the ^{1 H-NMR} spectrum of the biomass modified phenolic resin of the present invention (4.5 It is more preferable that the ratio of the peak of ˜6.0 ppm is 1% or less of the total integrated value of the peaks derived from hydrogen bonded to carbon atoms (peaks of 0.2 to 7.5 ppm). Particularly preferably, it is 0.5% or less. Alkyl chain unsaturated bonds may not be substantially contained. If the ratio of the peak derived from the alkyl chain unsaturated bond hydrogen is not more than the above upper limit, a biomass-modified phenol resin having a high biomass content can be easily obtained, and a cured product obtained by mixing and reacting with a curing agent. Is excellent in heat resistance. When the peak ratio of unsaturated bonds is higher than the above upper limit, not only the heat resistance may be lowered, but gelation due to polymerization of unsaturated bonds is likely to occur during the reaction, which is industrially stable. As a result, biomass-modified phenolic resin may not be obtained. The reason why the obtained biomass-modified phenolic resin is reacted with a curing agent such as hexamethylenetetramine, resol type phenolic resin, and cured resin is high in heat resistance, but it is not clear why the biomass (a ) Since the resin itself is an aromatic compound, the resin skeleton is excellent in heat resistance, the resulting biomass-modified phenol resin has less unsaturated bonds, so that thermal decomposition at unsaturated bond sites is suppressed, and the alkyl chain It is considered that by introducing phenols directly, the phenols trap radicals generated at the time of thermal decomposition and suppress chain decomposition.

The biomass-modified phenol resin of the present invention is not particularly limited. For example, biomass in which phenols (b) are added to biomass (a) containing alkyl chain unsaturated bonds to reduce alkyl chain unsaturated bonds. After obtaining the derivative (c), the biomass derivative (c) can be obtained by reacting with the aldehyde source (d). Details of each manufacturing process will be described later.

  The biomass (a) containing an alkyl chain unsaturated bond used in the biomass-modified phenolic resin of the present invention is not particularly limited, and examples thereof include cinnamic acid, cinnamaldehyde, caffeic acid, ferulic acid, coumaric acid and the like. And a biomass-derived aromatic compound containing an alkyl chain unsaturated bond such as a biomass-derived unsaturated alkylphenol containing a phenolic hydroxyl group. Preferred are biomass-derived unsaturated alkylphenols containing phenolic hydroxyl groups, such as cashew nut shell liquid (cashew oil), urushi extract, cardanol, curdall, methyl curdal, anacardic acid, urushiol, laccol, thiol, and the like. And a purified product thereof. More preferred are cardanol, curdle, methyl curdle, cashew nut shell liquid, and purified products thereof. From the viewpoint of cost, cashew nut shell liquid and its purified product are particularly preferable. These can be used alone or in combination of two or more. When the biomass (a) containing an alkyl chain unsaturated bond is an aromatic compound, a biomass-modified phenol resin having a high biomass introduction rate can be easily obtained, and a cured product having excellent heat resistance can be obtained. . Furthermore, because it is a biomass-derived unsaturated alkylphenol containing a phenolic hydroxyl group, the biomass itself contains phenol, so it can take many reaction points even if the amount of phenol introduced is small, with a high biomass introduction rate. Excellent reactivity. In addition, it is possible to reduce the number of aliphatic tertiary carbon binding sites that are relatively susceptible to thermal decomposition generated by the addition of phenols, and even in biomass-derived structures, the phenol structure traps radicals generated during thermal decomposition and suppresses decomposition. Unlike other animal and vegetable oils and fats, since there is no easily decomposable functional group such as an ester group, a cured molded product can be obtained with excellent heat resistance.

  As the phenols (b) used in the biomass-modified phenol resin of the present invention, at least one selected from phenol, cresol, resorcin, catechol, hydroquinone, pyrogallol, phloroglucinol, and a saturated alkylphenol having 2 to 9 alkyl chain carbon atoms. It is preferable that it contains. A saturated alkyl chain having a carbon number within the above range may have a branched chain in the alkyl chain, and the substitution position of the alkyl chain can be any of ortho, meta, and para-substituted alkylphenol compounds. . Examples of the saturated alkylphenol having 2 to 9 alkyl chain carbon atoms include ethylphenol, propylphenol, isopropylphenol, butylphenol, secondary butylphenol, tertiary butylphenol, amylphenol, tertiary aminophenol, hexylphenol, heptylphenol, octylphenol, Tertiary octylphenol, nonylphenol, and tertiary nonylphenol. From the viewpoint of reactivity, phenol, cresol, resorcin, catechol, hydroquinone, and a monosaturated alkyl compound having 2 to 9 carbon atoms in which one alkyl chain is substituted on the phenol nucleus are preferable. From the viewpoint of biomass content, more preferred are phenol, cresol, resorcin, catechol, and hydroquinone. These can be used alone or in combination of two or more.

A method for obtaining a biomass derivative (c) by adding a phenol (b) to an alkyl chain unsaturated bond of a biomass (a) containing an alkyl chain unsaturated bond is not particularly limited. For example, in the presence of a strong acid catalyst. And a method of heating a mixture of biomass (a) containing an alkyl chain unsaturated bond and phenols (b) at 50 to 200 ° C. The strong acid catalyst is not particularly limited. For example, aluminum chloride, aluminum bromide, ferric chloride, zinc chloride, boron trifluoride, stannic chloride, antimony chloride, gallium chloride, gallium bromide, hydrogen chloride, Examples include Lewis acids such as hydrogen bromide and protonic acids such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, sulfuric acid, and phosphoric acid. If necessary, the strong acid catalyst may be neutralized and removed, or the catalyst may remain in the biomass derivative (c) as it is. Moreover, according to the product form after processing, excess phenols (b) may be distilled off under vacuum thereafter, or phenols (b) may remain in the biomass derivative (c). . The amount of phenol (b), the peak is not particularly limited, derived from an alkyl chain unsaturated bond hydrogen in the ¹ H-NMR spectrum of the resulting biomass derivative (c) (4.5~6.0ppm It is preferable that the ratio is such that the ratio is not less than 1% of the total integrated value of peaks derived from hydrogen bonded to carbon atoms (peaks of 0.2 to 7.5 ppm).

  Examples of the aldehyde source (d) used in the biomass-modified phenolic resin of the present invention include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, and n-butyraldehyde. , Caproaldehyde, allyl aldehyde, benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicyl aldehyde and the like. These can be used alone or in combination of two or more. Among these aldehydes, those selected from formaldehyde and paraformaldehyde are preferable. Thereby, the reactivity at the time of synthesize | combining a phenol resin can be made high.

  As a method for synthesizing the biomass-modified phenolic resin of the present invention, for example, in the case of a novolak type, the biomass derivative (c) and phenols (b) obtained by the above-described method and the aldehyde source (d) are acidified. After reacting in the presence of a catalyst, water is removed by a dehydration step, or after reacting the biomass derivative (c) and the aldehyde source (d) in the presence of an acidic catalyst, water is removed by a dehydration step. It can be obtained by a method of removing, etc. In the case of the resol type, the biomass derivative (c) and phenols (b) obtained by the above-described method are reacted with the aldehyde source (c) in the presence of an alkaline catalyst, and then water is removed by a dehydration step. Can be obtained by a method of removing water, a method of removing water by a dehydration step after reacting the biomass derivative (c) and the aldehyde source (d) in the presence of an alkaline catalyst. Moreover, you may add the method of removing an unreacted monomer by a demonomer process after said reaction as needed.

  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 the said acidic catalyst, It can be 0.1 mass% or more and 10 mass% or less with respect to the biomass modified phenol resin whole.

  The alkaline catalyst used when synthesizing the resole-type biomass-modified phenolic resin is not particularly limited, and examples thereof include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, potassium hydroxide, and aqueous ammonia. , Tertiary amines such as triethylamine, alkaline earth metal oxides and hydroxides such as calcium, magnesium and barium, and alkaline substances such as sodium carbonate and hexamethylenetetramine. These may be used alone or in combination of two or more. can do. Although it does not specifically limit as the usage-amount of the said alkaline catalyst, It can be 0.1 mass% or more and 20 mass% or less with respect to the biomass modified phenol resin whole.

In the synthesis of the novolak-type biomass-modified phenol resin using the biomass derivative (c), the blending ratio of the aldehyde source (d) to the biomass derivative (c) and the phenols (b) is as follows: When phenols are 1000 parts by mass, the aldehyde source (d) is not particularly limited, but is preferably 5 parts by mass or more and 700 parts by mass or less.

  In the synthesis of a resole-type biomass-modified phenol resin using a biomass derivative (c), the blending ratio of the aldehyde source (d) to the biomass derivative (c) and the phenols (b) is as follows: When phenols are 1000 parts by mass, the aldehyde source (d) is not particularly limited, but is preferably 20 parts by mass or more and 2000 parts by mass or less.

  The softening point of the biomass-modified phenolic resin of the present invention is preferably 60 ° C. or higher, and more preferably 65 to 140 ° C. If it is less than the lower limit, it is difficult to handle at the time of molding, and if it exceeds the upper limit, the molding conditions become severe, so the range of use is limited.

  Next, the biomass-modified phenol resin composition and the biomass-modified phenol resin cured product of the present invention will be described. The biomass-modified phenolic resin composition of the present invention includes the biomass-modified phenolic resin of the present invention. However, when the biomass-modified phenolic resin is a novolak type, it is preferable to further include a curing agent (e). In addition, when biomass modified phenol resin is a resol type, it is not necessary to contain a hardening | curing agent (e).

  Although it does not specifically limit as a hardening | curing agent (e) used for the biomass modified phenol resin composition of this invention, For example, a hexamethylenetetramine, a resol type phenol resin, etc. are mentioned. Among these, hexamethylenetetramine is preferable from the viewpoint of the heat resistance of the cured product and the biomass content.

  The content of the curing agent (e) is not particularly limited, but when the curing agent (e) is hexamethylenetetramine, 1 part by mass or more and 40 parts by mass with respect to 100 parts by mass of the biomass-modified phenol resin. The following is preferred. More preferably, it is 2 to 30 mass parts. If the above upper limit is exceeded, unreacted misamethylenetetramine may remain and affect the strength, and if it is less than the lower limit, crosslinking may be insufficient and the strength of the cured product may be reduced. When the curing agent (e) is a resol type phenol resin, the amount is preferably 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the biomass derivative. More preferably, it is 10 to 50 mass parts. When the above upper limit is exceeded, it may not be possible to answer the demand for reduced heat resistance and environmental biomass content, and below the lower limit, crosslinking may be insufficient and the strength of the cured product may be reduced. .

  Various fillers can be mix | blended with the biomass modified phenolic resin composition of this invention. Various fillers are 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, Examples thereof include 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 fillers may be used alone or in combination of two or more. In addition, a colorant, a release agent, a curing catalyst, a curing aid, a coupling agent, a stress reducing agent, a flame retardant, a solvent, and the like are appropriately added to the biomass derivative composition of the present invention as necessary. Can do.

The method for obtaining the biomass-modified phenolic resin composition of the present invention is not particularly limited. For example, the above-mentioned compound is mixed at a predetermined compounding ratio, and a kneader such as a heating roll, a kneader, or a twin screw extruder is used. After being melt-kneaded and then cooled, pulverized or granulated, or obtained by 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. it can. The biomass-modified phenolic resin cured product of the present invention can be obtained by curing and molding the biomass-modified phenolic resin composition of the present invention by an ordinary molding method such as compression molding, transfer molding, injection molding or the like. The biomass-modified phenolic resin cured product (molded article) obtained in this way has the same heat resistance as existing phenolic resins and has excellent durability at high temperatures. Applicable to a wide range of applications such as products and peripheral equipment.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited by these examples. Further, “parts” and “%” shown in Examples and Comparative Examples are “parts by mass” and “% by mass”.

Example 1
1000 parts of phenol and 1000 parts of cashew oil (manufactured by Tohoku Kako, LB-7000) were mixed, 30 parts of boron trifluoride diethyl ether complex was added as an acid catalyst, and the reaction was performed at 120 ° C. for 6 hours. Thereafter, 100 parts of calcium hydroxide was added and neutralized, followed by filtration to remove the catalyst to obtain a reaction product containing biomass derivative A. To 2000 parts of the reaction product containing the obtained biomass derivative A and unreacted phenol, 212 parts of 37% formalin aqueous solution was mixed, 20 parts of oxalic acid was added as a catalyst, 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, 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 1560 parts of biomass-modified phenol resin A. The softening point of the obtained resin was 83 ° C., the free phenol was 0.1%, and the biomass content excluding unreacted phenols was 62%. Moreover, the ratio of the peak derived from the alkyl chain unsaturated bond hydrogen calculated | required from NMR was 0.1% or less with respect to the sum total of the peak derived from the hydrogen couple | bonded with the carbon atom.

(Example 2)
1000 parts of phenol and 1000 parts of cashew oil (manufactured by Tohoku Chemical Co., Ltd., LB-7000) are mixed, 60 parts of 96% concentrated sulfuric acid is added, and the reaction is carried out at 150 ° C. for 3 hours. Obtained. To 2000 parts of the reaction product containing the obtained biomass derivative B and unreacted phenol, 212 parts of 37% formalin aqueous solution was mixed, 20 parts of oxalic acid was added as a catalyst, 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, 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 1660 parts of biomass-modified phenol resin B. The softening point of the obtained resin was 87 ° C., the free phenol was 0.1%, and the biomass content excluding unreacted phenols was 59%. Moreover, the ratio of the peak derived from the alkyl chain unsaturated bond hydrogen calculated | required from NMR was 0.1% with respect to the total integrated value of the peak derived from the hydrogen couple | bonded with the carbon atom.

(Comparative Example 1)
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 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 C1333 parts. The softening point of the obtained resin was 95 ° C., the free phenol was 0.1%, and the biomass content excluding unreacted phenols was 38%. Moreover, the ratio of the peak derived from the alkyl chain unsaturated bond hydrogen calculated | required from NMR was 1.6% with respect to the sum total of the peak derived from the hydrogen couple | bonded with the carbon atom.

(Comparative Example 2)
1000 parts of phenol, 1000 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 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 unreacted phenol, distillation under reduced pressure was attempted until the temperature of the reaction mixture reached 170 ° C. However, gelation occurred during heating, and a resin could not be obtained.

(Comparative Example 3)
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 at 0.9 kPa, and unreacted phenol was distilled off by steam distillation to obtain P933 parts of phenol resin. The resulting resin had a softening point of 121 ° C. and free phenol of 0.1%.

(Evaluation)
Evaluation of the biomass-modified phenol resin obtained in Examples and Comparative Examples was performed as follows. 10 parts of hexamethylenetetramine was blended with each 100 parts of the obtained biomass-modified phenol resin and phenol tree, 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. The obtained cured product was measured for thermogravimetric analysis by thermogravimetric analysis (Seiko Instruments Inc., EXTRA TG / DTA6300, 250 ml / min under air flow), and the 5% thermogravimetric decrease temperature was evaluated as the thermal decomposition start temperature. went. Further, the elastic modulus of the cured product was measured at room temperature in accordance with JIS K 6911 “Bending test method of hard plastic”. The softening point of the resin was measured by a ring and ball softening point test method. Table 1 shows the evaluation results.

As shown in Table 1, the cured products of Examples 1 and 2 in which the biomass-modified phenol resin obtained by the present invention was cured with hexamethylenetetramine used an aromatic compound biomass containing an alkyl chain unsaturated bond. Compared to the cured product of Comparative Example 1 in which a cashew-modified phenolic resin having a large amount of unsaturated bonds was cured with hexamethylenetetramine, and Comparative Example 3 in which a general phenolic resin not using biomass was cured with hexamethylenetetramine. Although the biomass content was high, the thermal decomposition start temperature was as high as in Comparative Example 1 and Comparative Example 3, and it was found that heat resistance was excellent. Moreover, it turned out that the cured | curing material of Example 1, 2 has a low elasticity modulus compared with the cured | curing material of the comparative example 1 or the comparative example 3, and is excellent in a softness | flexibility and low elasticity. From the results of Comparative Example 2, it was found that it was difficult to obtain a biomass-modified phenol resin having a high biomass content by the conventional method. From these results, although the biomass derivative of the present invention has a high biomass content, the obtained cured product has high heat resistance equivalent to that of the existing phenol resin, and has excellent flexibility and low elastic modulus. Therefore, it can be suitably used for various applications.

According to the present invention, a biomass-modified phenolic resin having heat resistance equivalent to that of an existing phenolic resin and having excellent flexibility and low elastic modulus, and a biomass-modified phenolic resin composition obtained by using the same, and its Since a cured product can be obtained, it can be suitably used in applications that require high heat resistance and heat resistance and are required to have flexibility and low elasticity.

Claims (9)

Biomass (a) containing an alkyl chain unsaturated bond, phenols (b), aldehyde source (
d) a biomass-modified phenolic resin obtained using
The biomass (a) containing the alkyl chain unsaturated bond is an aromatic compound,
The structure derived from the biomass (a) containing the alkyl chain unsaturated bond is contained in a proportion of 50% by mass or more and 95% by mass or less ,
The peak derived from the alkyl chain unsaturated bond (peak of 4.5 to 6.0 ppm) in the 1H-NMR spectrum is a peak derived from hydrogen bonded to a carbon atom (0.2 to 7.5 ppm p). -H) less than 1% of the total integrated value,
A biomass-modified phenol resin having a softening point of 60 ° C or higher . The phenols (b) is phenol, cresol, resorcinol, catechol, hydroquinone, pyrogallol, according to claim 1 which contains at least one or more selected from phloroglucinol and alkyl chain saturated alkyl phenols having 2 to 9 carbon atoms Biomass modified phenolic resin. The biomass-modified phenol resin according to any one of claims 1 and 2 , wherein the biomass (a) containing the alkyl chain unsaturated bond is a biomass-derived unsaturated alkylphenol containing a phenolic hydroxyl group. The biomass-derived unsaturated alkylphenol contains at least one selected from cashew nut shell liquid, urushi extract, cardanol, curdall, methyl curdall, anacardic acid, urushiol, laccol, thiol, and purified products thereof. The biomass-modified phenolic resin according to claim 3 . The biomass-modified phenol according to any one of claims 1 to 4 , wherein the aldehyde source (d) contains at least one selected from formaldehyde, paraformaldehyde, trioxane, acetaldehyde, paraaldehyde, glyoxal, and hexamethylenetetramine. resin. A biomass-modified phenolic resin according to any one of claims 1 to 5 and a curing agent (
e) and a biomass-modified phenolic resin composition. The biomass-modified phenolic resin composition according to claim 6 , wherein the curing agent (e) contains at least one selected from hexamethylenetetramine and a resol type phenolic resin. A biomass-modified phenolic resin cured product obtained by heating and curing the biomass-modified phenolic resin composition according to claim 6 or 7 . (I) adding a phenol (b) to a biomass (a) containing an alkyl chain unsaturated bond to obtain a biomass derivative (c);
(II) The obtained biomass derivative (c) and phenols (b) and the aldehyde source (d
And (IIb), or the step (IIb) of reacting the obtained biomass derivative (c) with the aldehyde source (d),
A method for producing a biomass-modified phenolic resin, comprising: