JPS6147816B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula () (In the formula, R ₁ and R′ ₁ are hydrogen or methyl groups and cannot be methyl groups at the same time. R ₂ is hydrogen or methyl group. X ₁ is _a phenol or catechol residue. ₃ is hydrogen or X ₁ , one of which is always X _1. a and b are n = a
+b, 1≦n≦40, and 0≦b. This invention relates to a phenol or catechol adduct of a low polymer of butadiene or isoprene shown in the following formula with ethylene or propylene bonded to the terminal, and a method for producing the same. Alkyl derivatives of phenols are antioxidants,
It is used in lubricating oils, additives, plasticizers, phenolic resins, preservatives, fungicides, and insecticides, and occupies an important position in the organic chemical industry as a synthetic intermediate for cleaning agents. The phenols mentioned in the present invention having long-chain alkyl groups in their side chains have been found to be mainly used as phenolic resins in molding, lamination, coatings, and the like. Conventionally, phenols modified with such long-chain alkyl groups have been disclosed in Japanese Unexamined Patent Application Publication No. 1973-
Descriptions can be found in JP-A No. 20890, JP-A No. 50-61493, JP-A No. 50-109285, and JP-A No. 47-39220, but none of them have a clear structure. As shown in the general formula (), the compound of the present invention is a compound having a defined structure, in which phenol or catechol is bonded to the terminal unit of a long-chain alkyl group. The phenol or catechol adduct of the butadiene or isoprene low polymer of the present invention, in which ethylene or propylene is bonded to the terminal end, is a novel compound. Among the compounds of the present invention, particularly interesting are the cardanol or urushiol compounds described in claim 5. Cardanol is

【formula】 Urushiol is

[Formula] In both cases, phenol or catechol is bonded at the terminal position of a long alkyl chain.
Urushiol has been the main component of lacquer, the most respected paint since ancient times, and various attempts have been made to synthesize it. JP-A-51-54520 and JP-A-53-85889 describe the synthesis of urushiol-like substances from butadiene oligomers, but there is no clear description of the structure, and whether catechol is added to the end of the alkyl chain. I'm not sure. Natural lacquer has the major characteristic that it dries and hardens at room temperature due to the oxidizing enzyme latcase that is present in natural lacquer, but from the standpoint of enzymatic reactions, the structure of the substrate, such as the length of the alkyl side chain, has a subtle effect. considered to be a thing. As detailed in Example 3, the urushiol-like substance obtained by the present invention has a distinct structure, has catechol added to the terminal unit, and is extremely similar to urushiol. It differs from natural urushiol in that an alkyl group is added to the 4-position of catechol, but there are three double bonds in the alkyl side chain, saturated alkyl, monoene, diene,
It is expected to be more active than naturally occurring urushiol, which consists of a mixture of trienes. Various synthetic methods can be considered to obtain the compound of the present invention, such as copolymerizing hydroxystyrene during polymerization of butadiene or isoprene, but generally speaking, as the present inventors have done, butadiene or isoprene is It is preferable to synthesize a low polymer and add phenols to it. As a method for synthesizing low polymers of butadiene or isoprene, for example,
89788, JP-A-49-115189, etc. are recommended. Oller (GA) is a phenolization method.
Friedel-Crafts and Related Reactions
The alkylation reaction using a Friedel-Crafts type catalyst is recommended, as detailed in Chapter 14 of Volume 2 of Interscience Publishers Inc. 49-89788, JP-A-49-115189, etc. An example of a low polymer obtained by this method is the general formula () (In the formula, R ₁ and R' ₁ are hydrogen or a methyl group, and cannot be methyl groups at the same time. R ₂ is hydrogen or a methyl group, and n is 1 to 40.) Liquid polybutadiene or liquid polyisoprene whose main component is a compound with a double bond inside, and its characteristic is that it has a vinyl or isopropenyl group at the end derived from the use of ethylene or propylene as a chain transfer agent. be. Of course, the liquid polymer obtained by this method has a wide molecular weight distribution, and in order to make it compatible with the synthesis of cardanol and urushiol-like substances, the polymerization conditions must be selected to increase the portion with a lower degree of polymerization.
It is desirable to further narrow the molecular weight distribution by fractional distillation. For example, the liquid polymer obtained by the method described in Example 1 shown below contains as a main component a compound in the general formula () in which R ₁ and R′ ₁ are hydrogen and R ₂ is a methyl group, but it can be obtained by rectification and The following substances can be obtained by gel permeation chromatography.

[Table] The liquid polymer obtained by the method described in Example 6 below has the general formula ()
Although the main component is a compound in which R ₁ and R ₂ are methyl groups, the following substances can be obtained by rectification and gel permeation chromatografting.

[Table] * Vapor pressure osmometer The reaction between the above liquid polymer and phenol or catechol is usually carried out in the presence of a Friedel-Crafts type catalyst. As the Friedel-Crafts type catalyst, Lewis acids such as metal halides, Bränsted acids, activated alumina, and cation exchange resins can be used. As metal halides,
_AlCl3 , _AlI3 , _GaCl3 , CaBr3 _{, SbF5} , _SbCl6 ,
Examples include TiCl ₄ , ZrCl ₄ , ZnCl ₂ , FeCl ₃ , BF ₃ , BCl ₃ and the like, and complexes thereof with Lewis bases are also used. BF ₃ ether complexes and BF ₃ phenol complexes are preferably used. Examples of brainsted acids include H ₂ SO ₄ , HF, H ₃ PO ₄ , FSO ₃ H, polyphosphoric acid,
Examples include CF ₃ COOH, P-toluenesulfonic acid, benzenesulfonic acid, HClO ₄ and the like. In addition to activated alumina, silica-alumina, silica-magnesia, silica-zirconia, and even activated clay are used, and it is also possible to use a combination of these. Although the use of a solvent is not always necessary, it makes it easier to relax reaction conditions and suppress side reactions such as intermolecular reactions. Although it is not preferable to use a large amount of a polar substance as a solvent since it may cause catalytic activity, ethers such as tetrahydrofuran can also be used as a solvent as in Examples 3 and 4. Generally, a solvent inert to the Friedel-Crafts reaction, such as nitrobenzene, is used. The charging ratio of liquid polymer and phenol or catechol varies depending on the target compound, but it is usually 0.1 to 10 parts by weight, preferably 0.5 to 4 parts by weight, of phenol or catechol per 1 part by weight of liquid polymer. Liquid polymers do not necessarily use purified products with a single molecular weight;
Mixtures with a broad molecular weight distribution may also be used. Reaction temperature is 10℃~200℃, preferably 40℃
~120°C, but is limited by the molecular weight of the liquid polymer and the type of solvent. The amount of catalyst depends on the reaction temperature and degree of solvent dilution;
50℃~90℃ for _HClO4 (70wt% aqueous solution) catalyst
In this case, it is used in an amount of 0.01 to 0.5% by weight based on the total amount of reaction liquid. The reactants can be charged either in one go or in a continuous manner, but as always in alkylation reactions, it is important to increase the stirring efficiency. The reaction time varies depending on the reaction temperature, solvent, etc., but it can be used without a solvent.
At 50°C, the reaction time is 30 minutes to 3 hours when using 0.05 weight percent of HClO ₄ (70 wt%). The reaction is stopped by adding a base such as an amine or by adding a large amount of water. After the reaction is complete, depending on the application, subsequent reactions may be carried out with unreacted substances still present; however, if it is necessary to remove unreacted substances, solvent extraction,
Purification methods such as vacuum distillation and steam distillation are used. The phenol or catechol adduct obtained by the present invention can be subsequently condensed with formaldehyde or the like and used as a varnish, or purified and used as a substitute for cardanol or urushiol. The reaction product of Example 1 was subjected to a condensation reaction by adding formalin and ammonia without removing unreacted substances, and it can be said to be a "synthetic" cashew varnish, which is hard, glossy, oil resistant, and heat resistant. It has excellent hot water resistance, chemical resistance, and electrical insulation, and is suitable for vehicles, ships, buildings,
In addition to furniture, it can be used as chemical-resistant paint for chemical machinery, insulating varnish, etc. In addition, the compound obtained in Example 3 has a molecular structure very similar to natural urushiol, is active against latcase, and has better drying properties and coating performance than synthetic urushiol obtained from similar attempts in the past. Very good condition. Even if the urushiol-like substance of Example 3 was added as an extender up to 4 parts by weight per 1 part by weight of natural lacquer, the drying properties and coating performance of natural lacquer were hardly reduced, depending on the conditions. can produce a coating that is superior to natural lacquer alone in terms of hardness, gloss, etc. Moreover, even if this product is used alone, it dries and hardens in 15 to 20 minutes at 160°C when a drying agent such as cobalt naphthenate is added, and the resulting coating film is in no way inferior to the baked coating film of natural lacquer. The present invention will be specifically explained in detail below with reference to Examples, but the present invention is not limited thereto. Example 1 A butadiene low polymer was synthesized as follows. In a 100 ml flask equipped with a stirring rotor, add 20 ml of dehydrated and deoxygenated toluene, 7.4 ml of a 0.2 mol/toluene solution of nickel naphthenate, 2 g of butadiene, and 2 g of triethylaluminum.
14.8ml of 1mol/toluene solution, 8.8ml of 0.167mol/toluene solution of triphenylphosphine, 1mol/toluene solution of benzotrichloride.
Add 7.4ml and mix the catalyst at 60℃ for 30 minutes. Next, put 400 g of dehydrated and deoxidized toluene into a stainless steel autoclave with a stirring blade and a pressure resistance of 20 kg/cm ² , and add the catalyst solution prepared above. Next, 50% of the dehydrated and distilled anhydrous butadiene
g, add 100 g of dehydrated anhydrous propylene, 60
Increase temperature to ℃. Separately, 400 g of dehydrated and distilled anhydrous butadiene was placed in a stainless steel autoclave with a pressure resistance of 20 kg/cm ² , and dehydrated anhydrous propylene.
Prepare one with 160g added, and add 70g at a time every 30 minutes after the temperature of the polymerization tank 3 rises to 60℃.
Butadiene and propylene were added in portions from the monomer tank and polymerized for a total of 5 hours. The mixture was cooled to room temperature, unreacted propylene and butadiene were purged, 14.8 ml of isopropyl alcohol in toluene (2 mol/solution) was added, and the polymerization was stopped by stirring for 10 minutes. The contents were taken out into a beaker, left overnight, and the precipitated catalyst was filtered off. This reaction solution was distilled under reduced pressure using a Widmer improved fractionator, and the polymer was concentrated and fractionated to separate it into three fractions. 178℃
The remaining portion that could not be distilled under the conditions of
mmHg) was designated as the fourth fraction. The results of fractional distillation are shown in Table 1.

[Table] By subjecting each fraction to gas chromatography and gel permeation chromatography, the first fraction was determined by the general formula () with n=2,
It was confirmed that the second fraction was composed of components n = 3, the third fraction was composed of components n = 4, and the fourth fraction was composed of components n = 5 and 6. The results of molecular weight measurements using a vapor pressure permeometer also support the fact that rectification is occurring. In addition, when we conducted infrared spectrum analysis of each fraction, we found that 1.
Instead of the vinyl group absorption at ~906 cm ^-1 observed in the infrared spectrum of 2-polybutadiene
Absorption based on vinylidene groups was observed at 896 cm ^-1 . Therefore, in the produced polymer, there is virtually no vinyl group in the side chain, and the molecular terminal has the general formula ()
As shown in Figure 2, it was observed that it was converted into a vinylidene group. The phenol addition reaction of the second fraction thus obtained (a compound consisting of 3 units of butadiene and 1 unit of propylene) was carried out as follows. After adding 40 g of the above second distillate and 40 g of phenol to a 200 ml four-necked flask equipped with a stirring blade, a thermometer, and a cooling tube, the inside of the flask was purged with nitrogen, and the internal temperature was brought down to 50 ml.
Set to ℃. Add 34.2μ of perchloric acid (70wt% aqueous solution) using a microsyringe under strong stirring (900rpm).
Add at once. The reaction solution turns brown. A large fever is observed, and the internal temperature reaches 60°C after 1 minute, but it quickly subsides and returns to 50°C after 10 minutes.
After continuing the reaction at 50° C. for an additional 15 minutes, the reaction was stopped by adding 0.4 ml of triethylamine. When triethylamine was added, white smoke was generated and the coloring of the reaction solution weakened and became transparent and yellow. A small amount of sample was taken and the reaction rate of phenol and butadiene-propylene co-oligomer was determined by gas chromatography. The reaction rate of phenol was 25.7%, and the reaction rate of cooligomer was 53.6%, meaning that on average one molecule of phenol was added per molecule of cooligomer. Methanol is added to the reaction solution while stirring to precipitate the phenol adduct of the cooligomer.
By repeating this operation three times, the catalyst and most of the unreacted phenol are extracted and removed with methanol. Subsequently, unreacted cooligomer was distilled off under reduced pressure to obtain a yellow transparent liquid.
I got g. Elemental analysis of this material reveals C84.23.
H10.01, calculated value for a compound with one molecule of phenol added to one molecule of cooligomer
It showed good agreement with C84.56, H10.07, and O5.37. When the liquid film was sandwiched between rock salt plates and the infrared absorption spectrum was measured, it was found that
The absorption based on the vinylidene group at 896 cm ^-1 has disappeared, and in its place, absorptions based on the vinylidene group at 3400 cm ^-1 (phenolic hydroxyl group ν _OH ), 1590 cm ^-1 and 1490 cm ^-1 (benzene nucleus), and 1360 cm ^-1 (phenolic hydroxyl group _δOH ),
Absorption related to out-of-plane bending vibration of the phenol nucleus was observed below 1220 cm ^-1 (ν _C - _C ) and 900 cm ^-1 . According to the measurement of the NMR spectrum, the absorption based on the terminal vinylidene group at δ4.65 observed in the raw material oligomer has disappeared, and the absorption due to the benzene nucleus proton at δ6.5 to 7.2 is a symmetrical multiple.
It is observed that Also, an absorption is observed at δ~1.0 that is thought to be based on the methyl group at the β position of the benzene nucleus. It was also confirmed from the magnitude of the integrated intensity of the benzene nucleus protons that this compound was made by adding one molecule of phenol to one molecule of cooligomer. When measuring gel permeation chromatography, raw material cooligomer (elution volume 100ml)
A single peak appears at an elution volume of 96 ml instead of the peak. Therefore, this compound does not include those to which two or more molecules of phenol are added per cooligomer molecule or those whose molecular weight has been increased by crosslinking between molecules. Furthermore, by comparing with the SADTLER standard spectra of 2-ethylphenol, 3-ethylphenol, and 4-ethylphenol, it was identified that the addition position of phenol is mainly at the 4-position. As a result of the above analysis, the obtained compound has the general formula () where a=3, b=0, n=a+b=3
It was found that this is a phenol adduct of a butadiene trimer in which R ₁ and R′ ₁ are hydrogen and R ₂ is a methyl group, with propylene bonded to the end, and the phenol addition position is the 4-position. did. Example 2 Regarding the fourth fraction of the butadiene-propylene co-oligomer obtained in Example 1 (a 1/1 mixture of a compound consisting of 5 units of butadiene and 1 unit of propylene and a compound consisting of 6 units of butadiene and 1 unit of propylene) also carried out the phenol addition reaction in a similar manner. The reaction was carried out at 50°C for 1 hour and 15 minutes, then at 80°C.
The temperature was raised to ℃ and continued for an additional 1 hour and 15 minutes. A small amount was sampled during the reaction and analyzed in the same manner as in Example 1. The results are shown in Table 1.

[Table] In addition to the disappearance of the vinylidene group absorption at 896 cm ^-1 in the infrared absorption spectrum of the above product, as the reaction time progresses, the absorption of vinylidene groups at 3400 cm ^-1 , 1590 cm ^-1 , 1490 cm ^-1 ,
It was observed that the absorption intensity increased below 1360 cm ^-1 , 1220 cm ^-1 and 900 cm ^-1 . The absorption associated with the trans double bond at 960 cm ^-1 decreased significantly as the reaction time progressed. In the NMR spectrum, the absorption of the terminal vinylidene group at δ4.65 disappears, and as the reaction time progresses, δ5.33 (-CH=), δ2.67
Decrease in absorption intensity of (-CH ₂ -C=) and δ6.5-7.2
(benzene nuclear proton), δ1.65 (-CH ₂ -C-
An increase in the absorption intensity of φ) and δ1.34(−CH ₂ −) was observed. Furthermore, by comparing with the SADTLER standard spectra of 2-ethylphenol, 3-ethylphenol, and 4-ethylphenol, it was identified that the addition position of phenol is mainly at the 4-position.
Infrared absorption spectra and NMR spectra revealed that phenol added to the internal double bonds in addition to the terminal vinylidene groups as the reaction time progressed. Compound A obtained from the above analysis has the general formula () where a=5, b=0, n=a+
It is a mixture of b=5, a=6, b=0, n=a+b=6, and compound B is a mixture of a=4, b=1, n=a+
It is a mixture of b=5, a=5, b=1, n=a+b=6, and compound C is a mixture of a=3, b=2, n=a+
It can be seen that it is a mixture of b=5, a=4, b=2, n=a+b=6, and the addition position of phenol is the 4-position. (R ₁ , R′ ₁ are hydrogen and R ₂ is a methyl group) Example 3 Using the second fraction of the butadiene-propylene co-oligomer obtained in Example 1, using catechol instead of phenol, and adding urushiol to A similar compound was synthesized. Add 40% of the above second distillate to a 200ml four-necked flask equipped with a stirring blade, thermometer, and condenser.
Add 40g of catechol and 15ml of tetrahydrofuran and set the temperature to 50℃. Add perchloric acid (70wt) under strong stirring.
% aqueous solution) was added at once to 51.4μ using a microsyringe. Although the reaction solution was instantly colored brown, no rapid rise in internal temperature as seen in Example 1 was observed. After 15 minutes, 0.6 ml of triethylamine was added to stop the reaction. The results of gas chromatography showed that the reaction rate of catechol was 14.9% and the reaction rate of butadiene oligomer was 25.2%, which means that 1.1 molecules of catechol were added per molecule of cooligomer. The reaction solution was washed several times with water and then subjected to steam distillation to remove unreacted catechol and cooligomer. 15.2 g of dark brown viscous material was obtained. The elemental analysis value is
C80.36, H9.67, calculated values for a compound with one molecule of catechol added to one molecule of cooligomer
It showed good agreement with C80.25, H9.55, and O10.19. In the infrared absorption spectrum, the vinylidene group absorption at 896 cm ^-1 observed in the raw material cooligomer disappeared. The newly appeared absorption is 3400cm ^-1 and 1600cm
^-1 , 1490cm ^-1 , 1360cm ^-1 , 1250cm ^-1 , 1210cm ^-1 ,
1190cm ^-1 , 1100cm ^-1 , 860cm ^-1 , 800cm ^-1 , 780cm
^-1 and 730 cm ^-1 , and the absorption related to the trans double bond at 960 cm ^-1 remained almost unchanged. By comparing with the SADTLER standard spectra of 3-methylcatechol and 4-methylcatechol, the addition position is considered to be the 4-position. NMR
In the spectrum, the disappearance of the absorption of the terminal vinylidene group at δ4.65 and the appearance of benzene ring protons at δ6.6 to 6.85 can be clearly seen. Broad absorption of olefin protons with δ5 to 6 is observed, but
It disappears with heavy water substitution and a peak that appears to be HDO appears at δ4.7, so it is thought to be a phenolic hydroxyl group. A large absorption appears at δ1.3, but 4
This corresponds to the absorption position of the methyl group in -t-butyl-catechol. Furthermore, the absorption of benzene ring protons also shows a dichotomous pattern, which matches well with the spectrum of 4-t-butylcatechol. In gel permeation chromatography, a single peak appears at an elution volume of 95 ml instead of the peak of the raw material cooligomer (elution volume of 100 ml). Therefore, this compound does not include those in which two or more molecules of catechol are added per cooligomer molecule or those in which the molecular weight is increased by crosslinking between molecules. From the results of the above analysis, the compound obtained above is In the general formula (), a=3, b=0,
It turned out to be a catechol adduct of a butadiene trimer with propylene bonded to the terminal, where n=a+b=3, R _{1 and} R' ₁ are hydrogen, and R ₂ is a methyl group. Example 4 A catechol adduct of the fourth fraction of the butadiene-propylene co-oligomer obtained in Example 1 was synthesized in accordance with Example 3. The reaction was carried out at 50°C for 30 minutes and then continued under reflux conditions for a total of 5 hours. The results are shown in Table 2.

[Table] Infrared absorption spectrum of the above product, 896 cm ^-1
In addition to the disappearance of vinylidene group absorption, as ^the reaction time progresses, ^the
-1 , 1360cm ^-1 , 1250cm ^-1 , 1210cm ^-1 , 1190cm ^-1 ,
1100cm ^-1 , 860cm ^-1 , 800cm ^-1 , 780cm ^-1 , 730cm ^-1
The absorption intensity for the trans double bond at 960 cm ^-1 decreased. In the NMR spectrum, the absorption of the terminal vinylidene group at δ4.65 disappears, and as the reaction time progresses, the absorption at δ5.33 (-CH
=), δ2.67 (-CH ₂ -C=) absorption intensity decrease, δ6.5-7.2 (benzene nucleus proton), δ1.65
(-CH ₂ -C-φ), an increase in the absorption intensity of δ1.34 (-CH ₂ -) was observed. As a result of such analysis,
It was found that as the reaction time progressed, catechol was added not only to the terminal vinylidene group but also to the internal double bond. Similarly to Example 3, by comparing the SADTLER standard spectra of 3-methylcatechol and 4-methylcatechol with the obtained spectra of compounds D and E, the addition position of catechol was determined to be 4.
- It was identified that the The obtained compound D has the general formula () where a=
5, b=0, n=a+b=5 and a=6, b=0,
It is a mixture where n=a+b=6, and compound E is a mixture where a=
4, b=1, n=a+b=5 and a=5, b=1,
It is a mixture of n=a+b=6, and it can be seen that the addition position of catechol is the 4-position (R ₁ ,
R′ ₁ is hydrogen and R ₂ is a methyl group). Example 5 An ethylene-bonded butadiene low polymer was synthesized as follows. Catalyst preparation is done in a 100ml machine with a stirring rotor.
In a flask, add 10 ml of dehydrated and deoxygenated toluene and 0.2 mol of nickel naphthenate/toluene solution.
1.5 ml, 1 g of butadiene, 3 ml of a 1 mol/toluene solution of triethylaluminum, 1.8 ml of a 0.167 mol/toluene solution of triphenylphosphine.
ml and 1.5 ml of a 1 mol/toluene solution of benzotrichloride were added, and the mixture was stirred and mixed at 60°C for 30 minutes.
Next, 206 g of dehydrated and deoxidized toluene was placed in a 1.5 stainless steel autoclave with a pressure resistance of 20 kg/cm ² equipped with a stirring blade, and the catalyst solution prepared above was added. Next, dehydrated and distilled anhydrous butadiene
Add 58g and close the autoclave valve.
Remove the cooling from the autoclave and start heating it up, setting the reaction temperature to 20℃. At this time, ethylene was introduced from an ethylene cylinder that had been connected in advance, and the reaction was carried out for a total of 4 hours at a reaction temperature of 20° C. and a pressure of 4.5 kg/cm ² . After purging unreacted butadiene and ethylene to stop polymerization, the mixture was concentrated to obtain 44 g of liquid polymer. The viscosity was 10 centipoise (25°C) using a falling ball viscometer. The obtained polymer was subjected to fractional distillation using the same apparatus as in Example 1. The results are shown in Table 3. Molecular weight was measured using a vapor pressure permeameter. The infrared absorption spectrum of the obtained polymer has
There is a peak at 906 cm ^-1 , indicating that the vinyl group derived from ethylene is at the end. NMR spectra were measured for each fraction. Table 4 shows the results.
Shown below.

【table】

【table】

[Table] The theoretical values in Table 4 are, in the structural formula H-(CH ₂ -CH=CH-CH ₂ )- _o CH=CH ₂ , n=2 for the first fraction and n=2 for the second fraction.
3. The third fraction is a numerical value assuming that n=4. Furthermore, by performing gas chromatography and gel permeation chromatography on each fraction, it was confirmed that each fraction consisted of a single component. As a result of the above analysis, the first fraction is a compound consisting of 2 units of butadiene and 1 unit of ethylene, the second fraction is a compound consisting of 3 units of butadiene and 1 unit of ethylene, and the third fraction is a compound consisting of 4 units of butadiene and 1 unit of ethylene. It is clear that the compound consists of A phenol or catechol addition reaction was performed on each fraction according to Examples 1 and 3. Table 6 shows the synthesis of the phenol adduct of the above third fraction (a compound consisting of 4 butadiene units and 1 ethylene unit). The reaction was heated to 70°C for 1 hour, then raised to 100°C and continued for an additional 5 hours. Dehydrated toluene was used as the reaction solvent.

[Table] In the infrared absorption spectrum of the above product, in addition to the disappearance of the vinyl group absorption at 906 cm ^-1 observed in the raw material cooligomer, the absorption at 3400 cm -1 and 3400 cm ^-1 as the reaction time progresses.
1590cm ^-1 , 1490cm ^-1 , 1360cm ^-1 , 1220cm ^-1 and
The absorption intensity below 900 cm ^-1 increased, and the absorption intensity of the trans double bond at 960 cm ^-1 decreased. In the NMR spectrum, δ4.63 (CH ₂ = C-) disappears, and as the reaction time progresses, δ5.3 (-CH
=), the absorption intensity of δ2.0 (-CH ₂ -C=) decreased, and the absorption intensity of δ1.65 (-CH ₂ -C-φ) and δ1.34 (-CH ₂ -) increased. Therefore, it was found that as the reaction time progressed, phenol was added not only to the terminal vinyl group but also to the internal double bond. Furthermore, by comparing with the SADTLER standard spectra of 2-ethylphenol, 3-ethylphenol, and 4-ethylphenol, it was identified that the addition position of phenol is mainly at the 4-position. From the above analysis, compound F is a compound with a = 4, b = 0, n = a + b = 4 in the general formula (), and compound G is a compound with a = 3, b = 1, n = a + b = 4, It was found that the addition position of phenol was the 4-position. (R ₁ , R' ₁ , and R ₂ are all hydrogen) Example 6 An isoprene low polymer was synthesized as follows. In a 100 ml flask equipped with a stirring rotor, add 20 ml of anhydrous toluene and nickel naphthenate.
3.64 ml of 0.2 mol/toluene solution, 2 g of dehydrated and distilled isoprene, 8.0 ml of 0.909 mol/toluene solution of ethylaluminum sesquichloride.
ml, add 7.27 ml of 0.02 mol triphenylphosphine/toluene solution and prepare the catalyst at -30°C for 30 minutes. Next, 1.5 with a stirring blade with a pressure resistance of 20Kg/cm ²
Add this catalyst solution to a stainless steel autoclave, add 190 ml of anhydrous toluene, 270 g of anhydrous isoprene distilled after dehydration, and anhydrous propylene.
Add 68g and polymerize at 60°C for 7 hours. After stopping the reaction in the same manner as in Example 1, the solvent was distilled off.
229.5g of polymer was obtained. The viscosity was 13.3 centipoise at 30°C. The obtained polymer was subjected to polymer fractionation using the same apparatus as in Example 1. Gas chromatography and gel permeation of each fraction
By taking chromatography, the first fraction is a compound consisting of 2 units of isoprene and 1 unit of propylene, the second fraction is a compound consisting of 3 units of isoprene and 1 unit of propylene, and the third fraction is a compound consisting of 4 units of isoprene. It was confirmed that it was a compound consisting of one unit of propylene and one unit of propylene. Table 7 shows the physical property values of each fraction. Synthesis of the phenol adduct of the above-mentioned second fraction (compound consisting of 3 units of isoprene and 1 unit of propylene) was carried out according to Example 1. Isoprene-propylene co-oligomer 20g, phenol 20
g, toluene 40ml, P-toluenesulfonic acid 0.3
After reacting at 80°C for 2 hours, the reaction was stopped with triethylamine. According to gas chromatography, the reaction rate of phenol was 28.4% and the reaction rate of cooligomer was 70.6%. After washing with water and distilling under reduced pressure, 15 g of a dark brown liquid was obtained.
Elemental analysis values were C84.56 and H10.54. It was in good agreement with the calculated values C84.71, H10.59, and C4.7 for a compound in which one molecule of phenol was added to one molecule of cooligomer. It was found from the infrared absorption spectrum and NMR spectrum that the terminal isopropenyl group had disappeared. Furthermore, by comparing with the SADTLER standard spectra of 2-ethylphenol, 3-ethylphenol, and 4-ethylphenol, it was identified that the addition position of phenol is mainly at the 4-position. Therefore, in the general formula (), this compound has a
=3, b=0, n=a+b=3, R ₁ and R ₂ are phenol adducts of methyl groups, and the phenol addition position is the 4-position.

【table】

Claims (1)

[Claims] 1 General formula () (In the formula, R ₁ and R′ ₁ are hydrogen or a methyl group, and cannot be methyl groups at the same time. _{R 2 is} hydrogen or a methyl group. It is a residue.
X ₂ and X ₃ are either hydrogen or X ₁ , and one of them is always X ₁ . a and b are n=a+b, 1≦n≦40, 0
≦b is an integer. ) A phenol or catechol adduct of a low polymer of butadiene or isoprene with ethylene or propylene attached to the terminal. 2. The phenol or catechol adduct according to claim 1, wherein in the general formula (), b=0 and R ₂ is hydrogen. 3. The phenol or catechol adduct according to claim 1, wherein in the general formula (), b=0 and R ₂ is a methyl group. 4. The phenol or catechol adduct according to claim 1, wherein in the general formula (), b=0, R ₁ and R' ₁ are hydrogen, and R ₂ is hydrogen or a methyl group. 5 In general formula (), b=0, 2≦a≦10,
The phenol or catechol adduct (cardanol or urushiol analogue compound) according to claim ₁ , wherein R 1 and R' 1 are hydrogen _, and R ₂ is hydrogen or a methyl group. 6. The phenol or catechol adduct according to claim 1, wherein in the general formula (), b=1 and R ₂ is hydrogen. 7. The phenol or catechol adduct according to claim 1, wherein in the general formula (), b=1 and R ₂ is a methyl group. 8. The phenol or catechol adduct according to claim 1, wherein in the general formula (), b= ₁ , R 1 and R' ₁ are hydrogen, and R ₂ is hydrogen or a methyl group. 9. The phenol or catechol adduct according to claim 1, wherein in the general formula (), b=2 and R ₂ is hydrogen. 10. The phenol or catechol adduct according to claim 1, wherein in the general formula (), b=2 and R ₂ is a methyl group. 11. The phenol or catechol adduct according to claim 1, wherein in the general formula (), b=2, R ₁ and R' ₁ are hydrogen, and R ₂ is hydrogen or a methyl group. 12 General formula () (In the formula, R ₁ and R' ₁ are hydrogen or a methyl group, and cannot be methyl groups at the same time. R ₂ is hydrogen or a methyl group, and n is 1 to 40.) Alternatively, a method for producing a phenol or catechol adduct of a propylene-bonded butadiene or isoprene low polymer and phenol or catechol, which is characterized by reacting the low polymer with phenol or catechol in the presence of a Friedel-Crafts type catalyst.