JPS60228580A - Addition reaction product between tung oil and catechol and production thereof - Google Patents

Abstract

PURPOSE:To provide the titled product which has a specified structure and is useful as a reactive plasticizer for phenolic and epoxy resins, an antioxidant and a Japanese lacquer substitute. CONSTITUTION:An addition reaction product between tung oil and catechol, which has the formula I, wherein one of three X's is a group of formula II or IIIand the other two are a group of formula II, III or IV or a combination thereof. The reaction product is used as a reactive plasticizer for phenolic and epoxy resins, an antioxidant, a Japanese lacquer substitute, etc., and can be obtd. by dissolving catechol in a solvent, adding tung oil thereto and reacting them in the presence of a Friedel-Crafts catalyst.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention IQ 7 A combination of tung oil and catechol which is used as a reactive agent for S-nol resins and epoxy resins, an anti-fouling agent, and as a substitute material for lubricants. I do not know about the reaction between the additional reaction substances and the manufacturing method, 〇 10 cities ÷ each crown → [conventional technology] The present inventors have previously conducted basic reaction analysis on the reaction between tung oil and monovalent dienol using infrared absorption, nuclear magnetic resonance, liquid chromatography, and other instrumental analyses.

■ In the chemical formula of tung oil, how much force should be attached to the conjugated 2N bond of tung oil at the ortho position or the nihara position of the phenolic u7s nork nucleus? Rheostearin #I
A maximum of 2 moles of phenols can be added to the base, that is, a maximum of 6 moles of phenols can be added to 1 mole of tung oil. It was found that when one phenol was reacted with Zl/-1, the unreacted diene was activated, and the reaction between the two tung oils progressed to form a polymer.

[Purpose of the invention]

The purpose of the present invention is to prepare an addition reaction substance between tung oil and catechol, and was developed as a result of a detailed study of the reaction between tung oil and catechol based on the above findings.

[Structure of the invention]

Regarding the addition reaction substance of tung oil and catechol shown by the chemical formula It is used as a reactive 5Jm agent for phenolic resins and epoxy resins, as an anti-fouling agent, and as a substitute for lacquer. For example, the addition of uninvented tung oil and catechol, which is a similar compound to urushiol, the main component of natural lacquer. 'tl to the reactant
：Used as a substitute for urushiol 〇Another aspect of the present invention is the reaction between tung oil and catechol. In addition to methyl alcohol, it can be reacted in the presence of a cold Friedel-Crafts catalyst and used as a reaction bath agent.

Ether alcohol, flobyl alcohol, acetone, methyl alcohol, benzene, toluene, xylene, cyclohexanone, dioxane, etc. are used.

As a Friedelkland catalyst, in addition to para-toluene sulfone, sulfuric acid, phosphoric acid, hydrogen fluoride, etc., and aluminum chloride, zinc chloride, etc. can be used alone or in combination. Catechol has a 175-2 It is commonly understood as a reaction bath agent such as methyl alcohol in an amount of 1/2 to 1/2 moles of tung oil per 1 mole of catechol.
00 Add paratoluene at α05 to 2 Aji% to the oil and react with a Riedel-Crafts catalyst such as sulfone M for 2 to 20 hours at 60 to 100°C.The reactant was tung oil. Since the catechol addition reaction substance is a round substance, it is washed several times with the reaction thickener IM Deshun distilled water under reduced pressure to remove unreacted catechol. ◎ Remove water by drying under reduced pressure in the air. oily tung oil
A catechol addition reaction product is obtained.

In order to derive the structure of this addition reactant, we performed a fractional bath solution using acetone as a solvent and water as a non-bath agent.
A * Go 7Co, that is, bath additive threads with a large proportion of water are 730 @ with 6 moles of catechol, or Samurai n gradually increasing the proportion of acetone, gradually increasing the proportion of catechol or Shinai with a small amount of catechol. The decision to create the compound by DJX Hormono was carried out using chromatography, nuclear magnetic resonance, and infrared absorption analysis. Confirmation that it is a single component and determination of molecular weight using Shinhye chromatography? '? Then, it was confirmed by nuclear magnetic resonance that catechol was reacting at the benzene nucleus position and that the 2M bond of tung oil was reacting by infrared absorption. EXAMPLE 1 Catechol 600 gs para-toluene sulfone (L
2 gs Methyl alcohol 250 gk mixed at 60℃
Heat the mixture to zero and remove the catechol from the foil. ◇ Add 120 g of tung oil to this mixture and react at 80°C for 5 hours. Methyl alcohol was removed from the reaction mixture by reducing the pressure to zero.
Then, the reaction catechol was removed by washing several times with distilled water. Next, the water was removed by vacuum drying to obtain an oily tung oil-catechol reaction product. t A mixture of acetone and water (mixture ratio 4/1 to 1/4)
) It was made into a single pot using the 1-fraction bath solution method.

Figure 1 is a liquid chromatography chart of the tung oil-catechol addition reaction product of Example 1, catechol in the m family, and tung oil, where the molecular weight is shown on the horizontal axis. The relationship between m output (count #i) and molecular weight can be seen on a scale from the liquid chromatography chart of a slow-retarding substance. Tung oil - with catechol 7
Nuclear magnetic resonance creation chart of 1Il1 reactants is a busy comparison 0 #! Figure 3 compares the infrared spectroscopy side charts of tung oil and the tung oil-catechol addition reaction product of Example 1.

Figure 4 is a chromatograph of the tung oil-caro reaction product with catechol (H"4m?lJ1) [decomposition product obtained by ester decomposition with methyl alcohol]. The explanation for the O symbol is as follows.

1. Catechol peak, 2. Tung oil peak, 3. Beetle of the tung oil-catechol attached blade I] reaction product, 4. Nuclear magnetic resonance chart of the tung oil-catechol addition reaction product.

Nuclear magnetic resonance chart of 5-acenalized π-tung oil-catechol-attached sword cutter, 6-catechol 10H proton signal, 7-catechol -()COCH.

Proton signal, 84 -CH3 proton signal of oil, 9 Signal of tetramethylsilane, 10 Infrared absorption spectrum of tung oil, 11 Infrared absorption spectrum of tung oil-catecholic force O anticarving, 12 Binary bond of tung oil It was found that the molecular weight of 16benzec was about 1100, and the molecular weight of this compound was found to be 1090 when the molecular weight of this compound was determined using a vapor pressure equilibrium molecular type measuring device.
When lv1 tung oil (molecule 1i872) is reacted with 2 moles of catechol (molecular weight 11G), the product is then acetylated according to the legend, and the nuclear magnetic resonance tJt of the acetylation i11 is obtained. I was beaten
(Fig. 2) Before acetylation, a phenolic -○H signal was observed, but it disappeared into the acetylated 1-OR signal! + In addition, a proton signal of 10 COCHs was generated, It was confirmed that the -OH group of catechol was not involved in the reaction with tung oil. Furthermore, the protons of -CHs in tung oil (there are 9 in 1 mole of tung oil) and the protons of -CHs in acetylated catechol (
It was also found by infrared spectroscopy that 2 moles of catechol were added to 1 mole of tung oil at an nt ratio of 3:4. The conjugated 2ffi bond in tung oil has been reduced to 779 in the reaction economy, and the catechol nucleus has been oxidized. When the product was analyzed using adult chromatography, a peak of eleostearin methyl and an adduct Iy of 1 mole of catechol added to eleostearin methyl were observed (Figure 4). From the results, the structure of the compound obtained here has the above (
1) It is confirmed that the compound is X or two and one (Q) is n friend.

Example 2゜Catechol 700 g, paratoluenesulfone t! R.E.
1.57 g s Inglobil Alcohol 250gr
Mix and heat to 60°C to remove catechol. To this mixture was added 37 g' of tung oil, and the mixture was reacted at 80° C. for 16 hours. Globyl alcohol was removed from the reaction mixture under reduced pressure, and unreacted catechol was removed by washing several times with #c distilled water. Next, water was removed by vacuum drying to obtain an oily tung oil-catechol reactant.
~'/q)=0 Figure 5 is a liquid chromatography chart of the tung oil-catechol addition reaction product of Example 2.

FIG. 6 is a comparison of the nuclear magnetic resonance side chart hV of the tung oil-catechol addition reaction vI and the acetylated tung oil-catechol addition reaction product of Example 2.

FIG. 7 is an extra spectroscopic measurement chart of the tung oil-catechol-applied sword tail of Example 2.

Is Figure 8 implemented? For the tung oil-catechol addition reaction of lJ2;'
This is a dispersion chromatography chart of l#c methyl alcohol aliquot.

Explanation about the symbols is as follows.

16 Peak of tung oil-catechol addition reaction product 17 Nuclear magnetic resonance chart of tung oil-catechol reaction product 18 Nuclear magnetic resonance chart of acetylated tung oil-catechol addition reaction product 19 Signal of catechol-OH proton 20 One ococn of catechol s proton signal 21 Tung oil (
H3 Proton shift 22 Signal of tetramethylsilane 26 Absorption due to double bond of tung oil 24 Absorption due to benzene ring 7X complex 25 Eleostearin Enemy methyl and catechol 2 moles Pitch 0 Snout peak Rate from the liquid chromatography chart in Figure 5 - It was found that the molecular weight was about 1500 because it was a peak.0 Also, when the molecular weight of this compound was measured using a vapor pressure equilibrium molecular weight measuring device, it was 1510 l! 11. Tung oil (molecular weight 87
When 6 moles of catechol (molecular weight 110) were reacted with 2), the theoretical molecular type 1562 (identified). Figure 6) As in Example 1, acetylation disappeared into the 10H signal, and KotaniichiOCOC)I
The proton signal of m was detected.

In addition, one channel of tung oil. The integral ratio of protons (9 exist in 1 mole of tung oil) and protons of one OCOCH3 of acetylated catechol (61i6j exist in 1 mole of acetylated catechol) is 1/4, and catechol is present in 1 mole of tung oil. It was confirmed that 6 moles of shinaiguchi were present.In addition, infrared spectroscopy revealed that the conjugate of tung oil was found to be a combination of two conjugates.
It was found that direct conversion was occurring in the catechol nucleus. Katooctopus compound [ester decomposition in methyl alcohol in the presence of sodium hydroxide, W# product was analyzed by liquid chromatography.

Only the peak of the reaction product in which 2 moles of catechol was added to methyl eleostearin was detected. (Figure 8) From the above analysis results, it is clear that this is the structure of the samurai monster. l11 or s:1M Mixed with 5g of sword mouth anti-carving of Example 2 and 7g of raw lacquer, ``Lyashi'' and ``Kurome''
and applied lacquer paint. When this lacquer paint was applied to a piece of wood and left in a bath for a day, it solidified and was able to form a lacquer film similar to natural lacquer. The absorption measurements are as follows: Liquid chromatography: Toyo So4 HLC-801 model τ used;
G30C102 wood, G2CJQQ 4 columns were constructed using tetrahydrone as the mobile phase in a self-aligned column, and the mixture was run at 2% flow rate at a flow rate of 1.5 ml/day.

Nuclear resonance: Roroform t used in Hitachi R-24 type
The distance was measured using a sample concentration of t60% as a medium, a sweep speed of 2 Hz/sec, and tetramethylsilane as a standard substance.

Infrared component'/l = Hitachi #! 0 measured by the coating film method using Model 2J35 [Yashu of the invention] Addition reaction product of tung oil and catechol due to non-invention) J
! irs got n trap.

[Brief explanation of drawings]

Figures 1, 2, and 6 show fL obtained in Example 1.
Liquid chromatography, nuclear magnetic resonance, and infrared spectroscopy charts of yc compound. Figures 5, 6, and 7 are the samurai's monster a offering Romato, nuclear magnetic resonance, and infrared spectroscopy charts in Example 2, and Figure 8 a is the This is a Shinhye chromatography chart of a decomposed product obtained by ester decomposition with nt methyl alcohol. PM Figure 4 PPM

Claims (1)

[Claims] 1. CHmh-CO()-(CHmh X (CH proverb)
sCHs1 CH-COO(CHm)y -x -(CH,)-CH
sCHm(00(CH鵞)7
An addition reaction substance of tung oil and catechol represented by the chemical formula s. 2, X or two (5) and one (Q is the addition reaction substance of tung oil and catechol described in Fankyoku No. 13A of the Okina ff claim 0 6, all three X's (G)) An addition reaction substance of tung oil and catechol described in item 1 of dry music. 4. Add tung oil to the catechol scaled in the reaction bath agent 7
# Genetics of addition reactants of tung oil and catechol characterized by reaction in the presence of Riedel-Crafts catalyst. 5. Tung oil is 1/1o to '/2 per mole of catechol
00 mole Claim 4 d Process for producing own tung oil and catechol