JPS61148218A - Production of phenolic resin containing unsaturated bond - Google Patents

Abstract

PURPOSE:To obtain the titled resin, having unsaturated bonds, and good vulcanizability, and useful for rubber modifiers, etc., by reacting a specific cyclopentenylphenol based compound or further a phenol based compound with an aldehyde in the presence of an acid catalyst. CONSTITUTION:A phenolic resin, containing unsaturated bonds, and obtained by reacting a cyclopentenylphenol based compound expressed by formula I (R1 and R2 are H, alkyl, halogen or cyclopentenyl; H is linked to at least two sites in the p- and o-positions with respect to OH group) or further a phenol based compound expressed by formula II (R3, R4 and R5 are H, OH, carboxyl, halogen, 1-15C alkyl, alkenyl, etc.; H is linked to at least two sites in the p- and o-positions with respect to the OH group) with an aldehyde in the pres ence of an acid catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a novel phenolic resin having unsaturated bonds.

(Prior Art) Several polymers derived from alkenylphenols have been reported. For example, the Journal of Polymer Science
er 5science) A-1, Volume 7.

On pages 2175 and 2405 (1969).

Polymers of parahydroxystyrene have been reported. This polymer is a compound obtained by a radical polymerization reaction of vinyl groups, and has a repeating unit represented by formula 1.

Also, Organic Synthetic Chemistry Vol. 34, p. 1000 (1976)
reported a dimer of isopropenylphenol,
This has a structure represented by formula 1.

JP-A-56-59859 discloses the production of a polymer having a repeating unit represented by formula 9 by radical copolymerization of p-isopropenylphenol and acrylonitrile.

It's a trench, according to Japanese Patent Application Laid-open No. 55-145626.

Alkylation reactants of allyl alkylphenol and phenol are disclosed.

(However, 9m is 1 or 2.R is a substituent.)

(Problems to be Solved by the Invention) As mentioned above, conventional polymers derived from alkenylphenols utilize carbon-carbon unsaturated double bonds, and one reactive carbon in the polymer - It does not have carbon unsaturated double bonds or has a low molecular weight.

Therefore, rubber modifiers, foundry river sand binder resins, etc. are not suitable because they lack vulcanizability or have low molecular weights.

The present invention provides a new phenolic resin free from such problems.

(Failure to solve the problem) The present invention is based on the general formula [ID (However, in formula 9, R1 and R2 are hydrogen and an alkyl group.

Indicates a halogen or cyclopentenyl group, which may be the same or different, and in the above formula, p with respect to the OH group.
Hydrogen is bonded to at least two of the positions - and 〇- However, in formula 9, H, 3,) (, 4 and R + t are hydrogen,
hydroxyl group.

Carboxyl group,)) Rodan. An alkyl group or alkenyl group having 1 to 15 carbon atoms, an aliphatic hydrocarbon group having two carbon-carbon unsaturated double bonds, a substituted group thereof, an aromatic hydrocarbon group, or a substituted aromatic hydrocarbon group and these may be the same or different, in the above formula.

Reacting a phenolic compound in which hydrogen is bonded to at least two of the p-position and 〇-position relative to the OH group) with an aldehyde in the presence of an acidic catalyst. The present invention relates to a method for producing an unsaturated bond-containing phenolic resin characterized by the following.

As the cyclopentenylphenol compound represented by the general formula [I], 0-cyclopentenylphenol 1
m-Cyclopentenylphenol.

Examples include p-cyclopentenylphenol, 3-methyl-4-cyclopentenylphenol, 3,4-dicyclopentenylphenol, etc., and monoalkyl substituents other than those listed here include those shown in Table 1.

Flag 1 Monoalkyl substituent Table 1 (Continued) In Table 1, the propyl group is either n-propyl group or inopropyl group, and the butyl group is n-butyl group, 5
It is either an ec-butyl group or a tert-butyl group, and the pentyl group is either an n-pentyl group or other structurally isomeric groups.

Examples of the compound represented by the general formula [11] include phenol, cresol, xylenol, butylphenol, octylphenol, cardanol, cardol, urushiol, 2,2-bis(4-hydroxyphenyl)furopane, and phenylphenol.

Examples include anacardic acid, and cashew nut shell liquid may also be used.

Examples of the aldehyde used in the present invention include formaldehyde, paraformaldehyde, and acetaldehyde.

The acidic catalyst used in the present invention is sulfuric acid.

These include mineral acids such as nitric acid, hydrochloric acid, and boric acid, and organic acids such as I)-) luenesulfonic acid, oxalic acid, and formic acid.

The cyclopentenylphenol compound represented by the general formula [I] and the phenol compound represented by the general formula [■] are mixed so that the former/latter molar ratio is 1/9 to 1010. It's sweet to be treated like that.

In particular, it is preferable to mix it in an amount of 3/7 to 1010. If the amount of the cyclopentenylphenol compound is too small, no effect can be expected from using the compound. For rubber reinforcing agents, the above molar ratio is 1/9
~7/3 is preferred.

In particular, 33/67 to 60/40 is preferable.

The amount of aldehyde is 0 per mole of the total amount of the cyclopentenylphenol compound represented by the above general formula [I] and the phenol compound represented by the above general formula [■].
．． 5 to 1.1 mol is preferred. If the amount of aldehyde is too small, the molecular weight of the resin will be too small, and if it is too large, gelation will occur easily during synthesis.

The amount of the acidic catalyst is preferably 0.005 to 0.3% by weight, particularly preferably 0.01 to 0.2% by weight, based on the total amount of the nine reactants. If the amount of acidic catalyst is too low, the reaction rate will be low; if it is too large, side reactions such as alkylation reactions will occur more easily.
It becomes easier to gel.

The reaction in the present invention is an addition condensation reaction of the cyclopentenyl phenol compound or the compound, the phenol compound, and an aldehyde.

Preferably, the temperature is 50 to 130°C. If the reaction temperature is too low, the addition condensation reaction will be slow, and if the reaction temperature is too low, an alkylation reaction will occur between the double bond of the cyclopentenyl group and the phenol nucleus of the oil molecule, and in some cases gelation may occur. A suitable reaction time is 1 to 4 hours.

Preferably, the reaction is carried out in an organic solvent. Examples of solvents that can be used include aromatic solvents such as toluene, benzene, and xylene, chlorine-containing lubricants such as chloroform, carbon tetrachloride, and chlorobenzene, and ethyl ether.

After the reaction is completed, hydroxide) IJium, potassium hydroxide,
After neutralizing the acidic catalyst with a basic compound such as sodium carbonate, removing intermediate salts by filtration, etc., the phenolic resin of the present invention can be isolated by distilling off the solvent and unreacted monomers.

The unsaturated bond-containing phenolic resin obtained by the present invention is a novolac type resin, which is the above-mentioned cyclopentenyl phenol compound or an addition condensation product of the above-mentioned cyclopentenyl phenol compound, the above-mentioned phenol compound, and an aldehyde. The fact that the phenol resin has a cyclopentenyl group is confirmed by the observation of absorption based on hydrogen bonded to carbon constituting the double bond in the cyclopentenyl group at δll1fL 5.8 ppm in a nuclear magnetic resonance spectrum. You can also.

The cyclopentenyl group can be quantified by comparing the area intensity of this absorption with the area intensity of absorption based on hydrogen of the methylene group.

The phenolic resins obtained by the present invention are natural rubber, polyisoprene rubber, and polybutadiene rubber.

It is useful as a reinforcing agent for solid rubber such as styrene-butadiene copolymer rubber, and as a river sand binder resin for castings.

(Example) Next, an example of the present invention will be shown.

Example 11 Installing a fractionating head with stirrer, Y altimeter and cooling tube
j fc 2,000 ml 200 g (1,
25mo/.

〇Unit/p unit ratio = 1/6.8), carbolic acid 232.59
(2,5 moj!') and paraformaldehyde 14
．． 0.8g (formaldehyde equivalent: 3.75 mo/)
Add.

Further, 217.8 g of toluene as a solvent, 1.189 g of oxalic acid and 0.089 g of hydrochloric acid as catalysts were added and heated.
Start stirring and keep at 55-65°C for 1 hour.

The reaction was continued at 75-85°C for 1.5 hours and then at 95-103°C under reflux for 1.5 hours. After the reaction, the reaction solution was returned to room temperature and 200 g of acetone was added.

Neutralized with 30% NaOH aqueous solution. After removing the neutralized salt by filtration, it is desoluted with an evaporator and the degree of vacuum is 0.
．． Unreacted monomers were removed by vacuum distillation in a trench of 6 mm Hg + oil bath temperature of 200°C to obtain a brown novolac type phenolic resin (A) with a softening point of 91°C.

Weight average molecular weight of this substance (gel permeability chromatography, standard polystyrene equivalent).

(same below) was 1,803. Next, the results of nuclear magnetic resonance analysis of the phenol resin [A].

A peak derived from the five-membered ring double bond proton of the cyclopentenyl group was observed at δf[5.8 ppm, indicating that double bonds remained at a rate of 95% based on the charged cyclopentenyl phenol.

The cocondensation ratio of cyclobentenylphenoltocarboxylic acid in the t[,m fat was 43157 (molar ratio).

Example 2 5 fitted with a fractionating head with stirrer, thermometer and condenser
Cyclopentenylphenol 120.29 (0.75 mol, , t
root form/para form ratio -1/6.5 [molar ratio]).

Add 70.6 g (0.75 mol) of carbolic acid, 56.39 (1.5 mol) of haloformaldehyde, and further add 95.49 g of toluene as a solvent, 0.4739 g of oxalic acid as a catalyst, and 0.039 g of hydrochloric acid, and heat. ,
Stirring was started, and the reaction was carried out in the same manner as in Example 1. After that, the reaction solution was returned to room temperature, acetone 1509 was added, and the solution was neutralized with a 30% NaOH aqueous solution. After removing neutralized salts by filtration, it is desoluted in an evaporator, and vacuum distillation is performed at a vacuum degree of 1 mmHg and an oil bath temperature of 150°C to remove unreacted monomers, producing a brown novolac type phenol with a softening point of 75°C. Resin CB) was obtained. The weight average molecular weight of this product was 2.055.

Next, as a result of nuclear magnetic resonance analysis of the phenol resin [B], a peak derived from the five-membered ring double bond of the cyclopentenyl group was observed at 5.8 pI)m.

It was found that double bonds remained at a ratio of 90% to the charged cyclopentenylphenol. Further, the co-condensation ratio of cyclopentenylphenol and carbolic acid in the resin was 50150 (m) ratio).

Example 3 A 3 000 mf four-cell distillation vessel fitted with a fractionating head with stirrer, thermometer and condenser. Cyclopentenylphenol 721.29 (4,5mat) in a rubble flask
, ortho form/para form ratio -1/6.5 [molar ratio]).

423.69 g of carbolic acid (4.5 mof) and 337.8 g of Nonorah formaldehyde (9 mol),
Toluene 5729. Oxalic acid as catalyst 2,849. Add hydrochloric acid 0209, start heating and stirring, and heat at 50-60°C for 1 hour and at 78-84°C for 1 hour.
．． The reaction was continued for 5 hours and then for 1.5 hours under reflux at 95-104°C. After the reaction, the reaction solution 9 was returned to room temperature, acetone 5009 was added, and neutralized with a 30% Na011 aqueous solution. After removing the neutralized salt by filtration, it was desoluted in an evaporator, and the oil bath temperature was 18°C at a reduced pressure of 0.5 mm Hg.
Perform vacuum distillation at 0°C to remove unreacted monomers,
Brown novolac type phenolic resin with a softening point of 91°C [C
] was obtained. The weight average molecular weight of this product was 1,765. Next, as a result of nuclear magnetic resonance analysis of the phenolic resin [C], a peak derived from a five-membered ring double bond proton was observed at a δ value of 5.8pr)m, and a peak of 90% relative to the charged cyclopentenyl phenol was observed. It was found that a certain percentage of double bonds remained. The co-condensation ratio of cyclopentenylphenol and carbolic acid in the shredded resin was 50,150 (molar ratio).

Example 4 The reaction operation was exactly the same as in Example 3, and the neutralized salt was removed from the resulting neutralized reaction solution by filtration.

After desoluting, the degree of vacuum is 0.75 Hg, and the oil bath temperature is 215.
Perform vacuum distillation to ℃ to remove unreacted monomers,
Brown novolank type phenolic resin with a softening point of 105℃ [
D) was obtained. The weight average molecular weight of this product was 3,214.

Next, as a result of nuclear magnetic resonance analysis of the phenolic resin [D], a peak derived from the five-membered ring double bond of the cyclopentenyl group was observed at δflj = 5.8 ppm,
87% m based on the charged cyclopentenylphenol
It was found that a double bond remained at 111 bonds. Also,
The co-condensation ratio of cyclopentenylphenol and carbolic acid in the resin was 50,150 (molar ratio).

Example 5 Installing a fractionating head with stirrer, thermometer and cooling tube fc
, in 4 separate 500 ml flasks.

Sikuo-Nia 7 = Lua Enru 240.3 g (1
,5mo/.

56.3 g (1.5 mol) of ``ortho/hala ratio -1/6.5'' and ``paraformal technic'' were added, and 120.29 g (1.5 mol) of toluene and 0.47 oxalic acid were added as a solvent.
Add 0.032114 of 39° hydrochloric acid and start heating and stirring.

1 hour at 50-60°C, 1.5 hours at 78-84°C.

The reaction was further allowed to proceed for 1.5 hours under reflux at 95-104°C. After the reaction 9, the reaction bath was returned to room temperature, 150 g of acetone was added, and the mixture was neutralized with a 30% NaOH aqueous solution. After removing neutralized salts by filtration, it is desoluted in an evaporator, and vacuum distillation is performed at a vacuum degree of 1 mmHg to an oil bath of 150°C to remove unreacted monomers, resulting in a brown novolac type phenolic resin [E'' with a softening point of 60°C. The weight average molecular weight of this product was 1,023.

Next, as a result of nuclear magnetic resonance analysis of the phenol resin [E], a peak derived from the five-membered ring double bond of the cyclopentenyl group was observed at δ (i = 5.8 ppm).

Example 6 In exactly the same reaction vessel as in Example 3, Ncrobenjyl 7
c/-Lua 21.29 (4.5 mol, ol)/
para ratio = 1/6.5), cresol 486.69 = 18
- (4,5 mo/l', meta/para=3/2) and 337-8 g (9 mol) of paraform were added, and 572 g of solvent toluene and 2.849° of oxalic acid and 2 og of hydrochloric acid were added as catalysts, Start heating and stirring.

1 hour at 50-60°C, 1.5 hours at 78-84°C.

The reaction was further allowed to proceed for 1.5 hours under reflux at 95-104°C. After the reaction, one reaction solution was returned to room temperature, acetone 5009 was added, and neutralized with a 30 q6 NaOH aqueous solution. After removing the neutralized salt by filtration, it is desoluted with an evaporator,
Oil bath temperature up to 180℃ with reduced pressure of 0.5mmHg,
Perform vacuum distillation to remove unreacted monomers and reduce the softening point to 9.
A brown novolac type phenol resin [F] at 4°C was obtained. The weight average molecular weight of this product was 3.500.

Next, as a result of nuclear magnetic resonance analysis of the phenolic resin CP,1, a peak derived from the five-membered ring double bond of the 7 clobentenyl group was found at δ value = 5.8 pI), and also at δf value = 5.8 pI).
The proto (molar ratio) of the methyl group of cresol was 2.2 ppm.

[Application Examples 1 to 6] Using the novolac type phenolic resins obtained in Examples 1 to 6, each component was mixed in the formulation shown in Table 2. This mixture was carried out using a B-type Banbury mixer (capacity 250c).
Kneading was carried out in the usual manner in step c), and sulfur, a vulcanization accelerator, and hexamethylenetetramine were kneaded into the obtained kneaded product at 30 to 40°C using two rolls.

The obtained rubber composition was heated at 150°C and 14kgf/cm2.
Press vulcanization was carried out for 20 minutes to obtain a 2 mm thick vulcanized rubber sheet.

Table 2 Formulation [Comparative Application Example 1] A fractionating head equipped with a stirrer, a thermometer and a cooling tube was installed. 500mJ 4 Rose Paraple Flask VC Carbolic Acid 9
49 (1,□mol), 37.5% formaldehyde aqueous solution 52.79 (0.65mol) and 50% para-toluenesulfonic acid aqueous solution 0.456 as catalyst
Add 9 and start heating and stirring.

0.5-1.0 hours at 50-60℃, 1 at 78-82℃
．． 0 to 2.0 hours, and then 1 to 2.0 hours under reflux at 98 to 100°C.
The reaction proceeded for 2 hours. After the reaction, the reaction solution was returned to room temperature, 200 g of acetone was added, and neutralized with a 30 $ NaOH aqueous solution. After removing the neutralized salt by filtration, it is desoluted in an evaporator, and further vacuum distillation is performed at a vacuum degree of 1100 mm 1- (to an oil bath temperature of 160 °C) to remove unreacted monomers and produce a pale yellow novolak with a softening point of 95 °C. A phenol resin was obtained.Furthermore, the procedure was exactly the same as in Application Examples 1 to 6, except that the phenol resin obtained here was used in place of the novolak type thermosetting resin obtained in Examples 1 to 6. A vulcanized rubber sheet with a thickness of 2TIITII was obtained.

[Comparative Application Example 2] A fractionating head equipped with a stirrer, a thermometer, and a cooling tube was installed. soomI! Cresol (ortho form/para form = 3/2, molar ratio) 1089 in a paraplegic flask
(1 mol), halaformaldehyde 37.5g (1”
Add 709 toluene as solvent and 0.159 50% para-toluenesulfonic acid as catalyst.
．． Add 1.50% of oxalic acid and start heating and stirring at 70-80°C for 1 hour.

The reaction was allowed to proceed under reflux at 90-95°C for 1-3 hours.

In addition, each item was boiled at 25°C to raise the temperature in about 3 hours.

A reflux dehydration operation was performed. After the reaction, one reaction solution was returned to room temperature, acetone 2009 was added, and neutralized with a 30% NaOH aqueous solution. After removing the neutralized salt by filtration, it was desoluted using an evaporator, and further vacuum distillation was performed at a vacuum degree of 100 mmHg and an oil bath temperature of 170°C to remove unreacted monomers, resulting in a pale orange product with a softening point of 100°C. Obtained Novolank type phenolic resin.

Furthermore, a 2 mm thick trickle rubber was prepared in exactly the same manner as in Application Examples 1 to 6, except that the novolac type phenol resin obtained here was used in place of the novolac type phenol resin obtained in Examples 1 to 6. Got a sheet.

Using the Tacom sheets obtained in Application Examples 1 to 6 and Application Comparative Examples 1 to 2, the hardness was measured using a JIS A type spring type hardness tester at room temperature.

The 100%, 300 thymodulus, tensile strength and elongation were measured by punching out vulcanized rubber sheets into JI No. 83 dumbbells and using a Johnpa set tensile strength tester at room temperature.

The results are shown in Table 3.

1゛, 1.1゛Self (Effects of the Invention) According to the present invention, a new novolac type thermosetting resin can be produced, and the resin can be used as a rubber modifier (especially as an elongation modifier). It is useful and also useful as a resin binder for castings.

Claims (1)

[Claims] 1. General formula [I] ▲ Numerical formula, chemical formula, table, etc.▼ [I] (However, in the formula, R_1 and R_2 represent hydrogen, an alkyl group, a halogen, or a cyclopentenyl group, These may be the same or different, and in the above formula, hydrogen is bonded to at least two of the p-position and o-position with respect to the OH group) or a general cyclopentenylphenol compound represented by Cyclopentenylphenol compound represented by formula [I] and general formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[II] (However, in the formula, R_3, R_4 and R_5 are hydrogen, hydroxyl group, carboxyl group, Halogen, an alkyl group or alkenyl group having 1 to 15 carbon atoms, an aliphatic hydrocarbon group having two carbon-carbon unsaturated double bonds, or a substituted group thereof, an aromatic hydrocarbon group, or a substituted aromatic hydrocarbon group A phenolic compound represented by the above formula, which may be the same or different, and in which hydrogen is bonded to at least two of the p-position and o-position relative to the OH group. A method for producing an unsaturated bond-containing phenolic resin, which comprises reacting with an aldehyde in the presence of an acidic catalyst. 2. A patent claim in which a cyclopentenylphenol compound represented by the general formula [I] and a phenol compound represented by the general formula [II] are blended such that the former/latter molar ratio is 1/9 to 10/0. A method for producing an unsaturated bond-containing phenolic resin according to item 1.