JPH04359007A - Modified phenolic resin composition and its production - Google Patents

Abstract

PURPOSE:To obtain the subject composition having remarkably high flexibility and toughness and useful for laminated board, varnish, etc., by reacting formaldehyde to a reaction product of a phenolic compound and a specific long-chain dialdehyde. CONSTITUTION:The objective composition is produced by reacting (A) a phenolic compound with (B) a long-chain dialdehyde of formula (n is 5-18) having aldehyde groups on both terminals in the presence of an acidic catalyst (e.g. methanesulfonic acid) at a ratio of 0.1-0.3mol of the component B based on 1mol of the hydroxyl group of the component A, removing unreacted component A from the reaction mixture and reacting the reaction product of the component A and the component B with (C) formaldehyde in the presence of a basic catalyst (e.g. triethylamine). The reaction of the component A with the component B is preferably carried out at 80-160 deg.C and the reaction of the component C with the reaction product of the component A and the component B is carried out preferably in a solvent such as toluene at 80-100 deg.C.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a resol-type modified phenol resin composition obtained by reacting formaldehyde with a reaction product of a long-chain dialdehyde having aldehyde groups at both molecular ends and phenol, and a method for producing the same. The present invention also relates to a modified phenolic resin composition having excellent flexibility and toughness that can be used as a laminate, a molding material, a composite material, or a varnish, and a method for producing the same.

0002

[Prior art] Phenolic resin has heat resistance, electrical properties,
It has excellent mechanical properties and is used in various applications such as molding materials, laminates, composite materials, and varnishes. However, since phenolic resins generally have the disadvantage of being hard and brittle, their applications may be limited. As a method for improving this drawback, a method is known in which the resin is modified with vegetable oils such as tung oil, dehydrated castor oil, cashew nut kernel oil, urushiols, or alkylphenols to impart flexibility to the resin. However, although these conventional methods can impart flexibility, they still have the disadvantage of insufficient toughness.

0003

[Problems to be Solved by the Invention] As a result of research aimed at obtaining a phenolic resin that has flexibility and toughness that cannot be obtained by conventional methods, the present invention has developed a long-chain dialdehyde resin having aldehyde groups at both molecular ends. We obtained the knowledge that a resol-type modified phenol resin obtained by reacting formaldehyde with a reaction product of This is what we have come to complete.

[0004] The purpose is to provide a modified phenolic resin composition which has excellent flexibility and excellent toughness and is suitable for use in applications such as laminates, molding materials, composite materials, foams, and varnishes. There is something to do. Another object of the present invention is to provide a modified phenolic resin composition for producing extremely strong laminates with excellent punching workability, water resistance, and electrical properties.

[0005]

[Means for Solving the Problems] The present invention provides a method for combining a phenol with a long-chain dialdehyde represented by the general formula (1) having an aldehyde group at both molecular ends.
The present invention relates to a resol-type modified phenol resin composition in which a reactant in a proportion of 0.1 to 0.3 moles of long-chain dialdehyde per mole is reacted with formaldehyde.

[0006] The present invention also provides phenols and general formula (1)
After reacting with a long-chain dialdehyde having aldehyde groups at both molecular ends represented by the formula at a ratio of 0.05 to 0.1 mole of long-chain dialdehyde per mole of hydroxyl group of the phenol under an acidic catalyst, the unreacted The present invention relates to a method for producing a resol-type modified phenol resin composition, which is characterized by removing a part or most of the phenol and then reacting it with formaldehyde under a basic catalyst.

Examples of the long-chain dialdehyde having aldehyde groups at both molecular ends represented by the general formula (1) used in the present invention include 1,8-octanedial, 1,12-dodecanedial, 1 , 16-hexadecanedial, etc.

The phenols used in the present invention include phenol, cresol, xylenol, pt-butylphenol, bisphenol A, and resorcinol.
1 of valent and divalent phenols and their substituted products
Phenols containing 50 mol% or more of at least trifunctional or higher functional phenols are used. Preferred phenols are phenol and cresol.

[0009] The formaldehydes used in the present invention include formalin and paraformaldehyde.

An example of the chemical structure of the resol type modified phenol resin composition of the present invention is shown by general formula (2).

[0011]

[Chemical formula 1]

In general formula (2), four phenols are linked by a long chain dialdehyde having aldehyde groups at both molecular ends, a part of the phenol nucleus is methylolated with formaldehyde, and other phenol nuclei are connected by methylene bonds. It represents something that is connected to. That is,
Two phenol nuclei per aldehyde group are bonded to the aldehyde group of a long-chain dialdehyde that has aldehyde groups at both molecular ends at the ortho and para reactive positions on the phenol nucleus, and formaldehyde It reacts with the ortho and para reactive positions on the nucleus to form methylol groups and methylene bonds. Curing of the resin proceeds by the formation of methylene bonds through a condensation reaction between methylol groups and reactive sites on the phenol nucleus.

As can be seen from the structural example of general formula (2),
A long-chain hydrocarbon group that plays a role in imparting flexibility is present in the main chain of the phenolic resin. This structure is considered to be the reason for imparting flexibility and toughness to the modified resin composition of the present invention. For this reason, it is an essential condition in the present invention that the reaction between a phenol and a long-chain dialdehyde having aldehyde groups at both molecular ends is sufficiently completed. This is because if the reaction is insufficient, there will be many pendant compounds in which only one side of the long-chain dialdehyde is bonded to the phenol nucleus, resulting in a brittle resin.

In the present invention, the reaction product of a phenol and a long-chain dialdehyde having aldehyde groups at both molecular ends contains 0 long-chain dialdehyde per mole of hydroxyl group of phenol.
．． The proportion is 1 to 0.3 mole. Since long-chain dialdehyde is tetrafunctional, for example, when reacting trifunctional phenol with long-chain dialdehyde, if 0.125 mol or more of long-chain dialdehyde is reacted per 1 mol of phenol, the reaction will be completed before the reaction is completed. It turns into a polymer and becomes a gel. Therefore, by reacting 0.1 mole or less of long-chain dialdehyde per mole of hydroxyl group of phenol with phenol and removing unreacted phenol after the reaction is completed, long-chain dialdehyde per mole of hydroxyl group of phenol can be reacted with phenol. 0.1~
A resin with a preferred modification rate of 0.3 mol can be obtained. The reaction between phenols and long-chain dialdehydes produces 0.0.0.0 of long-chain dialdehyde per mole of hydroxyl group of the phenol.
It is preferable to carry out the reaction at a ratio of 0.05 to 0.1 mole, and to remove a part or most of the unreacted phenols after the reaction is completed.

Catalysts used in the reaction of phenols and long-chain dialdehydes in the present invention include para-toluenesulfonic acid, methanesulfonic acid, boron trifluoride, tin chloride, ferric chloride, and the like. Examples include acidic catalysts such as Friedel-Crafts type catalysts. The amount of the catalyst used is not particularly limited, but is preferably 0.01 to 2% by weight based on the total amount of phenols and linear compounds. Further, the reaction is preferably carried out at a temperature of 80 to 160°C. If necessary, the reaction may be carried out in a solvent such as toluene.

The proportion of formaldehyde to be reacted with the reaction product of phenol and long-chain dialdehyde is 0.5 to 2.
It is in the range of 0 mol. Catalysts used in this reaction include ammonia, triethylamine, ethylenediamine, hexamethylenetetramine, triethanolamine,
Basic catalysts such as barium hydroxide can be mentioned. The reaction is carried out in a solvent such as toluene at a temperature of 80 to 100
Preferably it is carried out at a temperature of .degree.

[0017]

EXAMPLES The present invention will be illustrated by the following examples.

(Example 1) A 5 liter flask equipped with a stirrer was charged with 940 g of phenol, 198 g of 1,12-dodecane dial and 15 g of p-toluenesulfonic acid, and reacted at 120° C. for 6 hours. The unreacted phenol content of this intermediate product was 50.2% by weight. No residual aldehyde groups were observed in the infrared absorption spectrum and nuclear magnetic resonance spectrum, indicating that the reaction was complete. Next, unreacted phenol was removed while heating under reduced pressure until the residual phenol content became 5%.

After diluting and neutralizing this by adding 600 g of toluene and 15 g of triethanolamine, 350 g of paraformaldehyde and 15 g of 25% aqueous ammonia solution were added.
was added, reacted at 90 to 100°C for 4 hours, then dehydrated and toluene-removed under reduced pressure, diluted by adding a 1/1 mixed solvent of toluene and methanol, and diluted with 1, A solution of a 12-dodecane dial modified resol type phenolic resin composition was obtained.

(Example 2) In a 5-liter flask equipped with a stirrer, 1080 g of cresol (a mixture of 60% m-cresol and 40% p-cresol), 250 g of 1,16-hexadecadial, and 17 g of para-toluenesulfonic acid were added.
g was charged and reacted at 120°C for 6 hours. The unreacted phenol content of this intermediate product was 49.7% by weight. No residual aldehyde group in 1,16-hexadecadial was observed in the infrared absorption spectrum and nuclear magnetic resonance spectrum, indicating that the reaction was complete.

[0021] Next, unreacted phenol was removed while heating under reduced pressure until the residual phenol content became 8%. To this, add 600g of toluene and 15g of triethanolamine.
After diluting and neutralizing by adding g, paraformaldehyde 3
50g, add 15g of 25% ammonia aqueous solution,
The reaction was carried out at ~100°C for 4 hours, then dehydrated and toluene removed under reduced pressure, diluted by adding a 1/1 mixed solvent of toluene and methanol, and the resin content was 1,16% by weight.
- A solution of a hexadecadial-modified resol type phenolic resin composition was obtained.

(Comparative Example 1) A 5 liter flask equipped with a stirrer was charged with 1200 g of phenol, 800 g of tung oil, and 5 g of paraenesulfonic acid, and reacted at 80° C. for 3 hours. Next, 800 g of toluene and 20 g of triethanolamine were added to dilute and neutralize, and then 500 g of paraformaldehyde and 30 g of 25% ammonia aqueous solution were added, and the mixture was reacted at 90 to 100°C for 4 hours, and then under reduced pressure,
Dehydrate and remove toluene, add 1000g of toluene and 1000g of methanol to dilute, and reduce the resin content to 50% by weight.
A solution of a tung oil modified resol type phenolic resin composition was obtained.

(Comparative Example 2) 1200 g of cresol (a mixture of 60% m-cresol and 40% p-cresol) and 50% formalin were placed in a 5 liter flask equipped with a stirrer.
50g, prepare 40g of 25% ammonia, 90~10
The reaction mixture was allowed to react at 0° C. for 3 hours, then dehydrated under reduced pressure, and diluted by adding 600 g of toluene and 600 g of methanol to obtain a solution of resol type phenol resin with a resin content of 51% by weight.

Table 1 shows the characteristics of the resins obtained in Examples 1 and 2 and Comparative Examples 1 and 2. The gelation time in Table 1 is 150℃
It represents the gel time on a hot plate. The cured product torque indicates the torque after 3 hours at 150° C. using a Curelastometer manufactured by Orientech (JSR Curelastometer Model IIIS, SRIS3105 die B type). As the resin hardens, the torque increases and reaches a constant value. The value after 3 hours is this constant value. The smaller the torque, the more flexible the cured product is. To measure toughness, take out the cured resin that has been measured using a curelastometer, cool it to room temperature, and then
It expresses the ease with which it breaks when bent, and items that are brittle and break easily are considered brittle, while items that bend without breaking are considered strong. Solvent resistance was determined by the appearance of the cured product after boiling it in MEK for 1 hour. As can be seen from the comparison of Examples 1 and 2 and Comparative Examples 1 and 2 in Table 1, the modified phenol resin composition of the present invention is extremely excellent in flexibility, toughness, and solvent resistance.

[0025]

[Table 1]

[0026]

Effects of the Invention The modified phenolic resin composition of the present invention has excellent flexibility and toughness, so it can be used in laminates, molding materials, etc.
It can be extremely suitably used in various applications such as composite materials, foams, and varnishes. In particular, when the modified phenolic resin composition of the present invention is used for a laminate, punching workability,
A strong laminate with extremely excellent water resistance and electrical performance can be obtained. The reason why the modified phenolic resin composition of the present invention has excellent flexibility and toughness that cannot be obtained by conventional methods is not fully clear, but the modified phenolic resin composition of the present invention has excellent flexibility and toughness that cannot be obtained by conventional methods. This is thought to be due to the fact that the core is tightly bound by the long chain saturated hydrocarbon main chain of the long straight dialdehyde which has flexibility.

Claims (2)

[Claims] Claim 1: Phenols and a long-chain dialdehyde represented by the general formula (1) having aldehyde groups at both molecular ends OHC-(CH2)n-CHO... (1) (n is 5 to 18) A resol-type modified phenol resin composition obtained by reacting a reactant with formaldehyde in a ratio of 0.1 to 0.3 mole of long-chain dialdehyde per mole of hydroxyl group of phenol. 2. Phenols and a long-chain dialdehyde represented by the general formula (1) having aldehyde groups at both molecular ends are combined in an amount of 0.05 to 0.1 mole of long-chain dialdehyde per mole of hydroxyl group of the phenol. Production of a resol-type modified phenol resin composition, which is characterized by reacting the composition under an acidic catalyst, removing a part or most of the unreacted phenols, and then reacting with formaldehyde under a basic catalyst. Method.