JPS6396180A - Novel glycidyl compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (Ar represents 6-14C aromatic hydrocarbon, 2,2-bisphenylpropane or diphenylmethane; R1 and R2 represent H, halogen atom, 1-5C hydrocarbon or 1-5C alkoxyl; R3 represents 20-500C hydrocarbon; n is 1-4). USE:A raw material for producing a hardened resin, which hardened product has superior mechanical properties, weather resistance, flexibility and toughness. PREPARATION:Polyolefins are added to phenols to afford a product expressed by formula II, which is further added with an epihalohydrin, and subsequently reacted with an aqueous solution of caustic alkali to afford the compound expressed by formula I. In addition of the polyolefins to the phenols, a cationic polymerization initiator selected from a protonic acid, Lewis acid, organometallic halide, halogen molecule and stabilized carbonium ion is preferably used as a catalyst.

Description

Detailed Description of the Invention "Industrial Application Field" The present invention relates to a novel glycidyl compound and a method for producing the same, and more specifically, a novel glycidyl compound and a method for producing the same that provide a cured product having excellent mechanical properties and weather resistance. Regarding.

"Conventional technology and problems" Epoxy resin has poor mechanical properties, heat resistance, electrical properties, etc.
Paints, electricity, adhesives, F
It is used as a matrix material for RP. However, cured resins generally lack flexibility and toughness;
Its range of use is limited due to its lack of weather resistance.

"Means for Solving the Problems" The present inventors have conducted intensive research on glycidyl compounds that provide cured products with excellent flexibility and toughness, and have not only met these requirements but also have excellent weather resistance, especially water resistance. We have discovered an improved glycidyl compound.

That is, the first aspect of the present invention is the following general 2N) (Cllz
CH-CHz O+-T-^r -R3(I)o
R, RZ (wherein Ar is a Ch-C+4 aromatic hydrocarbon i;2.
Represents any hydrocarbon group selected from 2-bisphenylpropane and diphenylmethane, R, and R2 are each a hydrogen atom, a halogen atom, a 01-C3 hydrocarbon group,
fftA group selected from 01 to C2 alkoxy groups, R
3 is C2° to C2°. The second aspect of the present invention for producing a new glycidyl compound represented by a hydrocarbon group of II) (wherein,
Ar represents an aromatic hydrocarbon M of 06 to C14; a hydrocarbon group selected from 2,2-bisphenylpropane and diphenylmethane; R+ and Rz are a hydrogen atom, a halogen atom, and a hydrocarbon of 01 to C2, respectively; Group, C5~
A substituent selected from C3 alkokyne groups, R1 is Cz
6 "= C5o. hydrocarbon group, n is an integer of 1 to 4) is added with epihalohydrin and then reacted with a caustic aqueous solution, the product is produced by the following general formula (I ) (wherein Ar, R1, Rz, R2, and n are each the same as described in claim 1).

In the glycidyl compound represented by the above formula, A may be substituted and bonded to any position of A.

The method for producing the novel glycidyl compound of the present invention can be roughly divided into two steps. First, in the first step, polyolefins are added to phenols using the following general formula ([
) %Formula%(I1) (wherein, Ar is an aromatic hydrocarbon group of 06 to CI; 2.
Represents either a hydrocarbon group selected from 2-bisphenylpropane and diphenylmethane, R+ and Rz are each a substituent selected from a hydrogen atom, a halogen atom, a C1-C5 hydrocarbon group, a C1-C5 alkoxy group, R3
is C2°~C3°. a hydrocarbon group, n is an integer from 1 to 4).

Here, R3 is a residue derived from polyolefin, and is not incorporated into the epoxy curing system, giving the cured resin flexibility, toughness,
Gives resistance to air. By changing the chain length of R1, the cured resin can be freely adjusted from hard to highly flexible.

The phenols used in this process include phenol,
(0-1m-1p-)cresol, (2゜3-12.4
-12.5-12,6-13.4-13.5-)xylenol, (α-1β-)naphthol, (I-,2-,9
-) Monohydric phenols such as anthrole; resorcinol, catechol, hydroquinone; biphenyl-4,4'-
Examples include dihydric phenols such as diols; so-called bisphenols such as 2,2-bis(4'-hydroxyphenyl)propane and bis(4-hydroxyphenyl)methane; and phenol-formalin condensates. Among these, monohydric phenols, dihydric phenols, and bisphenols are preferred because they are industrially available.

Examples of polyolefins include polymers or oligomers obtained by polymerizing cationic polymerizable monomers such as isobutyne, indene, styrene, and α-methylstyrene using cationic polymerization initiators as described below (e.g., manufactured by Idemitsu Petrochemical Co., Ltd.). (unhydrogenated polybutene, etc.); Cs, C
So-called petroleum resin obtained by cationic polymerization of 9 fractions;
Examples include polymers or oligomers of dienes such as butadiene and isoprene; and copolymers of these components such as isobutyne-isoprene copolymers. Polyolefins are required to have at least one unsaturated bond within the molecule.

For the addition of phenols and polyolefins, protic acids such as sulfuric acid, perchloric acid, and trifluoromethanesulfonic acid;
This is carried out using a cationic polymerization initiator such as a Lewis acid such as boron trifluoride, aluminum chloride, titanium tetrachloride, or tin tetrachloride; an organometallic halide; a halogen molecule; or a stable carbonium ion as a catalyst. Among them, trifluoromethanesulfonic acid is a strong acid and has high catalytic ability, and is therefore preferably used.

The reaction temperature and reaction time are 0 to 120°C for 1 to 24 hours. The catalyst is used in an amount of 1 to 10 parts by weight based on the polyolefin. As a solvent, halogenated hydrocarbons such as chloroform and methylene chloride; hydrocarbons such as henzene, toluene, and hexane; ketones such as methyl ethyl ketone and methyl isobutyl, and the like can be used. However, when the reaction temperature is set high, it is not preferable to use aromatic hydrocarbons.

The thus obtained addition product (n) is washed with water to remove the catalyst, unreacted monomers and solvent are distilled off under reduced pressure, and the product can be used as it is in the next step.

The second step is a step of glycidylating the phenolic hydroxyl group, and it is also possible to react shrimp halohydrin in the presence of caustic alkali as usual, but the present inventors conducted an addition reaction between the addition product (n) and shrimp halohydrin. It has been found that it is particularly suitable to carry out the reaction under an onium salt followed by the dehydrohalogenation reaction in an aqueous caustic solution.

Onium salts are generally well known as phase transfer catalysts, such as quaternary salts such as tetramethylammonium chloride and benzyltriethylammonium chloride.
Quaternary phosphonium salts such as triphenylmethylphosphonium bromide and tetraphenylphosphonium chloride; quaternary arsonium salts, etc. can be used.

Here, the phase transfer catalyst is 0.01 to 100 mol%, preferably 0.0% by mole based on the phenol moiety in the addition product (n).
Any amount within the range of 5 to 10 mol% can be used.

Shrimp halohydrin is used in an amount of equivalent mole or more, preferably 2 equivalents or more relative to the phenolic hydroxyl group.

As the shrimp halohydrin, epichlorohydrin, shrimp bromohydrin, shrimp iodohydrin, etc. can be used. The addition reaction between the addition reaction product (It) and shrimp halohydrin is carried out at 50 to 120°C for 30 minutes to 12 hours, preferably 80 to 120°C.
The reaction is carried out at 110° C. for 1 to 4 hours.

The obtained shrimp halohydrin is reacted with caustic alkali to perform a dehydrohalogenation reaction to obtain the glycidyl compound (I) of the present invention. As the caustic alkali, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, etc. can be used, and it is preferable to use it in the form of an aqueous solution for ease of handling. 1 to 2 parts, preferably 1.1
0 reaction salinity which is ~1.5 equivalents and reaction time is 20-9
10 minutes to 3 hours at 0℃, preferably 30 minutes at 40 to 70℃
It takes from minutes to 2 hours.

Excess epihalohydrin can also be distilled off before the dehydrohalogenation reaction. In this case, M as a diluent
It is preferable to use inert solvents such as ketones such as EK and MIBK; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as chloroform and methylene chloride.

After the reaction is complete, remove the salt produced by filtration or washing with water,
The desired product is obtained by distilling off unreacted epihalohydrin or the inert solvent used as a diluent.

"Action/Effect" Since the polyolefin chains of the novel glycidyl compound (I) of the present invention moderately lower the crosslink density, the obtained cured product is also moderately plasticized, and flexibility is satisfied without adding a plasticizer. Furthermore, since the polyolefin chain is a hydrophobic group, it has improved water absorption compared to normal epibis type epoxy resin. The glycidyl compound of the present invention can be cured alone or in combination with other epoxy compounds using a common epoxy resin curing agent. There are no particular restrictions on the curing agent, and acid anhydrides, aromatic/aliphatic amines,
Organic acids such as heterocyclic amines, polyamides, and polyphenols can be used.

In addition to the curing agent, various additives such as curing accelerators, fillers, reinforcing materials such as fibers, camping agents, pigments, and flame retardants may be added to the glycidyl compound of the present invention. You can also do it.

"Examples" A more specific explanation will be given below with reference to Examples, but the present invention is not limited by the Examples.

Example 1 20 g of Idemitsu Petrochemical Co., Ltd. polybutene (weight average molecular weight 350), 10 g of phenol, and 60 ml of toluene were added to a 100 mj+ Mitsuro flask and dissolved therein.

Trifluoromethanesulfonic acid 0.5 by syringe
ml was added and reacted at room temperature for 24 hours. 100rr
The catalyst was removed by washing twice with 1 liter of water, and the toluene was distilled off to obtain an addition product. This was dissolved in 92.53 g (I mol) of epichlorohydrin, and 2.27 g (I 0 mmol) of benzyltriethylammonium chloride was added thereto, followed by reaction at 100° C. for 1 hour. The temperature of the contents was lowered to 50° C., and 22 m 6 of a 5N aqueous sodium hydroxide solution (10 mmol of I) was added dropwise over 20 minutes. After the dropwise addition was completed, stirring was continued for another hour. Remove the aqueous layer by decantation,
There are 8! The layer was further washed four times with 100 ml of water. Excess epichlorohydrin was distilled off under reduced pressure to obtain the desired glycidyl compound. The epoxy equivalent measured by the hydrochloric acid/pyridine method was 384.

Example 2 A glycidyl compound was obtained in the same manner as in Example 1, except that the polybutene was changed to 20 g of polybutene manufactured by Idemitsu Petrochemical Co., Ltd. (weight average molecular weight 750). The epoxy equivalent weight was 874.

Example 3 Idemitsu Petrochemical Co., Ltd. 1 in a 100ml Mitsuro flask
, 10 g of 2-polybutadiene (with a weight average molecular weight of 1000), 10 g of O-cresol, and 30 ml of methyl isobutyl ketone were added and dissolved. 0.2 ml of trifluoromethanesulfonic acid was added, and the mixture was reacted at 100°C for 3 hours. The catalyst was removed by washing with water, and the solvent was distilled off to obtain 12.4 g of an addition product. 46.3g (0.5 mol) of this
was dissolved in epichlorohydrin, 0.455 g (2 mmol) of benzyltriethylammonium chloride was added, and the mixture was reacted at 100° C. for 1 hour. After cooling down to 50℃ 5
5.3 ml (26.7 mmol) of normal sodium hydroxide was added dropwise over 20 minutes, and the reaction was continued for an additional hour. By washing with water and distilling off epichlorohydrin, 13.4 g of the target glycidyl compound was obtained. The epoxy equivalent measured by the hydrochloric acid/pyridine method was 857.

Example 4 194 g of a glycidyl compound was prepared in the same manner as in Example 3, except that 100 g of 2,6-xylenol was used instead of 10 g of 0-cresol, and all other raw materials were increased by 10 times.
I got it. The epoxy equivalent weight was 435. Note that the glycidyl compound obtained here will be referred to as glycidyl compound 4 hereinafter.

Application Example 1 A cured product was obtained using glycidyl compound 4 obtained in Example 4. Table 1 shows the blending ratio, curing conditions, and physical properties of the obtained cured product. In addition, parts in the table indicate parts by weight.
The physical properties were measured in accordance with JIS K6911.

Application Example 2 The casting plate obtained in Application Example 1 with a thickness of 3 mm was cut into test pieces of 201 m in length and 20 m in width using a cutter.

The cutting surface was polished with sandpaper. After accurately reading the weight of each specimen to the nearest 10-'g,
1 in boiling deionized water for 1 hour.

After soaking, the test piece was gently wiped with cotton and its weight was measured.

The results are shown in Table 1.

Comparative Application Example 1 A cured product was obtained using Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd. The same measurements as in Application Example 1 were performed, and the results are shown in Table 1.

Comparative Application Example 2 The casting plate obtained in Comparative Application Example 1 was subjected to the same measurements as in Application Example 2, and the results are shown in Table 1.

Table 1 1) Hitachi Chemical Co., Ltd. Methylnadic anhydride 2) Benzyldimethylamine

Claims (1)

[Claims] 1. The following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, Ar is an aromatic hydrocarbon group of C_6 to C_1_4; 2,2-bisphenyl Represents any hydrocarbon group selected from propane and diphenylmethane, R_1, R_
2 is a hydrogen atom, a halogen atom, C_1 to C_5, respectively
R_3 is a hydrocarbon group of C_2_0 to C_5_0_0, and n is an integer of 1 to 4). 2. The following general formula (II) is a mixture of phenols and polyolefins ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, Ar is an aromatic hydrocarbon group of C_6 to C_1_4; 2, 2- Represents any hydrocarbon group selected from bisphenylpropane and diphenylmethane, R_1, R_
2 is a hydrogen atom, a halogen atom, C_1 to C_5, respectively
after adding epihalohydrin to the product represented by a hydrocarbon group of , a substituent selected from alkoxy groups of C_1 to C_5, R_3 is a hydrocarbon group of C_2_0 to C_5_0_0, and n is an integer of 1 to 4). The following general formula ( I
) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, Ar, R_1, R_2, R_3, and n are each the same as described in claim 1) Method for producing a novel glycidyl compound . 3. In adding polyolefins to phenols, a cationic polymerization initiator selected from protonic acids, Lewis acids, organometallic halides, halogen molecules, and stable carbonium ions is used as a catalyst according to claim 2. Production method. 4. Claims in which an onium salt selected from quaternary ammonium salts, quaternary phosphonium salts, and quaternary arsonium salts is used as a catalyst in adding epihalohydrin to a product obtained by adding polyolefins to phenols. The manufacturing method according to item 2.