JPH0426657A - Triple bond-containing polycyclic carbonate compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (A is condensed polycyclic aromatic hydrocarbon ring in which biphenyl ring or benzene ring is arranged in series, halogen up to three, 1-12C alkyl or substituent body thereof replaced by alkoxy or cyano; R<1> and R<2> are H or 1-12C alkyl; n is 1-3). EXAMPLE:4, 4'-Bis-propargyloxycarbonyloxybiphenyl. USE:A raw material of resin having heat resistance and having molecular orientation, liquid crystal property and optical anisotropy by a polycyclic aromatic hydrocarbon ring arranged in series. The compound is polymerized and cured by various metal catalysts, initiator or light, gamma ray and electron beam irradiation, etc., and useful as resin raw material for coating, etc., in which nonvolatile curing and endurance and heat resistance are required. PREPARATION:For example, a polycyclic phenol compound expressed by formula II is reacted with a chloroformate expressed by formula III in a solvent in the presence of an acid binding agent to provide the compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a non-volatile, self-curing polycyclic propargyl carbonate compound and a method for producing the compound.

It is known that compounds with triple bonds, such as Qingjingshujie ethynyl group and propargyl group, can be polymerized into polymers with conjugated systems by cleavage of the triple bond. Such compounds have recently attracted attention in the fields of paints, electrical and electronic equipment, etc. because of their polymerization mechanism and the unique physical and electrical properties of the resulting polymers. For example, JP-A-1-10821
No. 3 discloses a propargyl ether compound of a cresol novolak resin as a self-curing resin having a triple bond.

The present invention provides a carbonate compound that is a raw material for a resin that has excellent heat resistance by introducing a carbonate group, and has molecular orientation, liquid crystallinity, and optical anisotropy due to polycyclic aromatic hydrocarbon rings arranged in series. provide.

The present invention provides a polycyclic carbonate compound represented by -format (1) R1. In the formula, A is a biphenyl ring, a fused polycyclic aromatic hydrocarbon ring in which Hensen rings such as a naphthalene ring, anthracene ring, or naphthacene ring are arranged in series, or up to 3 halogens, C3-CI2 alkyl, C1 "C+z alkoxy, or a nuclear substitute thereof substituted with cyano, and R
1 and R2 independently mean hydrogen or C, -C, □alkyl, and n means I, 2 or 3.

The polycyclic carbonate compound of the formula (r) is prepared by converting a polycyclic phenol compound having the formula (II) CHEC-C-OC(1)-form A-←0H)7 in the presence of an acid binder or (2)-Form A-
←occp), can be prepared by reacting the chloroformate of a polycyclic phenol with an alcohol of I CH3C-C-OH.

■Aim: Polycyclic aromatic hydrocarbon groups that provide molecular orientation, liquid crystallinity, and optical anisotropy are known. These are biphenyl rings and fused rings in which two or more Hensen rings are arranged in series.
For example, naphthalene, anthracene, naphthacene, etc. The polycyclic phenol compound used in the present invention is
have up to 3 hydroxyl groups on these rings, and optionally 3
up to halogen, CI~C1□alkyl, 01~C1
゜It is a compound having an alkoxy or cyano group.

Specific examples of such compounds are shown below.

0-Phenylphenol m-Phenylphenol P-Phenylphenol 4.4''-Hydroxybiphenyl 2.2'-Hydroxybiphenyl 3-chloro-4,4'-dihydroxybiphenylate α-naphthol β-naphthol 2.6 -Cyhydroxynaphthalene 2.7-Cyhydroxynaphthalene Naphresorcin 2-Hydroxyanthracene 9-Hydroxyanthracene ■, 2-Dihydroxyanthracene 1.4-Dihydroxyanthracene ■, 5-dihydroxyanthracene 18-Dihydroxyanthracene 2.3-Dihydroxyanthracene 26 -dihydroxyanthracene 2.7-dihydroxyanthracene 1.9-dihydroxyanthracene 9.10-dihydroxyanthracene These are typical examples of polycyclic phenol compounds that can be used in the present invention, and the present invention is not limited thereto.

The carbonate compound of the general formula (1) of the present invention is prepared by adding at least 1 mole of chloroform-1 of the formula (II) to 1 mole of the hydroxyl group of the polycyclic phenol in an appropriate solvent in the presence of an acid binder. It can be produced by reaction.

? As the medium, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, methylene chloride, dichloroethane, etc. can be used. When the viscosity of the reaction system is low, it is also possible to carry out the reaction without a solvent.

Examples of acid binders include tertiary amines such as trimethylamine, triethylamine, and pyridine, hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide, sodium silicate, sodium aluminate, sodium carbonate, other inorganic bases such as potassium carbonate,
Additionally, alkali metal alcolades can be used. Preference is given to using tertiary amines.

It is preferable to carry out the reaction in an atmosphere of an inert gas such as nitrogen because the desired product with less coloring can be obtained.

The temperature may be from room temperature to the boiling point of the solvent.

Alternatively, the chloroformate compound obtained by reacting the polycyclic phenol with phosgene can be reacted with at least an equivalent amount of the alcohol of formula (nl) in the presence of an acid binder.

The solvent, the type of acid binder, and the reaction conditions that can be used may be the same as those for reacting the polycyclic phenol with the chloroformate of formula (II[).

The polycyclic carbonate compound of the present invention is polymerized and cured by various metal catalysts, initiators, or irradiation with light, gamma rays, electron beams, and the like. Therefore, it is useful as a resin raw material for paints, electrical and electronic materials, structural materials, nonlinear optical materials, etc. that require non-volatile curing, durability, and heat resistance.

Some examples of the present invention are shown below.

Example 1 4,4'-dihydroxybiphenyl 1 was placed in a flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a reflux condenser.
8.6 g and 50.6 g of methylene chloride. Og and 23°Og of triethylamine were added and dissolved.

To this, 26.0 g of propargylforme-1 was added dropwise over 1 hour, and the mixture was reacted at 30°C for 6 hours. After the reaction was completed, the contents were treated with a methylene chloride/deionized water mixture, the organic phase was separated, magnesium sulfate was added, and the mixture was allowed to stand overnight for dehydration. The magnesium sulfate was removed daily, methylene chloride was distilled off from the mouth liquid using a rotary evaporator, and the resulting crystals were recrystallized to obtain 4゜4゛-bis-propargyloxycarbonyloxybiphenyl. Yield: 93.6% Structure confirmation was performed by IR and 'H-NMR.

IR (cm-') 3330, 2110, 1750°'H
-NMR (δ, p p m) 2.55 (co=
c-).

4.86 (3C-CH2-), 7.30. 7.90
(P h) Example 2 In the same manner as in Example 1, 2,7-hydroxynaphthalene and propargyl chloroformate were reacted.
7-bis-(propargyloxycarbonyloxy)naphthazine was synthesized. Yield 83.6%, m, p, 94-
96°C IR (c++r') 3330, 2100.1755 heavy H
-NMR (δ, p p m) 2. 4
2 (CH=CJ.

4.86 (-'C-CH2-), 7.20.8.10
(P h) The following compound was synthesized in the same manner as in Example 1.

Example 3 1,8-bis(propargyloxycarbonyloxy)
Anthracene, yield 88.3% NMR (cm”) 330
0,2100.1760'H-NMR (δ, p p
m) 2.42 (co=c-)4.89 (:C
-CH2-), 7.10.8.20 (Ph) Example 4 3-chloro-44''-bis(propargyloxycarbonyloxy)biphenyl, yield 85.2% IR (cm-
')3300,2100.1760'H-NMR(δ,
p p m) 2.40 (CH=C-)4.87
(3C-CH2-), 7.10. 7.95 (P
h) Example 5 4-propargyloxycarbonyloxybiphenyl,
Yield 90.2% IR (cm-') 3300, 2100, 1760°16
10.1510'H-NMR (δ, p p m) 2.40 (C
H=C-)4.87 (=C-(:H2-)+7-10
．． 7.95 (P h) Example 6 Nipropargyloxycarbonyloxynaphthalene,
Yield 83.2% IR (cm-I) 3300, 2100, 1760°16
10.1510 H-NMR (δ, p p m) 2.42 (CI
=C-).

4.88 (=C-C)1. -), 7.10. 7.
95 (P h) Example 7 33''-dimethyl-4-4''-bis(propargyloxycarbonyloxy)biphenyl, yield 93.6% Example 8 4.4''-bis(1,■-dimethyl-3- Propynyloxycarbonyloxy)biphenyl, yield 83.6% IR (cm-') 3300, 2110, 1750°16
00.1500 H-NMR (δ, p p m) 2.55 (cH
=c-)4.86 (:C-CI(2-), 7.30.
7.90 (Ph) Example 9 1 mol of biphenyl-44''-bischloroformate and 2 mol of propargyl alcohol were reacted in the same manner as in Example 1 to produce 4,4''-bis(propargyloxycarbonyloxy). Biphenyl was synthesized. Yield: 63.6%. Structural confirmation by IR and 'H-NMR completely matched the product of Example 1.

Claims (1)

[Claims] General formula▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, A is a piphenyl ring, a fused polycyclic aromatic hydrocarbon ring in which benzene rings are arranged in series, or up to 3 halogen, C_1-C_1_2 alkyl, C_1-C_
1_2 alkoxy, or a nuclear substituent thereof substituted with cyano, R^1 and R^2 independently mean hydrogen or C_1-C_1_2 alkyl, n is 1, 2
Or 3. ) A polycyclic carbonate compound represented by