JPH0267248A - Novel (meth)acrylic ester - Google Patents

Abstract

NEW MATERIAL:Alicyclic acrylic or methacrylic esters of formula I (n is 0 or 1; R is H or methyl.) EXAMPLE:Tricyclodecanemethyl methacrylate. USE:Useful as the raw monomer of a resin excellent in optical properties, heat resistance and water resistance. Polymers prepared therefrom are useful as an optical material such as a lens or optical disk base, a light transmitting material such as an optical fiber and an optical material for optoelectronics such as a sealing compound for a light emitting diode. PREPARATION:An alcohol of formula II is subjected to dehydration condensation, e.g. with methacrylic acid and/or acrylic acid to obtain a compound of formula I. The compound of formula II is prepared by an oxo reaction of dicyclopentadiene.

Description

DETAILED DESCRIPTION OF THE INVENTION [Background of the Invention] (Industrial Application Field) The present invention provides a resin raw material having a novel tricyclodecane structure or pentacyclopentadecane structure and having excellent heat resistance, water resistance, and optical properties ( Regarding meth)acrylic acid ester. In addition, in the present invention, "(meth)acrylic acid ester"
This means both acrylic esters and methacrylic esters.

(Prior art) Methacrylic resin (PMMA resin), which has methyl methacrylate as a constituent unit, has good optical properties, is lightweight and easy to mold, and is used in many fields, and demand has increased in recent years. It's coming.

However, on the other hand, as the uses expand, the performance required of the raw material resin also increases, and there are fields in which improvements are desired. For example, when used as an optical element, the resin has the disadvantage of higher water absorption than polyolefin resin, polystyrene resin, or polycarbonate resin, and changes in environmental conditions may cause dimensional changes, warping, and refractive index. This causes changes in the optical system, making it unstable as an optical system. However, optical elements using PMMA resin are very good except for dimensional changes due to moisture absorption of the resin, and in recent years, new resins that have optical properties equivalent to PMMA resin but have improved moisture absorption have been developed. It is being considered. For example, JP-A-58-5318, JP-A-58-5354, and JP-A-58-1151.
No. 5 proposes copolymerizing methyl methacrylate with cyclohexyl methacrylate or benzyl methacrylate. However, although these copolymers certainly have improved hygroscopicity, they also have the problem of reduced heat resistance.

Furthermore, in order to improve heat resistance, JP-A-58-113214
Copolymerization with methacrylamide and maleic anhydride has been proposed in Japanese Patent Application Laid-Open No. 58-183714, but it is still not satisfactory.

[Summary of the invention]

(Problems to be Solved by the Invention) The present invention aims to solve the above-mentioned problems and provide a raw material monomer for a resin having excellent optical properties, heat resistance, and water resistance.

(Means for solving the problem) The novel compound of the present invention is represented by the following formula CI).

(Effects of the present invention) By homopolymerizing or copolymerizing a specific (meth)acrylic acid ester represented by formula [I], the optical properties, heat resistance, and water resistance derived from this specific monomer can be improved. It can be added to the produced polymer depending on the polymerization amount or content.

[Detailed description of the invention]

(Meth)acrylic acid ester (meth)acrylic acid ester (meth)acrylic acid ester according to the present invention has the above formula [
I].

R and n are as described above, but those in which R is methyl, particularly those in which n is 1, particularly those in which R is methyl, that is, pentacyclodecanemethyl methacrylate, particularly enjoy the effects of the invention described above.

(Synthesis) The novel monomer of the present invention can be synthesized by various methods,
It can be easily obtained by esterifying the alcohol represented by the following formula (II).

(n is 0 or 1) The alcohol shown in (n) can be easily obtained by subjecting dicyclopentadiene to an oxo reaction. It can also be synthesized by further reduction reaction via an aldehyde using an oxo reaction catalyst.

Although there are various esterification reactions, the compound shown in formula (1) can be easily synthesized by using the method shown below.

The first method is a dehydration condensation reaction between an alcohol of formula (I[] and methacrylic acid and/or acrylic acid. For this reaction, a suitable catalyst such as concentrated sulfuric acid, p-toluenesulfonic acid, phosphoric anhydride, etc. is usually used.

The second method is a transesterification reaction with an unsaturated fatty acid ester shown in the following formula Cm).

(R is CH or H, M is OCH3 or 0CH2CH
3) Also in this reaction, a suitable catalyst such as sodium methylate, t-BuOK, para-toluenesulfonic acid, etc. is used.

Furthermore, a third method is a method using a dehydrohalogenation reaction with an unsaturated fatty acid halide shown in the following formula (mV).

O (R is CH3 or HSX is CI or Br) In this reaction, an amine as a hydrogen halide acceptor must be added in excess of the alcohol, and the amine is preferably triethylamine, pyridine, or the like.

The crude product obtained in the above reaction can be purified by a conventional purification method such as vacuum capping.

Polymerization (Polymerization) These seven polymers have the same polymerizability as ordinary (meth)acrylic acid esters, so they can be made into polymers (often colorless and transparent) by performing radical polymerization, for example. It can be done.

As the radical polymerization initiator, for example, peroxides (including redox systems) such as benzoyl peroxide, lauroyl peroxide, and dicumyl peroxide, azo compounds such as azoisobutyronitrile, and photosensitizers may be used. It can also be polymerized by thermal polymerization, photopolymerization, or radiation polymerization. As the polymerization method, bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, and any other methods applicable to (meth)acrylic esters can be used.

These monomers give thermoplastic polymers by homopolymerization or copolymerization with monoethylenically unsaturated monomers such as methyl methacrylate, hexyl methacrylate, benzyl methacrylate, methacrylamide, styrene, etc., so they may be pelletized if necessary. Can be made into any molded product by injection molding or other molding methods that involve polymer melting,
In addition, di- or triethylenically unsaturated hexamers such as ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, methylenebis(meth)acrylamide, divinylbenzene, etc. It is also possible to produce a crosslinked polymer by copolymerizing with cast polymerization. Tricyclodecane dimethanol di(meth)acrylate is particularly preferred as a crosslinking agent, and its production, including its congeners, is described in JP-A-61-176618, JP-A-61-287913, JP-A No. 62-225508 Each publication is 1 U.S. Patent No. 4
, No. 131,729, etc. can be referred to.

Incidentally, it goes without saying that two or more types of heptamers represented by formula [I] can be polymerized.

(Applications of polymers) These polymers can be used as materials for optical materials such as lenses and optical disk substrates, as well as optical elements for optoelectronics such as optical transmission bodies such as optical fibers and sealants for light-emitting diodes. It is useful for

Experimental Example Reference Example 1 In a stainless steel autoclave with an internal volume of 500 m1,
132 g of dicyclopentadiene, RhH(CO) (
After charging 261.1 mg of 1F rifenylphosphine and 88 g of toluene, the inside of the vessel was purged several times with an equimolar mixed gas of carbon oxide and hydrogen, and the mixed gas was heated to 100 bar at room temperature. It was press-fitted until the end. This reactor was heated to 130°C. Rapid gas absorption occurred during the temperature rise (around 105° C.), and approximately the theoretical amount of gas was absorbed after 50 minutes. After cooling the reaction vessel, unreacted gas was purged, the contents were diluted with toluene, toluene was distilled off, and 127.0 g of tricyclodecanecarbaldehyde, the target product, was collected from the lid under reduced pressure.

Next, in a stainless steel autoclave with an internal volume of 500 m1, 100 g of the aldehyde obtained above and 1 g of ion-exchanged water were placed.
10. After charging 112 g of methanol and 5.02 g of ruthenium-alumina powder and purging the inside of the reactor with hydrogen gas, the same gas was pressurized at room temperature to 50 bar, and the reactor was heated to 130°C. After 5 hours, absorption of almost the theoretical amount of gas was completed. After cooling the reaction vessel, unreacted gas was purged, the contents were diluted and collected with methanol, and the catalyst was separated from the furnace. Methanol was distilled off to obtain 96.2 g of tricyclodecane methanol, the target product. Using cyclopentadiene trimer instead of dicyclopentadiene,
Pentacyclopentadecane methanol was obtained in the same manner as above.

Example 1 Tricyclodecane methanol 30g (0.18 mol)
, 18.9 g (0.22 mol) of methacrylic acid, 30 g of toluene, 1.2 g of para-toluenesulfonic acid, and a small amount of copper powder were placed in a 200 ml four-eye flask, and reacted for 3 hours at a reaction temperature of 90 to 130°C under a nitrogen atmosphere. I let it happen. After the reaction was completed, the organic layer was cooled, the excess acid was neutralized with an aqueous sodium hydroxide solution, and the organic layer was further diluted with an aqueous sodium sulfate solution.
After washing twice and distilling off toluene, tricyclodecane methyl methacrylate 25. 1g (0,107nof
) was obtained. The 'H-NMR spectrum data of the product was as shown below, and the IR spectrum was as shown in FIG.

δ: 6.06.5.48 2HE3-C-) δ: 1.93 3H(CH2-C-) δ: 0.7
~2.6715H (alicyclic proton) Example 2 Tricyclodecane methanol 16.9g (0.10ml
), acrylic acid8. gg (0.12 mol),
) Tricyclodecane methyl acrylate 16
．． 7g (0,076nof) was obtained. 'H of the product
-NMR spectral data are as follows and I
The R spectrum was as shown in FIG.

'H-NMR: δ:6. oo~6.602H (only "t-C-) δ: 5.
59-5.90 1H(CH2-C-)δ: 3.83-
3.96 2H (-C-0-9 condyle-) δ2 0.67-2
．． 8415H (alicyclic proton) Example 3 Pentacyclopentadecane methanol 30g (0,13
01), methacrylic acid 13.5g (0.15mol
) ,)30g of toluene 1.2 paratoluenesulfonic acid
32.0sr (0,107nof) of pentacyclopentadecane methyl methacrylate was obtained in the same manner as in Example 1 using 1g of copper powder and 12.4ff of copper powder. The 'H-NMR spectrum data of the product was as shown below, and the IR spectrum was as shown in FIG.

δ: 6.12~'5.542H (ri110-) only 1 δ: 1.79 3H (CH2-C) δ: 0.
65-2.72 21H (alicyclic proton) Example 4 Pentacyclopentadecane methanol 21.7g (0
,093nof), acrylic acid (0.11 mol
), 16.2 g (0,057 a+ol) of pentacyclopentadecane methyl acrylate was obtained in exactly the same manner as in Example 1, except that 21.7 g of toluene, 8.0 mg of copper powder and 869.1 μg of para-toluenesulfonic acid were used. Ta.

The 'H-NMR spectrum data of the product was as shown below, and the IR spectrum was as shown in FIG.

'H-NMR: δ: 6.02-6.502H(3-C-)6: 5.6
7-5.93 1H(CH2-C-)δ: 3.82-3
．． 93 2H(-C-0-3-)δ: 0.67-2.6
8 21H (alicyclic proton) Reference Example 2 To 36 parts by weight of the monomer obtained in Example 1, 64 TJ parts of tricyclodecane dimetatool dimethacrylate, 1.2 parts by weight of dicumyl peroxide, and "Irgacure 1" were added.
After adding 0.3 parts by weight of 844 (photosensitizer manufactured by Ciba Geigy) and uniformly mixing by heating, the mixture was poured into a spacer made of silicone rubber and a glass plate, irradiated with ultraviolet light, and heated at 160°C in an oven. After heating for 2 hours, a colorless and transparent cured product was obtained. The heat distortion temperature of this cured product is 148
The saturated water absorption in water at 60°C and 60°C was 0.57%, and the birefringence was extremely low.

It is a copy of.

FIG. 3 is a reproduction of the IR spectrum of the compound of Example 3.

FIG. 4 is a reproduction of the IR spectrum of the compound of Example 4.

Claims (1)

[Claims] Alicyclic acrylic ester or methacrylic ester represented by the following formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [I] (n is 0 or 1, R is hydrogen or methyl (represents a group)