JPH02108657A - Dicyclopentadiene derivative and polymerizable monomer composition containing the derivative - Google Patents

Abstract

NEW MATERIAL:The compound of formula (R<1> and R<2> are H or methyl). USE:Useful as a raw material for optical material, coating agent, sealant, paint, adhesive, etc. A polymer having balanced optical uniformity, low water- absorbance, high heat-resistance, abrasion resistance, etc., can be produced by the homopolymerization of the compound or copolymerization with other copolymerizable monomers. PREPARATION:The objective compound of formula can be produced e.g by dissolving bis(aminomethyl)tricyclo[5,2,1,0<2>,<6>]decane in a solvent such as pyridine or toluene and slowly dropping an allyl haloformate and/or methallyl haloformate to the solution in nitrogen atmosphere at -10-+10 deg.C. The amount of the formate is 2.0-2.5mol per 1mol of the decane compound used as a starting raw material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel dicyclopentadiene derivative and a polymerizable monomer composition comprising this derivative. The dicyclopentadiene derivative of the present invention is a compound with weak anaerobic properties, and the (co)polymer obtained by polymerizing this compound alone or a mixture of this compound and other copolymerizable monomers has a low anaerobic property. Optical materials with excellent optical uniformity, heat resistance, abrasion resistance, etc., and low water absorption, coating agents, sealants,
It is useful as paints, adhesives, etc., and is particularly suitable for optical materials.

[Conventional technology]

Conventional monomers for producing optical material resins include methyl methacrylate, diethylene glycol bisallyl carbonate, or bis(methacryloyloxymethyl)tricyclo(5,2,1,0''°6)decane and alkylene glycol di(meth). Monomer mixtures with acrylates (see JP-A-61-287913) are used.

However, the (co)polymers obtained from the above monomers or monomer mixtures do not have all of the optical uniformity, low water absorption, heat resistance, and abrasion resistance required of optical materials. do not have. For example, when (co)polymers obtained from the above monomers or monomer mixtures are used for lenses, optical disk substrates, etc., methyl methacrylate polymers have problems with water absorption and heat resistance, and bis( Although the copolymer of methacryloyloxymethyl)tricyclo(5,2,1,0''')decane and alkylene glycol (meth)acrylate has improved low water absorption, heat resistance, and abrasion resistance, it is still difficult to use as a raw material. Due to the strong anaerobic nature of certain methacrylates, uneven polymerization is likely to occur due to oxygen, and the polymer has the drawback of poor optical uniformity, resulting in practical problems such as uneven dyeing during post-processing.

Diethylene glycol bisallyl carbonate is an excellent monomer in terms of its low anaerobic properties, but it has high water absorption and is easily deformed by water absorption, and the range of initiators that can be used is limited. It is extremely difficult to improve the refractive index by introducing sulfur atoms into the molecular structure.

For this reason, particularly in industrial fields such as optical materials and sealants, polymerizable monomers that are low in anaerobic properties and have a relatively high refractive index are strongly desired.

[Problem B to be Solved by the Invention] An object of the present invention is to overcome the drawbacks of the conventional (co)polymers made of monomers or monomer mixtures, and to produce optical materials, coating agents, and sealants. Polymerization that is useful for producing polymers that can be used as raw materials for paints, adhesives, etc., and have various physical properties such as well-balanced optical uniformity, low water absorption, heat resistance, and abrasion resistance. The purpose of this invention is to provide a monomer with a high molecular weight.

[Means to solve the problem]

The present invention provides a dicyclobencdiene derivative represented by the following general formula (I).

In the formula C, R1 and R2 represent a hydrogen atom or a methyl group] The present invention further provides a compound represented by the general formula (I) alone or in combination with the compound in an amount of 15% by weight or more based on the total weight of the composition. A polymerizable monomer composition comprising 85% by weight or less of a copolymerizable monomer is provided.

The dicyclopentadiene derivative represented by the general formula (+) of the present invention can be obtained by the synthesis method described below. '(orR
”) = CI+2 is obtained as a mixture of compounds bonded to the 2 or 3 position and the 5.6 or 7 position of the dicyclopentadiene. The (meth)allyl methyl carbamate residue is attached to the above bond of the dicyclopentadiene ring. They are thought to bind at any position, but these are difficult to isolate.

The dicyclopentadiene derivative represented by general 2 (I) is synthesized as follows. The first method is to convert bis(aminomethyl)tricyclo(5,2,1°O2.6)decane into
For example, bis(
2.0 to 2.5 times the mole of allyl haloformate such as allyl chloroformate and/or methallyl bromo This is a method of synthesis by gradually dropping methallyl haloformate such as formate. The second method is bis(aminomethyl)tricyclo(5°2.1.0"
'b) This is a method in which phosgene acts on decane hydrochloride. The third method uses bis(isocyanatomethyl)tricyclo(5,2,1,0""6]decane as a raw material and uses a tin-based catalyst such as dibutyltin-2-ethylhexanoate or 1,4-diazabicyclo(2 ,2,2) 0.001 mol% to 5 mol% of amine catalyst such as octane
per mole of bis(isocyanatemethyl)tricyclo(5,2,1,0'')decane.
This is a method in which allyl alcohol and/or methallyl alcohol is added in an amount of 2.0 to 2.5 times the mole.

A mixture of compounds represented by formula (I) can be easily polymerized by heating in the presence of a polymerization initiator. During polymerization, a copolymerizable monomer that can be copolymerized with the polymerizable compound may be used in combination for the purpose of adjusting the viscosity of the compound and improving the hardness, impact resistance, and other properties of the polymer. can.

The amount of the copolymerizable monomer used in combination is particularly limited as long as it does not impair the optical uniformity, low water absorption, heat resistance, etc. of the polymer of the compound represented by the general formula (I). The amount is usually 85 parts by weight or less, preferably 50 parts by weight or less, based on 100 parts by weight of the total amount of the compound represented by formula (I) and the copolymerizable monomer.

Specific examples of preferable copolymerizable monomers include the following.

(I) Allyl compound ethylene glycol bisallyl carbonate, diethylene glycol bisallyl carbonate (CR-39)
,) diethylene glycol bisallyl carbonate, tetraethylene glycol bisallyl carbonate, pentaethylene glycol bisallyl carbonate, polypropylene glycol bisallyl carbonate, trimethylene glycol bisallyl carbonate, 3-hydroxypropoxypropanol bisallyl carbonate, glycerol bisallyl carbonate, triglycerol Bisallyl carbonate, bisphenol A diallyl ether, bisphenol S diallyl ether, ethylene glycol diallyl ether, diethylene glycol diallyl ether, triethylene glycol diallyl ether, 1,1.1-trimethylolpropane triallyl ether, neopentyl glycol diallyl ether,
Diallyl phthalate, triallyl isocyanurate, etc. or pre-reacted products thereof.

[■] Allylidene-based compounds diarylidene pentaerythritol, triarylidene sorbitol, diarylidene-2,2,6゜6-titramethylolcyclohexanone, triarylidenehexamethylolmelamine, diarylidene-D-glucobylanose, etc., or their preparations Reactant.

[■] (Meth)acrylate compound methyl (meth)
Acrylate, ethyl (meth)acrylate, butyl (
meth)acrylate, 2-ethylhexyl(meth)acrylate, octyl(meth)acrylate, dodecyl(
meth)acrylate, octadecyl(meth)acrylate, cyclohexyl(meth)acrylate, methylcyclohexyl(meth)acrylate, (iso)bornyl(
meth)acrylate, alkyl(meth)acrylate such as adamantyl(meth)acrylate, phenyl(meth)acrylate, benzyl(meth)acrylate, 1-
Naphthyl (meth)acrylate, fluorophenyl (meth)acrylate, chlorophenyl (meth)acrylate, bromophenyl (meth)acrylate, tripromofenyl (meth)acrylate, methoxyphenyl (meth)acrylate, cyanophenyl (meth)acrylate, biphenyl Aryl such as (meth)acrylate, bromobenzyl (meth)acrylate, or haloalkyl such as aralkyl (meth)acrylate, fluoromethyl (meth)acrylate, chloromethyl (meth)acrylate, bromoethyl (meth)acrylate, trichloromethyl (meth)acrylate (meth)acrylate, 2
Hydroxyethyl (meth)acrylate, (meth)acrylic acid polyethylene glycol ester, and alkylamino (meth)acrylate [.

Ethylene glycol dimethacrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 2-hydroxy-1,3-propanediol di(meth)acrylate, 1-(meth)acrylate )
Acryloyl-2-hydroxy-3-(meth)acryloylpropane, pentaerythritol tetra(meth)acrylate, 1,1.1-1-limethylolpropane tri(meth)acrylate.

Specific examples of polymerization initiators include 2,2'-azobis(2
, 4-dimethylvaleronitrile), 2゜2'-azobisisobutyronitrile, and other azo polymerization initiators; and peroxide polymerization initiators such as hensyl peroxide and diisopropyl peroxydicarbonate. . Further, two or more of these polymerization initiators may be used in combination.

The above polymerization initiators vary depending on their type, but
0.001 to 1 ot per 100 parts by weight of raw material monomer
It is used in the range of part a, more preferably 0.001 to 5
Used in parts by weight. If the amount of polymerization initiator is more than 10 parts by weight, the weather resistance coloring will be significantly deteriorated, and
If the amount is less than 0.01 parts by weight, the curing time becomes significantly longer, which is not preferable.

The heating temperature varies depending on whether or not a polymerization initiator is used, their type and blending ratio, but is usually room temperature to 2.
00°C, particularly preferably 50 to 130″C. The heating temperature may be increased stepwise. If the heating temperature is below room temperature, the polymerization time will be long, resulting in poor productivity. On the other hand, If the temperature exceeds 200''C, thermal deterioration will occur, which is not preferable.

Further, the polymerization time varies depending on the heating temperature, whether or not a polymerization initiator is used, their type and usage ratio, etc., but -i is 0.1 to 100 hours, more preferably 1 to 20 hours. If the polymerization time is shorter than 0.1 hour, curing will be insufficient, which is not preferable, and if it is longer than 100 hours, productivity will be impaired, which is not preferable.

The compound represented by general formula (I) or the polymerizable monomer composition of the present invention may optionally contain a polymerization inhibitor, ultraviolet absorber, antioxidant, mold release agent, antistatic agent, color adjusting dye, etc. It can be used by adding it to.

[Example] Hereinafter, the present invention will be described in more detail with reference to Examples.

In addition, the infrared absorption spectrum is JASCO manufactured by JASCO Corporation.
The '+1-NMR spectrum was measured using a ll-3 type device, and the '+1-NMR spectrum was measured using Hitachi's new R-24B with TMS as an internal standard.
Measured using a mold.

Various physical properties of the polymers obtained in the examples were measured by the following methods.

(I) Refractive index: 2
The refractive index at 0°C was measured.

(2) Light Transmittance Using a spectrophotometer (manufactured by Hitachi, Model 124), the transmittance of a flat plate with a thickness of 31 nI11 was measured by light having a wavelength of 550 nm.

(3) Glass transition temperature 'rg Using a viscoelasticity measuring device (manufactured by Orientic Co., Ltd., Rheopybron, DDV-II-BP type), read the peak (inflection point) of tan δ, and measure it on the sample (thickness 0. The glass transition temperature was 1 mm).

(4) Polymerization unevenness The presence or absence of polymerization unevenness due to oxygen inhibition, which appears particularly in the peripheral area of a 15a+ thick flat plate, was shown.

(5) Water absorption rate JIS-7209 (7) Using a sample piece, the sample was dried under reduced pressure at 50°C for 5 days and was immersed in water at 100"C for 2 hours. The percentage increase in weight was calculated as the dry weight. Shown as a standard.

Example 1 4.8-bis(aminomethyl)tricyclo[5°2,
1. 0"=' ) Deca7100.0g (0,515
mol) was dissolved in pyridine 600 n+7. While stirring the solution vigorously and keeping it at -5°C under a nitrogen atmosphere, 130.3 g of allyl chloroformate (2
, 1 mol) was slowly added dropwise. After dripping, 50″C
The reaction was completed by stirring for 30 minutes. After the reaction was completed, the reaction solution was diluted with chloroform, washed repeatedly with large amounts of water, and dried by adding anhydrous sodium sulfate.

After concentrating this solution under reduced pressure, it was purified by silica gel column chromatography (hexane: ethyl acetate-6: lv/v) to obtain a liquid compound (P-1) 16 represented by the following formula.
8 g (yield 90%) was obtained.

υ The TR spectrum of the obtained compound is shown in FIG. Moreover, the 'H-NMR spectrum (in CDCl z solution) is shown in FIG.

Example 2 In the same manner as in Example 1, except that 145.5 g (2.1 mol) of methallyl chloroformate was used in place of the allyl chloroformate used in Example 1, the following formula was used. A liquid compound (P-2) was obtained (yield 90%).
,.

IR spectrum data of the obtained compound and ')I-
The NMR spectrum data were as follows.

IR Spectrum Niji WAX (neat) cm33
25, 2940.1705.1535.1260.11
50°1000, 935' II-NMR spectrum: δ(CDCl z) I
) pIl15, 5-5.0 (68, m), 4.5
5 (48, d, J=7Hz) 3.3-2.9 (411,
m), 2.6-1.8 (20) 1. byv) Example 3 Instead of allyl chloroformate used in Example 1, 65 g (I, 05 mol) of allyl chloroformate
A liquid compound (P-3) represented by the following formula was obtained in the same manner as in Example 1, except that a mixture of 73 g (I, 05 mol) of 86%
).

[R spectral data and 'II-
The NMR spectrum data were as follows.

IR Spec 1: l/WAX (neat) c
m-'3320, 2905. 1705. 1530
．． 1257. 1150°'H-N liver spectrum: δ
(CDCl 3) l) +11116, 2~5.6
(LH, m), 5.5~5.0 (6tl, m)4
．． 55 (4H, d, J=711z), 3.3-2.
9 (4H,n)2,6-1.8 (I711,brm
) Example 4 Liquid compound (P-1) synthesized in Example 1/4゜8-bisallyloxycarboxymethyltricyclo(5,2,
1,02.6] Decane/diethylene glycol bisallyl carbonate = 40:30:30 (weight ratio)
4 parts by weight of diisopropyl peroxydicarbonate were dissolved in 100 parts by weight of the monomer mixture to obtain a uniform composition. This was injected into a glass plate mold with a spacer of a predetermined thickness, held at 35°C for 3 hours, and then heated to 50°C.
The temperature was raised at a rate of 3°C/hour until the temperature reached 50°C.
The temperature was raised at a rate of 6°C/hour from 80°C to 80°C. Thereafter, it was held at 80°C for 2 hours, and after demolding, it was annealed at 110"C for 2 hours. The obtained polymer was colorless and transparent. Table 1 shows its physical properties.

Example 5 Instead of the monomer mixture used in Example 4, a monomer mixture of liquid compound (P-3) synthesized in Example 3/diethylene glycol bisallyl carbonate = 70:30 (weight ratio) was used. A polymer was obtained in exactly the same manner as in Example 1, except for the following. The physical property values are shown in Table 1.

Example 6 A polymer was obtained in the same manner as in Example 4 using 100 parts by weight of the monomer mixture with a weight ratio of liquid compound (P-1)/methyl methacrylate synthesized in Example 1 = 70:30. Ta. The obtained polymer was colorless and transparent. The physical property values are shown in Table 1.

Comparative Example 1 A polymer was obtained in the same manner as in Example 4, except that diethylene glycol bisallyl carbonate was used instead of the monomer mixture used in Example 4. The physical property values are shown in Table 1.

Comparative Example 2 0.2 parts by weight of azobisisobutyronitrile was mixed and dissolved in 100 parts by weight of methyl methacrylate. This monomer solution was poured into the same mold as in Example 4, held at 35°C for 6 hours, and then heated at 2.5°C/2.5°C from 35°C to 50°C.
The temperature was increased from 50°C to 80°C at a rate of 6°C/hour, and then held at 80°C for 2 hours. After demolding 8
Annealing was performed at 0°C for 1 hour to obtain a polymer. The physical property values are shown in Table 1.

Comparative Example 3 A monomer was used in which 1.0 part by weight of hensyl peroxide was dissolved and mixed in 100 parts by weight of 4.8-bis(methacryloyloxymethyl)tricyclo(5,2,1,02.6) dehydrogen. Other than that, a polymer was obtained in the same manner as in Comparative Example 2. The physical property values are shown in Table 1.

Margin table below 1 Example 7 Liquid compound synthesized in Example 1! I! 71(P-1)10
0 parts by weight was heated to 50°C, and 4 parts by weight of Hensil peroxide was dissolved to obtain a uniform composition. This composition was cured in the same manner as in Example 4.

The physical property values are shown in Table 2.

Table 2 [Effects of the Invention] The dicyclopentadiene derivative of the present invention exhibits well-balanced optical uniformity, low water absorption, heat resistance, and resistance by polymerizing alone or with other copolymerizable monomers. Produces polymers with various physical properties such as abrasion resistance.

[Brief explanation of the drawing]

Figure 1 shows the IR spectrum of the compound of the present invention obtained in Example 1, and Figure 2 shows the 'H-NM spectrum of the same compound.
This is the R spectrum.

Claims (1)

[Claims] 1. A compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, R^1 and R^2 represent a hydrogen atom or a methyl group] 2. Compound represented by the general formula (I) according to claim 1 A polymerizable monomer composition consisting of: 3. Claim 1: 15% by weight or more based on the total weight of the composition
The polymerizable monomer composition according to claim 2, comprising the compound represented by general formula (I) and 85% by weight or less of a copolymerizable monomer.