JPH06322087A - Allylic oligomer containing fluorene skeleton - Google Patents

Abstract

PURPOSE:To obtain, without using a halogen or a sulfur compound, an allylic oligomer giving an organic glass which has a relatively small specific gravity, a high refractive index, and excellent impact resistance and is suited for use as an optical material, by forming a specific structure containing a fluorene skeleton. CONSTITUTION:This allylic oligomer has a structure represented by formula I (wherein A's each is an organic residue derived from a divalent carboxylic acid; R's consist mainly of organic residues derived from a diol and represented by formula II (where R<1> is H or CH3 and (l) and (m) each is 1-5) and preferably contain organic residues derived from another diol and/or a polyol having 3 or more hydroxyl groups; and (n) is 1-20). this oligomer is obtained without using a halogen or a sulfur compound. It has a relatively small specific gravity, a high refractive index, and excellent impact resistance and gives an organic glass suited for use as an optical material. The oligomer is usable in the fields where optical properties are important, such as a lens for glasses, a prism, an optical disk, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an allylic oligomer containing a fluorene skeleton, and more specifically, it has a relatively low specific gravity and a refractive index which can be used for eyeglass lens materials and other optical materials. The present invention relates to a material which gives an organic glass suitable as an optical material having high and excellent impact resistance.

[0002]

2. Description of the Related Art Conventionally, since organic glass is lighter in weight than inorganic glass, diethylene glycol bis (allyl carbonate) (hereinafter abbreviated as "CR-39") is used.
Organic glass made of a polymer such as or methyl methacrylate is used. However, the refractive index of these organic glasses is 1.49 to 1.50, which is lower than that of inorganic glass (1.523 in the case of white crown glass), and it is thicker than that of inorganic glass, and the merit of weight reduction is impaired. And
Further, when it is used as a lens for correcting visual acuity, there is a drawback that the appearance becomes worse when the degree is increased. For this reason, organic lenses with high refractive index have been developed, but in order to obtain plastics with high refractive index, introduction of halogen atoms other than fluorine and introduction of sulfur atoms into the molecular structure are carried out. Is common.

[0003]

However, these methods have a drawback that the specific gravity becomes heavy when a halogen atom is introduced, and when a sulfur atom is introduced, an odor peculiar to sulfur is generated during cutting. There was a drawback that it occurred.
The present invention has been studied for the purpose of solving the above drawbacks, without using a halogen element or a sulfur compound, relatively low specific gravity and high refractive index, as an optical material excellent in impact resistance It is to develop a material that gives a suitable organic glass.

[0004]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that they have an allyl ester group at the terminal and are internally formed from polyvalent saturated carboxylic acid and polyvalent saturated alcohol. As a raw material for synthesizing the derived allyl ester oligomer, it was found that the problem can be solved by using an allylic oligomer containing a fluorene skeleton obtained by using a specific compound as a diol, and finally the present invention was found. It came to completion.

The invention according to claim 1 of the present invention is an allylic oligomer containing a fluorene skeleton having the following structure. CH ₂ = CHCH ₂ O (COACOORO) _n COACOCH ₂ CH = CH ₂ where A is an organic residue derived from a divalent carboxylic acid, and R is a structural formula-1 derived from a diol. Is used as a main component, and n represents a number of 1 to 20. R ¹ in the structural formula- ¹ is hydrogen or a methyl group, 1, m
Represents an integer of 1 or more and 5 or less. Although low molecular weight raw material monomers such as allyl ester monomers remain in the synthesized oligomers, these residual monomers can be used as they are without separation. The included oligomer is also treated as an oligomer.

[0006]

[Chemical 2]

The invention according to claim 2 of the present invention comprises: an organic residue represented by the above structural formula-1 in which R is derived from a diol;
The allylic oligomer having a fluorene skeleton according to claim 1, which contains an organic residue derived from a diol other than the diol and / or a polyol having a valence of 3 or more. The allyl ester oligomer according to claim 2 of the present invention is an oligomer having an allyl ester group as a main component in the ester group at the molecular end and having the following repeating units. -(COACOORO)-structure-A- (COACOO) _X- ZO-COACOO- structure-B where x is an integer of 1 or more and 5 or less and Z is an organic residue derived from a polyol having X + 1 hydroxyl groups. The group, A is an organic residue derived from a divalent carboxylic acid, and R is a main component of the organic residue represented by the structural formula-1 (Chemical Formula 2).
R ^{1 in} Structural Formula-1 (Chemical Formula 2) is hydrogen or a methyl group,
l and m represent an integer of 1 or more and 5 or less.

Such an allyl-based oligomer is obtained by reacting the corresponding diallyl ester of dicarboxylic acid with the above structural formula-1.
It can be obtained by reacting with a diol corresponding to (Chemical Formula 2) in the presence of a transesterification reaction catalyst while distilling off allyl alcohol.

As a further industrially useful method, instead of the diallyl ester of dicarboxylic acid, a diester of a corresponding dicarboxylic acid with a lower aliphatic alcohol having 1 to 3 carbon atoms and allyl alcohol are used as raw materials. It can be obtained by reacting while distilling off the lower aliphatic alcohol.

Examples of the diol for deriving Structural Formula-1 (Chemical Formula 2) include compounds in which ethylene oxide or propylene oxide of 9,9-bis (4-hydroxyphenyl) -fluorene is added in an average of 2 mol to 10 mol. it can.

As the divalent carboxylic acid which gives A, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, β-methyladipic acid, pimelic acid, succinic acid, azelaic acid, sebacic acid, Nonanedicarboxylic acid,
Decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, 1,2- or 1,3- or 1,4
-Cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, diphenyl-P, P'-dicarboxylic acid, diphenyl-m, m'-dicarboxylic acid, 1,4- or 1,5- or 2,6- or 2 , 7-naphthalenedicarboxylic acid, diphenylmethane-p, p'-dicarboxylic acid, diphenylmethane-m, m'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, p-phenylenediacetic acid, p-carboxyphenylacetic acid, methyl Examples thereof include terephthalic acid, tetrachlorophthalic acid, maleic acid, fumaric acid, itaconic acid and citraconic acid. Among these, divalent saturated carboxylic acids containing a benzene ring such as terephthalic acid and isophthalic acid are preferable for increasing the refractive index.

In the present invention, diols other than the diol that induces Structural Formula-1 (Chemical Formula 2) can be used within a range where the refractive index is not lowered. Examples of such a divalent saturated alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,5-pentanediol and hexa. Methylene glycol, heptamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, undecamethylene glycol, dodecamethylene glycol, tridecamethylene glycol, eicosamethylene glycol, hydrogenated bisphenol-A, 1,
4-cyclohexanedimethanol, 2-ethyl-2,5
-Saturated glycol consisting only of carbon such as pentanediol, 2-ethyl-1,3-hexanediol and styrene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, ethylene oxide adduct of bisphenol-A, bisphenol Examples thereof include a divalent saturated alcohol containing an ether group such as a propylene oxide adduct of -A and a glycol containing bromine such as dibromonepentyl glycol.

In the present invention, a polyhydric alcohol such as glycerin, pentaerythritol or trimethylolpropane can be used in some cases. However, the use of these polyols may cause a decrease in the refractive index and an increase in the specific gravity, so it is better to use only a small amount.

As for the ratio of these used, in order to obtain an allyl ester oligomer having an allyl ester at the terminal, it is necessary to use less hydroxyl groups of diol than carboxyl groups of divalent saturated carboxylic acid. There is. Further, if the ratio of the functional groups used is too close, the molecular weight of the produced allyl ester oligomer will be too high, and the viscosity will be too high for use as an optical material. Therefore, the usage ratio of these is such that the ratio of carboxyl group / hydroxyl group is 10
Desirably, it falls between / 9 and 5/1, more preferably between 5/4 and 3/1.

The transesterification catalyst used is
Although conventionally known transesterification catalysts can be used, particularly preferred are alkali metals, alkaline earth metals and their oxides, and weak acid salts, Mn, U, Zn, Cd, Z.
oxides, hydroxides of r, Pb, Ti, Co and Sn,
Examples thereof include inorganic acid salts, alcoholates, organic acid salts, organic tin compounds such as cibutyltin oxide, dioctyltin oxide, and dibutyltin dichloride.

The amount used should be such that allyl alcohol can be extracted at an appropriate rate, although it depends on the activity of the catalyst. Generally, 0.0001 wt% to 1 w based on diallyl or dialkyl ester
t%, particularly preferably 0.001 wt% to 0.1 wt%
It is preferred to use degrees.

As an embodiment of the reaction, when a diallyl ester is used, it is heated above the boiling point of allyl alcohol, and when a dialkyl ester of a lower alcohol is used, it is heated above the boiling point of a lower alcohol for transesterification. The allyl alcohol or lower alcohol which is produced in a favorable manner for the production of is removed from the reactor out of the system by reactive distillation. Generally, the reaction is carried out under normal pressure or under pressure, but it is also effective to use a method of reducing the pressure in the reaction system to rapidly distill off allyl alcohol or lower alcohol as the conversion rate of the reaction increases.

As mentioned above, when the diallyl ester is used, if the reaction temperature is lower than the boiling point of allyl alcohol, the distillation of allyl alcohol cannot be carried out effectively, and if the temperature is too high, the thermal polymerization is carried out. Since there are problems such as
Generally between 100 ° C and 300 ° C, more preferably 1
It is selected from between 30 ° C and 250 ° C.

When a dialkyl ester of a lower alcohol is used, since the boiling point of the allyl alcohol to be reacted with the produced lower alcohol is close, heating at an excessively high temperature from the initial stage of the reaction causes allyl alcohol to be distilled out together with the lower alcohol. There is a fear. Therefore, an efficient rectification column is attached, and the reaction temperature is generally 80 ° C to 150 ° C, more preferably 90 ° C to 130 ° C in the initial stage of the reaction, and most of the lower alcohol is distilled. After that, it is better to select between 100 ° C. and 300 ° C., more preferably between 130 ° C. and 250 ° C. As the amount of allyl alcohol used in this case,
At least 0.2 molar equivalent is necessary with respect to the dialkyl ester, and usually 0.5 molar equivalent or more, preferably 1
It should be used in molar equivalents or more. However, if it is used in an excessively large amount, excess allyl alcohol must be removed, and the reaction rate does not always increase, so it should be kept at 20 molar equivalents or less.

A polymerization inhibitor such as hydroquinone may be allowed to coexist in the reaction solution depending on the reaction temperature.

As a method of taking out the oligomer after completion of the reaction, various methods can be carried out. For example, it is possible to remove the monomer from the produced allyl ester oligomer by distillation or reprecipitation for purification, but usually, it can be used even in the state where the diallyl ester monomer co-produced during the reaction or used as a raw material coexists. This is possible and industrially advantageous.

Further, it is possible to positively add a diallyl or triallyl type monomer for the purpose of adjusting the viscosity. Examples of such a diallyl or triallyl type monomer include diallyl phthalate, diallyl isophthalate, diallyl terephthalate and adipine. Examples thereof include diallyl acid, triallyl isocyanurate, triallyl trimellitate, diallyl 2,6-naphthalenedicarboxylic acid, and diallyl endic acid.

The oligomer thus obtained is characterized in that the refractive index is remarkably higher than that of a usual allyl ester oligomer. If desired, this novel oligomer can be used as it is or as a composition for optical materials by dissolving it in another polymerizable monomer to reduce the viscosity. Examples of such a polymerizable monomer include aromatic vinyl compounds, (meth) acrylic acid and its esters, unsaturated dibasic acids and their derivatives, saturated aliphatic or aromatic carboxylic acid vinyl esters and their derivatives, ( Examples thereof include vinyl cyanide compounds such as (meth) acrylonitrile, unsaturated hydrocarbons and halogenated unsaturated hydrocarbons.

As the aromatic vinyl compound, styrene, α-methylstyrene, α-ethylstyrene, α-
There are α-substituted styrenes such as chlorostyrene, and nuclear-substituted styrenes such as vinyltoluene, fluorostyrene, chlorostyrene, bromostyrene, chloromethylstyrene and methoxystyrene.

Examples of the (meth) acrylic acid and its ester include acrylic acid, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate.

As the unsaturated dibasic acid and its derivative,
There are dialkyl esters of maleic acid such as dimethyl maleate and diethyl maleate, and dialkyl esters of fumaric acid such as dimethyl fumarate and diisopropyl fumarate.

The vinyl ester of saturated aliphatic or aromatic carboxylic acid and its derivative include vinyl acetate, vinyl propionate, vinyl benzoate and the like.

As the unsaturated hydrocarbon, 1-hexene,
Examples include 1-octene and 4-vinylcyclohexene.

Examples of halogenated unsaturated hydrocarbons include vinyl chloride and vinyl bromide.

Further, a crosslinkable polyfunctional monomer can also be used,
As such, for example, diallyl carbonate, diethylene glycol diallyl carbonate, divinylbenzene, neopentyl glycol (meth) acrylate, difunctional adipate divinyl crosslinkable monomers such as divinyl adipate, trimethylolpropane tri (meth) acrylate, Examples thereof include trifunctional or higher functional crosslinkable monomers such as pentaerythritol tetra (meth) acrylate, diallylmaleate and diallyl fumarate.

A polymer having a double bond such as unsaturated polyester can also be used in the same manner as the reactive monomer.

As the polymerization initiator, a compound which generates a radical by heat or light can be used. However, since the polymerization may explosively proceed depending on the polymerization conditions, the initiator should be thoroughly examined before starting the polymerization. Should be selected.

Examples of the radical polymerization initiator that can be used in the polymerization include azo compounds such as 2,2'-azobisisobutyronitrile, dicumyl peroxide, t-butyl cumyl peroxide and di-t-butyl peroxide. Dialkyl peroxides such as oxides and tris (t-butylperoxy) triazine, peroxyketals such as 1,1-di-t-butylperoxycyclohexane and 2,2-di (t-butylperoxy) butane , T-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyase Rate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy Examples thereof include alkyl peresters such as cyacetate, t-butylperoxybenzoate, and di-t-butylperoxytrimethyl adipate.

The allyl-based oligomer having a fluorene skeleton of the present invention is used for optical materials, as well as a filler, a polymerization accelerator, a polymerization inhibitor, an internal mold release agent, a coupling agent, a pigment, and other additives. It is also possible to use as a molding material by mixing and using the above to the extent that the physical properties are not impaired.

Further, since this oligomer has an appropriate double bond, it can be used as a mixture with an unsaturated polyester resin, diallyl phthalate resin or the like.
It can also be used as a crosslinking agent for PR, chlorinated polyethylene, synthetic rubber and the like.

[0036]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. (Example 1) In a 2 liter three-necked separable flask equipped with a distillation apparatus, 500 g of diallyl terephthalate, bisphenol full orange hydroxyethyl ether (molecular weight 438.5, manufactured by Nippon Steel Chemical Co., Ltd., hereinafter BPHE
Was charged) and 0.5 g of dibutyltin oxide were charged, and the mixture was heated to 180 ° C. in a nitrogen stream to distill off the produced allyl alcohol. Allyl alcohol is 5
When about 0 g was distilled, the pressure inside the reaction system was reduced to about 20 Torr to accelerate the distillation rate of allyl alcohol. After distilling the theoretical amount of allyl alcohol, heating was continued for another hour. After that, the system was placed under a normal pressure nitrogen atmosphere and cooled to room temperature. 920 g of a polymerizable oligomer having almost no fluidity at room temperature was obtained. In this oligomer, 6.7 wt% of diallyl terephthalate monomer remained.

Example 2 A 2-liter three-neck separable flask equipped with a distillation apparatus was charged with diallyl isophthalate 7.
00 g, BPHE 415 g, dibutyltin oxide 0.
7 g was charged, and by substantially the same operation as in Example 1, 980 g of a polymerizable oligomer in the form of a viscous liquid at room temperature was obtained. This oligomer contained 32. diallyl isophthalate monomers.
8 wt% remained.

(Examples 3 to 5) An allyl ester oligomer was synthesized in substantially the same manner as in Example 1 except that the raw materials and the charged molar ratio were different. The results are also shown in Table 1.

(Comparative Example 1) The same procedure as in Example 1 was carried out except that 103 g of propylene glycol was used instead of BPHE used in Example 1. 430 g of a liquid polymerizable oligomer viscous at room temperature was obtained.

Comparative Example 2 The procedure of Example 1 was repeated, except that 641 g of an ethylene oxide 2 mol adduct of tetrabromobisphenol-A was used in place of the BPHE used in Example 1. 1002 g of a polymerizable oligomer having almost no fluidity at room temperature was obtained.

[0041]

[Table 1]

100 parts of the polymerizable oligomers obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were mixed with 2 parts of dicumyl peroxide, and cast polymerization was performed using a cellophane-tensioned glass plate (Example 1 was pressed. Molding), 130 ℃ 1 hour and 160
It was cured at 2 ° C. for 2 hours to obtain an organic glass molded product. Table 2 shows the physical properties of each example and comparative example.

Various physical properties were measured by the following test methods. 1. Light transmittance Measured according to ASTM D-1003. 2. Refractive index and Abbe number The Abbe refractometer (manufactured by Atago) was used for measurement. 3. Surface hardness (pencil hardness) According to JISK-5400, it is carried out with a load of 1 kgf,
The highest pencil hardness without scratches was shown. 4. Impact resistance In accordance with JISK-7211, the drop impact test method, a DuPont impact tester (manufactured by Toyo Seiki Seisakusho) was used to perform a test with a test piece thickness of 3 mm and a drop weight of 500 g, and a 50% breaking height. I asked. 5. Specific gravity Using an electronic hydrometer, the specific gravity at 23 ° C. was determined by the water displacement method.

[0044]

[Table 2]

[0045]

The conventional organic glass has a drawback that the specific gravity becomes heavy when a halogen atom is introduced, and the disadvantage that a sulfur-specific odor is generated during cutting when a sulfur atom is introduced. However, the allylic oligomer containing a fluorene skeleton of the present invention is suitable as an optical material excellent in impact resistance without using a halogen element or a sulfur compound, a relatively low specific gravity and a high refractive index. Since it is a material that gives organic glass, it can be used not only in spectacle lenses but also in fields such as prisms and optical disks where optical properties are important, and its industrial utility value is enormous.

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[Procedure amendment]

[Submission date] July 7, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction content]

[0006]

[Chemical 2]

Claims (2)

[Claims] 1. An allyl oligomer containing a fluorene skeleton having the following structure. CH ₂ = CHCH ₂ O (COACOORO) _n COACOCH ₂ CH = CH ₂ where A is an organic residue derived from a divalent carboxylic acid, and R is a structural formula-1 derived from a diol. Is used as a main component, and n represents a number of 1 to 20. R ¹ in the structural formula- ¹ is hydrogen or a methyl group, 1, m
Represents an integer of 1 or more and 5 or less. [Chemical 1] 2. R contains an organic residue derived from a diol and represented by the structural formula-1 and an organic residue derived from a diol other than the diol and / or a polyol having a valency of 3 or more. The allylic oligomer containing a fluorene skeleton according to claim 1.