JPH04366127A - Allylic oligomer containing sulfur atom and production thereof - Google Patents

Abstract

PURPOSE:To provide an allylic oligomer useful as the material of an org. glass which has a higher refractive index than that of conventional org. glasses and is suitable for a high-impact optical material. CONSTITUTION:An allylic oligomer of the formula: CH2=CHCH2O(COACOOR<1> SR<2>O)nCOACOOCH2CH=CH2 [wherein A is an org. group derived from a dicarboxylic acid; R<1> and R<2> are each a divalent org. group derived from a 2-10C aliph. hydrocarbon; and n is 1-20] contg. sulfur atoms is used as the material of an org. glass.

Description

[Detailed description of the invention]

0001

TECHNICAL FIELD The present invention relates to a novel allylic oligomer containing a sulfur atom and a method for synthesizing the same. More specifically, the present invention relates to a material that provides an organic glass suitable as an optical material having a high refractive index and excellent impact resistance, which can be used for eyeglass lens materials and other optical materials, and a method for manufacturing the same.

0002

[Prior Art] Conventionally, organic glasses are lighter than inorganic glasses, so diethylene glycol bis(
Organic glasses made of polymers such as allyl carbonate) and methyl methacrylate are used. However, the refractive index of these organic glasses is 1.49 to 1.50, which is lower than that of inorganic glasses (1.523 for white crown glass), and they are thicker than inorganic glasses, which negates the advantage of weight reduction. Moreover, when used as a vision correction lens, there was a drawback that the stronger the power, the worse the appearance.

In order to solve this problem, various organic glasses using diallylphthalate monomers have been proposed, but they have problems in terms of brittleness and transmittance. When the glass was diluted with water, the heat resistance and solvent resistance were impaired, resulting in insufficient performance as an organic glass. Furthermore, allyl esters having an allyl ester group at the end and the following structure derived from a polyvalent saturated carboxylic acid and a polyvalent saturated alcohol inside are also known. CH2=CHCH2O(CORCOOBO)nCORC
OOCH2CH=CH2 However, R is an organic residue derived from a divalent or trivalent saturated carboxylic acid, B is an organic residue derived from a divalent or polyvalent polyol, and n is 1 to 2.
Represents an integer of 0. This allyl ester gives a cured product with very good impact resistance, but in this case, because the aliphatic hydrocarbon B is used inside, even if terephthalic acid or isophthalic acid is used as the polyvalent saturated carboxylic acid, There was a drawback that the refractive index was lower than that of a cured product of diallyl terephthalate monomer or diallyl isophthalate monomer itself.

0004

OBJECTS OF THE INVENTION It is an object of the present invention to develop an allyl oligomer for optical materials having a high refractive index and excellent impact resistance, and a method for producing the same.

[0005]

[Means for Solving the Problems] In order to achieve the above object, the present inventors conducted intensive research and found that the present invention has an allyl ester group at the end and an internal structure composed of a polyvalent saturated carboxylic acid and a polyvalent saturated alcohol. By using a diol containing a sulfur atom as a raw material when synthesizing the derived allyl ester oligomer, the allyl ester oligomer can be made into an organic glass with a very high refractive index and excellent impact resistance after curing. The present invention was completed based on this discovery.

The first aspect of the present invention is an allyl oligomer having the following structural formula. CH2=CHCH2O(COACOOR1SR2O)n
COACOOCH2CH=CH2 [where A is an organic residue derived from a divalent carboxylic acid, R1 and R2 are divalent organic residues derived from an aliphatic hydrocarbon having 2 to 10 carbon atoms, n represents a number from 1 to 20]

[0007] The second invention of the present invention is an oligomer having an allyl ester group at the end and having the following repeating unit, -(COACOOR1SR2O)-
Structure-I-(COACOO)xZ-O-COACOO
- Structure - B [However, A is an organic residue derived from a divalent carboxylic acid, R1 and R2 have 2 to 2 carbon atoms.
A divalent organic residue derived from an aliphatic hydrocarbon consisting of ~100% range, the rest is structure-B,
Polystyrene equivalent number average molecular weight (Mn) measured by GPC (gel permeation chromatography) method
is 500 to 15,000, and the weight average molecular weight (MW
) is 1000 to 70000, and the MW/Mn ratio is 1.2 to 20.0.

[0008] Such allyl oligomers are obtained by transesterifying allyl alcohol with a diallyl ester of a corresponding dicarboxylic acid, a diol containing a sulfur atom, and optionally a polyol of divalent or higher valence in the presence of a transesterification catalyst. It can be obtained by reacting while distilling off. Furthermore, as an industrially useful method, instead of the diallyl ester of a dicarboxylic acid, a diester of the corresponding dicarboxylic acid with a lower aliphatic alcohol having 1 to 3 carbon atoms and allyl alcohol are used as raw materials to produce a lower aliphatic It can be obtained by reacting while distilling off the alcohol. The third invention of the present invention is a divalent carboxylic acid dimethyl or diethyl ester, a divalent polyol containing a sulfur atom,
A sulfur atom characterized by being obtained by reacting one or more types of saturated aliphatic polyols having a valence of 2 or more with allyl alcohol in the presence of a transesterification reaction catalyst while distilling off methanol or ethanol, if necessary. This is a method for producing allyl oligomers containing

The fourth aspect of the present invention is a divalent carboxylic acid diallyl ester, a divalent polyol containing a sulfur atom, and optionally a divalent or higher saturated aliphatic polyol.
This is a method for producing an allyl oligomer containing a sulfur atom, which is characterized in that it is obtained by reacting at least one type of allyl alcohol in the presence of a transesterification catalyst while distilling off allyl alcohol.

Examples of the sulfur-containing diol used in the present invention include thiodiethanol, bis(3-hydroxypropyl) sulfide, and bis(4-hydroxybutyl) sulfide.

Further, examples of divalent saturated carboxylic acids that give A include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, β-methyladipic acid, pimelic acid, corkic acid, azelaic acid, and 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-naphthalene dicarboxylic acid, diphenylmethane-p,p'-dicarboxylic acid, diphenylmethane-m,m'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, These include p-phenylene diacetic acid, p-carboxyphenylacetic acid, methyl terephthalic acid, and tetrachlorophthalic acid. Among these, divalent saturated carboxylic acids containing a benzene ring, such as terephthalic acid and isophthalic acid, are preferred in terms of increasing the refractive index.

[0012] Examples of dihydric saturated alcohols that give Z include ethylene glycol, propylene glycol,
1,3-propanediol, 1,4-butanediol,
1,3-butanediol, neopentyl glycol, 1
, 5-pentanediol, hexamethylene 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-pentadiol, 2-ethyl-1, Saturated glycols consisting only of carbon such as 3-hexanediol and styrene glycol, and ethers such as diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, ethylene oxide adducts of bisphenol-A, and propylene oxide adducts of bisphenol-A. Also included are dihydric saturated alcohols containing groups and glycols containing bromine, such as dibromoneopentyl glycol. Among these, when glycols such as propylene glycol, 1,3-butanediol, and dipropylene glycol are used, they have good compatibility with other copolymerizable monomers and the cured product has excellent transparency. In particular, depending on the sulfur-containing diol and divalent saturated carboxylic acid used, the oligomer will crystallize and will not dissolve with other monomers.
In that case, it is better to use propylene glycol, 1,3-butanediol, and dipropylene glycol together.

[0013] Examples of trivalent or higher polyhydric saturated alcohols include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol,
Examples include alkyl oxide adducts of isocyanuric acid. The use of these is preferable from the viewpoint of heat resistance, but since it significantly increases the viscosity of the produced allyl ester oligomer, it is better to use only a small amount.

Here, in order to obtain an allyl ester oligomer with an allyl ester at the end, sulfur-containing diols and other polyhydric diols are used more than the carboxyl group of the divalent saturated carboxylic acid. It is necessary to use less of the hydroxyl group of the alcohol. Furthermore, if the usage ratios of these functional groups are too close, the molecular weight of the produced allyl ester oligomer will increase significantly and the viscosity will become too high to be used as a raw material for optical materials. Therefore, the ratio of carboxyl group/hydroxyl group is from 10/9 to 5/1.
, more preferably between 5/4 and 3/1.

[0015] The transesterification catalyst used is as follows:
Conventionally known transesterification catalysts can be used, but particularly preferred are alkali metals, alkaline earth metals and their oxides, weak acid salts, Mn, U, Zn, Cd, Z
r, Pb, Ti, Co and Sn oxides, hydroxides,
These include inorganic acid salts, alcoholates, organic acid salts, and organic tin compounds such as dibutyltin oxide, dioctyltin oxide, and dibutyltin dichloride. The amount used should vary depending on the activity of the catalyst, but should be such an amount that allyl alcohol can be distilled off at an appropriate rate. Generally 0.00 for diallyl or dialkyl esters
01wt% to 1wt%, particularly preferably 0.001wt
It is preferable to use about % to 0.1 wt%.

As an embodiment of the reaction, when a diallyl ester is used, heating is performed above the boiling point of allyl alcohol, and when a dialkyl ester of a lower alcohol is used, heating is performed above the boiling point of the lower alcohol to carry out transesterification to form an oligomer. The allyl alcohol or lower alcohol produced is distilled out of the system from the reactor by reactive distillation so as to be advantageous for the production of. Generally, the reaction is carried out under normal pressure or increased pressure, but it is also effective to reduce the pressure in the reaction system and quickly distill off the allyl alcohol or lower alcohol, as this increases the conversion rate of the reaction.

As mentioned above, when diallyl ester is used, allyl alcohol cannot be effectively distilled off if the reaction temperature is below the boiling point of allyl alcohol, and if the temperature is too high, thermal polymerization may occur. Because there are problems such as
Generally between 100°C and 300°C, more preferably 1
Selected from 30°C to 250°C.

When a dialkyl ester of a lower alcohol is used, the lower alcohol produced and the allyl alcohol to be reacted have close boiling points, so if the reaction is heated to too high a temperature from the beginning, the allyl alcohol will distill out together with the lower alcohol. There is a fear. Therefore, in addition to installing an efficient rectification column, the reaction temperature is generally between 80°C and 150°C, more preferably between 90°C and 130°C in the initial stage of the reaction, so that most of the lower alcohols are distilled out. After that, the temperature should be selected from between 100°C and 300°C, more preferably between 130°C and 250°C. The amount of allyl alcohol used in this case is:
At least 0.2 molar equivalent is required based on the dialkyl ester, and usually 0.5 molar equivalent or more, preferably 1
More than molar equivalents should be used. However, if too much excess is used, excess allyl alcohol must be removed and the reaction rate will not necessarily increase, so the amount should be kept at 20 molar equivalents or less. Further, depending on the reaction temperature, a polymerization inhibitor such as hydroquinone may be allowed to coexist in the reaction solution.

Various methods can be used to take out the oligomer after the reaction is completed. For example, it is possible to purify the produced allyl ester oligomer by removing the monomer by distillation or reprecipitation, but it is usually possible to use it even in the presence of diallyl ester monomers that are produced as by-products during the reaction or used as raw materials. This is more advantageous from an industrial standpoint. In addition, for the purpose of adjusting viscosity,
It is also possible to actively add a diallyl or triallyl monomer, and examples of such diallyl or triallyl monomers include diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl adipate, triallyl isocyanurate, and triallyl trimeryl. tate, diallyl 2,6-naphthalene dicarboxylate, diallyl endic acid, and the like.

The structure of the oligomer described here was confirmed in the following experiment. A) Measurement and determination method of Mn and Mw by GPC method GP
Mn and Mw in terms of polystyrene are measured using C. S
HODEX column AC-80P, 802, 804, 80
6 are connected in series in this order, and measurements are made using chloroform as a solvent at a temperature of 25° C. and a flow rate of 1.0 ml/min.

■ First, using at least 10 types of commercially available standard polystyrenes with known average molecular weights,
The retention time of each of the diallyl terephthalate (DAT) monomers was determined. A calibration curve was created by approximating the relationship between average molecular weight and retention time using a cubic curve or a broken line. ■ Dissolve 20 mg of sample in 20 ml of chloroform,
Inject 0.5 ml through the line filter into the column using a loop injector. Based on the obtained elution curve data and the calibration curve created in (■), Shimadzu CR-3
Mn, Mw are automatically calculated in a data processing machine such as A.
seek. Here, the peak was divided at 10 second intervals, the molecular weight at each division point was set as Mi, and the height of the peak was set as Hi, and the calculation was performed using the following formula.

[0022]

B) 1 HNMR measurement Model used 1 HNMR: Hitachi R-24B oligomer uses deuterated chloroform as a measurement solvent. Tetramethylsilane (TM) was used as an internal standard substance.
S) is used.

[0024] Since the oligomer thus obtained has a sulfur element in its molecule, the refractive index may be dramatically higher than that of ordinary allyl ester oligomers.

[0025] This novel oligomer can optionally contain:
It can be used as it is or by dissolving it in other polymerizable monomers to lower its viscosity to form a composition for optical materials. Such polymerizable monomers include, for example, 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 include vinyl cyanide compounds such as meth)acrylonitrile, unsaturated hydrocarbons, and halogenated unsaturated hydrocarbons.

Examples of aromatic vinyl compounds include styrene, α-methylstyrene, α-ethylstyrene, α-
There are α-substituted styrenes such as chlorostyrene, and nuclear-substituted styrenes such as fluorostyrene, chlorostyrene, bromostyrene, chloromethylstyrene, and methoxystyrene.

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

[0028] Unsaturated dibasic acids and their derivatives include:
Examples include 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.

Vinyl esters of saturated aliphatic or aromatic carboxylic acids and their derivatives include vinyl acetate, vinyl propionate, vinyl benzoate, vinyl n-butyrate, and the like.

[0030] Examples of unsaturated hydrocarbons include 1-hexene,
Examples include 1-octene and 4-vinylcyclohexene.

Examples of halogenated unsaturated hydrocarbons include vinyl chloride and vinyl bromide. Additionally, cross-linking polyfunctional monomers can be used, such as di-functional cross-linking monomers such as diallyl carbonate, diethylene glycol diallyl carbonate, divinylbenzene, neopentyl glycol di(meth)acrylate, and divinyl adipate. Examples include trifunctional or higher functional crosslinking monomers such as trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, diallyl maleate, and diallyl fumarate.

[0032] Polymers having double bonds such as unsaturated polyesters can also be used in the same way as reactive monomers.

As a polymerization initiator, a compound that generates radicals when exposed to heat or light can be used, but depending on the polymerization conditions, the polymerization may proceed explosively due to the presence of sulfur atoms. Initiators should be selected after careful consideration. Examples of radical polymerization initiators that can be used during polymerization include azo compounds such as 2,2'-azobisisobutyronitrile, dicumyl peroxide, t-butylcumyl peroxide, di-t-
Butyl peroxide, tris (t-butyl peroxy)
Dialkyl peroxides such as triazine, 1,1-di-t-butylperoxycyclohexane, 2,2-di(
Peroxyketals such as t-butylperoxy)butane, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxy Oxyhexahydroterephthalate, di-t-butylperoxyazelate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate,
Examples include alkyl peresters such as t-butylperoxybenzoate and di-t-butylperoxytrimethyladipate.

In addition to optical material applications, fillers, polymerization accelerators, polymerization inhibitors, internal mold release agents, coupling agents, pigments, and other additives may be mixed and used to the extent that physical properties are not impaired. It is also possible to use it as a molding material.

Furthermore, since this oligomer has a moderate amount of double bonds, it can be used in combination with unsaturated polyester resins, diallyl phthalate resins, etc.
It can also be used as a crosslinking agent for PR, chlorinated polyethylene, synthetic rubber, etc. The present invention will be explained in more detail below.

[0036]

【Example】

Example-1 1,300 ml of diallyl terephthalate (hereinafter abbreviated as DAT) was placed in a 2 liter three-necked separable flask equipped with a distillation device.
After charging 430 g of 2,2'-thiodiethanol and 0.65 g of dibutyltin oxide, 1
The mixture was heated to 80° C. and allyl alcohol produced was distilled off. When about 250 g of allyl alcohol was distilled off, the pressure inside the reaction system was reduced to about 50 torr to accelerate the distillation rate of allyl alcohol. After the theoretical amount of allyl alcohol had distilled off, heating was continued for an additional hour. Thereafter, the inside of the system was placed under a nitrogen atmosphere at normal pressure and cooled to room temperature. 1,320 g of a crystalline polymerizable oligomer that was soft at room temperature was obtained.

FIG. 1 shows a 1 H NMR chart of this product. In Figure 1, the peak around 8.00 ppm shown as a is that of the circled proton of the organic residue represented by (Chemical formula 1), and the peak around 4.7 to 6.4 ppm shown as b is the proton of the organic residue represented by (Chemical 2) with a circle, and the peak around 4.5 ppm shown by c is the organic residue represented by (Chemical 3) with a circle. The peak near 3.0 ppm shown by d is (
This is the proton with a circle of the organic residue represented by Chemical Formula 4), and TMS is the peak of tetramethylsilane used as an internal standard.

[0038]

[Chemical formula 1]

[0039]

[Case 2]

[0040]

[Chemical formula 3]

[0041]

[C4]

Example 2 A 3-liter three-neck separable flask equipped with a distillation device was charged with 1025 g of dimethyl terephthalate, 430 g of 2,2'-thiodiethanol, 919 g of allyl alcohol, and 0.65 g of dibutyltin oxide, and then heated with a nitrogen stream. The mixture was heated to 150° C. and the generated methanol was distilled off. When the theoretical amount of methanol (337.8 g) was distilled off, the reaction temperature was raised to 180° C. and allyl alcohol was distilled off. When about 500 g of allyl alcohol was distilled off, the pressure of the reaction system was reduced to 50 torr to increase the rate of distillation of allyl alcohol. After excess allyl alcohol was distilled off, the reaction was continued for an additional hour. Thereafter, the inside of the system was placed under a nitrogen atmosphere at normal pressure and cooled to room temperature. 1,320 g of a crystalline polymerizable oligomer that was soft at room temperature was obtained.

Example-3 2,2'-thiodiethanol 430 used in Example-1
Example 1 except that 215 g of 2,2'-thiodiethanol and 134 g of propylene glycol were used instead of g.
I did the same thing. 1240 g of a polymerizable oligomer which was viscous and liquid at room temperature was obtained.

Example-4 Example-4 except that 1300 g of diallylisophthalate was used instead of 1300 g of DAT used in Example-3.
This was done in the same manner as in step 3. 1,320 g of a liquid polymerizable oligomer that was viscous at room temperature was obtained.

Comparative Example-1 2,2-'thiodiethanol 430 used in Example-1
The same procedure as in Example 1 was carried out except that 268 g of propylene glycol was used instead of 5 g. 1155 g of a polymerizable oligomer which was viscous at room temperature and was in a liquid state was obtained.

Table 1 shows the analytical values of the polymerizable oligomers obtained in Examples and Comparative Examples. 100 parts of the polymerizable oligomers obtained in Examples and Comparative Examples were mixed with 2 parts of dicumyl peroxide, and cured by cast polymerization using a cellophane-covered glass plate at 130°C for 1 hour and 160°C for 2 hours. An organic glass molded article was obtained. Table 2 shows the physical properties of each example and comparative example.
Shown below.

[0047]

[Table 1]

[0048]

[Table 2]

The various physical properties were measured using the following test methods. 1. Transmittance was measured according to ASTM D-1003. 2. The refractive index and Abbe number were measured using an Abbe refractometer (manufactured by Atago). 3. Surface hardness (pencil hardness) According to JISK-5400, carried out at a load of 1 kgf,
Indicated by the highest pencil hardness that will not cause scratches. 4. Impact Resistance In accordance with the falling weight impact test method of JISK-7211, a test was conducted using a DuPont impact tester (manufactured by Toyo Seiki Seisakusho) with a test piece thickness of 3 mm and a falling weight mass of 500 g, and the 50% fracture height was determined. I asked for

[0050]

Effects of the Invention The present invention provides an organic glass that contains sulfur atoms and is suitable as an optical material having a high refractive index and excellent impact resistance, which can be used for eyeglass lens materials and other optical materials. The present invention provides a novel allyl oligomer and a method for producing the same, and when the allyl oligomer containing sulfur atoms of the present invention is used, it has a higher refractive index and improved impact resistance compared to conventional organic glasses. Therefore, it can be used not only in eyeglass lenses but also in fields where optical properties are important, such as prisms and optical discs, and its industrial value is enormous.

[Brief explanation of the drawing]

FIG. 1 shows a 1 H NMR chart of the allylic oligomer of the present invention.

Claims (4)

[Claims] Claim 1: An allylic oligomer having the following structural formula. CH2=CHCH2O(COACOOR1SR2O)n
COACOOCH2CH=CH2 [where A is an organic residue derived from a divalent carboxylic acid, R1 and R2 are divalent organic residues derived from an aliphatic hydrocarbon having 2 to 10 carbon atoms, n represents a number from 1 to 20] [Claim 2] An oligomer having an allyl ester group at the end and having the following repeating units, -
(COACOOR1SR2O)-
Structure-I-(COACOO)xZ-O-COACOO-
Structure - B [However, A is an organic residue derived from a divalent carboxylic acid, R1 and R2 have 2 to 1 carbon atoms
A divalent organic residue derived from an aliphatic hydrocarbon consisting of 0;
The range is 0 to 100%, the rest is structure-B, and G
PC (gel permeation chromatography)
Polystyrene equivalent number average molecular weight (Mn) measured by method
is 500 to 15,000, and the weight average molecular weight (MW)
is 1000 to 70000, and the ratio of MW/Mn is 1
．． An allylic oligomer having a molecular weight of 2 to 20.0. 3. Transesterification of a divalent carboxylic acid dimethyl or diethyl ester, a sulfur atom-containing divalent polyol, optionally one or more divalent or higher saturated aliphatic polyols, and allyl alcohol. 1. A method for producing an allyl oligomer containing a sulfur atom, which is obtained by reacting in the presence of a reaction catalyst while distilling off methanol or ethanol. 4. A divalent carboxylic acid diallyl ester, a divalent polyol containing a sulfur atom, and optionally one or more types of saturated aliphatic polyols having a valence of more than 2 in the presence of a transesterification catalyst. A method for producing an allyl oligomer containing a sulfur atom, which is obtained by reacting while distilling off allyl alcohol.