JP3447080B2 - Vinyl phenyl compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] This invention relates to a polymerizable monomer.
Is useful as an optical material, and paints, inks,
Useful for adhesives, rubber vulcanizing agents, photosensitive resins, crosslinking agents, etc.
It relates to a novel vinylphenyl compound. [0002] 2. Description of the Related Art Conventionally, organic glass replaces inorganic glass.
Various studies have been conducted, but there are many disadvantages
No satisfactory properties have been obtained. For example,
Tyl methacrylate or diethylene glycol bis (ant
Polymerization of a monomer mainly composed of
The body is used as an optical material or lens,
The refractive index is as low as about 1.50. In recent years, in order to increase the refractive index, a monomer molecule has been used.
Considering the introduction of aromatic rings and sulfur atoms into the structure
For example, JP-A-3-157361 discloses the following:
formula [0004] Embedded image [0005] Sulfur-containing styrene derivatives as shown by
Have been proposed. However, on
The resin has a strong sulfur odor during polishing and molding, and is practical
Was not. Also, Japanese Patent Application Laid-Open No. 4-4211 discloses the following.
Notation [0006] Embedded image (Where R is an alkylene having 1 to 6 carbon atoms)
Sulfur-containing styrene derivatives such as
Resins obtained by polymerizing conductors have been proposed. But
In the styrene derivative, R in the molecule is the above alkylene.
In the case of a compound with an amino group, the length of the molecule is excessively long.
You. Therefore, the resin obtained by polymerizing the styrene derivative is:
Low physical properties such as heat resistance and impact resistance.
It was unsatisfactory. [0008] The prior art as described above
Below, a resin that can be suitably used for optical
High refractive index, high Abbe number, low specific gravity, heat resistance,
Excellent impact, light resistance and hard coat properties, resin polishing
There is a strong demand for materials that do not have a bad smell during molding. Therefore, the problem to be solved by the present invention
Is a polymerizable unit that can be a raw material for a resin having the above properties.
Is to provide a monomer. [0010] Means for Solving the Problems The present inventors have solved the above problems.
As a result of intensive research to overcome the
Vinyl with specific vinylphenyl structure having sil group
Is a novel polymerizable monomer that can achieve the above object.
And came to propose the present invention. That is, the present invention provides the following formula (1) [0012] Embedded image (However,k is 0,n is an integer of 0 or more
And m is 1 or 2).
Is a phenyl compound. In the present invention, the compound represented by the general formula (1)k is 0
You. Also,n may be an integer of 0 or more,
With the increase, the refractive index and heat resistance of the resin decreased.
Therefore, preferably 0 to 4, particularly 0 to 2 is suitable. What
When k and n are 0,-(CH₂)-Indicates a bond
You. The vinylphenyl compound of the present invention is specifically described
An example is as follows. 1,3-bis (4,4'-vinylphenyl)
Thio) -2-propanol, 1,6-bis (4,4′-
Vinylphenyl) -1,5-dithio-3-hexano
, 1,10-bis (4,4'-vinylphenyl)-
1,5,9-trithio-3,7-decanediol, 1,
7-bis (4,4'-vinylphenylthio) -4-thio
-2,6-heptanediol and the like. Furthermore, bis (4,3 ') of these compounds
-Vinyl) isomer and bis (3,3'-vinyl) isomer
The body can be mentioned. The compound of the present invention represented by the general formula (1)
The structure of the object can be confirmed by the following means. (A) Measurement of infrared absorption spectrum (IR)
By doing, 3550-3200cm^-1O-
Absorption based on H bond, 3150-2800 cm^-1Near
Absorption based on CH bond, 1650-1600 cm^-1Attached
Observe absorption near the terminal unsaturated hydrocarbon groups
Can be. (B)¹H-nuclear magnetic resonance spectrum (¹H-
NMR) to obtain the compound represented by the general formula (1).
Of hydrogen atoms present in the compounds of the present invention
You can know. That is, the compound of the present invention¹H-N
When measured by MR, the water on the aromatic ring was found near δ 7.4 ppm.
Peaks based on elemental atoms were observed, and δ 5.0 to 7.0 p
In pm, a peak based on a hydrogen atom derived from a vinyl group was found.
Can be In addition, each δ peak intensity is relatively compared.
By comparing the number of hydrogen atoms of each bonding group,
You can know. (C) By elemental analysis, carbon, hydrogen and
Calculate each weight percent of sulfur and further recognize the weight of each element
% Of oxygen by subtracting the sum of% from 100
Can be calculated, thus determining the composition formula of the compound
can do. Vinylphenylation represented by the general formula (1)
The compound may be obtained by any method.
The following methods can be mentioned when describing the manufacturing method.
You. When m = 1, the general formula (2) [0024] Embedded image (Where p is an integer of 0 or more).
Compound in the presence of sodium hydroxide
It is a method of reacting with drin. The compound represented by the general formula (2)
The molar ratio of rohydrin is usually 1 epichlorohydrin.
It is common to react 2 moles of (2) with respect to moles.
You. When m = 2, it is represented by the general formula (2).
Compound in the presence of sodium hydroxide
After reacting with phosphorus, the mixture is
This is a method for reacting. The compound represented by the general formula (2)
The charged molar ratio of rohydrin is usually epichlorohydrin.
1 mole of (2) is reacted for 1 mole, and further used.
(2) 1 mole of sodium sulfide was reacted with 2 moles
It is common to use In the above reaction, an organic solvent is generally used.
Is preferred. What is suitably used as the solvent
For example, methanol, ethanol, 1-propanol
And alcohols such as 2-propanol;
And hydroxide and dimethylformamide.
You. The temperature in the above reaction depends on the type of raw material, solvent
Generally, -40 to 80 ° C is preferable.
Good. The reaction time also depends on the type of raw materials,
Reacting the compound of general formula (2) with epichlorohydrin
Or reacting this reactant with sodium sulfide
In any case, usually from 10 minutes to 24:00
Time, preferably in the range of 30 minutes to 12 hours.
Minutes. During the reaction, stirring is preferable.
No. The desired product from the reaction system, that is, the above-mentioned general formula
The method for isolating and purifying the compound represented by (1) is particularly limited.
Instead, a known method can be adopted. The compound of the present invention represented by the general formula (1)
The material has high refractive index, high Abbe number, low specific gravity, heat resistance, light resistance,
A resin with excellent hard coat properties and no odor during polishing and molding
give. Using the vinylphenyl compound of the present invention,
When obtaining scientific materials, especially lens materials, the general formula
Unsaturation capable of radical copolymerization with the compound represented by (1)
Copolymerization with the monomer may be used. Illustrate the monomer
Then, it is as follows. In addition, acrylate and meta
The acrylate is generically referred to as (meth) acrylate.
Methyl (meth) acrylate, benzyl (meth) acrylate
, Phenyl (meth) acrylate, 2-hydroxyethyl
(Meth) acrylate, ethylene glycol di
T) acrylate, diethylene glycol di (meth) a
Acrylate, glycidyl (meth) acrylate, bisph
Enol-A dimethacrylate, 2,2-bis (4-
(Meth) acryloyloxyethoxyphenyl) propa
2,2-bis (3,5-dibromo-4- (meth) a
(Meth) such as acryloyloxyethoxyphenyl) propane
(T) acrylic acid ester compound; methylthio (meth) a
Acrylate, phenylthio (meth) acrylate, ben
Dilthio (meth) acrylate, ethanedithioldithio
E (meth) acrylate, benzenedithioldithio
(Meth) acrylate, xylylenedithioldithio
Thio (meth) acrylate such as (meth) acrylate
Ter compound: diallyl phthalate, diallyl terephthale
, Diallyl isophthalate, diallyl tartrate, epo
Diallyl succinate, diallyl malate, allylsin
Namate, allyl isocyanurate, chlorendate dia
Ryl, diallyl hexaphthalate, diallyl carbonate
Allylic compounds such as allyl diglycol carbonate
Styrene, divinylbenzene, chlorostyrene, α
-Methylstyrene, vinylnaphthalene, isopropenyl
Properties of naphthalene, bromostyrene, dibromostyrene, etc.
Aromatic vinyl compound; two or more (meth) acrylate groups
Having urethane (meth) acrylate or epoxy
(Meth) acrylate and the like. These monomers
Can be used alone or in combination of two or more. In the present invention, optical materials, especially lenses
When obtaining the material, the composition ratio of the monomer is determined by the general formula (1)
Is 20 to 100% by weight, especially 3% by weight.
It is preferably used in the range of 0 to 95% by weight. The compound of the present invention represented by the general formula (1)
The polymerization method of the polymerizable composition containing the product is not particularly limited,
Known casting polymerization methods can be employed. The polymerization initiation means is a seed
Radical polymerization initiators such as various peroxides and azo compounds
Use or irradiation of ultraviolet rays, α-rays, β-rays, γ-rays, etc.
Can be performed by a combination of the two. Typical polymerization
Illustrative methods include elastomer gaskets or spares.
Between the molds held by the
The polymerizable composition containing the initiator is injected, and the mixture is cured in an air furnace.
After the polymerization, a cast polymerization to be taken out is employed. The radical polymerization initiator is not particularly limited.
No known ones can be used.
Then, benzoyl peroxide, p-chlorobenzo
Il peroxide, decanoyl peroxide, lau
Diyl peroxide, acetyl peroxide, etc.
Acyl peroxide; t-butylperoxy-2-e
Tyl hexanoate, t-butyl peroxydicarbonate
, Cumyl peroxy neodecaneate, t-butyl par
Peroxyesters such as -oxybenzoate; diiso
Propyl peroxydicarbonate, di-2-ethyl
Xyl peroxydicarbonate, di-sec-butyl
Percarbonates such as peroxydicarbonate;
2,2'-azobisisobutyronitrile, 2,2'-a
Zobis (4-methoxy 2,4-dimethylvaleronitrile
), 2,2'-azobis (2,4-dimethylvaleroni
Tolyl), 2,2'-azobis (2-methylbutyronito
Ryl), 1,1'-azobis (cyclohexane-1-ca)
-Bonitrile). The radical polymerization
The amount of the initiator used depends on the polymerization conditions, the type of the initiator,
It depends on the type and composition of the compatible composition, and is generally limited
No, but generally 100 parts by weight of all monomers
It is preferable to use it in the range of 0.01 to 10 parts by weight. Among the polymerization conditions, particularly the temperature depends on the resin obtained.
Affects the properties of This temperature condition depends on the type of initiator
As it is affected by the amount and type of monomer,
Can not be limited, but generally starts polymerization at relatively low temperature
And slowly raise the temperature until the end of the polymerization.
It is preferable to perform a so-called taper type two-stage polymerization in which
Suitable. The polymerization time depends on various factors as well as the temperature.
The optimal time according to these conditions in advance.
It is preferred to determine
It is preferable to select the conditions so that is completed. Also, by a known photopolymerization using ultraviolet rays,
Casting polymerization can be carried out similarly. In this case, photopolymerization
Benzoin, benzoin methyl ether as initiator,
Benzoin butyl ether, benzophenol, aceto
Phenone, 4,4'-dichlorobenzophenone, diet
Xyacetophenone, 2-hydroxy-2-methyl-1
-Phenylpropan-1-one, benzylmethylketter
1- (4-isopropylphenyl) -2-hydroxy
C-2-methylpropan-1-one, 1-hydroxy
Clohexyl phenyl ketone, 2-isopropylthioki
Sandton and the like. These photopolymerization initiators are
0.001 to 5 parts by weight based on 100 parts by weight of the monomer.
It is common to use the box. Of course, during the polymerization, a releasing agent and an ultraviolet absorbing agent are used.
Absorbent, antioxidant, anti-coloring agent, antistatic agent, fluorescent dye
Various stabilizers such as ingredients, dyes and pigments, and additives such as fragrances are required
It can be selected and used according to. The resin obtained by the above method is
The following processing can be performed according to the application. Immediately
Dyeing using dyes such as disperse dyes, silane coupling
Agents, silicon, zirconium, antimony, aluminum
Hard coating agent mainly composed of sol of oxide such as chromium
Or with a hard coat agent containing an organic polymer as a main component
Hard coating treatment, SiO_Two, TiO_Two, ZrO
_TwoOf metal oxide thin films and organic polymer thin films
Processing such as anti-reflection treatment and anti-static treatment by coating etc. and
Secondary processing can also be performed. Further, the above-mentioned general formula (1) of the present invention is included.
When polymerizing the polymerizable composition, the heat resistance of the resulting resin and
Isocyanate compound in the composition to improve impact resistance
Things can also be added. The isocyanate compound
For example, ethylene diisocyanate, trimethylene
Diisocyanate, tetramethylene diisocyanate,
Hexamethylene diisocyanate, 2,2-dimethylpe
Butane diisocyanate, butene diisocyanate,
(Isocyanatoethyl) carbonate, bis (iso
Cyanate ethyl) ether, xylylene diisocyanate
, Α, α, α ', α'-tetramethylxylylenediene
Isocyanate, bis (isocyanateethyl) benzene
, Bis (isocyanatopropyl) benzene, bis
(Isocyanatomethyl) naphthalene, bis (isocyanate)
Natemethyl) diphenyl ether, bis (isocyanate)
Ethyl) phthalate, mesitylylene triisocyanate
Aliphatic polyisocyanates such as
Cyanate, bis (isocyanatomethyl) cyclohex
Sun, dicyclohexylmethane diisocyanate, cyclone
Rohexanediisocyanate, 2,2'-dimethyldisi
Chlohexylmethane diisocyanate, bis (4-iso
Cyanate-n-butylidene) pentaerythritol,
2-isocyanatomethyl-3- (3-isocyanate
Propyl) -5-isocyanatomethyl-bicyclo-
[2,2,1] Alicyclic polyisocyanate such as heptane
G, phenylene diisocyanate, tolylene diisocyanate
Nitrate, ethyl phenylene diisocyanate, dimethyl
Phenylenediisocyanate, diethylphenylenediyl
Socyanate, trimethylbenzene triisocyanate
G, naphthalene diisocyanate, methyl naphthalene di
Isocyanate, biphenyl diisocyanate, toluy
Zindiisocyanate, 4,4'-diphenylmethanedi
Isocyanate, 3,3'-dimethyldiphenylmethane
-4,4'-diisocyanate, bibenzyl-4,4 '
-Diisocyanate, diphenylmethane-2,4,4 '
-Triisocyanate, diphenyl ether diisocyanate
, Ethylene glycol diphenyl ether diiso
Cyanate, benzophenone diisocyanate, carba
Aromatic polyisocyanates such as sol diisocyanate
G, thiodiethyl diisocyanate, thiodipropyl di
Isocyanate, dimethyl sulfone diisocyanate
And sulfur-containing aliphatic compounds such as dithiodipropyl diisocyanate
Isocyanate, diphenyl sulfide-2,4'-di
Isocyanate, diphenyl sulfide-4,4'-di
Isocyanate, bis (4-isocyanatomethylben
Zen) sulfide, 3,3'-dimethoxy-4,4'-
Aromatic compounds such as diisocyanate dibenzyl thioether
Sulfide isocyanate, diphenyl disulfide-
4,4'-diisocyanate, 3,3'-dimethyldiph
Enyl disulfide-5,5'-diisocyanate,
4,4'-dimethoxydiphenyl disulfide-3,
Aromatic disulfide-based iso such as 3'-diisocyanate
Cyanate, diphenylsulfone-4,4'-diisocy
Annate, diphenylmethanesulfone-4,4'-dii
Socyanate, 4-methyldiphenylsulfone-2,
4'-diisocyanate, 4,4'-dimethoxydife
Nyl sulfone-3,3'-diisocyanate, 4,4 '
-Dimethyldiphenylsulfone-3,3'-diisocyanate
Nate, 4,4'-methoxybenzene ethylene sulfone
Aromatic sulfones such as -3,3'-diisocyanate
Socyanate and the like. Urethane with the above compounds
It is preferable to use a catalyst for the
The catalyst is not particularly limited, and a known catalyst may be used.
it can. Further, the hardness and dyeability of the resulting resin,
Contains isocyanate compound to improve impact
A polyol can also be added to the composition. The poly
Examples of all compounds include ethylene glycol and die
Tylene glycol, propylene glycol, butylene
Recall, glycerin, trimethylolethane, trime
Tyrol propane, pentaerythritol, dipentae
Risuritol, sorbitol, xylitol, hexane
Triol, diglycerol, triglycerol, tri
(2-hydroxyethyl) isocyanurate, cyclo
Butanediol, cyclopentanediol, cyclohexene
Sundiol, tricyclo [5,2,1,0^2.6] Deca
Dimethanol, dicyclohexanediol, hydroxy
Cypropyltricyclo [5,3,1,1] dodecano
, Cyclohexanetriol, dihydroxynaphthale
, Trihydroxynaphthalene, dihydroxybenze
, Biphenyltetraol, pyrogallol, bisphe
Nord A, xylylene glycol, di (2-hydroxy
Ethoxy) benzene, bisphenol A-bis (2-h
Droxyethyl ether) and the like. [0044] Further, a diamine containing a polyol sulfur atom
Examples of polyols having higher performance include bis [4- (H
Droxyethoxy) phenyl] sulfide, bis [4-
(2,3-dihydroxypropoxy) phenyl] sulf
Sulfide, bis (2-hydroxyethyl) sulfide, 1,
2-bis (2-hydroxyethylthio) ethane, bis
(2-hydroxyethyl) disulfide, 1,4-dithi
An-2,5-diol, bis (2,3-dihydroxy
Propyl) sulfide, tetrakis (4-hydroxy-
2-thiabutyl) methane, bis (4-hydroxyphenyl)
L) sulfone, 1,3-bis (2-hydroxyethylthio)
Oethyl) cyclohexane and the like. An isocyanate compound is added to the polymerizable composition.
When adding, (number of all hydroxyl groups in the composition) / (a
The number of isocyanate groups of the cyanate compound) is 0.5
~ 20, further added in the range of 0.8 ~ 10
Is preferred. Isocyanate in isocyanate compound
Of all hydroxyl groups in the polymerizable composition to the total number of groups
When the total number is less than 0.5, the urethanization reaction proceeds sufficiently.
Improve the hardness, heat resistance and impact resistance of the obtained resin without performing
Not only because the isocyanate group remains in the resin,
Moldability deteriorates, which is not preferable. More than 20
And urethane bonds in the resin are reduced, and sufficient effect is obtained.
I can't. [0047] The specific vinyl phenyl compound of the present invention
Has high refractive index, high Abbe number, low specific gravity, heat resistance,
Gives resin excellent in impact resistance, light resistance and hard coat properties
It is useful as a monomer. Also obtained from this monomer
The polished resin does not generate an odor or the like at the time of polishing and molding.
The reason why odor does not occur when polishing and molding resin is
Although it is not clear, the inventors of the present invention
Hydrogen contained in the above-mentioned vinylphenyl compound
It is presumed to be due to the effect of the xyl group. Therefore, the vinylphenyl compound of the present invention
Or copolymerization of the compound with an unsaturated monomer
Body, furthermore, said compound and isocyanate compound and poly
Copolymers with all are useful as organic glass,
For example, optical lenses such as spectacle lenses and optical device lenses
And prisms, optical disc substrates, optical
It can be suitably used for applications such as fiber. [0049] DESCRIPTION OF THE PREFERRED EMBODIMENTS In the following, in order to specifically explain the present invention, actual
The present invention will be described by way of examples, but the present invention is limited to these examples.
It is not specified. The vinyl phenol obtained in the examples was used.
Nyl compound and resin using the compound were tested as follows.
Various physical properties were measured by the method. (1) IR spectrum DIGILAB FTS-7 type Foury made by BIO-RAD
Use KBr method or liquid film method with d-conversion infrared spectrophotometer
It measured using. (2)¹H-NMR spectrum PXM-60SI type (60MHz) manufactured by JEOL Ltd.
Dilute the sample in CDCl3 using
Was used as an internal standard. (3) Elemental analysis Use CHN coder MT-2 type manufactured by Yanagimoto Seisakusho
Analysis of carbon and hydrogen, and sulfur and phosphorus
The measurement was performed using the Lasco combustion method. (4) Refractive index and Abbe number At 20 ° C using Abago refractometer manufactured by Atago Co., Ltd.
The refractive index and Abbe number were measured. Bromona in contact liquid
Phthalin or methylene iodide was used. (5) Appearance It was determined visually. (6) Specific gravity Electronic hydrometer (ED-120T) manufactured by Mirage Trading Co., Ltd.
Type) (7) Light fastness Long life xenon fade maker manufactured by Suga Test Machine Co., Ltd.
100 hours after placing the sample in the sampler (FAC-25AX-HC type)
After exposing to xenon light, color difference meter manufactured by Suga Test Instruments Co., Ltd.
Measure the YI of the sample with (SM-4) and compare it with the initial YI.
The amount of increase ΔYI. (8) Impact resistance 127cm height on a 2mm thick, 65mm diameter sample plate
The steel ball is dropped when the sample plate is broken.
1, 20 to 40 g when the weight is 20 g or less
2, 40 to 60 g, 3, 60 to 80 g
The case of 4, 80 g or more was evaluated with 5. (9) Hard coat properties Hard coat liquid (trade name: TS-56T, Soda Tokuyama)
Using a sample that can be hard-coated on the sample
、, those that could not be hard-coated were evaluated with x. (10) Heat resistance Insert the molded resin into the frame and heat to 120 ° C
After that, those without frame misalignment are marked with ○ and those with frame misalignment are marked with ×
evaluated. (11) Odor A ball mill made by Tokyo Optical Machinery Co., Ltd. (TOPCON ALE)
-60), the sample was balled. Terrible stench
1 that stinks, 2 stinks, slightly stinks
3 to do, 4 to almost no odor, totally odorless
Was rated on a scale of 5. Embodiment 1(Note that this embodiment is a reference example.
You. ) Three-port flap equipped with thermometer, stirrer and dropping funnel
45.0 g of 4-vinylbenzylmercaptan in sco
(0.300 mol) and epichlorohydrin 13.9
g (0.150 mol) and ethanol 400m
and cooled to 0 ° C. Do not mix the reaction solution well.
Sodium hydroxide aqueous solution (0.500 mol) 1
00 ml was slowly added dropwise. At this time, the reaction temperature was 10 ° C.
After completion of the dropwise addition, the mixture was further stirred at 30 ° C. for 1 hour.
Was. Thereafter, the reaction mixture is poured into water and extracted with ether.
And the organic layer is washed with dilute hydrochloric acid and dilute sodium carbonate aqueous solution.
After that, it was washed with water. Dry the organic layer over anhydrous magnesium sulfate
After drying, the solvent is distilled off under reduced pressure to give a pale yellow solid.
Got a body. This was recrystallized from heptane to form a colorless plate.
31.6 g of crystals (59% yield) were obtained. In the IR spectrum of this, 16
30cm^-1Absorption due to C = C bond, 3488 cm^-1
The absorption due to the -OH bond was observed in Fig. 1 (Fig. 1). The 1H-NMR spectrum of this product
(CDCl_ThreeIn solvent, tetramethylsilane standard, pp
m), many peaks derived from vinyl groups were found at δ 5 to 7 ppm.
As heavy lines (6H: a), due to aromatic ring at δ7.3 ppm
Next peak as a single line (8H: b), δ 3.7 pp
a single peak derived from the benzyl and alkyne protons
As one line (5H: c, e), δ 2.5 to 2.9 ppm
Multiple lines with peaks derived from methylene and hydroxyl groups
(5H: d, f) was observed (FIG. 2). Further, elemental analysis values (() indicate calculated values.
You. ) Indicates C: 70.53% by weight (70.74), H:
6.64% by weight (6.78), S: 18.20% by weight
(17.99), which was in good agreement with the calculated value. From the above results, the obtained crystals were as follows:
1,3-bis (4,4'-vinylbenzen represented by the structural formula
(Dilthio) -2-propanol (hereinafter abbreviated as VBP)
Was confirmed. [0066] Embedded image Embodiment 2(Note that this embodiment is a reference example.
You. ) Three-port flap equipped with thermometer, stirrer and dropping funnel
30.0 g of 4-vinylbenzyl mercaptan
(0.200 mol) and 18.5 epichlorohydrin
g (0.200 mol) and 200 m of ethanol
and cooled to 0 ° C. Do not mix the reaction solution well.
Sodium hydroxide aqueous solution (0.020 mol) 1
5 ml was gradually added dropwise. At this time, the reaction temperature is 10 ° C or less.
After completion of the dropwise addition, the mixture was further stirred at 30 ° C. for 1 hour.
Was. Next, the reaction solution was heated to 50 ° C.
7.8g (0.100mol) of 50ml aqueous solution
It was dripped slowly. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour.
Then, using the obtained reaction solution, in the same manner as in Example 1.
Separation, purification and recrystallization gave 22.7 g of colorless plate crystals (yield
51%). In the IR spectrum of this, 16
31cm^-1Absorption due to C = C bond, 3486 cm^-1
The absorption due to the -OH bond was observed. The 1H-NMR spectrum of this product
In the figure, a peak derived from a vinyl group appears at multiple lines at δ5 to 7 ppm.
As (6H: a), δ7.3 ppm derived from an aromatic ring
Peak at δ 3.8 ppm as a single line (8H: b)
Single line peaks from benzyl and alkyne protons
(6H: c, e) to δ 2.5 to 2.9 ppm
Peaks derived from styrene and hydroxyl groups are
(10H: d, f, g) was observed. Further, the elemental analysis values (() indicate calculated values.
You. ) Indicates C: 64.69% by weight (64.53), H:
6.71% by weight (6.77), S: 21.39% by weight
(21.34), which was in good agreement with the calculated value. From the above results, the obtained crystal was
1,7-bis (4,4'-vinylbenzene) represented by the structural formula
(Dilthio) -4-thio-2,6-heptanediol (hereinafter referred to as "dithio")
Below, abbreviated as VBH). [0072] Embedded image Examples 3 to 7(Note that Example 4 is a reference example.
is there. ) In Example 1 or Example 2, the raw material 4-vinyl
Rubenzyl mercaptan to various compounds shown in Table 1.
Modified and described in detail in Example 1 or Example 2.
In the same manner as described above, the vinylphenyl
Compound was synthesized. Table 1 shows the obtained vinyl foil.
The properties of the phenyl compound and the results of elemental analysis are also shown. The abbreviations in Table 1 represent the following compounds
Is shown. .Synthetic compounds VPP: 1,3-bis (4,4'-vinylphenylthio)
E) -2-propanol [0076] Embedded image VPN: 1,9-bis (4,4'-vinyl
Phenyl) -3,7-dithio-5-nonanol [0078] Embedded image VPH: 1,6-bis (4,4'-vinyl
Phenyl) -1,5-dithio-3-hexanol [0080] Embedded image VPD: 1,10-bis (4,4'-vinyl)
Ruphenyl) -1,5,9-trithio-3,7-decane
Diol [0082] Embedded imageVPHP: 1,7-bis (4,4'-vinyl)
Ruphenylthio) -4-thio-2,6-heptane [0084] Embedded image Raw materials VBM: 4-vinylbenzyl mercaptan VPM: 4-vinylphenyl mercaptan VPEM: 2- (4-vinylphenyl) ethyl mercap
Tan [0086] [Table 1][0087] [Table 2]Application Example 1 The compound obtained in Example 1 and its 3,3'-isomer
To 100 parts by weight of the mixture of 3,4'-isomers
T-butyl peroxy- as a radical polymerization initiator
Add 1 part by weight of 2-ethylhexanate and mix well
Was. This mixed solution is mixed with a glass plate and ethylene-vinyl acetate
Injected into a mold composed of gaskets consisting of coalescing
Then, cast polymerization was performed. Polymerization is performed in an air oven at 30 ° C
To 90 ° C gradually over 18 hours, 9
It was kept at 0 ° C. for 2 hours. After the polymerization, remove the mold from the air furnace.
Remove, allow to cool, remove polymer from mold glass
Was. The obtained polymer is colorless and transparent, and has a refractive index of
(N_D ²⁰1.647, Abbe number 29, specific gravity 1.19
Yes, light resistance, hard coat property, heat resistance
The degree of impact is3And the degree of odor was 4. Application Examples 2 to 16 Vinyl obtained in Examples 1 to 8 in the same manner as in Application Example 1.
Phenyl compound homopolymer or copolymerizable vinyl
A copolymer with a monomer was obtained. The physical properties of the obtained polymer
2 is shown. Incidentally, as a copolymerizable vinyl monomer,
The following abbreviations were used. St: styrene BzMA: benzyl methacrylate HEMA: 2-hydroxyethyl methacrylate 2G: diethylene glycol dimethacrylate Comparative application examples 1 and 2 In the same manner as Application Example 1, VBDD: 1,10-bis (4,4'-vinylbenzyl
Thio) -4,7-dithio-2,9-decanediol [0093] Embedded image Or VBE: 1,2-bis (4,4'-vinylbenzylthio)
E) ethane [0095] Embedded image Of the vinylphenyl compound represented by
A coalescence was obtained. Table 2 shows the physical properties of the obtained polymer. [0097] [Table 3]Application Example 17 80 parts by weight of the compound obtained in Example 1 and isocyanate
20 parts by weight of xylylene diisocyanate as a compound
Radical polymerization initiator based on 100 parts by weight of mixture
T-butyl peroxy-2-ethylene hexanate 1
Parts by weight and dilauric acid di-
Add 0.01 part by weight of n-butyltin and mix well.
Was. This mixed solution is mixed with a glass plate and ethylene-vinyl acetate
Injected into a mold composed of gaskets consisting of coalescing
Then, cast polymerization was performed. Polymerization is performed in an air oven at 30 ° C
To 90 ° C gradually over 18 hours, 9
It was kept at 0 ° C. for 2 hours. After the polymerization, remove the mold from the air furnace.
Remove, allow to cool, remove polymer from mold glass
Was. The obtained polymer is colorless and transparent, and has a refractive index of
(N_D ²⁰) 1.637, Abbe number 29, specific gravity 1.21
Yes, light resistance, hard coat property, heat resistance
The degree of impact was 4 and the degree of odor was 5. Application Examples 18 to 27 In the same manner as in Application Example 17, the vias obtained in Examples 1 to 4 were
Nylphenyl compounds and isocyanate compounds,
With polyol and copolymerizable vinyl monomer
A coalescence was obtained. Table 3 shows the physical properties of the obtained polymer. The isocyanate compound and polio
The tools indicated by the following abbreviations were used. • Isocyanate compound XDI: Xylylene diisocyanate HDI: Hexamethylene diisocyanate ・ Polyol β-TG: β-thiodiglycol [0103] [Table 4]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a chart of an infrared absorption spectrum of the vinylphenyl compound of the present invention obtained in Example 1. FIG. 2 is a chart of ¹ H-nuclear magnetic resonance spectrum of the vinylphenyl compound of the present invention obtained in Example 1.

Continued on the front page (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 323/16 C07C 323/18 C08F 12/30 CAPLUS (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] (Claim 1) The following formula (1) (Where k is 0, n is an integer of 0 or more, and m is 1 or 2).