JPH06340616A - New ethylenic unsaturated monomer - Google Patents

Abstract

PURPOSE:To obtain a compound having low viscosity, high refractive index and high polymerization rate. CONSTITUTION:This ethylenic unsaturated monomer comprises an acrylic acid or methacrylic acid ester of an aromatic substituent group-containing thioether alcohol. The ethylenic unsaturated monomer is usable as a diluent to be mixed with a polymer in the field requiring a high refractive index such as optical lens and high refractive index can be consistent with high polymerization rate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photopolymerizable monomer which gives a polymer having a low viscosity, a high polymerization rate and a high refractive index.

[0002]

2. Description of the Related Art Photopolymerizable monomers are currently used in a wide variety of fields to provide polymers used as paints, inks, adhesives, optical fibers or optical lenses.

Polymers for these applications may be made directly by polymerization of the corresponding monomers, but are often made by the method of making the final polymer in the form of its oligomers, as described below. This is especially the case when trying to introduce a polymer structure.

Polymers and plastics used in these fields are required to have excellent performances such as robustness, flexibility, and impact resistance. In order to meet these requirements, it has been attempted to introduce a structure suitable for various performances such as polyurethane, polyether, polyester, and polycarbonate into the polymer molecule, and in order to introduce such a structure into the final polymer, Generally, it has been often practiced to introduce these polymer structures into photopolymerizable monomers to form oligomers or to combine oligomers having these polymer structures with photopolymerizable polymers.

On the other hand, there is a method such as casting or coating for simultaneously performing the formation (that is, polymerization) and the molding of the polymer, and when the method using a so-called "syrup" composed of a polymer solution or an oligomer is applied. It is desirable that the syrup has a low viscosity to facilitate the work. However, the structure-introduced oligomer as described above often has a high viscosity due to the structure introduced. Therefore, at present, such an oligomer is usually used by mixing it with a diluent to reduce the viscosity. Diluents used in this application include copolymerizable ethylenically unsaturated monomers such as monofunctional (meth) acrylates such as methyl methacrylate and hydroxyethyl (meth) acrylate, and vinyl monomers such as N-vinylpyrrolidone and There are styrene, etc.

[0006]

However, the conventional diluent as described above has a high refractive index such as an optical lens made of a produced polymer due to the low refractive index of its polymer, rather than that of itself. It is difficult to use in the field where the index is required, and there is a problem that the polymerization rate is slow with those that give a polymer with a high refractive index, for example, styrene, and it can be used as a diluent that has both a high refractive index and a high polymerization rate. It has been desired to provide compounds.

[0007]

[Means for Solving the Problems]

[Summary of the Invention] <Summary> The present invention aims to provide a solution to the above points, and achieves this object by a specific (meth) acrylic acid ester, that is, an ester of a thioether alcohol having an aromatic substituent. Is what you are trying to do.

That is, the ethylenically unsaturated monomer according to the present invention comprises an ester of acrylic acid or methacrylic acid of a thioether alcohol having an aromatic substituent.

<Effect> The compound according to the present invention is a compound having a low viscosity, a high polymerization rate and a polymer having a high refractive index. The compound according to the present invention can be used as a monomer that simultaneously satisfies the requirements concerning the refractive index and the polymerization rate, or as a copolymerizable diluent.

DETAILED DESCRIPTION OF THE INVENTION <Novel (Meth) Acrylate (Definition)> The ethylenically unsaturated compound according to the present invention is a (meth) acrylic acid (that is, acrylic acid or methacrylic acid) of a thioether alcohol having an aromatic substituent. Acid) ester.

The ethylenic compound is preferably a compound represented by the following general formula [I]. ^{Ph 0 -R 1 -S-R 2} -O-CO-C (R 3) = CH 2 [I] ^{wherein, Ph 0, R 1, R} 2 and R ³ have the following meanings. Ph ⁰ : Phenyl group which may be substituted with up to 5 halogen atoms R ¹ : Hydrocarbon chain having 0 to 6 carbon atoms R ² : Hydrocarbon chain having 6 carbon atoms R ³ : Hydrogen or methyl group

R ¹ and R ² may be straight hydrocarbon chains or hydrocarbon chains having side chains, or cyclic hydrocarbons or unsaturated hydrocarbon groups such as phenylene groups, as long as they have no reactivity. But good. Further, it may be a hydrocarbon chain substituted as necessary.

When there is a halogen atom bonded to the benzene nucleus, its position may be any position of ortho, meta and para. The halogen atom to be replaced is preferably chlorine, bromine or fluorine. In particular, it may be substituted with two or more kinds of halogen atoms, but from the viewpoint of synthesis,
Those substituted with one type of halogen are preferred.

Specific examples of these include the following compounds. (1) Phenylmethylthioethyl = (meth) acrylate (Ph ⁰ : phenyl, R ¹ : C ₁ , R ² : C ₂ ) (2) p-chlorophenylmethylthioethyl = (meth) acrylate (3) o-chlorophenyl Methylthioethyl = (meth) acrylate (4) m-chlorophenylmethylthioethyl = (meth) acrylate (5) p-bromophenylmethylthioethyl = (meth) acrylate (6) o-bromophenylmethylthioethyl = (meth) acrylate ( 7) m-Bromophenylmethylthioethyl = (meth) acrylate (8) p-Fluorophenylmethylthioethyl = (meth)
Acrylate (9) o-Fluorophenylmethylthioethyl = (meth)
Acrylate (10) m-Fluorophenylmethylthioethyl = (meth) acrylate (11) 2-Phenylthioethyl = (meth) acrylate (Ph ⁰ : phenyl, R ¹ : C ₀ , R ² : C ₂ ) (12) p -Chlorophenylthioethyl = (meth) acrylate (13) o-bromophenylthioethyl = (meth) acrylate (14) m-fluorophenylthioethyl = (meth) acrylate (15) Phenylmethylthiobutyl = (meth) acrylate ( 16) 3-Phenylbutylthioethyl acrylate

From the viewpoint of simplicity of the synthetic method, preferred compounds among the above are phenylmethylthioethyl = methacrylate, phenylmethylthioethyl = acrylate,
And a nuclear halogen substitution product thereof.

<Novel (Meth) Acrylate (Synthesis)> The compound according to the present invention can be synthesized by any method that is purposeful with respect to the type of bond and / or introduction.

Generally, the compound according to the present invention comprises a thioether-bonded alcohol having an aromatic substituent represented by the following general formula [II] and (meth) acrylic acid under ester forming conditions, that is, By dehydrohalogenation reaction using (meth) acrylic acid as its acid halide,
Alternatively, (meth) acrylic acid as its lower alkyl ester is transesterified with its thioether alcohol, or by directly reacting (meth) acrylic acid and thioether alcohol under dehydrating conditions, or It can be synthesized by a reaction of a (meth) acrylic acid with thioether alcohol as an anhydride, that is, by reacting a (meth) acrylic acid compound represented by the following general formula [III] by a known method. it can. Ph ⁰ -R ¹ -S-R ² -OH [II] Here, Ph ⁰ , R ¹ and R ² are the same as those in formula [I]. Is.

A method for synthesizing the compound represented by the general formula [II] is described in, for example, J. Amer. Chem. Soc., 70 (1948), 3667. ^{_{CH 2 = C (R 3)}} CO-Y [III] wherein, R ³ is as defined in formula [I], Y is Y: lower alkoxy, preferably methoxy, hydroxyl, halogen atom or CH ^{_{2 = C (R 3) CO}} -O-
Is.

To obtain the compound of the present invention by reacting the compounds represented by the general formulas [II] and [III], specifically, in the case of transesterification under a base catalyst, in the case of dehydration esterification Is a dehydrohalogenating agent such as pyridine, trimethylamine or other tertiary amine in the case of synthesis with a (meth) acrylic acid halide under azeotropic dehydration conditions with an azeotropic agent in the presence or absence of an acid catalyst. The reaction may be performed in the presence.

<Use of New Ethylenically Unsaturated Monomer>
Since the compound according to the present invention itself has an ethylenically unsaturated bond, it can be polymerized and used as a resin in the same manner as a (meth) acrylic acid ester. This compound can also be used with various oligomers as an oligomer or as a diluent. Examples of the oligomer used in combination include polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, and the like. As these commercial products, Aronix M-
Polyester acrylates such as 6100, M-6200, M-7100 and M-8100 (all manufactured by Toagosei Kagaku), Viscoat 700, 3700 (all manufactured by Osaka Organic), and lipoxy SP-
1506, SP-2500, SP-4060 (above Showa High Polymer Co., Ltd.), Viscoat 540 (Osaka Organic Co., Ltd.), epoxy ester 300
2A (manufactured by Kyoei Yushi Co., Ltd.), epoxy resin such as Denacol DM-851, DM-811 (manufactured by Nagase & Co., Ltd.), art resin
UN-6060P (manufactured by Negami Kogyo Co., Ltd.) and NK ester U-4H
Examples include urethane acrylates such as A and U-108A (manufactured by Shin-Nakamura Chemical Co., Ltd.).

The compounds according to the invention can be used in combination with existing reactive diluents. Specific examples of existing diluents that can be used in combination include vinyl monomers such as styrene, vinyltoluene, N-vinylpyrrolidone and vinyl acetate, and monofunctional acrylates such as methyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate and isobornyl acrylate, And so on.

When the compound according to the present invention is used as its own polymer, it is of course possible to use it by copolymerizing it with a known radically polymerizable monomer.

As the radically polymerizable monomer,
(A) (meth) acrylic acid ester, for example, diethylene glycol = di (meth) acrylate, trimethylolpropane = tri (meth) acrylate, 2,2′-bis (4-
(Meth) acryloyloxyethoxyphenyl) propane = (meth) acrylate, 2,2′-bis (4- (meth) acryloyloxyethoxy-3,5-dibromophenyl) propane = (meth) acrylate and bis (meth) acryloyl Examples thereof include oxyethylthioxylylene = (meth) acrylate and the like, (b) allyl monomers such as diethylene glycol = bisallyl carbonate and diallyl phthalate, and (c) vinyl monomers such as divinylbenzene.

The monomer mixture of the compound according to the present invention and various oligomers can be polymerized by any known method. However, when energy rays such as ultraviolet rays are used, the monomer mixture may be polymerized faster. Many.
That is, it is possible to complete the polymerization in a shorter time by adding a photopolymerization initiator to the monomer mixture and irradiating it with ultraviolet rays, or by adding a thermal polymerization initiator and using UV irradiation and heating together. is there.

Examples of the photopolymerization initiator used in this way include 2,4,6-trimethylbenzoyl diphenylphosphine oxide, benzophenone, benzoin isopropyl ether, and 1-hydroxycyclohexyl phenyl ketone.

As an example of the thermal polymerization initiator, (a)
Organic peroxides such as benzoyl peroxide, t-butylperoxyisobutyrate, t-butylperoxy-2-ethylhexanoate, etc., as well as (b) inorganic peroxides such as hydrogen peroxide, potassium or ammonium persulfate. ,
(C) hydroperoxides such as cumene hydroperoxide, (D) azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), can give. The peroxide can also be used as a redox system in combination with a reducing agent.

The mixing ratio of these polymerization initiators is 0.005 to 10 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the polymerizable monomer.

[0028]

The following examples serve to illustrate the compounds according to the invention. Unless otherwise indicated
"Parts" refer to parts by weight.

Production Example / Synthesis of Thioether Alcohol A mercaptoethanol 197 was placed in a 3-liter four-necked flask equipped with a stirrer, thermometer, dropping funnel, and cooling tube.
Parts, methanol 1000 parts, pure water 500 parts, and sodium hydroxide 92.4 parts were added, and 266 parts of benzyl chloride was added dropwise from a dropping funnel while stirring and maintaining the temperature of the solution at 60 ° C. or lower. After the completion of dropping, the mixture is further heated and stirred at 60 ° C. for 1 hour, and then left to cool. Toluene 5
After adding 00 parts, the mixture was washed with a 5% aqueous sodium hydroxide solution in a separating funnel and then with pure water. After drying over magnesium sulfate and filtration, the solvent was distilled off under reduced pressure,
The product (2-benzylthioethanol) was obtained.

Example 1 A 2-liter four-necked flask was charged with 312 parts of 2-benzylthioethanol, 700 parts of methyl methacrylate, 0.4 parts of hydroquinone monomethyl ether and 4 parts of diethylhydroxyamine, and tetra-n-butoxy as a catalyst. 10 parts of ethane was added. While stirring, azeotropically remove the methanol produced at 90-100 ° C with methyl methacrylate.
Reacted for hours.

After completion of the reaction, excess methyl methacrylate was distilled off under reduced pressure, and 500 parts of toluene was added, followed by pickling with a 5% hydrochloric acid aqueous solution, alkali washing with a 5% sodium hydroxide aqueous solution, and washing with pure water. . 0.4 parts of hydroquinone monomethyl ether was added, and the solvent was distilled off under reduced pressure.

The nuclear magnetic resonance spectrum of the obtained product is as shown in FIG. From this, it was confirmed that the product was 2-benzylthioethyl methacrylate.
The product was colorless and transparent and had a viscosity of 8.5 cps. Also, the refractive index in the monomer state is 1.54, which is almost the same as that of styrene monomer, and the conventional reactive (meth) acrylate (the refractive index range is approximately 1.41 to 1.49).
It is expected that the polymer also has an excellent refractive index as compared with.

Application Example 1 (Solubility) 60 parts of 2-benzylthioethyl methacrylate obtained in Example 1 and 30 parts of urethane acrylate ("Art Resin UN-6060P" manufactured by Negami Kogyo Co., Ltd.) are heated and uniformly mixed. After that, it was left to cool. At this time, the solubility was good, and no phase separation or precipitation was observed even after standing for 1 month at room temperature.

Application Example 2 (Polymerization Behavior) To 30 parts of the above mixture, 0.2 part of 2,4,6-trimethylbenzoyldiphenylphosphine oxide ("Lucirin TPO" manufactured by BASF) as a radical polymerization initiator was added, and a thermal analyzer UV was used. -Exothermic heat of polymerization was examined by DSC (PDC-121 manufactured by Seiko Instruments Inc.). When irradiated with light having a wavelength of 365 nm at an intensity of 200 mW / cm ² , a large exothermic peak was observed 0.48 minutes after irradiation, and it was confirmed that the polymerization was promptly carried out. Also, using 20 parts of styrene, similarly urethane acrylate
The same measurement was carried out by uniformly mixing 10 parts of UN-6060P and 0.2 part of lucillin TPO, but a slight exotherm was observed 0.45 minutes after irradiation, but the polymerization hardly proceeded.

[0035]

INDUSTRIAL APPLICABILITY The novel compound according to the present invention has a low viscosity, a high refractive index and a high polymerization rate, as described above in the section of [Summary of the Invention].

[Brief description of drawings]

FIG. 1 is a ¹ H-NMR spectrum of 2-benzylthioethyl methacrylate produced in Example 1.

Claims (2)

[Claims] 1. An ethylenically unsaturated monomer comprising an acrylic acid or methacrylic acid ester of a thioether alcohol having an aromatic substituent. 2. The ethylenically unsaturated monomer according to claim 1, which is represented by the following formula [I]. ^{Ph 0 -R 1 -S-R 2} -O-CO-C (R 3) = CH 2 [I] ^{wherein, Ph 0, R 1, R} 2 and R ³ have the following meanings. Ph ⁰ : Phenyl group which may be substituted with up to 5 halogen atoms R ¹ : Hydrocarbon chain having 0 to 6 carbon atoms R ² : Hydrocarbon chain having 6 carbon atoms R ³ : Hydrogen or methyl group