JPH07145138A - Acrylic acid derivative - Google Patents

Abstract

PURPOSE:To obtain an acrylic acid derivative capable of providing a film excellent in mechanical strength and transparency without impairing adhesiveness characteristic of polyacrylate and providing a resin having high refractive index and useful also as an optical material. CONSTITUTION:An acrylic acid derivative, e.g. a compound of formula III. This compound is obtained by reacting an acrylate of formula I (R<1> is H or methyl) e.g. methacryloyl isocyanate with a compound of formula II [R<2> is a monovalent organic group having an active group capable of reacting with an isocyanate group; R<3> is H or a monovalent organic group; (n) is 3 or 4], e.g. 4-hydroxy-p-quater phenyl. A polymer containing one or two or more kinds of the acrylic acid derivatives obtained by the reaction as monomer components or a copolymer with other monomer copolymerizable with the polymer can be obtained and the polymer can be used as an elastomer by selecting the copolymer components and they can be molded by press molding, blow molding, etc.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel acrylic acid derivative, and more particularly to an acrylic acid derivative useful for optical materials such as optical lenses and various molded products.

[0002]

2. Description of the Related Art Methyl methacrylate resin (PMMA)
Is used for optical materials such as plastic lenses because it has excellent transparency and weather resistance and is superior in lightness, impact resistance and molding processability to inorganic optical materials. ing. However, the refractive index of PMMA is much smaller than that of inorganic materials (nd = 1.49), and therefore, JP-A-1-226870 and JP-A-3-109368 are used.
As seen in Japanese Patent Publication, a methacrylic acid derivative having an increased refractive index has been proposed. However, it is hard to say that the resin obtained using this methacrylic acid derivative has a sufficient refractive index.

Acrylate copolymers are generally viscous fluids, and polymers having a glass transition temperature of room temperature or lower are preferably used as raw materials for adhesives and pressure-sensitive adhesives. However, it is difficult to form a film from these polymers because they have viscosity at room temperature and weak mechanical strength.

To reduce the viscosity of the acrylate copolymer,
As an attempt to improve the mechanical strength, Japanese Patent Publication No. 53-45
As disclosed in Japanese Patent No. 3528, there is a method of synthesizing a polystyrene graft polyacrylate by copolymerizing an acrylate monomer and a polystyrene macromonomer. However, in this case, 30% by weight or more of the polystyrene macromonomer is required to obtain a film having sufficient strength, and the adhesiveness and weather resistance peculiar to polyacrylate are likely to be impaired.

Further, Japanese Patent Application Laid-Open No. 05-132524 discloses a method of copolymerizing an acrylate monomer and an acrylate monomer containing a quarterphenyl unit (the following formula (c)). By this method, an acrylate copolymer capable of producing a film can be obtained, but the strength of the film is poor.

The quarter phenyl unit has a rigid structure and is known as a liquid crystal mesogen. By introducing such a unit into the polymer, even when the amount thereof is relatively small, this portion acts as a physical crosslink due to the strong cohesive force of the liquid crystal unit, and a polymer capable of forming a film can be obtained. It is estimated that However, the strength of the film cannot be sufficiently expressed by the method disclosed in Japanese Patent Laid-Open No. 05-132524.

[0007]

[Chemical 3]

(In the formula, R ⁴ represents hydrogen or an alkyl group having 1 to 6 carbon atoms, R ⁵ represents a divalent organic group, and R ⁶ represents a hydrogen atom or a monovalent organic group.)

[0009]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances and provides a film excellent in mechanical strength and transparency without impairing the adhesiveness peculiar to polyacrylate. It is an object of the present invention to provide an acrylic acid derivative capable of obtaining a resin having a high refractive index which is useful as an optical material.

[0010]

In the present invention, it is possible to react an acrylate having an isocyanate group represented by the following formula (a) with a quarter phenyl or terphenyl group represented by the following formula (b) and an isocyanate group. It was found that an acrylic acid derivative obtained by reacting a compound having various active groups serves as a raw material for a film having excellent mechanical strength and transparency and a resin having a high refractive index.

[0011]

[Chemical 4]

(R ¹ in the formula represents either a hydrogen atom or a methyl group.)

[0013]

[Chemical 5]

(In the formula, R ² represents a monovalent organic group having an active group capable of reacting with an isocyanate group, and R ³ represents a hydrogen atom or a monovalent organic group having or not having the active group. The above compound (b) is a monovalent organic compound having an active group capable of reacting with one or two isocyanate groups at the para-position of a quarterphenyl group or a terphenyl group. A compound having a group bonded thereto, and the active group is bonded to the para-position of the quarterphenyl group or the terphenyl group directly or through an appropriate divalent organic group.

The active group capable of reacting with the isocyanate group is preferably a hydroxyl group, a carboxylic acid group or an amino group, and the divalent organic group is a quaterphenyl or terphenyl group with an ether bond, an ester bond or an amide bond. An alkylene group having 2 to 20 carbon atoms through is preferable.

Particularly, as the compound (b), 4-hydroxy-p-quaterphenyl (the following formula [1]), 4,
4 "'-dihydroxy-p-quarterphenyl (the following formula [2]), 4- (2-hydroxyethoxy) -p-quarterphenyl (the following formula [3]), 4,4"'-di (2-
Hydroxyethoxy) -p-quaterphenyl (formula [4]), p-quaterphenyl-4-carboxylic acid (formula [5]), p-quaterphenyl-4,4 ″ ′.
-Dicarboxylic acid (the following formula [6]), p-quaterphenyl-4-carboxylic acid (2-hydroxyethyl) (the following formula [7]), p-quaterphenyl-4,4 "'-di (carboxylic acid ( 2-hydroxyethyl)) (the following formula [8]), p-quaterphenyl-4-carboxylic acid (2-hydroxybutyl) (the following formula [9]), p-quaterphenyl-4,4 "'-di ( Carboxylic acid (2-hydroxybutyl)) (the following formula [10]), p-quaterphenyl-4-carboxylic acid amide (2-aminohexyl)
(The following formula [11]), p-quaterphenyl-4,
4 ″ ′-di (carboxylic acid amide (2-aminohexyl)) (the following formula [12]) is preferably used. These may be used alone or in combination of two or more.

[0017]

[Chemical 6]

The above-mentioned compound (a) and compound (b) are basically reacted in equimolar amounts, but the reaction may be carried out by adding a slight excess of either component. The reaction is carried out under conditions suitable for the usual reaction between isocyanate and active hydrogen, that is, 60 ° C to
It is preferably carried out in a solvent or in a bulk form at a temperature of 180 ° C. for 2 minutes to 24 hours. The reaction solvent is not particularly limited as long as it is a solvent that dissolves the compound (b) and reacts with the compounds (a) and (b), but is not limited to dimethyl sulfoxide (DMSO), N-methyl-pyrrolidone (NM).
Polar solvents such as P), dimethylformamide (DMF), dimethylacetamide (DMA) are preferred.

In the above reaction, as a catalyst, lithium, sodium, potassium, cesium, magnesium,
Metals such as calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium and manganese, their organometallic compounds, organic acid salts, metal alkoxides, metal oxides Etc. may be used.

Particularly preferable catalysts are calcium acetate, diacyl stannous tin, tetraacyl stannic tin, dibutyltin oxide, dibutyltin dilaurate, dimethyltin malate, tin dioctanoate, tin tetraacetate, triisobutylaluminum, tetrabutyltitanate, and dioxide. Germanium and antimony trioxide.

With the acrylic acid derivative obtained by the above reaction as a constituent, a polymer containing one or more kinds or a copolymer with a monomer copolymerizable therewith can be obtained.

Examples of the monomer to be copolymerized are styrene derivatives such as styrene, p-methyl-α-methylstyrene, p-chlorostyrene, p-cyanostyrene and divinylbenzene; (meth) acrylic acid, ethyl (meth).
Acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylamide , N, N-dimethyl (meth) acrylamide, methyl (meth) acrylate, phenyl (meth) acrylate, chlorophenyl (meth) acrylate, bromophenyl (meth) acrylate, benzyl (meth) acrylate, p-biphenyl (meth) acrylate, Naphthyl (meth) acrylate, 2-hydroxyethyl (meth)
Acrylate, glycidyl (meth) acrylate, epoxy (meth) acrylate, diethylene glycol (meth) acrylate, triethylene glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate, dimethacrylate of bisphenol A ethylene oxide adduct, tetra Bromobisphenol A ethylene oxide adduct dimethacrylate, p-bis (β-
(Meth) acryloyloxyethylthio) xylylylene and other (meth) acryl derivatives; diethylene glycol bisallyl carbonate, diallyl phthalate, diallyl epoxysuccinate, allylphenylsilane, diallyldimethylsilane, and other allyl compounds.

These may be used alone or in combination of two or more. When an elastomeric polymer having a glass transition temperature of room temperature or lower is desired, butyl acrylate, hexyl acrylate, octyl acrylate, decyl acrylate, lauryl acrylate, and 2-ethylhexyl acrylate are preferably used.

The polymerization can be carried out with a general radical polymerization initiator, and can be carried out by known techniques such as bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization.

The type of radical polymerization initiator used in the polymerization is not particularly limited, and a general initiator can be used. For example, peroxides such as benzoyl peroxide, t-butyl peroxyacetate and lauroyl peroxide, and azo compounds such as azobisisobutyronitrile (AIBN) and azobismethylvaleronitrile can be used. The amount of the polymerization initiator used is 0.01 to 1 with respect to the total monomers.
0 wt%, preferably 0.1-5 wt% is suitable.
The polymerization temperature is in the range of 20 to 120 ° C., and the reaction is preferably performed for about 1 to 70 hours. When carrying out by solution polymerization, a general polymerization solvent can be used as long as it is a solvent that dissolves the monomer to be used. For example, ethyl acetate, THF,
These are DMF, DMSO, NMP and the like.

The polymerization can also generally be carried out with a photopolymerization initiator. The type of initiator used is not particularly limited, and examples thereof include acetophenone-based compounds such as acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-hydroxycyclohexylphenylketone; benzoin; Benzoin compounds such as benzyl methyl ketal; benzophenone compounds such as benzophenone, methyl benzoylbenzoate, and 4-phenylbenzophenone compounds; and thioxanthone compounds can be used. The photopolymerization initiator is 0.0 with respect to the total monomer.
It is suitable to use 1 to 10% by weight, preferably 0.05 to 5% by weight, and the irradiation light amount is 0.01 to 100 J / c.
It is better to react at m ² .

Polymerization can also be carried out by combining radical polymerization and photopolymerization.

The acrylate polymer obtained as described above can be used as an elastomer by selecting a copolymerization component, and molding such as press molding, extrusion molding and blow molding is possible.

Molded articles are boots (CVJ boots, rack and pinion boots, etc.), canisters, side moldings, air duct hoses, coolant hoses, automobile parts such as tires, hydraulic hoses, thinner tubes, industrial tires, Rolls for printing, mechanical / industrial parts such as anti-vibration rubber, rubber switches, electric wire coating materials, transformer insulating materials, electric / electronic component materials such as speaker edges, gas barrier films, ICs
It can be used for sheet films including protective films, paints and adhesives, medical materials including coating materials for gastrocameras, sports equipment and the like.

Further, this polymer has a high refractive index,
It can also be used for optical applications such as optical lenses, antireflection multilayer films, optical waveguides, and viewing angle adjusting plates.

[0031]

EXAMPLES The present invention will be described below based on examples.

Example 1 (A) Synthesis of 4-methoxy-p-quarterphenyl In a glass flask, 3.6 g of magnesium pieces for Grignard reagent were placed, and under a nitrogen atmosphere, 4-bromobiphenyl was added from a dropping funnel. THF solution 150 containing 33.6 g
ml was added dropwise. A small amount of iodine was added to start the reaction, and then the reaction was carried out for 3 hours with stirring to prepare a Grignard reagent.

In a flask separate from the above, 4-bromo-4 '
-Methoxyphenyl 31.5g and NiCl as catalyst
₂ (dpppp) 108 mg (dpppp: 1,3-bis (diphenylphosphino) propane) was added, and further T
500 ml of HF was added. The Grignard reagent prepared above was added dropwise to this solution at 0 ° C. under nitrogen over about 1 hour. After completion of dropping, the reaction system was reacted for 5 hours to complete the reaction. The produced white solid was dissolved in sulfolane and then recrystallized to obtain 30.6 g of 4-methoxy-p-quaterphenyl (yield 76%).

(B) Synthesis of 4-hydroxy-p-quarterphenyl (HQP) In a three-necked flask, 25.2 g of 4-methoxy-p-quaterphenyl obtained in the above (A) and 5 methylene chloride were used.
00 ml was added and suspended. To this suspension, 50 ml of a methylene chloride solution containing 19.0 g of boron tribromide,
It was added dropwise under nitrogen over about 30 minutes. Then, the reaction system was reacted under reflux for 10 hours. After the reaction,
The precipitated solid was dissolved in DMSO and then recrystallized to give 4-hydroxy-p-quaterphenyl 21.6.
g was obtained (yield 89%).

(C) Synthesis of acrylate 200 ml of NMP was placed in a three-necked flask, and HQ was added thereto.
5.0 g (about 15.5 mmol) of P and 0.1 g (about 0.2 mmol) of dibutyltin dilaurate were added. The flask was heated to 70 ° C. to completely dissolve HQP.
Methacryloyl isocyanate (MAI) 3.4
50 ml of NMP in which g (about 31 mmol) was dissolved was added dropwise. After completion of the dropping, the system was stirred for 4 hours to continue the reaction. After completion of the reaction, the reaction solution was poured into 15 times the amount of methanol to deposit a white precipitate. The precipitate was filtered off and washed with methanol (yield 92%).

Next, the analysis results of acrylate are shown.

Structural formula

[0038]

[Chemical 7]

Molecular weight 433.5 (molecular weight was determined by mass spectrum measurement) 1H-NMR (unit: ppm based on tetramethylsilane) 6.8 to 7.8 M 17H CH benzene ring 6.0, 6.2 2S 2H CH ₂ = 1.9 S 3H CH ₃ − Elemental analysis result

[0040]

[Table 1]

(D) Polymerization A flask equipped with a stirrer was charged with 19.5 g of the acrylate obtained in the above (C), 0.5 g of AIBN, 18 g of methyl acrylate and 300 ml of DMSO, and the atmosphere was replaced with nitrogen. went. After this, the system was heated to 60 ° C.
Polymerization was carried out for a period of time, and after completion of the polymerization, the solution was poured into methanol to precipitate a polymer. The deposited polymer is
It was a white powder.

Example 2 The same composition as in item (D) of Example 1 was charged and polymerized, except that styrene was used instead of methyl methacrylate. The obtained polymer was a white powder.

Example 3 In a flask equipped with a stirrer, 10 g of the acrylate obtained in the above item (C) and A
0.5 g of IBN, 40 g of butyl acrylate, DMS
300 ml of O and 200 ml of ethyl acetate were charged, and the atmosphere was replaced with nitrogen. After that, the temperature of the system was raised to 60 ° C. and polymerization was carried out for 12 hours. After completion of the polymerization, the solution was poured into methanol to precipitate a polymer. The resulting polymer was elastomeric.

Comparative Example 1 In a flask equipped with a stirrer, 36 g of methyl methacrylate, 0.16 g of azobisisobutylnitrile (AIBN) and 200 m of DMF were placed.
Then, the same polymerization as in the item (D) of Example 1 was carried out to obtain polymethyl methacrylate (PMMA). The polymer was a white powder.

Comparative Example 2 Polystyrene (PSt) was obtained by charging and polymerizing with the same composition as in Comparative Example 1 except that styrene was used instead of methyl methacrylate. The polymer was a white powder.

The polymers obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were dissolved in DMSO and cast on a smooth film-forming plate to prepare cast films. Then, the refractive index of each film was measured at 23 ° C. with an Abbe refractometer. The results are shown in Table 2.

[0047]

[Table 2]

Regarding the films made from the polymers obtained in Examples 1 and 2, according to JISK6301,
Break strength and break elongation were measured using Shimadzu Autograph AG-5000. The results are shown in Table 3.

[0049]

[Table 3]

[0050]

As is clear from the above description, according to the acrylate derivative of the present invention, a polymer having a quarterphenyl unit introduced therein can be obtained, and a material such as a film having excellent mechanical strength and transparency is obtained. It is also possible to provide a resin having a high refractive index which is useful as an optical material for an optical lens, an antireflection multilayer film, an optical waveguide, and a viewing angle adjusting plate.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toranosuke Saito 5-17-21 Yamatedai, Ibaraki City (72) Inventor Hiroki Kadomachi 1-11-3 Minamikasugaoka, Ibaraki City

Claims (1)

[Claims] 1. An acrylic acid derivative obtained by reacting an acrylate having a general formula represented by the following formula (a) with a compound having a general formula represented by the following formula (b): (R ¹ in the formula represents either a hydrogen atom or a methyl group.) (In the formula, R ² represents a monovalent organic group having an active group capable of reacting with an isocyanate group, R ³ represents a hydrogen atom or a monovalent organic group, and n is 3 or 4.)