JPH02111743A - Acrylic acid derivative - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [R<1> is H or CH3; R<2> is ethylene, -CH(CH3)CH2 or -CH2CH(OH)CH2-; Y is direct bond, -SO2-, -CO- or -CR<3>R<3> (R<3> is H, 1-6C alkyl or phenyl); X<1> and X<2> are halogen; m and n are 0-3; p is 0-5]. EXAMPLE:2,2-Bis[3-phenyl-4-(2-acryloyloxyethoxyl)phenyl]propane. USE:A raw material for resins having high refractive indexes. PREPARATION:A dihydric alcohol or phenol of formula II is esterified with (meth)acrylic acid to provide the compound of formula I.

Description

[Detailed Description of the Invention] [Industrial Application Field] This invention relates to a new acrylic acid derivative, and more specifically, it is useful as a raw material for a high refractive index resin that can be suitably used as a molding material for eyeglass lenses, for example. acrylic acid derivatives.

[Prior art and problem to be solved by the invention 8] In order to reduce the weight of optical lenses, especially spectacle lenses, plastic materials have come to be widely used in place of conventional optical inorganic glass. Various proposals have been made regarding such materials.

For example, in JP-A-60-63214 (wherein R is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and X is a halogen atom excluding fluorine,
n is 0 and an integer of 1-4. In addition, R, X, and n, each of which is present in plural numbers, may be the same or different.) A homopolymer of the monomer represented by Plastic materials have been proposed that are made of copolymers containing:

However, the refractive index of this plastic material is at most 1
．． The refractive index is about 59 to 1.61, which is better than the refractive index of conventional optical inorganic glass, which is 1.53, but it does not fully satisfy various performance requirements in practical terms.

That is, the current situation is that resins and resin raw materials with even higher refractive indexes are required.

This invention was made based on the above circumstances.

An object of the present invention is to provide an acrylic acid derivative that can be suitably used as a raw material for a resin having a high refractive index.

[Means for Solving the Problems] In order to solve the above problems, as a result of intensive studies by the present inventors, it was found that acrylic acid derivatives having a specific structure are suitably used as raw materials for high refractive index resins. This invention was achieved by discovering what could be done.

The structure of this invention is linear formula (I): [In formula (1), R1 represents a hydrogen atom or a methyl group, R2 is -C1ltCH*-, Y is a direct bond,
-so, -, -co- and -shiRco (R2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group), xl
and x2 each represent a halogen atom, and m3
and n are 0 and an integer of 1 to 3, respectively, and P is 0 and an integer of 1 to 5, respectively. ] It is an acrylic acid derivative represented by

The acrylic acid derivative represented by the formula (1) is, for example, the following formula (■); The phenol is, for example, 2,2-bis[3-7enyl-4(2-hydroxyethoxy)phenyl represented by the following formula. ] Propane, (n) [In formula (II), R", Y, X',, X"
n and p have the same meanings as above. ] 2
It can be obtained by an esterification reaction between a hydric alcohol or phenol and (meth)acrylic acid.

2,2-bis[3-phenyl-4-hydroxyphenyl]propane, which is represented by the dihydric alcohol represented by the formula (n), and 2,2-bis[3-phenyl-4(2-hydroxy), which is represented by propoxy) phenylcoproban.

Examples include.

The dihydric alcohol or phenol represented by the formula (II) is, for example, a bis[3
-phenyl-4(2-hydroxyethoxy)phenyl]
Sulfone, and more.

It can be obtained by adding alkylene oxide to the bisphenol represented by formula (m), or it can also be obtained by reacting the bisphenol represented by formula (m) with alkylene carbonate or ω-halogenated alcohol.

Preferred examples of the alkylene oxide are as follows.

Examples include ethylene oxide and propylene oxide.

Suitable examples of the alkylene carbonate include ethylene carbonate obtained by the reaction of phosgene and ethylene glycol or ethylene oxide and carbon dioxide gas, and ethylene carbonate obtained by the reaction of phosgene and propylene glycol or propylene oxide and carbon dioxide gas. Examples include propylene carbonate.

Preferred examples of the ω-halogenated alcohol include ethylene bromohydrin, ethylene chlorohydrin, propylene bromohydrin, propylene chlorohydrin, and the like. Among these, ethylene bromohydrin is preferred.

Furthermore, the acrylic acid derivative represented by the formula (I) is
It can also be obtained by transesterifying a dihydric alcohol or phenol represented by the formula (■) with a lower alkyl ester of (meth)acrylic acid.

Examples of the lower alkyl ester of (meth)acrylic acid include ugly methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate.

Furthermore, the acrylic acid derivative represented by the above formula (I) can be obtained by a method of reacting a dihydric alcohol or phenol represented by the above formula (n) with a chloride of (meth)acrylic acid in the presence of a base. I can do it.

Furthermore, the acrylic acid derivative represented by formula (1) can be obtained by reacting a dihydric alcohol or phenol represented by formula (11) with glycidyl (meth)acrylate represented by the following formula; It can also be obtained by reacting an epoxy oligomer obtained by reacting the bisphenol represented by the formula (m) with shrimp herrochtrin and (meth)acrylic acid.

Examples of the shrimp helohydrin include shrimp chlorohydrin and shrimp bromohydrin.

The acrylic acid derivative of the present invention represented by the above formula (I) forms a polymer alone or by copolymerizing with other vinyl monomers.

Examples of the vinyl monomer include styrene, p-
Methyl-α-methylstyrene, p-chlorostyrene, p
- Styrene derivatives such as cyanostyrene, styrene oxide, divinylbenzene: phenyl (meth)acrylate, benzyl (meth)acrylate, naphthyl (meth)acrylate
Acrylate, 2.2-bis[4-(ω-(meth)acryloyloxypolyalkyleneoxy)phenyl]propane, 2.2-bis[3,5-dibromo-4-(ω-(
Aromatic (meth)acrylates such as meth)acryloyloxypolyalkyleneoxy)phenyl]propane; aromatic arylates such as diallyl phthalate and diethylene glycol bisallyl carbonate; and the like.

Among these, styrene derivatives are preferred when used as a molding material for eyeglass lenses, and styrene is particularly preferred.

As the polymerization method, a cast polymerization method can be suitably employed, especially from the viewpoint of use as a raw material for manufacturing eyeglass lenses.

That is, the acrylic # derivative of this invention or the acrylic acid derivative of this invention represented by the above formula (I) and the vinyl monomer are combined with a polymerization initiator and, if necessary, an ultraviolet absorber, an antioxidant, etc. Polymerization can be achieved, for example, by placing it in a lens-shaped mold and heating or irradiating it with ultraviolet light.

Examples of the polymerization initiator include benzoyl peroxide,
lauroyl peroxide, 2,5-dimethylhexane-2,5
- Peroxides such as dihydroperoxide and t-butyl peroxyacetate: Alibisisobutyronitrile, 2
．． Examples include azo compounds such as 2''-azobis-(2-amidinopropane) dihydrochloride, 2.2''-dimethyl azobisisoacetate, and 2.2'-azobis-(2,4-dimethylvaleronitrile).

Examples of the ultraviolet absorber include 2-hydroxybencyphenone, 2,4-hydroxybenzophenone, phenyl salicylate, 2,4-ditertiarybutylphenyl-3,5-ditertiarybutyl-4-hydroxybenzoate, ( Examples include 2-hydroxyphenyl)benzotriazole, (2-hydroxy-5-methylphenyl)benzotriazole, and ethyl-2-cyano-3,3-diphenylacrylate.

Furthermore, in the above polymerization, coloring inhibitors, fluorescent dyes, etc. can also be used as necessary.

For example, the refractive index of the copolymer of acrylic acid derivative and styrene of the present invention is about 1.63, and it can be suitably used as a raw material for manufacturing eyeglass lenses.

[Example] Next, an example of the present invention will be shown and the present invention will be explained in more detail.

(Example 1) In a two-cross flask equipped with a Dean-Stark separator with a stirrer, a thermometer, an air blowing tube, and a cooling tube, two
．． 468 g (1 mol) of 2-bis[3-phenyl-4-(2-hydroxyethoxy)phenyl]propane, 151 g (2.1 mol) of acrylic acid, 1 g of concentrated sulfuric acid, 0.5 g of hydroquinone and 1000 g of toluene. was charged and an azeotropic dehydration reaction was carried out for 6 hours.

The obtained product was washed three times with dilute alkaline water and then three times with water, dried over magnesium sulfate, and then toluene was removed under reduced pressure to obtain 545 g of the desired product.

When this target product was subjected to elemental analysis and 'H-NMR analysis, the following results were obtained.

Original i1L class upper C: Measured value 77.0% Theoretical value 77.1% H: 0 constant value 6.3% Theoretical value 6.3% O: Measured E1 16.7% Theoretical value 16.6% 'H- NMR±: δ (CDCu1)P
P■1.7 (6H,5) (411,t) (4H,t) (2H,dd) (2H,dd) (2H,dd) (+611) From these measurement results, this target object is as follows. It was recognized that it was 2,2-bis[3-phenyl-4-(2-acryloyloxyethoxy)phenyl]propane represented by the formula.

(Example 2) 2.2-bis[3-phenyl-
4-hydroxyphenyl]propane 3ao g (i mol), triethylamine 212 g (2.1 mol),
0.5 g of hydroquinone and 1000 ml of N-methylpyrrolidinone were charged, and 219 g (2.1 mol) of methacrylic acid chloride was added dropwise over 1 hour while cooling with water.

Methylene chloride was added to the obtained product, and after washing with water,
It was dried under reduced pressure to obtain 528 g of the target product.

When this target product was subjected to elemental analysis and 'H-NMR analysis, the following results were obtained.

Original value 81.5% Theoretical value 81.4% H: Measured value 6.2% Theoretical value 6.2% 0: Measured value 12.3% Theoretical value 12.4% 'H -NMR: δ (CDC statement: +) pp-1
,7 (611,s) 2.1 ([iH,s) 5.8 (211,s) 6.4 (28,s) 6.8-7.5 (1611) From these measurement results, this purpose The product was found to be 2,2-bis[3-phenyl-4-methacryloyloxyphenyl]propane represented by the following formula.

(Example 3) 2,2-bis[3-phenyl-4-
497 g of jepoxy compound (epoxy equivalent: 248) obtained by condensing 380 g (1 mol) of hydroxyphenylpropane and 370 g (4 mol) of epichlorohydrin in the presence of sodium hydroxide, 151 g of acrylic acid
g (2,1 mol).

2 g of lithium chloride and 0.5 g (0,004 mol) of hydroquinone monomethyl ether were charged and reacted for 4 hours at a temperature of 110° C. while blowing air to obtain 608 g of a product.

When this target product was subjected to elemental analysis and 'H-NMR analysis, the following results were obtained.

1st year IL result C: Measured value 73.4% Theoretical value 73.6% H: Measured value 6.4% Theoretical value 6.3% 0: Measured value 20.2% Theoretical value 20.1% 'H- NMR+: δ (CDC text x) pp■2
．． 7 (2H) 3.8-4.2 (10+1) 5.7 (211, dd) 6.0
(2H, dd)6.4 (21
1, dd) 6.8 - 7.5 (8+1) From these measurement results, this target product is essentially 2,2-bis[3-phenyl-4-(3-
It was recognized that it consisted of acryloyloxy-2-hydroxypropoxy)phenyl]propane.

(Example 4) In Example 1, the starting material was 2.2-bis[3-
Phenyl-4-(2-hydroxyethoxy)phenyl]
The same procedure as in Example 1 was repeated except that 468 g (1 mol) of propane was replaced with 491 g (1 mol) of bis[3-phenyl-4-(2-hydroxyethoxy)phenyl]sulfone, yielding 552 g of the target product. Obtained.

When this target product was subjected to elemental analysis and 'H-NMR analysis, the following results were obtained.

Yuan” Eye redness C: Measured value 68.4% Theoretical value 68.2% H: Measured value 5.3% Theoretical value 5.1% 0: Measured value 21.4% Theoretical value 21.4% δ (COC z) ppm (4H, t) (4+1.t) (2H, dd) (211, dd) (2H, dd) From these measurement results, this target product is bis [3 -Phenyl-4-methacryloyloxyethoxyphenyl] sulfone.

(Reference example) 50 parts by weight of 2,2-bis[3-fer-4-(2-acryloyloxyethoxy)phenyl]propane synthesized in Example 1, 50 parts by weight of styrene, and azobisiso as an initiator. Mix well with 1 part by weight of butyronitrile to make a homogeneous solution, then 1 part by weight in an n-type at 100°C.
The temperature was raised over 0 hours, and polymerization was further carried out at 100°C for 5 hours.

After the engagement was completed, the polymer was taken out from the mold and the refractive index of this polymer was measured.

The results were as follows.

Refractive index: 1.6:l (Atsube refractometer: 20°C, contact liquid: bromonaphthalene) [Effects of the invention] According to the present invention, a high refractive index resin that can be suitably used as a molding material for eyeglass lenses, for example. It is possible to provide an acrylic acid derivative useful as a raw material for.

Claims (1)

[Claims] (1) The following formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [However, in formula (I), R^1 represents a hydrogen atom or a methyl group, and R^2 represents -CH_2CH_2- , ▲ There are mathematical formulas, chemical formulas, tables, etc.▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, Y is a direct bond, -SO_2-, -CO-, and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R^3 represents either a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group), and X^1 and X^2 each represent a halogen atom. Further, m and n are each 0 or an integer of 1 to 3, and p is 0 or an integer of 1 to 5. ] An acrylic acid derivative represented by.