JPS59144735A - Biphenyl compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [R is CH2CH2, CH(CH3)CH2 or CH2CH(OH)CH2; R' is H or CH3; m and n are 1, 2 or 3]. EXAMPLE:2,2'-Bis(beta-acryloyloxyethoxy)biphenyl. USE:A polymerizable and crosslinkable monomer useful as paint, ink, adhesive, rubber vulcanizer, photosensitive resin, etc. Especially a monomer giving a transparent copolymer having high refractive index and useful as an organic glass lens for eye glasses. PREPARATION:The compound of formula I can be prepared e.g. by the esterification reaction, etc. of the compound of formula II with (meth)acrylic acid. The compound has high refractive index, excellent curing rate, high boiling point and excellent compatibility with other copolymerizable unsaturated monomers. A transparent copolymer having high refractive index and excellent surface hardness, solvent resistance, heat resistance, impact resistance, dyeability, etc. can be prepared in an extremely short time by the copolymerization of the titled compound with a mono(meth)acrylate compound having biphenyl skeleton.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel biphenyl compound, and more particularly to 2,2'-bis[ω-(meth)acryloyloxypolyalkyleneoxyubiphenyl represented by formula (1).

(1) R'R' 1 (wherein, R is -CH2CH, -1-CH(CH3)C
H2- or -CH2CH(Q H) CI (represents 2-, R' represents H or CH3, m and n independently represent 1 to 3
indicates an integer. ) The compound represented by the above formula (1) is a bifunctional monomer having a biphenyl skeleton, and the compound with such a structure is a new compound that has not been previously known, and is used as a polymerizable crosslinkable monomer in paints, inks, and adhesives. In addition to being useful in many applications such as vulcanizing agents for rubber and photosensitive resins, this compound is also extremely useful as a monomer that yields transparent copolymers with high refractive index, as will be explained later. It is a useful compound.

In recent years, various di(meth)acrylate monomers having an aromatic ring have been proposed for the purpose of increasing the refractive index, particularly in the field of organic glasses. These are intended to obtain a high refractive index resin by uniformly mixing the di(meth)acrylate monomer and other unsaturated monomers that can be combined (typically (2)) and then polymerizing the mixture. However, because the di(meth)acrylate heptamers often have low solubility, crystals tend to precipitate at room temperature in the coexistence with other unsaturated monomers that can be copolymerized, and they have poor stability. There is. On the other hand, in order to improve these drawbacks, di(meth)acrylate 7mer is prepolymerized in a molten state, and then the di(meth)acrylate is
It has been proposed to make a stable liquid prepolymer by adding other unsaturated monomers copolymerizable with 1 to 1. This method attempts to solve problems such as monomer leakage from the mold, gasket swelling, and polymerization shrinkage by pre-polymerizing to a low level and adjusting the viscosity during cast polymerization, but the polymerization activity is extremely low. A low polymer that maintains a constant viscosity, refractive index, etc. in order to stop polymerization before gelling a monomer having a high (meth)acryloyl group and to stabilize the refractive index and other properties of the polymer. (3) It has the disadvantage that it is difficult to manufacture a composite.

The present inventors conducted extensive research in view of these points, and found that the compound represented by formula (1) not only has a high refractive index but also a high boiling point compound with excellent curing speed. The present invention was achieved based on the discovery that it also has excellent compatibility with other possible unsaturated materials. The high boiling point of the compound 2N) means that (i) it is difficult to handle; (ii) it is difficult to handle;
) The odor is extremely low or almost non-existent, (iii
) has the advantage of being less toxic.

The compound of formula (1) according to the present invention can be synthesized by various methods, and specific examples thereof are as follows. In addition, in the following method, the synthesis reaction conditions can generally be those in similar known reaction techniques.

(1) Dihydric alcohol represented by the following formula ([) and (meth)
A method of carrying out an esterification reaction with acrylic acid.

(11) A method of transesterifying a dihydric alcohol represented by the following formula (It), a lower alkyl ester of (meth)acrylic acid, and (4).

(iii) A dihydric alcohol represented by the following formula (U) and (
A method of reacting meth)acrylic acid with chloride in the presence of a base.

The dihydric alcohol of formula (n) (wherein R, m and n are as defined above) is generally prepared by adding a substituted or unsubstituted alkylene oxide to 2.2'-biphenol or by adding a substituted or unsubstituted alkylene oxide to 2.2 It is obtained by addition-condensing '-biphenol with a substituted or unsubstituted alkylene carbonate.

Therefore, according to this method, m in the monomer of formula (1)
, n is determined by the molar ratio of reaction between 2,2'-biphenol and substituted or unsubstituted alkylene oxide or the molar ratio of reaction between biphenol and substituted or unsubstituted alkylene carbonate.

As the substituted or unsubstituted alkylene oxide used in synthesizing these polyoxyalkylene compounds (5), propylene oxite' or ethylene oxide is used. Further, as the substituted or unsubstituted alkylene carbonate, propylene carbonate or ethylene carbonate I. is used.

In addition to the methods (i), (ii) and (mountain) above, formula (1)
) can also be synthesized by the methods (iv) and (v) below.

(iv>1 dihydric alcohol represented by formula (Tl) or 2
．． 2'-biphenol as glycidyl (meth)acrylate
Method of reacting with 1-.

(v) A method of reacting a dibricidyl ether-based epoxy resin obtained by reacting 2.2'-biphenol with epiherohydrin and (meth)acrylic acid.

As mentioned above, the compound of formula (I) according to the present invention is useful as a polymerizable monomer that provides a transparent copolymer with a high refractive index. Previously, we filed a patent application as Japanese Patent Application No. 57-1967396) (filed on November 11, 1981).

In other words, inorganic glass has traditionally been used in many applications due to its excellent transparency, hardness, scratch resistance, weather resistance, etc. However, on the other hand, it has the drawbacks of being brittle, easily broken, and heavy. have. On the other hand, organic glass has advantages that inorganic glass does not have, such as lightness, safety, resistance to breakage, processability, and dyeability, and polymers such as polymethyl methacrylate polycarbonate and diethylene glycol diallyl carbonate are suitable for this purpose. It's being used. In particular, lightness and safety are strongly required for applications such as eyeglass lenses.
There are extremely high expectations for organic glass. However, polystyrene with a high refractive index (refractive index 1.59)
Since polycarbonate (refractive index 1.59) is a thermoplastic resin, it is easily molded by injection molding, so it is prone to molding distortion, and its heat resistance and solvent resistance are poor, so its use as eyeglasses is naturally limited. be. On the other hand, diethylene glycol diallyl carbonate made by cast molding has a low refractive index (refractive index 1.50) and has the disadvantage of being thicker than inorganic glass (7) threaders. In order to improve this drawback, several prior art techniques have been proposed to increase the refractive index.

However, in all of these techniques, a uniform mixture of a monomer composition and a polymerization initiator is injected into a casting jig and then thermally polymerized over a long period of time to obtain the desired cured product without optical distortion. However, the time required for one cycle of molding is extremely long, for example, 10 hours, resulting in low productivity.

In contrast, by copolymerizing the di(meth)acrylate compound of formula (I) having a biphenyl skeleton with a mono(meth)acrylate compound (or other monomer) having a biphenyl skeleton, it is possible to A transparent copolymer having a high refractive index (for example, a refractive index of 1.58 or more) and excellent surface hardness, solvent resistance, heat resistance, impact resistance, dyeability, etc. can be obtained.

Hereinafter, the present invention will be explained in more detail with reference to Examples.
It goes without saying that the scope of the present invention is not limited to these Examples.

(8) Example 1 In 21 four-separable flasks equipped with a Dean-Stark separator with a stirrer, a thermometer, an air inlet, and a condenser, 2,2'-bis(β-hydroxyethoxy) was added.
389.56 g of biphenyl, 307 g of acrylic M, 5.4 g of paratoluenesulfonic acid, 1.4 g of hydroquinone
2 g and 380 mL of toluene were charged, and an azeotropic dehydration reaction was carried out for 6 hours. At this time, the reaction product is 2,2'-bis(β-acryloyl, kidiethoxy)biphenyl95
．． 4%, by-products 4.6%, and no raw materials or monoacrylates were observed. The analysis was carried out by gas chromatography under the following conditions.

Silicon 0V-47 column (2m), injection temperature 300°
C1 power ram temperature 280°C, FID, carrier gas (nitrogen) 60mA/min.

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

The boiling point of the obtained target product 2.2'-bis(β-acrylo(9)-oxyethoxy)biphenyl is 200℃ or higher/
It is 0.5 mm and 11 g, and the infrared analysis result (using a spectrophotometer for JASCO MJASCO 8-31R)
is as shown in FIG. Also, refractive index < n20)
The results of nuclear magnetic resonance (NMR) analysis were as follows. NMR analysis was performed using JEOL's FX-
'100 ('H=100MHz,"'C=25MH
z) was carried out.

n': 1.55B'H-NMR: δ (CD Cj!3) ppm4.1
4 (4H, t, J=6Hz).

4.33 (4H, t, J=6Hz).

5.79 (2H, dd, J=3゜ ], 0Hz), 6.07 (2H, dd.

J=10.17Hz).

6.39 (2H, dd, J=3゜ 17Hz), 6.8-7.4 (8H.

m) 13C-NMR: δ (CD0℃3) pp City 63, t
(t), 66.1 (t).

(lO) 112.9 (d), 1 22.7 (d
).

1 26.6 (s> , 1 28.6 (
d).

1 30.0 (d,), 1 31.3
(t).

1 31.9 (d), 1 56.1.
(s).

167.3(S) Example 2 549.4 g of 2,2'-bis(ω-hydroxypropoxy)biphenyl and 306 g of acrylic acid as starting materials
．． The target product 2,2'-bis(ω-methacryloyloxyproboxy)biphenyl (R-- in formula (1)
CH(CH,) C)(,0-1R'-H% m=n
=2) was obtained. The analytical values of the obtained target product were as follows (the analytical method was the same as in Example 1).

Boiling point: >200°C/0.5 mm11g0 nb; 1.523 IR analysis: Ester 1725-30 (C=C); vinyl terminal 1640 (C=C).

990 (outside CH plane), 14-15 (inside CH plane); Ether 1060-65; Methyl group 1360i Phenyl 16 (10°1504; O
-substituted product 760 H-NMR: δ (CDCI!3) 1.23 (6H, d, J=714z).

1.27 (6H, d, , J=7T(z).

3.7-4.4 (12H, m,).

5.57 (2H, dd, J-3゜ 10Hz), 5.94 (2H, dd.

J=10.16Hz).

6.25 (2H, dd, J=3.16Hz > ,
6.8-7.4 (8H, m) 2β with ridge stirrer, thermometer, air inlet and cooling pipe
Put epichlorohydrin and 2 into four separable flasks.
．． Jepoxy compound obtained by condensation with 2'-biphenol in the presence of caustic soda (bp 180-182°C
/ 0.4 +n Hg, epoxy equivalent 155) 310
g, 134 g of acrylic acid, 2 g of lithium chloride, 0.14 g of hydroquinone monomethyl ether, and while blowing air, the reaction was carried out at 110 to 120°C until the acid value became 3 or less to obtain essentially 2.2'- The target product consisting of bis(3-acryloyloxy-2hydroxypropoxy)biphenyl (in formula (I), R= -CI(2-
CH(OH) CI20-9R' = H, rn# n
” 1) was obtained.

n:;1.575 IR analysis: Ester 1725-30 (C=C) i-terminal vinyl 1640 (C=C).

1415 (inside CH plane), 990 (outside CH plane); ether 1060-1065° phenyl 1600, 1504
．． C)-substituted phenyl 760; alcohol OH 470'H-NMR analysis: δ(CDCl2) 2.74 (2H, 6rs).

3.8-4.2 (10H, m).

5.58 (2H, dd, J=2゜ 10Hz), 5.94 (2H.

(13) dd, J=1 0. 15Hz).

6.22 (21-1, dd, J=2゜1 5H
z), 6.8-7.4 (8H.

m) Example: Target product 2.
2'-bis(ω-methacryloyloxyjethoxy)biphenyl (R-CH2CH20-1R in formula (I)
'=CI3, m=n=2) was obtained. The analytical values of the obtained target product were as follows (analytical method is the same as Example 1)
.

Boiling point = 200°C or higher - h/0.5 mmHgn"
: 1.515 IR analysis: Ester 1725-30 (C-0); terminal vinyl 1640 (C=C).

1415 (inside CH plane), 990 (outside CH plane): ether 1060-1065° phenyl 1600, 1504i
0-(14) Substituted phenyl 760'H-NMR analysis: δ(CD(1!3)1.97
(6H, d, J-2Hz), 3.7-4.3 (16H, m),
5.57 (2H, m).

6.14 (2H, d, J=1.5Hz),
6.8-7.4 (8H.

m) Example 5 759.4 g of 2,2'-bis(ω-hydroxytripropoxy)biphenyl and 3 methacrylic acid as starting materials
Targets 2 and 2' were prepared in the same manner as in Example 1 except that 18 g was used.
-bis(ω-methacryloyloxytripropoxy)biphenyl (in formula (I), R=-CH(CH3) C
H20-1R'=CH3, m-n=3) was obtained. The analytical values of the obtained target product were as follows (the analytical method was the same as in Example 1).

Boiling point: 200°C or higher/0.5 mmHg20.

nl), 1.509 IR analysis: Ester 1725-30 (C=C) i-terminal vinyl 164.0 (C=C).

1415 (inside CH plane), 990 (outside CH plane); Ether 1060-1065; Phenyl 1600.150
4;o-substituted phenyl 760'H-NMR analysis: δ(DMSO-d6) 1.21
(6H,d, J=7Hz), 1.23 (6H,d.

J-7Hz), 1.28 (6H.

d, J=7H2), 1.98 (6H, d, J=2Hz).

3.6-4.4 (18H2, m).

5.61 (2H, m), 6.13 (2H, d
, J=1.5Hz).

6.8-7.4 (8H, m) 2-(β-hydroxyethoxy)-2' as anal starting material
-(ω-hydroxyjethoxy)biphenyl 429.4
The target product 2-(β-acryloyloxyethoxyl) was prepared in the same manner as in Example 1 except that 246 g of
-2'-(ω-acryloyloxyjethoxy)biphenyl (in formula (I), R=-CH2CH2-1R'=
H, m=l, n-2) was obtained. The analytical values of the obtained target product were as follows (the analytical method was the same as in Example 1).

Boiling point: above 200°Ca/0.5 mmHgno':l
: 1.527 IR analysis: Ester 1725-30 (C=C) i-terminal vinyl 1640 (C=C).

1415 (inside CH plane), 990 (outside CH plane); ether 1060-1065i phenyl 1600, 1504i
0-substituted phenyl 760'H-NMR analysis: δ (Acetone -%) 3.1
~4.3 (16H, m).

5, 6-6.3 (6H, complex) 6.7
~7.4 (8H, m) 25 parts by weight of 2,2'-bis(β-acryloyloxyethoxy)biphenyl synthesized in Example 1 was mixed with 75 parts by weight of O(17) biphenyloxyethyl acrylate II
f, 0.5 parts by weight of 2-pendiyl-2-hydroxypropane, 0.5 parts by weight of triphenylphosphine as an anti-yellowing agent.
1 part by weight and 0.2 part by weight of 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole as an ultraviolet absorber were mixed to form a homogeneous composition. After pouring this into a mold for glass eyeglass lenses and degassing, 2KW
The front and back sides were each irradiated for 4 seconds at an irradiation distance of 1Qcm using a high-pressure water string lamp.

Thereafter, the mold was removed and heat treated in an oven at 100° C. for 1 hour to obtain a colorless and transparent eyeglass lens with no optical distortion.

The physical properties of the spectacle lens thus obtained were as follows.

(1) Refractive index = 1.606 The refractive index at 20'C was measured using an Atsube refractometer. Bromonaphthalin was used as the contact liquid.

(2) Hardness: 115 (18) It was measured using a Rockwell hardness tester.

(3) Surface condition: When the surface condition of the front and back surfaces of the lens was visually observed, both the front and back surfaces were smooth.

(4) Light transmittance: 91 Measured using a haze meter (manufactured by Mega Test Instruments 01).

(5) Shock resistance test: Based on FDA standards, height 127c
A steel ball with a diameter of 15.9 x m and a weight of 16.2 g was dropped from the Inn, but it did not break.

(6) Heat resistance: After being left in a hot air dryer at 120° C. for 3 hours, visual observation revealed that no lens coloration or surface distortion was observed.

(7) Dyeability: A lens was immersed in a 0.2% Disperse Brown 3 aqueous solution, immersed at 92'C for 10 minutes, pulled out, thoroughly washed with water, and dried. No uneven staining was observed in this dyed lens.

[Brief explanation of drawings]

FIG. 1 is an IR analysis chart 1 of 2,2'-bis(β-acryloyloxyethoxy)biphenyl synthesized in Example 1. (19) Procedural amendment (voluntary) April 1982? Commissioner of the Japan Patent Office Kazuo 1, Indication of the case 1982 Patent Application No. 18031 2, Name of the invention biphenyl compound 3, Relationship with the ministry case making the amendment Name of patent applicant (200) Showa Denko K.K. 4. Agent address: Shizuko Toranomon Building, 8-10 Toranomon-chome, Minato-ku, Tokyo 105 Telephone (504) 0721 5.? ili "Detailed Description of the Invention" column of the original subject specification. 6. Details of the amendment (a) On page 11, line 11 of the specification, "methacryloyloxypropoxy" is amended to "racryloyloxypropoxy". (b) Page 13, line 4, [2-hydroxypropoxy]
is corrected to 12-hydroxypropoxy. (c) On page 14, line 7, "[...tripropoxy)biphenyl" is amended to "r...jethoxy)biphenyl". or more (,2)

Claims (1)

[Claims] 1. General formula (wherein R is -CH2CH2-1-CH(C horse) CH2
7 or -CH2CH(OH) CH2-, R' represents H or C, m and n independently represent integers from 1 to 3) ) Acryloyloxypolyalkyleneoxyubiphenyl.