JPH0551404A - Production of di(meth)allyl diphenate-based polymer - Google Patents

Abstract

PURPOSE:To provide the title polymer containing little residues derived from residual monomer and/or polymerization initiator, thus more suitable as a material for optical use. CONSTITUTION:The objective polymer can be obtained by polymerizing (A) an ethylenic unsaturated monomer mixture containing >=20wt.% of (meth)allyl diphenate monomer using (B) a polymerization initiator system composed of (1) a perester- and/or percarbonate-based initiator of 80-120 deg.C in 10hr half-life temperature and (2) another initiator of >=50 deg.C but <80 deg.C in 10hr half-life temperature.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a di (meth) allyl diphenate polymer having a high refractive index and mainly used for optical applications such as spectacle lenses.

[0002]

2. Description of the Related Art Polymers of allylic monomers as optical resins are polymerized relatively slowly, and the resulting polymers have little optical distortion. Therefore, optical characteristics such as spectacle lenses are important. It is often used for various purposes. Among them, di (meth) allyl diphenate polymers are especially
It has attracted attention because of its relatively high refractive index.

Regarding the di (meth) allyl diphenate polymer, JP-A-63-23908 proposes a plastic lens material containing di (meth) allyl diphenate as a main component. 60-90% by weight of di (meth) allyl acid and other copolymerizable vinyl monomers 4
It is described that 0 to 10% by weight of a radical initiator selected from known organic peroxides and azo compounds is used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the monomers. Has been done.

[0004]

Problems to be Solved by the Invention Diphenic acid di (meth)
Allyl monomer is a method using a conventional polymerization initiator,
The degree of completion of polymerization is low, and residual monomers are likely to remain in the resulting polymer. When the amount of residual monomers is large, the heat resistance and mechanical strength of the polymer are low, and further the physical properties deteriorate with time. The polymerization method described in JP-A-63-23908 is the same, and the amount of residual monomer is large in the polymerization using a low-temperature active initiator having a 10-hour half-life temperature of 50 ° C. or lower such as diisopropyl peroxydicarbonate. .. In addition, when a large amount of the initiator is used to complete the polymerization, the amount of the residual initiator in the obtained polymer becomes large, which adversely affects the physical properties of the polymer.

An object of the present invention is to polymerize monomers containing di (meth) allyl diphenate with a relatively small amount of a polymerization initiator to obtain a polymer having a high degree of completion of polymerization.

[0006]

SUMMARY OF THE INVENTION The present invention provides an unsaturated monomer mixture containing at least 20% by weight of di (meth) allyl diphenate monomer having a 10-hour half-life temperature of 80.degree.
120 ° C, perester-based and / or percarbonate-based polymerization initiator (a) and a 10-hour half-life temperature of 50 ° C
A method for producing a di (meth) allyl diphenate polymer, which comprises polymerizing using a polymerization initiator system comprising a polymerization initiator (b) at a temperature below -80 ° C.

In the present invention, the di (meth) allyl diphenate monomer is an allyl alcohol of diphenic acid or a diester of methallyl alcohol. And, the amount is required to be at least 20% by weight in the unsaturated monomer mixture in view of optical properties represented by a refractive index. The larger the amount, the higher the refractive index. From the balance of optical properties and mechanical properties, 30 to 80% by weight is preferable.

In addition to the above-mentioned di (meth) allyl-based diphenate monomer, the monomer mixture may be a polyfunctional or monofunctional unsaturated monomer.

For example, as the polyfunctional monomer,
2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis [4- (2-acryloyloxyethoxy) phenyl] propane, 2,2-bis [4-
(2-methacryloyloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloyloxypolyethoxy) phenyl] propane, 2,2-bis [4-
(Acryloyloxypolyethoxy) phenyl] propane, 2,2-bis [4- (3-methacryloyloxy-
2-hydroxypropyloxy) phenyl] propane,
2,2-bis [4- (2-methacryloyloxypropyloxy) phenyl] propane, 2,2-bis [3,5
-Dichloro-4- (2-methacryloyloxyethoxy) phenyl] propane, 2,2-bis [3,5-dibromo-4- (2-methacryloyloxyethoxy) phenyl] propane; 2,2-bis [3,5 -Dibromo-4
-(2-Acryloyloxyethoxy) phenyl] propane; 2,2-bis [3,5-dibromo-4- (3-methacryloyloxy-2-hydroxypropyloxy)]
Phenyl] propane; derivatives of bisphenol A such as 2,2-bis [3,5-dibromo-4- (2-methacryloyloxypropyloxy) phenyl] propane, or 2,2-bis [4- (2-methacryloyloxy) Derivatives of bisphenol S such as ethoxy) phenyl] sulfone, divinylbenzene, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, nonaethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, hexanediol dimethacrylate, etc. Is mentioned.

Examples of the monofunctional monomer include styrenes such as styrene, chlorostyrene and bromstyrene, (meth) methacrylate such as methyl methacrylate, ethyl acrylate, glycidyl methacrylate, benzyl methacrylate, phenyl methacrylate and tribromophenyl methacrylate. Acrylic acid esters; acid anhydrides such as maleic anhydride and citraconic anhydride; maleimides such as ethyl maleimide, phenyl maleimide, o-chlorophenyl maleimide, cyclohexyl maleimide, diethyl phenyl maleimide; and the like.

Of these monomers, the polyfunctional monomer has the function of increasing the polymerization rate, and also improves the mechanical strength, solvent resistance and machinability of the resulting polymer. Depending on the type of monofunctional monomer, the characteristics such as the mechanical strength and the refractive index of the polymer to be produced are improved, so these monomers are appropriately selected according to the intended use, and one or more kinds are used.

Specifically, the polymerization initiator (a) is, in the case of a perester type, di-t-butylperoxyhexahydroterephthalate (10-hour half-life temperature 83 ° C.), di-t-butyl peroxyazelate (99 ° C.). ), T-butylperoxy-3,5,5-trimethylhexoate (100 ° C.),
Examples thereof include t-butyl peroxyacetate (103 ° C), t-butylperoxybenzoate (105 ° C) and t-butylperoxylaurate (98 ° C).

Examples of the percarbonate system include t-butyl peroxypropyl carbonate (97 ° C.) and t-amyl peroxyisopropyl carbonate (96 ° C.).

Of these polymerization initiators, t-butylperoxyisopropyl carbonate, t-amylperoxyisopropyl carbonate, and t-butylperoxybenzoate are preferred because they have a particularly high effect of increasing the degree of completion of polymerization of the polymer. More preferably, it is t-amyl peroxyisopropyl carbonate. These polymerization initiators (a) can be used alone or in combination of two or more.

The polymerization initiator (b) is specifically, for example, a perester type t-butyl peroxy-2 ethylhexanoate (74 ° C.), t-butyl peroxypivalate (56 ° C.), t-butyl peroxyisobutyrate (78 ° C) and other lauroyl peroxide (62
C.), benzoyl peroxide (72.degree. C.), azobisisobutyl nitrile (65.degree. C.), and the like, but the above-mentioned perester type initiators are particularly preferable because they are easy to handle.
Also preferred is t-butyl-peroxy-2 ethylhexanoate. These mainly have the effect of causing the polymerization to occur at an appropriate rate. These polymerization initiators (b)
Can be used alone or in combination of two or more.

The amount of each of these polymerization initiators (a) and (b) used is 0.0 with respect to 100 parts by weight of the monomer mixture.
It is preferable to use in the range of 5 to 1.5 parts by weight, and the total amount of the polymerization initiators (a) and (b) used is 0.1 to 2
It is preferably used in the range of parts by weight. If this amount is below these ranges, the degree of completion of polymerization is low and the amount of residual monomers increases, which is not preferable. On the other hand, if the amount exceeds this range, the amount of the residual initiator is increased, so that the obtained polymer is colored and odor is generated, and the mechanical strength of the obtained polymer is lowered, which is not preferable.

To obtain an allyl polymer by the method of the present invention,
It can be carried out by a well-known cast polymerization method. Specifically, it is obtained by vacuum degassing a raw material liquid added with a polymerization initiator to a monomer mixture, then injecting it into a mold having a predetermined shape such as a flat plate shape or a lens shape, and heating the mold. .. In addition, after preliminarily polymerizing, it may be injected into a mold to polymerize. As temperature conditions,
The temperature may be appropriately determined depending on the kind of the monomer used, but the temperature is sequentially raised from about 40 ° C. to about 120 ° C. for 10 to 30 hours.

[0018]

EXAMPLES The present invention will be specifically described below with reference to examples.
All parts in the text mean parts by weight. The physical properties were measured by the methods shown below.

Amount of unreacted monomer: The polymer was extracted with acetone, and the extract was determined by gas chromatography. Heat resistance: In accordance with JIS K-7206 (Measurement of Vicat softening point), the temperature is expressed in ° C when the indenter penetrates 0.1 mm.

The abbreviations used in the examples have the following meanings. DPA: diallyl diphenate BPEA: 2,2-bis [4- (2-acryloyloxyethoxy) phenyl] fluor TO: t-butyl peroxy 2-ethylhexanoate (perester type) TB: t-butyl peroxybenzoate ( Perester type) BIC: t-butyl peroxyisopropyl carbonate (percarbonate type) TX: t amyl peroxyisopropyl carbonate (percarbonate type) IPP: diisopropyl peroxydicarbonate (percarbonate type) AIBN: 1,1-azobis Isobutyronitrile (azo type) CHP: cumene hydroperoxide (hydroperoxide type) BTH: 1,1-di-t-butylperoxy-3,3,5-
Trimethylcyclohexane (ketal system) BCH: 1,1-di-t-butylperoxycyclohexane (ketal system) PHV: n-butyl-4,4-bis (t-butylperoxy) parerate (ketal system) TBT: tris (t) -Butylperoxy) triazine (alkyl-based)

Example 1 50 parts of diallyl diphenate, 2.2-bis [4- (2
-Acryloyloxyethoxy) phenyl] propane:
50 parts, and as a polymerization initiator, t-butyl-peroxy-2 ethylhexanoate: 1.0 part, t-butyl peroxybenzoate: 0.3 part were mixed, put in a glass mold, and placed in an air oven at 50 ℃ to 120 ℃
The temperature was raised stepwise over 21 hours to polymerize. The amount of unreacted monomer in the obtained polymer was measured. The results are shown in Table 1.

Examples 2 to 3 and Comparative Examples 1 to 5 Experiments were conducted in the same manner as in Example 1 with the monomer composition and the polymerization initiator composition shown in Table 1. The results are shown in Table 1.

[0023]

[Table 1]

Example 4 Diallyl diphenate: 35 parts, 2,2-bis [3,5-
Dibromo-4- (2-methacryloyloxyethoxy)
Phenyl] propane: 25 parts, 2,2-bis [4- (2
-Acryloyloxyethoxy) phenyl] propane:
20 parts, tribromophenyl methacrylate: 10 parts,
To a monomer mixture consisting of 10 parts of benzyl methacrylate, t-butyl-peroxy-2 ethylhexanoate: 0.7 parts and t-butyl peroxybenzoate: 0.3 part were added as a polymerization initiator, and the mixture was made of glass. Pour into mold and in air oven from 50 ℃ to 120 ℃ 21
Polymerization was performed by gradually raising the temperature over time. The results are shown in Table 2.

Examples 5 to 7 and Comparative Example 6 Example 4 except that the polymerization initiators shown in Table 2 were used.
An experiment was conducted in the same manner as in. The results are shown in Table 2.

[0026]

[Table 2]

Example 8, Comparative Examples 7-10 Diallyl diphenate: 35 parts, 2,2-bis [3,5-
Dibromo-4- (2-methacryloyloxyethoxy)
Phenyl] propane: 25 parts, 2,2-bis [4- (2
-Acryloyloxyethoxy) phenyl] propane:
To a monomer mixture consisting of 6 parts, tribromophenyl methacrylate: 10 parts, benzyl methacrylate 10 parts, and diethylphenylmaleimide 15 parts, a polymerization initiator having the composition shown in Table 3 was added and poured into a stainless mold. Polymerization was performed by gradually increasing the temperature from 50 ° C. to 120 ° C. in an air oven over 21 hours. The results are shown in Table 3.

[0028]

[Table 3]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masahiko Moriya 5-1 Sokai-cho, Niihama-shi, Ehime Sumitomo Chemical Co., Ltd. (72) Inventor Hisashi Kaburagi 3-5-11, Doshomachi, Chuo-ku, Osaka Japan Sheet Glass Co., Ltd. (72) Inventor Satoshi Ishizuka 3-5-11 Doshumachi, Chuo-ku, Osaka City Japan Sheet Glass Co., Ltd. (72) Inventor Akio Takigawa 3-5-11 Doshumachi, Chuo-ku, Osaka Japan Sheet Glass Within the corporation

Claims (2)

[Claims] 1. An unsaturated monomer mixture containing at least 20% by weight of di (meth) allyl diphenate monomer, which is a perester or / and a 10-hour half-life temperature of 80 ° C. to 120 ° C. A percarbonate-based polymerization initiator (a) and 10
Polymerization initiator (b) having a time half-life temperature of 50 ° C to less than 80 ° C
A method for producing a di (meth) allyl diphenate polymer, which comprises polymerizing using a polymerization initiator system comprising 2. A polymerization initiator system, wherein the polymerization initiators of (a) and (b) are each contained in an amount of 0.05 to 1.
The manufacturing method according to claim 1, wherein the amount is 5 parts by weight and the total is 0.1 to 2 parts by weight.