JP3193422B2 - Method for producing polymer having epoxy group terminal - Google Patents

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 polymer containing an epoxy group at a terminal.

[0002]

2. Description of the Related Art Heretofore, epoxy groups have been mainly used for improving adhesive strength based on their reactive chemical structure. Direct introduction into the polymer main chain by a radical polymerization reaction is mainly performed by copolymerizing an epoxy group-containing monomer, for example, glycidyl (meth) acrylate with another copolymerizable monomer. It was done.

[0003]

However, in a radical copolymerization reaction, it has been impossible to selectively introduce an epoxy group into an arbitrary position of a polymer main chain. In particular, the fact was that it was not possible to introduce an epoxy group into the terminal of the polymer by using the above-mentioned method of radical copolymerization.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies on these problems, and as a result, when an organic peroxide having a specific chemical structure is used as a polymerization initiator at the time of a radical polymerization reaction, heavy polymerization occurs. It has been found that it is possible to introduce an epoxy group as a functional group at the terminal of the coalescence, and the present invention has been achieved.

That is, in the method of the present invention, when the polymerizable monomer is (co) polymerized, the amount of the polymerizable monomer is 2% by weight or more and 10% by weight or less. Using an organic peroxide represented by the general formula (1) as an initiator.

[0006]

Embedded image

(Here, n is 1 or 2. When n = 1, R represents a phenyl group, a linear or branched alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. A substituted fernyl group. When n = 2, R is an ethylene group, an ethynylene group, an m- or p-phenylene group.)

The monomer which can be used in the present invention is not particularly limited as long as it has radical polymerizability. For example, styrene, substituted styrene, α-methylstyrene, acrylic acid and methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate,
Acrylates such as 2-ethylhexyl acrylate and 2-vidroxyethyl acrylate, and methacrylic acid, methyl methacrylate, and ethyl methacrylate;
Methacrylic esters such as butyl methacrylate and 2-vidroxyethyl methacrylate, glycidyl methacrylate, vinyl acetate, acrylonitrile, methacrylonitrile, acrylamide, maleic acid, itaconic acid, maleic anhydride, and further ethylene, vinyl chloride, chloride Vinylidene, butadiene, isoprene and the like.

These monomers can be used not only for a homopolymerization reaction but also for a copolymerization reaction of a monomer mixture depending on the intended use of a paint, an adhesive or the like. In particular, the use of a styrene monomer represented by styrene is preferred for increasing the rate of introduction of epoxy groups to the terminal of the polymer main chain, since the recombination termination reaction takes precedence in the polymerization reaction. . If necessary, for example, n-dodecylmercaptan, or thioglycolic acid having a carboxyl group may be used as a chain transfer agent in the polymerization system.

The polymerization initiator which can be used in the present invention, in the general formula (1), n is 1 or 2, but when n = 1,

[0011]

Embedded image

[0012] Specifically, t-butyl, t-
Amyl, t-hexyl, t-octyl, α-cumyl, m
-Isopropylcumyl and the like. If n = 2,

[0013]

Embedded image

Specifically, 1,1,4,4-
Tetramethylbutylene, 1,1,4,4-tetramethyl-2-butynylene, α, α, α /, α / -tetramethyl-m-xylylidene, α, α, α /, α / -tetramethyl-p -Xylylidene and the like. Specifically, as an example of an epoxy group-containing organic peroxide, from the general formula (1),
t-butyl glycidyl peroxide, t-amyl glycidyl peroxide, t-hexyl glycidyl peroxide, α-cumyl glycidyl peroxide, t-
Octyl glycidyl peroxide, which contains 1
It has one epoxy group. Also, the general formula (1)
From 2,5-dimethyl-2,5-di (glycidylperoxy) hexane, 2,5-dimethyl-2,5-di (glycidylperoxy) hexyne-3, α, α / −bis (glycidylperoxy) ) -P-isopropylbenzene and α, α / -bis (glycidylperoxy) -m-isopropylbenzene, which have two epoxy groups per molecule. These epoxy group-containing polymerization initiators are usually used alone. However, if necessary, it can be used in combination with a polymerization initiator having a carboxylic acid or a hydroxyl group as a functional group. These organic peroxides having at least one epoxy group represented by the general formula (1) are easily synthesized by reacting epichlorohydrin with a predetermined monofunctional or bifunctional hydroperoxide in an alkaline aqueous medium. .

The amount of the initiator depends on the polymerization method and conditions, but is generally 0.1 to 10 parts, preferably 0.5 to 5.0 parts, per 100 parts of the total monomers. is there. If the amount is less than 0.1 part, the polymerization is too slow.
If the amount is more than 1 part, the control of polymerization becomes difficult and is not practical.

[0016] The polymerization method of the present invention can be carried out in a usual bulk,
Solution or suspension polymerization method. Polymerization at a constant temperature and polymerization of a heating type can also be used. Further, the present invention can also be applied to a so-called continuous drop polymerization method in which a mixture of an initiator and a monomer is dropped at a constant speed into a polymerization solvent prepared in advance.

[0017]

EXAMPLES The contents of the present invention will be described more specifically based on examples.

Example 1 A brown glass ampoule having a capacity of 5 ml was charged with 2.0 g of styrene as a monomer and 0.04 g of t-butylglycidyl peroxide [1] as a polymerization initiator, and cooled under dry ice. After the upper part of the ampoule was purged with nitrogen gas, it was sealed. Polymerization was carried out for 5 hours in an oil bath set at 120 ° C. After completion of the polymerization, the ampule was opened, the contents were taken out, and reprecipitation purification was performed at least twice with a methanol / hexane system. For the purified sample, residual monomers were determined by gas chromatography, and the conversion was calculated. If necessary, the molecular weight of the polymer was checked by gel permeation chromatography.
Further, for the purified polymer, the presence or absence of an epoxy group in the polymer was confirmed by FT-IR analysis. The results are shown in Table 1.

Example 2 Example 1 except that the monomer was changed to methyl methacrylate.
The polymerization was carried out according to The results are shown in Table 1.

EXAMPLE 3 As monomers, 1.0 g of methyl methacrylate and 1.0 g of styrene were used.
Copolymerization was carried out in the same manner as in Example 1 except that g was changed.
The results are shown in Table 1.

EXAMPLE 4 1.6 g of styrene and 0.4 g of butyl acrylate were used as monomers.
Copolymerization was carried out in the same manner as in Example 1 except that the above was changed to. The results are shown in Table 1.

Example 5 An epoxy group-containing polymerization initiator was used as 2,5-dimethyl-2,2
Styrene was polymerized according to Example 1, except that 5-di (glycidylperoxy) hexane [2] was used.
The results are shown in Table 1.

Example 6 Styrene was polymerized in the same manner as in Example 1 except that the polymerization initiator was t-amylglycidyl peroxide [3] and the polymerization temperature was changed to 115 ° C. The results are shown in Table 1.

Example 7 Styrene was polymerized according to Example 6, except that the polymerization initiator was changed to t-hexylglycidyl peroxide [4]. The results are shown in Table 1.

Example 8 Styrene was polymerized in the same manner as in Example 1 except that the polymerization initiator was changed to α-cumylglycidyl peroxide [5] and the polymerization temperature was 110 ° C. The results are shown in Table 1.

Example 9 Example 1 was repeated except that the polymerization initiator was t-octylglycidyl peroxide [6] and the polymerization temperature was changed to 100 ° C.
The polymerization of styrene was carried out according to The results are shown in Table 1.

Example 10 The polymerization initiator was t-butyl glycidyl peroxide,
Styrene was polymerized in the same manner as in Example 1 except that 0.02 g of thioglycolic acid was added as a chain transfer agent. The results are shown in Table 1.

Example 11 Copolymerization was carried out in the same manner as in Example 1, except that 1.9 g of styrene and 0.1 g of glycidyl methacrylate were used as monomers. The results are shown in Table 1.

Example 12 Styrene was prepared in the same manner as in Example 1 except that the polymerization initiator was 0.03 g of t-butyl glycidyl peroxide and 0.01 g of mono-t-butyl peroxymaleate. Polymerization was performed. The results are shown in Table 1.

Comparative Example 1 Styrene was polymerized in the same manner as in Example 1 except that the polymerization initiator was changed to t-butyl peroxybenzoate. The results are shown in Table 1.

Comparative Example 2 Polymerization was carried out in the same manner as in Example 1 except that the polymerization initiator was 0.01 g of t-butyl glycidyl peroxide, the monomer was methyl methacrylate, and the polymerization temperature was changed to 70 ° C. went. The results are shown in Table 1.

Table 1 Production of Epoxy Group-Containing Polymer Example Polymerization initiator Chain transfer agent Polymerization temperature Monomer (g) (g) (° C) (g) 1 [1] 0.04 120 Styrene (2.0) 2 [1 ] 0.04 120 Methyl methacrylate (2.0) 3 [1] 0.04 120 Styrene / methyl methacrylate (1.0 / 1.0) 4 [1] 0.04 120 Styrene / butyl acrylate (1.6 / 0.4) 5 [2] 0.04 120 styrene (2.0 ) 6 [3] 0.04 115 Styrene (2.0) 7 [4] 0.04 115 Styrene (2.0) 8 [5] 0.04 110 Styrene (2.0) 9 [6] 0.04 100 Styrene (2.0) 10 [1] 0.04 Thioglycolic acid 120 Styrene 0.01 (2.0) 11 [1] 0.04 120 Styrene / glycidyl methacrylate (1.9 / 0.1) 12 [1] / Mono-t-butyl maleate 120 Styrene 0.03 / 0.01 (2.0) Comparative example 1 t-butyl halide-benzene Over preparative 120 styrene 0.04 (2.0) 2 (1) 0.01 70 methyl methacrylate (2.0)

Polymerization initiators [1] to [6]: monofunctional and bifunctional organic peroxides containing an epoxy group. Polymerization rate (%): The amount of residual monomer in the polymer was determined by gas chromatography, and the polymerization rate was calculated. Weight average molecular weight (Mw): All molecular weights of the polymer are
Gel permeation chromatography (GPC)
And calculated as a polymerization average molecular weight (Mw) in terms of polystyrene. Epoxy group in polymer: The presence or absence of an epoxy group in the polymer was confirmed by FT-IR analysis. Here, the case where an epoxy group is present is represented by + while the case where no epoxy group is present is represented by-.

Examples Polymerization rate Molecular weight Epoxy groups (%) in polymer Mw 198.8 42900 + 299.1 51100 + 398.78.748600 + 499.3 43300 + 599.6 57000 + 699 0.0 61800 + 799.5 959 9900 + 8 99.0 71000 + 9 98.9 13500 + 10 99.0 20900 + 11 98.8 41400 + 12 99.8 43600 + Comparative example 199.4 43200-219 .4 35600 −

[0035]

As described above in detail, the present invention uses an epoxy group-containing organic peroxide as a polymerization initiator.
The introduction of an epoxy group to the terminal of the polymer became possible easily by the radical polymerization reaction. Therefore, it has great industrial value.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-235302 (JP, A) JP-A-2-49010 (JP, A) Chemical Abstracts, Vol. 97, (8), Abstract No. 56282 (1982) Chemical Abstracts, Vol. 99, (22), Abstract No. 176440 (1983) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/32-4/38 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A weight of 2 parts by weight based on a polymerizable monomer.
% And 10% by weight or less of an organic peroxide represented by the general formula (1) as an initiator, and (co) polymerizing a polymerizable monomer. A method for producing a polymer having an epoxy group terminal. Embedded image (Here, n is 1 or 2. When n = 1, R is substituted by a phenyl group, a linear or branched alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. A phenyl group. When n = 2, R is an ethylene group, an ethynylene group, an m- or p-phenylene group.)