JP4889937B2 - Thiocyanate (co) polymer - Google Patents

Description

The present invention relates to a (co) polymer of 4- (2-thiocyanatoethoxy) phenyl (meth) acrylate and a method for producing the same.
The notation of (meth) acrylate indicates both acrylate and methacrylate compounds, and the notation of (co) polymer indicates a homopolymer of the above compound and a copolymer containing at least one unit of the above compound.

  Thiocyanate and thiocyanate compounds are used as antibacterial agents, fungicides, insect repellents, herbicides, chelating agents, etc., but especially thiocyanate ester alkylene dithiocyanate, especially methylene dithiocyanate is useful. Widely used as a highly effective antibacterial agent. For example, an antifouling paint containing a compound having a thiocyanate group (Japanese Patent Laid-Open No. 2002-47112; Patent Document 1), an isothiocyanate ester compound or a soil improver containing these compounds (Japanese Patent Laid-Open No. 9-95402) Patent Document 2, JP-A-10-117662; Patent Document 3) are known.

  However, among the alkylene dithiocyanates, only a part of the thiocyanate compounds that are usefully used are thiocyanate compounds, which are relatively low molecular weight compounds that are easy to elute, antibacterial agents, etc. In order to solve these problems, in order to solve these problems, it has been a shortcoming that the life span is short because it evaporates or volatilizes to use, and that many thiocyanate esters have an irritating odor. The problem is that thiocyanate ester compounds are adsorbed on an adsorbent carrier such as zeolite to extend the life and reduce odors, but this is not an effective solution.

JP 2002-0471112 A JP 09-095402 A Japanese Patent Laid-Open No. 10-117662

  Therefore, in the present invention, unlike conventional alkylene dithiocyanates, there is no odor, and the novel antibacterial agent, fungicide, insect repellent or herbicide has the same effect as conventional alkylene dithiocyanates. An object is to provide a homo- or copolymer of a thiocyanate compound.

  As a result of earnest research to develop more useful compounds among the thiocyanate compounds, the present inventor has obtained a polymer of a (meth) acrylate ester of a thiocyanate ester compound represented by the following general formula (1). To complete the present invention.

General formula (1)
(In the formula, R represents hydrogen or a methyl group, and n represents an integer of 2 or more.)

  That is, an object of the polymer of the present invention is to provide a homo or copolymer in which n of the compound represented by the following chemical formula (2) or (3) is 2 or more.

Chemical formula (2)

Chemical formula (3)

More specifically, the present invention is characterized by the following configurations.
[1] Poly [4- (2-thiocyanatoethoxy) phenyl (meth) acrylate] represented by the following general formula (1).
(In the formula, R represents hydrogen or a methyl group, and n represents an integer of 2 or more)

General formula (1)
[2] A copolymer comprising at least one unit of the following general formula (1) as a comonomer.
(In the formula, R represents hydrogen or a methyl group, and n represents an integer of 2 or more)

General formula (1)
[3] The monomer is a vinyl monomer selected from ethylene, propylene, (meth) acrylonitrile, acrylamide, styrene, vinyl acetate, (meth) acrylic acid or (meth) acrylic acid ester compound, etc. The copolymer of [2] above.
[4] The (co) polymer according to any one of [1] to [3], wherein the molecular weight is in the range of 2,000 to 300,000.

  In the present invention, 4- (2-thiocyanatoethoxy) phenyl (meth) acrylate which is a monomer of the general formula (1) and other monomers used for copolymerization include ethylene, propylene, (meth) acrylonitrile, Vinyl monomers having a vinyl group such as acrylamide, styrene, vinyl acetate, (meth) acrylic acid or (meth) acrylic ester compounds are suitable.

  The copolymer containing the (meth) acrylic acid polymer of thiocyanate ester represented by the general formula (1) and 4- (2-thiocyanatoethoxy) phenyl (meth) acrylate of the present invention is high. It is a molecular compound and has almost no odor. Taking advantage of this advantage, it can be used as an antibacterial agent, fungicide, insect repellent or herbicide similar to conventional alkylene dithiocyanates.

The homopolymer and copolymer of the present invention are represented by the following general formula (1).
(In the formula, R represents hydrogen or a methyl group, and n represents an integer of 2 or more)
If the polymer of the present invention has n of 2 or more, that is, a polymer having a molecular weight of 498.58, the odor is hardly perceived, but considering the volatilization or volatilization of the components, the molecular weight range is from 2000 to 300,000 is suitable.

General formula (1)

  To produce the (co) polymer of the present invention, first, hydroquinone is reacted with 1,2-dihalogenoethane such as 1,2-dibromoethane in an ethanol solvent in the presence of an alkali catalyst in the presence of 4- (2-bromoethoxy). ) Phenol, this is reacted with a (meth) acryloylating agent such as (meth) acryloyl chloride in a THF solvent under a triethylamine catalyst to give 4- (2-bromoethoxy) phenyl (meth) acrylate, followed by a DMF solvent In this reaction, potassium thiocyanate is reacted to produce 4- (2-thiocyanatoethoxy) phenyl (meth) acrylate.

  As the alkali when the alkali is allowed to act on the hydroquinone, in addition to potassium hydroxide, alkali metal hydroxide such as sodium hydroxide, alkaline earth metal hydroxide such as calcium hydroxide, alkali metal such as sodium or oxidation Basic metal oxides such as silver can be used.

  As 1,2-dihalogenoethane, 1,2-dichloroethane and the like can be used in addition to 1,2-dibromoethane. Furthermore, examples of the (meth) acryloylating agent include acid halides such as acrylic acid, methacrylic acid, acryloyl chloride, and methacryloyl chloride.

  In the reaction in which ethylene side chains are introduced into hydroquinone, 1,2-dihalogenoethane is added as described above, and alcohols such as methanol and ethanol in which an alkali is dissolved are used as a solvent. The reaction temperature at this time is below the boiling point of a solvent, Preferably it is 0-100 degreeC, More preferably, it is 20-80 degreeC. If it is less than 0 ° C., the reaction between hydroquinone and 1,2-dihalogenoalkane hardly occurs, and if it exceeds 100 ° C., by-products in which ethylene side chains are introduced into both hydroxyl groups increase. The boiling point of methanol and ethanol used as the reaction solvent is preferably set as the reaction temperature.

In addition, the reaction of 4- (2-halogenoethoxy) phenol having 1,2-dihalogenoethane acting on hydroquinone to form an ethylene side chain and a (meth) acryloylating agent can be performed by using a reaction solvent. This reaction can vary depending on the (meth) acryloylating agent. When an acid halide such as acryloyl chloride or methacryloyl chloride is used, an ether such as diethyl ether or tetrahydrofuran can be used as a reaction solvent.
The reaction temperature is room temperature or lower, usually, preferably −20 to 10 ° C. when the acid halide is dropped, and −20 to 20 ° C. after the dropping is completed. When the temperature is lower than −20 ° C., the reaction between 4- (2-halogenoethoxy) phenol and the (meth) acryloylating agent hardly occurs, and when the temperature exceeds 20 ° C., the polymerization reaction easily occurs.

The reaction of 4- (2-halogenoethoxy) phenyl (meth) acrylate esterified by the action of the (meth) acryloylating agent and a thiocyanate such as potassium thiocyanate is carried out by using a reaction solvent. It can be carried out. As the reaction solvent, a ketone such as acetone or an amide such as N, N-dimethylformamide is used.
The reaction temperature can be not higher than the boiling point of the solvent, usually -20 to 60 ° C, more preferably 20 to 50 ° C. When the temperature is lower than −20 ° C., the reaction between 4- (2-halogenoethoxy) phenyl (meth) acrylate and thiocyanate hardly occurs, and when the temperature exceeds 60 ° C., the polymerization reaction easily occurs.

As the thiocyanate, for example, alkali metal salts such as potassium thiocyanate, sodium thiocyanate or lithium thiocyanate can be used.
The obtained thiocyanate compound is purified using column chromatography or thin layer chromatography.
The purified compound was identified by NMR method, FT-IR method and GC-MS method to confirm 4- (2-thiocyanatoethoxy) phenyl (meth) acrylate.

  To (co) polymerize 4- (2-thiocyanatoethoxy) phenyl (meth) acrylate obtained by the above reaction, potassium peroxodisulfate, benzoyl peroxide, α, α′-azobisiso Butyronitrile or lauroyl peroxide is produced by radical solution polymerization using toluene, benzene, tetrahydrofuran, or the like as a solvent.

The initiator is the same as described above, water is used as the solvent, and “Emalex OA12” (manufactured by Nippon Emulsion Co., Ltd., compound name: polyoxyethylene octyl ether), “Neugen YX-500” ( It can also be produced by radical emulsion polymerization using Daiichi Kogyo Seiyaku Co., Ltd., compound name: polyethylene glycol lauryl ether).
Furthermore, the initiator is the same as described above, radical suspension polymerization using water as a solvent, further, alkyllithium, cumyl potassium, naphthalene sodium or phenylmagnesium bromide as an initiator, tetrahydrofuran as a solvent, It can also be produced by anionic polymerization using toluene or diethyl ether.

  Poly [4- (2-thiocyanatoethoxy) phenyl (meth) acrylate], which is the target compound of the present invention, is converted from a hydroquinone raw material to 4- (2-thiocyanatoethoxy) phenyl (meth) acrylate monomer of thiocyanate ester. FIG. 1 shows a reaction formula when the production is carried out through the process.

In addition, the (co) polymer manufactured by this invention can be identified by NMR method and FT-IR method.
Further, the average molecular weight of the (co) polymer can be measured by a GPC method, a viscosity method or the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, the scope of the present invention is not limited to this.

<Production of homopolymer>
Preparation of poly [4- (2-thiocyanatoethoxy) phenyl acrylate];
In a Kjeldahl flask, 5 g of 4- (2-thiocyanatoethoxy) phenyl acrylate and 0.066 g of α, α'-azobisisobutyronitrile (AIBN) were dissolved in 50 ml of toluene, and inert gas replacement was performed. Then, the mouth was sealed and reacted at 50 ° C. for 25 hours. The reaction product was precipitated in diethyl ether and further washed with diethyl ether. The precipitate was dried under reduced pressure to obtain poly [4- (2-thiocyanatoethoxy) phenyl acrylate].
Table 1 shows the yield, properties, average molecular weight, and ¹ H-NMR and FT-IR measurement data.

<Production of homopolymer>
Production of poly [4- (2-thiocyanatoethoxy) phenyl methacrylate];
In a Kjeldahl flask, 5 g of 4- (2-thiocyanatoethoxy) phenyl methacrylate and 0.0624 g of AIBN were dissolved in 50 ml of toluene, and after inert gas replacement, the mouth was sealed and 25 ° C. at 25 ° C. Reacted for hours. The reaction product was precipitated in diethyl ether and further washed with diethyl ether. The precipitate was dried under reduced pressure to obtain poly [4- (2-thiocyanatoethoxy) phenyl methacrylate].
Table 1 shows the yield, properties, average molecular weight, and ¹ H-NMR and FT-IR measurement data.

<Manufacture of copolymer>
Production of [4- (2-thiocyanatoethoxy) phenyl methacrylate] -methyl methacrylate copolymer;
In a Kjeldahl flask, predetermined amounts of 4- (2-thiocyanatoethoxy) phenyl methacrylate (A) shown in Table 2, predetermined amounts of methyl methacrylate (B) shown in Table 2, and amounts shown in Table 2 AIBN (C) was dissolved in 50 ml of toluene and purged with inert gas, and then the mouth was sealed and reacted at 50 ° C. for 25 hours. The reaction product was precipitated in diethyl ether and further washed with diethyl ether. The precipitate was dried under reduced pressure to obtain each copolymer [1] to [3] in Table 2.
Table 2 shows the yield, copolymerization ratio, and average molecular weight of each copolymer obtained.

Reaction formula for the synthesis of the polymer of the present invention

Claims (1)

Poly [4- (2-thiocyanatoethoxy) phenyl (meth) acrylate] represented by the following general formula (1).
(In the formula, R represents hydrogen or a methyl group, and n represents an integer of 2 or more)

General formula (1)