JPS6215214A - Production of copolymer - Google Patents

Abstract

PURPOSE:To obtain a phosphoric acid group-containing copolymer capable of readily imparting chelating ability, antistatic property, biological affinity, etc., to a high polymer, by polymerizing a specific phosphoric acid group- containing vinyl monomer with another vinyl monomer in the presence of a radical polymerization initiator. CONSTITUTION:For example, a phosphoric acid group-containing vinyl monomer, obtained by reacting a monoalkali metal monoalkylphosphate with glycidyl (meth)acrylate and expressed by the formula [R1 is H or methyl; R2 is 1-26C alkyl; M is H, alkali (earth) metal, alkanolamine, alkylamine or ammonium] is polymerized with another vinyl monomer, e.g. (meth)acrylic acid, in the presence of a radical polymerization initiator e.g. diisopropyl poeroxydicarbonate, in an amount of preferably 0.05-5.0wt% based on the monomers, preferably at 20-80 deg.C temperature to afford the aimed phosphoric acid group-containing copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a copolymer containing phosphoric acid groups.

(Conventional techniques and problems) In the field of polymer chemistry, research is underway to impart various functions to polymer compounds. There is research on imparting functions such as chelating ability and antistatic ability to polymer compounds.Furthermore, on the other hand, physical functions such as surface activity, which is unique to amphiphilic compounds having hydrophilic and hydrophobic groups, are being studied. There is research on imparting the ability to aggregate and organize (self-organizing ability) to polymeric compounds, and research on simply imparting hydrophobicity to polymeric compounds.

Furthermore, research has recently been actively conducted to apply polymer compounds not only to engineering but also to fields such as medicine and pharmacy, and in such cases, compounds with good compatibility with living organisms are desired. A type of phosphoric acid ester called phospholipid exists in large quantities in living organisms, and therefore compounds with a phosphoric acid group are expected to have excellent biocompatibility.For example, phosphoric acid monoesters of long-chain alkyl alcohols are Alkali metal or alkanolamine salts are widely used as cleansing agents that are less irritating to the skin. Furthermore, these phosphoric acid esters also have excellent properties in terms of the above-mentioned surfactant ability. Phosphate group-containing polymers are being studied in various ways as polymer compounds with new functions due to the distinctive properties of these phosphate group-containing compounds, but it is difficult to industrially obtain polymers with phosphate groups. Therefore, a technology that can be easily manufactured industrially has been desired.

[Means for solving problems]

Under these circumstances, the inventors of the present invention have conducted intensive research and have found that a phosphate ester group-containing vinyl having a specific group can be obtained with high purity and high yield from easily available raw materials through simple operations. The present invention was completed based on the discovery that the monomer has excellent copolymerizability and that a phosphoric acid group-containing copolymer can be easily obtained.

That is, the present invention is based on the following formula (I)% formula% (wherein R1 is a hydrogen atom or a methyl group, R2 is a carbon number 1
~36 straight-chain or branched alkyl groups, the group represents hydrogen atoms, alkali metals, alkaline earth metals, alkanolamines, alkylamines, or ammonium) and other vinyl monomers. The present invention provides a method for producing a copolymer, which is characterized by polymerizing in the presence of a radical polymerization initiator.

In the present invention, the phosphoric acid ester represented by formula (I) has been proposed by some of the inventors of the present invention, in which glycidyl methacrylate or glycidyl acrylate is added to a monoalkali metal salt of a highly purified phosphoric acid monoester. It can be easily produced industrially by reaction.

That is, a monoalkali metal salt of a monoalkyl phosphoric acid represented by formula (n) is reacted with glycidyl methacrylate or glycidyl acrylate represented by formula (III) to produce a phosphate ester, and if necessary acidified and further treated with a base. It can be easily produced by neutralizing with.

(n) (Ill) 0HOM' (in the formula, "gate" represents an alkali metal, and R,, R, are the same as above) In the phosphoric ester represented by formula (I), R2 has 1 to 1 carbon atoms. 36 straight chain or WE chain alkyl groups include methyl, ethyl, butyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, tocosyl, triacontyl, 2=ethylhexyl, 2-hexyldecyl, 2-octylundecyl, 2
-decyltetradecyl, 2-undecylhexadecyl,
Examples include 2-tetradecyl octadecyl and monomethyl branched isostearyl groups, among which those having 8 to 36 carbon atoms are preferred from the viewpoint of surface activity and self-organizing ability.

In the above reaction formula, the monoalkyl phosphate represented by formula (n) is produced by reacting a phosphorylating agent such as phosphorus pentoxide, phosphorus oxychloride, or polyphosphoric acid with an organic hydroxy compound having a corresponding alkyl group. It can be obtained by obtaining phosphoric acid and then neutralizing it, and it may be obtained by any of these methods.

In the above reaction, glycidyl methacrylate or glycidyl acrylate represented by formula (I[[) is
It is preferable to carry out the reaction in an amount of 1 to 10 mol, particularly 3 to 5 mol, per 1 mol of the monoalkali metal salt of monoalkyl phosphoric acid represented by II).

The solvent used in the reaction is preferably an inert polar solvent, such as water, methyl alcohol, ethyl alcohol, etc., with water being particularly preferred.

The reaction temperature is preferably 30 to 100°C, particularly 50 to 90°C.

Furthermore, polymerization inhibitors or polymerization inhibitors may be added during the reaction, such as hydroquinone monomethyl ether, hydroquinone, 2゜2'-methylenebis(4-
ethyl-6-t-butylphenol) etc. to glycidyl methacrylate or glycidyl acrylate.
It is preferable to add ~10.000 ppm.

The reaction solution thus obtained contains, in addition to the target compound phosphoric ester, an unreacted compound represented by the formula (I[[) or a hydrolyzate thereof. Depending on the purpose of use, it is possible to use the reaction product obtained from this reaction solution as it is, but it is also possible to further refine this product to obtain a highly pure product. For example, dodecyl 2-
Sodium hydroxy-3-methacryloyloxypropyl phosphate [R1=CH3, R in the compound of formula (I)
z=C+Jzs, M=Na, hereinafter, compound (I'/)
In the case of 1), after reacting glycidyl methacrylate with an aqueous solution of monosodium dodecyl phosphate, the water is distilled off, or the reaction solution is saturated with an electrolyte such as sodium chloride or potassium chloride, and the organic matter is removed with ethyl ether. After extraction with an organic solvent such as, ethyl ether was distilled off and separated from water, unreacted glycidyl methacrylate was extracted and separated with a non-polar solvent such as n-hexane, and acetone was further added to produce the product. By precipitating sodium dodecyl 2-hydroxy-3-methacryloyloxyprobyl phosphate and separating it from the hydrolyzate of glycidyl methacrylate soluble in acetone, the target product with good purity can be obtained. Note that, if unreacted glycidyl methacrylate is completely hydrolyzed after the reaction is completed, the subsequent purification step will be facilitated.

Acid form of dodecyl 2-hydroxy-3-methacryloyloxypropyl phosphorus fl! (For the compound of formula (I), R1=CH3, Rz=C+2Hzs -M=H), the aqueous solution of Na salt obtained as above is made acidic with an acid, such as hydrochloric acid, and then made with a solvent such as ethyl ether. It can be obtained by extraction. Furthermore, it can be converted into various salts by reacting with alkanolamine, ammonia, alkylamine, etc.

Furthermore, the vinyl monomer to be copolymerized with the phosphoric acid group-containing monomer represented by formula (I) may be a monomer that is not copolymerizable, such as an anionic monomer. Monomers include (meth)acrylic acid, crotonic acid,
Unsaturated such as vinylbenzoic acid, vinylsulfonic acid, styrenesulfonic acid, 3-acrylamide, -2,2-dimethylpropane-1-sulfonic acid, vinyltoluenesulfonic acid - unsaturated such as basic acids, maleic acid, fumaric acid Dibasic acids and their monoesters, and monomers having carboxylic acid or sulfonic acid groups such as maleic anhydride, etc., and cationic monomers include vinylpyridine, 2-methyl -monovinylpyridines such as 5-vinylpyridine, N,N-dimethylaminostyrene, N
, styrenes having a dialkylamino group such as N-dimethylaminomethylstyrene, dialkylamino groups of (meth)acrylic acids such as N,N-dimethylaminoethyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate. esters having N-(N
', N'-dimethylaminoethyl)(meth)acrylamide, N-(N''Nl-diethylaminopropyl)
(meth)acrylamides having a dialkylamino group such as (meth)acrylamide, unsaturated amines such as (meth)allyldimethylamine, (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acrylamidopropyltrimethylammonium chloride, etc. Examples include ammonium salts having unsaturated groups, and also nonionic monomers (meth)acrylic acid alkyl esters (alkyl groups are linear or branched and have 1 carbon number).
~18), glyceryl (meth)acrylate, polyethylene glycol (meth)acrylate, glycidyl (meth)acrylate, allyl glycidyl ether, vinyl acetate, acrylonitrile, styrene, alkyl-substituted styrene (alkyl group has 1 to 18 carbon atoms), (meth) ) acrylamide, vinylpyrrolidone, etc. It is also possible to use a mixture of two or more of these copolymerization partner monomers.

The copolymer of the present invention can be subjected to solution polymerization, emulsion polymerization, suspension polymerization, or bulk polymerization depending on the group represented by R2 or its purpose in the presence or absence of a crosslinking agent or in the presence of a conventional radical polymerization initiator. It can be obtained by radical polymerization of the monomer represented by formula (I) and a vinyl monomer as a copolymerization partner monomer.

As the radical polymerization initiator, known radical polymerization initiators can be used depending on the copolymerization conditions, and as the oil-soluble radical polymerization initiator, for example, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, benzoyl Peroxides such as peroxide, trichloroacetyl peroxide, perfluorobutyl peroxide, azo compounds such as 2,2''-azobisisobutyronitrile, 2. Examples of water-soluble radical polymerization initiators include hydroperoxides such as hydrogen peroxide, peroxides such as potassium persulfate, or 2.2''-azobis(2-amidinopropane) hydrochloride. Azo compounds such as the following can be used. It is also possible to use a mixture of two or more of these polymerization initiators, and it is also possible to use them as a redox polymerization initiator by adding chromium ions, sulfite ions, hydroxylamine, hydrazine, etc. . Photopolymerization is also possible, and carbonyl compounds such as benzoin isobutyl ether, peroxides such as benzoyl peroxide, and azo compounds such as 2.2°-azobisisobutyronitrile are also used as photosensitizers. Further, in addition to these catalysts, sodium bisulfite, sodium thiosulfate, ferrous ammonium sulfate, etc. may be used in combination as a promoter.

The amount of the polymerization initiator added is usually 0.05 to 0.05 to the monomer.
Preferably it is 5.0% by weight.

Further, as a crosslinking agent, a polyfunctional ethylenically unsaturated monomer copolymerized with the monomer represented by formula (I) is used, such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, etc. , and polyethylene glycol di(meth)acrylate, glycerin tri(meth)acrylate, divinylbenzene,
Trivinylbenzene, N,N'-methylenebisacrylamide, etc. can be used in desired amounts.

The solvent used in the polymerization reaction is not particularly limited, but depending on the polymerization method, water, lower alcohols such as methanol, ethanol, and isopropanol, aliphatic hydrocarbons such as n-hexane and cyclohexane, benzene, toluene, Aromatic hydrocarbons such as xylene, organic ethers such as diethyl ether, diisopropyl ether, and tetrahydrofuran, halogenated hydrocarbons such as ishacyclomethane, chloroform, and chlorobenzene, or ketones such as acetone and methyl ethyl ketone, or Examples include amides such as dimethylformamide and dimethylacetamide, and sulfoxides such as dimethylsulfoxide and sulfolane. Further, the above solvents may be used in combination.

The polymerization temperature during polymerization may be within the normal polymerization temperature range, and is suitably 0 to 100°C, preferably 20 to 80°C.

The molecular weight of the resulting copolymer is not particularly limited, and can be obtained by controlling the polymerization conditions, ranging from liquid low molecular weight polymers to plastic high molecular weight polymers. By adding a chain transfer agent such as , thioglycolic acid, or mercabutoethanol, the molecular weight of the resulting polymer can be controlled.

[For production]

Since the copolymer of the present invention contains a phosphoric acid group, it is possible to easily introduce a function as a phosphoric acid group into a polymer compound according to the present invention, and the ion exchange ability, chelating ability, and
Functions such as antistatic ability and biocompatibility are imparted to the polymer compound, and when R2 of the monomer represented by formula (I) is a long-chain alkyl group, the resulting polymer compound has a hydrophobic group. At the same time, it imparts surfactant-like properties to polymeric compounds, expanding the uses of polymeric compounds as polymeric surfactants, emulsifiers, and dispersants.

〔Effect of the invention〕

The phosphoric acid group-containing copolymer of the present invention has surfactant ability, is highly safe for the human body, and can be produced industrially with great advantage. Therefore, it can be widely used in fields such as engineering and medicine.

Examples] The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 27! equipped with a stirrer, reflux condenser and nitrogen gas inlet tube!
Add sodium dodecyl 2-hydroxy-3-methacryloyloxypropyl phosphate (compound (
(2) ) 30.9 g (0.07 mol), glyceryl methacrylate [hereinafter referred to as compound (V) 1 23.
Prepare 2g (0.14 mol) and add 950 ml of ion-exchanged water.
g was added and completely dissolved.

Blow nitrogen gas into this solution to drive out dissolved oxygen.
Furthermore, 500 mg of potassium persulfate was added and dissolved, and the temperature was raised to 70°C. The mixture was further heated and stirred for 4 hours while maintaining the temperature at 70°C. When the sample collected from the reaction system at this time was analyzed by HPLC (high performance liquid chromatography, the same applies hereinafter), no peaks of unreacted compound (IV) or compound (V) were observed, and all monomers were I can see that you reacted. After the polymerization was completed, the reaction system was frozen and freeze-dried to obtain a white powder copolymer of compound (IV) and compound (V).

This copolymer was soluble in a tit solution of ethanol/water and had the property of gelling this solution.Example 2: A four-eye flask equipped with a stirrer, a reflux condenser, and a nitrogen gas inlet tube. Sodium dodecyl 2-hydroxy-3-methacryloyloxypropyl phosphate (compound (IV)
) 15g (0,036 mol), 2-dimethylaminoethyl methacrylate [hereinafter referred to as compound (Vl)]
5.7 g (0,036 mol) was added, and 100 g of ion-exchanged water was added to completely dissolve it. Nitrogen gas was blown into this solution to drive out dissolved oxygen, and 0.1 g of potassium persulfate was added and dissolved, followed by heating at 65° C. for 8 hours under a nitrogen stream. Pour the reaction solution into isopropanol 2I! The precipitated white solid was filtered out and dried under reduced pressure under heat to obtain 11.2 g of a copolymer of compound (TV) and compound (Vl).

The nitrogen and phosphorus contents of the copolymer determined by elemental analysis are 2.4% and 4.9%, respectively, and these values are for a copolymer containing approximately equal moles of both compound (IV) and compound (Vl). It shows the formation of polymer.

Example 3 In a four-eye flask equipped with a stirrer, a reflux condenser, and a nitrogen gas inlet tube, sodium octyl 2-hydroxy-3-methacryloyloxypropyl phosphate [R9=CL in the compound represented by formula (I), Rz=CsHI1, M
=Na, hereinafter referred to as compound (■)) 13.5g (
0,036 mol), methacryloyloxyethyltrimethylammonium chloride [hereinafter referred to as compound (■)] 7
．． 4 g (0,036 mol) was added, and 100 g of ion-exchanged water was added to completely dissolve it. Nitrogen gas was blown into this solution to drive out dissolved oxygen, and 0.1 g of potassium persulfate was added and dissolved, followed by heating at 65° C. for 8 hours under a nitrogen stream. At the end of the reaction, the reaction mixture turned into a white gel-like substance. The product was dispersed in a large amount of water, washed, filtered, and then dried under reduced pressure under heat to obtain 17.2 g of a copolymer of compound (■) and compound (■).

The nitrogen and phosphorus contents of the copolymer determined by elemental analysis are 2.5 and 5.3%, respectively, and these values are for a copolymer containing approximately equal moles of both compound (■) and compound (■). It shows the properties of the polymer.

Example 4 Cyclohexane 2 was added to a 500 ml four-bottle flask equipped with a stirrer, reflux condenser, dropping funnel, and nitrogen gas inlet tube.
50 ml was charged, nitrogen gas was blown in to drive out dissolved oxygen, and the temperature was raised to 75°C.

Separately, in a flask, 30 g of acrylic acid was added to 40 g of ion-exchanged water with 13.4 g of 98% caustic soda while cooling from the outside.
It was neutralized with a solution of g. Next, 0.1 g of potassium persulfate and 5 g of Compound (IV) were added and dissolved, and then nitrogen gas was blown into the solution to remove oxygen present in the aqueous solution.

This solution was added dropwise to the above Yotsuro flask over 30 minutes to polymerize.

After the polymerization was completed, the reaction was continued for an additional hour while maintaining the temperature at 75°C. Thereafter, the solvent cyclohexane was distilled off under reduced pressure, and the remaining polymer portion was dried under reduced pressure at 80 to 100°C to obtain a small granular copolymer having a center particle size of 100 to 350 tttn.

Claims (1)

[Claims] 1. Formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R_1 is a hydrogen atom or a methyl group, and R_2 is a straight or branched chain having 1 to 36 carbon atoms. in the presence of a radical polymerization initiator. A method for producing a copolymer, characterized by polymerization.