JPS6215210A - Novel polymer containing phosphate group and production thereof - Google Patents

Abstract

PURPOSE:To industrially easily obtain the titled novel polymer usable widely in fields such as engineering, medicine, etc., having surface active ability, self tissue properties and high safety to human body, obtained by polymerizing a specific phosphoric ester monomer. CONSTITUTION:A monomer shown by the formula I [R1 is H or methyl; R2 is 1-36C alkyl; M is H, alkali (earth) metal, etc.,] is polymerized in the presence of a polymerization initiator such as diisopropyl peroxydicarbonate, etc., preferably at 20-80 deg.C to give the aimed polymer consisting of a repeating unit shown by the formula II. The monomer shown by the formula I, for example, is obtained by reacting a high-purity phosphoric monoester alkali metallic salt with glycidyl (meth)acrylate. The amount of the polymerization initiator used is preferably 0.05-5wt% based on the monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel phosphoric acid group-containing polymer and a method for producing the same.

[Conventional technology and problems]

In the field of polymer chemistry, research is underway to impart various functions to polymer compounds. One example is the imparting of chemical functions, such as the chelating ability and antistatic ability of phosphoric acid groups. There is research into adding functionality to polymer compounds. On the other hand, physical functions such as surface activity, i.e., research on imparting to polymer compounds the property of assembling and organizing by themselves (self-organizing ability), which is unique to amphiphilic compounds having hydrophilic and hydrophobic groups. There is.

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 amounts in living organisms, and therefore compounds with a phosphoric acid group in their structure are expected to have excellent biocompatibility.For example, phosphoric acid of long-chain alkyl alcohol Monoester 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. It was confirmed that Nanatsumar has excellent polymerizability and surface activity, and that a phosphate group-containing polymer can be easily obtained, and that the obtained phosphate group-containing polymer has self-assembly properties. Heading: The present invention has been completed.

That is, the present invention provides the following formula (1) (wherein, R3 is a hydrogen atom or a methyl group, and R2 has a carbon number of 1
~36 linear or branched alkyl groups, h represents a hydrogen atom, an alkali metal, an alkaline earth metal, an alkanolamine, an alkylamine, or ammonium). Yes, and furthermore, the following formula (II) 0 0
From the repeating structural unit represented by the formula (I), characterized in that the monomer represented by HOM (wherein R,, R2, and N are the same as above) is polymerized in the presence of a radical polymerization initiator. The present invention provides a method for producing a polymer.

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

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

(I[[) (IV) (In the formula, H represents an alkali metal, and R+ and Ih are the same as above) In the phosphoric ester represented by formula (n), a carbon number of 1 to 36 represented by R2 Straight-chain or branched 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 (III) is obtained 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 monoalkyl 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 (IV) 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 phosphoric acid ester represented by formula (■), an unreacted compound represented by formula (IV) or a hydrolyzate thereof. This product can be further purified to obtain a highly pure product. For example, sodium dodecyl 2-hydroxy 3-methacryloyloxypropyl phosphate [R,
= C113, Rz; C+Jzs, M=Na, hereinafter referred to as compound (V)], after reacting glycidyl methacrylate with an aqueous solution of monosodium dodecyl phosphate, water is distilled off or the reaction is The liquid is saturated with an electrolyte such as sodium chloride or potassium chloride, and the organic matter is extracted into an organic solvent such as ethyl ether.The ethyl ether is then distilled off to separate it from water. For example, after extraction and separation with n-hexane, acetone is further added to produce dodecyl 2-
By precipitating sodium hydroxy-3-methacryloyloxypropyl phosphate and separating it from the acetone-soluble glycidyl methacrylate hydrolyzate, a highly pure phosphate ester represented by formula (n) can be obtained. Obtainable. 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 phosphate [R6 in the compound of formula (II)]
・For (jh, Rz=C+□H,,,M=H), the aqueous solution of Na salt obtained as above is made acidic with an acid such as hydrochloric acid, and extracted with a solvent such as ethyl ether. Obtainable. Furthermore, it can be converted into various salts by reacting with alkanolamine, ammonia, alkylamine, etc.

In the present invention, the polymer represented by the formula (1) can be prepared in the presence or absence of a crosslinking agent, in the presence of an ordinary radical polymerization initiator, depending on the group represented by R2 or its purpose.
It can be obtained by radically polymerizing the monomer represented by formula (II) by solution polymerization, emulsion polymerization, suspension polymerization, or bulk polymerization.

As the radical polymerization initiator, known radical polymerization initiators can be used depending on the solubility of the monomer represented by the formula (■)°, and as the oil-soluble radical polymerization initiator, for example, diisopropyl peroxydicarbonate, G2
- Peroxides such as ethylhexyl peroxydicarbonate, benzoyl peroxide, trichloroacetyl peroxide, perfluorobutyl peroxide, 2
, 2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and other azo compounds, and water-soluble radical polymerization initiators include, for example, hydrogen peroxide. Hydroperoxides such as, peroxides such as potassium persulfate, or azo compounds such as 2,2'-abbis(2-amidinopropane) hydrochloride, etc. 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 (II) is used,
For example, ethylene glycol di(meth)acrylate,
It is possible to use desired amounts of diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, glycerin tri(meth)acrylate, divinylbenzene, trivinylbenzene, N,N'-methylenebisacrylamide, etc. .

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 hasychloromethane, chloroform, and chlorobenzene, or ketones such as acetone and methyl ethyl ketone, Other 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 polymer 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. Chain transfer agents such as thioglycolic acid and mercaptoethanol can be added to control the molecular weight of the resulting polymer.

[For production]

In the present invention, the fact that the polymer represented by formula (I) has self-assembly property means that, for example, a polymer of sodium dodecyl 2-hydroxy-3-methacryloyloxyprobyl phosphate [formula (I) In the compound represented by R,
, C)], , Rz=C+ tuts, M=Na) shows a flow birefringence phenomenon and forms a liquid crystal structure.

〔Effect of the invention〕

The phosphoric acid group-containing polymer of the present invention has surface activity and self-assembly properties, 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.

〔Example〕

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

Example 1 Sodium dodecyl 2-hydroxy-3-methacryloyloxypropyl phosphate (compound (■
)), 450 g of ion-exchanged water was added to dissolve it, and nitrogen gas was blown in to drive out dissolved oxygen. Furthermore, 500 mg of potassium persulfate was added and dissolved, and the temperature was raised to 70°C.

The viscosity of the reaction system increased near 50℃, but even further at 70℃
The mixture was heated and stirred for 4 hours. When the sample collected from the reaction system at this time was analyzed by HPLC (high performance liquid chromatography, the same applies hereinafter), no peak of unreacted compound (V) was observed, and the monomer compound (V) was It can be seen that everything was polymerized. After the polymerization was completed, the reaction system was frozen and freeze-dried to obtain 50 g of a white powder polymer.

When the molecular weight of this polymer was measured by gel permeation chromatography in terms of polyethylene oxide, the average molecular weight was about 200,000.

Additionally, this polymer was soluble in water and had the property of turning water into a gel. Furthermore, this polymer had the property of gelling methanol.

The IR spectrum of the obtained polymer was determined by the KBr method.
As shown in the figure.

Example 2 A mixture of 49.5 parts by weight of compound (V), 49.5 parts by weight of water, and 1 part by weight of benzoin isobutyl ether was spread thin between slide glasses and irradiated with light for 2 hours under a nitrogen stream. A colorless and transparent film that is sparingly soluble in water was obtained.

Further, a mixture of 49 parts by weight of Compound (V), 49 parts by weight of water, 1 part by weight of benzoin isobutyl ether, and 1 part by weight of ethylene glycol dimethacrylate was similarly spread between slide glasses and stretched thinly, and under a nitrogen stream. When irradiated with light for 2 hours, a colorless and transparent film that is poorly soluble in water was obtained.

Example 3 In a 500 ml four-eye flask equipped with a stirrer, reflux condenser, dropping funnel and nitrogen gas inlet tube, 25 ml of n-hexane was added.
0 ml, dissolve 0.8 g of sorbitan monostearate, blow nitrogen gas to drive out dissolved oxygen, and heat at 65°C.
The temperature rose to . In a separate flask, 0.0% potassium persulfate was added to an aqueous solution of 20g of compound (V) dissolved in 100ml of water.
1 g, N,N'-methylenebisacrylamide 0.
After adding and dissolving 0.1 g of the aqueous solution, nitrogen gas was blown into the aqueous solution to remove oxygen dissolved in the aqueous solution. This aqueous monomer solution was added dropwise to the four-eye flask over 30 minutes for polymerization. After the polymerization was completed, the reaction was continued for an additional hour while maintaining the temperature at 65°C. Thereafter, the solvent n-hexane was distilled off under reduced pressure to obtain a granular polymer. This polymer contains 35 methanol per gram of sample.
It had the property of absorbing 33g of water.

Example 4 Hexadecyl 2-hydroxy-
3-Sodium methacryloyloxypropyl phosphate [R, =CH3, R in the compound represented by formula (I[)]
z□C+Jhs, M=Na-, hereinafter referred to as compound (Vl)) 4.2 g was charged, 30 g of methanol was added and dissolved, and dissolved oxygen was driven out by blowing in nitrogen gas. This reaction solution was heated to 60°C, and while stirring, 2.2゛-
Azobis(2,4-dimethylvaleronitrile) 42m
An initiator solution prepared by dissolving g in 10 g of methanol was added dropwise,
Polymerization was further carried out for 5 hours. When the sample taken from the reaction system at this time was analyzed by HPLC, it was found that unreacted compounds (V
Almost no peak of l) was observed, indicating that the monomer compound (Vl) was almost completely polymerized. After polymerization,
The reaction solution was cooled, methanol was distilled off under reduced pressure, and the mixture was dried to obtain a bulky polymer.

[Brief explanation of drawings]

FIG. 1 is an IR spectrum of the polymer obtained in Example 1.

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. (M represents a hydrogen atom, an alkali metal, an alkaline earth metal, an alkanolamine, an alkylamine, or ammonium). 2. Formula (II) ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R_1 is a hydrogen atom or a methyl group, R_2 is a straight or branched chain alkyl group having 1 to 36 carbon atoms, and M is a Formula (I) ▲ Formula, which is characterized in that a monomer represented by a hydrogen atom, an alkali metal, an alkaline earth metal, an alkanolamine, an alkylamine or ammonium is polymerized in the presence of a radical polymerization initiator. Chemical formula,
There are tables, etc. ▼ (I) (In the formula, R_1 is a hydrogen atom or a methyl group, R_2 is a linear or branched alkyl group having 1 to 36 carbon atoms, M is a hydrogen atom, an alkali metal, an alkaline earth metal, A method for producing a polymer consisting of a repeating structural unit represented by alkanolamine, alkylamine or ammonium.