GB2172889A

GB2172889A - Phosphoric esters

Info

Publication number: GB2172889A
Application number: GB08606632A
Authority: GB
Inventors: Junya Wakatsuki; Toru Kato; Tomihiro Kurosaki
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 1985-03-20
Filing date: 1986-03-18
Publication date: 1986-10-01
Also published as: JPS61215398A; GB8606632D0; GB2172889B; DE3609491A1

Abstract

Phosphoric esters of the following general formula <IMAGE> in which R' represents a hydrogen atom or a methyl group, R represents a linear or branched alkyl group having from 1 to 36 carbon atoms or a linear or branched fluoroalkyl group at least one hydrogen atom of which is substituted with a fluorine atom and which has from 1 to 36 carbon atoms, and M represents a hydrogen atom, an alkali metal, ammonium, or a salt of an alkylamine or an alkanolamine, have good surface activity, self-organizability and polymerizability, and are highly safe to the human body. When polymerized, the resulting polymers have wide utility in the engineering and medical fields.

Description

SPECIFICATION Phosphoric esters 1) Field of the invention This invention relates to novel phosphoric esters and more particularly to phosphoric esters having good surface activity, self-organizability (which may be hereinafter referred to simply as S.O.), and polymerizability.

2) Description of the prior art Cells are the minimum unit of a living body and are covered with cell membranes. This cell membrane has various functions such as cell separation, sectional formation, cell movement, transport of substances, transmission of information and the like, and is a source of life activity.

On the other hand, in the field of polymer chemistry, intensive studies have been recently made on synthetic polymer membranes which have such functions as the cell membranes in order to apply the polymer membranes to wide fields such as of engineering, medical science, and pharmacology.

For instance, studies have been made on separation membranes of polymers having the function of substance transport. In the field of engineering, artificial polymer membranes have now been widely used industrially as ion-exchange membranes, membranes for dialysis, membranes for ultrafiltration, gas separation membranes, membranes for reverse osmosis and the like. In the medical field, extensivestudies have been made on solute-permeable membranes for purification of blood as used in artificial kidney, gas permeable membranes for purification of blood as used in artificial lung, and the like.

Moreover, studies of microcapsules having the section-protective function have been made. Artificial polymer membranes have been applied, for example, to microcapsulation of perfumes and duplicating papers in which inks are microcapsulated.

For the application of microcapsules having a permeating function, there have been studied microcapsulation of a drug derivery system or carrier of enzymes, artificial erythrocyte and the like.

It has been revealed that cell membranes have a bimolecular phospholipids membrane. Accordingly, natural phospholipids (natural liposomes) are used to make a bilayer vesicle similar to a cell membrane and the vesicle is utilized as a model substance of a vital membrane in order to elucidate various phenomena in biological membranes. The biological membrane is systematically oriented by the physical property of phospholipid molecules, or the property of self-gathering and organization inherent to an amphiphilic compound having both hydrophobic and hydrophilic groups and thus, forms a bilayer structure.

Thus, known artificial polymer membranes are completely different in structure from biological membranes.

In recent years, however, a variety of compounds have been found which have S.O. and are capable of forming a bilayer membrane structure, including not only natural phospholipids, but also synthetic compounds. Accordingly, artificial liposomes could be prepared using synthetic compounds. Moreover, polymeric liposomes in which the bilayer structure is stabilized by polymerization have been extensively studied. For this purpose, there has been prepared a compound, used as a monomer, having a polymerizable hydrophobic or hydrophilic group, e.g. a compound of the following formula (IV) was prepared by Regan et al [Journal of the American Chemical Society, 105,2975(1983)].

These natural, artificial and polymer liposomes are considered to be a kind of microcapsule and the application of these liposomes to engineering and medical sciences in the future is now expected. In consideration of monomers as a material for the membrane, such monomers should have not only good chemical properties, but also surface activity and physical properties such as S.O. In addition, the monomers should favorably have good biocompatibility on future application for biomedical use. Natural phospholipids just have desired functions or properties such as surface activity, S.O., biocompatibility and the like, and compounds obtained by introducing polymerizable groups into phospholipids have been noticed more and more.

Since phospholipids of high purity are difficult to obtain and expensive, there is a demand of a development phosphoric ester monomers which are easy to prepare industrially and which have good surface activity, S.O. and polymerizability and are highly safe to human body.

Summary of the invention Under these circumstances in the art, the present inventors have intensively made studies and, as a result, found that novel phosphoric esters having a specific group have good surface activity, S.O. and polymerizability. The resulting polymers have good film formability and antistaticity. The esters can be synthesized from inexpensive and readily available starting materials in high yield and high purity. The present invention is accomplished based on the above finding.

According to the present invention, there is provided a phosphoric ester of the following general formula (I)

in which R' represents a hydrogen atom or a methyl group, R represents a linear or branched alkyl group having from 1 to 36 carbon atoms or a linear or branched fluoroalkyl group at least one hydrogen atom of which is substituted with a fluorine atom and which has from 1 to 36 carbon atoms, and M represents a hydrogen atom, an alkali metal, ammonium, or a salt of an alkylamine or an alkanolamine.

Brief description of the drawings Figure 1 is a phase diagram of a phosphoric ester compound (V)/H2O system of the invention.

Figure 2 is an IR spectrum diagram of the compound (V).

Detailed description of the invention and preferred embodiments In Japanese Patent Publication No. 55-2235, there is described an adhesive for human hard tissue which comprises a polymer of a phosphoric ester having at least one polymerizable functional group.

The phosphoric ester having at least one polymerizable functional group may be within the scope of the compound of the above general formula (I) according to the invention. However, in the above patent publication, the compound of the formula (I) is not particularly described and the polymer is used as an adhesive. In this sense, the compound (I) of the invention is believed to be a novel compound.

The phosphoric esters of the general formula (I) of the invention can be readily prepared, for example, by a process in which glycidyl methacrylate or acrylate of the formula (Ill) is reacted with a monoaikali metal salt of a monoalkyl phosphate of the formula (II) according to the following reaction formula to obtain a phosphoric ester (la), which is, if necessary, subjected to acidification and neutralization with a base.

in which M' represents an alkali metal, and R and R' have the same meanings as defined before, respectively.

In the phosphoric esters of the formula (I), the linear or branched alkyl groups having from 1 to 36 carbon atoms and represented by R include, for example, methyl, ethyl, butyl, octyl, decyl, dodecyl tetradecyl, hexadecyl, octadecyl, docosyl, tetracosyl, triacontyl, 2-ethylhexyl, 2-hexyldecyl, 2-octyldodecyl, 2decyltetradecyl, 2-undecylhexadecyl, 2-tetradecyloctadecyl, emery-isostearyl and the like groups.

The fluoroalkyl groups whose at least one hydrogen group is substituted with a fluorine atom include, for example, tridecafluorooctyl, heptadecafluorododecyl, heneicosafluorododecyl, pentacosafluorotetrade- cyl, nonacosafluoro hexadecyl, tritriacontafl uorooctadecyl, 2-pentafl uo roethyl pentafl uoroh exyl, 2tridecafluorohexyltridecafluorodecyl, 2-heptadecafluorooctylheptadecafluorododecyl, 2 heneicosafluorodecylheneicosafluorotetradecyl, 2-pentacosafluorododecylpentacosafluorohexadecyl, 2 nonacosafluorotetradecylnonacosafluorooctadecyl and the like groups.

These alkyl or fluoroalkyl groups should preferably have from 8 to 36 carbon atoms in view of surface activity and S.O. Most preferably, there are used dodecyl, hexadecyl, octadecyl, 2-hexyldecyl, 2-octyldodecyl, 2-decyltetradecyl, tridecafluorooctyl, heptadecafluorodecyl, heneicosafluorododecyl, and 2tridecafluorohexyltridecafluorodecyl groups.

In the practice of the invention, these alkyl and fluoroalkyl groups are called "alkyl group".

In the formula (I), R' is preferably methyl group.

The monoalkyl phosphates of the formula (II) in the above reaction formula are prepared by reacting a phosphorylating agent, such as phosphorus pentaoxide, phosphorus oxychloride, polyphosphoric acid or the like, with organic hydroxy compounds having corresponding alkyl groups to obtain monoalkyl phosphates and neutralizing the phosphates. The monoalkyl phosphates (II) may be prepared by any methods, but should preferably have a high purity. If the monoalkyl phosphate (II) has a low purity and contains large amounts of secondarily produced impurities, the following problems may be involved.

When dialkyl phosphates which are secondarily produced when using phosphorylating agents such as phosphorus pentaoxide and phosphorus oxychloride are contained, the surface activity and S.O. of the monoalkyl phosphate lower or even disappear. Further, in a subsequent reaction with epoxy compounds, the purity of an intended compound lowers with the attendant disadvantage that it becomes difficult to obtain the intended compound of high purity by purification.

Orthophosphoric acid which are secondarily produced on use of polyphosphoric acid as the phosphorylating agent will lower the yield of reaction with epoxy compounds with a lowering of purity of an intended compound. In addition, purification is difficult for obtaining a highly pure intended compound.

Accordingly, the purity of the monoalkyl phosphate (II) should preferably be not less than 90 wt%. A process for industrially producing such a highly pure monoalkyl phosphate is preferably a process developed by some of the present inventors (Japanese Patent Application No. 59-138829).

The use of polyoxyethylene-added alkyl monophosphates instead of the monoalkyl phosphate (II) is not favorable because the polyoxyethylene-added alkyl monophosphate cannot be obtained in high purity.

Moreover, compounds obtained by using polyoxyethylene-added alkyl monophosphates have non-ionic (surface active) moieties in the molecule thereof and have thus poor S.O.

In the above reaction, glycidyl methacrylate or glycidyl acrylate (III) should preferably be used in an amount of from 1 to 10 moles, most preferably from 3 to 5 moles, per mole of the monoalkali metal salt of monoalkyl phosphate (Il).

If the reaction is effected without conversion of the monoalkyl phosphate into the monoalkali metal salt, a trialkyl phosphate formed by reaction of additional 1 mole of compound (III) is by-produced along with an intended compound. The reaction system after completion of the reaction is acidic, so that the ester bonds are apt to suffer hydrolysis, with a lowering in yield of the intended compound. In order to carry out the reaction, it is essential that the monoalkyl phosphate be used in the form of a monoalkali metal salt.

The solvents used for the reaction should preferably inert polar solvents including, for example, water, methyl alcohol, ethyl alcohol and the like, of which water is most preferable.

The reaction temperature is generally in the range of from 30 to 100 C, preferably from 50 - 90"C.

On reaction, polymerization inhibitors or retarders may be added and include, for example, hydroquinone monomethyl ether, hydroquinone, 2,2'-methylenebis (4-ethyl-6-t-butylphenol) and the like. These agents are preferably used in an amount of from 50 to 10000 ppm of glycidyl methacrylate or acrylate.

The resulting reaction solution contains, aside from a phosphoric ester which is an intended compound, an unreacted compound of the formula (III) or a hydrolyzate thereof, which is glyceryl methacrylate. The reaction product obtained from the reaction solution may be used as it is depending on the use, and may be purified to obtained a highly pure product. For instance, with sodium salt of dodecyl 2-hydroxy-3-methacryloyloxypropyl phosphate [R' = CH3, R = C,2H2s, M = Na in the formula (I) and hereinafter referred to as compound (V)], a pure product can be obtained as follows.Glycidyl methacrylate is added for reaction to an aqueous solution of sodium dodecyl phosphate, followed by either removing the water by distillation or saturating the reaction solution with an electrolyte such as sodium chloride or potassium chloride, and extracting an organic matter in an organic solvent such as ethyl ether, and then distilling off the ether. Thereafter, unreacted glycidyl methacrylate is separated by extraction with a nonpolar solvent such as n-hexane, to which acetone is added to precipitate sodium salt of dodecyl 2-hydroxy-3-methacryloyloxypropyl phosphate, thereby separating glyceryl methacrylate, which is a hydrolyzate of glycidyl methacrylate, and is soluble in acetone, to obtain the intended product of high purity. It will be noted that after completion of the reaction, when unreacted glycidyl methacylate is completely hydrolyzed, a subsequent purification procedure becomes easy.

The acid-type dodecyl 2-hydroxy-3-methacryloyloxypropyl phosphate [R' = CHs, R = C,2H25, M = H in the formula (I)] is obtained by adding an acid such as, for example, hydrochloric acid to the aqueous solution of the Na salt to render the solution acidic, and extracting the phosphate by extraction with a solvent such as ethyl ether.

Depending on the reaction condition, there may be formed a small amount of a phosphoric ester of the following general formula (VI) aside from the phosphoric ester of the general formula (I).

in which R', R and M have the same meanings as defined before, respectively.

The compounds of the formula (I) have surface activity and S.O., and this will be seen from Figure 1 showing a phase diagram in an aqueous system of the compound (V), revealing that liquid crystal is formed. The polymerizability of the compound of the invention is confirmed from the fact that when a photopolymerization initiator or an ordinary aqueous polymerization initiator is added, for example, to an aqueous solution of the compound (V) and light or heat is applied to the solution, polymerization takes place and the resulting polymer has film formability.

The phosphoric esters of the invention have surface activity, S.O. and polymerizability and are substantially harmless against human body. In addition, the esters can be prepared in an industrially, very advantageous manner. Accordingly, they has wide utility in the engineering and medical fields.

The present invention is described by way of examples.

Example 1 Two hundreds grams of monododecyl phosphate having a purity of 97% [0.73 moles, AV1 (mg of KOH necessary for neutralization of 1 g of the phosphoric monoester sample to a first equivalence point) of this sample = 210.3, AV2 (mg of KOH necessary for neutralization of 1 g of the phosphoric monoester sample to a second equivalence point) = 420.8] was charged into a reactor, to which 750 ml of 1 N sodium hydroxide aqueous solution was added, followed by agitation and increasing the temperature to 70"C to obtain a uniform system. The acid value of the reaction system (mg of KOH necessary for neutralization of 1 g of sample) was found to be 42.9. Thereafter, while the reaction system was maintained at 70"C, 533 g (3.75 moles) of glycidyl methacrylate was gradually added, followed by agitation at the temperature for 9 hours.At this time, the acid value of the reaction system was approximately zero, revealing that the reaction was completed. The sample from the reaction system was subjected to the HPLC (high-pressure liquid chromatography), revealing the peak of unreacted glycidyl methacrylate. Agitation was further continued to a total reaction time of 20 hours, at which glycidyl methacrylate was completely hydrolyzed. The reaction solution was cooled down to room temperature and charged into a separating funnel, followed by saturation with sodium chloride and extraction twice with each 500 g of ethyl ether.The ethyl ether was distilled off under a reduced pressure, and 500 g of acetone was added to the resulting non-volatile liquid residue, followed by allowing to chill at 5"C. After one day, separated crystals were collected and recrystallized from acetone to obtain 178 g of white crystals of sodium dodecyl 2-hydroxy-3-methacryloyloxypropyl phosphate.

aH-NMR: 8 0.8 ppm (t, 3H, -P-OCH2(CH2)10CH3) 81.2 ppm (broad s, 20H,-P-OCH2(CH2).oCH3) 8 2.0 ppm (s, 3H, CH2=C-CH3) 8 3.7 -4.3 ppm (broad, 8H,

8 5.5 ppm (broad s, 1H,

5 6.1 ppm (broad s, 1H,

13C-NMR

5 (ppm): n 14.1, a 18.3, m 23.0, j 26.1, ik 30.2, t 32.3, g 65.2, e 68.7, b 126.5, c 136.2 Standard sample: Si(CH3)4 IR (KBr): Figure 2 Elementary Analysis c/o Hol P(%) Na(%) Found 52.53 8.38 7.2 5.3 Calculated 53.02 8.43 7.2 5.3 The results of the HPLC analysis revealed that the purity was 98 to 99%.

Test Example 1 To a mixture of the sodium dodecyl 2-hydroxy-3-methacryloyloxypropyl phosphate [compound (V)] obtained in Example 1 and water in 50/50 was added benzoin isobutyl ether, as a photopolymerization initiator, in an amount of 2% of the compound (V), followed by light irradiation for 2 hours in a stream of nitrogen, thereby obtaining a colorless transparent rubber-like material. This sample [sample of the mixture of compound (V) and water in 50/50 to which the photopolymerization initiator was added] was sandwiched between slide glasses and thus made thin, followed by light irradiation for 2 hours in the same manner as mentioned above, thereby obtaining a colorless transparent film-like material.

Alternatively, K2S2O8 as polymerization initiator was added to an aqueous solution of about 10% compound (V) in an amount of 1% of the compound (V), followed by heating at 60 to 70"C for 4 to 5 hours, thereby obtaining a colorless, transparent, highly viscous aqueous solution. This polymer product was placed on a slide glass and allowed to stand to obtain a colorless transparent film-like material. This polymer product was capable of being gelled in water or methanol.

Example 2 In the same manner as in Example 1, 200 g (0.55 moles) of monooctadecyl phosphate having a purity of 97% (AV1 = 160.7, AV2 = 321.5) was dissolved in 573 ml of 1 N sodium hydroxide aqueous solution at 55"C (at which the acid value of the reaction system was 40.3), to which 407 g (2.86 moles) of glycidyl methacrylate was gradually added, followed by agitation at the temperature for 20 hours. The acid value of the reaction system was approximately zero, revealing that the reaction rate of the monalkyl phosphate was approximately 100%. Subsequently, the reaction solution was cooled down to 0 C and the resulting crystals were collected by filtration. The filter cake was washed with acetone and dried to obtain 198 g of white crystals of sodium octadecyl 2-hydroxy-3-methyacryloyloxypropyl phosphate.

Elementary Analysis: C(%) H(%) P(%) Na(%) Found 58.22 9.28 5.9 4.5 Calculated 58.35 9.40 6.0 4.5 The results of the analysis of HPLC revealed that the purity was over 99%.

Example 3 Twenty grams (0.057 moles) of mono-2-hexyldecyl phosphate having a purity of 92% (AV1 = 167.2, AV2 = 329.8) was dispersed in 59.6 ml of 1 N sodium hydroxide aqueous solution (at which the acid value of the reaction system was 39.5), to which 25.4 g (0.178 moles) of glycidyl methacrylate was gradually added at 70"C, followed by agitation at the temperature for 30 hours. The acid value of the reaction system was approximately 1.1, revealing that the reaction rate of the monoalkyl phosphate was approximately 97%. Subsequently, the reaction solution was analyzed by HPLC with the result that peaks of the hydrolyzate of glycidyl methacrylate and a new product were observed.The product was separated from the reaction solution by HPLC and the solvent was distilled off under reduced pressure to 23.5 g of sodium 2-hexyldecyl 2-hydroxy-3-methacryloyloxypropyl phosphate.

1H-NMR: # 0.9 ppm (t, 6H, -CH2CH3 x 2) 61.3 ppm (broad s, 24H,

1.9 ppm (s, 3H, CH2 = C-CH,) 8 3.4 - 4.5 ppm (broad, 9H,

8 5.5 ppm (broad s, 1H,

8 6.1 ppm (broad s, 1H,

13C-NMR:

8(ppm): q 14.2, a 18.3, p 22.7, k 27.0, n 29.8, m 30.1, j 30.8, e 31.1, o 32.0, i 38.6, g 64.8, f 65.6, e 68.2, h 71.1, b 126.3, c 136.1, d 167.5.

Standard sample: Si(CH3)4 Elementary Analysis: C(%) H(%) P (%) Na(%) Found 56.56 8.88 6.4 5.0 Calculated 56.78 9.12 6.4 4.7 The results of the HPLC analysis revealed that the purity was 98 to 99%.

Example 4 Twenty grams (0.043 moles) of mono-2-decyltetradecyl phosphate having a purity of 94% (AV1 = 134.2, AV2 = 267.1) was charged into a reactor, to which 47.8 ml of 1 N potassium hydroxide aqueous solution was added and agitated, followed by increasing the temperature to 70"C to form a uniform dispersion (at which the acid value of the reaction system was 37.9). While keeping the reaction system at 70"C, 20.4 g (0.143 moles) of glycidyl methacrylate was gradually dropped, followed by agitation at the temperature for 20 hours. The acid value of the reaction system was approximately 1.5, revealing that the reaction rate of the monoalkyl phosphate was about 96%.The resulting product was collected by HPLC and the solvent was distilled off under reduced pressure to obtain 23.4 g of potassium 2-decyltetradecyl 2-hyd roxy-3-methacryloyloxypropyl phosphate.

Elementary Analysis: C ( /0) Hol f /0) Na(%) Found 60.23 9.61 5.0 6.1 Calculated 60.55 9.84 5.0 6.4 The results of the analysis of HPLC revealed that the purity was 98 to 99%.

Example 5 Twenty grams (0.13 moles) of monobutyl phosphate having a purity of 99% (AV1 = 360.6, AV2 = 721.3) was charged into a reactor, to which 129 ml of 1 N sodium hydroxide aqueous solution was added and agitated, followed by dissolution at 70"C (at which the acid value of the reaction system was 46.7).

While keeping the reaction system at 700C, 91.4 g (0.64 moles) of glycidyl methacrylate was gradually dropped, followed by agitation at the temperature for 20 hours. The acid value of the reaction system was approximately zero, revealing that the reaction rate of the monoalkyl phosphate was approximately 100%. The resulting product was collected by HPLC and the solvent was distilled off under reduced pressure to obtain 37.2 g of sodium butyl 2-hydroxy-3-methacryloyloxypropyl phosphate.

Elementary Analysis: c/o { /0) P { /0) Naf /O) Found 41.03 6.28 9.6 7.2 Calculated 41.52 6.33 9.7 7.2 The results of the analysis of HPLC revealed that the purity was 98 to 99%.

Example 6 95.5 g (0.19 moles) of heptadecafluorodecyl phosphate having a purity of 97% (AV1 = 108.9, AV2 = 217.0) was charged into a reactor, to which 185 ml of 1 N sodium hydroxide aqueous solution was added and agitated, followed by heating to 700C to make a uniform system. The acid value of the reaction system was 36.8. While keeping the reaction system at 70 C, 104.5 g (0.74 moles) of glycidyl methacrylate was gradually added, followed by agitation at the temperature for 9 hours, at which the acid value of the reaction system was approximately zero, revealing that the reaction was completed. The sample was analyzed by HPLC with the result that a peak of unreacted glycidyl methacrylate was observed.Agitation was further continued to a total time of 20 hours, at which it was found that glycidyl methacrylate was hydrolyzed completely and that peaks of glyceryl methacrylate which was a hydrolyzed product at the epoxy moiety and of an intended compound were recognized. The reaction solution was cooled down to room temperature, to which 200 g of acetone was added, followed by cooling to -5 C to obtain 92 g (yield 70%) of heptadecafluorodecyl 2-hydroxy-3-methacryloyloxypropyl phosphate sodium salt.

aH-NMR: 8 2.0 ppm (s, 3H, CH2 = C-CH3) 8 2.6 ppm (tt, 2H, -P-OCH2CH2CF2-) 8 3.5 - 4.5 ppm (m, 7H,

8 5.6 ppm (broad s, 1H,

6.1 ppm (broad s, 1H,

13C-NMR:

8 (ppm): a 18.5, i 33.4, h 58.7, e 66.5, g 67.6, f 69.9, b 126.5, c 137.6, d 168.9.

Standard sample: Si(CH3)4 Elementary Analysis: C(%) H(%) F(%) P(%) Na(%) Found 28.53 2.33 45 4.3 3.3 Calculated 28.83 2.13 46 4.4 3.3 The results of the HPLC analysis revealed that the purity was 98 to 99%.

Test Example 2 K2S2Os as a polymerization initiator was added to an aqueous solution of about 10% of sodium heptadecafluorodecyl 2-hydroxy-3-methacryloyloxypropyl phosphate [compound (Vl)] obtained in Example 6 in an amount of 1% of the compound (VI), followed by heating at 60 to 70 C for 4 to 5 hours, thereby obtaining a colorless, transparent, highly viscous aqueous solution. The polymerized product was placed on a slide glass and allowed to stand to obtain a colorless transparent film-like material.

This highly viscous aqueous solution had an anisotropic property and a systematic liquid crystal structure.

Example 7 Twenty grams (0.025 moles) of 2-tridecafluorohexyltridecafluorodecyl phosphate having a purity of 92% (AV1 = 70.1, AV2 = 139.8) was dispersed in 24.8 ml of 1 N sodium hydroxide aqueous solution (at which the acid value of the reaction system was 31.1), to which 14.2 g (0.10 mole) of glycidyl methacrylate was gradually added at 70 C, followed by agitation at the temperature for 30 hours. At this time, the acid value of the reaction system was approximately zero, revealing that the reaction rate of the monoalkyl phosphate was approximately 100%. The reaction solution was analyzed by HPLC, revealing that peaks of the hydrolyzate of glycidyl methacrylate and a new compound were found. The resulting product was collected by HPLC and the solvent was distilled off under reduced pressure to obtain 21.5 g (yield 89%) of sodium 2-tridecafluorohexyltrideca-fluorodecyl-2-hydroxy-3-methacryloyloxypropyl phosphate.

Elementary Analysis: C (%) H (%) F (%) P (%) Na(%) Found 28.71 1.52 50 3.1 2.7 Calculated 29.07 1.49 52 3.3 2.4 The results of the analysis of HPLC revealed that the purity was 98 to 99 /O.

Claims

1. A phosphoric ester of the general formula (I)

in which R' represents a hydrogen atom or a methyl group, R represents a linear or branched alkyl group having from 1 to 36 carbon atoms or a linear or branched fluoroalkyl group at least one hydrogen atom of which is substituted with a fluorine atom and which has from 1 to 36 carbon atoms, and M represents a hydrogen atom, an alkali metal, ammonium or a salt of an alkylamine or an alkanolamine.

2. An ester as claimed in claim 1 wherein the linear or branched alkyl group having 1 to 36 carbon atoms is selected from one or more of methyl, ethyl, butyl, octyl, decyl, dodecyl tetradecyl, hexadecyl, octadecyl, docosyl, tetracosyl, triacontyl, 2-ethylhexyl, 2-hexyldecyl, 2-octyldodecyl, 2-decyltetradecyl, 2 undecylhexadecyl, 2-tetradecyloctadecyl and emery-isostearyl.

3. An ester as claimed in claim 1 or claim 2 characterised in that the fluoroalkyl groups are selected from one or more of tridecafluorooctyl, heptadecafluorododecyl, heneicosafluorododecyl, pentacosafluorotetradecyl, nonacosafluorohexadecyl, tritriacontrafluorooctadecyl, 2-pentafluoroethylpentafluorohexyl, 2-tridecafluorohexyltridecafluorodecyl, 2-heptadecafluorooctylheptadecafluorododecyl, 2 heneicosafluorodecylheneicosafluorotetradecyl, 2-pentacosafluorododecylpentacosafluorohexadecyl, and 2-nonacosafluorotetradecylnonacosafluorooctadecyl.

4. An ester as claimed in any preceding claims wherein the alkyl and fluoroalkyl groups each have from 8 to 36 carbon atoms.

5. An ester as claimed in any preceding claim characterised in that R' is a methyl group.

6. A process for the production of a phosphoric ester as claimed in any one of the preceding claims in which a glycidyl methacrylate or acrylate having the general formula:

is reacted with a monoalkali metal salt of a monoalkyl phosphate having the general formula (II)

to produce a phosphoric ester.

7. A process as claimed in claim 6 wherein the phosphoric ester is subjected to acidification and/or neutralization with a base.

8. A process as claimed in claim 6 or claim 7 wherein the monoalkyl phosphates are prepared by reacting a phosphorylating agent with organic hydroxy compounds having corresponding alkyl groups to obtain monoalkyl phosphates and neutralizing the phosphates.

9. A process as claimed in claim 8 wherein the phosphorylating agent is selected from one or more of phosphorus pentaoxide, phosphorus oxychloride and polyphosphoric acid.

10. A process as claimed in any one of claims 6 to 9 characterised in that the glycidyl methacrylate or glycidyl acrylate is present in an amount of 1 to 10 moles per mole of monoalkali metal salt of monoalkyl phosphate.

11. A process as claimed in any one of claims 6 to 10 wherein the reaction is carried out in the presence of an inert polar solvent.

12. A process as claimed in claim 11 wherein the inert polar solvent is selected from one or more of water, methyl alcohol and ethyl alcohol.

13. A process as claimed in any one of claims 6 to 11 wherein the reaction is carried out at a temper ature within the range of 30"C to 100 C.

14. A process as claimed in any one of claims 6 to 13 wherein the reaction is carried out at a temperature within the range of 50"C to 90"C.

15. A process as claimed in any one of claims 6 to 14 wherein the reaction is carried out in the present of polymerization inhibitors and/or retarders.

16. A process as claimed in claim 15 wherein the polymerization inhibitors or retarders are present in an amount of 50 to 10000 ppm of glycidyl methacrylate or glycidyl acrylate.

17. A process as claimed in claim 15 or claim 16 wherein the polymerization inhibitors or retarders are selected from one or more of hydroquinone monomethyl ether, hydroquinone, 2,2'-methylenebis (4ethyl-6-t-butylphenol).

18. Phosphoric esters and methods of preparing them substantially as described in any one of the specific examples hereinbefore set forth.

19. Each and every novel embodiment substantially as herein described taken either separately or in combination.