CA1322555C - Phosphinyl-containing ethylenically unsaturated compounds - Google Patents

Abstract

ABSTRACT

The invention relates to (hydroxy) phosphinylalkyl acrylate, (hydroxy)phosphinylalkyl methacrylate, (dihydroxy)phosphinylalkyl acrylate, methacrylate or ethacrylate or an alkali metal, alkaline earth metal or ammonium salt thereof. These compounds are useful in preparing polymeric compositions when homopolymerized or copolymerized with compounds containing polymerizable 1,2-ethylenically unsaturated moieties. The polymeric compositions prepared are useful in latex paints, in plastic-metal laminates, coatings for metals and in adhesives. Polymeric compositions prepared from compounds containing 1,2-ethylenically unsaturated moieties are often contacted or applied to metals in various ways.

31,248C-F -44-

Description

1 32~

NOVEL PHOSPHINYL-CONTAINING
ETHYLENICALLY UNSATURATED COMPOUNDS

This invention relates to novel phosphinyl-containing ethylenically unsaturated compounds, and polymers containing such compounds.
A divisional application, divided out o~ this parent application, has been filed which relates to the polymeric composition which are obtained when the novel phosphinyl-containing ethylenically unsaturated compounds of this inventionare homopolymerized or copolymerized with compounds containing polymerizable 1,2-ethylenically unsaturated moieties. The polymeric compositions of the divi~ional application are u~eful in latex paints, in plastic-metal laminates, coatings for metals, and in adhesiveæ. Such polymeric compositions pxepared from compounds containing 1,2-ethylenically unæaturated moieties are often contacted or applied to metals in various ways.
A major problem is to find a polymeric compo~ition which has good adherence to particular metals. What is needed is a polymeric composition prepared from compounds containing 1,2-ethylenlcally unsaturated moieties which have good adherent properties to metal, and other substrates.
In one aspect, this invention is a novel phosphinyl-containing ethylenlcally unsaturated compound selected from (hydroxy)phosphinylalkyl acrylic ester and a (dihydroxy)phosphinylalkyl acrylic eæter, partlcularly including acrylate, methacrylate and ethacrylate esters, as well as the corresponding ammonium, alkali metal, and alkaline earth metal .~ ~

2 6~693-3~92 salts thereof. These compounds are hereinafter referred ~o as "HP
Acrylic Monolner" or `'DHP Acrylic ~lonomer".
In one aspect, the invention of the divisional application is a polymer obtained by the polymerization of:
(a) an HP or DHP Acrylic Monomer and (b) at least one copolymerizable 1,2-ethylenically unsaturated monomer.
In yet another aspect, this invention is a process for the preparation of an ammonium, alkali metal or alkaline earth metal salt of an, HP or DHP Acrylic Monomer in salt form.
Thus the invention of the present parent application provides a process for the preparation of an ammonium, alkali metal or alkaline earth metal salt of a (dihydroxy)phosphinylalkyl acrylate, methacrylate or ethacrylate comprising the steps of (a) transesterifying a dialkylphosphonoalkyl acrylate, methacrylate or ethacrylate with a trialkylhalosilane in an aprotic solvent to produce an intermediate bis(trialkylsilyl)phosphonoalkyl acrylate, methacrylate or ethacrylate, and (b) saponifying the thus-formed intermediate bis(trialkylsilyl)phosphonoalkyl acrylate, methacrylate or ethacrylate with a base to produce a salt.
According to a further aspect of the invention of the parent application there is provided a process for preparing (hydroxy)phosphinylalkyl compound of the formula C' ~2~
2a 64693-3992 H0 - P - CtR )2OOC-C(R J=CH2 wherein R is hydrogen, methyl or ethyl and R2 is selected independently from hydrogen and alkyl of 1-10 carbon atoms, comprising the steps of:
(a) condensing hypophosphorous acid with an aldehyde or ketone of 1-10 carbon atoms to produce an intermediate 1-hydroxyalkylphosphorouæ acid compound and (b) esterifying the thus-produced intermediate 1-hydroxyalkylphosphorous acid compound with acrylic, methacrylic acid or ethacrylic acld.
According to the first aspect of the invention of the divisional application there is provided a polymeric composition which comprises the reactlon product of~
(a) a phosphinyl-containing ethylenically unsaturated compound selected from (hydroxy) phosphinylalkyl acrylate, (hydroxy)phosphinylalkyl methacrylate, (dihydroxy~phosphinylalkyl acrylate, methacrylate or ethacrylate, or an alkali metal, alkaline earth metal or ammonium salt thereof; and (b) between 0 and 99.5 weight percent of a compound containing a polymerizable 1,2-ethylenically unsaturated moiety.
According to anothe:r aspect of the invention of the divislonal application there is provided a polymeric composition which comprises the reaction product of:

C`
.
;

J ~.J ~ ~
2b 64693-3992 (a) between 0.5 and 99 percent by weight of a (hydroxy)phosphinylalkyl acrylate, (hydroxy) phosphinylalkyl methacrylate, or an alkali metal, alkaline earth metal or ammonium salt thereof; and (b) between 1 and 99.5 percent by weight of two or more compounds which contain a polymerizable 1,2-ethylenically unsaturated moiety.
According to a further aspect of the invention of the divisional applicatlon there is provided a polymer which is the product of polymerization of 1,2-ethylenically unsaturated monomers comprising a DHP Acrylic Monomer selected from a (d1hydroxy)phosphinylalkyl acryla$e, methacrylate or ethacrylate or an ammonium, alkali metal or alkaline earth metal alt thereof.
The polymeric compositions prepared from the 1,2-ethylenically unsaturated (hydroxy)phosphinyl and (dihydroxy)phosphinyl-containing compounds have surprisingly good adherence to many metals. Furthermore, the polymeric compositions have enhanced anticorrosive properties.
Preferred HP Acrylic Monomers are those represented by the following formula:

-3~

- R1 o R2 0 OH
~ " ' " /
CH2 = C - CO - C - P \ (I) or Rl O R2 o CH2 = C - CO - C - P - Oe~ _ M~ (II) a wherein:
R is hydrogen or methyl;

R is separately in each occurrence hydrogen or C1_~0 alkyl;
M is an alkali metal, alkaline earth metal or ammonium; and a is 1 or 2.
3 In the embodiment wherein M is an ammonium moiety or an alkali metal, a is 1. In the embodiment wherein M is an alkaline earth metal, a is 2.
In the above formula, R2 is preferably hydrogen or C1_3 alkyl, more preferably hydrogen or methyl, and most preferably hydrogen. R1 is most preferably 31,248C-F -3-~ ~ 7 ~

methyl. M i9 preferably an ammonium molety or an alkall metal. M is more preferably an ammonium moiety, potass1um or sodium. Prererably, a is 1.
The (hydroxy)phosphinylalkyl acrylates and (hydroxy)phosphinylalkyl methacrylates can be preparecl by the reaction Or hypophosphorous acid with a suitable aldehyde or ketone to prepare an ~-hydroxyalkylphos-phorous acid, which is thereafter reacted with acrylic or methacrylic acid to prepare the novel compounds.
This reaction sequence is exemplified by equat10ns III
and IV.

O O
(H0~2PH + R2CR2----~HO--P--C~R2)20H (III) O Rl O O O
ll 2 ~ 2 ~1 1 HO--P- C(R ~20H + CH2- C -COH--~HO- P-C(R )20C- C =CH2 (IV) H

3 wherein Rl and RZ are as defined hereinbefore.
In the first step of thi~ process, the hypophosphorous acid 1s contacted with a suitable aldehyde or ketone in a ratio of between 3:1 and 1:1.
In this reaction there cannot be an excess Or aldehyde or ketone as such an excess would result in multiple 31,248C-F -4-,..

additions of aldehyde or ketone to the acid. This process is done in an aqueous solution. It is preferable to add the aldehyde or ketone to an aqueous solution of the hypophosphorous acid, as this reaction is exothermic and slow addition results in much better control of the reaction temperature.
Generally, this step can be run at any temperature at which the reaction proceeds. Preferable temperatures are between 20C and 100C, with temperatures between 70C and 90C being most preferred.
This process may be run at any pressure at which the reaction occurs. Atmospheric, subatmospheric and superatmospheric pressures may be used.
Atmospheric pressure is preferred. Although not necessary, it is advantageous to run this reaction under an inert gas atmosphere. Examples of inert gases include nitrogen and argon.
Any reaction time which gives the desired conver-sion is suitable. Generally, reaction times of between three and ten hours are preferable. Upon completion of the reaction, the water solvent is stripped off.
The hydroxyalkylphosphorous acid prepared in the above-described reaction is then contacted with methacrylic acid or acrylic acid in a ratio of between 3 3:1 and 1:3, with a ratio of between 2:1 and 1:2 being preferred, and with a ratio of 1:1 being most preferred. Where there is an excess o~ one reagent, it is preferable that that reagent be methacrylic or acrylic acid. This process is generally run in an inert organic solvent. Examples of preferred inert - 31,248C-F -5-organic solvents are aromatic hydrocarbons and chlorinated solvents. Among more preferred solvents are perchloroethylene and xylene. It is preferred that the solvent used have a boiling point over 100C, and most preferred that the solvent have a boiling point over 120C.
This reaction is done in the presence of an esterification catalyst. Preferred esterification cataly ts are strong acids. More preferred strong acids include ulfonic acids, sulfuric acids and phosphoric acid. A most preferred catalyst is p-toluene sulfonic acid.
Any temperature at which the reaction proceeds is suitable. This reaction is preferably done at the reflux temperature of the solvent. It is more preferable that the reflux temperature be over 100C, with a reflux temperature of over 120C being most preferred.

During the course of this process, water is formed as a by-product. It is preferred to remove the water as formed7 as the process is an equilibrium process and the removal of water drives the reaction to completion.
This reaction ma~ be run at atmospheric and uperatmospheric pressures. Atmospheric pressure is 3 preferred. An inert atmosphere can be used.
Reaction times which give the desired converqion are suitable. Preferable reaction times are between four and ten hours.

31,248C-F -6-Preferred DHP Acrylic Monomers are those correspondlng to the formula Rl O R2 o !l I 11 /
CH2 = C - CO - C - P ( V ) or 1 0 M0Oe Rl o R2 o /

CH2 = C - CO - C - P (VI) R2 M~0~

whereln Rl ls hydrogen, methyl or ethyl r R2 ls selected indepen-dently from hydrogen and alkyl of 1-10 carbon atoms and M+ is an ammonlum cation, an alkali metal catlon or 1/2 an alkallne earth cation.
It will be understood that the ammonium catlon can be represented as NH4+; the alkali metal catlons as ~i+l Na+, K , Rb and Cs+ and that "1/2 an alkallne earth metal catlon'l wlll corre-spond to 1/2 Mg++r 1/2 Ca++, 1/2 Ba++ or 1/2 Sr++. Therefore, a typlcal alkallne earth, the calclum salt, can be represented by the structure:

`

', ~ :

-8~ 3 - , ,. \
CH2= C - C0 -C - P - 0) -Ca (VII) _ ~ R2 / 2 1 Pre~erred monomers in accordance with the foregoing formulas are those wherein Rl is hydrogen or methyl and R2 i selected independently from hydrogen and alkyl of 1-3 carbon atoms. Most preferably, the DHP Acrylic Monomer is (dihydroxy)phosphinylmethyl methacrylate, that is, a compo~nd wherein Rl is methyl and R2 is hydrogen.
Preferred salts are those wherein Ml is an ammonium cation, a ~odium cation or a potassium cation.
. The DHP Acrylic Monomers can be prepared by reaction between a dialkylphosphonoalkyl acrylic ester and a trialkylhalosilane to produce an intermediate bis(trialkylsilyl)ester, which is saponified to a corresponding salt and can be acidified to produce a DHP Acrylic Monomer in the form of a free acid.
Dialkylphosphonoalkyl acrylic esters are known compound~ and are di~clo~ed by O'Brien et al. in U. S.
3o Patent~ 2,934,555 and 3,030,347.

Dialkylphosphonoalkyl acrylic esters are made by adding a dialkyl hydrogen phosphite to an aldehyde or ketone to produce an intermediate dialkyl 1-hydroxyalkylphosphonate, which is converted to an 31,248C-F -8-i; ~

. ` .

~ ~ ~ 2i J~
acrylic ester by reaction with an acrylic halide in the presence of a hydrogen chloride acceptor.
The reactions can be represented by the equations R2CR2 + H-P(Oalk)2 ~ HOC(R2)2P(Oalk)2 (VIII) O O O

H2C=CRlCOX + HOC(R2)2P(Oalk)2 + base - a (IX) CH2=CR COOC(R2)2P(Oalk)2 + base-HX

wherein alk is lower alkyl; X is chlorine, bromine or iodine; and "base" is a hydrogen halide acceptor.

Because formaldehyde and lower aldehydes are more reactive with the dialkyl hydrogen phosphites than higher aldehydes or ketones, it is preferred to make and use the lower members of the series of compounds for use as intermediate~.
3 Further conversion of a dialkylphosphonoalkyl acrylic ester to the DHP Acrylic Monomer can be represented, in the case using chlorotrimethylsilane, by the equations:

31,248C-F -9 ~ ~ , ~3 CH2=CR1COO(R2)2P(Oalk)2 + 2 Me3SiX ~~~----~ (X) Q

CH2=CR1COOC(R2)2P(OSiMe3)2 CH2=CRlCOOC(R2)2P(OSiMe3)2 ~ 2 MOH (XI) O

CH2=CR1COOC(R2)2P(O-+M)2 o CH2=CR COOC(R2)2 P(O +M)2 + 2 HX------------------;- (XII) CH2=CR1COOC(R2)2P(OH)2 + 2 MX
o wherein Me is methyl; and alk, M and X are as above or HX corresponds to a strong acid other than a hydrohalic acid.
Transesterification of the dialkylphos-phonoalkyl acrylic ester with trialkylhalosilane is done in an aprotic solvent, for example acetonitrile, benzene, toluene, dimethylformamide, dimethyl sulfoxide or the like. The use of acetoniSrile is preferredO

At least two moles of trialkylhalosilane are employed for each mole of dialkylphosphonoalkyl acrylic 31,248C-F -10-~ ~ f~ 3 ester. It ls preferred to use two moles of a halotrlmethylsllane.
Although it is posslble to use iodotrlmethylsllane for thls re-action, it has been found that the transesterification can be car-ried out readlly uslng chlorotrlmethylsilane if a stolc~liometrlc amount of an iodlde donor is present in the reactlon mlxture.
Accordingly, it is preferred to use a reactlon mixture containing two moles of chlorotrlmethylsilane and two moles of an alkali metal lodide, preferably sodium lodide or potassium lodlde.
The reaction can be carrled out at any temperature at which the reactlon wlll occur. However, the reactlon occurs wlthin a reasonable amount of tlme at room temperature. Accor-dlngly, reactlon temperatures of from 15C to 50C are preferred.
The reactlon can be done at any pressure. However, the reactlon occurs readlly under amblent condltlons so that the use of pressure or vacuum apparatus ls unnecessary. Therefore, the reaction ls preferably done at atmospherlc pressure.
Owing to the hydrolytlc lnstablllty of trlalkylhalo-sllanes, it ls preferred to conduct the reactlon under essentlally anllydrous condltlons. The use of a drylng agent, e.g., a calclum chlorlde or Drlerlte~ owned by W.A. Hammond & Sons, tube, ls pre-ferred. It ls further preferred to conduct the reactlon under a dry inert atmosphere, for example, under dry nltrogen or dry argon.
At the end of the reactlon, the mlxture ls hydrolyzed by addltlon of at least two moles of water per mole of bis(trialkyl-silyl)phosphonoalkyl acryllc .~ ~
~' ~22- ~
1, 646~3-3~9~
ester. The mix-ture is stirred to permi~ separation of a slightly soluble salt, which is removecl by filtration. The intermediate is subjected to hydrolysis with a base, which cleaves the trialkylsilyl groups and produces a corresponding metal salt.
This reaction occurs readily at room temperature and pressure, so that elevated pressures and temperatures need not be employed.
The salt can be used directly in the preparation of the polymeric compositions. The (dihydroxy)phosphinylalkyl acrylic compound can be polymerized in the form of the salt andr if desired, the resultiny polymer can be acidified to convert the salt to the corresponding acid form.
The resulting monomeric salt can be converted to the free acid by treatment with a stoichiometric amount of a mineral acid, such as hydrochloric, hydrobromic, hydroiodic, sulfuric or phosphoric acid.
The polymeric compositions comprise the product ob~ained by vinylic polymerization of an HP or a DHP Acrylic Monomer. The polymeric compositions include homopolymers o~ the HP or DHP
Acrylic Monomers as well as copolymers with at least one other 2~ compound containing a polymerizable 1,2-ethylenically unsaturated moiety.
The copolymeric compositions preferably comprise the reaction product of (a) between ~.5 percent and 99 percent by weight of an HP or a DHP Acrylic Monomer; and (b) between 99.5 percent and 1 percent by weight of at least one copolymerizable 1,2-ethylenically unsaturated compound.
The copolymeric compositions more preferably contain C

~2~ 3 between 1 percent and 10 percent by weight of the novel HP or DHP
Acrylic Monomers, and most preferably, between 1 percent and 5 percent by weight of the HP or DHP Acrylic Monsmer.
The novel compounds are usually clear, viscous li~uids which are soluble in water and polar organic solvents, such as methanol, ethanol and dimethyl sulfoxide.
The salts of the (hydroxy~phosphinylalkyl acrylate, (hydroxy)phosphinylalkyl methacrylate, (dihydroxy)phosphinylalkyl acrylate, methacrylate, or ethacrylate are prepared by contacting the (hydroxy)phosphinylalkyl acrylate, (hydroxy)phosphinylalkyl methacrylate, with a base which contains an alkali metal, alkaline earth metal or an ammonium moiety in water under conditions such that the salts are formed. Conditions for such reactions are well-known to those skilled in the art. Examples of preferable bases include ammonium hydroxides, alkali metal hydroxides, al~ali metal carbonates, alkaline earth metal hydroxides and alkaline earth metal carbonates.
Alkali metal refers herein to lithium, sodium, potassium, rubidium and cesium. Preferred alkali metals are lithlum, potassium and sodium, with potassium and sodium being most preferred. Alkaline earth metal refers herein to beryllium, magnesium, calcium, strontium and barium. Preferred alkaline earth metals are magnesium and calcium.
Any compound which contains a polymerizable 1,2-ethylenically unsa~urated moiety is useful. Examples of such compounds include monovinyl aromatics, such as styrene, p-vinyl toluene, p-chlorostyrene; ,~-ethylenically unsaturated acids, such as acrylic acid and methylacrylic acid; alkyl esters of a,~-14 1 3 ~ 5 6469~-3992 ethlenlcally unsaturated monocarboxylic acids, containing from 1 to 18 carbon atoms in the alkyl group, such as methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate and methyl methacrylate;
a,~-ethylenically unsaturated nitriles, such as acrylonitrile and methacrylonitrile; a,~-ethylenically unsaturated amides, such as acrylamide and methacrylamide; vinyl esters, such as vinyl acetate and vinyl propionate; vinyl halides, such as vinyl chloride and vinyl bromide; vinyl ethers such as vlnyl methyl ether and vinyl ethyl ether; vinyl ketones, such as vinyl methyl ketone and vinyl ethyl ketone; vlnylldene halldes, such as vinylidene chloride and vinylidene bromide; hydroxyalkyl esters of acrylic and methacrylic acids, such as hydroxypropyl acrylate, hydroxyethyl acrylate, and hydroxybutyl acrylate; nitrlles of ethylenlcally unsaturated carboxylic acids such as acrylonltrile and methacrylonitrile;
ethylenically unsaturated carboxylic acids such as acrylic acid;
ethylenically unsaturated alcohols such as allyl alcohol and aromatic compounds su~stituted with 1,2-ethylenically unsaturated moieties such as, styrene, vinyl toluene and tert-butylstyrene.
The polymeric cdmpositlons are prepared by methods well-known in the art. Suitable polymeri~ation techniques include solution C

-15~ J~3~

polymerization, dispersion polymerization, emulsion polymerization, bulk polymerization, and heterogeneous polymerization. These polymerizations can be done in continuous or batchwise manner where appropriate.

In one embodiment, the polymeric compositions of this invention can be prepared by free radical initiated solution polymerization. In particular, the phosphinyl-substituted 1,2-ethylenically unsaturated monomers are homopolymerized, or copolymerized with one or more compounds which contain a polymerizable 1,2-ethylenically unsaturated moiety, in an organic solvent medium in the presence of a free radical type catalyst under an oxygen-free atmosphere. The monomeric constituents are mixed and polymerized in the proportions set out hereinbefore.
Exemplary solvents include the lower alkanols such as ethanol, propanol, and butanol; aromatic hydrocarbons such as toluene, benzene and xylene;
halohydrocarbons such as methylene chloride and tetrachloroethane and others such as butyl acetate and butoxyethyl acetate.
Representative catalysts employed in free-radical catalyzed polymerizations include azo and peroxide-types; e.g., peroxides such as benzoyl peroxide, hydroperoxides such as t-butyl hydroperoxide;
peracids such as perbenzoic acid; peresters, such as t-butyl peroctoate; and azo compounds such as azobisisobutyronitrile. Free radical catalyzed polymerization is readily effected at temperatures of from room temperature (20C) to 200C under atmospheric to superatmospheric pressure at catalyst concentrations of 0 in the case of thermal initiation to 5 weight 31,248C-F -15--16~ J '~ ~ J ;~

percent based on weight of monomers, preferably from 0.01 to 5 weight percent of catalyst in pure form or in an inert solvent for the catalyst. Thermal initiation generally occurs at temperatures between 60C-120C.

Often, it may be necessary to employ a chain regulator in order to provide a molecular weight in the range desired. Examples of chain regulators that may be employed include long chained alkyl mercaptans, e.g., t-dodecyl mercaptan of the formula:

H3CC(CH3)2CH2C(CH3)2CH2C(CH3)2SH, (XIII) short chained alkyl mercaptans such as butyl mercaptan and 2-hydroxyethyl mercaptan; isopropanol, isobutanol, long chained alcohols, e.g., lauryl alcohol, octyl alcohol, cumene, carbon tetrachloride, tetrachloroethylene, and trichlorobromomethane. The amount of chain regulator that may be employed depends on the particular system and the conditions and may vary from O to 5 weight percent based on monomer weight. Illuetratively, the use of from O to 1 weight percent of t-dodecyl mercaptan serves to provide as wide a range of molecular weight in aqueous media as i5 desirable.
In another embodiment, the polymeric compositions of this invention can be prepared by ionic polymerization techniques.
3o Representative ionic catalysts include lithium based catalysts, e.g., metallic lithium, alkyl lithium and other lithium compounds, and Ziegler catalysts, e.g., reducible halide of titanium or vanadium in combination with aluminum trialkyl, or diethylaluminum chloride, or lithium aluminum hydride. Ionic 31,248C-F -16--17- ~ V3 'J '~ ' '~ ') polymerization is advantageously carried out in an inert hydrocarbon solvent such as lower alkane or lower aromatic hydrocarbon at temperatures in the order of -20C to 140C under pressures ranging from atmospheric to superatmospheric and in the presence of from 1 to 200 ppm of ionic catalyst based on weight of monomers.
Polymerization can be similarly effected by cationic catalysts at temperatures of from -100C to 100C. Such catalysts include the etherates of boron trifluoride and aluminum trichloride and Ziegler catalysts such as the reaction product o~ reducible transition metal compounds, such as titanium tetrachloride or trichloride and reducing organo metallic compounds such as triethyl aluminum or diethylaluminum chloride.
In another embodiment, low pressure polymerization techniques can be used wherein the compounds containing the polymerizable 1,2-ethylenically unsaturated moieties are alpha-olefins.
The low pressure polymerization of alpha-olefins with catalyst systems composed of a partially reduced, heavy transition metal component and organometallic reducing component to form high density, high molecular weight, solid, relatively linear polymers is well-known. Characteristically, such polymerizations are carried out in an inert organic liquid diluent under an inert atmosphere and at relatively low temperatures, e.g., 0C to 100C, and low pres~ureq, e.g., 0 to 100 psig. Typical transition metal components are the halides, oxyhalides, alkoxides and metals selected from Groups IVB, VB, VIB and VIII
of the Periodic Table o~ Elements appearing in the Handbook o~ ChemistrY and Physics, 48th ed., Chemical Rubber Company. Common organometallic components 31,248C-F -17--18~ 3~-~ 3 include the metal alkyls, metal alkyl halides and dihalides, metal hydrides and similar compounds in which the metals are selected from groups IA, IIA and IIIA of the Periodic Table of Elements. The alpha-olefin polymers produced by low pressure polymerizationgenerally have molecular weights in the range of 100,000 to 300,000 or even as high as 3,000,000~
In yet another embodiment, the polymeric composition of this invention can be prepared by emulsion polymerization, wherein the monomer~ are dispersed in an aqueous medium containing a free radical type catalyst and a stabilizing emulsifier or mixture of emulsifiers. Suitable free radical catalysts include the persulfates (including ammonium, sodium and potassium persulfate), hydrogen peroxide, the perborates, and the percarbonates. Organic peroxides may also be used either alone or in addition to an inorganic peroxygen compound. Typical organic peroxides include benzoyl peroxide, tert butyl hydroperoxide, cumene peroxide, acetyl peroxide, caproyl peroxide, tert-butyl perbenzoate, tert-butyl diperphthalate and methyl ethyl ketone peroxide. The usual amount of catalyst required is roughly from 0.01 to 3.0 weight percent, based on the monomer mix. In order to enhance rate of polymerization, improve polymer properties, and to reduce undesirable side reactions, it is often desirable to activate the 3 catalyst. Activation of the catalyst also has the effect of lowering the temperature required to polymerize the monomers. The activation may be best accomplished by using a redox system in which a reducing agent within the limit of 0.001 to 6.0 weight percent based on the monomers is present, in addition 31,248C-F -18-lg 64693-~992 to the pero~ide catalyst. Many examples of such redox systems are known. Agents such as hydrazine or a soluble oxldizable sulfoxy compound, lncluding the alkali metal salts of hydrosulfites, sul-foxlates, thiosulfates, sulfites and bisulfltes can be employed.
Redox systems may be actlvated by the presence of a small amount (a few parts per million) of polyvalent metal lons. Ferrous ions are commonly and effectlvely used, or a tertiary amine which ls soluble ln the reactlon medium may also be used as an actlva~or.
Suitable stabilizing emulsiflers include the anionic and nonionlc surfactants. Examples of suitable anlonlc surfactants lnciude the alkyl aryl sulfonates, the alkall metal alkyl sul-fates, the sulfonated alkyl esters and the fatty acld soaps. Spe-cific examples of these well-known emulsifiers, for the purpose of illustration and not for llmltation, are sodlum butylnaphthalene sulfonate, sodium lauryl sulfate, dlsodlum dodecyldlphenyl ether dlsulfonate, N-octadecyl dlsodlum sulfosucclnamate, dlhexyl sodlum sulfosuccinate and dioctyl sodium sulfosucclnate. A preferred anlonlc surfactant is dlsodlum dodecyldlphenyl ether dlsulfonate.
Suitable nonionlc surfactants lnclude the polyethenoxy agents, e.g., ethylene glycol polyethers and ethylene nonylphenol polyethers, and the like; fatty acld esters of polyhydric alco-hols, e.g., propylene glycol fatty acid ester. Other suitable nonionic emulsifiers are descrlbed in Becher, Em~lsions: Theory and Practlce, 2d. ed., Reinhold Publlshlng Corporation, New York, 221-225 (1965). A preferred nonlonlc emulsifier ls ethylene nonylphenol r 31. ?~ ?_3 ?3 polyether having 40 moles of ethylene oxide per mole of nonylphenol.
The amounts of surfactants required depend primarily on the concentrations of monomers to be handled and, to a further extent, with the choice of kind of surfactants, monomers, and proportions of monomers. Generally, the amount of emulsifying agent required falls between 0.5 and 10 weight percent of the mixture of monomers. A preferable emulsifier system C for preparing the latexe~ of this invention is~
mixture of from 0.1 part to 0.5 part of an anionic surfactant and from 4 parts to 5 parts of a nonionic surfactant per 100 parts monomer- used in the preparation of the latex. Latexes which do not have a measurable amount of coagulum are readily obtained when the amount is from 0.2 to 0.3 part of anionic surfactant and from 4.0 parts to 4.2 parts of nonionic surfactant per 100 parts of monomer.
Polymerization of the monomers is suitably carried out at temperatures between room temperature and 100C, preferably between 65C and 80C. As mentioned previously~ the use of catalyst activators lowers the required temperature of polymerization.
During polymerization, the temperature may be controlled in part hy the rate at which the monomers are supplied and polymerized and/or by applied cooling.
As taught in the art, emulsion polymerization may be per~ormed batchwise or continuously. It is possible to work entirely batchwise, emulsi~ying the entire charge of monomers and proceeding with polymerization. It is usually advantageous, however, to start with part of the monomers which are to be used 31,248C-F -20---21 ~ r~ - J

and add the remainder of the monomer or monomers as polymerization proceeds. An advantage of gradual monomer addition lies in reaching a high solids content with optimum control and with maximum uniformity of product.
In yet another embodiment, heterogeneous polymerization techniques may be used to prepare the polymeric compositions of this invention.
Heterogeneous catalysts are readily obtained by mixing an alkyl aluminum with a reducible compound of a metal of Groups IVA, VA, VI~ and VIII of the Periodic Chart.
Examples of alkyl aluminum compounds which may be used include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-pentyl aluminum, diethyl aluminum chloride and diethyl aluminum hydride. Metals of the above-listed groups include titanium, zirconium, hafnium, thorium, uranium, vanadium, niobium, tantalum, chromium, molybdenum,. tungsten and iron. Examples of suitable reducible compounds of these metals include halides, e.g., chlorides and bromides; oxyhalides, e.g., oxychlorides; complex halides, e.g., complex fluorides;
freshly precipitated oxides or hydroxides; and organic compounds, e.g., alcoholates, acetates, benzoates, or acetyl acetonates. Titanium compounds are preferred, for example, titanium tetrachloride, titanium oxychloride or titanium acetyl acetonate. An 3 especially preferred heterogeneous catalyst is a mixture of triisobutyl aluminum and titanium tetrachloride. Such catalyst systems are prepared by dissolving each of the catalyst components in an inert liquid vehicle such as hexane under an oxygen- and moisture-free atmosphere, e.g., nitrogen, argon, helium 31,248C-F -21--22~ 3 and the like. Actual procedures for preparing these catalyst systems are described in more detail in U.S.
Patent Nos. 3,113,115 and 3,257,332 of Karl Ziegler et al.

The heterogeneous catalyst process is carried out in the absence of molecular oxygen, carbon monoxide, carbon dioxide and water in a conventional reaction vesqel which permits bubbling of the monomers through the inert vehicle which contains the catalyst.
The polymerization is conducted at temperatures in the range of between 30C and 100C and preferably between 85C and 95C. For convenience of handling the gaseous alpha-olefins, the polymerization zone is maintained 1~
under a pressure between atmospheric and 115 pounds per square inch gauge (790 kPa gauge) for the first stage, preferably at a pressure in the range of between 55 and 65 psig (380 and 450 kPa gauge). In a preferred embodiment, the fir~t stage is carried out in the presence of a molecular weight polymerization control agent such as hydrogen, acetylene, and other commonly employed chain transfer agents. If hydrogen i~ used as the molecular weight control agent, the amount of hydrogen employed ranges from 1 to 90 mole percent based on the monomer feed, and preferably from 25 to 50 mole percent. However, it is preferred that the molecular weight control agent not be present during polymerization of the second stage. The polymerization 3 process may be carried out in a batchwise or continuous manner.
Upon completion of polymerization, any excess monomer is vented. The mixture is then treated by any conventional method to deactivate the catalyst and remove the catalyst residues and recover the polymer 31,248C-F -22--23- l 3f~ ~ 3~

mixture. In one method, deactivation of the catalyst is accomplished by washing the slurry mixture with an alcohol such as methanol, n-propanol and isopropanol.
The polymer is then separated from the diluent, e.g. by decantation, filtration or other similar method, after which the polymer is dried.
In yet another embodiment, the polymeric composition of this invention may be prepared by bulk polymerization, wherein the monomeric components are directly contacted in the presence of a catalyst. In bulk polymerizations, free radical catalysts may be used. Such free radical catalysts are described hereinbefore. Polymerization catalyst concentrations are generally between 0.001 and 5 weight percent.
Temperatures are between room temperature (20C) and 200C. Atmospheric and superatmospheric pressures may be used. Due to problems in the dissipation of heat in exothermic bulk polymerizations, bulk polymerization may either be terminated at relatively low conversions of between 40 and 60 weight percent and excess monomer distilled off, or the polymerization may be carried out in two steps. In the first step, a large batch of monomer is polymerized to an intermediate conversion and then, for ease of heat dissipation, the polymerization is completed in thin layers. The reaction may be carried to completion while the monomer-polymer mixture flows either through a small diameter tube or down the walls of a column or by free fall in thin streams.
In yet another embodiment, the polymeric compositions of this invention may be prepared by suspension polymerization techniques. In suspension polymerization, the catalyst is dissolved in the 31~248C-F -23--24~

monomer, the monomer is dispersed in water, and a dispersing agent is incorporated to stabilize the suspension formed. Suspending agents are generally water-soluble organic polymers, such as poly(vinylalcohol), poly(acrylic acid), methyl cellulose, gelatin and various pectins; and water insoluble inorganic compounds such as kaolin, magnesium silicates, aluminum hydroxide, and various phosphates.
Free radical catalysts described hereinbefore are useful for these suspension polymerizations.
Generally, catalyst concentrations of between 0.001 and 5 weight percent based on the monomer are used.
Temperatures of between rGom temperature (20C) and 200C are suitable. The polymers prepared are in the form of finely granulated beads which are easily recovered by filtration and dried.
The choice of the particular polymerization process to be used depends upon the particular monomer system used and the desired properties of the polymeric composition. Those skilled in the art can well make such choices.

The polymeric compositions of this invention have increased adhesion to metals and anticorrosion properties. These polymeric compositions are useful in latex paint~, coatings for metals, plastic-metal laminateq and adhesives.
The following examples are provided for illustrative purposes only, and not intended to limit the scope of the invention or the claims. All parts and percentage are by weight unless otherwise specified.

31,248C-F -24--25- ~ v~ ~ J ~J '~

Examele 1 A - Preparation of Hydroxy-meth~lphosphorous Acid In a 500-ml, 3-neck flask, fitted with a magnetic stirrer, thermometer, nitrogen inlet and condenser, was placed 264 g of 50 percent hypophosphorous acid. The solution was heated to 80C
while ~tirring. Paraformaldehyde (66 g) was then added portionwise (2 1/2 g portions) over a period of 30 minutes. A~ter addition was complete, the solution was held at 80C for 3 hourq. An additional 4 g of paraformaldehyde was added and heating was continued for 3 more hours. The clear solution was then stripped of water on a rotary evaporator, 100 ml of absolute t ethanol added, then stripped again. This yielded a clear liquid which was characterized by 13C and 31P
nuclear magnetic resonance.
[~ 31P = 30.0 ppm; JpH = 549 Hz]
B - Preparation of (Hydroxy)phos-phinylmethyl Methacrylate A 2-liter, 3-neck flask, fitted with a mechanical stirrer, nitrogen sparge, and a modified Dean Stark trap and condenser was charged with the following reactants:
96.0 grams (1 mole) hydroxymethylphosphorous acid 258 grams (3 mole) methacrylic acid 0.4 grams phenothiazine 0.8 grams benzyltrimethylammonium chloride 31,248C~F -25--26~ i3 0.4 grams p-toluenesulfonic acid 1 Liter perchloroethylene While stirring and keeping a nitrogen sparge, the mixture was heated to reflux for 7 hours during which time 17.8 ml oY water was collected.
The two-phase mixture was then cooled and extracted three times with 600 ml of water. The combined water extracts were stripped on a rotary evaporator. Final removal of water and excess methacrylic acid was accomplished by vacuum distillation.
The product, a clear viscous liquid, was characterized by 13C and 31P nmr.
[~ 31P = 21.8 ppm; JpH = 565 Hz]
ExamPle 2 - CoPol~mer Pre~aration A polymer containing the following monomers was prepared:

- 31,248C-F -26--27~
,CH3 CH3 tCH2-Ct- tCH2-Ct tCH2-Ct C // \ / C O OH
O OCH3 O-C4Hg o O-CH2-P \
H

by weight 53% 45% 2%

In a 1-liter, round-bottom fla~k fitted with a mechanical ~tirrer was placed:
79.5 g methyl methacrylate 67.5 g butyl acrylate 3.0 g hydroxyphosphinylmethyl methacrylate 0.75 g benzoyl peroxide 700 mls methyl ethyl ketone The solution was refluxed for 3 hours. Methyl ethyl ketone (300 ml) was distilled off leaving a clear, highly viscous solution.
ExamDle 3- PreParation of (DihYdroxY)Dhosphinvlmethyl-Methacrylate To a 2-liter 3-necked flask9 fitted with a mechanical ~tirrer, thermometer and addition funnel was 3~ charged one liter of acetonitrile, 236 g (1 mole) of diethylpho~phonomethyl methacrylate, (CH3CH2012P(-O)CH20COC(CH3)=CH2, and 300 g (2 moles) 31,248C-F -27--28~ ~.?,2~

sodium iodide. The mixture was stirred for 2 hours at room temperature. To the stirred mixture was added drop by drop through the addition funnel 217 g (2 moles) of trimethylchlorosilane over a period of 1 hour. Stirring at room temperature was continued ~or 2 hours after the addition was complete. Water (36.0 g, 2 moles) was added dropwise to the resulting mixture, which was stirred overnight at room temperature.
The precipitated salt was removed by filtration and washed with 200 ml of acetonitrile. To the ~iltrate was added 800 ml of absolute ethanol and then 80.0 g (2 moles) of sodium hydroxide in portions of 5 g each. The mixture was stirred for 4 hours. The resulting precipitate of the disodium salt of (dihydroxy)phosphinylmethyl methacrylate, Na202P(=O)CH200CC(CH3)=CH2, was removed by filtration, washed with absolute ethanol and dried under vacuum.
The yield was 184 g (82 percent).
The disodium salt, dissolved in water, was converted to acid by addition of concentrated hydrochloric acid to pH below 1. The resulting solution was diluted with an equal volume of absolute ethanol and concentrated using a rotary evaporator heated at 40C. Ethanol was added periodically during the process to replace the ethanol/water azeotrope being removed. After all of the water was removed, precipitated sodium chloride was removed by filtration, and washed with ethanol. The filtrate and washings were concentrated to give a viscous, light yellow liquid, which rapidly turned darker yellow-brown upon exposure to light.

31,248C-~ -28-The product was characterized by nuclear magnetic re onance analysis as follows:

O O CH3 (d) , ............... .
(HO)2P - CH2 - O - C - C = CH
(a) (b) (c) (e~

31p, ô = 19.7, 2Jp~ = 8.5 Hz in CDCI3; = 16.0, 2JPH = 8.5 Hz in water '3C ~ (ppm) a 57 9, JPC = 170.0 HZ
b 167.0, 3JPC = 9.8 Hz c 1 17.4 d 17.8 e 134.9 Exam~le 4 Copolymerization of (DihYdroxy)~hosphinylmethyl Methacrylate with Acr~lic Acid To a 100-ml round-bottom flask were charged 30 3 g of toluene, 9.5 g of acrylic acid, 0.5 g of (dihydroxy)pho~phinylmethyl methacrylate, and 0.1 g of benzoyl peroxide. The solution was heated under a nitrogen atmosphere with magnetic stirring. At approximately 95C, an exotherm began and white polymer began to precipitate. The mixture was held at approximately 100C for 30 minutes and then cooled. The 31,248C-F -29-3 0 ~

resulting polymer was removed by filtration, washed with fresh toluene, and dried under vacuum. A 31P nmr of the polymer gave a new, slightly broadened peak at 14.5 ppm wrt H3P04.
- Example 5 Copolymerization of (Dih~droxy)phos~hin~lmethyl MethacrYlate with Acr~lic Acid The copolymerization of Example 2 was repeated using 150 ml of H20 as solvent and 0.015 g of Wako~ V-50, owned by Wako Pure Chemical Industries Ltd., [2,2'-asobis (2-amidinopropane)hydrochloride)] as the initiator. Heating the solution to 90C initiated an exotherm. The solution was held at 90C for l hour. A- 31P nmr of the water soluble copolymer gave a new peak at 14O3 ppm wrt H3PO4.
Example 6 - Preparation of Latex The following ingredients were mixed in a 1-liter beaker to prepare an emulsion:
400 ml water 48 g Triton X-200 (28% solids) Trademark of Rohm and Haas, alkylaryl-ether sulfonate-anionic surfactant) 160 g methyl methacrylate (1.6 moles) 240 g ethyl acrylate (2.4 moles) 0.8 g ammonium persulfate .. .. .
6.8 g Ho_p_cH2_3c_c_cH2 (0.04 mole).

H

31,248C-F -30--31 ~ v~

In a reaction vessel consisting of a 2-liter, 3-necked, round-bottom flask fitted with a condenser, addition funnel, nitrogen inlet, thermometer and a mechanical stirrer was placed 100 ml of water and 100 ml of prepared emulsion. The flask was heated to 820C
under a nitrogen blanket. The mixture began to reflux and the temperature was raised to ~0C. When the reflux began to slow, the remainder of the emulsion was added dropwise so that the pot temperature remained at 880C to 92C. After the addition was finished, the temperature was raised to 97C for one hour. The emulsion was then cooled to room temperature and filtered through a paint strainer.
Example 7 Preparation of Styrene-butadiene Latex Incorporatin~
(DihYdroxy)phosphin~lmethyl MethacrYlate (a) Emulsion polymerization was done as follows: initially the reactor was charged with 73 parts by weight of water, O.Q1 part by weight of pentasodium salt of ~carboxymethylimino) bis(ethylenenitrilo)tetraacetic acid ~1 percent solution) and 0.70 part by weight of seed latex (polystyrene, 270~, (27 nm)39.7 percent solids). To this mixture was added concurrently a first stream of 62 parts by weight of styrene and 0.5 parts by weight of tert-dodecyl mercaptan; a second stream of 38 parts by weight of butadiene; a third stream of 15 parts by weight of water, 0.7 parts by weight of sodium persulfate, 0.1 part by weight of 10 percent ammonium hydroxide and 0.5 part by weight of sodium salt of dodecylated sulfonated phenyl ether (45 percent solution) and a fourth stream of 12 parts by weight of water and 2.0 parts by weight of the disodium salt of 31,2~8C-F -31-w J ~3 (dlhydroxy)phosphinylmethyl methacrylate. The polymerlzatlon was carrled out at 90C and the additlon tlme was 4 hours.
The product contalned 4S.2 percent by welght of sollds and had a partlcle diameter of 1730A (173 nm).
(b) A modlfled latex was prepared as above, uslng 4.0 parts by welght of the dlsodium salt of (dlhydroxy)phosphinyl-methyl methacrylate. The resulting latex contalned 40.6 percent by welght of sollds and had a particle dlameter of 1730A (173 nm).
The foregolng latexes can be used for paper coatlng and ln industrial coati.ngs.
Example 8 - Flash Rust Test A latex was prepared by the procedure descrlbed in Example 6 from the followlng ingredlents: 400 ml of water, 48 g of Trlton X-200 (28 percent sollds), 160 g of methyl methacrylate, 240 g of ethyl acrylate, 0.8 g of ammonium persulfate, and 4.0 g of methacryllc acld. This latex was lncluded for comparative purposes.
On a cold rolled steel panel, coatings of the latex pre-pared ln Example 6 and the comparative latex were placed on dlf-ferent parts of the panel. The coatings were allowed to alr dryand were then heated at 150C for one hour.
The clear coatings obtained were scribed with an X, and a vial of water was turned over onto each X. After being left overnlght, the portlon of the panel coated wlth the comparative latex demonstrated a hlgh ~c- -,--33- ~ ~ ?J~

degree of rusting, whereas the portion coated with the latex from example 6 demonstrated little or no rusting.
The example shows that a latex containing the ~ ~."~ J~s-f~,~fC7,S
monomers o~ this invention dcmonstrate enhanced corrosion prevention properties.
Example 9 - PreParation of Latex In a 1-gallon glass reactor provided with an agitator and a device for monitoring the reactor temperature was placed an initial charge comprising 70 parts by weight of deionized water and 2 parts by weight of seed latex (95 percent styrene, 5 percent acrylic acid with sodium lauryl sulfate as surfactant, 280A (28 nm). The reactor was purged with nitrogen, agitated, and heated to 90C. The monomer charge comprising 49.5 parts by weight of methyl methacrylate, 49.5 parts by weight of n-butyl acrylate and 1.0 parts by weight of (hydroxy)phosphinylmethyl methylmethacrylate was added to the reactor at time = 0 minute for a total of 120 minutes at a feeding rate of 400 cm3/hr. The initiator charge comprising 97.56 parts by weight of deioni~ed water, 1.22 parts by weight of NaHC03 and 1.22 parts by weight of Na2S20g was added to the reactor beginning at time = 0 minute for a total of 150 minutes at a feeding rate of 123 cm3/hr.
3 Following the addition of all the initiator charge (i.e. at time = 150 minutes), the mixture was continued to be agitated at 90C under nitrogen for 30 minutes. The product contained approximately 50 percent solids.

31,248C-~ -33-~ 3 4 ~ ~L 3 r~ J a) The latex produced in accordance with the above procedure is suitable for use in industrial coatings, architectural coatings, plastic coatings, paper coatings, adhesives and high barrier coatings. A clear coating composition comprising this latex exhibited good salt-fog corrosion resistance as tested by ASTM
B117 method.
Example 10 A pigmented, high gloss, anticorrosive paint for metals was prepared by blending the following ingredientc at room temperature:
Latex prepared in Example 9 150 g (ph = 103, adjusted with EDA, 0.1 weight percent NaN02 added) 25% non-ionic surfactant/12.5 % 1.2 g wetting zgent Ball - Milled Pigment Grind 100 g H20 (1000 parts by weight) TiO2 (1000 parts by weight) Dispersant (1 part by weight) 25% non-ionic surfactant/12.5% wetting o.8 g agent (added to ball-milled pigment grind) Methyl carbitol 7.2 g Defoamer/non-ionic surfactant, emulsifier 0.6 g (1:1 mixture) Urethane-ba~ed polymeric associative thickener 0.4 g 31,248C-F -34--35~ 3 The paint showed good corrosion resistance, blistering resistance and high gloss (90 sheen at 60 angle).

31,248C-F -35-

Claims (16)

1. A phosphinyl-containing ethylenically unsaturated compound selected from (hydroxy)-phosphinylalkyl acrylate, (hydroxy)phosphinylalkyl methacrylate, (dihydroxy)phosphinylalkyl acrylate, methacrylate or ethacrylate, or an alkali metal, alkaline earth metal or ammonium salt thereof.

2. A compound as claimed in Claim 1 which is represented by the formula (I) (II) wherein R1 is hydrogen or methyl;
R2 is separately in each occurrence hydrogen or C1-10 alkyl:

M is an alkali metal, alkaline earth metal or ammonium;

and a is 1 or 2.

3. A compound as claimed in Claim 2, wherein R2 is hydrogen or C1-3 alkyl.

4. A compound as claimed in Claim 3, wherein R2 is hydrogen or methyl.

5. A compound as claimed in Claim 4, wherein R2 is hydrogen.

6. A compound as claimed in Claim 3, wherein R1 is methyl.

7. A compound as claimed in Claim 1, represented by the formula (V) or (VI) wherein R1 is hydrogen, methyl or ethyl; R2 is selected independently from hydrogen and alkyl of 1-10 carbon atoms and M+
is an ammonium or alkali metal cation, or 1/2 an alkaline earth metal cation.

8. A compound as claimed in Claim 7, wherein R1 is hydrogen or methyl and R2 is selected independently from hydrogen and alkyl of 1-3 carbon atoms.

9. A compound as claimed in Claim 7, wherein R1 is hydrogen or methyl and R2 is hydrogen or alkyl of 1-3 carbon atoms.

10. A compound as claimed in Claim 7, wherein R1 is methyl and R2 is hydrogen.

11. (Dihydroxy)phosphinylmethyl methacrylate, a compound as claimed in Claim 7.

12. A process for the preparation of an ammonium, alkali metal or alkaline earth metal salt of a (dihydroxy)phosphinylalkyl acrylate, methacrylate or ethacrylate comprising the steps of (a) transesterifying a dialkylphosphonoalkyl acrylate, methacrylate or ethacrylate with a trialkylhalosilane in an aprotic solvent to produce an intermediate bis(trialkylsilyl)phosphonoalkyl acrylate, methacrylate or ethacrylate, and (b) saponifying the thus-formed intermediate bis(trialkylsilyl)phosphonoalkyl acrylate, methacrylate or ethacrylate with a base to produce a salt.

13. The process of Claim 12, including the further step of acidifying the thus-formed salt with a strong acid to produce a (dihydroxy)phophinylalkyl acrylate, methacrylate or ethacrylate.

14. The process of Claim 12 wherein:
(a) the salt is of the formula wherein R1 is hydrogen or methyl; R2 is selected independently from hydrogen or alkyl of 1-10 carbon atoms and M+ is an ammonium or alkali metal cation or 1/2 an alkaline earth metal cation;
(b) the trimethylhalosilane is selected from a chloro-, bromo-, or iodotrimethylsilane;
(c) the dialkylphosphonoalkyl acrylate or methacrylate is of the formula wherein alk is alkyl of 1-4 carbon atoms; and (d) the base is ammonium hydroxide or an oxide or hydroxide of an alkali metal or alkaline earth metal.

15. The process of Claim 14, wherein R1 is hydrogen or methyl; R2 is hydrogen or alkyl of 1-3 carbon atoms; alk is alkyl of 1-4 carbon atoms; the aprotic solvent is acetonitrile; the trimethylhalosilane is trimethylchlorosilane and the process is carried out in the presence of sodium iodide.

16. A process for preparing (hydroxy)phosphinylalkyl compound of the formula wherein R1 is hydrogen, methyl or ethyl and R2 is selected independently from hydrogen and alkyl of 1-10 carbon atoms, comprising the steps of:
(a) condensing hypophosphorous acid with an aldehyde or ketone of 1-10 carbon atoms to produce an intermediate 1-hydroxyalkylphosphorous acid compound and (b) esterifying the thus-produced intermediate 1-hydroxyalkylphosphorous acid compound with acrylic, methacrylic acid or ethacrylic acid.