The invention is (hydroxy)-phosphinylalkyl acrylate, (hydroxy)-phosphinylalkyl methacrylate or an alkali metal, alkaline earth metal or ammonium salt thereof. In another aspect, the invention is a polymeric composition which comprises the reaction product of: PA0 (a) between about 0.5 and 100 percent by weight of a (hydroxy)-phosphinylalkyl acrylate, (hydroxy)-phosphinylalkyl methacrylate or an alkali metal, alkaline earth metal or ammonium salt thereof; and PA0 (b) between about 0 and 99.5 weight percent of a compound containing a polymerizable 1,2-ethylenically unsaturated moiety.

BACKGROUND OF INVENTION 
This invention relates to novel 1,2-ethylenically unsaturated 
(hydroxy)-phosphinyl-containing compounds, and polymers containing such 
compounds. 
The novel 1,2-ethylenically unsaturated (hydroxy)-phosphinyl-containing 
compounds of this invention are useful in preparing polymeric compositions 
when copolymerized with compounds containing polymerizable 
1,2-ethylenically unsaturated moieties, or homopolymerized. 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. 
A major problem is to find a polymeric composition which has good adherence 
to particular metals. What is needed is a polymeric composition prepared 
from compounds containing 1,2-ethylenically unsaturated moieties which 
have good adherent properties to metal, and other substrates. 
SUMMARY OF INVENTION 
The invention is (hydroxy)-phosphinylalkyl acrylate, 
(hydroxy)-phosphinylalkyl methacrylate or an alkali metal, alkaline earth 
metal or ammonium salt thereof. 
In another aspect the invention is a polymeric composition which comprises 
the reaction product of: 
(a) between about 0.5 and 100 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 about 0 and 99.5 weight percent of a compound containing a 
polymerizable 1,2-ethylenically unsaturated moiety. 
The polymeric compositions prepared from the 1,2-ethylenically unsaturated 
(hydroxy)-phosphinyl-containing compound of this invention, have 
surprisingly good adherence to many metals. Furthermore, the polymeric 
compositions have enhanced anticorrosive properties. 
DETAILED DESCRIPTION 
The novel compounds of this invention preferably correspond to the formula: 
##STR1## 
wherein: R.sup.1 is hydrogen or methyl; 
R.sup.2 is separately in each occurrence hydrogen or C.sub.1-10 alkyl; 
M is an alkali metal, alkaline earth metal or ammonium; and 
a is 1 or 2. 
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, R.sup.2 is preferably hydrogen or C.sub.1-3 alkyl, 
more preferably hydrogen or methyl, and most preferably hydrogen. R.sup.1 
is most preferably methyl. M is preferably an ammonium moiety or an alkali 
metal. M is more preferably an ammonium moiety, potassium or sodium. 
Preferably, a is 1. 
The novel compounds of this invention are generally clear viscous liquids 
which are soluble in water and polar organic solvents such as methanol and 
dimethylsulfoxide. 
The (hydroxy)-phosphinylalkyl acrylates and (hydroxy)-phosphinylalkyl 
methacrylates can be prepared by the reaction of hypophosphorous acid with 
a suitable aldehyde or ketone to prepare an 
.alpha.-hydroxyalkylphosphorous acid, which is thereafter reacted with 
acrylic or methacrylic acid to prepare the novel compounds. This reaction 
sequence is exemplified by equations I and II. 
##STR2## 
wherein R.sup.1 and R.sup.2 are as defined hereinbefore. 
In the first step of this process, the hypophosphorous acid is contacted 
with a suitable aldehyde or ketone in a ratio of between about 3:1 and 
1:1. In this reaction there cannot be an excess of aldehyde or ketone as 
such as excess would result in multiple 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 about 20.degree. C. and 
100.degree. C., with temperatures between about 70.degree. C. and 
90.degree. C. 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, argon and the like. 
Any reaction time which gives the desired conversion is suitable. 
Generally, reaction times of between about 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 about 3:1 and 1:3, with a ratio of between about 2:1 and 1:2 being 
preferred, and with a ratio of about 1:1 being most preferred. Where there 
is an excess of 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 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 100.degree. C., and most preferred that the solvent 
have a boiling point over 120.degree. C. 
This reaction is done in the presence of an esterification catalyst. 
Preferred esterification catalysts are strong acids. More preferred strong 
acids include sulfonic 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 100.degree. C., with a 
reflux temperature of over 120.degree. C. being most preferred. 
During the course of this process water is formed as a by-product. It is 
preferred to remove the water as formed, as the process is an equilibrium 
process and the removal of water drives the reaction to completion. 
This reaction may be run at atmospheric and superatmospheric pressures. 
Atmospheric pressure is preferred. An inert atmosphere can be used. 
Reaction times which give the desired conversion are suitable. Preferable 
reaction times are between four and ten hours. 
The salts of the (hydroxy)-phosphinylalkyl acrylate or 
(hydroxy)-phosphinylalkyl methacrylate are prepared by contacting the 
(hydroxy)-phosphinylalkyl acrylate or (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, alkali 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 lithium, 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. 
The polymeric compositions of this invention comprise the reaction product 
of a (hydroxy)-phosphinylalkyl acrylate, (hydroxy)-phosphinylalkyl 
methacrylate or an alkali metal, alkaline earth metal or ammonium salt 
thereof, and a compound containing a polymerizable 1,2-ethylenically 
unsaturated moiety. The polymeric compositions of this invention 
preferably contain between about 1 and 10 weight percent of the novel 
phosphinyl-substituted 1,2-ethylenically unsaturted compounds of this 
invention, and more preferably between about 1 and 5 percent of the 
phosphinyl-substituted 1,2-ethylenically unsaturated compounds. 
In another aspect of this invention, the polymeric compositions comprise 
the reaction product of 
(a) between about 0.5 and 99 percent by weight of a 
(hydroxy)-phosphinylalkyl acrylate, (hydroxy)-phosphinylalkyl methacrylate 
or an alkali metal, alkaline earth metal or an ammonium salt thereof; and 
(b) between about 1 and 99.5 percent of two or more compounds which contain 
a polymerizable 1,2-ethylenically unsaturated moiety. 
Any compound which contains a polymerizable 1,2-ethylenically unsaturated 
moiety is useful in this invention. Examples of such compounds include 
monovinyl aromatics, such as styrene, p-vinyl toluene, p-chlorostyrene; 
.alpha.,.beta.-ethylenically unsaturated acids, such as acrylic acid and 
methylacrylic acid; alkyl esters of .alpha.,.beta.-ethylenically 
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; .alpha.,.beta.-ethylenically unsaturated 
nitriles such as acrylonitrile and methacrylonitrile; 
.alpha.,.beta.-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 vinyl methyl ether and vinyl ethyl ether; vinyl ketones, such as 
vinyl methyl ketone and vinyl ethyl ketone; vinylidene halides, such as 
vinylidene chloride and vinylidene bromide; hydroxyalkyl esters of acrylic 
and methacrylic acids such as hydroxypropyl acrylate, hydroxyethyl 
acrylate, and hydroxybutyl acrylate; nitriles of ethylenically unsaturated 
carboxylic acids such as acrylonitrile and methacrylonitrile; 
ethylenically unsaturated carboxylic acids such as acrylic acid; 
ethylenically unsaturated alcohols such as allyl alcohol; aromatic 
compounds substituted with 1,2-ethylenically unsaturated moieties such as, 
styrene, vinyl toluene, tert-butylstyrene and the like. 
The polymeric compositions of this invention are prepared by methods 
well-known in the art, and such preparations are not the point of this 
invention. Suitable polymerization techniques include solution 
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, tetrachloroethane and the 
like; 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; per-acids 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 about room temperature (about 20.degree. 
C.) to about 200.degree. C. under atmospheric to superatmospheric pressure 
at catalyst concentrations of 0 in the case of thermal initiation to about 
5 weight percent based on weight of monomers, preferably from about 0.01 
to about 5 weight percent of catalyst in pure form or in an inert solvent 
for the catalyst. Thermal initiation generally occurs at temperatures 
between 60.degree. C.-120.degree. C. 
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: 
EQU H.sub.3 CC(CH.sub.3).sub.2 CH.sub.2 C(CH.sub.3).sub.2 CH.sub.2 
C(CH.sub.3).sub.2 SH 
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 0 to about 5 weight percent based on monomer weight. Illustratively, 
the use of from 0 to about 1 weight percent of t-dodecyl mercaptan serves 
to provide as wide a range of molecular weight in aqueous media as is 
desirable. 
In another embodiment, the polymeric compositions of this invention can be 
prepared by ionic polymerization techniques. 
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 polymerization is advantageously carried out in an inert 
hydrocarbon solvent such as lower alkane or lower aromatic hydrocarbon at 
temperatures in the order of about -20.degree. C. to about 140.degree. C. 
under pressures ranging from atmospheric to superatmospheric and in the 
presence of from about 1 to 200 ppm of ionic catalyst based on weight of 
monomers. Polymerization can be similarly effected by cationic catalysts 
at temperatures from -100.degree. C. to 100.degree. C. Such catalysts 
include the etherates of boron trifluoride and aluminum trichloride and 
Ziegler catalysts such as the reaction product of 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., 0.degree. C. to 100.degree. C., and low pressures, 
e.g., 0 to 100 psig. Typical transition metal components are the halides, 
oxyhalides, alkoxides and the like of metals selected from Groups IVB, VB, 
VIB and VIII of the Periodic Table of Elements appearing in the Handbook 
of Chemistry and Physics, 48th ed., Chemical Rubber Company. Common 
organometallic components 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 
polymerization generally have molecular weights in the range of about 
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 monomers 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, methyl ethyl ketone peroxide and the like. The usual 
amount of catalyst required is roughly from about 0.01 to about 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 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 limits of about 0.001 
to about 6.0 weight percent based on the monomers is present in addition 
to the peroxide catalyst. Many examples of such redox systems are known. 
Agents such as hydrazine or a soluble oxidizable sulfoxy compound, 
including the alkali metal salts of hydrosulfites, sulfoxlates, 
thiosulfates, sulfites and bisulfites and the like can be employed. Redox 
systems may be activated by the presence of a small amount (a few parts 
per million) of polyvalent metal ions. Ferrous ions are commonly and 
effectively used, or a tertiary amine which is soluble in the reaction 
medium may also be used as an activator. 
Stabilizing emulsifiers suited for the purposes of this invention include 
the anionic and nonionic surfactants. Examples of suitable anionic 
surfactants include the alkyl aryl sulfonates, the alkali metal alkyl 
sulfates, the sulfonated alkyl esters, the fatty acid soaps, and the like. 
Specific examples of these well-known emulsifers, for the purpose of 
illustration and not for limitation, are sodium butylnaphthalene 
sulfonate, sodium lauryl sulfate, disodium dodecyldiphenyl ether 
disulfonate, N-octadecyl disodium sulfosuccinamate, dihexyl sodium 
sulfosuccinate and dioctyl sodium sulfosuccinate. A preferred anionic 
surfactant is disodium dodecyldiphenyl ether disulfonate. 
Suitable nonionic surfactants include the polyethenoxy agents, e.g., 
ethylene glycol polyethers, ethylene nonylphenol polyethers, and the like; 
fatty acid esters of polyhydric alcohols, e.g., propylene glycol fatty 
acid ester; and the like. Other suitable nonionic emulsifiers are 
described in Becher, Emulsions: Theory and Practice, 2d. ed., Reinhold 
Publishing Corporation, New York, 221-225 (1965). A preferred nonionic 
emulsifier is ethylene nonylphenol 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 about 0.5 and about 10 
weight percent of the mixture of monomers. A preferable emulsifier system 
for preparing the latexes of this invention is a mixture of from about 0.1 
part to about 0.5 part of an anionic surfactant and from about 4 parts to 
about 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 about 0.2 to about 
0.3 part of anionic surfactant and from about 4.0 parts to about 4.2 parts 
of nonionic surfactant per 100 parts of monomer. 
Polymerization of the monomers is suitably carried out at temperatures 
between about room temperature and about 100.degree. C., preferably 
between about 65.degree. C. and about 80.degree. C. As mentioned 
previously the use of catalyst activators lowers the required temperature 
of polymerization. During polymerization, the temperature may be 
controlled in part by the rate at which the monomers are supplied and 
polymerized and/or by applied cooling. 
As taught in the art, emulsion polymerization may be performed batchwise or 
continuously. It is possible to work entirely batchwise, emulsifying 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 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, VIA 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, 
diethyl aluminum hydride and the like. 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 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 and 
the like. Actual procedures for preparing these catalyst systems are 
described in more detail in U.S. Pat. Nos. 3,113,115 and 3,257,332 of Karl 
Ziegler et al. (incorporated herein by reference). 
The heterogeneous catalyst process is carried out in the absence of 
molecular oxygen, carbon monoxide, carbon dioxide and water in a 
conventional reaction vessel 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 about 30.degree. C. 
and 100.degree. C. and preferably between about 85.degree. C. and 
95.degree. C. For convenience of handling the gaseous alpha-olefins, the 
polymerization zone is maintained under a pressure between about 
atmospheric and 115 pounds per square inch gauge (psig) for the first 
stage, preferably at a pressure in the range of between about 55 and 65 
psig. In a preferred embodiment, the first 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 is used as the molecular weight control agent, the amount of 
hydrogen employed ranges from about 1 to about 90 mole percent based on 
the monomer feed, and preferably from about 25 to about 50 mole percent. 
However, it is preferred that the molecular weight control agent not be 
present during polymerization of the second stage. 
The polymerization 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 mixture. 
In one method, deactivation of the catalyst is accomplished by washing the 
slurry mixture with an alcohol such as methanol, n-propanol, isopropanol 
and the like. 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 (about 20.degree. C.) and 200.degree. C. 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 about 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 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 about 0.001 and 5 weight percent based on the 
monomer are used. Temperatures of between room temperature (about 
20.degree. C.) and about 200.degree. C. 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 anticorrosive properties. These polymeric compositions are 
useful in latex paints, coatings for metals, plastic-metal laminates, 
adhesives, and the like.

SPECIFIC EMBODIMENTS 
These examples are provided for illustrative purposes only, and are not 
intended to limit the scope of the invention or the claims. All part and 
percentages ar by weight unless otherwise specified. 
EXAMPLE 1 
A--Preparation of Hydroxymethylphosphorous Acid 
In a 500-ml, 3-neck flask, fitted with a magnetic stirrer, thermometer, 
nitrogen inlet and condenser, is placed 264 g of 50 percent 
hypophosphorous acid. The solution is heated to 80.degree. C. while 
stirring. Paraformaldehyde (66 g) is then added portionwise (.about.21/2g 
portions) over a period of about 30 minutes. After addition is complete, 
the solution is held at 80.degree. C. for 3 hours. An additional 4 g of 
paraformaldehyde is added and heating is continued for 3 more hours. The 
clear solution is then stripped of water on a rotary evaporator, 100 ml of 
absolute ethanol added, then stripped again. This yielded a clear liquid 
which is characterized by .sup.13 C and .sup.31 P nuclear magnetic 
resonance. 
[.delta. .sup.31 P=30.0 ppm; J.sub.PH =549 Hz] 
B--Preparation of (Hydroxy)phosphinylmethyl Methacrylate 
A 2-liter, 3-neck flask, fitted with a mechanical stirrer, nitrogen sparge, 
and a modified Dean Stark trap and condenser is 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 
0.4 grams p-toluenesulfonic acid 
1 liter perchloroethylene 
While stirring and keeping a nitrogen sparge, the mixture is heated to 
reflux for 7 hours during which time 17.8 ml of water is collected. 
The two-phase mixture is then cooled and extracted three times with 600 ml 
of water. The combined water extracts are stripped on a rotary evaporator. 
Final removal of water and excess methacrylic acid is accomplished by 
vacuum distillation. 
The product, a clear viscous liquid, is characterized by .sup.13 C and 
.sup.31 P nmr. 
[.delta. .sup.31 P=21.8 ppm; J.sub.PH =565 Hz] 
EXAMPLE 2 
Copolymer Preparation 
A polymer containing the following monomers is prepared: 
##STR3## 
In a 1-liter, round-bottom flask fitted with a mechanical stirrer is 
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 is refluxed for 3 hours. Methyl ethyl ketone (300 ml) is 
distilled off leaving a clear, highly viscous solution. 
EXAMPLE 3 
Preparation of Latex 
The following ingredients are 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 
##STR4## 
______________________________________ 
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 is placed 100 ml of water and 100 ml of prepared 
emulsion. The flask is heated to 82.degree. C. under a nitrogen blanket. 
The mixture begins to reflux and the temperature is raised to 90.degree. 
C. When the reflux begins to slow, the remainder of the emulsion is added 
dropwise so that the pot temperature remains at 88.degree. C. to 
92.degree. C. After the addition is finished, the temperature is raised to 
97.degree. C. for one hour. The emulsion is then cooled to room 
temperature and filtered through a paint strainer. 
EXAMPLE 4 
Flash Rust Test 
A latex is prepared by the procedure described in Example 3 from the 
following ingredients: 400 ml of water, 48 g of Triton X-200 (28 percent 
solids), 160 g of methyl methacrylate, 240 g of ethyl acrylate, 0.8 g of 
ammonium persulfate, and 4.0 g of methacrylic acid. This latex is not an 
example of the invention, and is included for comparative purposes. 
On a cold rolled steel panel, coatings of the latex prepared in Example 3 
and the comparative latex are placed on different parts of the panel. The 
coatings are allowed to air dry and are then heated at 150.degree. C. for 
one hour. 
The clear coatings obtained are scribed with an X, and a vial of water is 
turned over onto each X. After being left overnight, the portion of the 
panel coated with the comparative latex demonstrates a high degree of 
rusting, whereas the portion coated with the latex from Example 3 
demonstrates little or no rusting. 
The example demonstrates that a latex containing the monomers of this 
invention demonstrate enhanced corrosion prevention properties.