FI85860B - New ethylenically unsaturated compounds containing phosphinyl - Google Patents

Description

! 85860

The present invention relates to novel phosphinyl-containing ethylenically unsaturated compounds and to polymers containing such compounds.

The novel phosphinyl-containing ethylenically unsaturated compounds of this invention are useful in preparing polymer combinations by homopolymerization or copolymerization with compounds containing polymerizable 1,2-ethylenically unsaturated moieties. The polymeric compositions prepared are useful in latex paints, plastic metal laminates, metal coatings and adhesives. Polymeric combinations made from compounds containing 1,2-ethylenically unsaturated moieties are often attached or adapted to metals in various ways.

The big problem is to find a polymeric combination that has good adhesion to the metals used.

What is needed is a polymeric combination made from compounds containing 1,2-ethylenically unsaturated moieties that have good adhesion properties to metals and other materials.

One object of the present invention is to provide a novel phosphin-25-ethylenically unsaturated compound. . selected from (hydroxy) phosphinylalkyl acrylic ester and (dihydroxy) phosphinylalkyl acrylic ester, especially comprising acrylate, methacrylate and ethacrylate esters, as well as their corresponding ammonium, alkali metal and alkaline earth metal salts. Hereinafter, these compounds are referred to as "HP acrylic monomer" or "DHP acrylic monomer".

· ']; Another object of this invention is a polymer, '. obtained by polymerization: 2 85860 (a) HP or DHP acrylic monomer and (b) at least one copolymerizable 1,2-ethylenically unsaturated monomer.

Another aspect of this invention is a process for preparing an ammonium, alkali metal or alkaline earth metal salt from an HP or DHP acrylic monomer in the form of a salt.

Polymeric combinations prepared from the 1,2-ethylenically unsaturated (hydroxy) phosphinyl and (dihydroxy) phosphinyl-containing compounds of this invention have surprisingly good adhesion to many metals. In addition, polymeric compounds have increased anti-corrosion properties.

Preferred HP acrylic monomers 15 of this invention are those having the following formula:

1 o 0H

R1 0 R2 0 / CHp = c - CO - C - p 'ά (I) r2

20 K

or f R1 0 R2 0 \ 25 CH2 = C - CO - C - P - 0Θ \ - M® (II)

and V

1 2 wherein R is hydrogen or methyl; is independently at each occurrence hydrogen or C 1-10 alkyl; M is al- · _. potassium metal, alkaline earth metal or ammonium; and a is 1 or 2.

In an embodiment where M is an ammonium moiety or an alkali metal, a is 1. In an embodiment where M is an alkaline earth metal, a is 2.

3 85860 2

In the above formula, R is preferably hydrogen or C 1-2 alkyl, more preferably hydrogen or methyl, and most preferably hydrogen. R1 is most preferably methyl. M is preferably an ammonium moiety or an alkali metal. More preferably, M is an ammonium moiety, potassium or sodium. Preferably a is 1.

(Hydroxy) phosphinylalkyl acrylates and (hydroxy) phosphinylalkyl methacrylates can be prepared by reacting hypophosphorous acid with a suitable aldehyde or ketone to prepare οό-hydroxyalkylphosphoric acid to prepare new compounds of acrylic acid, which are then reacted with acrylic acid. This series of reactions is illustrated by examples in Equations III and IV.

0 0 "I» 15 (H0) 2PH + R2 CR2 HO-P-C (R2) pOH (III) f

B

20 2? 1 2 2 0 R1 (IV) HO-PC (R2) 20H + CH2 = C-COH - »H0-PC (R2)? 0C-C = CHo I / 2 2 hn 1.2 where R and R are defined as above.

· '· *; In the first step of the process, the hypophosphorous acid is combined with the appropriate aldehyde or ketone: in a ratio of between 3: 1 and 1: 1. There can be no excess of aldehyde or ketone in this reaction, as such an excess would result in multiple aldehyde or ketone additions to the acid. This method is performed in • aqueous solution. It is preferred to add the aldehyde or ketone to the aqueous hypophosphoric acid solution, as this reaction is exothermic and the slow addition results in much better monitoring of the reaction temperature.

____: 35 Generally, this phase can be run anywhere in the warm · • · · 4 85860

In a patient where the reaction is progressing. Preferably the temperatures are between 20-100 ° C, with temperatures between 70-90 ° C being most preferred.

This preparation method can be run at any pressure at which the reaction takes place. Atmospheric, subatmospheric and superatmospheric pressures can be used. Atmospheric pressure is preferred. Although not necessary, it is preferable to run this reaction in an inert gas atmosphere. Examples of inert gases are nitrogen-10 pi and argon.

Any reaction time that gives the desired conversion is suitable. In general, reaction times of from 3 to 10 hours are preferred. After completion of the reaction, the aqueous solvent is removed.

The hydroxyalkylphosphoric acid prepared in the reaction described above is then combined with methacrylic acid or acrylic acid in a ratio of 3: 1 to 1: 3, with a ratio of 2: 1 to 1: 2 being preferred, and a ratio of 1: 1 being most preferred. If an excess of 20 single reagents is present, it is preferred that this reagent be methacrylic or acrylic acid. This preparation method is generally carried out in an inert organic solvent. Examples of preferred inert organic solvents are aromatic hydrocarbons and chlorinated solvents. More preferred solvents are perchlorethylene and xylene. It is preferable that the boiling point of the solvent used is above 100 ° C, and most preferably, the boiling point of the solvent is above 120 ° C.

This reaction is carried out 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. The most preferred catalyst is p-toluenesulfonic acid.

Any temperature at which the reaction proceeds is • v: 35 suitable. This reaction is preferably carried out at the reflux temperature of the solvent 5,85860. It is preferred that the reflux cooling temperature be above 100 ° C, with the most preferred reflux temperature being above 120 ° C.

During this manufacturing process, water is formed as a by-product. It is preferable to remove the water formed, since the production method is an equilibrium production method and the removal of water drives the reaction in the direction of termination.

This reaction can be carried out at atmospheric and superatmospheric pressure. Atmospheric pressure is edul-2_q linen. An inert atmosphere can be used.

Reaction times that give the desired conversion are suitable. Preferred reaction times are between 4 and 10 hours.

Preferred DHP acrylic monomers of the invention are those having the formula:

1 5 OH

R1 0 R2 0 / * 1 »I» I / CH2 = C - CO - C - p / (V)

R2 ^ OH

20 or 1 o Μ®0Θ R1 0 R2 0 / »··» »» / · **: CH2 ϊ C - CO - C - / (VI) I. 25 'R2 ^ Μφ0θ "- · ..1 2 - wherein R is hydrogen, methyl or ethyl, R is independently hydrogen and alkyl of 1 to 10 carbon atoms, and M is an ammonium cation, an alkali metal cation or a 1/2 earth: alkali cation.

It is to be understood that the ammonium cation may be: represented as NH +; alkali metal cations as Li +, Na +, + + +. As K, Rb and Cs and that "1/2 alkaline earth metal cation" corresponds to 1/2 Mg ++, 1/2 Ca ++, 1/2 Ba ++ or 1/2 Sr ++. 35 Thus a typical alkaline earth metal , the calcium salt may be represented by the structure:

O

/ R1 O R2 O \ / I ft t I! \ [CH2 = C - CO -C - P - o) -Ca (VII) 5 v Λ

According to the above formulas, preferred monomers .1. 2 are those wherein R is hydrogen or methyl and R is independently selected from hydrogen and alkyl of 10 to 3 carbon atoms. The most preferred DHP acrylic monomer is (dihydroxy) phosphinyl methyl methacrylate, i.e., a compound wherein R is methyl and R is hydrogen.

Preferred salts are those in which M + is an ammonium cation, a sodium cation or a potassium cation.

DHP acrylic monomers can be prepared by the reaction of a dialkylphosphonoalkyl acrylic ester and a trialkyl halosilane to form the intermediate bis (trialkylsilyl) ester, which is saponified to the corresponding salt and can be oxidized to produce the DHP acrylic monomer in the free acid form.

Dialkylphosphonoalkyl acrylic esters are known compounds and are disclosed in U.S. Patent Nos. 2,934,555 and 3,030,347 to O'Brien et al., Which is incorporated herein by reference.

Dialkylphosphonoalkyl acrylic esters are prepared by adding a dialkyl hydrogen phosphite to an aldehyde or ketone to prepare a dialkyl 1-hydroxyalkyl phosphonate intermediate which is converted to an acrylic ester by reaction with an acrylic halide in the presence of a hydrogen chloride acceptor.

The reactions can be represented by the equations: 1 »· • · · 7 85860 R2CR2 + H-P (Oalk) 2-► HOC (R2) 2P (0alk) 2 (VIII)

»T I» u ^ * 11 c v J

0 0 0 5 H2C = CR1C0X + H0C (R2) 2P (0alk) 2 + einäs - (IX)

O

CH2 = CR1C00C (R2) 2P (Oalk) 2 + a · HX

O

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

Because formaldehyde and lower aldehydes are more reactive with dialkyl hydrogen phosphites than with higher aldehydes or ketones, it is preferred to make and use lower members of the series of compounds for use as intermediates.

Further conversion of dialkylphosphonoalkyl acrylic esters to DHP acrylic monomer can be represented, using chlorotrimethylsilane, by equations: 85860

O

CH2 = CR1C00 (R2) 2P (Oalk) 2 + 2 Me3SiX -► (X)

O

CH2 = CR1C00C (R2) 2P (OSiMe3) 2

O

CH2 = CR1COOC (R2) 2P (OSiMe3) 2 + 2 MOH-► (XI)

O

CR1C00C = CH 2 (R 2) 2 P (0 '+ M) 2

O

CH2 = CR1C00C (R2) 2 P (CT + M) 2 + 2 HX -> (XII) C. c. \ / o CH2 = CR1C00C (R2) 2P (OH) 2 + 2 mx 20 c o where Me is methyl; and alk, M and X are as above or HX corresponds to a strong acid other than hydrohalic diacid.

The transesterification of the dialkylphosphonoalkyl acrylic ester with a trialkyl halosilane is carried out in an approotic solvent, for example, acetonitrile, benzene, toluene, dimethylformamide, dimethyl sulfoxide or the like. The use of acetonitrile is preferred.

. . At least two moles of trialkylhalosilane are used for each mole of dialkylphosphonoalkyl acyl ester. It is preferred to use two moles of halotrimethylsilane. Although it is possible to use iodotris-methylsilane for this reaction, it has been found according to the invention that the transesterification can be easily performed using chlorotrimethylsilane if a stoichiometric amount of iodide donor is present in the reaction mixture. Correspondingly, it is preferred to use a reaction mixture containing two moles of chlorotrimethylsilane and two moles of alkali metal iodide, preferably sodium iodide or potassium iodide.

The reaction can be carried out at any temperature at which the reaction takes place. However, the reaction takes place within a reasonable time at room temperature.

Accordingly, temperatures between 15-50 ° C are preferred.

The reaction can be carried out at any pressure. However, the reaction easily takes place under ambient conditions, so the use of pressure or vacuum equipment is unnecessary. Thus, the reaction is preferably carried out at atmospheric pressure.

Due to the hydrolytic instability of trialkyl halosilanes, it is preferable to carry out the reaction under substantially anhydrous conditions. The use of desiccants such as calcium chloride or Drierite tubing is preferred. In addition, it is preferred to carry out the reaction in a dry inert atmosphere, for example, a dry nitrogen or dry argon atmosphere.

Towards the end of the reaction, the mixture is hydrolyzed by adding at least two moles of water per mole of bis (trialkylsilyl) phosphonoalkyl acrylic ester. The mixture is stirred to allow the sparingly soluble salt to separate, which is removed by filtration. The intermediate is hydrolyzed with a base which cleaves the trialkylsilyl groups to form the corresponding metal salt. This reaction easily occurs at room temperature and pressure, so elevated pressures and temperatures do not need to be used. Suo-35a can be used directly in the preparation of the polymeric combinations of this invention. The (dihydroxy) phosphinylalkyl acrylic compound can be polymerized in the form of a salt, and if desired, the resulting 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 combinations of this invention comprise a product obtained by vinyl polymerization of an HP or DHP acrylic monomer. Polymeric combinations of this invention include homopolymers of HP or DHP acrylic monomers, as well as copolymers of at least one other compound containing a polymerizable 1,2-ethylenically unsaturated moiety.

The copolymer combinations preferably comprise 0.5 to 99% by weight of HP or DHP acrylic monomer of (a); and 99.5-1% by weight of at least one copolymerizable 2Q 1,2-ethylenically unsaturated compound, the reaction product.

The copolymer combinations of this invention more preferably contain 1-10% by weight of the novel HP or DHP acrylic monomers of this invention, and most preferably 1-5% by weight of 25 HP or ° HP acrylic monomer.

The novel compounds of this invention are generally clear viscous liquids that are soluble in water and polar organic solvents such as methanol, ethanol and dimethyl sulfoxide.

The salts of 3Q (Hydroxy) phosphinylalkyl acrylate, (hydroxy) -phosphinylalkyl methacrylate, (dihydroxy) phosphinylalkyl acrylate, methacrylate or ethacrylate are prepared by combining with α-allyl: alkali 85860 metal or ammonium moiety, in water under conditions where salts are formed. The conditions for such reactions are well known to those skilled in the art. Examples of preferred bases are ammonium hydroxy-5 dit, alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides and alkaline earth metal carbonates.

The alkali metal here refers to lithium, sodium, potassium, rubidium and cesium. Preferred alkali metals are lithium, potassium and sodium, of which potassium and sodium are most preferred. Alkaline earth metals herein refer to beryllium, magnesium, calcium, strontium and barium. Preferred alkaline earth metals are magnesium and calcium.

Any compound containing a polymerizable 1,2-ethylenically unsaturated moiety is useful in this invention. Examples of such compounds are monovinyl aromatics such as styrene, p-vinyltoluene, p-chlorostyrene,%, 4-N-ethylenically unsaturated acids such as acrylic acid and methylacrylic acid; alkyl esters of β-ethylenically unsaturated monocarboxylic acids containing 1 to 18 carbon atoms in the alkyl group, such as methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate and methyl methacrylate; N, N-ethylenically unsaturated nitriles such as acrylonitrile and methacrylonitrile; β-ethylenically unsaturated amides such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate and vinyl propionate; vinyl halides such as vinyl chloro-3Q ride 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 -____ 35 such as hydroxypropyl acrylate, hydroxyethyl 12,86060 acrylate and hydroxybutyl acrylate; nitriles of ethylenically unsaturated carboxylic acids such as acrylonitrile and methacrylonitrile; ethylenically unsaturated carboxylic acids such as acrylic acid; ethyl-5-ethylenically unsaturated alcohols such as allyl alcohol and aromatic compounds substituted with 1,2-ethylenically unsaturated moieties such as styrene, vinyltoluene and tert-butylstyrene.

The polymeric compounds of this invention are prepared by methods well known in the art, and such methods are not the subject of this invention. Suitable polymerization techniques include solution polymerization, dispersion polymerization, emulsion polymerization, slurry polymerization, and heterogeneous polymerization. These polymerizations may be carried out continuously or in batches, if appropriate.

In one embodiment, the polymeric combinations of this invention can be prepared by free radical initiated solution polymerization. In particular, phosphinyl-substituted 1,2-ethylenically unsaturated monomers are homopolymerized or copolymerized with one or more compounds containing a polymerizable 1,2-ethylenically unsaturated moiety in an organic solvent medium in the presence of a free radical-type catalyst in an oxygen-free atmosphere. The monomeric ingredients are mixed and polymerized in the proportions described above.

Examples of solvents include lower alkanols such as ethanol, propanol and butanol; aromatic carbohydrates such as toluene, benzene and xylene; halogenated hydrocarbons such as methylene chloride and tetrachloroethane and others such as butyl acetate and butoxyethyl acetate.

- Representative catalysts used in free radical catalyst polymerization are of the azo and peroxide-35 type; e.g. peroxides such as benzoyl peroxide, <85860 hydroperoxides such as t-butyl hydroperoxide; peracids such as perbenzoic acid; peresters such as t-butyl peroctoate; and azo compounds such as azobis-isobutyronitrile. The free radical catalyzed polymerization is carried out efficiently at temperatures from room temperature (20 ° C) to 200 ° C at atmospheric-superatmospheric pressure, with catalyst concentration from 0 to 5% by weight in the case of thermal start-up, preferably based on the weight of the monomer, preferably 0.01-5% by weight of catalyst in pure form or in an inert solvent for the catalyst. Thermal start-up usually takes place at temperatures between 60-120 ° C.

It is often necessary to use a chain regulator to keep the molecular weight in the desired range. Examples of chain-regulating reagents that can be used include long chain alkyl mercaptans, e.g., t-dodecyl mercaptan of the formula: H3CC (CH3) 2CH2C (CH3) 2CH2C (CH3) 2SH (XIII) 2SH short chain alkyl mercaptans such as butyl mercaptan ; isopropanol, isobutanol, long chain alcohols, e.g. lauryl alcohol, octyl. . alcohol, cumene, carbon tetrachloride, tetrachlorethylene and trichlorobromomethane. The amount of chain control reagent that can be used depends on the particular system and conditions and can range from 0 to 5% by weight based on the weight of the monomer. Illustratively, the use of t-dodecyl mercaptan in an amount of 0.1% by weight covers as much as a broad molecular weight range in an aqueous medium as desired.

: In another embodiment, the polymeric combinations of this invention can be prepared by ion polymerization methods.

Preferred ion catalysts are lithium base catalysts, e.g., metal lithium, alkyllithium, and other lithium compounds, and Ziegler catalysts, e.g., reducing titanium or vanadium halide in combination with aluminum trialkyl or diethylaluminum chloride or lithium aluminum hydride. The ion polymerization is preferably carried out in an inert hydrocarbon solvent such as a lower alkane or lower aromatic hydrocarbon at temperatures on the order of -20 ° C to 140 ° C, pressures from atmospheric to supernatural and from 1 to 200 ppm of ionic catalyst base, based on the weight of the monomer. The polymerization can likewise be enhanced with cation catalysts at temperatures between -100 ° C and 100 ° C. Such catalysts include ethers of boron trifluoride and Aluminum trichloride and Ziegler catalysts such as reactive aluminum compounds such as titanium tetrachloride or trichloride and reducible organometallic compounds such as triethylaluminum or diethylaluminum.

In another embodiment, alpha-203 nepolymerization processes can be used in which the compounds containing polymerizable 1,2-ethylenically unsaturated moieties are alpha-olefins.

Vacuum polymerization of alpha-olefins with a catalyst system consisting of a partially reduced heavy transition metal component and an organometallically reducing component to form high density, high molecular weight, solid, relatively linear polymers is well known. Typically. The polymerizations are carried out in an inert organic 3Q liquid solvent in an inert atmosphere at relatively low temperatures, e.g. between 0-100 ° C and low pressures, e.g. between 0-100 psig (0-690 ·. · kPa). Typical transition metal components are halides. , oxyhalides, alkoxides and metals selected from 35 groups IVB, VB, VIB and VIII of the Periodic Table of the Elements, 15 85860, presented in the Handbook of Chemistry and Physics 48th Edition, Chemical Rubber Company. are metal alkyls, metal alkyl halides and dihalides, metal hydrides and similar compounds in which the metals are selected from the Periodic Table of the Elements IA, IIA and IIIA Alpha-olefin polymers prepared by vacuum polymerization generally have a molecular weight of up to 10,000 or even in the range of 100,000-300 000.

In yet another embodiment, the polymeric combination of the present invention can be prepared by emulsion polymerization in which the monomers are decomposed in an aqueous medium containing a free radical-type catalyst and a stabilizing emulsifier or mixture of emulsifiers. Suitable free radical catalysts include persulfates (including ammonium, sodium and potassium persulfates), hydrogen peroxide, perborates and percarbonates. Organic peroxides can also be used either alone or in combination with an inorganic pepoxygen compound. Typical organic peroxides include benzoyl perocide, tert-butyl hydroperoxide, cumene peroxide, acetyl peroxide, caproyl peroxide, tert-butyl perbenzoate, tert-butyl diphthalate and methyl ethyl ketone peroxide. The usual amount of catalyst required is from about 0.01 to 3.0% by weight, based on the monomer mixture. In order to increase the rate of polymerization, improve the properties of the polymers and reduce undesired side reactions, it is often desirable to activate the catalyst. Catalyst activation. . 1a also has the effect of lowering on polymerization; / required temperature. The activation is best performed using an oxidation-reduction system in which the reducing agent is present in the range of 0.001 to 6.0% by weight, relative to the monomers present in addition to the peroxide catalyst. Many examples of such reductive reduction systems are known in FIG. 85860. Substances such as hydrazine or a soluble oxidizable sulfoxy compound, including alkali metal salts of hydrosulfites, sulfoxylates, thiosulfates, sulfites and bisulfites, may be used. Oxidation-reduction systems can be activated in the presence of small amounts (a few parts per million) of multivalent metal ions. Ferro ions, or a tertiary amine soluble in the reactant, are usually and effectively used as an activator.

Suitable stabilizing emulsifiers for the purposes of this invention include anionic and nonionic surfactants. Examples of suitable anionic surfactants are alkylarylsulfonates, alkali metal alkyl sulfates, sulfonated alkyl esters and fatty acid soaps. Specific examples of these well-known emulsifiers for the purpose of describing, but not limited to, sodium butyl naphthalene sulfonate, sodium lauryl sulfate, disodium dodecyl di-20 ° phenyl ether disulfonate, N-octadecyl disodium sulfosuccinamate, dihexyl succinate, dihexyl The preferred anionic pfnta active agent is disodium dodecyl diphenyl ether di sulfonate.

Suitable nonionic surfactants include polyethenoxy materials, e.g., ethylene glycol polyethers and ethylene nonylphenol polyethers, and the like; fatty acid esters of polyhydric alcohols, e.g. propylene glycol fatty acid ester. Other suitable nonionic emulsifiers are described in Becher Emulsions: Theory and. . Practice, Second Edition, Reinhold Publishing Corporation,

New York, 221-225 (1965). The preferred nonionic emulsifier is ethylene nonylphenol polyether with 40 moles of ethylene oxide per mole of nonylphenol.

35 The amounts of surfactants required li 17 85860 depend primarily on the concentration of the monomers to be treated, and more broadly, on the surfactants, monomers and monomer ratios selected. In general, the amount of emulsifier required is between 0.5 and 10% by weight of the mixture of monomers. The preferred emulsification system for preparing the latices of this invention is a mixture of 0.1 to 0.5 parts of anionic surfactant and 4 to 5 parts of nonionic surfactant per 100 parts of monomer used in the preparation of the latex.

Latexes without a measurable amount of coagulate are readily obtained in an amount of 0.2 to 0.3 parts of anionic surfactant and 4.0 to 4.2 parts of nonionic surfactant per 100 parts of monomer.

The polymerization of the monomers is carried out according to purpose 15 at temperatures between room temperature and 10 ° C, preferably between 65 and 80 ° C. As mentioned above, the use of catalyst activators lowers the required polymerization temperature. During the polymerization, the temperature can be partially controlled by the rate at which the 2q monomer is fed and polymerized and / or by the cooling used.

As taught in the art, emulsification polymerization can be performed batchwise or continuously. On mah-! it is possible to work completely batchwise, emulsifying the batch monomer charge and continuing with the polymerization. However, it is usually useful to start with some of the monomers used and to add residues of the monomer or monomers as the polymerization continues. The benefit of gradual monomer addition is in achieving a high solids content of 3q, optimal control, and maximum product. . uniformity.

In another embodiment, the heterogeneous polymerization technique can be used to prepare the polymeric combinations of this invention.

Heterogeneous catalysts are readily obtained by mixing 18,858,8 with an alkylaluminum reducing metal compound from groups IVA, VA, VIA and VIII of the Periodic Table. Examples of alkylaluminum compounds that can be used include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-pentylaluminum, diethylaluminum chloride and diethylaluminum hydride. Metals from the groups listed above include titanium, zirconium, hafnium, thorium, uranium, vanadium, niobium, tantalum, chromium, molybdenum, yolf-1Q ram and iron. Examples of suitable reducing compounds for these metals include halides, e.g. chlorides and bromides; oxyhalides, e.g. oxychlorides; halide complexes, e.g. fluoride complexes; freshly precipitated oxides or hydroxides; and organic compounds, e.g., alcoholates, acetates, benzoates, or acetylacetonates. Titanium compounds are preferred, for example, titanium tetrachloride, titanium oxychloride or titanium acetylacetonate. A particularly preferred heterogeneous catalyst is a mixture of triisobutylaluminum and titanium tetrachloride. Such catalyst systems are prepared by relying on each catalyst component in an inert liquid solvent such as hexane in an oxygen- and moisture-free atmosphere, e.g., nitrogen, argon, helium, and the like. Existing methods for preparing these catalyst systems are described in more detail in U.S. Patent Nos. 3,113,115 and 3,257,332 to Karl Ziegler et al.

The heterogeneous catalyst process is performed without molecular oxygen, carbon monoxide, carbon dioxide, and water in a standard reaction vessel that allows monomerization. . bubbling through an inert solvent containing a catalyst. The polymerization is carried out at temperatures between 30 and 10 ° C and preferably between 85 and 95 ° C. To facilitate the handling of gaseous alpha-olefins, the polymerization zone is maintained at a pressure between atmospheric and 115-19,88860 pounds per square inch (190 kPa) in the first stage, preferably at a pressure between 55 psig and 65 psig (380-450 kPa). reading). In a preferred embodiment, the first step is performed in the presence of a molecular weight polymerization control agent, such as hydrogen, acetylene, and other commonly used chain transfer agents. If hydrogen is used as a molecular weight control, the amount of hydrogen used is from 1 to 90 mol%, based on the monomer feed, and preferably from 25 to 30 mol%. However, it is preferred that no molecular weight control agent be present during the second stage of polymerization. The polymerization process can be carried out in a batch or continuous manner.

Upon completion of the polymerization, any excess monomer-15 is removed. The mixture is then treated by any conventional method to deactivate the catalyst and remove catalyst residues and recover the polymer mixture. In one method, catalyst deactivation is performed by washing the slurry mixture with an alcohol such as methanol, n-propanol and isopropanol. The polymer is then separated from the solvent, e.g. by decantation, filtration or the like, after which the polymer is dried.

In yet another embodiment, the polymeric combination of this invention is prepared by slurry polymerization in which the monomer components are combined immediately in the presence of a catalyst. Free radical catalysts can be used in the bulk polymerization. Such free radical catalysts have been described above.

Polymerization catalyst concentrations are generally in the range of. : 0.001-5% by weight. Temperatures are between room temperature (20 ° C) ··· and 200 ° C. Atmospheric and supernatural pressures can be used. Due to heat loss problems in exothermic slurry polymerization, slurry polymerization 35 can be limited to either relatively low conversions of 40-60% by weight and excess monomer is distilled off, or the polymerization can be performed in two steps. In the first step, the large monomer charge is polymerized for intermediate conversion and then to reduce heat loss, the polymerization is completed by thin layer chromatography. The reaction can be completed because the monomer-polymer mixture flows either through a small diameter tube or along the column walls or in a free-falling flow.

In another embodiment, the polymeric combinations of this invention can be prepared by a suspension polymerization technique. In suspension polymerization, the catalyst is dissolved in the monomer, the monomer is dispersed in water, and a dispersant is added to stabilize the resulting suspension. Suspending agents are generally water-soluble organic polymers such as poly (vinyl alcohol), poly (acrylic acid), methylcellulose, gelatin and various pectins; and water-insoluble inorganic compounds such as kaolin, magnesium silicate, aluminum hydroxide, and various phosphates. The free radical catalysts described above are useful in these suspension polymerizations. Generally, catalyst concentrations between 0.001 and 5% by weight, based on the monomer, are used. Temperatures ranging from room temperature (20 ° C) to 25,200 ° C are suitable. The polymers produced are fine-grained beads that are easily recovered by filtration and dried.

The choice of a particular polymerization method depends on the particular monomer system used and the desired properties of the polymer combination. Those skilled in the art can easily make these choices.

The polymeric compositions of this invention have increased attachment to metals and have anti-corrosion properties. These polymer combinations:: 35 are useful in latex paints, metal coatings, 21,858,860 plastic-metal laminates and adhesives.

The following examples are presented for illustrative purposes only and are not intended to limit the scope or claims of the invention. All parts and percentages are by weight unless otherwise indicated.

Example 1 Hydroxymethylated and phosphoric acid preparation A 500 ml three-necked flask equipped with a magnetic stirrer, a thermometer, a nitrogen inlet and a condenser was charged with 264 g of 50% hypophosphoric acid. The solution was heated to 80 ° C with stirring. Paraformaldehyde (66 g) was then added portionwise (2 1/2 g portions) over 30 minutes. After the addition, the solution was kept at 80 ° C for 3 hours. An additional 15 g of paraformaldehyde was added and heating was continued for an additional 3 hours. The clear solution was separated from water on a rotary evaporator, 100 ml of absolute ethanol was added, then separated again. This gave a clear solution, which was identified by C and P nuclear magnetic resonance.

C ^> 31p = 30.0 ppm; Preparation of JpH = 549 Hz 7 'B - (Hydroxy) phosphinylmethyl methacrylate 25 A 2-liter three-necked flask equipped with a mechanical stirrer, a nitrogen inlet, and a modified Dean Stark separator and condenser was charged with the following reactants: 1Q 96.0 g (1Q 96.0 g) 258 g (3 moles) of methacrylic acid 0.4 g of phenothiazine 0.8 g of benzyltrimethylammonium chloride *: ·: 0.4 g of p-toluenesulphonic acid 35 1 liter of perchlorethylene 22 85860

With stirring and maintaining nitrogen bubbling, the mixture was heated to reflux for 7 hours, during which time 17.8 ml of water was collected.

The biphasic mixture was then cooled and extracted three times with 600 ml of water. The combined aqueous extracts were removed on a rotary evaporator. The final removal of excess methacrylic acid and water was performed by vacuum distillation.

The product, a clear viscous liquid, was identified at 10 ° C and nmr.

/ ~ $ 31P = 21.8 ppm? JpH = 565 Hz7

Example 2 15 Copolymer Preparation

A polymer was prepared containing the following monomers: ch3 ch3 fCH2-Ct tCH2-C ·) · + CH2- «

20 n P

// \ // \ °,. / H

0 0CH3 0 0 «Ci | Hg 0 0-CH2“ P // 25 by weight. 53¾ 45¾ 2%: In a one-liter round-bottomed flask equipped with a mechanical stirrer was placed: 79.5 g of methyl methacrylate 30 67.5 g of butyl acrylate -; 3.0 g hydroxyphosphinyl methyl methacrylate 0.75 g benzoyl peroxide 7QQ ml methyl ethyl ketones

The solution was refluxed for 3 hours. Methyl ethyl ketone (300 mL) was distilled off to leave a clear, .1. very viscous solution.

23 85860

Example 3 Preparation of (dihydroxy) phosphinylmethyl methacrylate A 2-liter three-necked flask equipped with a mechanical stirrer, thermometer and additional funnel was charged with 1 liter of acetonitrile, 236 g (1 mole) of diethylphosphonomethyl (CH3), CH3 CH 2 OCO (CH 3) = CH 2, and 300 g (2 moles) of sodium iodide. The mixture was stirred for 2 hours at room temperature. 217 g (2 moles) of trimethylchlorosilane were added dropwise to the stirred mixture via addition funnel over one hour. Stirring was continued at room temperature for 2 hours, after which 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 filtrate was added 8Q0 ml of absolute ethanol and then 80.0 g (2 moles) of 2Q sodium hydroxide, in 5 g portions. The mixture was stirred for 4 hours. The precipitate of the obtained (dihydroxy) phosphinyl methyl methacrylate, the disodium salt Na 2 O 2 P (= O) CH 2 OCO (CH 3) = CH 2, was removed by filtration, washed with absolute ethanol and dried in vacuo. The yield was 184 g (82%).

The disodium salt, dissolved in water, was converted to acid by the addition of concentrated hydrochloric acid below pH 1. The resulting solution was dissolved in an equal volume of absolute ethanol and concentrated using a rotary evaporator, heated to 40 ° C. Ethanol was added periodically during the process to replace the removed ethanol / water azeotrope. After all the water was removed, the precipitated sodium chloride was removed by filtration and washed with ethanol. The filtrate and washings were concentrated to give a viscous, pale yellow solution, which quickly turned dark yellow-brown under the influence of light.

24 85860

The product was identified by nuclear magnetic resonance analysis as follows: 0 0 CHo (d)

n n i J

5 (HO) pP - CHp - 0 - C - C = CHp

(a) (b) (c) (eT

31P, δ = 19.7, JJpH = 8.5 Hz in CDCl 3 = i6.0.2JpH = 8.5 Hz in water 10 i3C _S_ (ppm)

a 57.9, Jpc = 170.0 Hz

b 167.0, 3Jpc = 9.8 Hz 15 c 117.4 d 17.8 e 134.9 20

Example 4 Copolymerization of (dihydroxy) phosphinyl methyl methacrylate with acrylic acid A 100 ml round bottom flask was charged with 30 g of toluene, 9.5 g of acrylic acid, 0.5 g of (dihydroxy) phosphinyl methyl methacrylate and 0.1 g of g: 11a benzoyl peroxide. The solution was heated under nitrogen pressure with a magnetic stirrer. At about 95 ° C, an exothermic reaction began and the white polymer precipitated. The mixture was kept at about 100 ° C for 30 minutes and then cooled.

The resulting polymer was removed by filtration, washed with toluene and dried in vacuo. The nmr of the polymer gave a new, slightly wider peak at 14.5 ppm.

25 85860

Example 5 Copolymerization of (dihydroxy) phosphinyl methyl methacrylate with acrylic acid

The copolymerization of Example 2 was repeated using 5,150 mL of H 2 O solvent and 0.015 g of Viako V-50 ^ 2,2 1 -azabis- (2-amidinopropane) hydrochloride oil as the initiator. Heating the solution to 90 ° C initiated an exothermic reaction. The solution was kept at 90 ° C for one hour. The P nmr of the water-soluble copolymer gave a new peak at 14.3 ppm.

Example 6 Preparation of latex

The following ingredients were mixed in a 1 liter beaker to form an emulsion: 15,400 ml of water 48 g of Triton X-200 (28% solid) Rohm and Haas trademark alkylaryl ether sulfonate anionic surfactant) 160 g of methyl methacrylate (1 .6 moles) 20 240 g of ethyl acrylate (2.4 moles) Q, 8 g of ammonium persulfate OO ce3 6.8 g HO-P-CH2-OC-C = CH2 (0.04 moles)

'H

To a reaction vessel comprising a 2-liter three-necked flask equipped with a condenser, an addition funnel, a nitrogen outlet, a thermometer and a mechanical stirrer were added 100 ml of water and 100 ml of the prepared emulsion. The flask was heated to 82 ° C in a nitrogen-30 jacket. The mixture began to reflux and the temperature was raised to 90 ° C. As reflux began to slow --- the remaining emulsion was added dropwise to maintain the flask temperature at 88-92 ° C. After the addition was complete, the temperature was raised to 97 ° C over one hour.

The emulsion was then cooled to room temperature and protected. was passed through a paint filter.

85860 26

Example 7

Preparation of styrene-butadiene latex containing (dihydroxy) phosphinylmethyl methacrylate (a) Emulsion polymerization was carried out as follows: The initial reactor was charged with 73 parts by weight of water, 0.01 parts by weight of (carboxymethylimino-bis (ethylenenitrile) tetra pentosodium salt of acetic acid (1% solution) and 0.70 parts by weight of seed latex (polystyrene, 270 Å, 39.7% solids) to which was added a first stream of 62 parts by weight of styrene and 0, 5 parts by weight of tert-dodecyl mercaptan, second stream with 38 parts by weight of butadiene, third stream with 15 parts by weight of water, 0.7 parts by weight of sodium persulphate, 0.1 part by weight of 10% ammonium hydroxide and 0.5 part by weight of the sodium salt of dodecyl sulfonate phenyl ether (45% solution) and a fourth stream of 12 parts by weight of water and 2.0 parts by weight of the disodium salt of (dihydroxy) phosphinyl methyl methacrylate, was performed on 9 At 0 ° C and the addition time was 2q 4 hours.

The product contained 45.2% by weight solids and had a particle diameter of 1730A (173 nm).

(b) The modified latex was prepared as above using 4.0 parts by weight of the disodium salt of (dihydroxy) phosphinylmethyl methacrylate. The resulting latex contained 40.6% by weight solids and had a particle diameter of 173A (173 nm).

The latices described above can be used as paper coatings and industrial coatings.

30 Example 8 Rust test of a coated surface

The latex was prepared by the method of Example 6 from the following ingredients: 400 mL of water, 48 g of Triton X-20Q (28% solids), 160 g of methyl methacrylate, 240 g of ethyl acrylate, 0.8 g of ammonium per: 27 85860 sulfate, and 4 g of .0 g of methacrylic acid. This latex was not an example of the invention and was included for comparison purposes.

On the cold steel surface of the roller conveyor, the latex coatings and reference latices prepared in Example 6 were placed in different parts of the surface. The coatings were allowed to air dry and then heated to 150 ° C for one hour.

The resulting clear coatings were stained with X and the water ampoule was poured onto each X. After overnight, the surface portion coated with the reference latex showed a high degree of rust, while the latex coated portion of Example 6 showed little or no acceptance.

The example shows that 1 athe containing these monomers of the present invention showed increased anti-rust properties.

Example 9

Latex Preparation A 2Q 1 gallon glass reactor equipped with a stirrer and apparatus to control the reactor temperature was charged with an initial charge of 70 parts by weight of deionized water and 2 parts by weight of seed latex (95% styrene, 5% acrylic acid sodium lauryl sulfate). as a surfactant, 280 Å (28 nm) The air was removed from the reactor with nitrogen, stirred and heated to 90 ° C. A monomer charge containing 49.5 parts by weight of methyl methacrylate, 49.5 parts by weight of n-butyl acrylate and 1.0 part by weight of (hydroxy) phosphinylmethyl methyl 3q methacrylate, were added to the reactor at a time of = 0 minutes to a total time of 120 minutes at a feed rate of 3 at 40 ° cm / hour An initial charge containing 97.56 parts by weight of deionized water, 1.22 parts by weight of NaHCO 3 and 1.22 parts by weight of Na 2 O 2/8 / Hit into the reactor in time = 0 minutes to a total time of 150 minutes at a feed rate of 123 cm 2 / hour.

28 85860

Following the addition of the initial charge (i.e. over 150 minutes), stirring of the mixture was continued at 90 ° C under nitrogen pressure for 30 minutes. The product contained about 50% solids.

The latex prepared according to the above method is suitable as a factory coating, a construction coating, a plastic coating, paper coatings, adhesives and high barrier coatings. The clear coating combination containing this latex showed good inhibition of salt spray corrosion when tested by the ASTM B 117 method.

Example 10

A pigmented, high-gloss anti-corrosion paint for metals was prepared by mixing the following ingredients at room temperature: 150 g of the latex prepared in Example 9 (pH = 103, adjusted to EDA, 0.1 wt%).

NaNC »2 added) 25% non-ionic surfactant 1.2 g / 12.5% wetting agent

Pigment grinding ball mill 100 g 20 H2O (1000 parts by weight)

TiCl 2 (1000 parts by weight) dispersant (1 part by weight) 25% nonionic surfactant 0.8 g substance / 12.5% wetting agent (added to pigment grinding ball mill) 25 Methylcarbitol 7.2 g

Anti-foaming agent / non-ionic surface - 0.6 g substance, emulsifier (1: 1 mixture)

Thickener combining urethane-base polymer 0.4 g

The paint showed good corrosion resistance and a high 30 gloss (90 gloss at a 60 ° angle).

Claims (12)

1. M®0® R1 0 R2 O / I n in / ch2 = c - CO - C - (VI) R2 M®0® characterized in that R1 represents hydrogen, methyl or ethyl; R 2 is independently hydrogen or alkyl having 1-10 carbon atoms, and M * represents an ammonium or alkali metal cation, alkali metal cation or 1/2 alkaline earth metal cation. 1. PH 1. Phosphinyl containing ethylenically unsaturated compound selected from the group (hydroxy) phosphinylalkyl acrylate, (hydroxy) phosphinylalkyl methacrylate, (dihydroxy) phosphinylalkyl acrylate, methacrylate or ethacrylate, or an alkali metal or alkaline earth metal, these. A compound according to claim 1, having the formula: I * / ch 2 = c - CO - C - p / '(I) R2 15 / tai R1.0 R2 R2 In It \ CH2 = C-C0-CP - q © \ - M® (II) 20 'p' V 'V. characterized in that R1 is hydrogen or with-. . 25 tyl; R 2 is independently hydrogen or C 1-6 alkyl; M represents alkali metal, alkaline earth metal or ammonium; and a is 1 or 2. A compound according to claim 1, having the formula 85860 A compound according to claim 2 or 3, characterized in that R 2 is hydrogen or C 1-3 alkyl. Polymer composition, characterized in that it comprises a reaction product of: a) between 0.5-100% by weight (hydroxy) phosphinylalkyl acrylate, (hydroxy) phosphinylalkylmethacrylate, (dihydroxy) phosphinylalkyl acrylate, methacrylate or ethacrylate, or an alkali metal, alkaline earth metal or ammonium salt: 30 of these; and b) between 0-99.5% by weight of a compound containing a polymerizable 1,2-ethylenically unsaturated moiety. 5 R1 O R2 0 / * 11 I If / ch2 = c - CO - C - P ^ (v) r2 OH tai 10 Polymer composition according to claim 5, characterized in that the reaction product contains: 36 85 860 a) 1-10% by weight (hydroxy) phosphinyl acrylate, (hydroxy) phosphinylalkyl methacrylate, (dihydroxy) phosphinyl alkyl acrylate, methacrylate or ethacrylate or an alkali metal, alkaline earth metal or ammonium salt thereof; and b) between 90-99.5% by weight of a compound containing a polymerizable 1,2-ethylenically unsaturated moiety. Polymer composition according to claim 5 or 6, characterized in that the (hydroxy) phosphinyl alkyl acrylate, (hydroxy) phosphinyl alkyl methacrylate 10 and the alkali metal, alkaline earth metal and ammonium salt thereof correspond to the formula R1 0 R2 0 / »» » f It / ch 2 = C - CO - c - where R 1 is hydrogen or methyl; and R2 is hydrogen or C1-10 alkyl. Polymer composition according to claim 5 or 6, characterized in that the DHP acrylic monomer has the formula (H0)? P-C (R2) 2-O-C-CR1 = CH2 cit I * 0 0. . 25. T 1 (M + +) O 2 P-C (R 2) 2-O-C-CR 1 = CH 2 where R 1 is hydrogen, methyl or ethyl; R 2 may independently represent hydrogen or alkyl with 1-10 carbon atoms and M + denote an ammonium or alkali metal cation or 1/2 alkaline earth metal cation. 9. Process for the preparation of a (hydroxy) -1 Phosphorylalkyl compound of the formula: H f H0-PC (R2) 200C-C (R1) = CHp fl uc o where R1 represents hydrogen, methyl or ethyl, and R2 may independently represent hydrogen or alkyl of 1-10 carbon atoms, characterized in that it comprises steps wherein (a) hypophosphoric acid is condensed with an aldehyde or ketone of 1-10 carbon atoms, the intermediate being a 1-hydroxyalkylphosphoric acid compound and (b) the thus-obtained 1-hydroxyalkyl hypophosphoric acid intermediate esterified with acrylic, methacrylic or ethacrylic acid. Process for the preparation of a compound according to claim 3, characterized in that it comprises steps wherein (a) the dialkylphosphonalkyl acrylate, methacrylate or ethacrylate is transesterified with the trialkyl halosilane in an apotic solvent, wherein as intermediate bis (trialkylsilyl), methacrylate or ethacrylate is obtained. (B) the thus obtained intermediate bis (trialkyl silyl) phosphonalkyl acrylate, methacrylate or ethacrylate is desulfurized with em base to prepare a site, and (c) the said site is oxidized to produce said compound in the form of free acid. .30 Process for preparing a polymeric composite according to any of claims 5-8, characterized in that copolymers are comprised between 0.5-100% by weight of monomer (a) and between 0-99.5% by weight of monomer (b). ), or between 1-10 wt% monomer (a) and between 90-99 35 wt% monomer (b). 38 85860 Latex composition, coating composition or adhesive composition, characterized in that it comprises a polymer composition according to any of claims 5-8.