JPH08225585A - Polymer composition containing new phosphinyl-containing ethylenically unsaturated compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polymer composition containing a reaction product of a (hydroxy)phosphinylalkyl (meth)acrylate with a polymerizable unsaturated compound.

SOLUTION: This novel polymer composition for latex paints, plastic-metal laminates, coatings for metals, adhesives, etc., is obtained by copolymerizing 0.5-100 pts.wt. of (A) a (hydroxy)phosphinylalkyl (meth)acrylate expressed by formula I (R¹ is H or methyl; R² is H or a 1-10C alkyl), a (dihydroxy) phosphinylalkyl (meth)acrylate or (dihydroxy)phosphinylethyl acrylate expressed by formula II or an alkaline(earth) salt expressed by formula III (M⁺ is ammonium, an alkali metal cation, 1/2 alkaline earth metal cation) with 0-99.5 wt.% of (B) a compound containing a polymerizable 1,2-ethylenic unsaturated ingredient.

COPYRIGHT: (C)1996,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to polymers containing novel phosphinyl-containing ethylenically unsaturated compounds.

[0002] The novel phosphinyl-containing ethylenically unsaturated compounds are homopolymerizable or polymerizable 1,2-
It is useful for producing a polymer composition when it is copolymerized with a compound containing an ethylenically unsaturated component. The polymer compositions produced are used in latex paints, plastic-metal laminates, metal coatings, and adhesives. Polymer compositions prepared from compounds containing 1,2-ethylenically unsaturated components are often contacted or applied to the metal in a variety of ways.

The search for polymer compositions that have good adhesion to certain metals is a major problem. The required composition is a polymer composition made from a compound containing a 1,2-ethylenically unsaturated component that has good adhesion to metals and other substrates.

In one aspect, the present invention relates to (hydroxy) phosphinylalkyl acrylates and (dihydroxy) phosphinylalkyl acrylates, especially including the esters of acrylates, methacrylates and α-ethyl acrylates, and these It is a novel phosphinyl-containing ethylenically unsaturated compound selected from the group consisting of the corresponding ammonium salts, alkali metal salts and alkaline earth metal salts. These compounds will be referred to below as "HP acrylic monomers" or "DHP acrylic monomers".

In another aspect, the present invention provides a polymer obtained by polymerizing the following monomers: (a) HP or DHP acrylic monomer and (b) at least one copolymerizable 1,2-ethylenically unsaturated monomer. Is.

In yet another aspect, the invention provides H in the form of a salt.
A method for producing an ammonium salt, an alkali metal salt, or an alkaline earth metal salt of a P or DHP acrylic monomer.

The polymer compositions prepared from the 1,2-ethylenically unsaturated (hydroxy) phosphinyl and (dihydroxy) phosphinyl containing compounds of the present invention have surprisingly good adhesion to many metals. Further, the polymer composition has enhanced corrosion resistance.

A preferred HP acrylic monomer of the present invention has the formula:

Embedded image Wherein, R ¹ is hydrogen or methyl, R ^2, independently of one another, hydrogen or C ₁ ~ ₁₀ alkyl, M is an alkali metal, alkaline earth metal or ammonium;
a is 1 or 2].

[0009] In the above formula, R ² is preferably hydrogen or C ₁ ~ ₃ alkyl, more preferably hydrogen or methyl, most preferably hydrogen. Most preferably R ¹ is methyl. M is preferably an ammonium group or an alkali metal, more preferably an ammonium group, potassium or sodium. It is preferable that a is 1.

(Hydroxy) phosphinylalkyl acrylate and (hydroxy) phosphinylalkylmethacrylate are reacted with hypophosphorous acid and a suitable aldehyde or ketone to form an α-hydroxyalkylphosphite, and then It can be prepared by reacting it with acrylic acid or methacrylic acid to form a new compound. This reaction sequence is shown in equations III and IV.

[0011]

[Chemical 4] Wherein R ¹ and R ² are as defined above. In the first step of the process, hypophosphorous acid is contacted with a suitable aldehyde or ketone in a ratio of 3: 1 to 1: 1. . In this reaction, the aldehyde or ketone cannot be present in excess, since such excess results in the multiple addition of the aldehyde or ketone to the acid. This process takes place in aqueous solution. Since this reaction is an exothermic reaction, it is preferable to add the aldehyde or ketone to the aqueous solution of hypophosphorous acid. Slow addition will give very good control of the reaction temperature.

Generally, this step can be carried out at a temperature at which the reaction proceeds, but the preferred temperature is from 20 ° C to 100 ° C, and the most preferred temperature is from 70 ° C to 90 ° C.

This process can be carried out at a pressure at which the reaction takes place. Atmospheric pressure, subatmospheric pressure and superatmospheric pressure can be used, but atmospheric pressure is preferred. Although not absolutely necessary, it is advantageous to carry out this reaction in an inert gas atmosphere. Examples of inert gases are nitrogen and argon.

The reaction time is suitable so as to give the desired conversion. Reaction times of 3 to 10 hours are generally preferred.
At the end of the reaction, the water solvent is stripped off.

The hydroxyalkyl phosphite prepared by the above reaction is added with methallylic acid or acrylic acid 3: 1.
To 1: 1 ratio, preferably 2: 1 to 1: 2 ratio, most preferably 1: 1 ratio. When one reagent is present in excess, it is preferred that the reagent is methacrylic acid or acrylic acid. This process is generally preferably carried out in an inert organic solvent. Examples of preferred inert organic solvents are aromatic hydrocarbons and chlorinated solvents. Particularly preferred solvents are perchlorethylene and xylene. The solvent used preferably has a boiling point higher than 100 ° C, most preferably a solvent having a boiling point higher than 120 ° C.

This reaction is carried out in the presence of an esterification catalyst. The preferred esterification catalyst is a strong acid. Particularly preferred strong acids are sulfonic acid, sulfuric acid and phosphoric acid. The most preferred catalyst is p-toluene sulfonic acid.

The temperature at which the reaction proceeds is suitable as the reaction temperature. The reaction is preferably carried out at the reflux temperature of the solvent. Reflux temperatures above 100 ° C. are preferred and reflux temperatures above 120 ° C. are particularly preferred.

During the course of this process, water is formed as a by-product. This process is an equilibrium process and it is desirable to remove the water produced, as removal of water promotes the completion of the reaction.

The reaction can be carried out at and above atmospheric pressure, with atmospheric pressure being preferred. An inert atmosphere can be used.

Reaction times are suitable which allow the desired conversion. The preferred reaction time is 4 to 10 hours.

A preferred DHP acrylic monomer of the present invention has the formula:

Embedded image [Wherein R ¹ is hydrogen, methyl or ethyl, and R ^{2 is}
From the group consisting of hydrogen and C ₁ ~ ₁₀ alkyl, selects no relationship to each other, M ⁺ is a compound corresponding to the ammonium cation, an alkali metal ion or 1/2 alkaline earth metal cations,].

The ammonium cation can be represented as NH ₄ ⁺ and the alkali metal cations are Li ⁺ , Na ⁺ , K
Can be expressed as ⁺ , Rb ⁺ and Cs ⁺ ,
Alkaline earth metal cation "is 1 / 2Mg ⁺⁺ , 1 / 2Ca
It is understood to correspond to ⁺⁺ , 1 / 2Ba ⁺⁺ or 1 / 2Sr ⁺⁺ . Thus, a typical alkaline earth metal calcium salt is represented by the following structural formula:

[Chemical 6] Preferred monomers according to the above formula, R ¹ is hydrogen or methyl, R ² is not related to each other, is a monomer as selected from the group consisting of hydrogen and C ₁ ~ ₃ alkyl. The most preferred DHP acrylic monomer is (dihydroxy) phosphinylmethyl methacrylate, ie R
¹ is a compound methyl, R ² represents hydrogen.

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

The DHP acrylic monomer reacts a dialkylphosphonoalkylacrylic acid ester with a trialkylhalosilane to form an intermediate bis (trialkylsilyl) ester, which is saponified to the corresponding salt,
It can be prepared by acidification to form the DHP acrylic monomer as the free acid.

Dialkylphosphonoalkyl acrylic acid ester is a known compound, and is a compound of O'Brien (O'Br).
ien) et al. in U.S. Pat. Nos. 2,934,555 and 3,030,347, which are hereby incorporated by reference.

Dialkylphosphonoalkyl acrylates are prepared by adding a dialkyl hydrogen phosphite to an aldehyde or ketone to form an intermediate dialkyl 1-hydroxyalkyl phosphonate which is reacted with an acrylic halide in the presence of a hydrogen chloride acceptor. It can be produced by reacting and converting to an acrylic ester.

These reactions have the following formula:

[Chemical 7] [Wherein, alk is lower alkyl, X is chlorine, bromine or iodine, and "base" is a hydrogen halide acceptor].

Since formaldehyde and lower aldehydes are more reactive towards dialkyl hydrogen phosphite than higher aldehydes or ketones, it is preferred to form and use the lower elements of the series of compounds used as intermediates.

The reaction for further conversion of the dialkylphosphonoalkyl acrylate to the DHP acrylic monomer, when using chlorotrimethylsilane, can be represented by the following formula:

Embedded image [Wherein, Me is methyl, M and X are as described above, or HX corresponds to a strong acid other than hydrohalic acid] Transesterification reaction of dialkylphosphonoalkylacrylic acid ester with trialkylhalosilane Is carried out in an aprotic solvent such as acetonitrile, benzene, toluene, dimethylformamide, dimethylsulfoxide and the like. The use of acetonitrile is preferred.

At least 2 moles of trialkylhalosilane are used per mole of dialkylphosphonoalkyl acrylate. It is preferred to use 2 moles of halotrimethylsilane. Although iodotrimethylsilane can be used in this reaction, according to the present invention, the transesterification reaction is readily carried out using chlorotrimethylsilane when a stoichiometric amount of iodide donor is present in the reaction mixture. It is known to be. Therefore, it is preferable to use a reaction mixture containing 2 mol of chlorotrimethylsilane and 2 mol of an alkali metal iodide (preferably sodium iodide or potassium iodide).

The reaction can be carried out at a temperature at which the reaction can occur. However, the reaction can occur at room temperature within a reasonable time. Therefore, a temperature of 15 ° C to 50 ° C is preferable.

The reaction can be carried out at any pressure, but the reaction readily takes place under ambient conditions where no pressure equipment or vacuum equipment is required. Therefore, it is preferred to carry out the reaction at atmospheric pressure.

Since trialkylhalosilanes are hydrolytically unstable, it is preferred to carry out the reaction under essentially anhydrous conditions. Desiccant, eg calcium chloride or Dr
The use of ierite tubes is preferred. It is preferred to carry out the reaction under an anhydrous, inert atmosphere, such as anhydrous nitrogen or anhydrous argon.

At the end of the reaction, the mixture is hydrolyzed by adding at least 2 mol of water per mol of bis (trialkylsilyl) phosphonoalkyl acrylate.
The mixture is stirred to separate the fuel soluble salts and filtered off. This intermediate is hydrolyzed with base to cleave the trialkylsilyl group to form the corresponding metal salt. Since the reaction readily occurs at room temperature and pressure, it is not necessary to use elevated pressure or elevated temperature. This salt can be used directly in the preparation of the polymer composition of the present invention. The (dihydroxy) phosphinylalkyl acrylic compound can be polymerized in the salt form, but if desired, the resulting polymer can be acidified to convert the salt to the corresponding acid form.

The monomer salt formed can be converted to the free acid by treating with a stoichiometric amount of an inorganic acid such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid or phosphoric acid. .

The polymer composition of the present invention comprises HP or DH.
Includes products obtained by vinyl polymerization of P acrylic monomers. The polymer composition of the present invention comprises HP or DHP.
It includes homopolymers of acrylic monomers as well as copolymers with at least one other compound containing a copolymerizable 1,2-ethylenically unsaturated component.

The copolymer composition comprises (a) HP or D
It is preferred to include a reaction product of 0.5 to 99 wt% HP acrylic monomer and (b) 99.5 to 1 wt% of at least one copolymerizable 1,2-ethylenically unsaturated compound.

The copolymer composition of the present invention preferably comprises from 1 to 10% by weight of the novel HP or DHP acrylic monomer of the present invention, most preferably from 1 to 5% by weight of HP or DHP acrylic monomer.

The novel compounds of the present invention are usually clear, viscous liquids which are soluble in water or polar solvents such as methanol, ethanol and dimethylsulfoxide.

(Hydroxy) phosphinylalkyl acrylate, (hydroxy) phosphinylalkyl methacrylate, (dihydroxy) phosphinylalkyl acrylate, (dihydroxy) phosphinylalkyl methacrylate, or (dihydroxy) phosphinylalkyl α-ethyl Acrylate salts are (hydroxy) phosphinylalkyl acrylate, (hydroxy) phosphinylalkyl methacrylate, (dihydroxy) phosphinylalkyl acrylate, (dihydroxy) phosphinylalkyl methacrylate or (dihydroxy) phosphinylalkyl α- Ethyl acrylate,
It is prepared by contacting with a base containing an alkali metal, alkaline earth metal or ammonium component in water under conditions such that a salt is formed. Conditions for such reactions are well known to those of skill in the art. Examples of preferred bases are ammonium hydroxide, alkali metal hydroxides, alkali metal carbonates,
They are alkaline earth metal hydroxides and alkaline earth metal carbonates.

Alkali metal here means lithium, sodium, potassium, rupidium and cesium.
Preferred alkali metals are lithium, potassium and sodium, with potassium and sodium being most preferred. The alkaline earth metals here are beryllium, magnesium, calcium, strontium and barium. The preferred alkaline earth metals are magnesium and calcium.

A compound containing a polymerizable 1,2-ethylenically unsaturated component is used in the present invention. Examples of such compounds are monovinyl aromatic compounds such as styrene, p-vinyltoluene, p-chlorostyrene; α, β-ethylenically unsaturated acids such as acrylic acid and methacrylic acid; eg methyl. α containing acrylate, ethyl acrylate, such as 2-ethylhexyl acrylate and methyl methacrylate, a C ₁ ~ ₁₈ alkyl group,
β-ethylenically unsaturated monocarboxylic acid alkyl esters; α, β-ethylenically unsaturated nitriles, such as acrylonitrile and methacrylonitrile; α, β-ethylenically unsaturated, such as acrylamide and methacrylamide. Amides; eg, vinyl acetate and vinyl propionate, vinyl esters; eg, vinyl chloride and vinyl bromide, vinyl halides; eg, vinyl methyl ether and vinyl ethyl ether, vinyl ethers; eg vinyl methyl ketone and vinyl Vinyl ketone, such as ethyl ketone; for example, vinylidene chloride and vinylidene bromide,
Vinylidene halides; hydroxyalkyl esters of acrylic acid and methacrylic acid such as hydroxypropyl acrylate, hydroxyethyl acrylate and hydroxybutyl acrylate; nitriles of ethylenically unsaturated carboxylic acids such as acrylonitrile and methacrylonitrile; An ethylenically unsaturated carboxylic acid such as an acid; an ethylenically unsaturated alcohol such as allyl alcohol; and a 1,2-ethylenically unsaturated component such as styrene, vinyltoluene and t-butylstyrene. It is a substituted aromatic hydrocarbon.

The polymer composition of the present invention is prepared by methods well known in the art, but such preparation is not the point of the present invention. Suitable polymerization methods include solution polymerization, dispersion polymerization,
There are emulsion polymerization, bulk polymerization, and heterogeneous polymerization.
These polymerizations can be carried out continuously or, where appropriate, batchwise.

In one embodiment, the polymer composition of the present invention can be prepared by free radical initiated solution polymerization. In particular, a phosphinyl-substituted 1,2-ethylenically unsaturated monomer is homopolymerized in an organic solvent in the presence of a free radical type catalyst in an atmosphere containing no oxygen, or a polymerizable 1,2-ethylenically unsaturated component is added. Copolymerize with one or more compounds including. Mix the monomer components,
Polymerize at the above ratio.

Typical solvents are lower alkanols such as ethanol, propanol, and butanol;
Aromatic hydrocarbons such as toluene, benzene and xylene; halogenated hydrocarbons such as methylene chloride and tetrachloroethane; and other solvents such as butyl acetate and butoxyethyl acetate.

Typical catalysts used in free radical catalyzed polymerization are of the azo and peroxide types; peroxides such as benzoyl peroxide; hydroperoxides such as t-butyl hydroperoxide; perbenzoic acid. Peracids; peresters such as t-butyl octoate; and azo compounds such as azobisisobutyronitrile. Free radical catalyzed polymerization is carried out at a temperature of room temperature (20 ° C.) to 200 ° C. under a pressure of atmospheric pressure or higher, and from 0 wt% to 5 wt%, preferably pure in the case of a thermal initiation reaction, based on the weight of the monomer. It is easily carried out in the form or in a solvent inert to the catalyst at a catalyst concentration of 0.01 to 5% by weight. Thermal initiation reactions generally occur at temperatures between 60 ° C and 120 ° C.

It is often necessary to use chain regulators to obtain the desired range of molecular weights. Examples of chain regulators that may be used, for example, the following _{formula: H 3 CC (CH 3)} 2 CH 2 C (CH 3) 2 CH 2 C (CH 3) t- dodecyl mercaptan having ₂ SH (XIII) Long chain alkyl mercaptans such as; butyl mercaptan and short chain alkyl mercaptans such as 2-hydroxyethyl mercaptan; isopropanol, isobutanol, long chain alcohols such as lauryl alcohol, octyl alcohol, cumene, carbon tetrachloride, tetrachloroethylene. And trichlorobromomethane. The amount of chain regulator used depends on the particular system and conditions and varies from 0 to 5% by weight, based on the weight of the monomer. For example, t-
The use of 0 to 1% by weight dodecyl mercaptan serves to provide a wide range of molecular weights in aqueous media as much as desired.

In another embodiment, the polymer composition of the present invention can be prepared by an ionic polymerization method.

Typical ionic catalysts are lithium-based catalysts such as metallic lithium, alkyllithium and other lithium compounds, and in combination with, for example, trialkylaluminum or diethylaluminium chloride or lithium aluminum hydride, There are Ziegler catalysts, such as reducing halides of titanium or vanadium. Ionic polymerization is carried out in an inert hydrocarbon solvent such as lower alkane or lower aromatic hydrocarbon,
It is carried out at a temperature of about 20 ° C. to 40 ° C. and a pressure in the range of atmospheric pressure or higher in the presence of 1 to 200 ppm of an ionic catalyst based on the weight of the monomer. Polymerization is similarly carried out at a temperature of −100 ° C. to 100 ° C. with a cation catalyst. Such catalysts include ether adducts of boron trifluoride and aluminum trichloride as well as reducing transition metal compounds (eg titanium tetrachloride or titanium trichloride) and reducing organometallic compounds (eg triethylaluminum or diethylaluminium chloride). There are Ziegler catalysts such as reaction products.

In another embodiment, the low pressure polymerization method can be used when the compound containing a polymerizable 1,2-ethylenically unsaturated component is an α-olefin.

It is well known to form high density, high molecular weight solid, relatively linear polymers by low pressure polymerization of α-olefins with a catalyst system consisting of partially reduced heavy transition metal components and organometallic reducing components. Is. Such polymerizations are typically carried out in an inert organic liquid diluent under an inert atmosphere at relatively low temperatures (eg 0-100 ° C.) and low pressures (eg 0-100 psig). Typical transition metal components are found in the Handbook of Chemistry
Do Physics ( Handbook of Chimi
stry and Physics 48th edition, Chemical Rubber Company (Chemical Rubber)
r Company) publications are halides, oxyhalides, alkoxides of metals selected from Groups IVB, VB, VIB and VIII of the Periodic Table of the Elements. General organic metal components include metal alkyls,
Metal alkyl halides and dihalides, metal hydrides and similar compounds, the metal being selected from Groups IA, IIA and IIIA of the Periodic Table of the Elements. Α-olefin polymers produced by low pressure polymerization generally have a
Molecular weight in the range of 000 to 300,000 and 3,000
It even has a molecular weight of the order of 10,000.

In yet another embodiment, the polymer composition of the present invention is prepared by emulsion polymerization in which the monomers are dispersed in an aqueous medium containing a free radical catalyst and a stabilizing emulsifying agent or mixture of emulsifying agents. Suitable free radical catalysts include persulfates (including ammonium persulfate, sodium persulfate and potassium persulfate), hydrogen peroxide, perborates and percarbonates. Organic peroxides can also be used alone or in addition to inorganic peroxygen compounds. Typical organic peroxides include benzoyl peroxide, t
-Butyl hydroperoxide, cumene peroxide, acetyl peroxide, caproyl peroxide, t-butyl perzone zoate, t-butyl diperphthalate and methyl ethyl ketone peroxide. The usual catalyst requirement is about 0.01-based on the monomer mixture.
It is 3.0% by weight. It is often desirable to activate the catalyst to increase the degree of polymerization, improve the properties of the polymer and reduce unwanted side reactions. Activation of the catalyst also has the effect of lowering the temperature required for polymerizing the monomer. This activation is best achieved by using a redox system in addition to the peroxide catalyst in which the reducing agent is present in the range of 0.001 to 6.0% by weight, based on the monomer. Many examples of such redox systems are known. Agents such as hydrazine or soluble oxidizable sulfoxide compounds including hydrosulfite, sulfoxylates, thiosulfates, sulfites and alkali metal bisulfite salts can be used. Redox systems are activated by the presence of small amounts (several ppm) of polyvalent metal ions. Generally, ferrous ions are effectively used. Alternatively, a tertiary amine soluble in the reaction medium can be used as an activator.

Suitable stabilizing emulsifiers for the present invention include anionic and nonionic surfactants.
Examples of suitable anionic surfactants include alkyl aryl sulfonates, alkali metal alkyl sulfonates,
Sulfonated alkyl esters and fatty acid soaps.
Examples of such well-known emulsifiers include, by way of illustration and not by way of limitation, sodium butylnaphthalene sulfonate, sodium lauryl sulfate, disodium dodecyl diphenyl ether disulfonate, N-octadecyl disodium sulfosuccinamate, dihexyl. Sodium sulfosuccinate and dioctyl sodium sulfosuccinate. A particularly preferred anionic surfactant is disodium dodecyl diphenyl ether disulfonate.

Suitable nonionic surfactants are polyethenoxy agents such as ethylene glycol polyethers, ethylene nonylphenol polyethers and the like, fatty acid esters of polyhydric alcohols such as propylene glycol fatty acid esters. Other suitable nonionic emulsifiers are Becher's emulsions: Theory
And actual (Emulsion; Theory and P
ractice second edition, Reinhorudo publisher (Rein
hold Publishing Cooratio
n) (New York), pp. 221-225 (1965).
Are described in. A particularly preferred nonionic emulsifier is ethylene nonylphenol polyether containing 40 moles of ethylene oxide per mole of nonylphenol.

The required amount of the surfactant mainly depends on the concentration of the monomer to be treated, but it further relates to the selection of the kinds of the surfactant and the monomer, and the ratio of the monomer. Generally, the required amount of emulsifier is 0.5 to 10% by weight of the monomer mixture. A preferred emulsifier system for making the latex of the present invention is the monomer 100 used in making the latex.
It is a mixture of 0.1 to 0.5 part of anionic surfactant and 4 to 5 parts of nonionic surfactant per part. Monomer 10
When the amount of the anionic surfactant is 0.2 to 0.3 part and the nonionic surfactant is 4.0 to 4.2 parts per 0 part, it is easy to form a latex containing no agglomerates. Can be obtained.

Polymerization of the monomers is suitably carried out at temperatures between room temperature and 100 ° C, with temperatures between 65 ° C and 80 ° C being more preferred. As already mentioned, the use of catalyst activators reduces the required temperature for the polymerization. During the polymerization, the temperature is controlled in part by the monomer feed and the rate of monomer polymerization and / or the implementation of cooling.

As taught by the prior art, emulsion polymerization can be carried out batchwise or continuously.
It is also possible to carry out the whole batch operation by emulsifying the total amount of the monomers and proceeding with the polymerization. However, it is usually advantageous to start with some of the monomers used and to add the remaining monomers as the polymerization proceeds. The advantage of gradually adding the monomer is that a high solids content can be obtained and the product can be optimally controlled to maximize product homogeneity.

In yet another embodiment, a heterogeneous polymerization method is used to prepare the polymer composition of the present invention. Heterogeneous catalysts are alkylaluminum and Group IVA, V of the Periodic Table.
It is easily obtained by mixing a reducible compound of a Group A, Group VIA and a Group VIII metal. Examples of alkyl aluminum compounds that can be used include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-pentyl aluminum, diethyl aluminum chloride, and diethyl aluminum hydride. The metals of the above groups are titanium, zircon, hafnium,
Thorium, uranium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten and iron.
Examples of suitable reducible compounds of these metals are halides (eg chloride and bromide); oxyhalides (eg oxychloride); halide complexes (eg fluoride complexes); freshly precipitated oxides or hydroxides. And organic compounds such as alcoholates, acetates, benzoates or acetylacetonates. For example,
Titanium compounds such as titanium tetrachloride, titanium oxychloride, or titanium acetylacetonate are preferred. A particularly preferred heterogeneous polymerization catalyst is a mixture of triisobutylaluminum and titanium tetrachloride. Such a catalyst system is
It is prepared by dissolving each catalyst component in an inert liquid vehicle such as hexane under an atmosphere free of oxygen and water, for example, an atmosphere of nitrogen, argon, helium or the like. The actual method for preparing these catalyst systems is described in detail in US Pat. Nos. 3,113,115 and 3,257,332 to Carl Ziegler et al.

The heterogeneous catalysis process is carried out in the absence of molecular oxygen, carbon monoxide, carbon dioxide and water in a conventional reactor in which the monomer is bubbled through an inert vehicle containing the catalyst. Polymerization is 30 ° C to 10
It is carried out at a temperature in the range of 0 ° C, preferably in the range of 85 ° C to 95 ° C. For the convenience of handling gaseous α-olefins, the first step in the polymerization zone is atmospheric pressure to 115 lb /
It is maintained under a pressure of in ² gauge (790 Kpa gauge), preferably under a pressure of 55 to 65 psig (380 to 450 Kpa). In a preferred embodiment, this first step is carried out in the presence of molecular weight regulators such as hydrogen, acetylene, and other commonly used chain transfer agents. When hydrogen was used as a molecular weight regulator, the amount of hydrogen used was in the range of 1 to 90 mol% used for the monomer feed. However, it is desirable that no molecular weight regulator be present during the second stage polymerization. The polymerization process can be carried out batchwise or continuously.

At the end of the polymerization, excess monomer is released. The mixture is then treated by conventional methods to deactivate the catalyst to remove catalyst residues and recover the polymer mixture. In one method, the slurry mixture is mixed with methanol, n-
The catalyst is deactivated by washing with an alcohol such as propanol and isopropanol. The polymer is then separated from the diluent by decantation, filtration or other similar method, after which the polymer is dried.

In yet another embodiment, the compositions of the present invention are prepared by bulk polymerization, where the monomer components are contacted directly in the presence of a catalyst. Free radical catalysts are used in bulk polymerization. Such a free radical catalyst has been described above. Polymerization catalyst concentration is generally 0.00
1 to 5% by weight, and the temperature is from room temperature (20 ° C) to 200
Up to ℃. Atmospheric pressure and pressures above atmospheric pressure can be used. Due to the problem of heat dissipation in exothermic bulk polymerization, either bulk polymerization is terminated at a relatively low conversion efficiency of 40-60 wt% to distill off excess monomer, or the polymerization is carried out in two stages. The method is done. In the first stage, a large batch of monomer is polymerized to an intermediate conversion stage, then the polymerization is completed in thin layers to facilitate heat dissipation. The reaction is carried out until the reaction is complete, either by flowing the monomer-polymer mixture through a small diameter tube or by letting the column wall down or free-falling as a trickle.

In yet another embodiment, the polymer composition of the present invention is made by the suspension polymerization method. In suspension polymerization, the catalyst is dissolved in the monomer, the monomer is dispersed in water, and a dispersant is added to stabilize the suspension formed. Suspending agents are generally water-insoluble organic polymers such as, for example, poly (vinyl alcohol), poly (acrylic acid), methylcellulose, gelatin and various pectins and, for example, kaolin, magnesium silicate, aluminum hydroxide, And water-insoluble inorganic compounds such as various phosphates. The free radical catalysts described above are useful for these suspension polymerizations. Generally, a catalyst concentration of 0.001 to 5% by weight, based on the monomer, is used. A temperature between room temperature (20 ° C) and 200 ° C is suitable. The polymer formed is in the form of finely divided beads and is easily recovered by filtration and drying.

The choice of the particular polymerization method used depends on the particular monomer system used and the desired properties of the polymer composition. Those skilled in the art are well able to make such selections.

The polymer composition of the present invention has enhanced adhesion to metals and corrosion resistance. Such polymer compositions are useful in latex paints, metal coatings, plastic-metal laminates and adhesives.

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

Example 1 A. Production of hydroxymethyl phosphite 50% in a 500 ml-three neck flask equipped with magnetic stirrer, thermometer, nitrogen inlet and reflux condenser.
264 g of hypophosphorous acid were charged. The solution was heated to 80 ° C. with stirring. Next, paraformaldehyde (66
g) was added in portions (2.5 g) over 30 minutes. After the addition was complete, the solution was maintained at 80 ° C for 3 hours. Add 4 g of paraformaldehyde and add 3 more
Heating was continued for an hour. Water was removed from the clear solution on a rotary evaporator, 100 ml absolute ethanol was added and stripped again. This resulted in a transparent liquid featuring ¹³ C and ³¹ P nuclear magnetic resonance.

[Δ ³¹ P = 30.0 ppm; J _PH = 549 Hz] B. (Hydroxy) phosphinyl methyl methacrylate
Manufacturing of mechanical stirrer, nitrogen sparger and improved Dea
A 2-liter, 3-necked flask equipped with a n Stark trap and reflux condenser was charged with the following reactants: Hydroxymethylphosphorous acid 96.0 g (1 mol) methacrylic acid 258 g (3 mol) phenothiazine 0.1. 4 g benzyltrimethylammonium chloride 0.8 g p-toluenesulfonic acid 0.4 g perchlorethylene 1 liter The mixture was heated at reflux for 7 hours while maintaining stirring and nitrogen sparge, during which time 17.8 ml of water was collected.

The two-phase mixture is then cooled and 600 ml of water are added.
And washed three times. The combined water extracts were stripped on a rotary evaporator. Final removal of water and excess methacrylic acid was achieved by vacuum distillation.

The product, which is a clear, viscous liquid, is ¹³ C and ³¹
Characterized by Pnmr.

[Δ ³¹ P = 21.8 ppm; J _PH = 565 Hz] Example 2 Copolymer Preparation A polymer containing the following monomers was prepared:

[Chemical 9] In a 1 liter round-bottomed flask equipped with a mechanical stirrer were charged the following ingredients: Methyl methacrylate 79.5 g Butyl acrylate 67.5 g Hydroxyphosphinyl methyl methacrylate 3.0 g Benzoyl peroxide 0.75 g Methyl ethyl ketone 700 ml This solution was refluxed for 3 hours. Methyl ethyl ketone (30
After distilling off (0 ml), a clear and highly viscous solution was obtained.

Example 3 (Dihydroxy) phosphinyl
Preparation of Methyl Methacrylate In a 2 liter-three neck flask equipped with mechanical stirrer, thermometer and addition funnel, 1 liter of acetonitrile,
Diethylphosphonomethyl methacrylate, 236 g (1
_{Mol), (CH 3 CH 2 O} ) 2 P (= O) CH 2 OCO
C (CH ₃ ) = CH ₂ and sodium iodide 300 g
(2 mol) was charged. The mixture was stirred at room temperature for 2 hours. To the stirred mixture was added 217 g (2 mol) of trimethylchlorosilane dropwise from the addition funnel over 1 hour. After the addition was completed, stirring at room temperature was continued for 2 hours. Water (36.0 g, 2 mol) was added dropwise to the resulting mixture and the mixture was stirred at room temperature overnight.

The salt which has precipitated is filtered off and washed with acetonitrile 20
It was washed with 0 ml. To the filtrate was added 800 ml of absolute ethanol, and then 50.0 g (2 mol) of sodium hydroxide was added.
g was added. The mixture was stirred for 4 hours. The precipitate formed, the disodium salt of (dihydroxy) phosphinylmethyl methacrylate, Na ₂ O ₂ P (= O) CH ₂ OO
Was filtered off _{CC (CH 3) = CH 2} ,, washed with absolute ethanol and dried under vacuum. The yield was 184 g (82%).

The disodium salt dissolved in water was converted to the acid by addition of concentrated hydrochloric acid below pH 1. The resulting solution was diluted with an equal volume of absolute ethanol and concentrated by rotary evaporation heated to 40 ° C. Ethanol was added periodically during this process to replenish the ethanol / water azeotrope to be removed. After all the water was removed, the precipitated sodium chloride was filtered off and washed with ethanol. The filtrate and washings were concentrated to give a viscous, pale yellow liquid. The liquid rapidly turned dark tan upon exposure to light.

The product was characterized by nuclear magnetic resonance as follows:

[Chemical 10] Example 4 With (dihydroxy) phosphinylmethyl methacrylate
Copolymerization 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) phosphinylmethylmethacrylate, and 0.1 g of benzoyl peroxide. The solution was heated under a nitrogen atmosphere while stirring with a magnetic stirrer. At about 95 ° C, an exotherm started and white polymer began to precipitate. The mixture was maintained at about 100 ° C. for 30 minutes and then cooled. The polymer formed was filtered off, washed with fresh toluene and dried under vacuum. ³¹ Pnmr of polymer is 14.5ppm
A new, slightly broader peak was generated in wrt H ₃ PO ₄ .

Example 5 With (dihydroxy) phosphinylmethyl methacrylate
150 ml of H ₂ O as a solvent for copolymerization with acrylic acid, Wako as an initiator
Example 2 using 0.015 g of V-50 [2,2'-azobis (2-amidinopropane) hydrochloride]
The copolymerization of was repeated. An exotherm began when the solution was heated to 90 ° C. The solution was maintained at 90 ° C for 1 hour. The ³¹ Pnmr of the water-soluble copolymer is 14.3 ppm wrt
A new peak was generated in H ₃ PO ₄ .

Example 6 Preparation of Latex The following ingredients were mixed in a 1 liter beaker to give an emulsion: Water 400 ml Triton X-200 (28% solids) (Rohm & Haas trade name, alkylaryl 48 g ether sulfonate). Anionic surfactant) Methyl methacrylate 160 g (1.6 mol) Ethyl acrylate 240 g (2.4 mol) Ammonium persulfate 0.8 g

[Chemical 11] After cooling under reflux, 100 ml of water and 100 ml of the prepared emulsion were placed in a reactor consisting of a 2 liter three-necked flask equipped with an addition funnel, a nitrogen inlet, a thermometer and a mechanical stirrer.
I and I were charged. The flask was heated to 82 ° C under a nitrogen blanket. When the mixture begins to reflux the temperature is 90 ° C
Rose to. When the reflux began to slow down, the rest of the emulsion was added dropwise, maintaining the pot temperature at 88 ° C-92 ° C. After the addition was complete, the temperature was raised to 97 ° C for 1 hour.
The next emulsion was cooled to room temperature and filtered through a paint strainer.

Example 7 (Dihydroxy) phosphinylmethylmethacrylate
Preparation of Styrene-Butadiene Latex Containing (a) Emulsion Polymerization was Performed as Follows: The reactor was first charged with 73 parts by weight of water, the pentasodium salt of (carboxymethylimino) bis (ethylenenitrilo) tetraacetic acid (1% solution). )
0.01 parts by weight and 0.70 parts by weight of seed latex (polystyrene, 270 Å (27 nm) 39.7% solids) were charged. A first stream consisting of 62 parts by weight of styrene and 0.5 parts by weight of t-dodecyl mercaptan was added to this mixture at the same time; a second stream of 38 parts by weight of butadiene; 15 parts by weight of water, 0.7 parts by weight of sodium persulfate. % Stream of ammonium hydroxide and 0.5 part by weight of the sodium salt of dodecylated sulfonated phenyl ether (45% solution); and 12 parts by weight of water and (dihydroxy) phosphinylmethylmethacrylate. Disodium salt 2.
A fourth stream consisting of 0 parts by weight was added. The polymerization was carried out at 90 ° C. and the addition time was 4 hours.

The product contains 45.2% by weight of solids, 1
It had a particle size of 730Å (173 nm).

(B) An improved latex was prepared as described above using 4.0 parts by weight of the disodium salt of (dihydroxy) phosphinylmethylmethacrylate. The latex produced contained 40.6% by weight solids,
It had a particle size of 30Å (173 nm).

The above latex can be used for paper coating and industrial coating.

Example 8 Rust Generation Test The following ingredients: 400 ml of water, Triton X-200.
(Solid 28%) 48 g, methyl methacrylate 160
A latex was prepared from g, 240 g of ethyl acrylate, 0.8 g of ammonium persulfate and 4.0 g of methacrylic acid according to the method described in Example 6. This latex was included for comparison and not as an example of the invention.

Different portions of the cold rolled steel panel were coated with the latex coating prepared in Example 6 and the control latex coating. Air dry the coaching, 15
Heat to 0 ° C. for 1 hour.

Write an X mark on the obtained transparent coating,
A bottle of water was spilled on each x. After standing overnight, the control latex-coated part showed a high degree of rust, while the latex-coated part of Example 6 showed little or no rust.

This example demonstrates that the latex containing the monomer of the present invention is anticorrosive.

Example 9 Production of Latex A 1-gallon glass reactor equipped with a stirrer and reactor temperature monitor was charged with 70 parts by weight of deionized water and seed latex (95% styrene, sodium lauryl sulfate as a surfactant). Containing 5% acrylic acid, 280Å (28nm)
A primary charge containing 2 parts by weight was charged. The reactor was purged with nitrogen, stirred and heated to 90 ° C. Methyl methacrylate 49.5 parts by weight, n-butyl acrylate 4
A monomer charge containing 9.5 parts by weight and 1.0 parts by weight of (hydroxy) phosphinylmethylmethacrylate was charged to the reactor over a total of 120 minutes, starting from 0 minutes, for 40 minutes.
Addition was at a feed rate of 0 cm ³ / hour. Deionized water 97.5
6 parts by weight, NaHCO ₃ 1.22 parts by weight and Na ₂ S ₂ O
₈ 1.22 parts by weight of initiator charge to the reactor,
123 cm ³ starting from 0 minutes and taking a total of 150 minutes
/ H feed rate.

After all the initiator charge has been added (ie, at 150 minutes), the mixture is placed under a nitrogen atmosphere at 90 ° C.
The stirring was continued for 30 minutes. The product contained about 50% solids.

The latex produced according to the above method is suitable for industrial coatings, architectural coatings, plastic coatings, paper coatings, adhesives and advanced barrier coatings. The transparent coating composition containing this latex showed good corrosion resistance to salt fog as tested by the ASTM B117 test method.

Example 10 A colored high gloss anticorrosion 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 by EDA, NaNO _2). 0.1% by weight addition) 25% nonionic surfactant / 12.5% wetting agent 1.2 g ball-milled pigment 100 g H ₂ O (1000 parts by weight) TiO ₂ (1000 parts by weight) Dispersant (1 part by weight) 25% nonionic surfactant / 12.5% wetting agent 0.8 g (added to ball mill crushed pigment) methyl carbinol defoamer / nonionic surfactant, emulsifier 0.6 g (1: 1 mixture) Mainly urethane 0.4 g of polymer-associated thickener as component This paint showed good corrosion resistance, blister resistance and high gloss (90 scenes at an angle of 60 °).

The embodiment of the present invention is as follows.

(1) (hydroxy) phosphinylalkyl acrylate, (hydroxy) phosphinylalkyl methacrylate, (dihydroxy) phosphinylalkyl acrylate, (dihydroxy) phosphinylalkyl methacrylate, (dihydroxy) phosphinylalkyl α -Ethyl acrylate, and phosphinyl-containing ethylenically unsaturated compounds selected from the group consisting of alkali metal salts, alkaline earth metal salts and ammonium salts thereof.

(2) The following equation

[Chemical 12] Wherein, R ¹ is hydrogen or methyl, R ² is hydrogen or C ₁ ~ ₁₀ alkyl independently, M ⁺ is an alkali metal, alkaline earth metal or ammonium, a is 1
Or 2].

(3) The following equation:

[Chemical 13] [Wherein R ¹ is hydrogen, methyl or ethyl, and R ^{2 is}
Independently selected from the group consisting of hydrogen and C ₁ ~ ₁₀ alkyl, M ⁺ is an ammonium compound of the claim 1 wherein is represented by an alkali metal is a cation or 1/2 an alkaline earth metal cation] it is.

[0093] (4) R ² is the second term is a hydrogen or C ₁ ~ ₃ alkyl or a compound of the third term describes.

(5) The following elements: (a) (hydroxy) phosphinylalkyl acrylate, (hydroxy) phosphinylalkyl methacrylate, (dihydroxy) phosphinylalkyl acrylate, (dihydroxy) phosphinylalkylmethacrylate or ( Dihydroxy) phosphinylalkyl α
-Ethyl acrylate, or its alkali metal salt, alkaline earth metal salt or ammonium salt 0.5 to 100
A polymer composition comprising, by weight, (b) a reaction product of 0 to 99.5% by weight of a compound containing a polymerizable 1,2-ethylenically unsaturated component.

(6) The reaction product has the following components: (a) (hydroxy) phosphinylalkyl acrylate, (hydroxy) phosphinylalkyl methacrylate, (dihydroxy) phosphinylalkyl acrylate, (dihydroxy) phosphinyl Alkyl methacrylate or (dihydroxy) phosphinylalkyl α
1 to 10% by weight of ethyl acrylate or its alkali metal salt, alkaline earth metal salt or ammonium salt, and (b) 90 to 99% by weight of a compound containing a polymerizable 1,2-ethylenically unsaturated component. The polymer composition according to item 1.

(7) (Hydroxy) phosphinylalkyl acrylate, (hydroxy) phosphinylalkyl methacrylate, and their alkali metal salts, alkaline earth metal salts or ammonium salts are represented by the following formula:

Embedded image Wherein, R ¹ is hydrogen or methyl, R ² is hydrogen or C ₁ ~ ₁₀ alkyl as] the first term is a corresponding compound or polymer composition of the second Claims.

(8) The (dihydroxy) phosphinylalkyl acrylic monomer has the following formula:

[Chemical 15] [Wherein R ¹ is hydrogen, methyl or ethyl, and R ^{2 is}
Regardless one another and selected from the group consisting of hydrogen and C ₁ ~ ₁₀ alkyl, and M ⁺ is an ammonium, paragraph 1, represented by alkali metal is a cation or 1/2 an alkaline earth metal cation], or The polymer composition according to item 2.

[0098] (9) the steps of: (a) hypophosphorous acid C ₁ ~ ₁₀ aldehyde or C ₁ ~ ₁₀
Condensing with a ketone to form an intermediate 1-hydroxyalkyl phosphite compound, and (b) the intermediate 1-hydroxyalkyl phosphite compound thus obtained is acrylic acid, methacrylic acid or Esterification with α-ethylacrylic acid, including the formula:

Embedded image [Wherein R ¹ is hydrogen, methyl or ethyl, and R ^{2 is}
Method for producing represented by (hydroxy) phosphinyl alkyl compound by selecting from the group consisting of hydrogen and C ₁ ~ ₁₀ alkyl independently] is.

(10) Next step: (a) transesterification of dialkylphosphonoalkyl acrylate, dialkylphosphonoalkyl methacrylate, or dialkylphosphonoalkyl α-ethyl acrylate with a trialkylhalosilane in an aprotic solvent. Forming an intermediate bis (trialkylsilyl) phosphonoalkyl acrylate, bis (trialkylsilyl) phosphonoalkyl methacrylate, or bis (trialkylsilyl) phosphonoalkyl α-ethyl acrylate; (b) thus Bis (trialkylsilyl) phosphonoalkyl acrylate, bis (trialkylsilyl) phosphonoalkyl methacrylate, which is an intermediate formed by
Or bis (trialkylsilyl) phosphonoalkyl α
Saponification of ethyl acrylate with a base to form a salt; (c) acidification of the salt to produce the desired compound in the form of the free acid.

(11) Copolymerizing 0.5 to 100% by weight of the monomer (a) and 0 to 99.5% by weight of the monomer (b), or 1 to 10% by weight of the monomer (a) and the monomer (b). The method for producing a polymer composition according to any one of items 5 to 8 above, which comprises copolymerizing 90 to 99% by weight.

(12) A latex composition, a coating composition or an adhesive composition containing the polymer composition as described in any one of the above items 5 to 8.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09J 143/02 JDF C09J 143/02 JDF (72) Inventor Gerald Kay McKeewen Virginia, USA 23005 , Axland, Box 648, Route 3, County Road 665 (72) Inventor Frank Boerher Chen 48640, Michigan, United States, Mount Vernon Drive 2709, Midland

Claims (6)

[Claims] 1. The following elements: (a) (hydroxy) phosphinylalkyl acrylate, (hydroxy) phosphinylalkyl methacrylate, (dihydroxy) phosphinylalkyl acrylate, (dihydroxy) phosphinylalkyl methacrylate or (dihydroxy). ) Phosphinylalkylethyl acrylate, or an alkali metal salt, alkaline earth metal salt or ammonia salt thereof in an amount of 0.5 to 100% by weight, and (b) a compound containing a polymerizable 1,2-ethylenically unsaturated component 0 to A polymer composition comprising 99.5% by weight of the reaction product. 2. The reaction product has the following components: (a) (hydroxy) phosphinylalkyl acrylate, (hydroxy) phosphinylalkyl methacrylate, (dihydroxy) phosphinylalkyl acrylate, (dihydroxy) phosphinylalkyl. A compound containing 1 to 10% by weight of methacrylate or (dihydroxy) phosphinylalkylethyl acrylate, or an alkali metal salt, alkaline earth metal salt or ammonium salt thereof, and (b) a polymerizable 1,2-ethylenically unsaturated component. Claim 1 consisting of 90-99% by weight
The polymer composition according to the item. 3. A (hydroxy) phosphinylalkyl acrylate or (hydroxy) phosphinylalkyl methacrylate has the following formula: Wherein, R ¹ is hydrogen or methyl, R ² is independently hydrogen or C ₁ ~ ₁₀ alkyl as each other] polymer composition ranges paragraph 1 or paragraph 2 wherein the equivalent to a compound claimed Stuff. 4. The (dihydroxy) phosphinylalkyl acrylic monomer has the following formula: [Wherein R ¹ is hydrogen, methyl or ethyl, and R ^{2 is}
Independently from each other, are selected from the group consisting of hydrogen and C ₁ ~ ₁₀ alkyl, and M ⁺ is ammonium, an alkali metal cation or 1/2 an alkaline earth metal cation]
A polymer composition according to claim 1 or 2 represented by: 5. A copolymer of 0.5 to 100% by weight of the monomer (a) and 0 to 99.5% by weight of the monomer (b), or 1 to 10% by weight of the monomer (a) and 9 of the monomer (b).
The method for producing a polymer composition according to any one of claims 1 to 4, which comprises copolymerizing with 0 to 99% by weight. 6. A latex composition comprising the polymer composition according to any one of claims 1 to 4,
A coating composition or an adhesive composition.