DE2365583A1 - TERPOLYMER COMPOUND - Google Patents

Description

P 23 ^z l-6 651.5-4 $ - Tr.A.

E. I. DU POBfT DE NEKOUES AND COMPANY 10th and Market Streets, Wilmington, Delaware 19898, V.St.A.

Terpolymer mass

The present invention relates to compositions containing terpolymers, in particular from aromatic, ethylenically unsaturated monomers, ethylenically unsaturated nitrile monomers and Ethylenically unsaturated acid monomers contain existing terpolymers and a use of these compositions for Production of aqueous systems.

The compositions according to the invention give, if they are used with suitable Liquids and auxiliaries, such as amino resins or Epoxy resins, correctly, have been formulated, can coatings (tin vessels), the cured films of which are excellent Have taste and smell characteristics, d. that is, the cured films neither affect the taste or smell of add something to food that has been in contact with it.

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add, still, change that smell or taste. Besides that the films are extremely resistant to attack by boiling water, solvents, acids and conditions normally found in food and beverage processing encountered. In addition, these films adhere well to metals in general and to tin-free steel and tinned steel and untreated aluminum in particular.

These materials can be used completely at extremely low temperatures without the use of external catalysts hardened. For example, a preferred, according to the invention Bake for 60 to 90 seconds at 205 ° C to form a hard, untreatable film hardened. The fuel savings achieved by this very unusual and unexpected property hardly need to be elaborated on.

The present as solutions or organosols, according to the invention Masses can be produced in normal plants. They have unusually high solids contents and remain but - even over long periods of time - stable and consistent against weaning.

Furthermore, the compositions according to the invention can easily be converted into aqueous Systems are transformed. Given the current demands for pollution reduction this completely unexpected property is particularly beneficial.

The invention relates to a mass containing a Terpolymer

(A) at most 80% by weight of a monomer represented by the structural formula

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?1 C " C = I. S ^H 2

is represented in which R, R. *, R ~ and R ^ are hydrogen or are alkyl radicals with 1 to 5 carbon atoms,

(B) at least 15% by weight of an ethylenically unsaturated Nitrile monomers and

(C) 5 to 35% by weight of an ethylenically unsaturated acid monomer, .

where (A), (B) and (C) make up a total of 100%, which is characterized in that the mass 40 to 70%, based on the weight of the mass, of a terpolymer of 10 to 80% by weight of ( A).,. 15 to 80% by weight of (B) and 9 to 25% by weight of (C), some or all of the pendant carboxyl groups of the terpolymer being neutralized with HIL or an organic amine whose boiling point is less than 250 ° C have been ₅ and contains a carrier who in turn. ·

(1) an organic liquid that becomes a medium Is capable of hydrogen bonding, or

(2) a combination of (1) with less than about 50 wt% an organic liquid that is capable of strong hydrogen bonding,

contains as well as a use of this composition in which some or all of the pendant carboxyl groups of the terpolymer with NH, or an organic amine whose boiling point is less than 250 C, have been neutralized for production an aqueous system by slowly adding an appropriate amount of water with agitation to the organic system.

Representative for monomers (A) are styrene, α-methylstyrene, and vinyl toluene. The one in terms of film end properties

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best terpolymers are those in which the monomer (A) is styrene.

The monomers (A) are preferably present in the terpolymer in concentrations of 10 to 80% by weight, more preferably 10 to 65 % and even more preferably 30 to 50%, based on the weight of the polymer. For some purposes 10 to 30%, for others 50 to 65% may be best. Even 10 to 50% or 65 to 80% may be preferred in some cases.

The monomer (B) can be any ethylenically unsaturated nitrile that can be used with the others for the preparation of the Terpolymers used monomers is copolymerizable.

This nitrile monomer is preferably one represented by the structural formula

?
-C-CN

represented monomer, in which R and IL denote hydrogen, alkyl radicals with 1 to 18 carbon atoms, tolyl, benzyl or phenyl and E ~ hydrogen or methyl.

The best polymers for film end properties are those ifelche as hitrile monomer or acrylonitrile Contain methacrylonitrile.

The terpolymers preferably contain from 20 to 70 percent, and more preferably from 35 to 50 percent, of the monomeric monomer, based on the weight of the polymer. It may be desirable for some purposes to use 15 to 20 % or 50 to 70%. If circumstances dictate, you can choose 50 to 80% or 70 to 80%.

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The monomer (C) can be any ethylenically unsaturated, monobasic or dibasic acid or an anhydride, which is copolymerizable with the other monomers used to prepare the terpolymer.

Representative monobasic acids are those represented by the structural formula

R CH ₂ = C - COOH

are represented in which E is hydrogen or an alkyl radical means having 1 to 6 carbon atoms.

Suitable dibasic acids are those produced by the Formulas

HOOC R ₀

C C -

"COOH

or

HOOC COOH

are represented in which R ^ and R _{2 are} hydrogen, alkyl radicals with 1 to 8 carbon atoms, halogen, cycloalkyl with up to 7 carbon atoms or phenyl.

Half esters of these acids with alkanols containing 1 to 18 carbon atoms on iron are also suitable.

The monomer is preferably itaconic acid, acrylic acid, meth-

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acrylic acid, maleic acid or maleic anhydride. In terms of final properties, the best terpolymers are the- ' in which the acid monomer itaconic acid or acrylic acid is.

These acid monomers are preferably present in concentrations of from 10 to 18 %, and more preferably from 12 to 16%, based on the weight of the total polymer. For more specific purposes, 9-10% or 10-12% may be preferred. Circumstances may even dictate that there is 16 to 18 % or even 18 to 25%.

The best terpolymer according to the invention in terms of the overall final properties of the film is a styrene / acrylonitrile / itaconic acid (40 to 55/35 to 45/12 to 16) terpolymer, where the numbers are the weight ratios of the monomer units represent.

The compositions according to the invention can be produced that the terpolymers are either dispersed or dissolved in an organic liquid. In both states they can after using crosslinking agents a suitable approach has been made, can be used as can coatings. However, if these solutions or organosols are in aqueous Systems are to be converted, so the polymer must first be in a liquid, which in water either completely or partially soluble, and then some or all of the pendant carboxylic acid groups of the terpolymer can be neutralized with ammonia or an amine.

The degree of neutralization, i.e. h «, which neutralized mole% of Carboxylic acid groups depends on the rheological and morphological properties desired for the aqueous product abο This is familiar to the specialist.

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The amount of ammonia or amine used to achieve this Degree of neutralization is to be used, is calculated from the initial acid number of the terpolymer so that some or all of the pendant carboxylic acid groups are neutralized * Usually 4-0 bis are neutralized 100% and preferably 80 to 100% of these groups.

This neutralization can be done with ammonia, which is preferably in In the form of a 28% solution in water, or with any primary, secondary or tertiary, organic mono- or polyamine that "has a boiling point less than than 250 ° C. This definition includes a large class of organic amines, among who find each other.

1. aliphatic ^ or cycloaliphatic amines or alkanolamines with 1 to 4 carbon atoms, such as methylamine, ethylamine, triethylamine, ethanolamine or diethylethanolamine;

2. cyclic amines, such as morpholine, piperidine, cyclohexylamine, Pyridine or pyrrolidine;

3. aromatic amines such as aniline, benzylamine or diphenylamine and

4. polyfunctional amines such as ethylene diamine, diethylene triamine and triethylenetetramine.

In the preferred compositions, about 80 % of the pendant carboxylic acid groups in the terpolymers are neutralized with triethylamine or diethylethanolamine.

The resulting solution or organosol of the neutralized or partially neutralized terpolymer can then be converted into an aqueous system by simply adding water with agitation.

The neutralized or partially neutralized terpolymer can, if so ₍ desired, be isolated by adding solvents by vacuum distillation or other suitable means

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MassnaTimen is stripped.

The compositions according to the invention are produced by. Polymerize suitable monomers in the correct amounts in an organic liquid medium. The nature this fluid is important for the result.

Preferably the liquid medium consists of a water-soluble ketone (any ketone from which at least Dissolve 10 g in 100 g water). Acetone and methyl ethyl ketone are representative. This medium can be up to 10% by weight less water-insoluble Tolerate ketones «, optionally the ketone can contain less than about 50% by weight

(A) an ethylene glycol or diethylene glycol monoalkyl ether (in which the alkyl group has 1 to 4 carbon atoms contains) or diacetone alcohol and / or

(b) an alkanol having 1 to 4 carbon atoms or one Also contain alkanediols with 1 to 7 carbon atoms.

The best medium is methyl ethyl ketone, as such or as a 50/50 parts by weight mixture of methyl ethyl ketone and Isopropanol is used.

On the other hand, the medium can also be from

(A) 20 to 80% by weight, based on the total medium, of ethylene carbonate or propylene carbonate and

(b) 20 to 80% by weight, based on the entire medium an organic liquid which is miscible with (a) and in water up to an extent of at least 10 g each 100 g of water is soluble.

exist.

Representative of such miscible, organic liquids are alkanols with 1 to 4 carbon atoms (preferably Isopropanol) «, acetone, methyl ethyl ketone, ether alcohols, esters

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of ether alcohols, diacetone alcohol and tetrahydrofuran. That (a) to (b) weight ratio in this organic liquid Medium is preferably about 50/50.

Usually, a catalyst or a polymerization initiator is used in the usual amount in the process. This can be any free radical initiator that with a half-life of 1/2 to 2 1/2 hours at the reflux temperature of the organic, liquid used Medium decomposed. The best results seem to be obtained with tertiary butyl peroxy pivalate and tertiary butyl peroxy isobutyrate to become.

The terpolymers are produced by first purchasing a reaction vessel with a mixture of 40 to 60% based on the weight of the total batch, of appropriate monomers and about 40 to 60% based on the weight of the total Batch to which the selected, organic, liquid medium is charged. 6/10%, based on the weight of the monomer charge, of catalyst are then added.

The reaction mass is then stirred to about 70 ° C heated.

After the temperature of the reaction mass reaches 70 ° C heating is turned off and an exothermic reaction usually begins. The temperature of the reaction mass then slowly increases until refluxing begins. The refluxing is generally about Continued for 1 hour without heat. Then as much heat is added as is needed to reach the reflux temperature Hold for 15 minutes.

At the end of this period there is an additional 0.6% catalyst is added and the heating is stopped. If the reaction mass is overly viscous at this point, organic can

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Liquid (usually the same as that used initially was added) to keep the solids level at about 55 wt.%.

As much heat is then added as is needed to maintain the reflux temperature. After another Hour during which the reaction takes place at reflux temperature goes on, an additional 0.6% catalyst is added and then the reaction is allowed to continue for 1 hour and Drain for 15 minutes at reflux temperature.

This was followed by another addition of 0.6% catalyst, and another hour followed, during which the reaction proceeded at reflux temperature.

At the end of this period, the polymerization is usually complete. The physical state of the reaction mass depends to a large extent on the composition of the polymeric product and the choice of media; he can from one viscous solution to a high solids organosol. The solids content or viscosity can even be so high that the addition of more organic liquid is necessary to remove the mass from the reaction vessel to be able to take out.

At this point you have a choice, either from the solution or -to add a can coating compound to the organosol or to convert this organic system into an aqueous system.

If you choose to make a can coating compound directly, you simply add the reaction product a crosslinking agent too.

The crosslinking agents that are found in these systems have proven to work best, conventional aminoplast resins such as urea-formaldehyde resins, melamine-formaldehyde

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Resins and phenol-formaldehyde resins. These aminoplasts lie in the final coating compositions usually in concentrations from 5 "to 50% and preferably from 10 to JO% on the weight of the polymer solids.

Epoxy resins can also be used successfully as crosslinking agents when combined with aminoplast resins will. Representative of these epoxy resins are the well-known condensation products of bisphenol A (para, para-isopropylidenediphenol) or bisphenol F (4,4'-dihydroxydiphenylmethane) with epichlorohydrin. These products show Epoxy equivalent weights from 185 to 2500 with the lower end of this range being preferred.

These epoxy resins are usually used in concentrations of from about 10 to 50% and preferably from about 20 to 30%, / based on weight of polymer solids.

Although such coating compounds are usually quite satisfactory, If desired, conventional auxiliaries such as pigments, lubricants and leveling agents can also be used to add.

If the organosol or solution systems are to be converted into aqueous systems (regardless of whether they are used as coating compounds be prepared or not), the terpolymer must first be added to these solutions or organosols, as already declared to be neutralized or partially neutralized with ammonia or an amine. The ammonia or organic Amines can be added directly or dissolved in a carrier or suspended in this form. The neutralization occurs almost instantly.

After neutralization, the organosol or the solution, if necessary, with a crosslinking agent, exactly as it has already been explained, then it is slow Water added with agitation. The amount of added

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Water is left at the discretion. There doesn't seem to be any to give lower or upper limit, because water can be added in any amount without affecting the terpolymer fails. Usually, for use as a can coating, water is added until the solids content is reached of the mass approximately 15% to 25%, based on the Weight of the total mass.

The coating compositions can be applied to a substrate by conventional methods, such as spraying, brushing, dipping or roller coating, be applied. In a conventional can coating process, the masses are on the inside sprayed on a can or with rollers as a coating on sheet metal material before the can is manufactured. In either case, the substrate is usually aluminum or steel.

In the usual case, the masses are sprayed on in such a way that a coverage of 2 to 6 mg per 6.4-52 cm (dry) results. The coatings are then cured by being at temperatures of about 90 seconds to about 5 minutes 175 ° to 205 ° C.

In the examples, all parts are by weight.

example 1

The following were entered in a boiler:

Parts ■

Acrylonitrile. 119.10

Styrene 139.82

Methyl ethyl ketone - 198.18

Tertiary butyl peroxypivalate 1.8

Itaconic acid - 4-1.10

The reaction mixture was then heated to reflux temperature and held at that temperature for 1 hour and 15 minutes.

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Tertiary butyl peroxypivalate was then added at 0.6% of the monomer charge. The reaction mass was then refluxed for an additional 60 minutes held at which point an additional 0.6% of tertiary butyl peroxypivalate was added. After 10 minutes at reflux temperature were 50 parts of methyl ethyl ketone admitted. The reflux temperature was maintained for 1 hour, and then another portion of 0.6% tertiary butyl peroxypivalate was added.

The reflux was continued for an additional 1 1/2 hours continued to form an organosol of a styrene / acrylonitrile / itaconic acid terpolymer (4-6.6 / 39.7 / 13.7) containing 55 wt% polymer solids.

This organosol was cooled to room temperature. 4-5.5 Parts were with 9 »4 parts of a methylated melamine-I-malaldehyde resin added with mixing. 50 g of triethylamine were then added to this mixture (theoretically 100% neutralization of all pendant carboxylic acid groups).

Then 110.3 parts of water were slowly added to this batch to give an aqueous system containing 19 »1 % polymer solids. The carrier consisted of 80% water and 20 % organic liquid.

This mass was made with a wire-wound rod made of aluminum that had been treated with zinc phosphate for corrosion protection was, peeled off, and baked for 2 minutes at 205 ° C to form a tough, adhesive, flexible surface lacquer.

Example 2

The procedure of Example 1 was repeated by 198.18 parts of a 50/50 mixture of methyl ethyl ketone and Isopropanol used instead of methyl ethyl ketone, 50 parts

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Butylcello sol ve 1/2 hour after the last catalyst addition was added and the pH of the aqueous end system was adjusted to 8 with triethylamine. An equivalent result was obtained. .

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Claims (10)

Claims 1. Composition containing a terpolymer from (A) at most 80% by weight of a monomer which is caused by the Structural formula is represented in which R, R ^, R, and R _{3 are} hydrogen or alkyl radicals with 1 to 5 carbon atoms, (B) at least 15% by weight of an ethylenically unsaturated Nitrile monomers and (C) 5 to 35% by weight of an ethylenically unsaturated acid monomer, where (A), (B) and (C) make up a total of 100%, characterized in that the mass 40 to 70%, based on the weight of the mass, of a terpolymer of 10 to 80% by weight of (A ), 15 to 80% by weight of (B) and 9 to 25% by weight of (C), with some or all of the pendant carboxyl groups of the terpolymer with NH or an organic amine whose boiling point is less than 250 ⁰ C is, have been neutralized, and contains a carrier which in turn (1) an organic liquid capable of medium hydrogen bonding, or (2) a combination of (1) with less than about 50% by weight of an organic liquid that makes a starch Is capable of hydrogen bonding, contains. 509832/08 13
-15 - FFD-7166 DiV. 2. mass according to claim 1 _? characterized in that the organic liquid is a water-soluble ketone or a water-soluble ketone which is less than about 50% by weight (a) an ethylene glycol or diethylene glycol monoalkyl ether (where the alkyl groups contain 1 to 4 carbon atoms) or a diacetone alcohol and / or (b) an alkanol having 1 to 4 carbon atoms or of an alkanediol having 1 to 7 carbon atoms. 3. Dispersion according to claim 2, characterized in that (A) is styrene. 4. Composition according to claim 2, characterized in that (B) is a nitrile which is represented by the structural formula RR ₀ C = C - CW is represented in which R and R .. are hydrogen, alkyl radicals having 1 to 18 carbon atoms, tolyl, benzyl or phenyl and R _{2 is} hydrogen or methyl. 5. Composition according to claim 4, characterized in that the nitrile is acrylonitrile or methacrylonitrile. 6. Composition according to claim 2, characterized in that (C) Acrylic acid, methacrylic acid, itaconic acid, maleic acid or maleic anhydride. 7. Composition according to claim 6, characterized in that the Acid is itaconic acid. -16-509832 / 0813 FFD-7166 DiV. 8. Composition according to claim 2, characterized in that (A) is styrene, (B) acrylonitrile, and (C) itaconic acid. 9. Use of a composition according to claim 1 , in which some or all of the pendant carboxyl groups of the terpolymer have been neutralized with ISH »or an organic amine whose boiling point is less than 250 ^° C., for the preparation of an aqueous system by slowly adding a suitable one Amount of water, while moving, to the organic system. 10. Use according to claim 9 _r characterized in that the terpolymer of 15 to 80 GeV / -% of (A) 2O to 75 wt .-% of (B) and 9 to 25 wt .-% of (C) consists. - 17 ' ■ Ä 8-3 2 / ff 8 13