DE1495287B2 - PROCESS FOR THE PREPARATION OF MODIFIED MALEIC ACID ANHYDRIDE MIXED POLYMERIZES OR THEIR SALTS - Google Patents

Description

It is known that carboxyl group-containing vinyl copolymers can be composed of two or more Produce vinyl monomers at least one of which has a carboxyl group.

Allow mixed polymers of methacrylic acid, acrylic acid or crotonic acid and other vinyl monomers are advantageously used in thermosetting coating compositions, in conjunction with one or more substances that react therewith, e.g. B. an epoxy resin, an amine resin or an epoxidized vegetable oil.

Alternatively, these acidic copolymers can be used in the form of the corresponding salts with volatile bases such as ammonia or amines in coating compositions which can be diluted with water use with water-thinnable amine resins.

A process is known from US Pat. No. 2,977,334 in which copolymers of maleic anhydride with ethylene are esterified to give half-esters will. Ethylene and maleic anhydride copolymerize with essentially the same molecular parts. When using such copolymers for the production of paints, varnishes and Lacquers have shown that the films obtained are relatively brittle and fragile and only have a low resistance to water and alkalis.

The same disadvantages arise with the corresponding use of the method designed in FIG Documentation of Belgian patent 603 338 products manufactured. Following this procedure is initially a dispersion of a copolymer of maleic anhydride and methyl methacrylate manufactured. This dispersion is then further treated with a plasticizer, forming a gel arises. It is said to be made extensible in the plastisol system, with the polymer and the plasticizer have reactive groups so that a reaction occurs in addition to the solution during the film formation.

The method according to the invention relates to production modified maleic anhydride copolymers or their salts by esterification of a Maleic anhydride copolymer with at least 1 mol per anhydride group of a compound with at least two alcoholic hydroxyl groups by heating under reflux and is characterized by that a copolymer consisting of 5 to 50 percent by weight maleic anhydride with at least 25 percent by weight of an alkyl acrylate or methacrylate, the alkyl group of which has a maximum of 4 carbon atoms contains, if necessary together with

ίο vinyl toluene, or styrene, has been manufactured in the Half-esters converted and optionally then by adding a volatile base in known per se Way is transferred into the salt.

As could be demonstrated by the results of comparative experiments, the method according to the invention does not have the above-mentioned disadvantages when used for paints, varnishes or lacquers.
Both in the acidic form and in the salt form, the modified copolymers prepared according to the invention can be used in coating compositions alone or in conjunction with amine resins, epoxy resins and other polyfunctional materials.

The maleic anhydride copolymers themselves are from Journal of Polymer Science 5 (1950), pages 256 to 257, are known and are conveniently in solution in a volatile aromatic solvent such as Benzene, xylenes or commercially available higher-boiling aromatic solvents been. Optionally, other solvents, such as methyl ethyl ketone, either alone or as a mixture have been used with an aromatic solvent, provided that the solvent does not contain any functional groups associated with

an anhydride group can react. Usual initiators, e.g. B. the organic peroxides and hydroperoxides, possibly smaller amounts of chain regulators and initiator activators are at the Polymerization has been used. To avoid exothermic reactions and to obtain a To ensure a uniform product, it is advisable that all mixed monomers and Initiators or a partial amount has been added to the solvent, which is then used during a certain Time has been kept at the desired temperature.

You can use two or more alkyl esters of methacrylic acid or acrylic acid in which the alkyl group contains not more than 4 carbon atoms, to modify the properties of the final products. Styrene or vinyl toluene can optionally have been used as further mixed monomers, but the mixed monomers must be in in all cases contain at least 25 percent by weight of the acrylic acid ester. The proportion of maleic anhydride is 5 to 50 percent by weight of the total monomers present.

In the compound used for modifying the maleic anhydride copolymer according to the invention with at least two alcoholic hydroxyl groups it can be a simple polyhydroxyalkane act like glycerin or trimethylolpropane. You can also use a more complex material, z. B. a partial fatty acid ester of glycerol, the

z. B. arises as a reaction product of a polyhydric alcohol and a triglyceride vegetable oil, furthermore an alkyd resin with residual hydroxyl groups or a condensate of a poly-crystalline phenol with

3 4

Epichlorohydrin, provided there are at least two alcohols.

has metallic hydroxyl groups. ester copolymers with volatile bases in coating

The modification of the maleic anhydride mixed compositions with water-thinnable amine resins,

polymer is expediently carried out with completely aqueous dispersions of epoxy resins and water-

Reflux and temperatures between 80 and 150 ⁰ C. 5 dilutable phenol-formaldehyde condensates

To prevent premature gel formation, turn it over.

Required to use at least one molecular equivalent The curing of these compositions, the clear or the polyalcohol per anhydride group. can be pigmented, takes place in the oven expediently. With a complex substance that takes part in the reaction at temperatures between 120 and 200 ° C, z. B. in the case of an alkyd resin, one takes an io if necessary in the presence of small amounts of curing mean value for the molecular weight of the accelerator in question, surface-active substances and substances, which can be modified by means of an experimental reaction,
checks. Since the maleic acid produced according to the invention

The alkyd resin preferably has a minimum of hy-half ester interpolymer, both hydroxyl and hydroxyl

hydroxyl value of 50 mg KOH / g. Containing 15 carboxyl groups, it is assumed that one

If the esterification between the maleic acid- better hardening with amine resins and with formaldehyde anhydride copolymers and the hydroxyl groups demodified acrylamide copolymers in comparison holding connection is complete, which is possible to those who can only be recognized by a carer is that the acid value does not go back any further - vinyl copolymers containing boxyl groups, if an alcohol or alcohol ether is added, it is aimed. This is analogous to the known alkyd solvents to, in the cold state, a clear amine resin coating compositions, in which there is as Get solution. it is certain that the function of the carboxyl groups of the

In the case of water-thinnable coating composite alkyd resin is mainly catalytic, while

tions a simple polyvalent one mainly uses the hydroxyl groups of the alkyd resin

Alcohol, e.g. B. trimethylolpropane or glycerol to 25 with the functional groups of the amine resin

to modify the maleic anhydride copolymer,
adorn. A minimum amount must be used in the copolymer

of maleic anhydride to be present to a pro-Embodiments
duct to get that after neutralizing with

a base is soluble in water. This minimum quantity is 30 for example
depends on the type and amount of mixed monomers used in the polymerization step. if

the lower alcohol esters part A are used as mixed monomers
the methacrylic and acrylic acid used, it shows the production of a maleic anhydride-S ₁ Ch that 8 percent by weight maleic anhydride is an ethyl acrylate mixed polymer
attracted to the total amount of monomers, usually enough. When using styrene a The following materials were required in a 2 liter higher proportion of maleic anhydride. Bottle given:
When good solubility in water can be achieved

should the amount of styrene or vinyl toluene 40 maleic anhydride 10 g

Amount of lower alkyl acrylate or methacrylate, ethyl acrylate 20 g

do not exceed. Di-tertiary-butyl peroxide Ig

When the technical grade xylene used in the polymerization step is 490 g

Solvent is immiscible with water, it is

It is advisable to distill it off at reduced pressure

Heren. The modification with polyalcohol is then refluxed. At reflux, the following became

in the absence of the solvent, and the product thoroughly mixed materials as a continuous stream

is finally attached with ammonia or a volatile within 90 minutes:

Amine treated before dilution with alcohol

and / or alcohol-ether solvents, given 50 maleic anhydride 39 g

if mixed with water. A content of ethyl acrylate 421 g

Alcohol or alcohol ether solvent is he-di-tert-butyl peroxide 14 g

wishes as those made from these products

Coating compositions in their use. The batch was refluxed for an additional 2 hours

suitable viscosity a sufficiently high proportion of 55 is kept. The copolymer solution was clear, and

contain non-volatile substances. the content of nonvolatile matter was 49.0 ° / _0th

Alternatively, one can use a during the esterification

Use water-miscible solvent, pre- Part β

exposed that it does not contain any groups beginning with a »,, ·, = ·. r> j. i ^ ma

Anhydride group can react, and that there is a ge 60 Modification of the product according to Part A

Suitable solvent for the polymerization step 380 g of the solution were placed in a 500 cc bottle

has been. Examples of such solvents are given in Part A. The xylene was in one

Ethylene glycol monoethyl ether monoacetate and the pressure of about 50 mm QS distilled off, the

methyl ether of ethylene glycol, diethylene glycol and temperature finally reached 14O ⁰ C. The resin

similar glycols and glycol ethers. 65 was cooled and the bottle vented to the atmosphere.

The maleic acid produced according to the invention ventilates. After cooling to 8O ⁰ C were 20 g

half-ester copolymers can advantageously be added in the case of glycerine, and the batch was

Use coating compositions. constant reflux reheated to 135 ⁰ C. To

The batch was cooled to remain at 135 ° C for 2 hours. The acid value of the product was 53 mg KOH / g. After cooling, the following substances were found attached:

Saturated aqueous ammonia solution

(Density 0.88) 19 g

Isopropanol 10 g

Water 160 g

After thorough stirring, a clear solution with a non-volatile content of 50.0% was obtained Substances and a viscosity of 880 Stoke. The solution could be used without precipitation of the resin with unlimited Amounts of water to be diluted.

Part C.
Use of the mixed polymer half ester

A portion of the product from Part B was one third of its weight based on the non-volatile Substances mixed with recrystallized hexamethoxymethylmelamine. This mixture was in a Grind ball mill with a sufficient amount of titanium dioxide pigment so that there is a ratio of 0.75: 1 between the pigment and the binder. The paste was made with a 3: 1 isopropanol-water mixture to a viscosity of 100 seconds (cup no. 4 British Standard 1733 [1955]) diluted. This paint was sprayed onto tin-plated metal sheets that were baked in an oven at 120 ° C for 30 minutes became. The resulting films had an excellent gloss, they were tough, and they lasted to be wiped off with xylene for 1 minute, and the alkali resistance was excellent. After further baking at 120 ° C. for one hour the films showed only a slight loss of gloss or whiteness Appearance.

Example 2

Of the product A of Example 1, 67 have been g at total reflux with 100 g of a 45 ° / ₀ with oil-modified alkyd resin, as a 50 ° / ₀ solution in commercially available xylene (prepared from phthalic anhydride, glycerol and dehydr. Castor oil, acid number 20 up to 30 mg KOH / g, viscosity of the 48 to 52 percent by weight solution in xylene 35 to 45 Stokes at 25 ° C), stirred and heated on a steam bath. After 3 hours the product was cooled.

A non-volatile mixture of 4 parts of this product with 1 part of a commercially available one butylated melamine formaldehyde condensate was mixed in a ratio of 3: 1 with xylene and ethylene glycol monoethyl ether diluted to a viscosity of 120 seconds (Ford cup No. 4) and applied to a degreased, tinned sheet metal sprayed. The film, treated in the oven at 150 ° C. for 30 minutes, was tough and flexible and showed good adhesiveness. The film withstood xylene wiping for 1 minute.

Example 3

200 g of product A according to Example 1 and a commercially available diphenylolpropane-epichlorohydrin condensate were added Heated 50 g on a steam bath at full reflux for 3 hours.

A mixture of 4 parts of this adduct and 1 part of a commercially available butylated melamine-formaldehyde condensate, based on the non-volatile substances, was with a 3: 1 mixture of xylene and ethylene glycol monoethyl ether diluted to a viscosity of 120 seconds (Ford cup no. 4) and sprayed onto degreased, tin-plated metal sheets. These were Treated in the oven for 30 minutes at 150 ° C. Clear films with good resistance to were formed Solvent.

Example 4
Part A

Preparation of an 80:20 weight percent ethyl acrylate-maleic anhydride copolymer

The following materials were placed in a 2 liter bottle:

Maleic anhydride 10 g

Ethyl acrylate 20 g

Commercial xylene 490 g

Di-tertiary-butyl peroxide Ig

The batch was heated to reflux and the following mixture was poured in as a continuous stream Course of 90 minutes attached:

Maleic anhydride 88 g

Ethyl acrylate 372 g

Di-tertiary-butyl peroxide 14 g

The batch was refluxed for an additional 2 hours and a clear solution was obtained 50.5% non-volatile substances.

part B

Production of a maleic acid half-ester copolymer

The following materials were in a 1 liter bottle given:

Alkali Refined Soybean Oil 439 g (1 mol equivalent)

Clycerin 92 g (2 molar equivalents)

Lead acetate 0.176 g

The above mixture was heated to 240 ° C. under nitrogen with stirring for 40 minutes Temperature held and then cooled; the product is referred to as B in the following.

The following materials were placed in a 500cc bottle:

Product B 99.3 g

Product according to Part A 250.0 g

The batch was heated to full reflux and held at that temperature for 3 hours. After cooling to room temperature, 100 g of n-butanol were added, resulting in a clear, pale yellow solution, referred to below as C will.

Test treatment in the oven:

a) Product C - 5 parts, based on the non-volatile substances. 1 part of a commercially available butylated Melamine-formaldehyde condensate, also related to the non-volatile substances.

This mixture was mixed with a 2: 1 mixture of xylene and butanol to a viscosity of 120 seconds (Ford Cup No. 4) thinned and tinned on

7 8

Sprayed sheet metal. The sheets were in the oven 30 Mi- it was a modified with formaldehyde

utes kept at 120 ⁰ C; one and then butylated styrene-acrylamide mixed poly-

soft, clear film achieved. When rubbing the film with merisat.

The xylene film was not removed for 1 minute. The mixture was made with a 2: 3 mixture

b) Product C - 5 parts, based on the non- 5 xylene and butanol to a viscosity of 120 se-

volatile substances. 1 part of a commercially available letter (Ford cup no. 4) diluted and then on

phenylolpropanepichlorhydrins (epoxy equivalent 190 separate steel panels sprayed for 30 minutes

up to 210 g). were treated at 150 ⁰ C in the oven. It came into being

This mixture was treated with a 2: 1 xylene clear and tough film, which was treated with xylene (2 minutes)

Do not wipe off the butanol mixture to a viscosity of 120 seconds or allow it to soften.

(Ford cup No. 4) diluted and tinned. In relation to the non-volatile substances, the following

Sprayed sheet metal. After 30 minutes of treatment in the mixture:

Oven at 150 ° C resulted in a clear, tough film, the _{χ part of modified} maleic anhydride mixed poly-

when wiping with xylene with a duration of merisat

Was not removed for 1 minute. is _{1 part of one} modified with 47% soybean oil

Example 5 alkyd resin.

The following materials were poured into a 2 liter mixture. The mixture was made up with a 2: 1 mixture

Bottle: xylene and butanol to a viscosity of 120 seconds

Commercially available xylene 490 g ^{20 den} ( ^Ford - ^{ßecher No. 4} ) diluted on clean steel '

Tertiary dodecyl mercaptan '.'. '.'. '.'. '.'. '.'. Ig ^blec ^ ^e injected and then 30 minutes at 18O ⁰ C.

treated in the oven. Tough, clear films are also created

The mixture was heated to full reflux of excellent resistance to then becoming the following pre-made xylene.
Solution as a continuous stream in the course of 25 If a color was exactly according to Example 1, Part C,

2 hours attached: manufactured, but then with 10 percent by weight (loading

Q, j 264 6 e moved to the non-volatile binder) of the bisphenol

Butyl acrylate 1764g epichlorohydride condensation product (epoxy resin)

Maleic anhydride ''.'.'.'.'.'.'.'.'.'.'.'.'. 49Jo g ¹ ^ ** "' ? ° T *" -, ^ ^au f ^V 5 ^rzi "" ^te " ^BI , ^echen ' ^the

Di-tertiary-butyl peroxide 14.7 g ^{were treated in the oven for 3} ° for 30 minutes at 150 ° C,

flexible and had good resilience

After the end of the mixing process, the mixture was replaced by solutions of detergents,
refluxed for an additional 3 hours. The The following is a report on Vergleichsver batch is cooled to 8O ⁰ C, and were given search, which make up the surprising Fort 73.7 gTrimethyloIpropan schrittlichkeit (1.1 moles per anhydride group) 35 of the present invention Verbeigefügt. The batch was reheated to 13O ⁰ C drive products obtained from the use thereof for another 2 hours at this temperature ang overall production of paints, lacquers and varnishes keep clear. During cooling, 200 g of ethylene were obtained.

glycol monoethyl ether added. The product was. , _..__ ".

a clear, water-white solution. 40 ·· ^Ver g ^{IeIch with} USA.-Patent 2,977,334

,,. ,. . “The product conformed to the USA patent specification

Test treatment in the oven Example 17. According to the information in the patent

a) In relation to the non-volatile substances, the half-ester with an excess of ethylene must be as follows Mixture prepared: glycol to be heated. Since details about the

Modified maleic anhydride - ^{45 H} ° ^{he of the} excess is missing, three test copolymers were made of 70 parts ™ ^h ™ ^m '<various excess amounts, namely

Commercially available butalated ^d , ^{er 1} V ¹ "' ² " and 5 times the amount of the theory of ethylene

Melamine-formaldehyde- ^ ⁰⁰ &quot; employed.

Condensate 15 parts 1.1 times the amount of ethylene glycol

Commercially available diphenylolpro- " ⁵ ^,,".,

panepichlorhydrin condensate _J ^Since _D ^s product was unusable because

(Epoxy equivalent 190 to 210 g) 15 parts of ^the reaction mixture _and after heating at 80 ^ C

gelled for 15 minutes. It solidified and

This mixture became insoluble with a 2: 1 mixture.

Xylene and butanol to a viscosity of 120 Se- 55 - ~ _e , .. · _Α ·,,

announce (Ford cup no. 4) diluted and diluted to ² - ^{2 foldc Men} S ^e ethylene glycol

tin-plated sheets sprayed. These were lasted for 30 minutes.

treated in an oven at 150 ⁰ C. A clear, viscous mixture resulted after heating to 2 (XVC during

Films that wipe with xylene for at least 15 minutes. Even by humiliating the

Withstood 2 minutes. 60 action temperature could not prevent gelling

b) In relation to the non-volatile substances was prevented.

the following mixture is prepared: If the heating is stopped before the start of gelation

Modified maleic anhydride was broken, the product was heterogeneous and forms i

Copolymer 1 part has a ^{solid and hard} coating.

Modified Acrylamidmischpoly- ^6s _3- f _{5 ache} quantity of ethylene glycol

merisat 3 parts,> · ,,, ·, _L · ·. ,

The response could be brought to a point

In the case of the modified acrylamide copolymer, in which the mixture cools down

remained homogeneous. However, the final product formed a soft coating that was found to be very sensitive to Showed water and dilute alkalis.

In contrast, the product esterified according to the invention according to Example 2 formed hard coatings, which were resistant to water and dilute alkalis.

II. Comparison with Belgian patent specification 603 338

As in I, a product produced according to Example 2 of the invention was used as a comparison sample.

The product of the Belgian patent specification was prepared according to the instructions in Example 1. That after Part A of the example provided a product

creamy, stable dispersion having a solids content of 49 ° / _0. According to procedure of Part B was plasticized it with trimethylolpropane.

Films made with the product were heated in the oven to cure. The films were true resistant to organic solvents, but cloudy and exhibited less resistance against diluted alkalis.

The product was pigmented with titanium dioxide to form a simple spread. After this After curing, the film had too weak a gloss, which corresponds to the haze of the unpigmented film.

In contrast to this, there were no such defects in the product produced according to the invention.

Claims (1)

ϊ 495 287 Claim: Process for the production of modified maleic anhydride copolymers or their salts by esterification of a maleic anhydride copolymer with at least 1 mol per anhydride group a compound having at least two alcoholic hydroxyl groups by heating under reflux, characterized in that a copolymer consisting of 5 to 50 percent by weight maleic anhydride with at least 25 percent by weight of an alkyl acrylate or methacrylates, the alkyl group of which contains at most 4 carbon atoms, optionally together with vinyl toluene or styrene, is converted into the half-ester and optionally then by adding a volatile base in a manner known per se in the salt is transferred.