DE1204410B - Process for the production of homo- or copolymers of methylol ethers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

C08f

German KL: 39 c- 25/01

Number: 1204 410

File number: F31521IVd / 39c

Filing date: June 27, 1960

Opening day: November 4, 1965

The production of polymers and copolymers of polymerizable organic compounds, which the grouping

-OC-N-CH ₂ -OR ₂

R ₁

and in which R _{1 is} a hydrogen atom or an alkyl group and R _{2 is} an alkyl group is known. In particular, acrylic and methacrylmethylol alkyl ethers, such as, for example, methyl or ethyl ethers, are described as compounds of the type mentioned. According to this process, it is possible to produce unbranched polymers containing methylol alkyl ether groups which, in the second stage, can be crosslinked by the action of hydrolyzing agents such as acids at elevated temperature. This crosslinking takes place in the presence of hydrolyzing agents preferably above 100.degree. C., while in the absence of hydrolyzing agents such as acids, crosslinking temperatures of up to 150.degree. C. are necessary. The products obtained in this way are synthetic resins or elastomers, which are suitable for various purposes in plastics technology. ^a 5

There has now been a process for the preparation of homopolymers or copolymers of methylol ethers by polymerizing methylol ethers with one or more organic compounds containing at least one polymerizable double bond, in bulk, in solution or in emulsion at temperatures between 20 and 70 ^° C. and in Found the presence of activating agents, which is characterized in that the methylol ether is a methylol alkenyl ether of the formula

O
RCN-CH ₂ -OR ₃ I.

Process for the production of homo- or
Copolymers of methylol ethers

Applicant:

Paint factories Bayer Aktiengesellschaft,

Leverkusen

Named as inventor:

Dr. Karl Dinges, Cologne-Stammheim;

Dr. Erwin Müller, Leverkusen

called ethers, those from the corresponding methylol compounds by etherification with allyl alcohol in an acidic medium the following can be obtained:

CH ₃

CH ₂ = C - CO • NH • CH ₂ -O - CH ₂ -CH = CH ₂ CH ₂ = CH-CO-NH-Ch ₂ -O-CH ₂ -CH = CH ₂

used, in which R is the remainder

or
CH ₂ = CH -

CH ₃

CH ₂ = C-

R _{1 is} a hydrogen atom, an alkyl or aryl radical and R _{2 is} an alkenyl radical.

The typical representatives of the methylol alkenyl ethers are, surprisingly, the methacrylic and acrylamide methylol allyl can be such compounds, the two polymerizable double bonds contain, convert in such a way in uncrosslinked polymers or copolymers that only the Carbonyl group adjacent double bond is covered by the polymerization. The resulting high molecular weight, thermoplastic products that are at room temperature in aqueous solution or aqueous Emulsion can be stored unchanged, therefore still contain reactive methylolalkenyl ether groups, the further crosslinking reactions are accessible.

The methylol alkenyl ethers used are much more stable at temperatures below 60 ° C acidic agents than the corresponding alkyl ethers. It must z. B. the polymerization of alkyl ethers according to the procedure of the German Auslegeschrift 1 035 363 (column 1, line 18 and all examples) are preferably carried out in a neutral or slightly alkaline range. In contrast, you can the alkenyl ethers in the whole pH range from 3 to 9, so also in a relatively strongly acidic Area can be polymerized without premature reaction of the methylol ether groups and thus crosslinking entry.

According to the process of the invention, using specific monomers mentioned above

509 720/442

3 4

both homo- and copolymers prepared cycloalkyl, aralkyl radical or together for one will. Copolymers can be any proportions of heterocyclic radical, such as the morpholine radical, on said special components, d. H. of about The polymerization of methylolalkenyl ethers can

0.5 to 99 mol percent, but with contents alone or in a mixture with other polymerisiervon 1 to 15 mole percent of particular interest 5 free compounds both in block and in are. Solution, but preferably in aqueous solution or in

Emulsions are suitable for the production of copolymers, depending on the type of monomers to be used as copolymerizable monomers. The mandatory this most diverse organic compounds having one or temperatures are between 20 and 70 ° C, preferably more polymerizable carbon-carbon io example between 40 and 60 ⁰ C.

fabric double bonds. Examples include: The activating agents for stimulating the polymer

Acrylic acid or methacrylic acid and their esters with cation can use the known radical formers, such as saturated monovalent aliphatic or cycloaliphatic inorganic per compounds, for example alkaline compounds Alcohols with 1 to 20 carbon atoms, persulfates, perboates and a wide variety of orga-acrylic and Methacrylic acid amide, acrylic and methacrylic peroxy compounds such as diacyl peroxides, nitrile, aromatic vinyl compounds such as styrene and e.g. B. Benzoyl peroxide, also such as alkyl hydroperoxides Styrene derivatives, vinyl chloride, vinylidene chloride, vinyl di - tert. - butyl hydroperoxide, cumene hydroperoxide, esters such as vinyl acetate, vinyl propionate, monovinyl p-menthane hydroperoxide and dialkyl peroxides, ferethers, conjugated diolefins with 4 to 6 carbon ner azo compounds such. B. Azodiisobutyric acid atoms, such as butadiene, chloroprene or isoprene. 20 dinitrile can be used.

It is also possible to work with mono-networks with a crosslinking effect in many cases

mers with several olefinically unsaturated groups redox systems to reduce the polymerization temperatures in amounts of about 0.01 to 10%> based on the low, for example those based on Weight of total monomers used, persulfates and pyrosulfites and bisulfites, form such as z. B. glycol diacrylate, glycol dimethacrylate, 25 aldehyde sulfoxylate or formamidinesulfinic acid. at Acrylic acid and / or methacrylic acid allyl esters, di- Working in an alkaline medium can even be vinylbenzene or substitution products of the above-mentioned redoxy compounds which are understandably suitable for this purpose. The selection of these monomers is made systems, d. H. Combinations with diethylenetriamine, depending on the desired properties of the mixed triethanolamine can be used. It is straightforward polymers. In general, one or more 30 are also possible, in combination with heavy metal elastifying acting monomers, such as conjugated salts, such as those of iron or copper, given diolefins, Acrylic esters, with one or more expired using complexing agents, such as strengthening monomers such as styrene, acrylic pyrophosphates or ethylenediaminetetraacetic acid, nitrile, vinyl chloride, combined. to work.

It is of course also possible, as a mixed 35 The height of the molecular weight or the length of the polymerization component unsaturated polymer and polymer chains formed can be sable in known compounds with self-crosslinking groups by additive substances such. B. to use pen, as for example in the long-chain alkyl mercaptans with preferably 12 to German Auslegeschriften 1 035 363 and 1102 404 16 carbon atoms or z. B. Diisopropylxantho- and the Belgian patent 591126 described 40 gandisulfid (see. Zeitschrift für Makromolekulare are. Suitable mischpolymerisationsbaren Kompo- Chemistry, 3, p. 53, [1949]), or by appropriate nents that the introduction of self-crosslinking group variation of the Allow the amount of activator or the reaction, for example, the methylol temperature can be influenced,
ether of the acrylic acid or methacrylic acid amide in the manufacture of the copolymers

The following general formula II represents the pH to be maintained within wide limits

vary, expediently between pH 3 and 9, whereby

CH ₂ = C N CO CH ₂ OR ₂ gjch} _m the case of preparing latexes reemulgierbarer

I H maintaining a pH between 4 and 7 has proven its worth.

RR ₁ As emulsifiers in the homo- or

50 interpolymerization in the process of the invention

in which R stands for a hydrogen atom or a methyl group, R _{1 stands} for a hydrogen atom, the alkyl, emulsifiers, such as salts of long-chain aralkyl or aryl radicals, R _{2 stands} for an alkyl or fatty acids, salts of Alkylsulfuric acid esters, salts, cycloalkyl radicals, such as the methyl, ethyl, n-propyl, of alkylsulfonic acids or alkyl-arylsulfonic acids, isopropyl, η-butyl, isobutyl, cyclohexyl group 55 salts of fatty acid condensation products and others. more, also cationic emulsifiers such as salts of

In an analogous manner, Mannich bases of acrylic, alkylamines, arylamines and salts of quaternary acid amides and methacrylic acid amides can be used, ammonium compounds as well as non-ionic emulsifiers which are used by the general formula III below,
As illustrated, 60 re-emulsifiable latices are obtained by using

j ^ the listed monomers in aqueous dispersion

/ ■ ' ³ using nonionic emulsifiers

CH ₂ = C CO · N CH ₂ N- III character, preferably at a pH value below 6

^X R ₄ and at a temperature below 50 ⁰ C with olefi-

R Ri 65 mixed monomers with hydrophilic groups

polymerized and the dispersions obtained

in which R and R _{1 have} the same meaning as in the pH values of about 6.5 to 9. Here, Formal! have and R ₃ and R ₄ for an alkyl, as monomers also those olefinically unsaturated

5 6

Compounds are used in which only after the formaldehyde and the condensation in Interpolymerization of hydrophilic groups, for example solvents such as gasoline, carbon tetrachloride wisely by saponification. or the like, in the presence of catalytic amounts of alkali

Suitable olefinic monomers with hydrophilic alcoholates such as sodium methylate (pH about 8 groups are, for example, α, unsaturated 5/3-olefinically to 10) carried out at temperatures of about 40 to 50 ⁰ C carboxylic acids such as acrylic acid, methacrylic acid, maleic. The separated methylol compound acid, half-ester of maleic acid with saturated is then suspended in an allyl alcohol excess of aliphatic or cycloaliphatic alcohols, expediently in the ratio of size monoesters of ", ^ - unsaturated monocarboxylic acids properly about 1: 5, and the etherification with polyhydric alcohols such as glycol, diethylene- io introduction of gaseous hydrochloric acid at about 30 to glycol, trimethylolpropane, glycerol. Made at 50 ^° C. olefinically. After about 20 to 30 minutes, unsaturated compounds, which after saponification contain neutral hydrophilic groups with alkali carbonate or bicarbonate, are, for example, filtered, filtered and the excess allyl alcohol in the vinyl ester, in particular vinyl acetate and vinyl propio vacuum, distilled off. The allyl ether is obtained in this way, as well as maleic anhydride. Of the 15 monomers mentioned for N-methylol methacrylamide having a boiling point, acrylic acid has proven to be particularly suitable from 110 to 112 ° C. at 0.5 Torr, or the allyl ether has proven to be particularly suitable. N-methylol-acrylamides with a boiling point of

As emulsifiers of a nonionic character, the 105 to 107 ° C at 0.5 Torr, in yields of about known reaction products of ethylene oxide with 70 to 75% of theory.

long-chain fatty alcohols or with phenols suitable to be used as starting monomers preferably reaction products with more allyl ethers of N-methylolamides of unsaturated carals 10 ethylene oxide units are used. Of course, carboxylic acids can also be used For the production of re-emulsifiable latices, re-etherification processes can be obtained, ion-active emulsifiers, in particular anion-active, due to their properties already under mild

Emulsifiers, in addition to the non-ionic conditions mentioned, are overactive into insoluble crosslinking products Find emulsifiers application. However, the inventively obtainable can be added the amount of these ion-active emulsifiers in all- Polymers and copolymers for production generally not more than 0.5%, calculated on that of any shaped bodies, impregnations, excess weight of the monomers used. Can be used on trains and bonds. the ion-active emulsifiers come z. B. alkyl sulfates 30 possibility of the crosslinking reaction under or addition products of sulfuric acid under long-term, mild conditions, chain olefins in question. In particular, it allows such cross-linking reactions

The advantageous properties of the invention, especially of temperature-sensitive ones according to prepared polymers result special carrier materials to make. Special user from the fact that the crosslinking of the polymers or 35 training areas of the present process Copolymers on the one hand by purely thermal, therefore in the field of textile printing, leather treatment the polymerizate via a polymerisation process and paper coating, the allyl groupings can be triggered. In the examples listed below

In contrast to the parts containing alkyl methylol ethers, parts by weight are, unless otherwise stated. The alkenyl 4 ° crosslinking occurs in polymers

methylol ether under considerably milder conditions. example 1

Although a thermal crosslinking at temperatures

up to about 150 ⁰ C can be effected, it is other- 18 parts of a sodium salt of a long-chain

On the other hand, a purely thermal crosslinking of paraffin sulfonic acid and 6 parts of a polyethoxylated one is also possible The 45 fatty alcohols (100%) that can be stored unchanged at room temperature are demineralized into 450 parts Emulsions dissolved by evaporation of the emulsion on the water and with 0.2 parts of sodium hydroxide To achieve water bath. Extensive crosslinking adjusted to a pH of 7.6. 180 parts can finally also at room temperature under butyl acrylate, 108 parts of styrene and 12 parts of the correspondingly long storage times, for example methacrylamide methylol allyl ethers 10 to 20 hours. On the other hand, 50

it can be favorable that the crosslinking of the poly _{— CH 2} = C — CONH — CH ₂ —O — CH ₂ —CH = CH ₈ merizates act in the presence of acids or acidic substances

the compounds under even milder conditions CH ₃

he follows. This is due to the easier cleavage of the

Allyl ethers in comparison with the alkyl ethers are mixed and added to the aqueous phase respectively. Stir added.

The preparation of the starting monomers with The polymerization takes place at 45 ⁰ C by addition

Alkenylmethylolether groups that are not the opposite of 0.18 parts of potassium persulfate and 0.10 parts state of the invention can be done by first triethanolamine. After 5 to 6 hours, it becomes more stable obtained in the presence of small amounts of polymerization latex, in which 95 to 97% of the used Prevent how hydroquinone, phenthiazine or monomers are polymerized. Copper, the corresponding methylol compounds, will use the polymer from this dispersion

associated acid amides, so the acrylamides or methanol precipitated and briefly between filter paper Methacrylamide, dried by condensation of these amides, the plastic can be dissolved in Dissolve the formaldehyde or formaldehyde releasing agents such as dimethylformamide smoothly. Substances, especially paraformaldehyde, shown when this plastic dispersion is dry

will. Here, preferably equimolar suitable documents are created clear, transparent Amounts of up to a single molar excess of films, which after 10 to 15 hours already at room temperature

I 204 410

temperature become completely insoluble in acetone, chloroform or dimethylformamide.

If the plastic dispersion is adjusted to a pH value between 2 and 5 before it dries, or If the drying is carried out in an acidic atmosphere, the crosslinking takes place at room temperature in much shorter time.

The coatings and impregnations produced with this 10% aqueous plastic solution are more suitable By adding small amounts of acidic substances, documents can be removed even at room temperature make insoluble in a short time.

Example 5

B e ι s ρ ι e 1 2 A solution of 550 parts is made _{in a stirred vessel}

In 600 parts of deionized water, 24 parts of 10 water and 30 parts of a reaction product are obtained Reaction product of a long-chain 15 to 20 moles of ethylene oxide and 1 mole of o-oxydiphenyl

methane and 5 parts of a formaldehyde-naphthalenesulfonic acid condensation product submitted. In this

of a reaction product of an alcohol (C _{12 -C 14} ) dissolved with 440 to 616 parts of ethylene oxide and 1.5 parts of a formaldehyde-naphthalenesulfonic acid condensation product. After adding 1.2 parts of potassium persulfate, 1.8 parts of sodium ester, 45 parts of ethyl acrylate, 100 parts of acrylumpyrosulfite and setting a pH of 4.5 nitrile, 25 parts of styrene, 12 parts of methacrylamide, the monomer mixture is 200 parts Acrylic acid butyl ester, 100 parts of styrene, 80 parts of acrylonitrile and 20 parts of methacrylamide methylol allyl ether were added to the aqueous phase. The polymerization at 40 ^° C. is complete after about 5 hours, 96% of the monomers used have been polymerized.

After drying with water, the stable latex formed can easily be converted into plastic agents such as acetone, chloroform and dimethylform emulsion redisperse. If the dried amide.

Latex film, however, about 5 hours at room temperature - Example 6

Left on the doorstep, this property is complete

disappeared, and the now crosslinked plastic example 1 was repeated, with the only one

film can also be used in solvents such as dimethyl 30 difference that methacrylamide methylol allyl ether formamide no longer dissolve. by the corresponding butenyl ether of the formula

a mixture of 300 parts of butyl acrylate

methylol allyl ether and 0.25 part of n-dodecyl mercaptan and 32.5 parts of 47% acrylic acid in 200 parts of water. The received, approximately A 37 to 38% dispersion results in clear films on drying, which are then reassembled with water let redisperse. After a few hours of storage at room temperature, crosslinking takes place and thus complete insolubility in the usual solution

Example 3

CH _a

CH ^===: CHo

Example 7

CH ₂ = CC-NH-CH ₂ -O-CH ₂

In a 101 capacity stirred autoclave with V2A-Aus 35 CH ₂ = CC NH CH O CH

clothing is a solution of 180 parts of the changing,

Settlement product of 1 mole of cetyl alcohol and 15 to 20 moles of ethylene oxide, 30 parts of a condensation product from formaldehyde and naphthalenesulfonic acid, 50 parts of 46% acrylic acid and 3850 40 was replaced. Parts of water presented. A mixture of 1350 parts of butadiene, 450 butyl acrylate is emulsified in this solution, 35 parts of acrylonitrile, 90 parts of acrylic

amidmethylolallyläther and 6 parts of tert. Dodecyl- The same experiment was carried out again

mercaptan. After the mixture has been heated to 35 ° C., 20 parts of sodium pyrosulfite and 20 parts of potassium persulfate - each dissolved in 200 m ^{3 of} water - are added with the corresponding pentenyl ether of the formula. At about 33 and 60% conversion, 40 parts of 46% acrylic acid in 100 parts of water are added. The polymerization has ended after 25 hours. 5 °

The approximately 37 to 38% latex shows excellent mechanical stability. The plastic films produced therewith on suitable substrates can be crosslinked both by lying for a long time at room temperature and by brief heating to 130 ^° C. and thus made insoluble in all solvents.

Example 4

20 parts of acrylamide and 20 parts of the allyl ether of methylol methacrylamide are dissolved in 360 parts of deionized water. After displacing the air with nitrogen is heated to 6O ⁰ C and activated with 0.008 parts of sodium salts of ethylenediaminetetraacetic acid and 0.004 part of FeSO ₄ -7 H ₂ O. When 0.70 part of potassium persulfate is added, the polymerization begins, which is complete after 5 to 6 hours with a yield of 96 to 97%.

CH ₃

- CHo - CHo - CH = CH ₈

The latices obtained had the same properties as the latex of Example 1 and contained likewise about 95 to 97% of the monomers used as polymer.

Claims (1)

Claim: Process for the production of homopolymers or copolymers of methylol ethers by Polymerization of methylol ethers with one or more organic compounds that are at least contain a polymerizable double bond, in bulk, in solution or in emulsion at temperatures between 20 and 70 ° C and in the presence of activating agents, thereby characterized in that the methylol ether is a methylol alkenyl ether of the formula R — C — N —CH ₂ —O —R ₂ ίο 10 used, in which R is the remainder or CH _a R ₁ denotes a hydrogen atom, an alkyl or aryl radical and R ₂ denotes an alkenyl radical. Publications considered: German Auslegeschrift No. 1035 363. 509 720/442 10.65 ® Bundesdruckerei Berlin