DE1088718B - Process for the production of crosslinked copolymers - Google Patents

Description

GERMAN

The invention relates to a process for preparing cross-linked blended polymers, which is characterized in that a monomeric, polymerizable, a, ^ unsaturated lower aliphatic carboxylic acid, particularly acrylic acid, which can be up to 90 ° ₀ contain / of another unsaturated, copolymerizable with their monomers , of 0.0005 to 20 ° / ₀ of a polyalkenylierten element of the group IV. of the periodic system preferably in an inert, substantially anhydrous organic liquid at 0 to about 100 ° C, especially at 20 to 90 ° C, in the absence of oxygen, and is copolymerized with the aid of a catalyst which forms free radicals, the polyalkenylated element having the following structure:

Method of manufacture
cross-linked copolymer

in which R is a terminal unsaturated alkenyl radical with 2 to 4 carbon atoms, Y is a saturated hydrocarbon radical with 1 to 10 carbon atoms, η is a number from 2 to 4 and M is an element of group IV of the Periodic Table with an atomic weight of at least 28 is.

The copolymers and their salts are insoluble in water, but have the ability even in the presence dissolved ionic substances, to swell rapidly and strongly in water. The copolymers and their salts thicken, even in extremely low concentrations, with water to form gels, the practically constant viscosity retain, even during prolonged aging.

It is already known that water-insoluble copolymers containing carboxyl groups can be obtained by polymerization of monomers containing carboxyl groups, such as acrylic acid, maleic acid or their anhydrides and the like, in the presence of polyfunctional monomers such as divinylbenzene; unsaturated diesters such as diallyl maleate or ethylene glycol dimethacrylate; Diallyl or divinyl ethers; Polyallyl ethers of polyhydric alcohols and other substances, see U.S. Patents 2,340,110, 2,340,111, 2,533,635 and 2,798,053). These known copolymers have a number of disadvantages, which the copolymers according to the invention have do not exhibit. Those obtained by interpolymerization of divinylbenzene and carboxyl groups Copolymers that can be prepared from monomers are not uniformly crosslinked. The copolymers from Divinylbenzene and carboxyl group-containing monomers consist of heterogeneous mixtures of completely insoluble, slightly swellable and completely soluble copolymers, if vinylbenzene in quantities 5 weight percent or less is used in the polymerization batch. When interpolymerizing Carboxyl group-containing monomers with unsaturated diesters, diallyl and divinyl ethers is obtained copolymers that are grown in water at high temperatures

Applicant:

The BF Goodrich Company,
Akron, Ohio (V. St. A.)

Representative:
Dr.-Ing. A. v. Kreisler, Dr.-Ing. K. Schönwald,

Dipl.-Chem. Dr. phil. H. Siebeneicher

and Dr.-Ing. Th. Meyer, patent attorneys,

Cologne 1, Deichmannhaus

Claimed priority:
V. St. v. America 9 December 1957

doors and can easily be hydrolyzed at room temperature in the presence of alkaline and acidic substances after prolonged aging. The previously known copolymers containing insoluble carboxyl groups shrink considerably in water when relatively high concentrations of water-soluble ionic materials are added. In the case of many of the previously known copolymers containing insoluble carboxyl groups, a certain degree of molecular degradation takes place in water, as can be seen from the reduction in viscosity which takes place at high temperatures after a certain time or at room temperature after prolonged aging. Moreover, the known copolymers and their salts have frequently several hours are stirred only a little or no need ability, water at concentrations of 0.25 ° / ₀ to thicken under, and for the complete dispersion of the copolymers in water.

In contrast, the copolymers according to the invention have an amazing ability to absorb water in the presence of a large amount Thicken quantities of dissolved ionic salts and even in extremely low concentrations as well as being completely in water in a few minutes

009 590/444

disperse and form a kind of slime that too retains a substantially constant viscosity upon aging at high temperatures.

It has been found that useful, fast swelling, ion-resistant copolymers can be produced with an unusual thickening ability, if a, j8-olefinically unsaturated monomers containing or their anhydrides carboxyl covered with about 0.0005 to 20 ° / ₀ (on the weight of remaining polymerizable constituents) of a crosslinking agent composed of a polyalkenylated element of group IV of the Periodic Table with an atomic weight of at least 28, copolymerized. In the following, the term "crosslinking agent" includes compounds of the structure

in which R is an alkenyl radical with 2 to 4 carbon atoms and a terminal unsaturated group, such as vinyl, allyl and methallyl, Y is a non-olefinically unsaturated hydrocarbon radical with 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, amyl, Hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, phenyl and naphthyl, η is a number from 2 to 4 and M is an element of group IV of the Periodic Table with an atomic weight of at least 28, including Si, Ge, Sn and Pb belong. The properties of the copolymers vary depending on the nature of the monomers containing carboxyl groups or acid anhydride groups and on the nature and amount of the crosslinking agent. If 0.0005 to 20 percent by weight of crosslinking agent is used in the copolymer, water-insoluble copolymers are obtained which are capable of absorbing large amounts of water, especially in the form of their salts, so that they swell many times their volume. These copolymers are similar to the naturally occurring water-swellable gums, such as tragacanth, which are commonly used as thickening and suspending agents. But they are far superior to these. The properties of the copolymers according to the invention can be varied in a controllable manner by changing the amount of crosslinking agent used in the polymerization mixture. If maximum thickening effectiveness and ionic resistance are desired, copolymers containing between 0.01 and about 0.5 percent by weight of crosslinking agent are particularly suitable. On the other hand, when the interpolymer contains from about 0.0005 to about 20% crosslinking agent, rapid dispersibility, resistance to hydrolytic degradation and excellent thickening efficiency are obtained. Depending on the type of monomeric system used and the degree of crosslinking achieved, the swelling index in water varies between more than 24,000 and 5.

The water-swellable copolymers according to the invention are suitable for the production of printing pastes, for thickening flood water when extracting crude oil, sand suspensions in oil and water wells, car polishes and cleaners, household polishes and cleaners, suspension elements and the like the copolymers containing carboxyl groups according to the invention with compounds of the structure

For the preparation of the copolymers one uses monomeric mixtures, the two essential monomers Containing ingredients in certain proportions, one of which is an olefinic unsaturated carboxylic acid, such as acrylic acid, maleic acid or maleic anhydride, sorbic acid and the like, and the other is the crosslinking agent. Other monoolefinic monomers can optionally be present in the monomeric mixture, even predominantly Amounts to be included, being extraordinarily

ίο useful water-soluble, water-swellable carboxyl groups containing copolymers are obtained.

In the case of the α, / 3-olefinically unsaturated acids, the close proximity of the strongly polar carboxyl groups to the double bond of the carbon atom is a strongly activating one Effect so that substances of this structure can be polymerized very easily.

Typical monoolefinically unsaturated monocarboxylic acids that are used to produce the crosslinked copolymers suitable according to the invention are, inter alia, acrylic acid, methacrylic acid, ethacrylic acid, α-fluoro, chloro, bromo- and iodoacrylic acid and crotonic acid and their anhydrides.

The typical monoolefinically unsaturated polycarboxylic acids include maleic acid, fumaric acid, citraconic acid, Mesaconic acid, glutaconic acid or their anhydrides and halogen-substituted derivatives of these acids or Anhydrides.

Typical polyunsaturated monocarboxylic acids are piperic acid, sorbic acid, their anhydrides as well their halogen-substituted derivatives.

All of the olefinically unsaturated acids listed above and their halogenated derivatives and Anhydrides are hereinafter referred to as "a, /? - olefinically unsaturated lower aliphatic acids ”.

The preferred monomers according to the invention are acrylic acids of the general structural formula

CH ₂ = C-COOH

are cross-linked, in which M is Si or Sn, for use in liquid and paste-like dentifrices, Jellies, creams and ointments for medical purposes, hairdressing preparations, solid laxatives and the like.

in which A is hydrogen, halogen or a lower alkyl radical. Typical acrylic acids of this class are acrylic acid itself, methacrylic acid, ethacrylic acid, cc-haloacrylic acids as well as a practically equimolar mixture of maleic anhydride and another polymerizable therewith Monomers. α-Haloacrylic acids are easily formed on the halogen substituent hydrolyzed by hydroxyl and lactone groups. Of the above acids, acrylic acid becomes particular preferred because it is cheap and readily available and also forms particularly good polymers.

The amounts of monomers used to make the multicomponent interpolymers can similarly vary. Since the swellability (or the swelling index) of the weakly crosslinked copolymers depends mainly on the presence of small amounts of carboxyl groups in the copolymer chain, it is usually desirable to use the maximum number of carboxyl group-containing monomers and the minimum of other monomeric constituents that are required for the Water sensitivity, dispersibility, emulsifiability, thickening ability and other properties is allowed. Therefore in these mixed polymers, the carboxyl group-containing monomers should never be less than 10 ° / _0, and preferably not less than 20%, based on the weight of the entire monomeric mixture, constituting as.

Mixed polymers of several ingredients can be made from monomeric mixtures formed between

5 6

about 10 to about 95 ° / ₀ of carboxyl group-containing allylallylsilan, Trimethallylvinylsilan, Trivinylmethyl monomers such as acrylic acid, to "0.0005 silane to about 20%, divinyldimethylsilane, Trimethallylmethylsilan, from the described cross-linking agent and between Dimethallyldimethylsilan uws., as well as hydrocarbon about 5 to about 90 ° / Pass ₀ other monomers. For substituted Germane ^(as Tetraallylgerman, methallylgerman tetra-use as a water swellable synthetic rubber 5, tetravinyl German, Triallylmethylverwendet is preferably tripolymers by the German, tri-allylvinylgerman, Triallylmethallylgerman, polymerization of monomeric mixtures obtain diallyldimethylgerman, diallyldivinylgerman, diallyldiwill, the from 20 to 95 weight percent acrylic acid, methallylgerman, trivinylallylgerman, trivinylmethallyl-0.1 to 3 weight percent of a crosslinking agent of the german, divinyldimethallylgerman, trimethallylallylgerman and about 4 to 79 , 9 ° / comprise from ₀ one or io one, Trimethallylvinylgerman, Trivinyhnethylgerman, more additional monomers, en with the Divinyldimethylgerman, Trimethallylmethylgerman, di-acid and the crosslinking agent interpolymerizable methallyldimethylgerman etc., and hydrocarbon are, for example, maleic anhydride, N-methyl acrylamide, substituted tin compound such as tetraallyl tin, tetranethyl acrylamide, n-tert-butyl acrylamide, methylvinylmethallyl tin, tetravinyltin, triallylmethyltin, triether, ethyl vinyl ether, n-butyl vinyl ether, styrene and allyl vinyl tin, triauylmethallyl tin, isobutylene dimethyl. Mixed polymers can be prepared from mixtures of tin, diallyldivinyltin, diallyldimethallyl tin, trivon maleic anhydride, a vinyl alkyl ether such as vinylallyl tin, trivinylmethallyl tin, divinyldimeth-methyl vinyl ether, and a crosslinking agent of the allyltin, trimethallylmethyltin, trimethallylvinyltinlylallyltinyl, in which the amount of trimethallylvinyltinlylallyltinyl, trimethallylvinyltinlyl allyltin, trimethallyl vinyl tin, trimethallyl vinyl tin, trimethallyl vinyl tin, trimethalethallyl vinyl tin, trimethallyl vinyl tin, trimethallyl vinyl tin, trimethallyl vinyl tin, trimethallyl vinyl tin, trimethallyl vinyltinlyl allyl tin, trimethallyl vinyl tin, tri Vinyl ether is practically equivalent to the molar 20 methyltin, dimethallyldimethyltin, etc., as well as the carbon amount of maleic anhydride. It goes without saying that hydrogen-substituted lead compounds, such as tetraallyl the other monomers in slightly less than the maximum amounts of lead, tetramethallyl lead, tetravinyl lead, triallylmethyl lead, have to be used if two of the triallyl vinyl lead, triallylmethallyl lead, diallyldimethyl lead, diallyldimethyl monomers specified above Diallyl divinyl lead, diallyl dimethallyl lead, trivinyl can be used. 25 allyl lead, trivinylmethallyl lead, divinyldimethallyl lead, further monomers which are suitable for the production of the pre-trimethallyl allyl lead, trimethallyl vinyl lead, trivinyl copolymers described below from several methyl lead, divinyldimethyl lead, trimethallylmethyl lead, other dimethyl lead and other mono-methyl lead, monomers are
such as fluorine, chlorine, bromine, iodine and ethoxystyrenes, preference is given to crosslinking agents with four alkenyl acrylamide, methacrylamide, N, N-dimethylacrylamide, 30 groups of 2 to 4 carbon atoms per molecule, because they result in acrylonitrile, methacrylonitrile, Vinylidene cyanide, methyl a greater crosslinking effectiveness is obtained, acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, typical examples of these are tetraallylsilane, tetra-amyl acrylate, hexyl acrylate, heptyl acrylate, octyl vinylsilane, tetramethallylsilane, vinyl acrylate, methyl methacrylate, diallyldivinylsilane, methyl methacrylate, diallyldivinylsilane, methyl methacrylate, diallyldivinylsilane, methyl methacrylate, diallyldivinylsilane, methyl methacrylate, diallyldivinylsilane, Tetraallylgerman, tetravinylacetate, vinylpropionate, vinylbutyrate, isopropenyl acetate, 35 german, tetramethallylgerman, tetraallyl tin, tetra-isopropenyl propionate, isopropenyl butyrate, vinyl benzoate, vinyl tin, tetramethallyl ethyl chloride, vinyl tin, tetramethallyl ethyl chloride, tetramethallyl isopropyl chloride, vinyl, tetra-allyl ethyl chloride, tetramethallyl isopropyl chloride, vinyl, tetra-allyl isopropyl chloride, tetramethallyl isopropyl acetate, tetramethallyl isopropenyl acetate. Particularly cheap bromide, vinylidene chloride, vinylidene bromide, vinylidene are the polyalkenylsilanes, since they are cheap and the halochlorobromide, vinyl carbazole, vinyl pyrrolidone, vinyl silane intermediate products are easily available,
piperidine, vinylpyrimidine, methyl vinyl ketone, ethyl 40 The crosslinking agents according to the invention are vinyl ketone, methyl isopropenyl ketone, ethylene, dimethyl ζ. Β. by Grignard reaction between an alkenyl maleate, diethyl maleate, dimethyl fumarate, diethyl magnesium halide and the halide of an element fumarate and many others. In addition to these monoolefinic of the IV. Group of the Periodic Table with one monomer, many other divinyl, dialkenyl or atomic weights of at least 28 can be prepared. Tetraallylandere polyfunctional esters, amides, ethers, ketones, 45 tin 'is used, for example, by reacting about 5 moles of anhydrides and the like to produce the mixed polymers consisting of many constituents - allyl magnesium bromide with 1 mole of tin (IV) chloride in partial proportions, made of ethyl ether. The mixed alkylalkenyl compounds, especially those polyfunctional monomers, are prepared according to the same general rule, nominally as crosslinking agents or as monomers for driving, for example trivinylmethyl insolubilization is used, but can easily be saponified by treating 1 mole of trichloromethylsilane, and in addition to Hydroxyl, carboxyl and with about 4 moles of vinyl magnesium bromide in tetrahydro other hydrophilic groups are hydrolyzable. furan produced. In this reaction, allyl is added - for example, mixed polymers of magnesium acrylic bromide, methallyl magnesium bromide and and diesters such as diallyl maleate, ethylene glycol dimeth vinyl magnesium bromide are generally preferred over acrylate, acrylic anhydride, methacrylic anhydride, methacrylic anhydride, allylmagnesium chloride and many others, allylmagnesium chloride saponify and and vinyl magnesium chloride, since the bromides hydrolyze reaction by alkali or acid, with additional ones being more capable and more soluble in ether and yielding larger hydroxyl and / or carboxyl groups in the polymers. Which are introduced by reaction between the. Of the above-mentioned alkenyl magnesium halides and the halides of the additional monomers, n-methylacrylamide, 60 elements of group IV crosslinking agents obtained -acrylonitrile, methyl vinyl ether, ethyl vinyl ether, iso- are not always pure compounds, but in allbutylene and styrene are particularly suitable for the production of water - common mixtures containing different amounts of swellable rubbery copolymers. Contain alkenyl groups per molecule. An analysis of these typical crosslinking agents of the substances given above using the formula therefore only shows the average number of the types shown are 65 hydrocarbon-substituted alkenyl groups per molecule. If, however, these mixtures contain silanes such as tetraallylsilane, tetramethallylsilane, tetra, according to analysis, an average number of at least two vinylsilane, triallylmethylsilane, triallylvinylsilane, tri-alkenyl groups, they are suitable for the production of allylmethallylsilane, diallyldimethylsilane-containing diallyldimethylsilboxyl, insoluble-monosilanesilane groups, diallyl-dimethylsilane, or insoluble monosilane groups , Trivinylallylsilane, trimers according to the invention. Since the effectiveness of vinylmethallylsilane, divinyldimethallylsilane, Trimeth- 70 crosslinking agents according to the invention with increasing

7 8

The number of polymerizable groups per molecule increases, for the monomers but not for the mixed polymer, are preferably used crosslinking agents that act or in a mixture of such solvents that on average, two or more alkenyl groups each form a free radical which is soluble in the solvent Molecule included. For the preparation see also USA catalyst, such as benzoyl peroxide and azo-bis-isobutyro patent specification 2,628,246.5 nitrile. In this case, the product usually falls in the form of a very fine, friable and often flaky precipitate must be produced in the monomeric polymerization mixture, the two main monomers only rarely exist in certain amounts before or after removal of the solvent although the exact amounts are milled or further treated depending on the use desired properties of the copolymer within must. Suitable solvents for this process are further limits can fluctuate. The crosslinking agents include benzene, toluene, xylene, ethylbenzene, according to the invention easily copolymerize in tetrahydronaphthalene, hexane, heptane, octane, tetramonomers Mixtures of two ingredients, the chlorocarbon, methyl chloride, ethyl chloride, Äthylenais second component the dichloride containing carboxyl groups, bromotrichloromethane, chlorobenzene, acetone, Monomers contain when about 0.0005 to about 20% methyl ethyl ketone, etc., and mixtures of these and Crosslinking agents are present. Mixing 15 other solvents are used here.

polymers obtained in the form of their monovalent salts. The polymerization in a diluent can have a swelling index which can be between more than 24,000 and 5 in the presence of a catalyst which forms free radicals. Such copolymers are insoluble in a closed vessel under an inert atmosphere in water and organic solvents and at autogenous pressure or artificially induced, and the water sensitivity of these copolymers 20 pressure or in an open vessel under reflux is highest when the amount of crosslinking agent is carried out at atmospheric pressure will. The Polymeri-0.01 to 10 / is ₀ °, particularly when the mixing sation level can range from 0 ⁰ C and less to about polymer in the form of their monovalent salts are present. 100 ⁰ C, preferably vary between 20 and 90 ⁰ C polymers monovalent salts of this type, especially acrylic and depends to a high degree on the activity of the acid mixed polymers to 3% crosslinking agent 0.1 25 monomers used and catalysts and, swell with absorption of 1,000 times the molecular weight desired in the polymeric product. Amount of their own weight in water. If at the mixing polymers prepared at low temperatures have a copolymerization amount of 0.0005 to 10 ° / _0, a higher molecular weight than those, preferably 0.1 to 5 ° / ₀ with a crosslinking agent which are produced at higher temperatures . In virtually equimolar mixture of maleic acid 30 carrying out the polymerization at 50 to 9O ⁰ C under anhydride and another hereby mischpolymerisier- atmospheric pressure and is used using a free cash monomers are likewise radicals obtained forming catalyst, the polymer is mixed polymers with high swelling capacity. Such mostly only with a yield of 75 to 100 ° / ₀ of theo regering crosslinked interpolymers are artificial rubber tables amount in less than 10 hours, usually obtained in less-like substances in the production of mucilaginous 35 than 5 hours. Suitable free radical-forming compounds in place of naturally occurring rubber catalysts are the peroxides, such as sodium and potassium types, such as tragacanth gum, and are also suitable and ammonium persulfates, caprylyl peroxide, benzoyl for slimy mixtures, in which a natural peroxide and pelargonyl peroxide, hydrogen peroxide are used , Rubber because of its insufficient thickening power, cumene hydroperoxides, tert. Butyl diperphthalate, tert. Do not use instability and the flocculation or de-swelling caused by ionic substances 40 butyl perbenzoate, sodium peracetate, sodium percarbonate, etc., as well as azo-bis-isobutyronitrile and others. Furthermore can. the so-called "redox" catalysts and are suitable

Unusually stable aqueous dispersions - the activated heavy metal catalysts. the

insoluble pigments such as titanium dioxide are retained, polymerization can be triggered by radicals,

if you add 0.05 parts by weight of a crosslinked mixture 45 which is in the polymerization system by nuclear radiation,

polymer according to the invention, 10 parts by weight of titanium X-rays or UV rays are generated.

dioxide and 100 parts by weight of distilled water, which The strongly swelling copolymers according to

contains sufficient alkali to a final _pH value of the invention are particularly suitable for use in

to yield about 7, homogenized in a colloid mill. soft muddy mixtures. This mixed poly

In such dispersions the pigment is uniformly 50 kidneys usually attain their maximum volume in water

dispersed in the aqueous phase, a property that only after some of the free carboxyl groups in the

especially for water-based paints, coatings etc. mixed polymers with alkali, ammonium or amine salts

is useful. are converted. With increasing neutralization of the

According to the preferred production process for the free carboxyl groups, the volume of the copolymers according to the invention is increased, the polymer ratio of distilled water to the unit weight of the cation is carried out in an inert diluent, which gradually increases the copolymers to a maximum of 50 to 90 ° / ₀ and has a certain dissolving effect on one or more mono then decreases again to the extent that the fuller constituents, but practically not to the constant neutralization obtained, is achieved. A neutral interpolymer exercises. Be a bulk polymerization tion may vary from about 75 ° / ₀ results in a _pH value of about 7, even made, but is not expedient 60 is preferably a neutralizing agent as einmäßig because the resulting solid polymeric masses valent alkali such as sodium -, potassium, lithium, poorly reconditioned. The polymerization can ammonium hydroxide, or their carbonates and Biauch in an aqueous medium, carbonates or mixtures thereof used, as well as the water-soluble, free radical-forming catalyst amino bases with no more than one primary or containing, the product either in the form of a 65 secondary Amino group per molecule. Polyvalent bases, granular precipitates or a heavily swollen one such as calcium hydroxide, magnesium hydroxide or aluminum gel is obtained, both of which can either be used directly, minium hydroxide and all polyvalent metal cations or are slightly further crushed and dried have a strong swelling effect on the water. However, the preferred polymerization takes place in swollen copolymers and their salts; the absolute swelling in an organic liquid as a solvent is higher in spite of the presence of these metal ions

The reactions are performed in a closed vessel in an oxygen-free atmosphere at 50 ⁰ C. In each case, the polymerization is complete after 2 to 18 hours with the formation of a thick polymer slurry. The mixed polymers are filtered or centrifuged off, washed with fresh benzene and finally en in an air circulation of dried at 50 ⁰ C. The yield in each case is 98 to 100 ° / _0th The dried cake is a white crumbly mass that easily converts to a fine white powder. For each polymer, an aqueous mucilage is prepared by dispersing 1.5 g of the polymer in 100 g of distilled water containing sufficient NaOH to the final mucilage to give a p _H value of about. 7 The slime reaches its maximum swelling within 3 to 5 minutes after adding the mixed polymer to the diluted alkali. The viscosity in centipoise of the aqueous slime is determined in this and the following examples, unless otherwise indicated, with a Brookfield viscometer (10 rpm).

than natural rubbery substances such as gum tragacanth etc. in the presence of the same swelling reducing agents. Because of the effect on the viscosity and thixotropy of the water-swollen gel-like mixed polymers, it is sometimes desirable, etc. to neutralize the copolymers with up to 25 ° / ₀ of a polyvalent metal base such as calcium hydroxide and magnesium hydroxide.

The crosslinking agents used in the examples below can easily be passed through the reaction of an alkenyl magnesium halide with the corresponding silicon, germanium, tin and lead halide produce. The alkenyl magnesium halide is used in an excess of at least 1 mole. This coupling reaction is carried out on the basis of the following process for the preparation of the tetraallylgermanium explained. 5 moles of allyl magnesium bromide become slightly more with the slow addition of 5 moles of allyl bromide produced as 5 moles of magnesium turnings in anhydrous diethyl ether. The allyl magnesium bromide etherate is produced by the insoluble solid decanted and 1 mole germanium tetrachloride slowly to the allyl magnesium bromide etherate given. The mixture is refluxed for 4 to 8 hours and then with a Excess of dilute HCl hydrolyzed. The product comes from the dried organic layer obtained by stripping off the ether .. The somewhat viscous residual oil has an iodine number of 411, which is the same as the calculated iodine number of 429 for pure tetraallylgermanium.

The invention is illustrated in the following examples. The amounts of the ingredients are parts by weight, unless otherwise stated.

example 1

The crosslinking agents prepared in the manner described are used for batch production used by copolymers with acrylic acid. A range of copolymers made from acrylic acid and tetraallysilane with a different tetraallyl content becomes in this way from the following ingredients manufactured:

Parts

Acrylic acid (98 to 100% pure) 100

Tetraallylsilane. _. variable

Benzoyl peroxide 2.0

benzene

° / "Tetraallylsilane
in the polymer

Viscosity in cP at one

Mucilage content of
1.5% I 0.5 "/ ο I 0.125% 10.0156%

0.0005

0.1

0.5

1.0

2.0

18.0

280 100 120 10400 2,400 560 52800 21600 12000 198400 * 90 400 16,000 329600 27 200 320 5 0 0

1000

*) The clarity of the mucus becomes that of a mucus the same concentration and the same pH value from a mixed polymer of acrylic acid and 1% hexaallyl sucrose. The light transmission (wavelength 5000 Å) of the Acrylic acid and tetraallylsilane slime was 43% larger than that of acrylic acid and hexaallyl sucrose slime. the Measurements of light transmission were made with a Beckmann DK-2 recording spectrophotometer.

The extraordinary resistance of the crosslinked copolymers according to the invention against an ionic shrinking in water is shown in the following Table in which the viscosities l ° / _o aqueous mucilages at various concentrations of sodium chloride and a _pH value of about 7 are listed.

% Tetraallylsilane
in copolymers

0.2
0.3
0.4
0.5

Viscosities
1% NaCl | 2% NaCl | 3% NaCl | 4% NaCl

3,200

8,000

20,000

16,800

2,400
4,800
9,600
9,600

1,600
4,000
5,600
6,400

800
3.002
3,200
2,700

With more than 0.5 ° / ₀ tetraallylsilane crosslinked copolymers are less effective in 4 ° / ₀ NaCl solution as a thickening agent than the copolymers listed in the table. The copolymers according to the table are excellent thickeners for flushing water, as it is used in secondary processes for the extraction of crude oil, as they thicken the salt water usually used in the flushing processes, are very stable and also thanks to the sand and shale of the underground layers that make up the Crude oil is extracted, flow.

There were mixed polymers of 90% ethyl acrylate and 10 ° / "tetraallylsilane manufactured and boiled for 24 hours in a 20 ° / ₀ solution of NaOH, and in a 20 ° / ₀ by weight H ₂ SO ⁴ solution under reflux. The hydrolysis products in no way resembled the copolymers of acrylic acid and tetraallylsilane according to the invention. The 1.5% polymer containing mucus from the hydrolysiertenÄthylacrylat-tetraallylsilane interpolymer had no measurable viscosity at a p _H value of the 7th

60

Example 2

Following the procedure of Example 1, a series of copolymers were prepared from acrylic acid and 1% tetraallylsilane and investigated the influence of temperature, catalyst and solvent. There will be 1.5% Azo-bis-isobutyronitrile and 2.0% caprylyl peroxide or benzoyl peroxide are used. The amount of tetraallylsilane used is kept constant at 1%.

009 590 / 444-

11 temperature ⁰ C catalyst Viscosity ir
1.5%
concentration 12th solvent SO ⁰ C Azo-to-iso-bu-
tyronitrile 64,000 ι cP bsi p _a 7
0.125%
concentration acetone I. 184,000 1,600 Ethylene dichloride I. 26,400 12,800 toluene Caprylyl peroxide 2,700 6,400 Xylene I. 192,000 320 Hexane I. 196,800 32,000 Chlorobenzene 40 Benzoyl peroxide 200,000 9,600 benzene 32,200

Various organic diluents or mixtures of these of the type listed above are used. All copolymers described above can be quickly dispersed in the dilute Na O Η solution used to make the mucus, and all slimes are clear and colorless.

Concentration of polymers Viscosity in cP 20th
1.5%
1.0%
0.5%
0.25% 28,800
16,000
8,800
4,000

Example 3

Copolymers of methacrylic acid and Tetraallylsüan in an inert organic diluent are prepared by the process of Example 1. By varying the Tetraallylsüanmenge from 0.25 to 3.0 parts / 100 parts of methacrylic acid products are obtained with ten different thickeners natural sheep, all of which Büden viscous mucilages with a p _H value of the 7th Copolymers of Methyarylsäure and 2% Tetraaüylsüan form, for example aqueous gums at a p _H value of 7 at a concentration of 1.5, a viscosity of 131 200 cP at a concentration of 0.5, a viscosity of 36 000 cP and a concentration of 0.125% have a viscosity of 2 40OcP. These slimes are clear and show no noticeable decrease in viscosity when aged for several months at room temperature. Hydrolyzed either with acid nor with alkali copolymers of 90% methacrylate and 10% tetraallylsilane have a l, 5% solution in water and a _pH value of about 7 is a measurable increase in viscosity.

Example 4
From the following approach:

Parts

Acrylic acid (98 to 100%) 100

Acetic Anhydride 166

Tetraallylsuane 1.0

Benzoyl peroxide 2.0

Benzene 880

These mixed polymer slimes have excellent ion resistance.

Example 5

The copolymers in this example are produced from the following approach:

Parts

Maleic Anhydride '63

Methyl vinyl ether 37

Tetraallylsüan variable

Benzoyl peroxide 2.8

Benzene 880

The polymerization is carried out in a closed reaction vessel in an oxygen-free system at 50 ° C. in 2 to 18 hours carried out. The thick slurries are filtered or centrifuged and before drying of the copolymer washed with fresh benzene. The yields are quantitative, as are the dried copolymers are white powders.

The viscosities of the aqueous mucilages are determined in a Brookfield viscometer with spindle special "for highly viscous substances and at 4 rev./min.. The mucilages all have a _pH value of 7.

55

60

a mixed polymer is produced.

The reaction is carried out at 50 ° C. in a closed reaction vessel in the absence of oxygen. The polymerization time is 18 hours. The mixed polymer is isolated by filtration or centrifugation and dried in vacuo over solid KOH at 50 ° C. The cross-linked copolymers of polyacrylic is then mixed with distilled water to an aqueous mucilage having a _pH value of 7, are measured in the following viscosities.

% Tetraallylsilane 1.5% Viscosities in cP 0.5% 0.25% in the polymer 79 1.0% 21 9 0.5 128 38 44 26th 1.0 232 60 131 80 2.0 500 154 195 29 3.0 500

The slimes are as clear as water, the gels stringy when the tetraallyl acid content is low and stringy when the content is higher Tetraallyl acid content briefly. Similar copolymers are obtained when equimolar amounts of other alkyl vinyl ethers, such as ethyl vinyl ether, propyl vinyl ether and butyl vinyl ether used in place of methyl vinyl ether will.

Example 6

Following the procedure of Example 5, mixed polymers of maleic anhydride, isobutylene and tetraallylsilane are prepared. The weight ratio of maleic anhydride to isobutylene is kept constant at 63.5 and 36.5; the content of tetraallylsilane varies between 0.5 and 3.0 parts / 100 TeUe of the mixture of anhydride and isobutylene. Benzene is used as the diluent and 1% benzoyl peroxide is used as the catalyst. The copolymers of this example have properties similar to those of Example 5. For example have slimes from the copolymers of maleic anhydride, isobutylene, and 1% tetraallylsilane at a _pH value of 7 and at a concentration of 1.5, a viscosity of 100,000 cP, at a concentration of 0.5 a viscosity of 40,000 cP, at a concentration of 0.06 a viscosity of 1920 cP. All slimes are clear and extremely stable at normal and higher temperatures.
■ ο., · ,, ", -" ι 7

Copolymers of maleic anhydride, isobutylene, acrylic acid and tetraallylsilane are prepared by the method of Example 5. The proportions of maleic anhydride, isobutylene and acrylic acid in this example are kept constant at 57.25 parts, 32.75 parts and 10 parts, respectively, while the tetraallylsilane content is between 0.25 and 1.5 parts per 100 parts of the mixture of the others Monomers fluctuates. The dried copolymers are fine white powders. Aqueous mucilages of 1.5% tetraallylsilane containing copolymers have has an excellent viscosity at a _pH value of 7. For example, mucus at a concentration of 1.5 ° / ₀ of copolymers have a viscosity of 108,800 cP, at a concentration of 1 % a viscosity of 86 400 cP and at a concentration of 0.125% a viscosity of 6 400 cP. These copolymers divide into 2 to 5 minutes completely when stirred into dilute NaOH solution and yield gums with a p _H value of the 7th

Example 8

Copolymers of maleic anhydride, styrene, acrylic acid and tetraallylsilane are prepared by the method of Example 5. The ratio of maleic anhydride, styrene and acrylic acid is kept constant at 43.5, 46.5 and 10 parts, while the amount of tetraallylsilane fluctuates between 0.25 and 1.0 part / 100 part of the mixture of the remaining polymerizable ingredients. These copolymers are produced at 50 ^° C. in the absence of air using benzoyl peroxide as a catalyst. Aqueous mucus these mixed polymers with a _pH value of 7 are usually somewhat short. Has a typical mixed polymer of this type with a content of 0.5 ° / ₀ tetraallylsilane at a concentration of 1.5% and a viscosity of 95 200 cP at a concentration of 0.5, a viscosity of 35,600 cP at a concentration of 0.125 ° / ₀ a viscosity of 1120 cP.

Example y

Mixed polymers are produced from the following approach:

Acrylic acid (98 to 100% purity) 100.

Tetravinylsilane variable

± Senzoyl peroxide ^, U

The polymerization time is 2 to 18 hours at 50 ^° C. in closed containers in the absence of oxygen. The yields are quantitative. Aqueous mucilages with a _pH value of 7 are manufactured in 3 to 5 minutes after the addition of the copolymer to the aqueous alkali.

° / ₀ tetravinylsilane
in the polymer

0.0005

0.5

1.0

2.0

3.0

Viscosities in cP

1.5%
concentration

240

40,000

88,000

177,600

276,200

0.5 »/"
concentration

60

10,000

40,000

89,800

106,400

0.25 ° / ₀
concentration

0.125 ° / "
concentration

20th

3,000
28,800
48,000
38,400

1,600
20,800
20,800
10,400

All slimes are clear as water and extremely resistant to being swollen by ions.

Example 10

Using the method of Example 9, copolymers are prepared from methacrylic acid and tetravinylsilane. Copolymers with a high content of tetravinylsilane thicken water at a _pH value of about 7. For example, a mucus from a prepared in benzene at 70 ⁰ C and the benzoyl peroxide mixed polymers of methacrylic acid and 10% tetravinylsilane a viscosity of 20 cP at a concentration of Mixed polymers of 1.5%. In contrast, neither hydrolyzed with acid nor with alkali copolymers of 90% methacrylate and 1% tetravinylsilane in water at a _pH value of 7 and a concentration of 1.5% have a comparable viscosity.

silane used. The copolymers containing 1% tetravinylsilane has as an aqueous slime containing 1.5% of the copolymer, at a _pH value of 7, a viscosity of 37,000 cP at a concentration of 0.12, a viscosity of 1,600 cP and at a Concentration of 0.015% a viscosity of 160 cP.

Example 12

A single change is made in the polymerization batch of Example 5, namely tetravinylsilane is used for the tetraallylsilane. The copolymers are worked up in the manner described and quantitative yields are obtained in each case. The mucus containing 1.5% of the copolymer of maleic anhydride, methyl vinyl ether and 2% tetravinylsilane has, at a _pH value of 7, a viscosity of 2400 cP.

Example 11 Example 13

The composition of Example 4 is used. In the batch of Example 6, tetravinylsilane is used

applies, but instead of tetraallylsilane tetravinyl- 70 is used instead of tetraallylsilane. The mixed polymer

15 16

is isolated in quantitative yield. A 3 ° / ₀ tetra- in a 4% salt solution had a viscosity of 2400 cP. vinylsilane-containing polymer obtained in a natural rubber such as tragacanth gum, concentration of the copolymer of 5%, a fat, a 4% saline solution gives at the same polymer clear mucus with a _pH value of 7, a concentration only a negligible viscosity .

Has a viscosity of 140 cP. 5 _,. . . " _N

Example 19

Example 14 Tetramethallylsilane is similar to TetraaUylsilan as a comparison

Mixed wetting agents are prepared according to the method of Example 7, if they are present in proportions of 0.25 to 3% with polymers of maleic anhydride, isobutylene, acrylic methacrylic acid, acrylic acid and acetic anhydride, acid and 0.25 to 1.5% tetravinylsilane. The io maleic anhydride and methyl vinyl ether, maleic acid copolymers form aqueous mucilages with an anhydride, isobutylene and acrylic acid and Maleinsäurep _H value of 7. 1% tetravinylsilane containing anhydride, styrene and acrylic acid is polymerized, such as mixed polymers has, at a concentration of 1.5 ° / _{0 is described} in Examples 3, 4, 5, 7 and 8, respectively. A viscosity of 36,800 cP, at a concentration of 0.5% maleine, a viscosity of 20,000 cP and at a 15 acid anhydride, methyl vinyl ether and 3% tetramethallyl concentration of 0.015 ° / _0, a viscosity of 20 cP . silane. It has in a _pH value of 7 in water at a These polymers have an excellent ion Mischpolymerisatkonzentration of 1.5% a Viskobeständigkeit; Solid substances, such as coarse sand, remain at 172,800 cP at a concentration of 0.5%. Suspend evenly in such a slime for a long time - a viscosity of 88,000 cP and at a concentration. 20 tration of 0.125% a viscosity of 20 00OcP, example 15 while a copolymer of maleic anhydride,

Styrene, acrylic acid and 1% tetramethallylsilane in the form

The copolymers of this example differ from an aqueous slime at a concentration dea

of those of Example 8 in that tetravinylsilane copolymers of 1.5% have a viscosity of 72,500 cP,

is used in place of TetraaUylsilan. The mixing 25 at a concentration of 0.25% has a viscosity of

are all excellent polymeric thickeners having 2,400 cps at a _pH value of 7,

medium for water. The best features as to.

The viscosity and concentration are mixed polymers from example ZU

Maleic anhydride, styrene, acrylic acid and 1% tetra-dimethallyldimethylsilane and divinyldimethylsilane are

vinylsilane, which at a concentration of polymer 30 is slightly less effective than that in the preceding

crosslinking agents mentioned by 1.5% in distilled water at a _pH value examples. If they are in

of 7 have a viscosity of 480 cP. The thickening amounts of 0.25 to 3% containing carboxyl groups

Effectiveness of polymers of this type is even when the monomers are polymerized, they give rise to

Copolymers containing less than 0.25% tetravinylsilane but crosslinked copolymers, as can be seen from it,

included, good. 35 that copolymers of acrylic acid and 0.5% Divihyl-

Example 16 dimethylsilane with a concentration of the mixed poly-

kidneys of 1.5% have a viscosity of 14OcP,

Mixture produced according to the method of Example 1 while a copolymer of acrylic acid and 3%

polymers of acrylic acid and 0.5 to 3% triallylmethyl-dimethallyldimethylsilane a viscosity, determined in

silane are excellent thickeners for water 40 Brookfield viscometers with special spindle for high-

at a _pH value of 7. The viscosity of the aqueous viscous substances, of 69 in distilled water at a

Mucilages from copolymers of acrylic acid and 0.5% _pH value of 7 at a concentration of the mixing

Triallylmethylsilane fluctuate from 4800OcP with a polymer of 1.5%.

Concentration from 1.5% up to 800 cP at a concentration. .

tration of 0.015%. Such slimes hold solids 45 Example Zl

particles, such as titanium dioxide and carbon black, in copolymers of acrylic acid and 0.5 to 3% tri

Water, even with very low copolymers, methylvinylsilane, are excellent thickeners

concentrations, suspended. for water systems. For example, has a mixed polymer

. - ₁₁₇ from acrylic acid and 3% trivinylmethylsilane as aqueous

.Example 1 / _g0 gchleim at a _pH value of 7 and, in a concen-

Following the procedure of Example 1, a mixture of 1.5% will have a viscosity of 12,800 cP, in one

Acrylic acid and 0.5% to 5.0% diahyyldimet] ayl concentration of 0.5% has a viscosity of 2400 cP

silane and mixed poly- and in a concentration of 0.062% a viscosity according to the method of Example 5

mers from maleic anhydride, methyl vinyl ether and 32OcP.

0.5 to 3% diallyldimethylsilane produced. The effective 55.

Samples thickeners result in example ZZ in both cases

Mixed polymers containing 1 to 3% diallyldimethylsilane crosslinked carboxyl groups

contain. the copolymerization of diallyldivinylsilane with

Beis -ei jg containing one or more carboxyl groups

6o monomers are extremely effective thickeners

Mixed polymers made from acrylic acid and 0.5 to 3% tetra-medium and are highly resistant to

MethaUylsilan are in benzene at 50 ⁰ C in the presence of ionic deswelling. For example, have mixed polymers

of 2% benzoyl peroxide according to the method of acrylic acid and 2% diallyldivinylsilane for one

game 1 made. Such copolymers are made from a concentration of 1.5% a viscosity of 57 600 eP,

drawn thickeners for water, even in 65 at a concentration of 0.125% a viscosity

Presence of large amounts of salt. A 1% aqueous solution of 19,200 cP and at a concentration of 0.031%

Slime of a mixed polymer of acrylic acid and 2% has a viscosity of 3600 cP in distilled water

Tetramethallylsilan has at a _pH value of 7 in a _pH value of 7. The resistance to ion

2% saline solution has a viscosity of 8QOOcP, in one it follows from the fact that a 1% strength aqueous

3% saline solution has a viscosity of 4000 cP and 70 mucus with a p ^ value of 7 in a 1% strength

NaCl solution has a viscosity of 2480OcP, in one 2% NaCl solution has a viscosity of 13,600 cP, in a 3% NaCl solution a viscosity of 7,200 cP and has a viscosity of 4000 cP in a 4% solution.

Example 23

Cross-linked carboxyl-containing copolymers containing from 0.5 to 3% and 0.5 to 3% Tetraallyl- tetravinyl German, are extremely stable when they are aged in water at a _pH value of 7 at higher temperatures a longer time. This is an important property for applications where long shelf life or resistance to high temperatures is required. To illustrate this property, a 0, l% aqueous mucus with a _pH value of 7 from a mixed polymers of acrylic acid and 1% Tetraallylgerman was aged for 1 month at 65 ° C in a closed container. The viscosity of the slime was 12,000 cP at the beginning and at the end, ie there was no degradation of the copolymer. A 3% aqueous slime made from gum tragacanth with an initial viscosity of 42,000 cP and aged under the same conditions had a viscosity of only 2600 cP after aging at 65 ° C. for 28 days.

Mixed polymers of methacrylic acid and 0.5 to 6% tetraallylgerman are good thickeners for water, have excellent ion resistance and age well at high temperatures. An aqueous mucus from a mixed polymers of methacrylic acid and 2% Tetraallylgerman with a _pH value of 7 was in a concentration of 1.5% and a viscosity of about. 20,000 cP and a viscosity of 520 cP at a concentration of 0.062%. An aqueous mucus from a mixed polymer from maleic anhydride, methyl vinyl ether and 3% Tetraallylgerman has in at a _pH value of 7 and a concentration of 1.5% and a viscosity of 209 60OcP, at a concentration of 0.125% and a viscosity of 9600 cps, and a concentration of 0.062% a viscosity of 560OcP. An aqueous mucus from a mixed polymers of acrylic acid and 1% tetravinyl German with a _pH value of 7 was at a concentration of 1.5% and a viscosity of 25,600 cP at a concentration of 0.5% and a viscosity of 7800 cps, and at a concentration of 0.125% a viscosity of 200OcP. All copolymers form water-clear slimes.

Example 24

Mixed polymers of acrylic acid and 0.5 to 3% tetrallyl tin, acrylic acid and 0.5 to 3% tetravinyltin and acrylic acid and tetraallyl lead are excellent Thickener for water and just as stable as the corresponding German polymers. Mixed polymers Maleic anhydride, methyl vinyl ether and 0.5 to 3% tetravinyl tin retain their thickening effect over a wide range. A 1.5% slime one 1% tetravinyl lead containing copolymers has a viscosity of 4000 cP, a slime made of a 2% Tetravinyl-containing copolymers have a viscosity of 86,200 cP and a slime made from a copolymer with a content of 3% tetravinyl lead a viscosity of 131,200 cP. Mixed polymers of acrylic acid and tetraallyl lead have comparable properties.

Example 25

Mixtures of the crosslinking agents useful according to the invention often produce properties as good or better than a crosslinking agent alone. To illustrate, a number of crosslinked copolymers are prepared from acrylic acid with combinations of tetraallylsilane, tetraallylgerman and tetravayl tin according to the instructions of Example 1. The viscosity of aqueous mucilages of these copolymers are measured in a p _H range 6-8 and are listed in the table below.

Crosslinking agents

Tetraallylsilane ...
Tetraallylgerman
Tetravinyl tin ..

Percentage of crosslinking agent

in copolymers
AlBIClD

0.5
0.5

0.5
0.5

0.5
0.5

0.35
0.35
0.35

concentration
in the slime A. Viscosities
BIC 67.200
30,400
12,800 D. 1.5%
0.5%
0.125% 192,000
139,000
8,000 83.200
52,800
16,000 105,600
72,000
11.200

All of the mucilages are clear and stable as they age.

Example 26

This example is the use of a monomer other than one containing carboxyl groups Monomers in conjunction with a carboxyl group-containing monomer and a crosslinking agent described. A number of copolymers made from acrylic acid, acrylonitrile and tetraallylsilane are being investigated. The copolymers are in benzene at 50 ° C with 2% benzoyl peroxide according to that described in Example 1 Process made. An amount of 1% tetraallylsilane is constantly used, and the weight ratio of acrylonitrile to acrylic acid fluctuates between 90:10 and 75:25.

Weight ratio
of acrylonitrile
to acrylic acid

90:10
85:15
80:20
75:25

Viscosities of the aqueous
Slimes

1.5%

1.0%

0.5%

7.320

33,200

104,000

129,600

2.820

7,600

2,200

36,000

20th

40

200

300

Excellent swellable copolymers are obtained even with an acrylonitrile content of less than 75%. Even other hydrophobic monomers such as styrene, vinyl acetate, vinyl chloride, etc., or mixtures thereof, in place of Acrylonitrile results in hydrophilic copolymers with comparable properties.

Claims (1)

Patent claim Process for the production of crosslinked copolymers, characterized in that a monomeric, polymerizable, α, jö-unsaturated lower aliphatic carboxylic acid, especially acrylic acid, which can contain up to 90% of another unsaturated monomer copolymerizable with it, with 0.0005 to 20% of a polyalkenylated element of group IV of the periodic system, preferably in an inert, practically anhydrous organic liquid at 0 to 100 ^° C., especially at 20 to 90 ^° C., in the absence of oxygen and with the assistance 009 590/444 19 20 a free radical-forming catalyst mixed substance radical with 1 to 10 carbon atoms, η a number of 2 is polymerized, the polyalkenylated element up to 4 and M an element of the IV. Group of the Perio- has the following structure: dischen system with an atomic weight of little (Y) - ^ M- (R) _n,. at least 28 is. in which R is a terminal unsaturated alkenyl radical. with 2 to 4 carbon atoms, Y a saturated hydrocarbon USA.-Patent No. 2,628,246. © 009 590/444 8.60