DE1061071B - Process for the production of curable, rubber-elastic condensation products containing urea and urethane groups - Google Patents

Description

The invention relates to the production of curable, rubber-elastic, urea and urethane groups containing condensation products.

According to the invention, the procedure is that in an aqueous medium and in the presence of an acid-binding agent By means of a polyalkylene ether ^, ct / -bis- (chloroformic acid ester) at temperatures from about Q to 30 ° C, whose polyalkylene ether chain is interrupted or by sulfur atoms or arylene or cycloalkylene radicals Aryl or cycloalkyl radicals can be substituted, or a bis (chloroformic acid ester), which is terminated by a Hydroxyl group-containing polyesters made from aliphatic, cycloaliphatic, aromatic or araliphatic dicarboxylic acids and glycols, or a cOjCü'-Bis ^ chloraineic acid ester), which is derived from a long-chain, saturated or unsaturated one, optionally with halogen atoms or monovalent ones Hydrocarbon radicals derived from substituted co, a> '- glycol is, in each case a bis (chloroformic acid ester) with a molecular weight of 875 up to about 10,000 as well as phosgene and a diprimary aliphatic, cycloaliphatic or aromatic diamine mixed with one another, the molar ratio of the bis (chloroformic acid ester) to phosgene from 1: 0.15 to 1:20 and as a molar ratio of the diamine to Molecular sum of bis (chloroformic acid ester) and phosgene a value of 0.3: 1 to 2.0: 1 can be used.

In a typical and preferred embodiment According to the invention, condensation products are obtained by adding a mixture of 1 mol of a polytetramethylene ether-bis-chloroformic acid ester having a molecular weight of at least 875 and 0.15 to 10 moles Phosgene to a vigorously stirred, 2,4-toluenediamine, an acid acceptor, e.g. B. sodium hydroxide, and an acid-resistant emulsifier, e.g. B. the aqueous medium containing the sodium salt of the sulfuric acid ester of a higher alcohol. The educated Condensation polymer is insoluble in water. After the reaction has ended, the product is separated off from the reaction medium, washed and dried and can then optionally reacted further and cured to obtain the finished cured elastomer will. -. "

The bis (chloroformic acid esters) to be used according to the invention preferably have "molecular weights between 875 and 3500. Those here and elsewhere Molecular weights given in the description and claims are average values.

A preferred class of high molecular weight bis-chloroformic acid esters are the polyalkylene ethers-a>, a>'- bis- (chloroformic acid esters). These compounds have the formula Cl-COO (RO) _n CO-Cl, in which pure alkylene radical and ή denotes a whole number, the latter being large enough that the compound is a molecular process for the production of curable,

rubber-elastic, urea

and containing urethane groups

Condensation products

Applicant:

EI du Pont de Nemours and Company,
Wilmington, Del. (V. St. A.)

Representative: Dipl.-Ing. E. Prinz, patent attorney,
Munich-Pasing, Bodenseestr. 3 a

Claimed priority ":
V. St. v. America October 26, 1953
October 11, 1954

Albert S. Carter, New Castle, Del.,
and Maurice L. Emsberger, Wilmington, Del.

(V. St. A.),
have been named as inventors

Has a weight of at least 875, which corresponds to a polyalkylene glycol ether with a molecular weight of at least 750. The alkylene radical R preferably contains no more than about 10 to 12 carbon atoms. Not all alkylene groups need to be the same. The preferred polyalkylene ether-ω, ω '-bis (chloro ameisensäureester) is o / bis (chlorämeisensäureester), which is known Polytetramethylenäther- <w as Polybutylenäthercu, Co' bis- (chlorameisensäureester).

In those containing cyclic groups. Products are the cyclic ones introduced into the polyether chain Groups preferably phenylene, naphthylene or cyclohexylene radicals or alkyl containing these radicals or alkylene substituents, e.g. B. Tohiylen-, Phenyläthylen- or xylylene residues. Using, from polyalkylene-arylene-. or polyalkylene-cycloalkylene ethercu, cü'-bis- (chloroformic acid esters) manufactured products have improved freeze resistance compared to "the corresponding non-cyclic radicals" Products. . . -

Another class of bis (chloroformic acid esters) suitable for the invention are the sulfur-containing poly mixed ethers-a), ω '-bis- (chloroformic acid esters), which are obtained by reacting phosgene with a long-chain

909 560/436

3 4

Diol can be obtained which has a plurality of sulfur amino groups in the condensation product. A

and contains oxygen atoms in the linear chain. - Large excess acts as a stopping agent, as it all

Another valuable class of bis (chloro ant —COCl groups saturated and another condenser

acid esters) are the polyester-a>, a / -bis- (chloroformation is avoided. The diamine in

acid ester), which by the action of a phosgene 5 in an amount of about 100 to 130 ° / _{0 of} the theoretical

Excess on linear polyester with terminal stoichiometrically required amount may be present.

Hydroxyl groups are obtained. Although the reaction with the simultaneous addition of all

The primary diamine participating in the reaction is carried out three reaction participants or initially the

preferably aromatic. Typical, according to the invention, total diamine with either the phosgene or the

suitable diamines are the tolylenediamines, which can be converted into Phe- io bis (chloroformic acid ester)

nylenediamines, the alkylenediamines, e.g. B. ethylenediamine, but it is generally preferable to use a mixture of the

Tetramethylenediamine and decamethylenediamine and bis (chloroformic acid ester) and phosgene to one

cyclic diamines, ζ. B. Cyclohexyl diamine. One can aqueous, the diamine in suspension or in solution

also with mixtures, e.g. B. from 4,4'-methylene-bis-containing medium to be added. This is done in this way

(phenylamine) and heterocyclic diamines, e.g. B. Di- 15 the reaction of each of the reactants with the

aminopyridine, work. Amine hydrohalides, which are mostly diamine concurrently, and one obtains condensation

are insoluble in water, instead of diamines products with arbitrarily distributed urea and

be used. Urethane groups. For an easier implementation of the

When 1 molecule of the diamine reacts with 1 molecule of the bis it is sometimes beneficial to mix the

(chloroformic acid ester) reacts, according to the 20 bis (chloroformic acid ester) with the phosgene in one

following reaction equation to solve a urethane group ge solvent. The use of a solution

forms: means is recommended if you have a flowable

■ jvjjj ■ £ / -j ^ jj j_ ei C O O f X) O C O Cl mixture that is easy to use and

L wtt T? ' ² wtrrnn m nrnn _i_ ττπ ^{easily with the sus} p ^ension ° ^{that of the} solution of the diamine + JNH ₂ -K-JNHuUU- (A) -ULUU + MU _a; . The solvent can be _{mixed with anyone}

The reaction of a phosgene molecule with 2 molecules usually non-reactive substance, and

of the diamine results in the following reaction scheme, although preferably a hydrocarbon, z. B. toluene,

a urea group: xylene, benzene, be. A relatively fleeting one

Solvents, e.g. B. one boiling below 120 to 130 ° C,

NH ₂ - R '- NH ₂ + COCl ₂ + NH ₂ - R' - NH _{2 3o} ^ particularly favorable, as it is easily obtained from the

-> NH ₂ -R '- NHCONH - R' - NH ₂ + 2HCl condensation product can be removed. The bis

(chloroformic acid ester), which by reaction of

The phosgene obtained in the process according to the invention with a glycol of high molecular weight condensation product therefore contains a large number of was produced, often contains excess phosgene, urethane and urea groups, which the long- 35 and you then only need the additional phosgene-chain divalent radicals of the bis- (adjust the amount of chloroformic acid so that the desired quantity of ester is obtained) and obtain the two ratios derived from the diamine, which are connected either by addition or by valued residues. The properties of the condensation- Removal of phosgene takes place. If the bis (chlorination product depends to a high degree on the formic acid ester) is completely phosgene-free, the entire relative ratio of urea to urethane bonds 40 must be added.
The amount of water used as the reaction medium is atoms are probably much more reactive than not important. However, it is expedient to use the fairly dilute solutions or suspensions contained in the urethane groups and thus active to form points at which crosslinking takes place during possibly thorough mixing and intimate contact with the subsequent curing or vulcanizing reactants without excessive expenditure of force can. If less than achievable. The aqueous suspension or solution will be 0.15 mole of phosgene per mole of bis- (chloroformic acid - expediently at a temperature between the freezing ester) are used, are kept at the point of the invention and about 30.degree. At higher temperatures, the condensation product has too few urea doors, the bis (chloroformic acid ester) tends to form hydro groups for easy hardening. If this is lyse, and there are other undesirable molar ratios of phosgene to bis (chloroformic acid side reactions also take place).

ester) exceeds 10: 1, the condensation contains The aqueous reaction medium should be a reaction product very many urea groups and would then have with the conversion of the diamine with the Bisnach a high modulus upon curing; d. i.e., it is (chloroformic acid ester) and the phosgene formed stiff. If this ratio exceeds 20: 1, the sufficient amount of an acid acceptor will de-modulate the hydrochloric acid so high that the product will hold as an elastomer. Suitable acid acceptors include is almost useless. Preferably 0.7 to the alkali metal hydroxides, e.g. B. sodium hydroxide and 3 moles of phosgene per mole of the bis (chloroformic acid ester) buffer salts, e.g. B. Salts of the alkali metals with weak used. Acids produced with these proportions, such as sodium acetate, sodium borate. These verProducts are "easy to roll and, after binding, can either be in front of the reaction mixture cure favorable elasticity and modulus. or after mixing the bis (chloroformic acid ester)

The amount of diamine used should usually be added with phosgene and the diamine. Of the

be equal to or slightly greater than that for reaction with _pH value of the reaction mixture is suitably

the bis (chloroformic acid ester) and the phosgene kept between about 3 and 9, although the reaction

requisite equivalent amount, although 50 to 200 ° / ₀ 65 also takes place at a _pH-value up to 11,

this amount can be used. If not, to ensure adequate contact between the

To obtain enough diamine to react with all —XOCl reactants, it is expedient to add

Groups available that do not hydrolyze moderately an acid-resistant emulsifier to that with

converted groups to form free carboxyl bis (chloroformic acid ester), phosgene and the

groups. An excess of the diamine results in free 70 amine not reacting.

5 6

As the condensation progresses, the diamine, 2.63 parts of sodium carbonate and 0.2 part of a reaction product separates from the aqueous suspension, in the sodium salt of the sulfuric acid ester of a long-chain which is added as a more or less loose, elastomeric alkyl alcohol in 234 parts of water. The tem-mass is formed. This mass is from the aqueous temperature is during this addition to about 10 ⁰ C geMedium z. B. removed by simply lifting and 5 hold. A rubber then separates from this solution onto an ordinary rubber wash-like polymer. After standing overnight, it is rolled. This rolling mill, which is generally used in the rubber industry to wash the polymer with water and operate at 105 ° C, consists of at least one drying.

grooved roller, which is compared to another roller - Example 4
Cherishes. The condensation product is between the two io

Rollers pressed through, with water for washing out. Another sample of the same in Example 3 of water-soluble impurities is added. If the described polytetramethylene ether-cOjCo'-bis- ^ hlordas product becomes almost neutral, it comes to a formic acid ester) produced, only with the exception, ordinary dry rolling mill with smooth rollers and that the molar ratio of bis (chloroformic acid ester) is 100 to HO ⁰ C rolled until it is dry. 15 to phosgene is adjusted to 1: 1.18. The higher The process according to the invention is explained by the phosgene content makes the composition for use in the following examples, in which parts are to be understood as capable enough so that no solvent is added to parts by weight, unless otherwise required.

is noted. 26 parts of the reaction mass, which 25 parts of poly Example 1 ²⁰ tetramethylene ether -ω, ω '- bis - (chloroformic acid ester)

and 0.95 parts of phosgene become 270 parts

450 parts of a bis (chloroformic acid ester) solution, 1.63 parts of 2,4-tolylenediamine, 3.5 parts of sodium carbonate

which consists of 221 parts of polytetramethylene ether-bis- (chlorine and 0.5 parts of the sodium salt described)

formic acid ester), 8.6 parts of phosgene, 5.33 parts of tendem water were added with vigorous stirring. the

Hydrochloric acid and 215 parts of toluene, the temperature is slowly ^{kept at about 10 0} C, and it is stirred

for 36 minutes at 10 to H ⁰ C to 20.1 parts after the addition has ended for a further 10 minutes.

2,4-tolylenediamine, 20.8 parts of sodium hydroxide, a rubber-like polymer separates out,

2.5 parts of a dry sodium salt of the sulfuric acid which was washed with water and dried at 105 ⁰ C

acid ester of a fatty alcohol and 2000 parts of water.

containing stirred solution added. The obtained 30 A second polymer is produced in the same way.

Suspension is 12 minutes at 10 to 15 ° C and, with the exception that 3.81 parts of 2,4-toluene-

Stirred for 5 minutes at 20 ° C, after which they can be used over diamine.

Let stand at room temperature overnight. During this . .

Time the elastic polymer separates into more compact Example 5

Shape. It is removed, washed with water on a 35 A sample of the same polytetramethylene ether-co ^ '- bis-rubber mill with grooved rollers and (chloroformic acid ester) as in Example 4 is produced at 105 to 110 ° C on a rubber mill with only one exception that the ratio of smooth rollers dried. Bis- (chloroformic acid ester) to phosgene to 1: 8.57 solid-like elastomers are applied in the is put. Polymers are produced from this product using essentially the same process and with the same 40. The proportions of the reaction part components obtained as described above, except that they are as follows:
however, the molar ratio of bis (chloroformic acid ester) to phosgene varies. Molar ratio of diamine to bis- (chlorine-

formic acid ester) + phosgene 0.30 1.00.

Example 2 ^

To a rapidly stirred solution of 2.29 parts

len 2,4-tolylenediamine, 5.65 parts of sodium acetate Example 6

(CH ₃ COONa-SH ₂ O), 0.29 parts of the dry Na- 255 parts of polytetramethylene glycol ether with a

trium salt of the sulfuric acid ester of a fatty alcohol molecular weight of 1000 will slowly split into 210 parts

in 155 parts of water at 25 to 26 ° C from 18.77 parts of 50 liquid phosgene is added dropwise under reflux. One lets

Polytetramethylene ether-ro, ft) '- bis (chloroformic acid ester) during the addition while maintaining the back-

and 1.23 parts of phosgene existing mixture were added. river, the temperature will rise from 8 to 22 ° C, the

The mixture is stirred for a further 10 minutes after the addition has ended. The reaction mass is stirred for 1 hour at 22 to 25 ° C.

by. A soft, viscous, curdled stirs separates out and then under a pressure of 526 mm / Hg to the

Mass off. This is heated to 30 ° C. on a rubber mill with phosgene removed, up to 1.12 mol

grooved rollers and washed on a rubber phosgene per mole of polytetramethylene-ω, ω'-bis- (chlorine-

rolling mill with smooth rollers ^{dried at 105 to HO 0} C, formic acid ester) remain.

whereby a rubber-like product is obtained. 25 parts of this mass becomes 420 parts 7.84 parts

2,4-tolylenediamine, 6.86 parts of sodium hydroxide and

Example 3 6q ^ »^ parts of water containing sodium ^{alkyl sulphate}

vigorous stirring at 10 ⁰ C added. After further

The bis (chloroformic acid ester) of a polytetrame- 10 to 15 minutes stirring, the mass is allowed to stand,

ethylene glycol ether with a molecular weight of 2940 with a polymer separating out. It will be after

is separated with a molar ratio of phosgene to bis (chlorine standing overnight, washed with water and

formic acid ester) of 0.46: 1.0. Then dried around 65 at 105 ⁰ C, using a rubber

To increase flowability, benzene is added so that like polymer is obtained
the finished mixture 70.6% bis (chloroformic acid ester),

Contains 1.04% phosgene and 28.36% benzene. ^At P ^{lel 7}

37 parts of this mixture are slowly turned into a good The bis (chloroformic acid ester) of a polytetram

stirred solution of 1.51 parts of 2,4-toluene- 70 ethylene glycol ether with an average mol-

A molecular weight of 8610 is produced, with so much phosgene being removed that 2.55 moles of phosgene per mole of polytetramethylene ether - ω, ω '- bis - (chloroformic acid ester) remain. The mass is very viscous, so benzene is added to dilute it. The final composition is 59.3% benzene, 39.6% polytetramethylene ether-w, w'-bis- (chloroformic acid ester and 1.14% phosgene.

55 parts of this material slowly becomes a well-stirred mixture of 125 parts of water, 1.2 parts of 4-methyl-1,3-diaminocyclohexane, 1.5 parts of sodium hydroxide and 0.3 parts of sodium allyl sulfate about 10 ° C added. The mass is stirred for a further 10 to 15 minutes and then left to stand. It part a rubber-like mass. After several hours it is removed from the liquid with water washed and then dried at 105 ° C.

Example 8

A polytetramethylene ether - ω, ω '- bis - (chloroformic acid ester) is produced from polytetramethylene glycol ether with an average molecular weight of 3,100. The ratio of bis (chloroformic acid ester) to phosgene is adjusted to 1: 1.58.

25.25 parts of this mixture, which contain 24.09 parts of polytetramethylene ether - ω, ω '- bis - (chloroformic acid ester) and 1.16 parts of phosgene, are slowly added to a rapidly stirred solution of 4.24 parts of decamethylene diamine, 4 parts of sodium hydroxide, 1 part of sodium alkyl sulfate and 16 parts of tetrahydrofuran in 310 parts of water were added at room temperature. The polymer forms in the form of a fine emulsion, which slowly coagulates to form a solid polymer over a period of several days. The polymer is washed with water and dried at 105.degree.

Example 9

A mixture of phosgene and bis (chloroformic acid ester) is prepared as in the preceding examples, using a polytetramethylene glycol ether with a molecular weight of 2,630. Analysis of the mixture reveals 1 mol of polytetramethylene ether -ω, ω '- bis - (chloroformic acid ester) to 1.41 mol of phosgene. Separate portions of this mixture are then reacted with diamines in the same manner as in the previous examples, the conditions given in the table below being observed.

m-tolylenediamine

Diamine

1,5-diaminonaplithalin

Benzidine

Diamine

Toluene:

Pyridine (acid acceptor)

Bis- (chloroformic acid ester) -Phosgene mixture

Reaction temperature, ° C

Molar ratio of diamine to bis (chloroformic acid ester)

+ Phosgene

Raw polymer

3.05 *
160
15th
25.45

1.18

Easy to roll,
rubbery

3.86
160
100

25.04

1.18
soft,
rubbery

4.93
200
20th

25.35
15th

1.27
tough,
rubbery

'All of these products may be available under Formation of elastomers with good physical properties can be cured.

Example 10

The bis (chloroformic acid ester) of a polypropylene glycol ether with an average molecular weight of 830 is prepared. The mixture obtained contains 1.4 mol of phosgene per mol of polypropylene ether), a / bis (chloroformic acid ester). 25 parts of this mixture containing 21.84 parts of polypropylene ether - ω, ω ' - bis - (chloroformic acid ester) and 3.16 parts of phosgene are slowly added to an aqueous solution of 8.04 parts of m-tolylenediamine, 1 part of sodium alkyl sulfate and 10 parts of sodium carbonate added in 300 parts of water. The reaction mixture is stirred vigorously during the addition, and the temperature is maintained at 8 to 1O ⁰ C. The dispersion of the finely divided polymer converges on standing without stirring. The polymeric mass is separated off, washed with water and dried. _

Example 11

653 parts of polytetramethylene glycol ether with an average molecular weight of 2985 are slowly added to 490 parts of phosgene in a container equipped with a stirrer and reflux condenser. The temperature rises gradually from 8 to 16 ° C. during the addition. The mixture is then stirred at 16 to 17 ° C. for a further hour. The mixture is then heated under slightly reduced pressure without reflux at 30 ⁰ C until the molar ratio of phosgene to Polytetramethylenäther - ω, ω '- bis - (chlorameisensäureester) to 1.27: 1 is dropped, as determined by analysis. 176 parts of this mixture, which contain 169.1 parts of the bis (chloroformic acid ester) and 6.86 parts of phosgene, are converted into a vigorously stirred solution of 16.5 parts of m-toluenediamine, 0.9 parts of partially desulphonated sodium lignosulphonate, 76 parts Na ₂ HPO _4. ' 7H ₂ O and 97 parts of Na ₃ PO ₄ -12 H ₂ O in 1500 parts of water were added. The temperature during the addition is about 22 to 26 ° C. The polymer forms in the form of very fine particles with a diameter of less than 0.5 microns. On standing, the dispersion slowly coagulates, the precipitated polymer is filtered off, washed with water and dried.

Example 12

235 parts of polyethylene glycol ether with an average molecular weight of 1325, which are dissolved in 430 parts of toluene, are slowly added to 280 parts of phosgene dissolved in 172 parts of toluene. The reaction vessel is equipped with a stirrer and a reflux condenser for recycling evaporated phosgene. The temperature rises from 18 to 31 ° C. during the addition. The mixture is further stirred for a short time, after which you use to remove phosgene. flushed through a stream of nitrogen until an analysis shows a phosgene content of -1; 32 moles per mole of polyethylene ether ^ w '^ is ^ chloroformic acid ester), 203 parts of this 62.05 parts (polyethylene ether- ω, ω' -bis- (chloroformic acid ester), 5.58 ■ parts

9 10

Phosgene and mixture containing 135.37 parts of toluene.The general structural formula can be written as follows to a rapidly stirred solution of 6.27 parts:
m-tolylenediamine, 1.2 parts of sodium alkyl sulfate,

35 parts Na ₃ PO ₄ - 12 H ₂ O and 27 parts Na ₂ HPO ₄ - ΜΟ ^ Η ^ Ο ^ υ ^ ΗβΟ ^ Η ^ ϋ ^ Ο ^ Η,

7 H ₂ O in 550 parts of water were added. The temperature 5 where χ is high enough to give the average molar increase from 8 to 19 ° C during the addition.
Parted polymers slowly coagulate on standing. The 20 parts of a sulfur-containing polyethylene tetram

coagulated polymers are removed from the water, with ethylene glycol ethers to 140 parts of phosgene, Washed water and on a heated rubber mill as described in the previous examples, zuwalzwerk dried. After adding 8 parts of 1,3-bis-io added, and the excess phosgene is removed until (3-isocyanato-4-methylphenyl) urea per 100 parts of the molar ratio of phosgene to bis (chloro ant polymers and heating in a mold while acid ester) is 1.5. 18.2 parts of this mixture 15 minutes at 134 ° C., a soft, rubber-like product is mixed with 4.2 parts of toluene to form the mixture like fur. to make it more flowable, whereupon this slowly becomes a good

Example 13 * 5 stirred solution of 3.5 parts of m-toluenediamine,

5.6 parts of sodium carbonate and 0.1 part of ligninsulphonate 51 parts of a polyglycol ether of the following structure in 150 parts of water at from 5 to 10 ^° C. are added. That

y ν finely dispersed polymers slowly coagulate during

HO - (C ₄ H ₈ O),, .- CH ₂ - <^ V-CH ₂ -O (C ₄ H ₈ O) from _0. H-standing. After coagulation, it is washed out with water.

ao wash and then dried.

(x = 13 to 14)

Example 15

600 parts of 2-chlorobutadiene-1,3 and 154.8 parts of di-

holding, well-stirred vessel. The temethyl 2,2'-azo-bis (isobutyrate) are in 1560 parts temperature rises to about 18 ° C during the addition and 25 toluene is dissolved and heated to 88 to 90 ° C for 4.5 hours, Evaporated phosgene is condensed and then added 6 parts of 2,6-diisobutyl-4-methylphenol as Reflux condenser returned to the mass. After a short antioxidant to. The toluene is under vacuum Stirring, the mass is placed under a slight vacuum, removed, and the residue is dissolved in 1370 parts of diethyl and so much phosgene is removed that the molar ratio is dissolved in ether.

from phosgene to polytetramethylene xylylene glycol ether 30 54 parts of lithium aluminum hydride are 2740 a>, a> '- bis (chloroformic acid ester) is 1.5: 1. Parts of anhydrous diethyl ether are added, and the

25.4 parts of this mixture are heated to reflux with 4.3 parts of the mixture in order to dissolve as much toluene as possible when mixed to improve flowability. The ethereal solution of the chlorobutadiene polymer zuvon 4.13 parts of m-tolylenediamine and 6 parts of sodium is slowly added to this solution and then slowly added to a well-stirred solution, and the mixture is stirred for 2 hours under back carbonate and 0.15 part of sodium lignosulfonate in nut heated. The excess lithium aluminum hydride was added to 200 parts of water. The finely chopped polymer is made by carefully adding 155 parts of water and gradually precipitates on standing. The coagulated mass is destroyed. The mixture is washed with water by the heat of reaction and then dried, being heated strongly so that it refluxes. An extremely cold-resistant polymer is added. Add 40 then 25 ° / ₀ aqueous sulfuric acid until the

all solid is dissolved. The lower aqueous layer

Example 14 is peeled off and the essential layer is covered with

washed acid-free with saturated sodium carbonate solution,

A mixture of 549 parts of thiodiglycol in 200 then washed with water and dried. The ether parts of benzene, 405 parts of 1,4-butanediol and 13.5 parts of 45 are distilled off, 582 parts of a viscous, p-toluenesulfonic acid monohydrate are heated together in liquid polychloroprene glycol ether with a hydroxyl container, which has a Din-Stark number of 73.4, corresponding to an average template for the distillate. An azeotropic molecular weight of 1525, remains.
Mixture of water and benzene is distilled over and 170 parts of this polychloroprene glycol ether become

accumulates in the template. The slowly separating 50 to 560 parts of liquid phosgene in a benzene layer is returned to the system. After-agitator and reflux condenser equipped container from which about 146 Teüe of water have been distilled off, adds. During the addition, the temperature is a further 82.3 parts of thiodiglycol. The azeotropic up to 10 ° C. The system is subjected to a moderate vacuum. Distillation of water is continued until it sets, and so much phosgene is removed that 161.7 parts of water are removed. Towards the end of the 55 molar ratio of phosgene to the polychloroprene reaction, no more benzene is returned to the system- ω, ω'-bis- (chk> rameic acid ester) 1.5; 1 is
guided. 25 parts of this mixture become a well-mixed

The reaction mass is stirred hot with excess, stirred solution of 5.11 parts of m-tolylenediamine, aqueous sodium carbonate to neutralize the p-toluene 7.4 parts of sodium carbonate and 0.13 parts of lignin sulfonic acid. The aqueous layer is given 60 sulfonate in 250 parts of water at 9 to 12 ° C, removed, and the polyglycol ether layer is first coagulated with the finely ground polymer diluted hydrochloric acid and then with water until slowly and is separated, washed with water, neutral Washed out reaction. The product is dried with and processed into foils.
Treated activated carbon, filtered and dried under vacuum. The analysis gives: 65 Example 16

A linear polyester is known in the usual way

Hydroxyl number 77.3 way by heating 1,4-butanediol with adipic acid

Sulfur 19.9 ° / ₀ with removal of water to obtain a

Molecular weight of butylene polyadipate with a hydroxyl number

(calculated from the hydroxyl number) .. 1452 70 of 53.0, an acid number of 3.2 and a molecular

weight of 2000 manufactured. 137 parts of this polyester are slowly added to 210 parts of liquid phosgene in a container equipped with a stirrer and reflux condenser. The temperature rises from 8 to 16 ° C. during the addition. After further '$ about 30 minutes continuous stirring, phosgene is removed under partial vacuum, until the molar ratio of phosgene to bis (chlorameisensäureester) 1.28: 1. In the last stages is added to the mass of toluene, a sufficient flowability to "guarantee. The composition of the final product is 57.6 ° / ₀ of the bis derived from the polyester (chlorameisensäureestefs), 3.43% of phosgene and 38, 97% toluene. ■

35.3 parts of this mixture will be a hefty 15 " stirred solution of 3.16 parts of m-tolylenediamine, 4.6 parts of sodium carbonate and 0.15 parts of sodium lignosulfonate added in 175 parts of water at 10 to 15 ° C. A good dispersion of a granular is obtained Polymer. When standing, the polymer coagulates and is separated off, washed with water, dried and processed into foils.

• Instead of a single diamine and a single bis (chloroformic acid ester) To use for the preparation of the products according to the invention, mixtures of two or more of one or both of these compounds be used.

Rubber-elastic products obtained by the process according to the invention can, if appropriate after hardening, e.g. B. with a diisocyanate, for the production of foils, tubes, rods and other shaped pieces, Pneumatic or solid tires or parts thereof, inner tubes, belts, either from a piece of existing, layered or reinforced belts, hoses, mechanical objects, wire and cable jackets, footwear, coated fabrics, films, coating compositions, adhesives, porous structures and other products for which elastomers are suitable can be used.

According to the process according to the invention, products can be prepared which are essentially identical to those obtained by reacting the corresponding long-chain glycol with an organic diisocyanate and water in the appropriate molar proportions. The process according to the invention is extremely advantageous in that bis (chloroformic acid esters) with a high molecular weight are easier to prepare from the corresponding glycols than diisocyanates from the corresponding diamines, so that the starting materials for the process 5a according to the invention are cheaper. The process is also advantageous in that it is carried out using an aqueous, easy-to-stir slurry, while the formation of the same products by direct reaction between a "long chain glycol, a diisocyanate and a chain extender requires high performance mixing equipment.
The production of the starting materials used for the process according to the invention does not belong within the scope of the invention.

Claims (1)

Patent claims: 1. Process for the production of curable, rubber - more elastic, containing urea and urethane groups Condensation products, characterized in that one in an aqueous medium and in Presence of an acid-binding agent at temperatures from about 0 to 30 ° C a polyalkylene ether-ft) ^ '- bis- (chloroformic acid ester), whose poly- - alkylene ether chain through sulfur atoms or arylene or cycloalkylene radicals can be interrupted or substituted by aryl or cycloalkyl radicals, or one Bis- (chloroformic acid ester), that of a hydroxyl-terminated polyester from aliphatic, cycloaliphatic, aromatic or araliphatic dicarboxylic acids and glycols is derived, or a co, co'-bis (chloroformic acid ester), that of a long-chain, saturated or unsaturated, optionally by halogen atoms or monovalent hydrocarbon radicals substituted cw.cü'-glycol is derived, in each case a bis (chloroformic acid ester) with a molecular weight of 875 to about 10,000 and phosgene and a diprimary aliphatic, cycloaliphatic or aromatic diamine is stirred with one another, wherein the molar ratio of the bis (chloroformic acid ester) to phosgene is from 1: 0.15 to 1:20 and a value as the molar ratio of the diamine to the total molar amount of bis (chloroformic acid ester) and phosgene from 0.3: 1 to 2.0: 1 can be used. • 2. Process according to Claim 1, characterized in that the diamine and the acid-binding Agent-containing aqueous medium uses an acid-resistant emulsifier. 3. The method according to claim 1 and 2, characterized in that the bis (chloroformic acid ester) together with the phosgene in the form of a solution in a hydrocarbon such as toluene to the aqueous Reaction medium is added. Considered publications:
German patent specifications No. 907 599, 912 863. © 909 560/436 6.59