DE2633294A1 - Crosslinked block-copolymer prepn. - by reacting a di:isocyanate with the reaction prod. of a di:hydrazide, a bis-acetoacetamide and opt. a di-amine - Google Patents

Abstract

Unsatd. crosslinked block copolymers contain 100-30 wt.% units of formula -NHCOMe = CHCOH-A-NHCOCH=C(Me)NHNHCOO-D-OOCNH- (I) and 0-70 wt.% units of formula -NHC(Me)=CH-CONH-A-NHCO-CH=C(Me)NH-B-(IIe in which 1-70% of enamine gps. are crosslinked. The crosslinked enamine gp. are of formula (III). In the formulae, A and B are alkylene, arylene, polyalkylarylene or diarylenealkylene and D is an aliphatic polyether polyester or polycarbonate. X is 2-12C aliphatic, 6-14C aromatic or a 7-16 aliphatic-aromatic gp. The copolymer has good mechanical and optical properties e.g. low brittleness, high strength and transparency and it may be used as film, fibres mouldings, seals or coatings.

Description

Cross-linked, unsaturated block polyamides

The invention relates to novel, crosslinked polymeric compounds and their use as thread, fiber, film and coating material.

It is known that molded articles produced from uncrosslinked polymers like threads and foils under hot / wet conditions often do not have the desired dimensional stability own; in addition, sealants, films or lacquers generally consist of uncrosslinked Polymers have a lower resistance compared to materials made from cross-linked polymers for example against solvents.

Therefore efforts are made to obtain crosslinked polymers.

Technologically important for the usability of a network from polymeric plastics is what makes the crosslinking reaction in certain process engineering Can trigger processing steps in a targeted manner and it is guaranteed that the crosslinking speed and crosslink density due to influences of temperature, concentration and chemical Structure of the crosslinking component can be varied over a wide range.

This is the only way to avoid uncontrolled networking, for example, those with too high a degree of crosslinking and often adverse effects on the mechanical properties (such as excessive brittleness) of the consumer goods connected is.

It is known that isocyanates can be added to enamines. This synthesis is frequently used synthetically in low molecular weight chemistry (compare, for example, S. Hünig, K. Huebner, E. Benzig, Chem. Ber. 95, 926 (1962)). The addition can be represented by the following simplified formula scheme: This reaction also succeeds with linear polymers with enamine structures in the polymer chain like them. e.g. by polycondensation of bis-acetoacetamides of the formula (1) CH3COCH2CONH-A-NHCOCH2COCH3 (1) in which A stands for an alkylene, arylene, polyalkylarylene or a disarylenealkylene radical, with dihydrazide compounds of the general formula (2) NH2NHC00-D- 00CNHNH2 (2) in which D is the radical of an aliphatic polyether, aliphatic polyester or an aliphatic polycarbonate, optionally with the use of diamino compounds of the formula (3) NH2-B-NH2 (3) in which B is an alkylene or arylene -, Polyalkylenarylen- or Disarylenalkylenrest can be obtained.

The invention therefore relates to unsaturated, crosslinked polymers, 100-30% by weight, preferably 100-50% by weight, of structural units (Z) and to 0-70% by weight, preferably 0-50% by weight, of structural units (Y) composed, the enamine groups of which are 1 to 70% as crosslinked groups of the following structure The molecular weight of the uncrosslinked polymers, determined with the aid of gel permeability chromatography, is between 5,000 and 40,000.

As starting substances for the production of the polymers according to the invention the following compounds are suitable: (1) bis-acetoacetamides: CH3COCH2CONH-A-NHCOCH2 COCH3 (1), which e.g. either from the corresponding diketene and diamines according to Houben-Weyl: Methods of organic Chemie, Vol. VII / 4, page 236 and according to Ann. Rept.

Shionogi Research Lab. No. 5, 44 (1955) or from acetoacetic esters and Diamino compounds, e.g. according to Knorr, Ber. German Chem. Ges. 17, 545, (1884) preparative are easily accessible. The radical A preferably stands in the general formula (1) for an alkylene radical with C2-C12 for an arylene radical with C6-C12, for a polyalkylenearylene radical with C8-C16, or a bisarylene alkylene radical with -C13-C16, e.g. B. the structure -C6 H4-CR2-C6H4-, in which R stands for H or CH3.

The following compounds are particularly preferably used: (2) Diol-bis-carbonic acid ester hydrazides: NH2NHCO0-D-00CNHNH2, which e.g. can be represented according to DOS 1 593 864 and where D is the remainder of an aliphatic polyether, such as polytetrahydrofuran, Polypropylene oxide, polyethylene oxide, an aliphatic polyester, as e.g.

by polycondensation of alkylenediols with alkylenedicarboxylic acids or the residue of an aliphatic polycarbonate such as alkylenediol polycarbonate means.

The molecular weights of the introduction of the group D in the invention Polyethers, polyesters and polycarbonates used in polymers range between 200 and 6000, preferably-between 1000 and 4000; possibly the (3) Diamino compounds: NH2-B-NH2, where B is preferably an alkylene radical with C2-C12, an arylene radical with C6-C14, for a polyalkylenearylene radical with C8-C16 or a Bisarylenalkylenrest with C13-C164 such. B. a residue of the structure with -C 6H4 -CR2-C 6H4 -with R2, H or CH3. Ethylenediamine, propylenediamine, Pentamethylene diamine, hexamethylene diamine, phenylene diamine, p-aminomethylene benzylamine, Napthylenediamine or 4,4'-diaminodiphenylmethane and (4) organic polyisocyanates X- (NCO) x, in which X is an aliphatic radical with C2-C12, an aromatic Radical with C6-C14, an aliphatic-aromatic radical with C7-C16 and x is a is an integer from 2-3, preferably 2, stands.

Preference is given to polyfunctional isocyanates, such as hexamethylene diisocyanate, Trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, 1-methyl-2,4-diisocyanatocyclohexane, 1-isocyanatomethyl-5-isocyanato-1, 3,3-trimethylcyclohexane, 4,4'-diisocyanato-di-cyclohexylmethane, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, toluylene diisocyanate, m-xylylene diisocyanate, 1,3,5-triisopropylbenzene-2,4-diisocyanate, 1,5-naphthylene diisocyanate, diphenylmethane-4,4-diisocyanate, 2,2-bis- (4-isocyanato-phenyl) -propane and 4,4'-4 "-triisocyanatotriphenylmethane are used.

The polycondensation of the uncrosslinked polymeric compounds is preferably carried out so that equimolar amounts of the reaction components optionally in the presence of a solvent with a T of 20-2000C, preferably at 20-1400C, to react.

The water of reaction formed during the polycondensation must be included be removed from the reaction mixture as condensation progresses; a preferred one Embodiment of the separation of water is that either in the presence water-binding agents such as anhydrous calcium sulfate, calcium aluminate, silica gel, Sodium sulfate works or the water of reaction is removed by distillation condensed in vacuo, or the water by azeotropic distillation with a separates suitable solvent as a so-called "tractor".

The condensation runs quickly, quantitatively and with practically no side reactions, if you work in the presence of catalytic amounts of acids in amounts of 10 up to 300 ppm, based on the total amount by weight of the reaction condensation partners used, are used as preferred catalysts be mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, Sulphonic acids such as p-toluenesulphonic acid, carboxylic acids such as acetic acid, formic acid and called acidic ion exchange resins.

The polycondensation can take place in the presence or absence of a solvent such as methylene chloride1 chloroform, dichloroethane, tetrachloroethane, dimethylformamide, Dimethyl sulfoxide, hexamethylphosphoric trisamide, tetramethylurea or their Mixtures are carried out.

The crosslinking of the polymers, preferably after shaping, takes place at temperatures from 20 to 1600 ° C., preferably from 20 to 1000 ° C., in the absence or presence of the solvents mentioned instead.

For this purpose, the diisocyanates can preferably be used in the following weight ratios based on built-in bis-acetoacetamide, the following are used for crosslinking: parts by weight of bis-acetoacetamide built into the polymer = 1 to 70.

Parts by weight of diisocyanate Through the selection of the most diverse known, different reactive diisocyanates, by changing the amount of diisocyanate, based on bis-acetoacetamide built into the polymer, as well as by varying the Crosslinking temperature, it is procedurally possible without difficulties Crosslinking speed and crosslinking density in wide ~ areas to vary; aromatic, sterically unhindered diisocyanates, such as naphthylene diisocyanate, a practically instantaneous crosslinking of, for example, dissolved ones at room temperature Polymers, while aliphatic secondary or tertiary isocyanates hours or days at elevated temperatures.

With the help of these various possibilities of influence one can practically set any crosslinking speed desired in terms of application technology; so can for example to improve the shrinkage behavior of threads or foils fast cross-linking may be necessary, while in the paint area or at Sealing materials require slow crosslinking, the so-called "hardening" will.

When producing moldings from the polymers according to the invention the procedure is preferably such that, for example, to produce crosslinked Threads or cross-linked cast films, the polymer solutions in the required quantities Mixes isocyanate, uses it to produce the threads or foils and subsequently one Crosslinking, for example by heating, carried out.

Another way of networking is to have the Polymer solution with masked isocyanates, such as (bis- (N, -N-dimethyl-2-hydroxypropylamine) -adipimid) (compare DOS 2 508 783), added, and the crosslinking reaction by heating executes. The use of masked isocyanates thus enables production of one-pot mixes that are stable at room temperature, the at Cross-link heating. In this process route, the crosslinked, according to the invention Polymers are processed into seals, couplings, pressed parts, coatings.

Another object of the invention are therefore moldings from the polymers according to the invention, preferably threads, fibers, films, seals or Paintwork.

These moldings are characterized by very good mechanical and optical properties Properties such as low brittleness, good strength and transparency the end.

The parts given in the following examples relate on weight unless otherwise noted.

The specified limiting viscosity numbers t J were at 250C in dimethylformamide (DMF) and are given in dl / g.

Example 1 a) A mixture of 106.7 -75 parts by weight of polytetrahydrofurandiol-bis-carbonic acid ester hydrazide with a molecular weight of 2135, 85.2 parts by weight of N, N'-diacetoacetyl-hexamethylene-diamine, 0.005 parts by weight of p-toluenesulfonic acid and 600 parts by weight of chloroform are 1.5 Heated to the boil for hours, the water of reaction formed by azeotropic - Distillation with chloroform is removed from the reaction mixture.

Then 29 parts by weight of hexamethylenediamine are added and the mixture is boiled 1/2 hour under reflux and then distilled off for 8 hours chloroform / water, with by continuing to add absolute chloroform to the reaction mixture for this it is ensured that the concentrations of the reactants remain almost constant. The highly viscous solution thus formed can be diluted with chloroform to form films and threads are processed that have a softening point of approx.

-170 ° C. The polycondensate has a limiting viscosity number t £ 7DMF of 0.48.

b) - 100 parts by weight of a 15 strength solution of the polycondensate from example 1) in chloroform are mixed with 1 g ~ m-xylylene diisocyanate at room temperature. While stirring, a gel forms from the solution within a few minutes, which is im Vacuum drying. The remaining polymer is in all organic Solvent insoluble.

c) 100 parts by weight of a 15% solution of the polycondensate a) in chloroform are cast into a film with a layer thickness of 100 μm. This slide will in a 10 solution of diphenylmethane-4,4'-diisocyanate in dichloroethane for 2 minutes washed, then rinsed with 1,2-dichloroethane and then dried at 50.degree.

The film has only a slight stretch; it is insoluble in all organic solvents and transparent.

d) 100 parts by weight of a 15% solution of the polycondensate a) in chloroform 1 part by weight of bis (N, N-dimethyl-2-hydroxypropylamine) adipimide is added. A film cast from this mixture, which is dried at 400C and then 1 minute heated to 1400C, is practically insoluble in all organic solvents; the film is crosslinked and transparent. For example 2 a) A mixture of 110 parts by weight Polyhexane-1,6-diol carbonate-diol-bis-carbonic acid ester hydrazide with a molecular weight of 2200, 85.2 parts by weight of N, N'-di-acetoacetylhexamethylenediamine, 0.005 parts by weight Polyphosphoric acid and 700 parts by weight of methylene chloride are boiled for 1.5 hours. (For the removal of the water of reaction, see Example 1)). Then add 25.5 Parts by weight of pentamethylenediamine are added and the condensation then continues as in the example 1) continued. A highly viscous solution has formed after a reaction time of 14 hours formed from which the polymer has an intrinsic viscosity DMF of 0.47, can be isolated by evaporation of the solvent.

b) 500 parts by weight of a 20% strength solution of the polycondensate a) in dimethylformamide are at room temperature with 10 parts by weight of a 10% solution of 1,4-cyclohexyl diisocyanate stirred in dimethylformamide. One poured from this mixture and dried at 500C Foil is practically insoluble in all solvents and transparent.

Example 3 a) A mixture of 106.75 parts by weight of polytetrahydrofurandiol-bis-carbonic acid ester hydrazide with a molecular weight of 2135, 11.4 parts by weight of N, N'-bis-acetoacetylethylenediamine and 0.004 part by weight of p-toluenesulfonic acid are added with thorough stirring in vacuo 1000C condensed, the water of reaction being removed by distillation; After 3 hours the temperature is increased from 120 ° C. for one hour. After the reaction mixture has cooled down At room temperature a rubber-like mass has formed, which in chloroform is soluble and has an intrinsic viscosity E5 2 of 0.31.

b) 100 parts by weight of the product of the polycondensate a) with 2 g 1,3 1,3-phenylene diisocyanate added. This mixture is now processed at room temperature and 50 revolutions per minute for one hour in the Brabender Plastograph. The following overview shows the dependence of the torque of the plastograph on the processing time: Torque 99 110 180 205 215 (Kpm) Processing time 5 10 20 40 60 (min) As you can see there is an increase in the viscosity of the product as a function of time Example 4) caused by crosslinking with a diisocyanate.

Claims (2)

Claims: 1. Unsaturated, crosslinked polymers, 100-30% by weight of structural units (Z) and from 0-70% by weight of structural units (y) composed, the enamine groups of which are 1 to 70% as crosslinked groups of the following structure. A and B are identical or different for an alkylene> arylene, polyalkylarylene or a disarylene alkylene radical and D is the radical of an aliphatic polyether, aliphatic polyester or an aliphatic polycarbonate. 2. Transparent moldings, in particular threads, fibers, foils, seals or coatings made from polymers according to claim 1.