DE1237313B - Crosslinking of amorphous epihalohydrin polymers or copolymers - Google Patents

Description

Crosslinking of amorphous epihalohydrin polymers or copolymers The subject of the invention is a process for crosslinking amorphous epihalohydrin polymers or mixed polymers, which are made from monomeric epoxy compounds in the presence of a catalyst, consisting of the reaction product of 1 mol of an organoaluminum compound and 0.1 to 1.5 moles of a chelating agent and / or water and which have an RSV of at least 0.5, measured in a 0.1% solution of Have N-chloronaphthalene at 100 ° C. The inventive method is thereby characterized in that the crosslinking is effected with a polyamine or its salt. For making these amorphous epihalohydrin polymers and copolymers no protection is sought here.

By means of the crosslinking process according to the invention, these polymers can be converted into valuable rubber-like products.

In this document, polyamines are organic monomeric compounds understood with two or more amino groups. The amino groups can be primary, be secondary and tertiary amino groups.

Examples of such monomeric polyamines are hydrazine, aliphatic Amines such as ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine etc. up to alkylenediamines of 20 carbon atoms or more, diethylenetriamine ; cycloaliphatic amines such as melamine, piperazine, pyrazine; aromatic amines such as p-phenylenediamine, naphthalenediamine, biphenylenediamine and polymeric amines such as poly- (2-methyl-5-vinylpyridine).

Salts of the amines can also be used in place of the free amines be e.g. B. the hydrogen halide salts, where an alkaline compound such as z. B.

Calcium or barium oxide is added. Internal salts of the amines can can also be used e.g. B.

Hexamethylene diamine carbamate, and such salts can be with or decompose below the vulcanization temperature to the free amine.

The polyamine can be incorporated into the polymer in any desired manner or be added to it.

For example, the amine can be mixed with the polymer by simply grinding it be mixed evenly on a standard rubber mill. This is the amine evenly distributed through the polymer, and a uniform crosslinking is effected, when this mixture is then heated. Cold rolling processes can also be used be e.g. B. by means of rollers cooled to about 10 ° C, or the mixing can be at Room temperature or above can be carried out, in the latter case one roller is preferably slightly warmer than the other. Other methods of mixing of the amine with the polymer are known to the person skilled in the art and need not be listed here to become.

The amount of polyamine to be used is arbitrary and mainly depends on the desired degree of crosslinking. In general, about 0.5 to 10, preferably about 1 to 5% amine, based on the polymer weight, is added.

The temperature at which the crosslinking is carried out can be about vary over a wide range. The networking can take place during a few minutes Temperatures around 150 ° C or for several days at room temperature are brought about.

The temperature, however, also depends on the crosslinking agent applied polyamine.

In addition to the polyamine to be used as a crosslinking agent, also be incorporated into the substances of the reaction mixture. The one in rubber vulcanization commonly used additives, such as. B. extenders, fillers, pigments, plasticizers etc., can also be used here.

The presence of a filler and, in particular, of carbon black is advantageous and gives the best results as in rubber compounds.

From US Pat. No. 2,801,229 it is known to use Epon resins Cure polyamines, but these resins are completely different from the epihalohydrin polymers of the present invention. When epihalohydrins in the presence of organic Aluminum compounds are polymerized, the polymerization takes place via the Epoxy bonds so that the product is a polyether containing halomethyl groups that are attached to the main polymer chain. Such a polymer as it is according to The present invention is to be crosslinked, so does not contain epoxy groups, but the crosslinking is brought about by the halomethyl groups. On the other hand, the Eponharze of USA.-Patent 2,801229 by copolymerization of epichlorohydrin made with a polyhydric phenol or alcohol in an alkaline medium. the The resulting resins do not contain chloromethyl groups, but epoxy groups. That is why the hardening of such epon resins is caused by the reaction between the phenylenediamine and the epoxy groups.

The polymers to be crosslinked according to the invention are z. B. as follows manufactured. Protection is not sought for this production here.

A polymerization vessel was filled with a diluent under nitrogen and charged with epichlorohydrin. After the temperature equilibrium at 30 ° C., a Solution of the catalyst introduced. The catalyst solution had been prepared by diluting a 1 to 2 molar solution of an alkyl aluminum compound in n-heptane with ether on 0.5 molar addition of water and stirring of the solution at 30 ° C during 16 to 20 hours. After stirring the reaction mixture for 19 hours at 30 ° C the polymerization was interrupted by adding 4 parts of anhydrous ethanol. The mixture was then diluted with about 40 parts of ether, after which the ether-insoluble Polymer compound was collected and further washed with water. The polymer was if necessary cleaned by further measures. The interpolymers were made by the same process by adding ethylene oxide or propylene oxide.

Examples 1 to 4 Vulcanization was carried out by mixing on a two-roll mill (roll temperature 80 ° C.) for 5 to 7 minutes 100 parts of the polymer with the particular vulcanization formulation and subsequent vulcanization under pressure at 155 ° C. for 40 minutes. The vulcanization batch used (based on 100 parts of polymer) was: high-speed carbon black .......................... 30 sulfur ......... ...................- zinc oxide ...........................- stearic acid -Triäthylenediamine 4 Tetramethylthiuramdisulfid ..........- Mercaptobenzothiazole ..............- Water, acetone, tensile modulus, final Shore gel swelling At- solubility solubility strength 300% elongation hardness formation in toluene description game %% kg / cm2 kg / cm2% A 2%% 1 hard tough rubber 74 100 93 740 2 elastic rubber insoluble 83938033050100180 3 tough gum insoluble 21, 8 11, 2 650 37 4 tough rubber insoluble68, 28510095 Example 5 A poly (epichlorohydrin) with an RSV of 0.74 was crosslinked with hexamethylene diamine carbamate and mixed with various amounts of carbon black and neural silica, the crosslinking being carried out by heating to 150 ° C. for 40 minutes. The vulcanization approach and the properties of the vulcanizate follow: Compilation in parts I II III Polymer 100 100 100 Ruth 50-- Ruth 5- Neutral silica ........- 12, 5- Hexamethylene diamine carbamate 5 3 4 Tensile strength, kg / cm2 98 116 7, 2 100 ° / o modulus, kg / cm2 84 27, 6 4, 6 200 ° / o modulus, kg / cm2 39 300 ° /. Modulus, kg / cm2 .... 65, 4 400 ° / 0 modulus, kg / cm2 ... 106 Final elongation, ° / 0 .. 110 420 150 Shore hardness (A2) ......... 60 63 25 Volume percentage swelling High-low-rubber Solvent modulus-modulus-vulcanizate I II III Water 25 5 50 Glacial acetic acid 45 75 175 Methanol ......... 50 15 125 Ethylene glycol ..... <5 10 125 Acetone 190 210 435 Isopropyl ether 10 30 35 Toluene ............ 160 250 380 Isooctane .......... <5 <5 25 Cyclohexane ....... 5 15 25 Turpentine ......... <5 15 25 CC14 40 65 80 CS2 .............. 35 40 60

Claims (1)

Claim: Process for crosslinking amorphous epihalohydrin polymers or -mischpoiymeren, which from monomeric epoxy compounds in presence a catalyst consisting of the reaction product of 1 mol of an organoaluminum Compound and 0.1 to 1.5 moles of a chelating agent and / or water and have an RSV of at least 0.5, measured in a 0.1 / gene solution of a-chlorine- have naphthalene at 100 ° C, d a d u r c h characterized that one causes the crosslinking with a polyamine or its salt. References considered: U.S. Patent No. 2,801229.