POLYAMIDE MIXTURES WITH ACRYLONITIN.ILO / BUTADIEND POLYMERS WITH REDUCED GELENING, AND * AGENT ANTI-L INVENTION This invention relates to a method for making a homogeneous mixture of acrylonitrile / butadiene polymer and a polyamide which shows a reduced or reduced gel generation in the resulting mixture, and said mixture. Mixtures with reduced generation of acrylamide / butadiene polymer gel and parylaryl polyamides or polyamides are highly desirable for the extrusion of the tube or hose lining layers or a sheet material since the presence of particles of gel results in weak points in the hose tube either in the coating member or in the sheet as well as creates poor coating or extrusion results. Likewise, the gel particles tend to cover the meshes. More particularly, this invention provides a novel antigel agent that reduces gel formation during processing and use of the mixture. PREVIOUS TECHNIQUE The process of this invention produces an improved mixture - an alloy that has resistance to gel formation where a significant amount of gel is normally formed during the mixing process. Accordingly, the mixture has a more uniform dispersion of nylon. Usually, the processes of the prior art mix nylon of various types such as nylon, > , 6-6, up to nylon 12, etc., together with polymers of acp lom tp lo and butadiene at temperatures sufficient to melt nylon generally above 200ßC or more, but these elevated temperatures cause the resulting mixture to form a gel providing a mixture having a relatively high content of gel which causes the alloy, when extruded or formed into sheet, to present undesirable weaknesses as well as adhesion problems and difficulties in relation to the plugging of the meshes. In order to avoid or reduce gel formation, these mixtures are processed at higher temperatures, which results in a longer processing time and frequently inhomogeneous parts since the nylon is not uniformly distributed in the mixture. COMPENDIUM OF THE INVENTION AND PREFERRED MODALITY We have found that the presence of a special package of special chemical substances or antigel agents during the mixing of the acrylonitrile / butadiene polymer and the polyaramide or polya ida allows the mixing to be carried out at a higher temperature while reducing the gel formation which provides a more uniform dispersion in a shorter mixing time. The resulting mixture is essentially free of visual gel in accordance with that determined by the observation of a sample of the ba or e mixture. microscope where the gel appears in the form of lumps or similar in the ho a. These lumps are more evident when black carbon is present inside the mixture or on it. And indeed, the usual ASTM method for measuring the gel can be employed, but it has a time factor disadvantage compared to the observation of a leaf under the microscope. Normally, these special packages of chemicals or antigel agents are added to the polymers of acrylonitrile / butadiene and polyamide during the mixing operation with the materials mixed in a mixer heated to the melting point of the polyamide or above of said melting point. In addition, the chemicals in the special pack are added to the acrylonitrile / butadiene polymer, preferably finely divided, but, on the other hand, particular lick or polyarylamide, such as, for example, nylon 6,6-, can be added to the polyalkyl. 6, 7,8,12, etc., before mixing. Sometimes it is easier to add during the mixing process than to the individual parts of the mix. The special chemicals package is used in a ratio of 1 to 6 *? by weight based on 100 parts of the mixture of acrylonitrile / butadiene and polia ida, as for example nylon, but 3-4 * í seems to be the most economical proportion for the f na nate results. * Even though the acrylonitrile / butadiene polymers can be made within a range of about 5 to about 95V "by weight, they are available in well known 4o such as the degrees in which the acyl nitrile content of the mixture it is from 22 to 33% by weight. Since nylon polymers such as 6-6, 6 to 12 require a temperature of 20 * C and more, say 225 ° C to melt to allow the nylon polymers to mix with the acrylonitrile / butadiene polymer , the mixing is usually carried out in a mixer which can be heated as for example one of the well-known extruder mixers, for example W / P Warner, Pfleiderer or Leistritz and Berstorff. Unless nylon is heated to a temperature close to 200 * C to 225 * C, or above said temperature, it is extremely difficult to obtain a nylon uniformly dispersed in the acrylonitrile / butadiene polymer, and when the Acrylonitrile / butadiene polymer is mixed at these high temperatures, appreciable amounts of gels are obtained unless antigel agent is present. Therefore, due to the gel, desirable uniform dispersion is not obtained by the prior art process. The addition of a mixture of specific chemicals from the antigel agent package allows the nylon and the acrylonitrile / butadiene polymer to be heated to a temperature of 200 ° C to 225 ° C without increasing the gel formation. A series of blends of 80 parts of acrylonitrile / butadiene polymer and 20 parts of nylon 6 was mixed with special packages of chemicals listed below and tested for gel formation. Accordingly, 100 parts of acrylonitrile / butadiene polymer particles that passed through a 0.47625 cm mesh were mixed with one of the special chemical packages listed below:
PACKAGE A
tris-nonylphenyl phosphide 1.00 phr
3,5-di-tert-butyl-4-hydro: < idrocinnamate of 1.00 phr octadecyl
1, 5-di-tert-ami Iquinone 0.25 phr
disterthyldipropionate (DSTDP) 0.20 phr > PACKAGE B
U877A mix of 2: 1 of 0.64 phr
(diphosphite of bis 2,4-di-tert-butyl-1-phenylateritrile tol); Y
3,5-di-tert-butyl l-4-hydro: < ihidrocinnama or octadecyl
2,5-di-tert ~ ami lquinone 0.25 phr
DSTDP 0.20 phr
PACKAGE C
U877A 0.80 phr
2,5-di-tert-amylquinone 0.25 phr
disterthyldipropionate (DSTDP) 0.20 phr «•. • ..ß -« --- M «»?. ????. S-i8w «-i« -ßS «» «p.?.?.«.? « ! The use of any of these packs, ie, A, B and C provided blends with substantially 0 wt% gel. The ac i loni polymer. The butadiene containing the special chemical package was tested with 80 parts of polymer per 10 parts of special chemical package in a Haa e Rheschord machine to obtain a graph of the torque versus time. An example of two types of phenol antioxidants useful in this invention are the alkyquinones, such as, for example, tetrabutylhydroquinonate, or tert-hydroquinone, and the alkylaryl phenols. The alkyl substitute generally has 1 to 10 carbon atoms and the butyl radical is preferred to the heptyl radical. Examples of these alkylhydroqu. Highly desirable ipones are di-p-t-butyl, di-p-t-amyl and di-p-t-octylhydroquinones. Examples of the secondary or preventive antioxidants are diphosphite of bis (2,4-di-tert-butylphenyl) pentaerythiol and 3- (3,5-di-tert-butyl-4-hydro? Ifenyl) octadecyl propionate; others are Weston 618 known as diethiperilpentaerythritol diphosphite. { Weston D0PI known as diissoctyl phosphite, which is relatively volatile; Weston PTP known as heptakis (dipropi lengl icol) rifoßf itoj Weston TDP is phosphite of tri issdeci lo; Weston TI0P eß triisooctyl phosphite Westsn TLP is trilauryl phosphite; Weston 430 is tris (dipropi lengl icol) phosphide? Weston 600 is diphosphite of di ißodeci lpentaep tri ol; and Weßtsn 399 is tpsnoni phosphite 1 fem lo. These are representative examples of the above-mentioned secondary types of bulk types. Examples of the organic phosphite are diphosphite b- (2,4-d? -t-but? 1-phenyl-1-pentae-tri-tol, diphosphite di-sterai lpentaeri tri-ol, dialkyl and trialkyl phosphites). at 20 carbon atoms, the di- and tri- alkylapentaerythritol phosphites of one or two phosphite groups, and] alkyl radical contains from 3 to 18 carbon atoms, the phenyl phosphites and their alkyl alkylate phosphites and phosphites of g] phenyl icolate. Also when the list of primary antipolitics as well as antipodes; < secondary harvesters are extremely large, we have found it desirable to select or sift individual useful antioxidants in these packets by using the Haake Rheochord 90 system where samples of the antisickling agent and an acrylonitrile / butadiene polymer in pellets (no larger about 0.9525 cm) are mixed in the Haake Rheochord system and the time versus TQ (torque) and TTQ (total torque) at the indicated temperature are plotted by means of the Haake Rheschord machine. The paper temperature range for the graph is usually 0ßC to 250ßC. Therefore, by this method, a torque / temperature curve will be generated ver- ify test time with the Haate Rheochord system. The Haete Pheochord system was used to test either the animal agent or the special package of anionic chemicals to see if the antigel agent reduced the gel level to zero or close to zero. The results of these experiments indicated a combination of 4 materials that provided the best results. The nylon alloy with the acrylonitrile / butadiene polymer made up of 25 parts of nylon and 75 parts of acrylonitrile / butadiene polymer and 3 parts of HiSil 233, a silica powder fine, was used to help the mixing of the ingredients. Special packages of chemical substances or antigel agents, in accordance with the above, are made up of 4 different types of antioxidants in the broad sense. The use of the individual antioxidants does not provide the desired suppression of gel formation during the mixing of the nylon with the acrylonitrile / butadiene polymer. Accordingly, one aspect of this invention is to present a new combination of matter as a new antigel agent. The four different individual antioxidants can be classified as primary or chain-breaking antioxidants, such as, for example, alkyl hydroquinones and the complex phenol type, such as, for example, alkylphenol, alkylpheni-lphenol. The third class is 13 kind of secondary anti-aging or else d <; Protection as for example the organic phosphites listed above. The fourth class is the thioester smergetic agent, such as, for example, the Iodipropion, the isoplast, the thiopropionate, the thiopropionate, the thiodipropionate, and the related thioalkanoic acid of 3 to 30 carbon atoms and the alkylhydrocin ato, where they are preferred. alkyls of 4 or more carbon atoms up to 18 carbon atoms. The 4 kinds of special chemicals required to treat a chemical antigel agent that allows the pollamides to be mixed with acrylonitrile / butadiene polymers with the production of a minimum amount of gel in the mixture appears here in parts per hundred parts. of mixture when the preparations A, B and C were tested for the antigel agent in the ßißtem of Haake Rheochord. TABLE 1 alkyl hydroquinone 0.1 - 0.4 thioesteric ßinergetic agent 0.1 - 0.4 organic phosphite β 0.3 - 0.9 phenolic antio? Idant 0.5 - 1.5 The initial torsion torque recorded at the start of the Haake mixer was the fixed torsion torque, ie 14 Nm which dropped to a level below 8 Nm in about 1.6 minutes before rising to 8 Nm at three minutes and slowly set to a level slightly below 8 Nm at the end of 15 minutes of mixing with a peak temperature of approximately 235 ° C and a temperature ba at the end of the mixture of approximately lll'C. When the same mixture without any antigel agent was tested, the torque at 0.01 to 3.0 minutes was essentially 11.9 Nm with a minimum torque of approximately 6 minutes of 10.5 Nm and a maximum torque of 13.5 Nm at 270 ° c. These assays were repeated with a single antioxidant or unique stabilizer in the preparation, and an increase in gel over time was observed during the visual examination of the mixture under a microscope. The individual antioxidants do not suppress the formation of the gel during the period from the first minute to the third minute of the mixing operation as indicated by the torque developed during mixing in the Haake Rheochord mixer as well as the agents antigel of this invention. Individual antioagulants require a higher torque to stir the mixture at 3 minutes and a higher temperature while the antigel agents of this invention at 3 minutes allowed the mixture to be stirred at a lower torsion torque. and at a lower temperature. The lower torque and lower stirring temperature of the antigel agents of the present invention reduced the tendency of the mixture to gel with the standard preparation. The standard preparation (55 gram sample) with and without different amounts of antigel agents was mixed in an internal Haate mixer while the Haake torque curves were generated versus time to show the softness of the torque value after the mixture has reached its melting zone peak. The Haal mixer < e is adjusted to 220 ° C and used for 15 minutes at 60 rp for each sample. Two control samples were tested. One of the control samples was an acrylonitrile / butadiene polymer with three parts per hundred HiSil 233, sometimes designated here as the alloy, and the second control sample is the agentless mixture. antigel While some representative embodiments and details were presented for the purpose of illustrating the invention, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit or scope of the present invention.