BE531665A - - Google Patents

Description

       

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   The subject of the present invention is active organic fillers which improve the properties, in particular the mechanical properties, of high natural or synthetic polymers, such as natural rubber and its modifications, polychloroprene, butyl rubber, plastics. hardeners or thermoplastics, cellulose derivatives, starch, etc., or mixtures thereof.



   According to the invention, this improvement in the mechanical properties is achieved by means of active organic fillers which consist of transversely bonded, and therefore three-dimensional, polymerizates or copolymerizates, referred to below as vinyl fillers, and which are insoluble in high polymers that need to be mixed or incorporated.



   The new vinyl fillers can be obtained by polymerization or copolymerization of monomers or mixtures of monomers which have a structure causing the transverse bond, therefore which have several unsaturated bonds, which consequently contain several vinyl, or allyl, or vinyl-allyl groups. .



   Among the vinyl compounds, suitable for example divinylbenzene, ethylene glycol methacrylate, N, N-methylene-bis-aorylamide, etc .; from allylic compounds, for example triallyl cyanurate, N, N-diallyl-melamine, etc., and from compounds with vinyl and acryl groups, for example allyl acrylate, allyl methacrylate, etc. .



   Vinyl fillers which are obtained by copolymerization of a monomer or mixture of monomers yielding a transversely linked macromolecule, with a monomer or mixture of monomers or prepolymerized monomer not yielding linked macromolecules, have also been found suitable. transversely.



   According to the invention, also suitable for improving the mechanical properties of natural or synthetic high polymers, vinyl fillers obtained by the so-called “grafted” polymerization.



  To obtain this type of vinyl fillers, one "graft", by polymerization, on high molecular weight bodies, natural or synthetic, without-crosslinks or having only few crosslinks, or on a polymerizate or copolymerizate, a monomeric compound which provides a crosslink-forming macromolecule. In this way, one can impart to the copolymers properties which they did not previously exhibit.



   Small proportions of such a graft monomer may be sufficient to completely modify the properties of the primary vinyl fillers.



   Thus, for example, 1 to 5 parts of ethylene glycol dimethacrylate are already sufficient to cover the surface of 100 parts of a vinyl filler consisting of a styrol-divinylbenzene copolymer.



   By this "grafted" polymerization, it is not only possible to obtain "vinyl" fillers in accordance with the present invention from polymerisates or copolymerisates which are not transversely linked, or insufficiently linked transversely, which in themselves are not suitable, but also, to improve, strengthen or transform the properties of usable vinyl fillers, by polymerizing thereon monomers which give macromolecules which are transversely linked or not transversely linked.

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   This transplant can also be done several times.



   This "grafted" polymerization owes its importance to the fact that the quantity of generally expensive monomers which is necessary to prepare very active vinyl fillers can be considerably reduced, and that one can also take advantage in this preparation. more easily accessible monomers.



   Thus, for example, a vinyl filler can first be obtained by copolymerization of a single unsaturated monomer, such as styrol, with small amounts of a monomer which gives copolymers forming cross-links, such as divinylbenzene. , and then grafting onto this product a particularly active cross-linked polymerizate.



   Likewise, it is also possible, by graft polymerization, to convert soluble polymerizates into insoluble transversely bonded vinyl fillers.



   Examples of transversely bonded vinyl fillers, which can be prepared from non-transversely bonded or soluble polymerizates which can act as emulsifiers, can be found in Tables XXVII-2 and XXIX-1-4. grafted polymerization, and in Tables 1-6, XXI 1-5 and XXIV 1-4, examples in which, on transversely bonded and insoluble vinyl fillers, other transversely bonded polymerizates are grafted, or not transversely linked.



   The vinyl fillers obtained, according to the principles explained above, by homopolymerization, copolymerization or interpolymerization, can, as regards their structure, be divided into non-polar and polar vinyl fillers. While apolar vinyl fillers consist only of carbon and hydrogen, polar vinyl fillers still contain oxygen, halogens, nitrogen, etc., which form the polar groups such as carboxyl, hydroxel, halogen, amine, nitrile, amide, aldehyde, carbonyl, etc.



   In this division of vinyl fillers, no account is taken of residues, for example residues of catalysts or emulsifiers, possibly contained in these fillers and resulting from the preparation, and which may exist even in apo vinyl fillers. - milks.



   The polar groups may already exist in the monomers used to prepare the vinyl fillers, or else be incorporated subsequently into the vinyl fillers.



   It is thus possible to convert nonpolar vinyl fillers into polar vinyl fillers, or to incorporate other polar groups in polar vinyl fillers.

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    TABLE XXVII Vinyl fillers with polymer emulsifier
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 <tb> Mixture <SEP> n <SEP> XXVII <SEP> Control <SEP> -1 <SEP> -2
 <tb> Latex <SEP> elastomer <SEP> (weight <SEP> sec)
 <tb>
 
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 GR-S 1500 (Table III Recipe M) 000000.00000000008000000000000 100 100 100 Latex vinyl filler (dry weight) antity QOe8000GOOOOOOOOOQ09000QOOOQO.OOOCOOQOOOOOOOOOOOOCOOOOO00 20 20
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 <tb> Composition
 <tb> Emulsifier <SEP> polymer
 <tb>
 
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 Alpha protein .......... 20
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 <tb> copolymer <SEP> acrylamide-styrol-acid <SEP> metacrylic .......... <SEP> 20
 <tb> Monomers <SEP> vinyls
 <tb>
 
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 Styrol .......... ++ .......... 98 98 Divinylbenzene OGOO..g80G $ mOeOGo. #. G ... GOOOO ... OOOOQO..OO 2 2 Recipe polymerization 00.0..00.0 ..... 0.0 ... 0 ...... 0 ...... 0.

   (l) (2) Mixture Recipe (Table XII) .00 ... 00..00 ......... 0 ...... 0 .... 0 ....... FEE Amitrile IP ............................................... ... - - 2 Mooney ML-4 viscosity ....................................... ... 37 48 Vulcanization, minutes at 141 C ................................. 90 30 20 Results Elongation% ...................... 0 .......................... 320 560 730 Module 300% ............................ o ................ ...... 160 460 560 Hardness, Shore A durometer .......... 39 63 63 Tensile strength kg / cm2 ........... 15 102 195
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 <tb>% <SEP> increase <SEP> of <SEP> the <SEP> resistance <SEP> to <SEP> the <SEP> traction <SEP> ........... <SEP> 574% <SEP> 1193%
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   + Butadiene-styrol copolymer brand GR-S ++ Cross-linking agent Polymerization recipe:

   90 parts styrol, 10 parts divinylbenzene, 20 parts alpha soy protein (manufacturer: Clidden C), 700 parts water, 2 parts azobis- (isobutyronitrile), polymerization temperature 600 C, duration 12 h. 100% conversion.



  (2) Polymerization recipe: Step 1: 15 parts acrylamide, 2 parts methacrylic acid, 3 parts styrol, 300 parts water, 0.3 parts potassium persulfate, 0.15 parts sodium bisulfite, polymerization temperature 60 C, duration 2h. ; Step 2: 90 parts styrol, 10 parts divinylbenzene, 400 parts water, 2 parts azobis - (isobutyronitrile), polymerization temperature 60 C, duration 12h. 100% conversion.



  Step 2 produces a "grafted" vinyl filler.

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   According to the invention, it is possible, for example, to graft onto a vinyl filler of an apolar nature, by means of a graft polymerization, a polar body such as polyacrylonitrile, and where appropriate, in the same way, a second body. polar.



   Polar vinyl fillers, as well as non-polar fillers, may contain some residual double bonds. Their presence is often desired, because these residual ethylenic groups allow chemical reactions, for example the fixation of chlorine or bromine, which results in vinyl fillers having new properties. In this way, it is therefore possible, for example, to convert apolar vinyl fillers which still contain ethylenic groups into polar fillers.



   In the case of polar vinyl fillers, their properties are determined to a large extent by their polar groups.



   Thus, determined vinyl fillers, containing for example carboxyl groups, prepared from a vinyl or acrylic acid or from another acidic cross-linking agent, or vinyl fillers containing an acid derivative, obtained by reaction on the free double bonds of the vinyl filler, not only possess excellent properties in themselves, but these can be further enhanced by reacting vinyl fillers containing carboxyl groups with bodies such as, for example, ammonia, or its organic substitutes, for example organic mono, di, tri or tetrasubstituted ammonium compounds. This additional effect can be seen in Tables XVI and XVII, reproduced below.



   It has been observed that this effect on the new vinyl fillers is already obtained with small amounts of carboxyl (Table XVIII), so that the remaining part of the vinyl filler can be constituted by the relatively inexpensive vinyl and allylic monomers, for example styrol and divinylbenzene.



   As shown in Table XVII, reproduced below, the materials must be mixed and vulcanized immediately, when ammonia or fairly volatile amines are used, while in the case of amines with a higher molecular weight and less volatile, the materials can be preserved before mixing and vulcanization. However, it has been found that high molecular weight amines do not appear to be as active, so amines containing no more than seven carbon atoms per amine group are preferably used, see Table XVII.



   It has been found, however, that the volatility of low molecular weight amines can be decreased by introducing the nitrile group. Surprisingly, however, the introduction of nitrile groups has yet another advantage: the high natural or synthetic polymers are thus imparted excellent resistance to aging phenomena.



   The graft polymerization also allows for effective bonding of vinyl fillers with natural or synthetic high polymers.



  In such a case, according to the invention, it is possible to apply a chemically reactive graft, such as acrolein, methacrolein or crotonaldehyde, to the vinyl filler, which can then serve to reinforce the phenol resins. -formics, etc. Vinyl fillers grafted with vinyl ethers or polyoxygenated compounds, such as glycerin-monovinyl ether, or with polymerizable acids, such as acrylic or methacrylic acids, contain hydroxyl or carboxy groups.

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 which can then react chemically with other polyfunctional acids, or alcohols, or amines, or isocyanates, by polycondensation.

   In this way, hitherto unknown additives are obtained for natural or synthetic high polymers, capable of modifying the properties thereof in many ways.



   The improvements in the properties of natural or synthetic high polymers, which can be obtained by the addition of vinyl fillers, often depend on the mode of composition of the vinyl fillers.



   In Table I, the dependence which exists between the addition of various vinyl fillers and the improvement in the properties of one type of butadiene-styrol copolymer (GR- brand) has been shown by way of example. S).



   The vinyl fillers are added here in the form of latex, to the GR-S latex, which is then worked as usual, by coagulation and drying.



   This Table I not only demonstrates the advantages which are obtained by the addition of the various vinyl fillers, but it also demonstrates the advantage of inserting polar groups (1-4), in particular. those containing an active hydrogen (1-6), and it still shows the advantage of an apolar vinylic filler with graft polymerization, compared to a similar apolar copolymer vinyl filler, as well as the superiority of a polar vinylic filler with polymerization grafted with respect to a polar copolymer vinyl filler,
An important condition, to obtain the improvement sought, according to the invention, in the mechanical properties of the vinyl fillers, is that the vinyl fillers are insoluble, not only in the usual solvents,

   but especially in the high polymers that we want to mix or incorporate.



   One can easily measure this insolubility of vinyl fillers in solvents using a modified Oswald pipette, by determining the viscosity of a small amount of the concentrated latex diluted in a solvent, for water and also for vinyl compounds. - soluble ques.



   A suitable solvent is dioxane, which gives a colloidal dispersion of the vinyl filler. In specific cases, the action of dioxane can be further enhanced by using another solvent for the polymerisates, for example methyl isopropyloetone.

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  TABLE l Types of vinyl fillers reinforcing the gas
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 (a) Step it 90 parts tyrol and 10 parts divinylbenzene polymerized according to Recipe A
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 (Table III) in the form of latex.

   Then polymerized in step 2 after addition of 5 parts vinyltoluene, 5 parts divinylbenzene and 1.2 parts diisopropyl-benzene hydroperoxide (b) Stage 1: 70 parts styrol, 9 parts divinylbenzene and 10 parts methacrylic acid, polymerized according to recipe A (Tab III) in the form of latex. Then polymerized after addition of 10 parts isoprene, 1 part divinylbenzene, 1 part diisopropylbenzene hydroperoxide.

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   Since vinyl fillers are insoluble, their particles hardly influence the viscosity of the solvent, provided the particle concentration is low.



   But if we are dealing with a soluble polymerizate, the viscosity increases.



   The insolubility of vinyl fillers in high polymers can also be seen using an electron microscope, by examining high polymers with added vinyl fillers.



   By this insolubility in the high polymers which have to be mixed or incorporated, the vinyl fillers are essentially distinguished from the known additives which are soluble in the high polymers or swell in them, and which must be considered as property improving plasticizers. The effect obtained with these known additives results from the mixing laws, and it is the proportional average of the properties of the two components.



   The new vinyl fillers, on the other hand, do not dissolve in high polymers, do not swell, nor do they become part of the elastic or plastic continuum, but, as can be seen in the electron microscope. , they remain in small particles of spherical shape, which are distributed uniformly within the elastic and plastic material.



   Thus, the condition that the new vinyl fillers must still fulfill is that they are in colloidal form and retain this colloidal form even in the high polymers that are incorporated.
Examples of such colloidal vinyl fillers which improve the properties of high polymers are reproduced in Figs 1 to 6. The views taken under an electron microscope show the palladium shadows of the particles. The scale is shown in fig. 1. Figures 5 and 6 give similar photos on the same scale, namely the vinyl charge of fig. 2 in natural rubber, and the vinyl filler of FIG. 3 in butadiene-styrol copolymer (GR-S 100).



   The photos of figs. 1 to 4 show the order of magnitude of colloidal particles, in which the vinyl filler acts in a particularly advantageous manner, and in which they are kept in suspension by Brownian movements.



   Figures 5 and 6 show the degree of distribution of the insoluble vinyl fillers in a coagulate which has been obtained by mixing a latex of vinyl fillers with the latex of the elastomer in question, then by coagulating, in drying and laminating.



   It can be seen from these figures that the degree of distribution of vinyl fillers in the coagulate is maintained, whether the products have been vulcanized or not. This fact is also confirmed by the results of the solidity measurements. The composition of the different vinyl fillers according to figs. 1 to 6 is summarized in Table XXIII below.



   In order to obtain vinyl fillers having the properties and effects described, special requirements must be observed in the preparation of new vinyl fillers.



   In order to prepare transversely linked vinyl fillers of the desired particle size, the corresponding monomers or mixtures of monomers must be polymerized, suspended in a medium.

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 liquid place, such as water or an organic solvent in the presence or absence of emulsifiers.



   Without the addition of an emulsifier, the monomers at this particle size can be polymerized, for example in water, if a suitable polymerization catalyst is used, in a sufficient amount, or also, in some cases. determined, small amounts of water-soluble monomers.

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    TABLE XXIII Electronic images of vinyl charges
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 <tb> Mixture <SEP> n <SEP> XXIII <SEP> - <SEP> figure <SEP> -1 <SEP> -2 <SEP> -3 <SEP> -4 <SEP> -5 <SEP> -6
 <tb> Latex <SEP> elastomer <SEP> (weight <SEP> sec)
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 Natural rubber .......... 100 GR-S + 1500 O / llo & oooeaOCOOQ04) o.eOQOe.000800CC.OOOOOC00003000900000000 100 Latex vinyl filler (dry weight) Quantity .OGOoo..o..o..o. ...... oo..oe080 ... S ... ooO ".ooo.a.0800..0 20 20 Composition Styrol. # ... 083 ............ ................... eeGo ............ 93 8 0 78 80 78 Acrylonitrile .o., oo ...... *. * .......... *. * ...... o ...........



  Methyl methacrylate '...'.'.....'...'.'........... 0 ....... 80 Isoprene and .. CI ... ..0 ......... 0 ................................. 2 2 Butadiene. ....... e80 .......................................... 10 Methacrylic acid ........................................... 10 10 Acrylic acid ............................................... 10 10 Dimethacrylate ethylene glycol ........................... 10 Divinylbenzene .0 ................ ......... 0 ................. 2 10 10 10 10 Polymerization recipe (Table III) oo.e ... oooos ... o ..oes..o. (1) G F A G F Particle size of the vinyl filler ..................

   L ML MS S ML MS + Butadiene-styrol copolymer, lacking GR-S ++ Cross-linking agent +++ L: coarse; ML: half-fat; MS: semi-fine; S: fines (1) Monomers: 100 parts; water: 600 parts; of potassium: 3.0 parts sodium bisulfite: 1.2 parts.

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   If the polymerization is carried out in the absence of an emulsion-binder, it is usually necessary to polymerize in very dilute solutions.



   With this mode of polymerization, relatively low concentration latexes are obtained, which, in addition, often have an excess of ash-forming salts, but these can be removed from the apolar latexes, by ion exchangers or by electrodialysis.



   The low concentration of the latices obtained in this way can be increased by suitable measures, for example vacuum concentration or spray concentration.



   This additional preparation work makes the preparation of vinyl fillers more difficult and expensive. For this reason, the polymerization of the monomers or mixtures of monomers in the aqueous phase in the presence of an emulsifier is preferred.



   The emulsion polymerization itself can be carried out in any way, but such working conditions must be maintained as to result in insoluble end products transversely linked, having a colloidal particle size, and giving stable latexes.



   Some examples of polymerization mixtures are given in Table III, without the present invention being limited only to the use of vinyl fillers obtained in this way.



   The polymerization time is usually 6 to 12 hours; if the polymerization is not completed after 12 hours, a further catalyst can be added and the temperature raised.



   In specific cases, it is desirable that the vinyl fillers have a residue of double bonds, so that they are also vulcanizable. Divinyl monomers, such as divinylbenzene, or allyl-vinyl monomers, such as allyl methacrylate, or alternatively a diene such as butadiene, are then employed at moderate concentrations. In these cases, however, not only should the polymerization conditions be closely controlled in order to maintain some double bonds in the vinyl filler, but care must also be taken that the polymerization temperature does not rise.



  Any proportions of non-polar monomers can be removed in vacuo.

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By employing emulsifiers in the polymerization of the monomers or mixtures of monomers which give the vinyl fillers, latexes of these vinyl fillers are obtained which contain the emulsifier in solution.



   But in many cases these emulsifiers can have a disruptive action, which happens when the emulsifier can reduce the strength of natural rubber or other high natural or synthetic polymers, or when the emulsifier reduces the electrical resistance of the compounds. polymers intended for insulating uses, or when the emulsifier lowers surface tension, as for example in the manufacture of foam rubber, and therefore does not allow the desired degree of bubble formation, or when the presence of an emulsifier is undesirable for other reasons, such as, for example, in the preparation of the alkyd resins which are used to make Fibergas, etc.



   In this case, one must use vinyl fillers which are prepared by polymerization in the absence of emulsifiers.



   Often, the difficulties caused by the presence of heterogeneous emulsifiers can be eliminated, according to the invention, if polymer emulsifiers are used instead. '
Thus, for example, an alkaline solution of alpha protein gives a latex with very small particles of vinyl filler.



   Other polymeric emulsifiers are shown by way of example in Table XXVII.



   Insoluble cross-linked vinyl fillers prepared by the exemplary or other methods, can improve the properties, particularly the mechanical properties, of natural or synthetic high polymers.



   The vinyl fillers in accordance with the invention above all cause such reinforcement in natural rubber and other natural products of the rubber type, such as hevea, balata, gutta-percha, etc., as well as the modifications of these types of rubber, especially in chemical modifications of natural rubber, such as those obtained by hydrogenation, chlorination, hydrochlorination, introduction of oxygenated groups, etc., or in interpolymers obtained by polymerization of polymerizable compounds such as butadiene, styrol, acrylonitrile, etc., or their mixtures, in the presence of rubber latex, or in rubber mixtures and polymerizates obtained after mixing rubber latex and emulsions of polymer compounds, according to the usual treatment.



   By adding the new vinyl fillers to natural rubber or to the above modifications, the following advantages are obtained:
Rubber mixtures containing vinyl fillers exhibit tensile strengths which are much higher than the tensile strengths of other rubber mixtures not containing such additives.



   The low hysteresis of natural rubber is maintained and the increased heat build-up is also avoided.



   The natural appearance of natural rubber is not changed;

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 no coloration occurs, so the gloss or clarity of the dyes incorporated into the rubber is retained.



   The added vinyl fillers do not interfere with the transformation of rubber into thin membranes, fibers or coatings, nor with the process of covering and immersing objects.
Vinyl fillers also exert a favorable action in foam rubber, natural rubber or rubber latex, without hindering or making difficult the manufacture of foam rubber from the latex.



   By the addition of the new vinyl fillers, a reinforcement of the natural rubber latex occurs, and thus better products are obtained in the processing.



   Furthermore, with the aid of the new vinyl fillers, cured rubber articles with improved properties are also obtained.
In addition, the bonding ability of natural rubber products, especially with metals, is improved.



   The addition of vinyl fillers brings about, by removing or reducing the conductivity and polarization, improved electrical properties, especially for high frequencies.
By the use of special vinyl surface fillers, it becomes possible to regulate, or even reverse, certain properties. For example, by adding determined vinyl fillers, the internal friction or the polarity can be increased.
According to the invention, it is possible, according to the invention, to further influence the properties of natural rubber and of its modifications, by adding to them vinyl fillers which are insoluble therein, but which, however, can react with the rubber or with it. the bodies incorporated into it.



   A significant improvement in the properties is also obtained by the addition of the new vinyl fillers in high synthetic polymers of the rubber type, and therefore vulcanizable.



   The reinforcing effect of vinyl fillers can be observed both in nonpolar and polar homopolymerisates, which are obtained by polymerization of a monomer containing several ethylenic bonds, at least two of which are conjugated, in particular of dienes, such as butadiene isoprene, dimethylbutadiene, perylene, pentadiene-1,3-cyclodiene, chlorobutadiene.



   The same favorable effects can also be observed in high vulcanizable polymers obtained by copolymerization of two or more diene hydrocarbons, or in diene copolymerisates, nonpolar or polar, which are obtained by simultaneous polymerization (copolymerization) or successive (interpolymerization) of mixtures of monomers of which one or more monomers are conjugated dienes, while in the second component at least one monomer contains one or more unsaturated bonds and at the same time does not contain a polar group in the case of non-polar diene copolymerizates, but in contains in the case of polar diene copolymerizates
Types of these non-polar diene copolymerisates which can be reinforced with vinyl fillers,

   are for example the copolymerizates

  <Desc / Clms Page number 14>

 of butadiene and styrol or of butadiene or isoprene and isobutylene, etc., as well as the copolymerisates, for example of butadiene and of styrol, which contain a small proportion of a monomer giving a cross-linked polymerizate, such as divinylbenzene, which has the role of preventing the contraction of the copolymerisates, and diene copolymerizates which are obtained by polymerization of a diene with several vinyl hydrocarbons, for example styrol and vinyltoluene, and / or alpha-methylstyrol .



   Among the reinforceable polar diene copolymers are, for example, those obtained by copolymerization of chlorobutadiene with another nonpolar diene or by copolymerization of butadiene and acrylonitrile or of another polar monomeric compound.



   Similar results are also obtained with mixtures of polymerizates which are obtained, for example, by mixing latexes of polymerizates of the prescribed separate components after working the latexes.



   Such mixtures of polymerizates are obtained, for example, when polybutadiene is intimately mixed with a polymerizate of another monomer or a copolymerizate, for example of butadiene and styrol, in the form of their latexes, or when intimately mixed with the cylinder. dry polymerizates.



   The addition of vinyl fillers also produces numerous advantages in the high synthetic polymers of the rubber type, therefore vulcanizable, already mentioned, and this, for both self-reinforcing and non-self-reinforcing polymers.



   Thus, for example, the strength of the butadiene-styrol copolymerisates is increased, and products are thus obtained having a tensile strength so high that, hitherto, it could not be obtained without simultaneously having a coloration and / or a loss. transparency.



   This increase in strength properties is also felt in the high polymers present in emulsion or dispersion, so that, in the processing of these latexes, submerged objects, or foam products, etc., having improved properties are obtained.



   It is thus possible, by the addition of vinyl fillers, to impart to the copolymerizates formed on the butadiene-styrol base, for example of the GR-S type, a sufficiently high tensile strength to make them suitable for the manufacture of soft rubber. - se, while the additions made to natural rubber, etc. , are reduced or even suppressed.



   Surprisingly, the new vinyl fillers also provide a reinforcing effect in high self-reinforcing polymers, such as chloroprene, which have higher tensile strengths than butadiene copolymerizates. In addition, they provide all the advantages already described in the case of natural rubber, especially the increase in solidity properties, with simultaneous preservation of hysteresis and while avoiding the increased formation of heat.



   The new vinyl fillers also give favorable effects in those of the higher vulcanizable polymers which do not contain butadiene or butadiene homologues, for example polyethylene tetrasulfide, known as thiocol. This group of high vulcanizable reinforcing polymers also includes polymers of lactoprene, which do not contain diene components, and in which an exchange is used for the vulcanization.

  <Desc / Clms Page number 15>

 ester or a reaction in which a halogen is displaced.



   Also included in this group are high vulcanizable non-diene vinyl reinforcing polymers, mixed glycerophthalic resins, as well as polyesters, including those which are unsaturated and can be further polymerized by an organic peroxide, and polyesters which can be linked transversely by their extreme carboxyl or hydroxyl groups, for example by the reaction with an isocyanate with the formation of so-called isocyanate-polyester elastomers, of the vulcolano type
Surprisingly, the new vinyl fillers also produce a significant improvement in properties in high synthetic unvulcanizable polymers.

   both in the case of thermoplastic plastics and in hardenable plastics
Such improvement is caused, for example, in polymeric vinyl compounds, which are made with ethylene, iobutylene, vinyl chloride, vinylidene chloride, styrol, alpha-methylstyrol, chlorostyrol, vinyl ethers such as vinyl ethyl ether, vinyl alcohol and its esters, such as vinyl acetate, vinyl butyrate, vinyl ketones such as methyl vinyl ketone, methyl isopropyl ketone, vinyl acids. ques, for example acrylic acid, methacrylic acid, or their esters such as ethyl acrylate, methyl methacrylate, etc., or with nitrogenous vinyl monomers, such as vinylpyridine, acrylonitrile ,

   and co
Likewise, it is also possible to improve the copolymers obtained by copolymerization or interpolymerization of two or more of the monomers indicated, for example the vinyl chloride-vinylidene chloride copolymerizate.



   The new vinyl fillers also improve the properties of homopolymerisates or copolymerisates which have been prepared from dienes, and in which the vulcanizability has been removed by saturation of the unsaturated bonds, for example by hydrogenation, halogenation, hydrochlorination or the like. way.



   Among the high synthetic polymers which can be improved in their properties by the new vinyl fillers, it is also necessary to classify the polysulfones, such as for example the isobutylene-sulfur dioxide copolymers.



   Although these high synthetic polymers of the kind described above already exhibit high tensile strengths in themselves, these are further increased by the addition of vinyl fillers, especially when these contain plasticizers, without that it follows a hardening.



   The transparency of plastics is not only maintained, but even increased in some cases, even in the case where plastics contain dyes, pigments or luminescent substances as additives. If you possibly want a certain transparency of plastics, you can adjust it at will using these vinyl fillers.
Another advantage lies in the fact that the plasticizer "seeps" out of the synthetic material is avoided.



   In addition, the new additives also produce, in

  <Desc / Clms Page number 16>

 synthetic materials, improvements in properties similar to those produced in high vulcanizable natural or synthetic polymers.



   These improved properties of high unvulcanizable polymers are maintained even when these materials are processed into films, films, etc.



   With the aid of the new vinyl fillers, it is also possible to improve appreciably the properties of the curable plastics, such as phenolformic resins, phenolouric resins, for example of the bakelite type.



   The vinyl fillers in accordance with the present invention also reinforce cellulose derivatives, such as methylcellulose, ethylcellulose, hydroxyethylcellulose, cellulose ethers or cellulose esters, such as cellulose acetate, cellulose nitrate, etc. etc.



  The reinforcement of these cellulose derivatives is particularly effective when they contain plasticizers.



   Similar improvements are obtained by adding the new vinyl fillers to natural high polymers, for example starch.



   Given on the one hand the large number of vinyl fillers, which differ not only by their structure, their polar or non-polar character, but also by their possibilities of modification with regard to their reinforcing effects Given, on the other hand, the multiplicity of natural and synthetic high polymers, it appears understandable, without further explanation, that the properties of the latter can be influenced in different ways by means of vinyl fillers. To achieve maximum reinforcement, therefore, the appropriate vinyl filler, or a mixture of these fillers, must be added to each natural or synthetic high polymer.



   It has been found, for example, that only moderate reinforcement can be produced by adding nonpolar vinyl fillers to high vulcanizable synthetic polymers which, on expansion, do not crystallize automatically, which therefore belong to non-self-reinforcing types, as per example. for example diene homopolymers or copolymers, such as polybutadiene, butadiene-styrol copolymerisates of the GR-S type or butadiene-acrylonitrile copolymerizates, which have a relatively low tensile strength.



  On the other hand, with polar vinyl fillers, a much more pronounced increase in tensile strength is obtained; however, if polar vinyl fillers containing active groups which have the property of forming salts with organic acids or bases are added to these high polymers, even better tensile strengths are obtained in rubbers and rubber. vulcanized products derived therefrom; likewise, their abrasion resistance is greatly improved, even up to levels which can be compared to the highest values encountered in natural rubbers.



   With determined combinations of vinyl fillers and the synthetic rubber-like high polymers mentioned above, products can be obtained having a lower hysteresis than with the usual fillers.



   On the other hand, these differences between the reinforcing action of non-polar and polar vinyl fillers are not so strongly felt in the case of high natural or synthetic vulcanizable polymers, such as for example natural rubber, polychlorinated

  <Desc / Clms Page number 17>

 prene or butyl rubber, although here again polar vinyl fillers and so-called active polar vinyl fillers, containing active groups, give better results and are therefore preferable as additives.



   Besides the composition or the structure of the vinyl fillers which it is a question of adding to the high natural or synthetic polymers, the mode of their addition also has a great influence on the reinforcement obtained.
If the latex is coagulated separately from a vinyl filler, for example with salt and acid, and if it is dried at 80, no improvement, or only a small improvement, is observed. mechanical properties, upon incorporation by rolling into high plastic and elastic polymers, as shown in Table II.



   Apparently, the particles of the vinyl fillers do not distribute uniformly in the high polymers.



   Thus, the favorable action of these vinyl fillers depends on a good distribution in the elastomers or plastomers, a distribution which, according to the invention, is obtained only when the latex of the vinyl filler is added to the latex of the vinyl filler. high polymer that needs to be reinforced, and when the latex mixture is then worked in a known manner.
One can also see from Table II the favorable action which is obtained by such a mixture of vinyl fillers in dispersed form.
Another possibility of distributing a vinyl filler in a mixture of two or more high polymers consists, according to the invention, in colloidally distributing the latex of the vinyl filler which is to be used for reinforcing, in the latex of one of the high polymers,

   then adding this latex mixture to the latex of the other high polymer.



   One can also proceed as follows: one adds the vinyl filler, in the form of latex, to the latex of one of the polymer components, one precipitates the mixture, and the dry powder obtained after preparation is then added, to the cylinder, to the second dry polymer component.



  This method of incorporation is particularly advisable in the case of mixtures of polymeric bodies one of the components of which is soluble in the other, for example in the case of a mixture of two butadiene copolymers having different contents. in butadiene. One of the copolymers, for example one which has a butadiene content of about 20%, is soluble in a similar high butadiene copolymer.



   If the copolymer with a lower butadiene content is added to the latter, and the vinyl filler incorporated therein beforehand, the vinyl fillers also exert a reinforcing effect in the mixture.



   In such a case, the combination of an elastomer and the vinyl filler distributed therein can be used to reinforce other elastomers or plastomers.

  <Desc / Clms Page number 18>

 



    TABLE II
 EMI18.1
 Variation of the reinforcing effect of the vinyl fillers as a function of the mode of addition (solid or latex) in the case of butadiene-styrol copolymers.
 EMI18.2
 
 <tb>



  Mixed <SEP> n 1 <SEP> Control <SEP> -1 <SEP> Control <SEP> -2 <SEP> Control <SEP> -3
 <tb> Latex <SEP> elastomer <SEP> (reported <SEP> to <SEP> weight <SEP> sec)
 <tb> GR-S <SEP> + <SEP> 100 <SEP> (recipe <SEP> M-Table <SEP> XII ++ <SEP> ............. <SEP> 100 <SEP> 100
 <tb> GR-S + <SEP> 1500 <SEP> (Recipe <SEP> M-Table <SEP> XII) <SEP> ............... <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
 <tb> Load <SEP> vinyl <SEP> (reported <SEP> to <SEP> weight <SEP> sec)
 <tb> Quantity <SEP> ........................................ <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20
 <tb> Composition <SEP> ..................................... <SEP>
 <tb>



  Styrol <SEP> .......................................... <SEP> 78 <SEP> 78 <SEP> 96 <SEP> 96 <SEP> 80 <SEP> 80
 <tb> Vinylpyridine <SEP> ................................... <SEP> 10 <SEP> 10
 <tb> Methacrylate <SEP> of <SEP> methyl <SEP> .......................... <SEP> 10 <SEP> 10
 <tb> Butadiene <SEP> .......................................... <SEP> 2 <SEP> 2
 <tb> Acid <SEP> methacrylic <SEP> ................... <SEP> 10 <SEP> 10
 <tb>
 
 EMI18.3
 Divinylbenzene .................................. 2 2 2 2 10 10
 EMI18.4
 
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> (Table <SEP> III) <SEP> ............

    <SEP> B <SEP> B <SEP> B <SEP> B <SEP> A <SEP> A
 <tb> Elastomer <SEP> and <SEP> load <SEP> vinyl <SEP> mixed <SEP> sec <SEP> latex <SEP> sec <SEP> latex <SEP> sec <SEP> latex
 <tb> Mixture
 <tb>
 
 EMI18.5
 Recipe Table XII ................................ F F E E E E
 EMI18.6
 
 <tb> alpha-isopropylaminopropionitrile <SEP> .................. <SEP> 3 <SEP> 3
 <tb> Viscosity <SEP> Mooney <SEP> ML-4 <SEP> of <SEP> mix <SEP> ................... <SEP> 42 <SEP> 75 <SEP> 43 <SEP> 52 <SEP> 42 <SEP> 48
 <tb> Vulcanization, <SEP> minutes <SEP> to <SEP> 141 C <SEP> ..................... <SEP> 105 <SEP> 45 <SEP> 90 <SEP> 90 <SEP> 60 <SEP> 45
 <tb> Results
 <tb> Elongations <SEP>% <SEP> ..................................... <SEP> 360 <SEP> 835 <SEP> 450 <SEP> 885 <SEP> 700 <SEP> 785
 <tb> Module <SEP> 300 <SEP>% .......................................

    <SEP> 280 <SEP> 325 <SEP> 360 <SEP> 210 <SEP> 220 <SEP> 410
 <tb> Hardness, <SEP> durometer <SEP> Shore <SEP> A ........................... <SEP> 45 <SEP> 50 <SEP> 58 <SEP> 51 <SEP> 53 <SEP> 56
 <tb> Resistance <SEP> to <SEP> the <SEP> traction, <SEP> kg / cm2 <SEP> ................... <SEP> 23 <SEP> 149 <SEP> 37 <SEP> 98 <SEP> 38 <SEP> 228
 <tb>% <SEP> increase <SEP> of <SEP> the <SEP> resistance <SEP> to <SEP> the <SEP> traction .....

    <SEP> 544% <SEP> 176% <SEP> 502%
 <tb>
   + Butadiene-styrol copolymer brand GR-S ++ Prepared with Santomerse S-3 emulsifier +++ Cross-linking agent

  <Desc / Clms Page number 19>

 
Such vinyl filler, in combination with this polymer, provides a new possibility of using vinyl fillers, and this combination represents a valuable item of trade, which can, for example, be added to elastomers used in the manufacture of vinyl fillers. rubber soles.



   The strengthening effect that can be achieved with the new organic fillers also depends on the amount added to the natural or synthetic high polymers. This addition can vary between wide limits, but it should preferably not be more than two-thirds of the total volume of the final product, since the free space around the tightly packed spherical particles must at least be filled by the continuum.



   In the tables below, we have reproduced, to complete the explanation, the reinforcement which can be obtained, using the new vinyl fillers, in high natural or synthetic polymers, without this limiting the scope of the invention to the high types of polymers, amounts of vinyl fillers added, conditions of incorporation, etc., which are mentioned in these tables.



   In Table IV, examples of the reinforcement of natural rubber have been reproduced, both with a non-polar copolymeric vinyl filler and with a polar copolymeric vinyl filler.



   In these examples, latexes of natural rubber and vinyl filler were mixed, and coagulated by the addition of an acid-salt solution. The acid was 0.5% sulfuric acid, and the concentration of cooking salt was about 20%, the pH of the serum after coagulation was about 5. The coagulation was washed and dried, then worked and tested in the usual manner.



   The natural rubber sample exhibits a tensile strength of 218 kg / cm2, while the same rubber, reinforced with a polar and non-polar filler, exhibits a tensile strength of 270 and 323 kg / cm2 respectively.

  <Desc / Clms Page number 20>

 
TABLE IV Natural rubber reinforced with vinyl fillers
 EMI20.1
 
 <tb> Mixture <SEP> n <SEP> IV <SEP> Control <SEP> -1 <SEP> -2 <SEP> Comparison
 <tb>
 <tb> Rubber
 <tb>
 <tb>
 <tb> Latex <SEP> of <SEP> rubber <SEP> (reported <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
 <tb>
 <tb> to <SEP> weight <SEP> sec)
 <tb>
 <tb> Latex <SEP> of <SEP> load <SEP> vinyl
 <tb>
 <tb> (reported <SEP> to <SEP> weight <SEP> sec)
 <tb> Quantity <SEP> .............. <SEP> 20 <SEP> 20
 <tb>
 <tb> Composition <SEP> 20
 <tb>
 
 EMI20.2
 Styrol ..............

   
 EMI20.3
 
 <tb> Acrylonitrile <SEP> ................... <SEP> 95
 <tb>
 <tb> Dimethacrylate Ethylene glycol <SEP> <SEP> 5
 <tb>
 <tb> Divinylbenzene <SEP> .................. <SEP> 2
 <tb>
 <tb>
 <tb> ( <SEP> Agents <SEP> of <SEP> links <SEP> transversal)
 <tb>
 <tb>
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> the
 <tb>
 
 EMI20.4
 in charge of
 EMI20.5
 
 <tb> Latex <SEP> of <SEP> resin <SEP> comparable
 <tb>
 <tb>
 <tb> (reported <SEP> to <SEP> weight <SEP> sec)
 <tb>
 <tb>
 <tb> Latex <SEP> of <SEP> styrol <SEP> soluble <SEP> in <SEP> on
 <tb>
 
 EMI20.6
 rubber ..................... 20
 EMI20.7
 
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> latex
 <tb>
 
 EMI20.8
 of resin ........................

   AT
 EMI20.9
 
 <tb> Mixture
 <tb>
 <tb> Recipe <SEP> (Table <SEP> XII) <SEP> A <SEP> A <SEP> A
 <tb>
 <tb>
 <tb> Viscosity <SEP> Mooney <SEP> ML-4 <SEP> ............ <SEP> 31 <SEP> 32 <SEP> 68 <SEP> 53
 <tb>
 <tb>
 <tb> Vulcanization, <SEP> minutes <SEP> to <SEP> 141 C <SEP> ... <SEP> 60 <SEP> 45 <SEP> 45 <SEP> 30
 <tb>
 <tb>
 <tb>
 <tb> Results
 <tb>
 <tb>
 <tb> Elongations <SEP>% <SEP> ................. <SEP> 820 <SEP> 770 <SEP> 795 <SEP> 715
 <tb>
 <tb>
 <tb> Module <SEP> 300 <SEP>% <SEP> ................... <SEP> 200 <SEP> 380 <SEP> 500 <SEP> 410
 <tb>
 <tb>
 <tb> Hardness, <SEP> durometer <SEP> Shore <SEP> A <SEP> ......

    <SEP> 37 <SEP> 54 <SEP> 59 <SEP> 46
 <tb>
 <tb>
 <tb> Resistance <SEP> to <SEP> the <SEP> traction <SEP> kg / cm2 <SEP> 218 <SEP> 270 <SEP> 323 <SEP> 205
 <tb>
 <tb>
 <tb>
 <tb>% <SEP> increase <SEP> of <SEP> the <SEP> resistance <SEP> 24% <SEP> 48% <SEP> -5.8%
 <tb>
 <tb>
 <tb> to <SEP> the <SEP> traction
 <tb>
 

  <Desc / Clms Page number 21>

 
For comparison purposes, the tensile strength of the rubber was also measured after addition of polystyrol resin. These polystyrol resins are soluble in the rubber, harden the rubber somewhat and do not produce noticeable reinforcement, but very often decrease the tensile strength.



   In the comparative example, 20 parts of polystyrol were incorporated into 100 parts of polybutadiene. The determined tensile strength is, as indeed in the other experiments, the average of the two components.



   The second check of Table XIII shows almost the same figures as when forming 23 parts of polystyrol in 77 parts of polybutadiene "in situ". It is true that the two components were very intimately mixed, but not chemically linked together.



   It can be seen from Table V that the tensile strength of polybutadiene is increased by the addition of vinyl fillers, for both non-polar and polar vinyl fillers.



  Thus, the polybutadiene, together with a polar vinyl filler, gives a 550% increase in tensile strength.



   This improvement in tensile strength is also seen with a polybutadiene which contains an addition of soluble styrol resin.
If we combine polybutadienes with viscosity. Mooney high and low, values can be obtained which are more than double of those given in the tables for active vinyl fillers.



   The reinforcement which can be obtained, with the vinyl fillers, for the butadiene-styrol copolymers, and for both the hot and cold types of these copolymers, is shown in Table VI, in Table VI. case of the type of butadiene-styrol copolymer GR-S 15000
GR-S 1500 and other diene polymerizates exhibit an unpleasantly increased hysteresis by the addition of carbon black.



  This increase, however, is much less in the presence of active vinyl fillers. The addition of these new bodies is therefore useful when it is necessary to avoid the formation of heat in rubber products subjected to bending. These mixtures also exhibit very low abrasion.

  <Desc / Clms Page number 22>

 
TABLE V Polybutadiene reinforced with vinyl filler
 EMI22.1
 
 <tb> Mixture <SEP> n <SEP> V <SEP> Control <SEP> -1 <SEP> -2 <SEP> Comparison
 <tb>
 <tb>
 <tb> sound
 <tb>
 <tb>
 <tb>
 <tb> Latex <SEP> elastomer
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> (reported <SEP> to <SEP> weight <SEP> sec)
 <tb>
 <tb>
 <tb>
 <tb> Polybutadiene <SEP> ................

    <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
 <tb>
 <tb>
 <tb>
 <tb> (Recipe <SEP> L, <SEP> Table <SEP> III)
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Latex <SEP> load <SEP> vinyl
 <tb>
 <tb>
 <tb>
 <tb> (weight <SEP> sec)
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Quantity <SEP> ....................... <SEP> 20 <SEP> 20
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Composition
 <tb>
 <tb>
 <tb>
 <tb> Styrol <SEP> 90
 <tb>
 <tb>
 <tb>
 <tb> Metacrylate <SEP> of <SEP> methyl <SEP> ......... <SEP> 90
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Dimethacrylate Ethylene glycol <SEP> <SEP> + <SEP> 10
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Divinylbenzene <SEP> x <SEP> ................

    <SEP> 10
 <tb>
 <tb>
 <tb>
 <tb> (x <SEP> Agent <SEP> of <SEP> links <SEP> transversal)
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> the
 <tb>
 <tb>
 <tb>
 <tb> load <SEP> (Table <SEP> III) <SEP> ............. <SEP> C <SEP> A
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Latex <SEP> of <SEP> resin <SEP> comparable
 <tb>
 <tb>
 <tb>
 <tb> (weight <SEP> sec) <SEP>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Resin <SEP> styrol <SEP> soluble <SEP> in <SEP> the
 <tb>
 <tb>
 <tb>
 <tb> elastomers <SEP> ......................

    <SEP> 20
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> latex
 <tb>
 <tb>
 <tb>
 <tb> from <SEP> resin <SEP> (Table <SEP> III) <SEP> A
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Mixture
 <tb>
 <tb>
 <tb>
 <tb> Recipe <SEP> (-Table <SEP> III) <SEP> B <SEP> C <SEP> C <SEP> C
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Viscosity <SEP> Mooney <SEP> ML-4 <SEP> 19 <SEP> 67 <SEP> 65 <SEP> 57
 <tb>
 <tb>
 <tb>
 <tb> Vulcanization, <SEP> minutes <SEP> to <SEP> 141 C <SEP> 30 <SEP> 60 <SEP> 60 <SEP> 60
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Results
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Elongation <SEP>% <SEP> .................... <SEP> 465 <SEP> 400 <SEP> 300 <SEP> 250
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Module <SEP> 300% <SEP> ......................

    <SEP> 100 <SEP> 650 <SEP> 1040 <SEP> -
 <tb>
 <tb>
 <tb>
 <tb> Hardness, <SEP> durometer <SEP> Shore <SEP> A <SEP> ........ <SEP> 21 <SEP> 62 <SEP> 60 <SEP> 62
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Resistance <SEP> to <SEP> the <SEP> traction <SEP> kg / cm2 <SEP> 11 <SEP> 57 <SEP> 73 <SEP> 43
 <tb>
 <tb>
 <tb>
 <tb>% <SEP> increase <SEP> of <SEP> the <SEP> resistance
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> to <SEP> the <SEP> traction <SEP> .................

    <SEP> 406% <SEP> 550% <SEP> 281%
 <tb>
 

  <Desc / Clms Page number 23>

 
TABLE VI Butadiene-styrol copolymer reinforced with vinyl fillers
 EMI23.1
 
 <tb> Mixture <SEP> n <SEP> VI <SEP> Control <SEP> -1 <SEP> -2 <SEP> Comparison
 <tb>
 <tb>
 <tb> ¯¯¯¯¯¯¯¯¯ <SEP> ¯¯¯¯¯¯¯ <SEP> ¯¯¯ <SEP> ¯¯¯ <SEP> sound <SEP>
 <tb>
 <tb>
 <tb> Latex <SEP> elastomer <SEP> (weight <SEP> sec)
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> GR-S <SEP> 1500 <SEP> (Recipe <SEP> M, <SEP> tab. <SEP> III) <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Latex <SEP> load <SEP> vinyl
 <tb>
 <tb>
 <tb> (weight <SEP> sec)
 <tb>
 
 EMI23.2
 Quantity o000oooooaoooee.s.ooves 20 20
 EMI23.3
 
 <tb> Composition
 <tb>
 
 EMI23.4
 Styrol ........... 90
 EMI23.5
 
 <tb> Methacrylate <SEP> of <SEP> methyl <SEP> ...........

    <SEP> 90
 <tb>
 <tb>
 <tb> Dimethacrylate Ethylene glycolx <SEP> <SEP> 10
 <tb>
 <tb>
 <tb> Divinylbenzene <SEP> ........... <SEP> 10
 <tb>
 <tb>
 <tb> (x <SEP> Agent <SEP> of <SEP> links <SEP> transversal)
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> the <SEP> load <SEP> A <SEP> A
 <tb>
 <tb>
 <tb> (Table <SEP> III)
 <tb>
 <tb>
 <tb>
 <tb> Latex <SEP> of <SEP> resin <SEP> comparable
 <tb>
 <tb>
 <tb> weight <SEP> sec)
 <tb>
 <tb>
 <tb> Latex <SEP> of <SEP> styrol <SEP> soluble <SEP> in <SEP> on
 <tb>
 <tb>
 <tb> rubber <SEP> .................. <SEP> 20
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> latex
 <tb>
 <tb>
 <tb>
 <tb> from <SEP> resin <SEP> (Table <SEP> III) <SEP> .......

    <SEP> A
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Mixture
 <tb>
 <tb>
 <tb> Recipe <SEP> (Table <SEP> III) <SEP> ............ <SEP> F <SEP> E <SEP> D <SEP> D
 <tb>
 <tb>
 <tb>
 <tb> Viscosity <SEP> Mooney, <SEP> ML-4 <SEP> ............ <SEP> 37 <SEP> 57 <SEP> 53 <SEP> 75
 <tb>
 <tb>
 <tb> Vulcanization, <SEP> minutes <SEP> to <SEP> 141 C <SEP> .... <SEP> 90 <SEP> 90 <SEP> 30 <SEP> 60
 <tb>
 <tb>
 <tb>
 <tb> Results
 <tb>
 
 EMI23.6
 Elongation z0 .0 ................... 320 620 740 750
 EMI23.7
 
 <tb> Module <SEP> 300 <SEP>% ...................... <SEP> 160 <SEP> 440 <SEP> 430 <SEP> 200
 <tb>
 <tb> Hardness, <SEP> durometer <SEP> Shore <SEP> A <SEP> ........

    <SEP> 39 <SEP> 61 <SEP> 59 <SEP> 48
 <tb>
 <tb> Resistance <SEP> to <SEP> the <SEP> traction <SEP> (kg / cm2) <SEP> 15 <SEP> 168 <SEP> 211 <SEP> 65
 <tb>
 <tb>% <SEP> increase <SEP> resistance <SEP> to <SEP> the
 <tb>
 
 EMI23.8
 traction ........... 1.012% 1295% 333%

  <Desc / Clms Page number 24>

 
Carbon black - GR-S mixtures usually have a hardness of 60, provided that 50 parts of carbon black are mixed with 100 parts of GR-S. The active vinyl fillers give the same values with only 20 parts in 100 parts of GR-S. The tensile strength with 20 parts of active vinyl filler is equal to or greater than that obtained with 50 parts of carbon black.



   As shown in Table VI and Examples 5 and 6 of Table I, it is possible, using vinyl fillers, to increase the tensile strength of GR-S 1500 from 1000 to 1295%, these mixtures exhibiting less heat formation. than those containing 35 to 50 parts of rust.



   As long as the carbon black is replaced by vinyl fillers in the tires, the temperature of these tires can be reduced.



   The reinforcing effect of the active vinyl fillers can also be observed in diene-isobutylene copolymerisates of the type of butyl rubbers, as can be seen from Table VI-A.
To prepare the reinforced butyl rubber (example 2), 100 parts of butyl rubber type GR-1 18 were dissolved in 300 parts of methylene chloride, and emulsified with 10 parts of dismutated resin acid (Dresinate Acid 731 manufactured by the company Hercule Powder C) and 5 parts of a 28% ammonia solution. To this emulsion, 20 parts - based on the dry weight - of an active vinyl filler latex were added, and coagulated, after mixing well, with dilute sulfuric acid.

   After the usual treatment, we tried the mixture

  <Desc / Clms Page number 25>

 TABLE VI - A
 EMI25.1
 Isoprene copolymer reinforced with vinyl fillers
 EMI25.2
 
 <tb> Mixture <SEP> n <SEP> VI-A <SEP> Control <SEP> -1 <SEP> -2
 <tb>
 <tb> Elastomers <SEP> (reported <SEP> to <SEP> weight <SEP> sec)
 <tb>
 <tb> Rubber <SEP> butyl <SEP> GB-I <SEP> 18 <SEP> ...... <SEP> 100 <SEP> 100 <SEP> 100
 <tb>
 
 EMI25.3
 Dresinate 731 ........... 10 10
 EMI25.4
 
 <tb> Latex <SEP> load <SEP> vinyl
 <tb>
 <tb> (reported <SEP> to <SEP> weight <SEP> sec)
 <tb>
 
 EMI25.5
 Quantity o00oooooeseaooemsoswoveov 20 20 Composition Styrol ........... 90
 EMI25.6
 
 <tb> Divinylbenzene <SEP> ................

    <SEP> 10
 <tb>
 <tb>
 <tb> (x <SEP> Agent <SEP> of <SEP> links <SEP> transversal)
 <tb>
 <tb>
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> the <SEP> load <SEP> A
 <tb>
 <tb>
 <tb> (Table <SEP> III)
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Mixture
 <tb>
 
 EMI25.7
 Recipe ... 00 ..... 0.00 ..............

   (l) (1) (l)
 EMI25.8
 
 <tb> Viscosity <SEP> Mooney <SEP> ML-4 <SEP> .............. <SEP> 75 <SEP> 49
 <tb>
 <tb>
 <tb> Vulcanization, <SEP> minutes <SEP> to <SEP> 141 C <SEP> ..... <SEP> 45 <SEP> 60 <SEP> 90
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Results
 <tb>
 <tb>
 <tb>
 <tb> Elongation <SEP>% <SEP> 640 <SEP> 750 <SEP> 775
 <tb>
 <tb>
 <tb> Module <SEP> 300 <SEP>% ........................ <SEP> 155 <SEP> 160 <SEP> 190
 <tb>
 <tb>
 <tb>
 <tb> Hardness, <SEP> durometer <SEP> Shore <SEP> A <SEP> ........... <SEP> 40 <SEP> 38 <SEP> 49
 <tb>
 <tb>
 <tb>
 <tb> Resistance <SEP> to <SEP> the <SEP> traction <SEP> kg / cm2 <SEP> ...........

    <SEP> 31 <SEP> 59 <SEP> 80
 <tb>
 <tb>
 <tb>
 <tb>% <SEP> increase <SEP> of <SEP> the <SEP> resistance <SEP> to <SEP> the <SEP> 93 <SEP>% <SEP> 162
 <tb>
 <tb>
 <tb>
 <tb> traction
 <tb>
 (1) Mixing recipe (based on 100 parts butyl rubber):
5 parts zinc oxides, 1 part stearic acid, 0.5 part benzothiazyl disulfide, 1 part tetramethylthiuram disulfide, 2 parts sulfur.



   Butyl rubbers reinforced with active vinyl fillers give, for example, pipes which, at low temperatures, are not as stiff as mixtures loaded with carbon black.



   The reinforcing effect of the active vinyl fillers on the polar diene homopolymerisates is indicated in Table VII in the case of polychloroprene (neoprene); here, chlorinated vinyl fillers prove to be particularly effective.



   Similar results can also be observed with polar diene copolymerisates which consist on the one hand of butadiene or its homologues or mixtures thereof, on the other hand of other polar compounds, for example acrylonitrile. In Table VIII, the possible reinforcement by means of polar and non-polar fillers is indicated by way of example, in the case of two butadiene-acrylonitrile copolymers with a different acrylonitrile content.



   In the same way, the copolymerizates of

  <Desc / Clms Page number 26>

 butadiene which, instead of or next to acrylonitrile, contains other polar components, for example vinylaldehyde, vinyl ketone, vinylmethyloetone, acrolein, methacrolein, methylisopropylketone, acid acrylic, methacrylic acid, cinnamic acid as well as their esters of alcohols, phenols, etc., saturated or unsaturated, then the polar derivatives of nonpolar vinyl compounds, for example methacrylonitrile, vinylpyridine and vinylpyri- substituted dines; then, the polymerizable helogenocarbons, for example
 EMI26.1
 ple trichlorethylene, 1.1-difluoroethylene, etc ...



   Table IX shows the reinforcing effect of the vinyl fillers according to the present invention in polyethylene tetrasulfide (thion rubber) as a type of the vulcanizable high synthetic polymers not containing diene hydrocarbons.



   In addition to the vulcanizable synthetic high polymers, the properties of synthetic thermoplastic high polymers obtained by homopolymerization, oopolymerization or interpolymerization of the vinyl monomer compounds can also be improved.

  <Desc / Clms Page number 27>

 



     TABLE VII Polychloroprene reinforced with vinyl fillers
 EMI27.1
 
 <tb> Mixture <SEP> n <SEP> 7 <SEP> Control <SEP> -1 <SEP> -2
 <tb>
 <tb>
 <tb> Latex <SEP> elastomer
 <tb>
 <tb>
 <tb> (report <SEP> to <SEP> weight <SEP> sec)
 <tb>
 <tb> Polychloroprene <SEP> (1) <SEP> ....................... <SEP> 100 <SEP> 100 <SEP> 100
 <tb>
 <tb>
 <tb>
 <tb> Latex <SEP> load <SEP> vinyl
 <tb>
 <tb> (weight <SEP> sec
 <tb>
 
 EMI27.2
 Quantity 0'0 .... 00 ......................... <20 20 Composition o-chlorostyrol ooooaom..reeer..s..sss..sv 9E! Styrol .............. 2 Divinylbenzene ...................... 1.5 0.8
 EMI27.3
 
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> the <SEP> load <SEP> .......

    <SEP> B <SEP> B
 <tb>
 <tb> Table <SEP> III
 <tb>
 <tb>
 <tb>
 <tb> Mixture
 <tb>
 <tb>
 <tb> Recipe <SEP> (Table <SEP> III) <SEP> ...................... <SEP> G <SEP> G <SEP> G
 <tb>
 <tb>
 <tb> Viscosity <SEP> Mooney <SEP> ML-4 <SEP> ...................... <SEP> 200 <SEP> 200 <SEP> 200
 <tb>
 <tb>
 <tb> Vulcanization, <SEP> minutes <SEP> to <SEP> 141 C <SEP> ............. <SEP> 15 <SEP> 30 <SEP> 60
 <tb>
 <tb>
 <tb>
 <tb> Results
 <tb>
 
 EMI27.4
 Elongation% ................. 470 515 365 Modulus 300% ......................... ....... 545 1325 1530
 EMI27.5
 
 <tb> Hardness, <SEP> durometer <SEP> Shore <SEP> A <SEP> .................. <SEP> 52 <SEP> 73 <SEP> 70
 <tb>
 <tb> Resistance <SEP> to <SEP> the <SEP> traction, <SEP> kg / cm2 <SEP> ...........

    <SEP> 79 <SEP> 168 <SEP> 128
 <tb>
 <tb>% <SEP> increase <SEP> of <SEP> the <SEP> resistance <SEP> to <SEP> the
 <tb>
 
 EMI27.6
 traction 00 ............................. 111% 62% (1) Polychloroprene brand Neoprene 571 manufactured by du Pont de
Nemours to C.



  +) Cross-linking agent

  <Desc / Clms Page number 28>

 TABLE VIII
 EMI28.1
 Butaiene-acrylonitrile copolymer reinforced with vinyl fillers
 EMI28.2
 
 <tb> Mixture <SEP> n <SEP> VIII <SEP> Control <SEP> -1-2 <SEP> -3
 <tb>
 <tb> Latex <SEP> elastomer <SEP> (weight <SEP> sec)
 <tb>
 
 EMI28.3
 Butadiene-'acrylonitrile copolymer
 EMI28.4
 
 <tb> (1) <SEP> 100 <SEP> 100
 <tb>
 <tb>
 <tb>
 <tb> Copolymer <SEP> butadiene-acrylonitrile
 <tb>
 <tb>
 <tb>
 <tb> (2) <SEP> 100 <SEP> 100
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Latex <SEP> charges <SEP> vinyl <SEP> (weight <SEP> sec)
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Quantity <SEP> ..................... <SEP> 20 <SEP> 20 <SEP> 20
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Composition
 <tb>
 <tb>
 <tb>
 <tb> Methacrylate <SEP> of <SEP> methyl <SEP> 10
 <tb>
 <tb>
 <tb>
 <tb> Vinyipyridine <SEP> .............

    <SEP> 10
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Styrol <SEP> .................... <SEP> 90 <SEP> 78
 <tb>
 <tb>
 <tb>
 <tb> o-chlorostyrol <SEP> ............ <SEP> 96
 <tb>
 <tb>
 <tb>
 <tb> Divinylbenzene <SEP> ........... <SEP> 10 <SEP> 2 <SEP> 4
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> (x <SEP> Agent <SEP> of <SEP> links <SEP> transversal
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> the <SEP> load
 <tb>
 <tb>
 <tb>
 <tb> (Table <SEP> III) <SEP> A <SEP> B <SEP> B
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Mixture
 <tb>
 <tb>
 <tb>
 <tb> Recipe <SEP> (Table <SEP> III) <SEP> ........ <SEP> E <SEP> E <SEP> H <SEP> E
 <tb>
 <tb>
 <tb>
 <tb> Viscosity <SEP> Mooney <SEP> ML-4 <SEP> ........

    <SEP> 48 <SEP> 95 <SEP> 112 <SEP> 59
 <tb>
 <tb>
 <tb>
 <tb> Vulcanization, <SEP> minutes <SEP> to <SEP> 141 C <SEP> 60 <SEP> 45 <SEP> 20xx <SEP> 60
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Temperature <SEP> of <SEP> vulcanization <SEP> 154 C
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Results
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Elongations <SEP>% <SEP> .................. <SEP> 320 <SEP> 300 <SEP> 250 <SEP> 450
 <tb>
 <tb>
 <tb>
 <tb> Module <SEP> 300 <SEP>% <SEP> .................... <SEP> 380 <SEP> 1825 <SEP> - <SEP> 900
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Hardness <SEP> durometer <SEP> Shore <SEP> A <SEP> ....... <SEP> 50 <SEP> 75 <SEP> 100 <SEP> 63
 <tb>
 <tb>
 <tb>
 <tb> Resistance <SEP> to <SEP> the <SEP> traction, kg / cm2 <SEP> ..

    <SEP> 31 <SEP> 128 <SEP> 209 <SEP> 120
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>% <SEP> increase <SEP> of <SEP> the <SEP> resistance <SEP> 320 <SEP>% <SEP> 583% <SEP> 290 <SEP>%
 <tb>
 <tb>
 <tb>
 <tb> to <SEP> the <SEP> traction
 <tb>
 (1) Product Hycar 1513 (acrylonitrile 28%) manufactured by Goodrich C (2) Product Hycar 1514 (acrylonitrile 22%) manufactured by Goodrich C

  <Desc / Clms Page number 29>

 
TABLE IX Polyethylene tetrasulphide reinforced with vinyl fillers.

   
 EMI29.1
 
 <tb> Mixture <SEP> n <SEP> IX <SEP> Control <SEP> -1
 <tb>
 <tb> Latex <SEP> elastomer <SEP> (weight <SEP> sec)
 <tb>
 
 EMI29.2
 Polyethylene tetrussulfide (l) 616004.96 100 100 Latex vinyl filler (dry weight) Quantity moomosoerrseer.sooosr.s.mssv.rrr 20 Composition Acrylic acid esm..esossrrr.resrrrrrsoâr 10 Styrol GeGoaOGG ........ ............ e .. 80 Divinylbenzene x ..0 ....................... 10
 EMI29.3
 
 <tb> (x <SEP> Agent <SEP> of <SEP> links <SEP> transversal)
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> the <SEP> load <SEP> .......
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>



  (board <SEP> III)
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Mixture
 <tb>
 
 EMI29.4
 Recipe (Table XII) rmorsoeesrrp.r ... r ... r LL Mooney Viscosity ML-4 ... om ................ 20 30 Vulcanization, minutes to 1. . 0 r .............. 120 120
 EMI29.5
 
 <tb> Results
 <tb>
 
 EMI29.6
 Elongation at break% ..................... 500 800 Tensile strength, kg / cm2 a r e s. s. a s r r s 7 24
 EMI29.7
 
 <tb>% <SEP> increase <SEP> of <SEP> the <SEP> resistance <SEP> to <SEP> the <SEP> traction <SEP> 258%
 <tb>
 (1) Mixture of 90 parts thioool ST and 10 parts thiocol LP-2, manufactured by Thiokol Corp.



   In Table X, this favorable influence of vinyl fillers has been indicated, by way of example, in the case of a vinyl chloride-vinylidene chloride copolymerate. In the example given in this table, the vinyl filler latex was mixed for a short time with a Waring laboratory mixer at high speed, with the latex of vinyl chloride-vinylidene chloride copolymerizate, adding of octyl phthalate, the mixture was dried in a flat cuvette at 60 ° C., rolled on a hot laboratory rolling mill, and cooled. In this way, clear and smooth films were obtained, in which the test strips were cut. The tensile strength of these was measured using a Scott apparatus for tension tests. .



   From the figures shown in Table X it can be seen that the tensile strength of the copolymerizate is increased by more than 60% by the vinyl filler, while, as experience shows, the addition of a Styrofoam resin not transversely bonded, on the contrary, reduces the tensile strength by nearly 10%.



   Similar increases in tensile strength can be seen not only in other vinyl chloride copolymerisates, but also, as shown in Table XI, in the homopolymerisates, copolymerisates or interpolymerisates of others. vinyl compounds, for example derived from cellulose. The content of plasticizers, whatever their composition, has no influence whatsoever on the action of the vinyl fillers. As can be seen from Table XI, increases in tensile strength are obtained, both in the plyvinyl esters chosen as an example, such as ac-

  <Desc / Clms Page number 30>

 polyvinyl tate or polyvinyl butyrate, as in the copolymers styrolacrylonitrile, and ethylcellulose.



   The composition of the blends used in the experiments on natural or synthetic vulcanizable high polymers is shown in Table XII; mixtures, however, are only taken as models, and do not always give the best results, as has been shown by the example of chloroprene (Table VII).



  The chloroprene latex (Neoprene) 571 used in this table is, of course, an excellent film former, but it has too high a gel content, to give a mixture having a high tensile strength. However, this latex also, worked after addition of vinyl fillers, gives vulcanized products endowed with markedly improved properties. Likewise, the examples of Table VI-A-2 and Tables X and XI are given for demonstration purposes only, without showing the maximum values of possible reinforcements.



    PAINTINGS
Vinyl chloride-vinylidene chloride copolymer, reinforced with vinyl fillers.
 EMI30.1
 
 <tb>



  Mixed <SEP> N <SEP> X <SEP> Control <SEP> -1-2
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Latex <SEP> elastomer <SEP> (weight <SEP> sec)
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Copolymer <SEP> chloride <SEP> of <SEP> vinyl-
 <tb>
 <tb>
 <tb>
 <tb> chloride <SEP> of <SEP> vinylidene (l) <SEP> ....... <SEP> 80 <SEP> 80 <SEP> 80
 <tb>
 <tb>
 <tb>
 <tb> Phthalate Oxyl <SEP> <SEP> (plasticizer) <SEP>. <SEP> 20 <SEP> 20 <SEP> 20
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Latex <SEP> load <SEP> vinyl <SEP> (weight <SEP> sec)
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Quantity <SEP> ........................ <SEP> 20 <SEP> 20
 <tb>
 <tb>
 <tb>
 <tb> Composition
 <tb>
 <tb>
 <tb>
 <tb> Styrol <SEP> ......................... <SEP> 90
 <tb>
 <tb>
 <tb>
 <tb> Methacrylate <SEP> of <SEP> methyl <SEP> ....... <SEP> 90
 <tb>
 <tb>
 <tb>
 <tb> Divinylbenzènex <SEP> ...............

    <SEP> 10 <SEP> 10
 <tb>
 <tb>
 <tb>
 <tb> (Agent <SEP> of <SEP> links <SEP> transversal
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> the <SEP> load <SEP> A <SEP> A
 <tb>
 <tb>
 <tb> (Table <SEP> III)
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Results
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Elongation <SEP> of <SEP> break <SEP>% <SEP> 200 <SEP> 50 <SEP> 200
 <tb>
 <tb>
 <tb>
 <tb> Resistance <SEP> to <SEP> the <SEP> traction, <SEP> kg / cm2 <SEP> 86 <SEP> 143 <SEP> 143
 <tb>
 <tb>
 <tb>
 <tb>% <SEP> increase <SEP> of <SEP> the <SEP> resistance
 <tb>
 
 EMI30.2
 tensile strength ................ 65, 67, (1) Vinyl chloride-vinylidene chloride copolymer:
Latex 744 B from Dow Chemical C.

  <Desc / Clms Page number 31>

 



    TABLE XI Plastomers with vinyl fillers
 EMI31.1
 
 <tb> Mixture <SEP> n <SEP> XI <SEP> Control <SEP> -1 <SEP> Control <SEP> -2 <SEP> Control <SEP> -3 <SEP> Control <SEP> -4
 <tb> Latex <SEP> plastomer <SEP> (weight <SEP> sec)
 <tb> Acetate <SEP> of <SEP> polyvinyl <SEP> (1) <SEP> ............... <SEP> 100 <SEP> 100
 <tb> Butyrate <SEP> of <SEP> polyvinyl <SEP> (2) <SEP> ............... <SEP> 100 <SEP> 100
 <tb> Styrol-acrylonitrile <SEP> (3) <SEP> ................ <SEP> 100 <SEP> 100
 <tb> Ethylcellulose <SEP> (4) <SEP> ............... <SEP> 100 <SEP> 100
 <tb> Latex <SEP> load <SEP> vinyl
 <tb> ( <SEP> weight <SEP> sec) <SEP> (5) <SEP> ................. <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20
 <tb> Results
 <tb> Elongations <SEP> of <SEP> break <SEP>% ...............

    <SEP> 30 <SEP> 20 <SEP> 565 <SEP> 500 <SEP> 150 <SEP> 150 <SEP> 50 <SEP> 30
 <tb> Resistance <SEP> to <SEP> the <SEP> traction <SEP> kg / cm2 <SEP> ......... <SEP> 86 <SEP> 116 <SEP> 41 <SEP> 107 <SEP> 94 <SEP> 158 <SEP> 116 <SEP> 134
 <tb>% <SEP> increase <SEP> of <SEP> the <SEP> resistance <SEP> to <SEP> the
 <tb> traction <SEP> ............................. <SEP> 36% <SEP> 160% <SEP> 69% <SEP> 15%
 <tb>
   (1) KR-2 aqueous dispersion, manufacturer: Monsanto Chemical C.



  (2) Aqueous dispersion Whiting BRS, manufacturer: Monsanto Chemical C.



  (3) Latex Kralastio 4109A, manufacturer: Nagatuck Chemical Division of U.S. Rubber C. It is a styrolacrylonitrile copolymer, plasticized with 25-30 parts of butadiene-acrylonitrile copolymer according to US Patents No. 2,439,202, 2,505,349, 2,550,139. This is an example of a mixture of Class II elastomers and Class III plastomers, and this example shows the reinforcement of such a mixture by the vinyl filler.



  (4) Ethocel-castor oil, proportion 67:33; with ordinary ethocel (viscosity 50 cps), manufacturer: Dow Chemical C.



  (5) Preparation of the vinyl filler latex: styrol parts; parts divinylbenzene and 10 parts methacrylic acid, polymerized according to Table III, Recipe A, with adjustment of the latex to pH = 8 using 28% ammonium hydroxide.

  <Desc / Clms Page number 32>

 



    TABLE XII Vulcanization recipes (parts out of 100 parts vulcanizable material)
 EMI32.1
 
 <tb> Mixture <SEP> n <SEP> XII <SEP> A <SEP> B <SEP> C <SEP> D <SEP> E <SEP> F <SEP> G <SEP> H <SEP> I <SEP> J <SEP> K <SEP> L
 <tb> Oxide <SEP> of <SEP> magnesium <SEP> (light <SEP> .... <SEP> 4 <SEP> 20
 <tb> Oxide <SEP> of <SEP> zinc <SEP> ................. <SEP> 5 <SEP> 3 <SEP> 3 <SEP> 3 <SEP> 3 <SEP> 3 <SEP> 5 <SEP> 3 <SEP> 5 <SEP> 3 <SEP> 0.5
 <tb> Acid <SEP> stearic <SEP> 1 <SEP> 1 <SEP> 3 <SEP> 1 <SEP> 2 <SEP> 1 <SEP> 0.5 <SEP> 1.5 <SEP> 2 <SEP> ' <SEP> 3
 <tb> Disulfide <SEP> of <SEP> benzothiazyl <SEP> 1 <SEP> 1 <SEP> 0.5 <SEP> 4.5 <SEP> 1 <SEP> 1
 <tb> 2-mercaptobenzothiazol <SEP> ........ <SEP> 1 <SEP> 0.5 <SEP> 0.

    <SEP> 5 <SEP> 1
 <tb> N-cyclohexyl-2-benzothiazolsulfonamide <SEP> 1 <SEP> 1 <SEP> 1 <SEP>
 <tb> Monosulfide <SEP> of <SEP> tetramethylthiuram <SEP> ...................... <SEP> 0.15
 <tb> Accelerator <SEP> A-32 <SEP> ............. <SEP> 0. <SEP> 2 <SEP> 0. <SEP> 2 <SEP> 0. <SEP> 2
 <tb> Bisulfide <SEP> of <SEP> tetraethylthiuram <SEP> 0.15 <SEP> 0. <SEP> 2
 <tb> Sulfur <SEP> 2.5 <SEP> 2. <SEP> 5 <SEP> 2.5 <SEP> 2. <SEP> 5 <SEP> 2. <SEP> 5 <SEP> 2. <SEP> 5 <SEP> 2.0 <SEP> 2. <SEP> 5 <SEP> 4 <SEP> 2. <SEP> 5
 <tb> q-quinonedioime <SEP> ................ <SEP> 1.5
 <tb>
   + Reaction product of butyraldehyde and butylidene-aniline:

   manufacturer Monsanto Chemical C

  <Desc / Clms Page number 33>

 
Table XIII shows that the interpolymers of high natural or synthetic vulcanizable polymers and of nonpolar or polar monomeric vinyl compounds can also be significantly improved in their properties by the new vinyl fillers.



   To prepare the interpolymers, the monomers which were either styrol or methyl methacrylate were added to natural rubber, polybutadiene or polychloroprene latexes, together with about 0.5 part of hydroperoxide. of cumene per 100 parts of latex, and the mixture in closed bottles was heated to 60 ° C. After 12 hours, the interpolymerization was complete.



   The interpolymer latexes thus obtained were then mixed with the latexes of vinyl fillers indicated in Table XIII, the latex mixtures were coagulated with salt and acid, dried and used for the mixtures.



   It can also be seen, from example 2 of this Table, that a mixture of polybutadiene and polystyrol is also reinforced by the vinyl fillers.



   Similar effects are also obtained with the vinyl fillers in accordance with the present invention, in the case of mixtures of butadiene-styrol copolymers (GR-S 1500) and polybutadiene, or butadiene-acrylonitrile copolymers.

  <Desc / Clms Page number 34>

 



    TABLE XIII
 EMI34.1
 Reinforcement of interpolymers of natural rubber and elar; tomères, by cllarges V: B!, Z.- leagues.
 EMI34.2
 
 <tb>



  Mixed <SEP> n <SEP> XIII <SEP> Control <SEP> -1 <SEP> Control <SEP> -2 <SEP> Control <SEP> -3
 <tb>
 
 EMI34.3
 Latex, interpolymers (dry weight
 EMI34.4
 
 <tb> Composition <SEP> rubber <SEP> and <SEP> elastomer
 <tb> Latex <SEP> of <SEP> rubber <SEP> natural <SEP> 80 <SEP> 80
 <tb> Latex <SEP> of <SEP> polybutadiene <SEP> Tab. <SEP> III, <SEP> rec.L <SEP> 77 <SEP> 77
 <tb> Polychloroprene <SEP> (Latex <SEP> Neoprene <SEP> 571) <SEP> 95 <SEP> 95
 <tb> Monomer <SEP> interpolymerizable
 <tb> Methacrylate <SEP> of <SEP> methyl <SEP> ..................... <SEP> 20 <SEP> 20 <SEP> 5 <SEP> 5
 <tb> Styrol <SEP> ......................................

    <SEP> 23 <SEP> 23
 <tb> Latex <SEP> load <SEP> vinyl <SEP> (weight <SEP> sec)
 <tb> Quantity <SEP> 20 <SEP> 20 <SEP> 20
 <tb> Composition
 <tb> Methacrylate <SEP> of <SEP> methyl <SEP> 80 <SEP> 80 <SEP> 80
 <tb> Acid <SEP> methacrylic <SEP> 10 <SEP> 5 <SEP> 5
 <tb>
 
 EMI34.5
 Butadiene .................................. 5 5
 EMI34.6
 
 <tb> Dimethacrylate Ethylene glycol <SEP> <SEP> ... <SEP> 0.46. *. <SEP> 10 <SEP> 10 <SEP> 10
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> the <SEP> load
 <tb> Table <SEP> III <SEP> ........................................

    <SEP> A <SEP> B <SEP> B
 <tb> Mixture
 <tb> Recipe <SEP> (array <SEP> XII) <SEP> A <SEP> A <SEP> E <SEP> E <SEP> G <SEP> G
 <tb> Allylamine <SEP> 3 <SEP> 2
 <tb> Viscosity <SEP> Mooney <SEP> ML-4 <SEP> 28 <SEP> 29 <SEP> 118 <SEP> 200 <SEP> 200 <SEP> 200
 <tb> Vulcanization, <SEP> minutes <SEP> to <SEP> 141 C <SEP> 60 <SEP> 30 <SEP> 30 <SEP> 30 <SEP> 60 <SEP> 60
 <tb> Results
 <tb> Elongations <SEP>% <SEP> ................................... <SEP> 600 <SEP> 650 <SEP> 280 <SEP> 440 <SEP> 400 <SEP> 340
 <tb> Module <SEP> 300 <SEP>% ..................................... <SEP> 380 <SEP> 2400 <SEP> 750 <SEP> 585 <SEP> 980
 <tb> Hardness, <SEP> durometer <SEP> Shore <SEP> A <SEP> ........, ....., ......... <SEP> 41 <SEP> 77 <SEP> 61 <SEP> 72 <SEP> 56 <SEP> 81
 <tb> Resistance <SEP> to <SEP> the <SEP> traction <SEP> kg / cm2 <SEP> ..................

    <SEP> 129 <SEP> 237 <SEP> 56 <SEP> 81 <SEP> 60 <SEP> 93
 <tb>% <SEP> increase <SEP> of <SEP> the <SEP> resistance <SEP> to <SEP> the <SEP> traction <SEP> 82% <SEP> 46% <SEP> 56%
 <tb>
   + Cross-linking agent

  <Desc / Clms Page number 35>

 
Polybutadiene has excellent flexibility at low temperatures, so it is often added to butadiene-styrol copolymers.



   The mixtures of polymerizates shown in Table XIV were obtained by mixing the corresponding latexes, followed by salt and acid coagulation and drying, and then tested after the preparation of the mixture. The percentage increase in tensile strength, which is 774 and 598%, shows the increase in the various components, exceeding the average tensile strength, which is obtained by reinforcement with vinyl fillers.



   The latex mixtures obtained in a similar way by mixing natural latex and the latex of butadiene-styrol copolymers (GR-S types), mixtures used in the manufacture of foam rubber, can be reinforced with vinyl fillers, especially when they are manufactured without emulsifier, as shown in Table XXI.



   Further examples of the strengthening action of vinyl fillers are given in Table XV, and this explains the strengthening effect of the novel vinyl fillers on the mixture of a high butadiene-styrol copolymer. butadiene content (75% and more) (GR-S 1500) with a copolymer with a butadiene content of 20% and less.



  The latter is soluble in the higher butadiene content copolymer. Blends of this kind are used in making rubber soles or heels because the low butadiene copolymer improves stiffness and abrasion.



   In the examples of Table XV, the low butadiene copolymers were prepared by emulsion polymerization, and mixed with the latex of the high butadiene copolymers (GR-S 1500), with or without the addition of vinyl fillers.



  The comparative example of Table XV and Example 7 of Table XXII show that the transversely bonded styrol filler of the latter example produces a tensile strength that is 141 kg / cm2 higher than that of the unbound styrol resin. transversely (Pliolite S-3 resin), as shown in Table XV, - see also Table VI.

  <Desc / Clms Page number 36>

 



    TABLE XIV Elastomers mixed with vinyl fillers.
 EMI36.1
 
 <tb>



  Mixed <SEP> n <SEP> XIV
 <tb> Latex <SEP> elastomer <SEP> (weight <SEP> sec)
 <tb> Polybutadiene <SEP> (Table <SEP> III <SEP> Recipe <SEP> L) <SEP> 50
 <tb> Copolymer <SEP> butadiene-styrol <SEP> (Table <SEP> III <SEP> Recipe <SEP> M) <SEP> 50 <SEP> 50
 <tb>
 
 EMI36.2
 Butadiene-aorylonitrile copolymer + 50 Latex vinyl filler (dry weight) Quantity .................................... . * ................................ 20 20 Composition Methyl methacrylate .......... ..... 90 90
 EMI36.3
 
 <tb> dimethacrylate Ethylene glycol <SEP> <SEP> 10 <SEP> 10
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> load <SEP> (Table <SEP> III) <SEP> A <SEP> A
 <tb> Mixture
 <tb> Recipe <SEP> (array <SEP> XII)
 <tb> Viscosity <SEP> Mooney <SEP> ML-4 <SEP> 12 <SEP> 52
 <tb> Vulcanization, <SEP> minutes <SEP> to <SEP> 141 C ............................

    <SEP> 30 <SEP> 60
 <tb> Results
 <tb> Elongation <SEP>% <SEP> 800 <SEP> 450
 <tb> Module <SEP> 300 <SEP>% <SEP> 260 <SEP> 1180
 <tb> Hardness, <SEP> durometer <SEP> Shore <SEP> A <SEP> ................................ <SEP> 52 <SEP> 70
 <tb> Resistance <SEP> to <SEP> the <SEP> traotion <SEP> kg / cm2 <SEP> 115 <SEP> 155
 <tb>% <SEP> increase <SEP> resistance <SEP> to <SEP> the <SEP> traction <SEP> 774% <SEP> (1) <SEP> 598% <SEP> (2)
 <tb>
   + (B.F.

   Goodrich Hycar 1513 - 28 parts acrylonitrile) ++ Cross-linking agent (1) The control gives 13 kg / om2, average of the controls in Tables V and VI (2) The control gives 25 kg / om2, average of the controls in Tables VI and VIII

  <Desc / Clms Page number 37>

   TABLE XV Elastomer-vinyl resin combinations reinforced with vinyl fillers
 EMI37.1
 
 <tb> Mixture <SEP> n <SEP> XV <SEP> Control <SEP> -1 <SEP> Control <SEP> -2 <SEP> Comparison.
 <tb>



  Latex <SEP> elastomer <SEP> (weight <SEP> sec)
 <tb> GR-S <SEP> 100 <SEP> called <SEP> now <SEP> GR-S <SEP> 1500) <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
 <tb> Latex <SEP> elastomer <SEP> resin <SEP> vinyl <SEP> soluble <SEP> (weight <SEP> sec)
 <tb>
 
 EMI37.2
 Quantity oamo.soo.aoooo.ooooooooeoo.meo.osooooo0 20 20 20 20 20 Composition Styrol .oo ........ e .... oo ... o ..... ooo.e8 .. ... 90 90 80 80 Butadiene ......... ++ ........... 0 ... 0 ............ 10 10 20 20 Pliolite S-3 Resin ......................... 0. 100
 EMI37.3
 
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> the <SEP> resin, <SEP> table <SEP> III <SEP> A <SEP> A <SEP> A <SEP> A
 <tb> Latex <SEP> of <SEP> load <SEP> vinyl <SEP> insoluble <SEP> (weight <SEP> sec)
 <tb>
 
 EMI37.4
 Amount .........................................

   20 20
 EMI37.5
 
 <tb> Composition
 <tb> Styrol <SEP> ..................................... <SEP> 99.2 <SEP> 99. <SEP> 2
 <tb>
 
 EMI37.6
 Divinylbenzol .............................. 0.8 0.8
 EMI37.7
 
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> load <SEP>, <SEP> Table <SEP> III <SEP> B <SEP> B
 <tb> Mixture
 <tb> Recipe <SEP> (Table <SEP> III) <SEP> ............................ <SEP> F <SEP> F <SEP> F <SEP> F
 <tb> Viscosity <SEP> Mooney, <SEP> ML-4 <SEP> ........................... <SEP> 55 <SEP> 87 <SEP> 56 <SEP> 56 <SEP> 51
 <tb> Vulcanization, <SEP> minutes <SEP> to <SEP> 141 C .................... <SEP> 60 <SEP> 60 <SEP> 90 <SEP> 90 <SEP> 105
 <tb> Results
 <tb> Elongations <SEP>% <SEP> ................................... <SEP> 590 <SEP> 440 <SEP> 425 <SEP> 425 <SEP> 400
 <tb>
 
 EMI37.8
 Module 300% ..............................

   160 770 300 1020 460
 EMI37.9
 
 <tb> Hardness, <SEP> durometer <SEP> Shore <SEP> A <SEP> ........................ <SEP> 54 <SEP> 70 <SEP> 54 <SEP> 84 <SEP> 52
 <tb> Resistance <SEP> to <SEP> the <SEP> traction <SEP> kg / cm2 <SEP> .................. <SEP> 39 <SEP> 79 <SEP> 30 <SEP> 96 <SEP> 39
 <tb>% <SEP> increase <SEP> resistance <SEP> to <SEP> the <SEP> traction <SEP> ......... <SEP> 141 <SEP>% <SEP> 216%
 <tb>
   + GR-S butadiene-styrol copolymer, brand GR-S 10-20 ++ Pliolite S-3 resin is a dry product of Goodyear Tire & Rubber C. It is a styrol resin with 10-20% butadiene, and for this comparison it was incorporated, in the cylinder, in the GR-1500.



  +++ Cross-linking agent.

  <Desc / Clms Page number 38>

 



   Since the vinyl filler is insoluble in the elastomers, we can mix the vinyl filler in the form of latex with each of the two components, and coagulate the whole, then dry, and, in this form, add it, on the cylinder , to the other dried elastomer.



   Similarly reinforced blends of two high vulcanizable polymers can be seen from the examples in Table IX and reinforced blends of high vulcanizable and unvulcanizable polymers from Tables XI-3 and XXVI.



   As can be seen from Tables XVI to XIX, vinyl charges containing carboxyl groups, which can be prepared either by homopolymerization, interpolymerization or graft polymerization of a vinyl or allylic acid, or from of a three-dimensional acidic crosslinker, or by reaction of an acid derivative on the double bond of a partially unsaturated vinyl filler, are distinguished by a particularly good strengthening effect.

   It can also be seen, from Tables XVI and XVII, the favorable effect of ammonia, or of mono-, di-, tri- or tetrasubstituted organic ammonium compounds, used at the same time as these vinyl fillers; ammonia and low molecular weight amines perform better than high molecular weight amines, but the materials must be mixed and vulcanized immediately, if nitrile groups are not simultaneously introduced.



   In all of the examples of Tables XVI to XIX, the latexes of the carboxyl grouped vinyl fillers were mixed with the latexes of the elastomer, the mixture was coagulated, dried and then worked.

  <Desc / Clms Page number 39>

 



    TABLE XVI Elastic and plastic materials and vinyl fillers containing carboxylic groups which contain an addition of amines.
 EMI39.1
 
 <tb>



  Mixed <SEP> n <SEP> XVI-1 <SEP> -2-3 <SEP> -4 <SEP> -5 <SEP> -6
 <tb> Latex <SEP> of elastomers <SEP> and <SEP> plastomers <SEP> (weight <SEP> sec)
 <tb>
 
 EMI39.2
 I Natural rubber .................... 0 100
 EMI39.3
 
 <tb> IIA-1 <SEP> Polybutadiene <SEP> (Table <SEP> III, <SEP> Recipe <SEP> L) <SEP> ..... <SEP> 100
 <tb> IIA-2 <SEP> GR-S + 1500 <SEP> (Table <SEP> III <SEP> Recipe <SEP> M) <SEP> ........ <SEP> 100
 <tb> IIB-1 <SEP> Polychloroprene <SEP> (Neoprene <SEP> 571) <SEP> ................. <SEP> 100
 <tb> IIB-2 <SEP> Copolymer <SEP> butadiene-acrylonitrile <SEP> (Hycar <SEP> 1514) <SEP> 100
 <tb> III <SEP> Copolymer <SEP> chloride <SEP> of <SEP> vinyl <SEP> chloride <SEP> of <SEP> vinylidene
 <tb>
 
 EMI39.4
 (Dow Latex 774B) ....... o ... e..o ... oo.o ... o ... 100 Vinyl filler latex (dry weight) Quantity ....... .....................................

   20 20 20 20 20 20
 EMI39.5
 
 <tb> Composition
 <tb> Acid <SEP> acrylic <SEP> .................................. <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10
 <tb>
 
 EMI39.6
 Methacrylic acid .............................. 10 Styrol ................ ........................... 78 78 80 78 ... 80 80 Butadiene ............. .......................... e 2 2 2 Divinylbenzene ................... ................ 10 10 10 10 10 10
 EMI39.7
 
 <tb> ( <SEP> Agent <SEP> of <SEP> links <SEP> transversal)
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> the <SEP> load <SEP> (Tab. <SEP> III) <SEP> F <SEP> F <SEP> F <SEP> F <SEP> A <SEP> A
 <tb> Mixture
 <tb> Recipe <SEP> (Table <SEP> III) <SEP> .............................. <SEP> A <SEP> C <SEP> E <SEP> G <SEP> E
 <tb> Allylamine <SEP> .........................................

    <SEP> 3 <SEP> 3 <SEP> 3 <SEP> 3 <SEP> 3
 <tb>
 
 EMI39.8
 Mooney ML-Q viscosity ............................... 29 36 46 200 59
 EMI39.9
 
 <tb> Vulcanization, <SEP> minutes <SEP> to <SEP> 141 C <SEP> ..................... <SEP> 45 <SEP> 45 <SEP> 20 <SEP> 30 <SEP> 60
 <tb> Results
 <tb> Elongation <SEP>% <SEP> ....................................... <SEP> 725 <SEP> 1155 <SEP> 825 <SEP> 345 <SEP> 560 <SEP> 60
 <tb> Module <SEP> 300 <SEP>% <SEP> ........................................ <SEP> 500 <SEP> 170 <SEP> 375 <SEP> 1580 <SEP> 580
 <tb> Hardness, <SEP> durometer <SEP> Shore <SEP> A <SEP> ........................... <SEP> 54 <SEP> 49 <SEP> 63 <SEP> 72 <SEP> 60
 <tb> Resistance <SEP> to <SEP> the <SEP> traction <SEP> kg / om2 <SEP> .....................

    <SEP> 321 <SEP> 73 <SEP> 262 <SEP> 134 <SEP> 130 <SEP> 167
 <tb>% <SEP> increase <SEP> resistance <SEP> to <SEP> the <SEP> traction ............ <SEP> 47% <SEP> 550% <SEP> 1633% <SEP> 68% <SEP> 325% <SEP> 94%
 <tb>
   + Butadiene-styrol copolymer brand GR-S ++ 89 parts vinyl chloride-vinylidene chloride copolymer, with 20 parts of octyl phthalate as plasticizer.



  +++ Isoprene instead of butadiene.

  <Desc / Clms Page number 40>

 



    TABLE XVII Vinyl fillers with carboxyl groups with addition of amine as a reinforcing aid
 EMI40.1
 Mixture n .: RiVII Control -1 -2 -3 -4 -5 6 -7 -8 -9 -10 -11
 EMI40.2
 
 <tb> Latex <SEP> elastomer <SEP> (weight <SEP> sec)
 <tb> GR-S + <SEP> 1500 <SEP> (Tab.III <SEP> recipe <SEP> M) <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
 <tb> Latex <SEP> load <SEP> vinyl <SEP> (weight <SEP> sec)
 <tb> Quantity <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20
 <tb> Composition <SEP> ++
 <tb> Mixture
 <tb> Recipe-Table <SEP> XII) <SEP> F <SEP> I <SEP> C <SEP> C <SEP> C <SEP> C <SEP> C <SEP> C <SEP> C <SEP> C <SEP> C <SEP> C
 <tb> Derivatives Ammonia <SEP> <SEP> 0
 <tb> Ammonia <SEP> aqueous <SEP> (28 <SEP>%)

    <SEP> ......... <SEP> 4
 <tb> Allylamine <SEP> 3
 <tb> n-propylamine <SEP> .................. <SEP> 3
 <tb> di-n-propylamine <SEP> 3
 <tb> isopropylamine <SEP> ................. <SEP> 3
 <tb> diisopropylamine <SEP> ................
 <tb> diallylamine <SEP> ....................
 <tb> tri-n-butylamine <SEP> 6
 <tb> Hydroxide <SEP> of <SEP> trimethylbenzylammonium <SEP> to <SEP> 50 <SEP>% <SEP> ......... <SEP> 10
 <tb> n-isopropylgluoamine <SEP> 6
 <tb>
 
 EMI40.3
 Mooney ML-4 viscosity ........... 37 60 46 44 44 41 44 43 45 46 47 56
 EMI40.4
 
 <tb> Vulcanization, <SEP> minutes <SEP> to <SEP> 141 C <SEP> ..

    <SEP> 90 <SEP> 120 <SEP> 90 <SEP> 45 <SEP> 60 <SEP> 60 <SEP> 60 <SEP> 45 <SEP> 90 <SEP> 60 <SEP> 60 <SEP> 60
 <tb> Results
 <tb> Elongations <SEP>% <SEP> 320 <SEP> 330 <SEP> 850 <SEP> 720 <SEP> 650 <SEP> 650 <SEP> 655 <SEP> 720 <SEP> 755 <SEP> 730 <SEP> 750 <SEP> 780
 <tb> Module <SEP> 300 <SEP>% ..................... <SEP> 160 <SEP> 1800 <SEP> 330 <SEP> 550 <SEP> 445 <SEP> 495 <SEP> 490 <SEP> 380 <SEP> 440 <SEP> 330 <SEP> 330 <SEP> 330
 <tb> Hardness, <SEP> durometer <SEP> Shore <SEP> A <SEP> ......,. <SEP> 39 <SEP> 46 <SEP> 55 <SEP> 63 <SEP> 65 <SEP> 60 <SEP> 63 <SEP> 58 <SEP> 62 <SEP> 58 <SEP> 58 <SEP> 59
 <tb> Resistance <SEP> to <SEP> the <SEP> traction <SEP> kg / cm2 ..

    <SEP> 15 <SEP> 143 <SEP> 191 <SEP> 225 <SEP> 210 <SEP> 212 <SEP> 235 <SEP> 228 <SEP> 219 <SEP> 199 <SEP> 166 <SEP> 173
 <tb>% <SEP> increase <SEP> resistance <SEP> to
 <tb> the <SEP> traction <SEP> 844% <SEP> 1165% <SEP> 1390% <SEP> 1288% <SEP> 1300% <SEP> 1456% <SEP> 1407% <SEP> 1351% <SEP> 1216% <SEP> 997% <SEP> 1044%
 <tb>
   + Butadiene-styrol copolymer, GR-S brand Emulsion copolymer, 78 parts styrol, 10 parts acrylic acid, 2 parts isoprene, 10 parts divinylbenzene (cross-linking agent). Polymerized according to Tab. Recipe III F. Was used in all examples except mixtures 9-11, in which 2 parts methacrylic acid was used instead of 2 parts acrylic acid.

  <Desc / Clms Page number 41>

 



    RATE XVIII Variation of the vulcanization time depending on the carboxyl content of the vinyl fillers
 EMI41.1
 
 <tb> Mixture <SEP> n <SEP> XVIII <SEP> Control <SEP> -1 <SEP> -2 <SEP> -3 <SEP> -4
 <tb>
 
 EMI41.2
 Latex: elastomer (dry weight)
 EMI41.3
 
 <tb> GR-S + <SEP> 1500 <SEP> (Table <SEP> III <SEP> Recipe <SEP> M) <SEP> ............... <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
 <tb> Latex <SEP> load <SEP> vinyl <SEP> (weight <SEP> sec)
 <tb>
 
 EMI41.4
 Quantity oe ............... 20 20 20 20 20 20 Composition Styrol ..0 ................ 0 ... 0. .................. 89 88 87 85 80 Methacrylic acid ......................... ..... 1 2 3 5 10 Divinylbenzene ++ ................................

   10 10 10 10 10
 EMI41.5
 
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> the <SEP> load <SEP> (Table <SEP> III) <SEP> F <SEP> F <SEP> F <SEP> F <SEP> F
 <tb> Mixture
 <tb> Recipe <SEP> (array <SEP> III) <SEP> ............................. <SEP> F <SEP> E <SEP> E <SEP> E <SEP> E
 <tb> 1,2-dihydro-2,2,4-trimethylquinoline <SEP> .............. <SEP> 1 <SEP> 1 <SEP> 1
 <tb> Phenylbetanaphthylamine <SEP> ............................ <SEP> 1 <SEP> 1
 <tb> Amitrile <SEP> I.P. <SEP> +++ <SEP> ................................ <SEP> 2 <SEP> 2 <SEP> 2 <SEP> 3 <SEP> 4
 <tb> Viscosity <SEP> Mooney, <SEP> ML-4 <SEP> ............................ <SEP> 37 <SEP> 49 <SEP> 49 <SEP> 48 <SEP> 50 <SEP> 50
 <tb> Vulcanization, <SEP> minutes <SEP> to <SEP> 141 C <SEP> ....................

    <SEP> 90 <SEP> 30 <SEP> 45 <SEP> 60 <SEP> 90 <SEP> 90
 <tb> Results
 <tb> Elongations <SEP>% <SEP> ...................................... <SEP> 320 <SEP> 740 <SEP> 690 <SEP> 720 <SEP> 650 <SEP> 700
 <tb> Module <SEP> 300 <SEP>% <SEP> ......................................... <SEP> 160 <SEP> 475 <SEP> 500 <SEP> 480 <SEP> 550 <SEP> 530
 <tb> Hardness, <SEP> durometer <SEP> Shore <SEP> A <SEP> ............................ <SEP> 39 <SEP> 62 <SEP> 62 <SEP> 65 <SEP> 65 <SEP> 64
 <tb> Resistance <SEP> to <SEP> the <SEP> traction, <SEP> kg / cm2 <SEP> ..................... <SEP> 15 <SEP> 215 <SEP> 218 <SEP> 218 <SEP> 211 <SEP> 220
 <tb>% <SEP> increase <SEP> resistance <SEP> to <SEP> the <SEP> traction <SEP> .............

    <SEP> 1320% <SEP> 1342% <SEP> 1342% <SEP> 1295% <SEP> 1353
 <tb>
   + Butadiene-styrol copolymer brand GR-S ++ Cross-linking agent +++ Amitrile I.P. is alpha-isopropylaminopropionitrile

  <Desc / Clms Page number 42>

   TABLE XIX
 EMI42.1
 Influenpe of the proportion of divinylbel1zene in the fillers ZiaLlig,, a, groups ca "" bo: x:

  yl.L.9 ....?.!?. '
 EMI42.2
 
 <tb> Mixture <SEP> DO <SEP> XIX <SEP> Control <SEP> -1 <SEP> -2 <SEP> -3 <SEP> -4 <SEP> -5 <SEP> -6
 <tb> Latex <SEP> elastomer <SEP> (weight <SEP> sec)
 <tb> GB-S <SEP> 1500 <SEP> (Table <SEP> III, <SEP> recipe <SEP> M) <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
 <tb> Latex <SEP> load <SEP> vinyl <SEP> (weight <SEP> sec)
 <tb> Quantity <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20
 <tb> Composition
 <tb> Styrol <SEP> ....................................

    <SEP> 94 <SEP> 93 <SEP> 92 <SEP> 90 <SEP> 87 <SEP> 85
 <tb> Acid <SEP> methacrylic <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5 <SEP> 5
 <tb> Divinyibenzene <SEP> (DVB) <SEP> 1 <SEP> 2 <SEP> 3 <SEP> 5 <SEP> 8 <SEP> 10
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> the <SEP> load <SEP> (Table <SEP> III) <SEP> F <SEP> F <SEP> F <SEP> F <SEP> F <SEP> F
 <tb> Mixture
 <tb> Recipe <SEP> (Table <SEP> III) <SEP> F <SEP> E <SEP> E <SEP> E <SEP> E <SEP> E
 <tb> Amitrile <SEP> I.P ................................. <SEP> 3 <SEP> 3 <SEP> 3 <SEP> 3 <SEP> 3 <SEP> 3
 <tb> Viscosity <SEP> Mooney <SEP> ML-4 <SEP> ........................ <SEP> 37 <SEP> 52 <SEP> 50 <SEP> 51 <SEP> 53 <SEP> 55 <SEP> 59
 <tb> Vulcanization, <SEP> minutes <SEP> to <SEP> 141 C <SEP> ...............

    <SEP> 90 <SEP> 45 <SEP> 45 <SEP> 45 <SEP> 60 <SEP> 60 <SEP> 60
 <tb> Results
 <tb> Elongations <SEP>% <SEP> 320 <SEP> 800 <SEP> 750 <SEP> 780 <SEP> 710 <SEP> 690 <SEP> 680
 <tb> Module <SEP> 300 <SEP>% <SEP> ................................. <SEP> 160 <SEP> 440 <SEP> 440 <SEP> 445 <SEP> 555 <SEP> 475 <SEP> 560
 <tb> Hardness, <SEP> durometer <SEP> Shore <SEP> A <SEP> ....., ............. <SEP> 39 <SEP> 61 <SEP> 59 <SEP> 63 <SEP> 63 <SEP> 64 <SEP> 63
 <tb> Resistance <SEP> to <SEP> the <SEP> traction <SEP> kg / cm2 <SEP> 15 <SEP> 126 <SEP> 139 <SEP> 191 <SEP> 193 <SEP> 194 <SEP> 214
 <tb>
 
 EMI42.3
 % increase in tensile strength ..... 732% 8l6% 1160% 1179% 1186% 1319% + Butadiene-styrol copolymer brand GR-S ++ Cross-linking agent.

  <Desc / Clms Page number 43>

 



   Table XIX shows the influence of the proportion of cross-linking agent, in this case divinylbenzene, on the properties of vinyl fillers and the reinforcing effect of these fillers containing carboxyl groups in synthetic rubber.



   To obtain a tensile strength of 211 kg / cm2 with a vulcanized product of butadiene-styrol copolymer (GR-S 1500), this filler must contain approximately 10% of divinylbenzene. However, the content of the cross-linking agent necessary to obtain the maximum effects, to which the reinforcing properties should be attributed, is not the same for all vinyl fillers.



   For example, a vinyl filler prepared from vinyltoluene only needs about 5% divinylbenzene to exhibit the maximum reinforcing properties.



   The fillers containing carboxylic groups also improve the properties of vulcanizable elastomers containing diene hydrocarbons (Table IX) and thermoplastic elastomers (Table XVI).



   The favorable influence of the carboxyl groups incorporated in the vinyl fillers can be seen by comparing Example 6 of Table XVI with Examples 1 and 2 of Table X. The reinforcement of an unvulcanizable plastomer by a filler vinyl containing carboxyl groups is nearly 50% higher than that obtained by a vinyl filler not containing carboxyl groups.



   Table XVI (Example 1) further shows that the reinforcement of a natural rubber using an animated vinyl filler is essentially the same as that obtained using the much more expensive polar vinyl filler, according to Table IX, Example 2, and that, according to Example 3 (Table XVI), the reinforcement of the butadiene-styrol copolymer (GR-S 1500) with the vinyl filler containing carboxyl groups, using the amine , is greater than that obtained with the expensive polar vinyl filler of Example 2 (Table VI).



  * It can be seen further from Table XVII that, while the: amines (Examples 2 to 8) do not exhibit differences in the hardness and tensile strength of the vulcanized product, all of them increase the effect of fillers. vinyl containing carboxyl groups, unlike Example 1 in which an amine was not used.



   Finally, Table XVIII shows that a reduction from 10 to 1% of the carboxyl content of the vinyl filler does not produce a noticeable reduction in the strengthening effect, in the case where an amine is present at the same time. . This finding makes it possible to conclude that it is still possible to further lower the content of carboxyl groups, to a point where it would no longer significantly extend the vulcanization time, the favorable effect being however retained.



   Table XX shows the reinforcing effect which can be obtained with the polar reinforcing fillers in the case of natural rubber, depending on the nature of the crosslinker existing in these fillers.



   When using a polar vinyl filler based on polymeric acrylonitrile, ethylene glycol dimethacrylate or allyl acrylate should be preferred as crosslinkers rather than divinylbenzene.



   With a vinyl filler in which the polar component is methyl methacrylate, the cross-linking agent
 EMI43.1
 ¯I.J,., "" J 1f C .......) - ("'. J" "": Y

  <Desc / Clms Page number 44>

 They exert only a slight influence on the property of vinyl fillers to reinforce natural rubber.



   But in all cases, the vinyl filler significantly improves the tensile strength, already notable, of natural rubber.



  This is often to be attributed to the tendency to crystallize which natural rubber has.



   But from observations made on natural rubber, one could not predict that vinyl fillers would increase the tensile strength, generally much lower, of high synthetic polymers (elastomers) which do not exhibit this capacity. crystallization characteristic;

   nor could it be foreseen that a vinyl filler which reinforces a synthetic elastomer could further strengthen a self-reinforcing natural rubber *

  <Desc / Clms Page number 45>

   TABLE XX Natural rubber reinforced with polar vinyl fillers containing different cross-linking agents
 EMI45.1
 
 <tb> Mixture <SEP> n <SEP> XX <SEP> Control <SEP> -1 <SEP> -2 <SEP> -3 <SEP> -4 <SEP> -5 <SEP> -6
 <tb> Latex <SEP> rubber <SEP> and <SEP> elastomer <SEP> (weight <SEP> sec)
 <tb> Rubber <SEP> natural <SEP> ...................... <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
 <tb> Latex <SEP> load <SEP> vinyl <SEP> (weight <SEP> sec)
 <tb> Quantity <SEP> .....................................

    <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20
 <tb> Composition
 <tb> Acrylonitrile <SEP> ............................... <SEP> 95 <SEP> 95 <SEP> 95
 <tb> Methacrylate <SEP> of <SEP> methyl <SEP> ..................... <SEP> 99 <SEP> 90 <SEP> 90
 <tb> divinylbenzene <SEP> + <SEP> ............................ <SEP> 5 <SEP> 1.0
 <tb> Dimethacrylate <SEP> of <SEP> ethylene glycol <SEP> + <SEP> ......... <SEP> 5 <SEP> 10
 <tb> Acrylate Allyl's <SEP> <SEP> ......................... <SEP> 5 <SEP> 10
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> the <SEP> load <SEP>
 <tb> (Table <SEP> III) <SEP> .............................. <SEP> E <SEP> E <SEP> E <SEP> A ++ <SEP> A ++ <SEP> A ++
 <tb> Mixture
 <tb> Recipe <SEP> (Table <SEP> XII) <SEP> A <SEP> A <SEP> A <SEP> A <SEP> A <SEP> A <SEP> A
 <tb> Viscosity <SEP> Mooney <SEP> ML-4 <SEP> .........................

    <SEP> 31 <SEP> 66 <SEP> 68 <SEP> 68 <SEP> 50 <SEP> 52 <SEP> 59
 <tb> Vulcanization, <SEP> minutes <SEP> to <SEP> 141 C <SEP> 60 <SEP> 60 <SEP> 30 <SEP> 45 <SEP> 30 <SEP> 45 <SEP> 48
 <tb> Results
 <tb> Elongation <SEP>% <SEP> .................................. <SEP> 820 <SEP> 770 <SEP> 790 <SEP> 795 <SEP> 730 <SEP> 825 <SEP> 765
 <tb> Module <SEP> 300 <SEP>% <SEP> ................................... <SEP> 200 <SEP> 420 <SEP> 440 <SEP> 500 <SEP> 510 <SEP> 350 <SEP> 440
 <tb> Hardness, <SEP> durometer <SEP> Shore <SEP> A <SEP> .................. <SEP> 37 <SEP> 58 <SEP> 56 <SEP> 59 <SEP> 57 <SEP> 54 <SEP> 49
 <tb> Resistance <SEP> to <SEP> the <SEP> traction, <SEP> kg.cm2 <SEP> 218 <SEP> 278 <SEP> 336 <SEP> 323 <SEP> 268 <SEP> 271 <SEP> 279
 <tb>% <SEP> increase <SEP> resistance <SEP> to <SEP> the <SEP> traction ........

    <SEP> 54% <SEP> 48% <SEP> 23% <SEP> 21% <SEP> 26%
 <tb>
   + Crosslinker ++ Recipe A, except 5 parts Santomerse - 3 and 0.5 parts diisopropylbenzene hydroperoxide

  <Desc / Clms Page number 46>

 
Table XXI shows the reinforcing effect of vinyl fillers which have been obtained by interpolymerization or graft polymerization, and which are distinguished by the inexpensiveness of their manufacture.



   The favorable effect of these vinyl fillers appears above all in the comparison between the examples in Table XXI and those in Table XVIII. By the latter, it can be seen that if the carboxyl groups are lowered by 10 to 1%, the value of the tensile strength hardly changes, but the vulcanization time is lowered from 90 to 30 minutes.



   The vinyl fillers used in Table XVIII contain the carboxyl groups distributed uniformly throughout the mass. In contrast, the carboxyl groups of the vinyl fillers used in Table XXI are distributed on the surface of their particles. To obtain these vinyl fillers, carboxylated vinyl monomers were polymerized by grafting onto already insoluble styrol-divinylbenzene polymer particles, and in Examples 7, 6, 5, ten, five and four parts of this monomer were used. The vinyl fillers obtained in this way have the carboxyl groups on their surface in a much greater concentration than the vinyl fillers of Table XVIII; their quantity is so great that they require 90 minutes of vulcanization.

   In addition, the effect is found to increase if these excess amounts are reduced from 10 to 4 parts. From this it can be deduced that by further lowering the content of the components containing carboxyl groups in the graft polymerization vinyl fillers the possible reinforcement would not be reduced, but that perhaps it could even be increased further.

  <Desc / Clms Page number 47>

 



    TABLE XXI GR-S + with interpolymeric vinyl fillers prepared in 2 steps
 EMI47.1
 
 <tb> Mixture <SEP> n <SEP> XXI <SEP> Control <SEP> -1 <SEP> -2 <SEP> -3 <SEP> -4 <SEP> -5 <SEP> -6 <SEP> -7
 <tb> Latex <SEP> elastomer <SEP> (weight <SEP> sec)
 <tb> GR-S + <SEP> 1500 <SEP> (Table <SEP> III <SEP> Recipe <SEP> M) <SEP> ........... <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
 <tb> Latex <SEP> load <SEP> vinyl <SEP> (weight <SEP> sec)
 <tb>
 
 EMI47.2
 Quantity .o .......... 20 20 20 20 20 20 20
 EMI47.3
 
 <tb> Composition
 <tb> Step <SEP> of <SEP> polymerization <SEP> 1
 <tb> Styrol <SEP> .................................... <SEP> 90 <SEP> 90 <SEP> 90 <SEP> 90 <SEP> 61 <SEP> 60 <SEP> 50
 <tb>
 
 EMI47.4
 Divinylbenzene ++ .........................

   10 10 10 10 8 8 8 Polymerization step 2 Styrol .... O ............................. é8 25 25 30
 EMI47.5
 
 <tb> Acid <SEP> methacrylic <SEP> ....................... <SEP> 4 <SEP> 5 <SEP> 10
 <tb> Vinyltoluene <SEP> .............................. <SEP> 5
 <tb> Dimethacrylate Ethylene glycol <SEP> <SEP> ++ <SEP> 5 <SEP> 2 <SEP> 2 <SEP> 2 <SEP>
 <tb> Divinylbenzene <SEP> ++ <SEP> ......................... <SEP> 5
 <tb> Acrylate Allyl's <SEP> <SEP> ........................... <SEP> 5
 <tb> Cyanurate <SEP> triallylic <SEP> ...................... <SEP> 10
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> the <SEP> load
 <tb> (Table <SEP> III) <SEP> ................................ <SEP> A <SEP> A <SEP> A <SEP> A <SEP> A <SEP> A <SEP> A
 <tb> Mixture
 <tb> Recipe <SEP> (Table <SEP> XII) <SEP> ...........................

    <SEP> F <SEP> K <SEP> K <SEP> K <SEP> K <SEP> K <SEP> K <SEP> K
 <tb>
 
 EMI47.6
 Amitrile I.P .................................... 2 2 2
 EMI47.7
 
 <tb> Viscosity <SEP> Mooney. <SEP> ML-4 <SEP> 37 <SEP> 50 <SEP> 50 <SEP> 48 <SEP> 45 <SEP> 51 <SEP> 51 <SEP> 55
 <tb> Vulcanization, <SEP> minutes <SEP> to <SEP> 141 <SEP> C <SEP> ................. <SEP> 90 <SEP> 60 <SEP> 60 <SEP> 60 <SEP> 60 <SEP> 90 <SEP> 90 <SEP> 90
 <tb> Results
 <tb> Elongations, <SEP>% <SEP> ................................. <SEP> 320 <SEP> 650 <SEP> 620 <SEP> 650 <SEP> 600 <SEP> 630 <SEP> 640 <SEP> 660
 <tb> Module <SEP> 300 <SEP>% <SEP> .................................... <SEP> 160 <SEP> 420 <SEP> 435 <SEP> 440 <SEP> 450 <SEP> 535 <SEP> 520 <SEP> 540
 <tb> Hardness, <SEP> durometer <SEP> Shore <SEP> A <SEP> ........................

    <SEP> 39 <SEP> 61 <SEP> 63 <SEP> 63 <SEP> 62 <SEP> 67 <SEP> 69 <SEP> 70
 <tb> Resistance <SEP> to <SEP> the <SEP> traction <SEP> kg / cm2 <SEP> .................. <SEP> 15 <SEP> 163 <SEP> 186 <SEP> 157 <SEP> 150 <SEP> 219 <SEP> 220 <SEP> 202
 <tb>% <SEP> increase <SEP> resistance <SEP> to <SEP> the <SEP> traction <SEP> 994% <SEP> 1150% <SEP> 957% <SEP> 904% <SEP> 1372% <SEP> 1327% <SEP> 1254%
 <tb>
   + Butadiene-styrol copolymer brand GR-S ++ Cross-linking agent

  <Desc / Clms Page number 48>

 
By comparing the acid fillers (examples XXI-5, -6, -7) with the non-acidic vinyl fillers (examples XXI-1 to -4), it can be seen that the former give even better results than the vinyl fillers not containing no carboxyl groups,

   result which is in harmony with the results found for vinyl fillers obtained by copolymerization.



     Example XXI-2 further shows that an apolar vinyl filler with graft polymerization strengthens the nonpolar butadiene-styrol copolymer (GR-S 1500), just as certain polar vinyl fillers with grafted polarization. When compared with Example 3 of Table I, in which the vinyl filler consists of vinyltoluene cross-linked by divinylbenzene, and with Example 1 of Table VI, in which the vinyl filler consists of a bound styrol Transversely through the divinylbenzene, it is seen that with a graft polymerization vinyl filler, while using less vinyltoluene with the styrol and the divinylbenzene, a greater reinforcement is obtained than with any of the other polar vinyl fillers.



   Table XXI-A shows that vinyl fillers with a good reinforcing effect can also be obtained by injecting into the vinyl fillers an elastomer or natural rubber latex prepared in advance. The amount of elastomer latex used, with the vinyl fillers used in Table XXI-A, remains low; but it can be increased without the transverse bonding properties of vinyl fillers being excessively reduced.



   It can also be seen from this table that the graft is felt in the reinforcing properties to a much greater extent than the changes in the core character of the vinyl filler.



   We can see from Table XXII the reinforcing effect of vinyl fillers without emulsifier. This group of vinyl fillers is particularly suitable for addition to those high polymers which must have good electrical characteristics, and also wherever the presence of an emulsifier is troublesome.

  <Desc / Clms Page number 49>

 



    TABLE XXII Vinyl fillers without emulsifier and comparisons,
 EMI49.1
 
 <tb> Mixture <SEP> n <SEP> XXII <SEP> -1 <SEP> -2 <SEP> -3 <SEP> -4 <SEP> -6 <SEP> -7 <SEP> -8
 <tb> Latex <SEP> rubber <SEP> and <SEP> elastomer <SEP> (weight <SEP> sec)
 <tb>
 
 EMI49.2
 Natural rubber ............... 100
 EMI49.3
 
 <tb> Polychloroprene <SEP> (Latex <SEP> Neoprene <SEP> 571) <SEP> ............... <SEP> 100 <SEP> 100 <SEP> 100
 <tb> GR-S + <SEP> 1500 <SEP> (Tabo <SEP> III, <SEP> recipe <SEP> M) <SEP> ............... <SEP> 100 <SEP> 100 <SEP> 100 <SEP> mix <SEP> (1)
 <tb> Latex <SEP> load <SEP> vinyl <SEP> (weight <SEP> sec)
 <tb>
 
 EMI49.4
 Quantity 000 ............... 20 20 20 20 20 20 20 Composition Styrol ..ooooe..oooooo.eso.oeoooe.ee.ooooo000 96 96 99 98 98 98 98 Methacrylic acid eooosooo ... osoosoooooe.

   2 2 Nt-butyl-acrylamide ....................... 0 .. 1 Divinylbenzene ++ ............. ................ 2 2 1 1 1 2 2 N, N-diallylmelamine ...................... ...
 EMI49.5
 
 <tb>



  Recipe <SEP> of <SEP> polymerization <SEP> without <SEP> emulsifier
 <tb> (array <SEP> III) <SEP> ...................... <SEP> G <SEP> G <SEP> G <SEP> G <SEP> I <SEP> G
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> (Table <SEP> III)
 <tb> with <SEP> emulsifier <SEP> ................................ <SEP> A <SEP> +++ <SEP>
 <tb> Mixture
 <tb> Recipe <SEP> (-Table <SEP> XII) <SEP> ......................... <SEP> A <SEP> E <SEP> G <SEP> G <SEP> G <SEP> E <SEP> E <SEP> E
 <tb> Allylamine <SEP> ..................................... <SEP> 1. <SEP> 5 <SEP> 2. <SEP> 0
 <tb>
 
 EMI49.6
 Mooney ML-4 viscosity of the mixture ..0 ............

   12 43 200 200 200 47 53 48
 EMI49.7
 
 <tb> Time <SEP> of <SEP> vulcanization, <SEP> minutes <SEP> to <SEP> 141 C <SEP> 30 <SEP> 30 <SEP> 60 <SEP> 60 <SEP> 30 <SEP> 30 <SEP> 30 <SEP> 30
 <tb> Results
 <tb>
 
 EMI49.8
 Elongations ............................... 705 580 365 400 480 830 900 890 Modulus 300% 0 ...... ....................... 0 ... 430 460 1535 1200 904 222 390 290 Hardness, Shore A durometer ...... ee ... ..o ... eo 54 62 70 60 69 48 54 48
 EMI49.9
 
 <tb> Resistance <SEP> to <SEP> the <SEP> traction, <SEP> kg / cm2 <SEP> ..............

    <SEP> 240 <SEP> 117 <SEP> 128 <SEP> 98 <SEP> 172 <SEP> 58 <SEP> 180 <SEP> 139
 <tb> for <SEP> control, <SEP> see <SEP> table- <SEP> example <SEP> IC-C <SEP> VI-C <SEP> VII-C <SEP> VII-C <SEP> VII-C <SEP> VI-C <SEP> VI-C <SEP> VI-C
 <tb>% <SEP> increase <SEP> resistance <SEP> to <SEP> the <SEP> traction <SEP> 10 <SEP>% <SEP> 677% <SEP> 61% <SEP> 23% <SEP> 27% <SEP> 286% <SEP> 1090% <SEP> 818%
 <tb>
   + GR-S brand butadiene-styrol copolymer ++ Cross linking agent +++ 6 parts instead of 10 parts Santomerse-3 (1) Equal parts of the latex combinations of vinyl fillers and GR-S XXII were mixed -6 and XXJII-7, then we
 EMI49.10
 coagulated and vulcanized.

   It is remarkable that these mixtures of vinyl chsrge particles of relatively small colloidal size gave tensile strength 11% higher than the average value of the two components.



  1 \ .J.) -. . \ ... '. \ .... 0 1 u

  <Desc / Clms Page number 50>

   TABLE XXI - A
 EMI50.1
 GR-S + J.'OI l forg <3¯jLa}. '¯ (l!, ¯i3- "riu, yli9..u80 z 1 = gt e oeoey <.. J
 EMI50.2
 & 2ë1 allLP n. XXI-A COLlcheck -1 -2 -3 #### -5 Latex lastorn,: xt (à'Jidx sec)
 EMI50.3
 
 <tb> GR-S <SEP> 1500 <SEP> (array <SEP> III <SEP> Recipe <SEP> M) <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
 <tb> Latex <SEP> load <SEP> vinyl <SEP> (weight <SEP> sec)
 <tb> Quantity <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20
 <tb> Composition <SEP> ++
 <tb> Latex <SEP> of <SEP> rubber <SEP> natural <SEP> .................. <SEP> 5
 <tb> Latex <SEP> GR-S <SEP> 1500 <SEP> ++ <SEP> .............................. <SEP> 5
 <tb> Latex <SEP> polybutadiene <SEP> ++ <SEP> (Table <SEP> III <SEP> Recipe <SEP> L) <SEP> ..

    <SEP> 5
 <tb> Latex <SEP> polychloroprene <SEP> ++ <SEP> (1) <SEP> ....................
 <tb>



  Latex <SEP> butadiene-acrylonitrile <SEP> ++ <SEP> (2)
 <tb> Monomer <SEP> vinyl
 <tb> Styrol <SEP> .......................................... <SEP> 80 <SEP> 80 <SEP> 80 <SEP> 80 <SEP> 80
 <tb> Acid <SEP> Methacrylic <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10
 <tb> Divinylbenzene <SEP> +++ .............................. <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> the <SEP> load <SEP> (Table <SEP> III) <SEP> A <SEP> A <SEP> A <SEP> A <SEP> A
 <tb> Mixture
 <tb> Recipe <SEP> (Table <SEP> III) <SEP> ............................ <SEP> F <SEP> E <SEP> E <SEP> E <SEP> E <SEP> E
 <tb>
 
 EMI50.4
 alpha-isopropylaminopropionitrile ................ 4
 EMI50.5
 
 <tb> Viscosity <SEP> Mooney <SEP> ML-4 <SEP> ............................

    <SEP> 37 <SEP> 45 <SEP> 49 <SEP> 46 <SEP> 48
 <tb> Time <SEP> of <SEP> vulcanization, <SEP> minutes <SEP> to <SEP> 141 <SEP> C <SEP> 90 <SEP> 90 <SEP> 60 <SEP> 75 <SEP> 60 <SEP> 30
 <tb> Results
 <tb> Elongations <SEP>% <SEP> ................................... <SEP> 320 <SEP> 715 <SEP> 710 <SEP> 745 <SEP> 735 <SEP> 790
 <tb> Module <SEP> 300 <SEP>% ..................................... <SEP> 160 <SEP> 465 <SEP> 430 <SEP> 400 <SEP> 420 <SEP> 370
 <tb> Hardness, <SEP> durometer <SEP> Shore <SEP> A <SEP> ........................

    <SEP> 39 <SEP> 64 <SEP> 61 <SEP> 60 <SEP> 62 <SEP> 58
 <tb> Resistance <SEP> to <SEP> the <SEP> traction., <SEP> kg / cm2 <SEP> 15 <SEP> 192 <SEP> 192 <SEP> 192 <SEP> 207 <SEP> 196
 <tb>% <SEP> increase <SEP> resistance <SEP> to <SEP> the <SEP> traction <SEP> ll67% <SEP> 1169% <SEP> 1169% <SEP> 1272% <SEP> 1197%
 <tb>
   + Butadiene-styrol copolymer brand GR-S ++ (based on dry weight) +++ Cross-linking agent (1) Neop latex @@@ manufacturer-. E.I. du Pont de Nemours & Co.



  (2) Latex Hycar 1514, manufacturer: B. F. Goodrich.

  <Desc / Clms Page number 51>

 



   The Nt-butyl-acrylamide vinyl filler, used in Example 4, is a type of non-emulsifying amide vinyl filler, which to some extent strengthens a high polar polymer, such as for example polychloroprene. Such a vinyl filler with such a high polarity is suitable for reinforcing thermoplastic or curable plastics.



   As an example of a vinyl filler without emulsifier, with basic amine groups, N, N-diallylmelamine was cited (example
5); vinyl fillers of this kind are suitable for reinforcing natural rubber, vulcanizable and non-vulcanizable plastics.



   The particle size of vinyl fillers without emulsifier is determined for the most part by the solubility of the monomers in water, the distribution of the monomers in water and the ionization effect of the soluble salts, but it is determined for the most part by the number of polymerization initiating free radicals present, since each of these, if active, will release a particle. Therefore, by reducing the amount of the catalyst in the recipe which was used to obtain the examples in Table XXI, large particles are obtained, until the point where, finally, they become so large that they can no longer be kept in suspension by the Brownian movement, and no longer constitute very active vinyl charges.



   In the preparation of the very active vinyl fillers without emulsifier, the water content of the latex must be chosen such that the particles of the vinyl filler do not agglomerate and do not begin to coagulate with an apparent hardening effect.



  As soon as this occurs, further dilution in the preparation of the latex, or correction of the ion concentration thereof, or both at the same time, is required.



   Since it is possible, on the one hand, to enlarge the colloidal particles by varying the quantity of catalyst, and on the other hand to limit their size or to reduce it by using different quantities of emulsifiers, it is possible to obtain latexes. more or less milky or more or less transparent vinyl fillers. When a pigmented effect is required, larger particle vinyl fillers are used, while for transparency effects small particle vinyl fillers are used.



   In the figures, four sizes of vinyl fillers have been shown. Fig. 1 shows coarse vinyl filler particles, figo 2 semi-coarse particles, fig.3 semi-fine particles and figo 4 fine particles. Fig. 5 shows a natural rubber reinforced with vinyl filler particles according to fig. 2, and fig. 6 a synthetic rubber based on butadiene-styrol (GR-S 1500) reinforced with a vinyl filler according to fig. 6.



   Electronic photomicrographs - figs. 1 to 4 - were taken on the dried vinyl filler latex, as shadow views, with application of the high vacuum examination technique, with vaporized palladium, and are magnified 48,000 times.



     Figures 1 and 2 show the large particles of vinyl filler, which were obtained by polymerizing the monomers in water in the absence of an emulsifier, in the form of stable latexes (Table XXIII).



  Due to their coarse particles, the latexes were milky.

  <Desc / Clms Page number 52>

 



   Figs. 3 and 4 show small particles of a vinyl filler from which the latex was obtained by emulsion polymerization (Table XXIII). The latex of the vinyl filler according to fig.



  3 is a little cloudy, that of the vinyl filler according to FIG. 4 on the other hand, is crystal clear. The latter is used in all cases where it is a question of reinforcing high transparent polymers.



   The reinforced natural rubber according to fig. 5 was obtained by mixing the natural rubber latexes and vinyl filler, coagulating, drying and grinding, and freezing with liquid nitrogen and spraying. Fig. 5 shows that the vinyl filler is well distributed in the rubber.



   Fig. 6 shows the good distribution of the vinyl filler, which has been incorporated into the synthetic rubber in the same manner.



   The vinyl fillers according to the present invention are therefore distinguished by their particle size visible under an electron microscope, and their insolubility.



   The examples in Table XXIV show the reinforcing effect; ment of vinyl fillers containing inserted bonds, which have been subjected to a subsequent chemical treatment.



   Because the degree of unsaturated character of the vinyl filler can be controlled during its preparation, and hence the extent of chemical modification, chemically modified vinyl fillers can be obtained having high properties. changed properties.



   The unsaturated character of the vinyl fillers can be obtained by copolymerization or interpolymerization, or alternatively with mixtures of polymerizates, when the vinyl filler is a diene hydrocarbon, or contains one of these. Since the vinyl filler should be "fixed", the dienes content should be 22% or less, for example in the case of a vinyl filler based on butadiene and styrol, and the polymerization should be advanced. far enough so that the vinyl charge, thanks to the monomer which simultaneously produces crosslinks - for example divinylbenzol - becomes insoluble, but the local double bonds remain preserved.

   In these vinyl fillers which contain unsaturated bonds, oxygen, halogens and sulfur can be introduced, which can modify the chemical and physical properties, especially since these bodies can participate in new reactions, such as amidation, hydrolysis, oxidation, reduction, neutralization, esterification, etc.



   This subsequent chemical treatment of the vinyl fillers is preferably carried out in the vinyl filler emulsified in water, therefore in the vinyl filler latex.



   Despite the insolubility of the vinyl fillers, these reactions can take place, because due to the colloidal particle size of the vinyl fillers, the surface area to volume ratio, and hence the surface energy, is sufficient.



   Oxidation can take place with a water soluble oxidant, such as potassium permanganate, or with the use of oxygen or air in the presence of a cobalt catalyst, or with the aid of hydrogen dioxide.



   As an example of a chemically modified vinyl filler, a graft polymerization vinyl filler was chosen from Table XXIV, the core of which is constituted by a hard, insoluble and infusible colloidal core, onto which a soft coating has been grafted. , of

  <Desc / Clms Page number 53>

 rubber type, consisting of a transversely bonded polymer, which however is not absolutely necessary, since the core of the vinyl filler particle is also insoluble. This unsaturated vinyl filler was treated with bromine The chemical reaction takes place very quickly, if the two components, bromine and vinyl filler, are heated in the presence of ammonia, in a closed container, to about 100 Co In one night , the reaction is complete, and most of the bromine is removed.



   A carboxylated vinyl filler brominated with sodium hydroxide solution, according to Example 6 (Table XXIV), was treated in this manner, heated to about 100 ° C. in a closed container and allowed to stand overnight. Then the bromine was removed from the vinyl filler.

   The brominated vinyl filler treated with sodium hydroxide solution is hydrophilic and hydrocarburophobic, and produces a weak reinforcement of the butadiene-styrol copolymers of the GR-S type
The hydrophilic properties of brominated vinyl fillers treated with sodium hydroxide solution are further demonstrated by the ease with which the brominated latex forms a hard precoagulum, if not diluted, before the sodium hydroxide treatment, with approximately 10 parts of water

  <Desc / Clms Page number 54>

   TABLE XXIV Chemical treatment of unsaturated vinyl fillers
 EMI54.1
 
 <tb> Mixture <SEP> n <SEP> XXIV <SEP> Control <SEP> -1 <SEP> -2 <SEP> -3 <SEP> -4 <SEP> -5 <SEP> -6
 <tb> Latex <SEP> elastomer <SEP> (weight <SEP> sec)
 <tb> GR-S <SEP> 1500 <SEP> (Table <SEP> III <SEP> Recipe <SEP> M) <SEP> .............

    <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
 <tb> Latex <SEP> load <SEP> vinyl <SEP> (weight <SEP> sec)
 <tb> Quantity <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20
 <tb> Composition
 <tb> Step <SEP> of <SEP> polymerization <SEP> 1
 <tb> Styrol <SEP> ..................................... <SEP> 80 <SEP> 80 <SEP> 80 <SEP> 70 <SEP> 70 <SEP> 70
 <tb> Acid <SEP> methacrylic <SEP> ........................ <SEP> 10 <SEP> 10 <SEP> 10
 <tb> Divinylbenzene <SEP> ++ ......................... <SEP> 9 <SEP> 9 <SEP> 9 <SEP> 9
 <tb> Step <SEP> of <SEP> polymerization <SEP> 2
 <tb> Isoprene <SEP> ................................... <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10
 <tb> Divinylbenzene <SEP> ++ <SEP> ..........................

    <SEP> 1 <SEP> 1 <SEP> 1 <SEP> 1 <SEP> 1 <SEP> 1 <SEP>
 <tb> Processing Chemical <SEP>, <SEP> step <SEP> 3
 <tb> Bromine <SEP> ...................................... <SEP> 5. <SEP> 7 <SEP> 5.7 <SEP> 5.7 <SEP> 5.7
 <tb> Processing Chemical <SEP>, <SEP> step <SEP> 4 <SEP>
 <tb>
 
 EMI54.2
 Ammonia at 28 ..... w ... a .... s .... a ...... 4
 EMI54.3
 
 <tb> Hydroxide <SEP> of <SEP> sodium <SEP> ........................ <SEP> 2.8
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> load <SEP> (Table <SEP> III) <SEP> A <SEP> A <SEP> A <SEP> A <SEP> A <SEP> A
 <tb> Mixture
 <tb> Recipe <SEP> (Table <SEP> XII) ........................... <SEP> F <SEP> E <SEP> E <SEP> E <SEP> E <SEP> E
 <tb> Amitrile <SEP> I.P. <SEP> 4 <SEP> 4 <SEP> ' <SEP> 4
 <tb> Viscosity <SEP> Mooney <SEP> ML-4 <SEP> .........................

    <SEP> 37 <SEP> 39 <SEP> 56 <SEP> 51 <SEP> 50 <SEP> 50 <SEP> 54
 <tb> vulcanization, <SEP> minutes <SEP> to <SEP> 141 C <SEP> ................. <SEP> 90 <SEP> 60 <SEP> 75 <SEP> 75 <SEP> 75 <SEP> 120 <SEP> 150
 <tb> Results
 <tb> Elongations <SEP>% <SEP> .................................. <SEP> 320 <SEP> 540 <SEP> 630 <SEP> 650 <SEP> 740 <SEP> 815 <SEP> 700
 <tb> Module <SEP> 300 <SEP>% .................................... <SEP> 160 <SEP> 430 <SEP> 650 <SEP> 630 <SEP> 370 <SEP> 390 <SEP> 440
 <tb> Hardness, <SEP> durometer <SEP> Shore <SEP> A <SEP> ....................... <SEP> 39 <SEP> 58 <SEP> 63 <SEP> 65 <SEP> 63 <SEP> 65 <SEP> 65
 <tb> Resistance <SEP> to <SEP> the <SEP> traction, <SEP> kg / cm2 <SEP> ................

    <SEP> 15 <SEP> 122 <SEP> 175 <SEP> 177 <SEP> 217 <SEP> 192 <SEP> 134
 <tb>% <SEP> increase <SEP> resistance <SEP> to <SEP> the <SEP> traction <SEP> 705% <SEP> 1058% <SEP> 1067% <SEP> 1337% <SEP> 1172% <SEP> 784%
 <tb>
   + Butadiene-styrol copolymer brand GR-S ++ Cross-linking agent

  <Desc / Clms Page number 55>

 
Vinyl fillers which contain carbonyl groups can be subjected to the typical reactions of carbonyl groups.



  As types of carbonylated vinyl fillers, it has been indicated in Table XXV, among ketones, methyl vinyl ketone, and among aldehydes, methacrolein. As chemical reaction of these carbonylated vinyl fillers, the condensation of 'a phenol with the vinyl filler, and more especially a vinyl filler containing aldehyde groups
To prepare this condensation product, the latex of carbonyl-containing vinyl filler was mixed with the latex of a butadiene-styrol copolymer (GR-S 1500), the resulting mixture was coagulated and dried. This dried mixture is then ground resorcinol, and after addition of the other components of the mixture9 is vulcanized.

     The strengthening effect of these vinyl fillers having carbonyl groups, in itself excellent, is further enhanced by this subsequent chemical treatment.



   The active carbonyl group of vinyl fillers is particularly valuable when it comes to incorporating such vinyl fillers into high elastic or plastic polymers, or binding them to bodies which are contained in these high polymers.



   As shown in Tables XVI to XIX, the carboxyl group vinyl fillers, when mixed with ammonia or ammonia derivatives, have excellent reinforcing properties for high elastic polymers and. plastics.



   It can be seen from Table XXVI that one can improve the property of any vinyl filler of reinforcing high elastic and plastic polymers, if this filler is used in combination with an unbound resinous material containing carboxyl groups. , and whether, moreover, it is used in the presence of ammonia or of an ammonia derivative, namely a primary, secondary, tertiary or quaternary amine.

  <Desc / Clms Page number 56>

 
 EMI56.1
 



  TABLE XXVI - É3asom combinations: re-iastorrrre reinforced by rir3icues loads.
 EMI56.2
 



  Mixture n XXVI Control -1 2 ...... 3 .... 4 ..... -5 - .. 6 -?
 EMI56.3
 
 <tb> I <SEP> Latex <SEP> elastomer <SEP> (weight <SEP> sec)
 <tb> GR-.S + <SEP> 1500 <SEP> (Tab. <SEP> III <SEP> Recipe <SEP> M) <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
 <tb> II <SEP> Latex <SEP> elastomer <SEP> (weight <SEP> sec)
 <tb> Quantity <SEP> .......................................... <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20
 <tb> Composition
 <tb> Styrol <SEP> .., ........................................ <SEP> 85 <SEP> 85 <SEP> 81 <SEP> 81 <SEP> 81
 <tb> Butadiene <SEP> 15 <SEP> 15 <SEP> 15 <SEP> 15 <SEP> 15
 <tb> Acid <SEP> acrylic <SEP> ..................................
 <tb>



  Recipe <SEP> of <SEP> polymerization <SEP> (1) <SEP> (1) <SEP> (1) <SEP> (1) <SEP> (1)
 <tb> Latex <SEP> plastomer <SEP> (weight <SEP> sec)
 <tb> Acid <SEP> polyacrylic <SEP> (2) <SEP> 0.75 <SEP> 0. <SEP> 75 <SEP> 0.75 <SEP> 0.75
 <tb> Load <SEP> vinyl <SEP> (weight <SEP> sec)
 <tb> Quantity <SEP> ......................, .................. <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20
 <tb> Composition
 <tb> Styrol <SEP> ......................................... <SEP> 90 <SEP> 90 <SEP> 90 <SEP> 80
 <tb> Acid <SEP> methacrylic <SEP> ............................ <SEP> 10
 <tb> Divinylbenzene <SEP> ++ <SEP>, ............................. <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> load <SEP> (Tab. <SEP> III)
 <tb> Mixture
 <tb> Recipe <SEP> (Table <SEP> XII) <SEP> ............................

    <SEP> F <SEP> E <SEP> E <SEP> E <SEP> E <SEP> E <SEP> E <SEP> E
 <tb>
 
 EMI56.4
 Amitrile I.P ..................................... 3 3 3 3 3 3 5
 EMI56.5
 
 <tb> Viscosity <SEP> Mooney <SEP> ML-4 <SEP> 37 <SEP> 38 <SEP> 47 <SEP> 42 <SEP> 54 <SEP> 46 <SEP> 59 <SEP> 63
 <tb> Vulcanization, <SEP> minutes <SEP> to <SEP> 141 C <SEP> 90 <SEP> 60 <SEP> 90 <SEP> 60 <SEP> 60 <SEP> 30 <SEP> 60 <SEP> 90
 <tb> Results
 <tb> Elongation <SEP>% <SEP> 320 <SEP> 280 <SEP> 655 <SEP> 300 <SEP> 615 <SEP> 615 <SEP> 660 <SEP> 800
 <tb> Module <SEP> 300 <SEP>% <SEP> 160- <SEP> 445 <SEP> 500 <SEP> 675 <SEP> 490 <SEP> 680, <SEP> 490
 <tb> Hardness, <SEP> durometer <SEP> Shore <SEP> A .......................... <SEP> 39 <SEP> 52 <SEP> 60 <SEP> 63 <SEP> 78 <SEP> 59 <SEP> 78 <SEP> 81
 <tb>
 
 EMI56.6
 Resistance to.latra: ction, kg! Cm2, N '.' ';

  .............. 15 l6 l'If 2fil5, j5 179. 81 186 171% increased tensile strength 7% 1258% 1 2jb 1086 434% l132 $ 1030% + Butadiene copolymer- styrol brand GR-S ++ Cross-linking agent (1) Polymerization recipe: 100 parts monomer, 300 parts water, 1.5 parts azobis- (isobutyronitrile) 6 parts Santomerse-3, Polymerization temperature 60 C, duration 12 hours .



  (2) = Sodium polyacrylate. Manufacturer t Monomer-Polymer Inc.

  <Desc / Clms Page number 57>

 



   According to Exempt 1 of Table XXVI, a latex of butadiene-styrol copolymerized (Latex GR-S 1500) was mixed with a solution of sodium polyacrylate and the resulting mixture was coagulated with acid, and the resulting mixture was acid coagulated. dried, mixed with the appropriate additives, and vulcanized. Comparing with the control, it was found that the addition of polyacrylic acid to the synthetic rubber in question had no influence on the tensile strength.



   From Example 1 of Table VI, it could be seen that a vinyl filler consisting of 90 parts of styrol and 10 parts of divinylbenzol in a tensile strength of about 169 kg / cm2, when It is added to a latex of butadiene-styrol copolymer (GR-S 1500), which the latex mixture is coagulated, dried and vulcanized after mixing with the necessary additives.



   Example 2 of Table XXVI shows that the addition of a part of sodium polyacrylate to a latex of a butadiene-styrol copolymer of the GR-S 1500 type and to a latex of vinyl filler containing groups because - boxyle, gives, after preparation of the latex and vulcanization of the mixture, a tensile strength of about 211 kg / cm2 in the final product.



   Similar values are obtained using vinyl fillers containing carboxyl groups (see Tables XVI to XIX).



   An excellent reinforcement is thus obtained when, in admixture with a vinyl filler and a suitable amine, a carboxylic group material which is soluble or capable of distributing in an elastic or plastic material is used.

  <Desc / Clms Page number 58>

 



    TABLE XXV
 EMI58.1
 Vinylic charges- containing carbonyl groups, and their chemical ¯.tJ. ".
 EMI58.2
 
 <tb> Mixture <SEP> XXV <SEP> Control <SEP> -1 <SEP> -2 <SEP> -3
 <tb> Latex <SEP> elastomer <SEP> (weight <SEP> sec)
 <tb> GR-S + <SEP> 1500 <SEP> (Table <SEP> III <SEP> Recipe <SEP> M) <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
 <tb> Latex <SEP> load <SEP> vinyl <SEP> (weight <SEP> sec)
 <tb> Quantity <SEP> ............................................... ............. <SEP> 20 <SEP> 20 <SEP> 20
 <tb> Composition
 <tb> Styrol .............................................. ............................. <SEP> 80 <SEP> 70 <SEP> 70
 <tb>
 
 EMI58.3
 Methyl vinyl ketone ................................................. ............... 10 Methacrolein ................................. ....................................

   20 20 Divinylbenzene ............................................... .................. 10 10 10
 EMI58.4
 
 <tb> Recipe <SEP> of <SEP> polymerization <SEP> of <SEP> load <SEP> (Table <SEP> III) <SEP> ................................... <SEP> A <SEP> A
 <tb> Processing Chemical <SEP>
 <tb>
 
 EMI58.5
 Raseroine ................................................. .................... 1
 EMI58.6
 
 <tb> Mixture
 <tb> Recipe <SEP> (Table <SEP> XII) <SEP> ............................................... ................ <SEP> F <SEP> E <SEP> K <SEP> K
 <tb>
 
 EMI58.7
 Amitrile IP ................................................ ................. "." - - 1 1
 EMI58.8
 
 <tb> Viscosity <SEP> Mooney <SEP> ML-4 <SEP> ............................................... ................

    <SEP> 37 <SEP> 41 <SEP> 54 <SEP> 54
 <tb> Vulcanization, <SEP> minutes <SEP> to <SEP> 141 C <SEP> ............................................... ....... <SEP> 90 <SEP> 90 <SEP> 60 <SEP> 105
 <tb> Results
 <tb> Elongation <SEP>% <SEP> ............................................... ........................ <SEP> 320 <SEP> 600 <SEP> 720 <SEP> 740
 <tb>
 
 EMI58.9
 Module 300% .............................................., ........................ 160 470 370 350
 EMI58.10
 
 <tb> Hardness, <SEP> durometer <SEP> Shore <SEP> A <SEP> ............................................... .............

    <SEP> 39 <SEP> 67 <SEP> 58 <SEP> 59
 <tb> Resistance <SEP> to <SEP> the <SEP> traction <SEP> kg / cm2 <SEP> 15 <SEP> 162 <SEP> 152 <SEP> 165
 <tb>% <SEP> increase <SEP> resistance <SEP> to <SEP> the <SEP> traction <SEP> 970% <SEP> 909% <SEP> 999%
 <tb>
   + Butadiene-styrol copolymer brand GR-S ++ Cross-linking agent

  <Desc / Clms Page number 59>

 
In Table XV, the control examples show that an elastomer composed of styrol with 10 to 20% butadiene, mixed in the form of latex with a butadiene-styrol copolymer of the GR-S 1500 type in the form of latex, after coagulation, drying, mixing and vulcanization, gives products with tensile strengths of 35 to
42 kg / om2.



   The inclusion of a small amount of acrylic acid in such a polymer doubles the tensile strength which becomes about 81 kg / cm2, as shown in Example 5 of Table XXVI.



   Examples 1 and 2 of Table XV show that the combination of a soluble vinyl resin and an insoluble vinyl filler gives tensile strengths of 91 to 98 kg / ². Example 6 of
Table XXVI shows that a vinyl resin containing carboxyl groups gives a tensile strength greater than 183 kg / cm 2 for the vinyl resin-vinyl filler combination.



   According to Example 4 (Table XXVI), a similar effect is obtained by adding 0.75 part of polyacrylic acid to a vinyl resin containing no carboxyl groups and to a vinyl filler, in a butadiene-styrol copolymer of type GR-S 1500.



   It has thus been found, that high elastic, therefore vulcanizable, and plastic, non-vulcanizable polymers can be reinforced by the combination of a polymeric acid material and ammonia and / or an amine, together with a vinyl filler. , or by a vinyl charge containing carboxyl groups in combination with ammonia and / or an amine.



   Further, as can be seen from Table XXVI, the polyoarboxylic acid itself can be mixed, as a latex, with the vinyl filler latex, with no addition of ammonia, or a-. lead, to give a commercial product capable of being blended with the vulcanizable or unvulcanizable high polymers; the latex or the dry product obtained therefrom, and originating from such a combination, also represents a commercial product.



   It can be seen from Table XXVII that with a certain class of vinyl filler it is also possible to reinforce latexes of high vulcanisable or unvulcanisable polymers which, as a result of their subsequent use, must be free of lowering ingredients. surface tension. A condition of this kind is laid down, for example, for rubber latexes which are used in the manufacture of foam rubber.
If these ingredients which lower the surface tension have a detrimental influence, it is mainly because the different latex particles are covered with a thin layer of the emulsifier, which decreases the adhesion of the particles.



   Such vinyl fillers, free of ingredients which disturb the surface tension, have already been indicated in Table XXII; but the particles of these vinyl fillers are too large, so that they provide only limited reinforcement.



   However, in Table XXVII, vinyl fillers have been shown which have a smaller particle size, since these were obtained by emulsion polymerization, with the use of polymeric emulsifiers.



   But in the case of high molecular weight emulsifiers, the adhesion and cohesion forces between emulsifier, filler

  <Desc / Clms Page number 60>

 vinyl and high to reinforced polymers are sufficient to give high tensile strengths, even in the case where the elastomer latex, for example of the GR-S type, did not exhibit a high tensile strength. traction.



   Films with high tensile strength can therefore be obtained if latexes of a high vulcanizable (elastic) or unvulcanizable (plastic) polymer are prepared, either by removing the emulsifier, or by using a suitable polymeric emulsifier, and when reinforced with vinyl fillers which have also been prepared either in the absence of an emulsifier or in the presence of a suitable polymeric emulsifier.



   It is therefore only by the present invention that it has become possible to prepare a good foam rubber from butadiene-styrol copolymers (GR-S polymers).



   As polymer emulsifiers, it is possible to use both those of natural origin and those of synthetic origin.



   Alpha specimens of soybean are an example of such natural polymer emulsifiers.



   Synthetic polymeric emulsifiers can be prepared by the copolymerization of monomers having hydrophilic and hydrophobic properties, selected in the desired ratio to obtain a polymeric emulsifier which produces low particle size vinyl fillers.



   This type of polymer emulsifier is obtained, for example, by copolymerizing acrylamide, styrol and methacrylic acid in water, without addition of emulsifier and with addition of catalyst, at 60 ° C. (Table XVII, example 2) .



   The solid copolymer settles to the bottom of the container, but dissolves again when a sufficient quantity of sodium hydroxide solution is added to bring the pH to 8.0. The solution is transparent and exhibits only a weak Tyndall effect.



   To prepare the vinyl fillers, the monomeric compound, the catalyst and water are added to the already described solution of the polymer emulsifier, and this mixture is then subjected to a second polymerization. In this second polymerization step, the transversely bonded vinyl filler then forms.



   The vinyl filler latex thus prepared is then mixed with a latex of butadiene-styrol copolymer, for example of the GR-S 1500 type (Table XXVII, Example 2).



   By choosing different hydrophilic and hydrophobic monomers, as well as the polymerization catalyst, different polymer emulsifiers can be obtained, as well as vinyl fillers polymerized therein.



   If necessary, plasticizers can also be added to the polymeric emulsifier.



   Since the polymer emulsifier itself represents a polymerizate, it is also possible, according to the present invention, to obtain an active vinyl filler by graft polymerization, on the synthetic polymer contained in the emulsifier, a monomer or mixture of mono- polymers forming crosslinks, possibly even in the presence of polymers which do not form crosslinks.

  <Desc / Clms Page number 61>

 



   The technical progress achieved by the invention, which has been discussed in detail above, can be summarized as follows: a) by preparing high insoluble polymers with colloidal particle size, a new group of "organic fillers is created. active ", which give a number of advantages in elastic and plastic materials;

   b) when one of these "vinyl fillers" is distributed, especially with small colloidal particle size, in synthetic elastomers of low strength, such as for example those represented by butadiene-styrol copolymers, the tensile strength mixtures of rubber and the vulcanized products made therewith, as well as their abrasion resistance, are markedly improved, and even brought to figures which can be compared with the higher figures of natural rubber, when the added vinyl fillers are polar and contain active polar groups which have the ability to form salts with organic acids or bases;

   c) with certain combinations of elastomers and vinyl fillers, lower hysteresis products can be obtained than by using the fillers customary hitherto; the new vinyl fillers also have, surprisingly, a reinforcing action on the most diverse natural self-reinforcing rubbers, with high tensile strength;

   in specific cases, this reinforcement is produced while maintaining a low hysteresis in comparison with natural rubbers containing the usual fillers to date. e) Surprisingly, it has been found that the vinyl fillers, in oombinaiaoniaveo of the plastomers which themselves usually exhibit a high tensile strength, further increase this, while the transparency of plastomers or of products made with them. is increased, or remains unchanged, or that one can obtain a controllable opacity of the plastomers f) The present invention allows not only to prepare new vinyl fillers and their latexes, but also improved master batches, as well as improved vulcanized and unvulcanized reinforced products,

   and it indicates new processes for their preparation. g) It has been observed in this connection that the nature of the elastomer and the nature of the vinyl filler in a reinforced elastomer have a certain relation between them: (1) In the case of an elastomer which, on stretching, exhibits little or no crystalline properties, which is therefore of the type of non-self-reinforcing elastomers, such as for example polybutadiene, butadiene-styrol copolymers or butadiene-acrylonitrile, of the GR-S or GR-A type, the nature of the vinyl filler is of decisive importance in order to achieve a notable improvement in the strength of such a mixture.



  While nonpolar charges increase strength only to a small extent, on the other hand, active polar charges give a markedly greater increase in physical properties, and when such a charge contains reactive groups, which are capable of forming salts, we obtain solidities much higher than others.



   (2) If, on the other hand, an elastomer crystallizes on stretching, if it must therefore be classified in the type of so-called self-reinforcing elastomers, such as natural rubber, polychloroprenes, rubber

  <Desc / Clms Page number 62>

 butyl, etc., the chemical composition is then less important from the point of view of the strength of the final product, although again vinyl fillers containing polar and reactive groups give somewhat better results. better.



   (3) The following hypothesis probably gives a plausible explanation of these phenomena: the polar vinyl charges, especially those with reactive groups, participate in the vulcanization of the elastomer, or influence or increase it locally, and by following, do not only constitute solid colloidal particles which serve as fillers, but also bind the elastomer molecules to the vinyl filler particles, and in this way serve as crystallites or crystallitic combinations, as in elastomers. - self-reinforcing res.



     (4) Regarding point (e) above, it has been shown that, unlike the decrease in strength caused by the use of fillers in plastomers (see King and Wentworth, "Rax materials for elec- trie cables "(Raw Materials for Electric Cables) 1954, edited by Ernest Been, Ltd. London, page 169), the vinyl fillers of the present invention markedly increase the strength of plastomers, the reactive group polar fillers here being again, particularly active.



   CLAIMS.



   1. Organic active fillers for high molecular weight natural or synthetic materials - such as natural rubbers or modified types of natural rubber, or self-strengthening synthetic elastomers, or thermoplastic or heat-hardening plastics, derived from cellulose, starch, and., or their mixtures - characterized in that these fillers consist of polymerisates or copolymerisates with transverse bonds, insoluble in the high molecular weight materials to be added and coming from vinyl or allylic or vinyl-allyl monomers, optionally also mixed with other monomers, these fillers being said to be vinylic, which can also be modified by a chemical reaction,

   and exhibiting a colloidal order particle size.


    

Claims (1)

2. Active organic fillers according to claim 1, charac- terized in that the cross-linked vinyl fillers contain, in the mass and / or on the surface, reactive polar groups, such as carboxyl, hydroxyl, halogen, amine, etc. nitrile, amide, aldehyde, carbonyl, etc., which may possibly give rise to chemical reactions with natural or synthetic polymers to be incorporated, for example in poly-condensations and are used above all for filling non-self-contained elastomers. reinforcers or combinations thereof, particularly of the type of diene homopolymers or copolymers, for example: polybutadiene, butadiene-styrol copolymers or other butadiene-vinyl copolymers, etc. 3. Active organic fillers according to claims 1 and 2, characterized in that the cross-linked vinyl fillers contain reactive groups such as carboxyl, amino, pyridyl, and the like. possibly giving rise to chemical reactions with the natural or synthetic polymers to be incorporated, for example in polycondensations. <Desc / Clms Page number 63> 4. Active organic fillers according to claims 1 to 3, characterized in that they are obtained by polymerization or copolymerization of monomers, at least one of which contains several polymerizable ethylenic bonds, such as vinyl and allyl groups, for example: divinylbenzene, dimethylacrylate d ethylene glycol, NN-diallyl-bis-acrylamide triallyl cyanurate, NN-dial-lylmelamine, allyl acrylate, allyl methacrylate, etc. 5. Active organic fillers according to claims 1 to 4, characterized in that they are obtained by polymerization of the monomers or mixtures of monomers in the aqueous phase, in the absence or preferably in the presence of known emulsifiers or of. Polymer emulsifiers, the operation being carried out in one or more stages until insolubility in the high natural or synthetic polymers to be incorporated or added. 6. Active organic fillers according to claim 1 to 5, characterized in that, in order to prepare them, an emulsifier is first formed by copolymerization of hydrophilic and hydrophobic monomers in the presence of water and of a catalyst. polymer in which the monomers which produce the vinyl fillers generating transverse bonds are polymerized, optionally after dilution with water, with fixing of a determined pH and using a new catalyst, the whole until formation of cross-links. Active organic fillers according to Claims 1 to 6, characterized in that their preparation is carried out by means of graft polymerization, in which monomers or mixtures of monomers which give polymerisates or copolymerisates which may or may not form transverse bonds, are grafted on high polymers, natural or synthetic, already existing, transversely linked or not, the fillers being insoluble in the high polymers, natural or synthetic, which it is a question of incorporating. 8. Active organic fillers according to claim 1 to 7, characterized in that the vinyl fillers containing carboxyl groups contain, as a mixture, additional amounts of ammonia, and / or amines and / or nitrilamines. 9. Active organic fillers according to claims 1 to 8, characterized in that the cross-linked vinyl fillers containing aldehyde groups are treated with compounds which are capable of reacting with the aldehyde, such as for example. phenol, phenolic compounds, urea, etc. 100 Process for incorporating active organic fillers according to claims 1 and 2, characterized in that these are added, in latex form, to latexes, emulsions or dispersions of high natural or synthetic polymers, which are uses these mixtures as they are, in each case, for example to prepare films, coatings, etco, or by coagulation, washing and drying with or without the addition of fillers and / or plasticizers and / or anti-corrosives and / or or stabilizers and / or vulcanizers, and that they are optionally vulcanized. 11. Process for incorporating active organic fillers according to claims 1 to 10, characterized in that the filler latex is added, with organic transfer agents - preferably in the form of their latexes, - to latex from high natural or synthetic polymers, and whether one works the latex mixture of <Desc / Clms Page number 64> in a manner known per se, or that after having worked the mixture of vinyl filler latex and organic transfer agents, this mixture is added to the natural or synthetic high polymers in solid form, on a cylinder or in a cylinder. mixer. 12. High natural or synthetic polymers containing fillers according to 1 to 11. in appendix 3 drawings.