DE1494272A1 - Process for the production of solvent- and water-resistant, vulcanizable or hardenable plastic compounds - Google Patents

Description

Patent attorneys Dipi.-ing.Leinweber Dipi.-inglimmermann 1494272

Munich 2, Rosental7
Tel. 201989

? ir-ü rOLXfUSTIC SOcAn ^, - 15 Hue des Sablons, Paris

and

Place Gallig Coloabss »Soino

(France)

wi ^v i- ^ lu.'2n for the production of solvent and water-soluble, 2 ^ »vulcanisable or hardenable plastic mass ::»

(New) analysis documents

The invention relates to a method of manufacture. Löw "^ _w - ^ i" tcl- 'and water-resistant, vulcanizable construction ^ hardness:.' v. ^ Ilunstoffnasccn from at least one hydrophobic and ainie-./~.s one · .: hydrophilic polymer ". · ■■

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It is known * that carboxyl-rich, water-soluble polymers are insoluble in most organic solvents and do not swell in them, v; a3 distinguishes them from other polymers, as in 2.E. vcn- dom natural or synthetic rubber, polyvinyl chloride, polyamides, polyolefins »These are missing oins3 two polymers common solvent is a sign of their incompatibility *

In addition, the mechanical inclusion of a carboxyl-rich, water-soluble polymer, for example an ethylene-anhydride copolymer. maleic acid * in a hydrophobic polymer . he'terogenen opaque products of poor mechanical char acteristics _t and indeed below that of each of the outputs of these two polymers * polymers indicate the heterogeneity of Genischs in microscopic odor t ^> scopic respects and the resulting -schlechten mechanical properties in the same manner this Intolerance*

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A microscopic heterogeneity is evident especially due to the impossibility of * to obtain transparent or self-translucent products «The one from two hates formed by incompatible polymers are opaque «

According to the method according to the invention. a new substance connection can be produced, in which at least a carboxyl-rich, water-soluble polymer or a polymer * that is able to form carboxyl groups, is compatible with a hydrophobic polymer "

Water-soluble polymers are to be understood as meaning those which have the same pH in an aqueous medium or are soluble above 7 "

This polymer obtained by any process should be a. Have number of carboxyl groups, those above one determined for each type of polyamide Limit is »

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BATH

The special feature of the method according to the invention is that a latex consists of at least one hydrophobic Polymer with more than 2 percent by weight of a hydrophilic polymer consisting of an ethylenic unsaturated monomers with at least 50 percent by weight of carboxyl, acid anhydride or acid chloride groups on * was thawed and that is dissolved in water, is mixed homogeneously and finally the water from the mixture removed by evaporation »

The amount of the hydrophilic polymer (B) added is preferably between 5 and 95% the aqueous phase in any known manner, such as »b * simple mechanical. After being homogenized, the water can be removed from the best of the constituents by evaporation be separated «. This creates a solid product in the form of a transparent, fila-like mass, which all for a compatibility; has characteristic properties

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This hatred can be processed mechanically without theirs To lose homogeneity and transparency »

The term latex is an aqueous dispersion of a natural or synthetic hydrophobic To understand polymer, regardless of whether this polymer is formed directly in the aqueous medium has been or whether it is known in another form in itself

. \ y.is has been converted into an aqueous dispersion »The printing latex therefore comprises the aqueous emulsions and suspensions * the" hydrosols "* the latex plastics and 2 lasers, as described in" Polymer processes "by C + Jä * Schildknecht, Chapter 15 "Page 625/626 (Interscience Publishers Inc" New * York 1956) are defined "

The types of latex used according to the invention can optionally contain stabilizers, thickeners or crosslinking agents contain »These are only added in very small quantities in order to improve the dispersion and the To facilitate processing «According to the invention, mixtures of several types of latex can also be used within the limits, ii

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which the stability of the emulsions is not endangered, can be used.

External acidic (hydrophilic) aqueous solution Polymer (B) can add a solution of another water-soluble polymer to the latex dos hydrophobic polymer (A) Polymer (C) are added all of the properties decisive for the compatibility between the three polymers in this case «in particular this product is transparent, even after processing, deformation or other processing methods, insofar as these do not require any additional cloudiness, causes «

The dry product obtained in this way can be crosslinked It is in fact possible * the polymer (A) or the polymer (B) suitable amounts of a crosslinking agent or the like to add

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A particularly interesting case arises when the crosslinking agent for the hydrophilic polymer (b) is a polymer (C) which is itself soluble in water, for example a polyvinyl alcohol » The dispersion of the hydrophobic polymer is then used (A) added in the form of an aqueous solution in the same hatred, like the hydrophilic polymer (b).

The active groups of the polymer (C) should preferably equal in number to the number of carboxyl groups contained in the hydrophilic polymer « Ground the dispersion in the same proportion of the hydrophobic polymer two aqueous solutions of the polymers (B and C) added, both as un-. apply with the hydrophobic polymer (A)

This ternary mixture can be removed after removal of the water in a well-known ice by simple Networking Zr-närmen; for example react (B) and (C) with each other to form a network, which the girders of (A) includes · This polymer is suitable

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for vulcanizing, if you have given him suitable vulcanizing agents beforehand adds «

These products can be classified under those for elastomers or process plasto under normal conditions, and they are suitable for all common processes: processing in the most varied of mixtures, processing be crazy. Calendering * Pressure deformation »Injection deformation us «· The compatibility remains, and after all research work without the addition» of opacifiers Are the products transparent? They can be reinforced by the usual Zuaitit, by BuB der various kinds of silloates, titanium oxides or the like « The emulsion is equally suitable for all normal uses such as latex, wlt SoB * potting, Vertu ·· ** hardening or the like.

The polymer (B) consists of monomers, of one of which has at least one carboxyl group or can form this by hydrolysis. Examples of this are

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- * Acid anhydride or acid chloride groups with a Ethylene double bond * such as "B":

Acrylic acid, the alkylacrylic acids, like iiethycryläurevt of the crotonic acid « of sorbic acid * of cinnamic acid * of atropic acid, the Maleic acid * of fumaric acid, oleic acid, linoleic acid or other * such as itaconic acid, m-chlorocic acid, hydroiauconic acid * glutaconic acid, styrylacrylic acid, aconitic acid, vinyl acrylic acid *, gleostearic acid or from the anhydrides of these acids, such as

pt

e.g. acrylic anhydride, maleic anhydride, Citraconic anhydride, itaconic anhydride or the like, or of the chlorides of the corresponding Acids *

In the case of divalent acids, one part can be esterified *

When the acid (or the anhydride or the acid chloride) is copolymerized ■. with another ethylene-i »o-, the ratio of the proportions of the two monomers may vary, provided that the obtained

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Copolymer is water-soluble; however, these two monomers are preferably used in equimolecular proportions at*

As a crosslinking agent to react with the acid groups suitable oxides or hydroxides of polyvalent metals, salts of weak acids of these metals, or Polyamines * Di- or polyamides or imides, di- or polynitriles, di- or polyisocyanates, acid-di- or polychlorides, Di- or polyols as well as di- or polyepoxides

The crosslinking agent should have at least two functional groups that undergo a condensation reaction with an acid "These two groups can un- _it t behind the other different, as ζ · Β in the amino-alcohols, bring * *

Strong dehydrating agents can be used for crosslinking, which are located between the chains of the anhydride compounds accumulate, such as «B« phosphoric acid anhy- *

ff acetic anhydride or Ac e ty! chlorid * '

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BATH

All polymers are suitable for the invention Process not only the homopolymers or copolymers »but also mixtures thereof based on chemical feet through crosslinking, esterification or oxidation have been changed among each other "

Examples of polymers (A) ₁ which can be used as latex according to the invention are natural rubber, the synthetic rubbers derived from the dienes, butyl rubber, vinylidene polymer, including the halogenated vinylidene polyate and, in general, homopolymers and copolymers of the polymerizable olefinic compounds, the mildest »A · carbon detoxifying substance have a double bond, such as t» B »dl · polymer * of ilaleic acid and its esters as well as polytiny compounds.

Other examples of usable trfiadungagemie polymers (A) _t least Alkydhare · and Celluloseester and ethers "Ftrfter eigatn to Aminoplaat-Iuaetharse," he ι · Β »Earnstoff formaldehyde Polymeriaate and Anilinformal-

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dehydrogenate polymers and natural resins such as rosin and the various natural types of rubber as well as their derivatives and esters »

In the absence of all other additives, it occurs between the polymers used according to the invention (A) and (B) achieved compatibility in particular through the transparency of the mixtures in appearance; '

This compatibility is therefore due to the degree of transparency of the products produced according to the invention measurable"

In the absence of opacifiers, the transparency is determined by the extent of the film of the examined product absorbed light measured.

There is a body under the transparent mixture

_φ to understand who, if, he is in the form of a film of 1 mm

<° strength in a monochromatic light beam with a

-o wavelength of 3800 angstrum is brought, an im

The spectroscope shows a certain light absorption which is less than 12 tons , as has been observed for the polymer (A) under most conditions.

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The invention will now be based on the following examples

games explained in more detail *
example 1

375 g of a 40 # aqueous solution of low molecular weight polyacrylic acid au 1000 g of natural rubber latex emulsified with 60 1 »and stabilized by Allylaryl-.Polyätheralkohol elastomer added" Do allowed to homogenizing the product. Settle for 12 hours at ambient temperature and k can then it disks of 9O ⁰ C. After evaporation of the flow · αassers remains a transparent film, dor 25 parts of polyacrylic acid per 100 parts of natural rubber. This is processed in an operating by iieibung at 8O ⁰ C cylinder mixer "After a plastic ilasse formed after a few minutes analogous to that * the one extending under the same conditions with natural rubber" alone yields Then, to 125 parts of this product, 5 parts zinc oxide * 3 Parts sulfur and 1 part vulcanization accelerator of the substituted mercaptobenzothiazole type

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BADORlGIhIAt

(Santocure) introduced * The products obtained in this way can be deformed by pressure and vulcanized ^{at 142 ° C. in the course of 30 minutes.}

To the excellent properties of the above Product highlighting became essentially the

The above composition is made up of the appropriate mixture, in which, however, the individual constituents merely penetrate Mixing in a standard cylinder mixer were introduced * After evaporation of the hater from the 40 # igen aqueous solution of low molecular weight polyacrylic acid, this remains behind as a powdery residue «

Such mechanical mixtures are opaque macroscopically heterogeneous and have after vulcanization poor mechanical properties * The same happens * if the water instead of evaporating through Xoagulation of the latex is separated «These properties result from Table I»

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Example 2

358 g of a 15 # aqueous solution of a JUhylen- ^ ialeinsäureanhydrid Copolyaerisats are with 231.5 g of a 20% aqueous solution of a polyvinyl alcohol mixed·

The resulting uncolored, homogeneous aqueous solution contains approximately equal amounts of COOH and OH groups. 706 g of this solution are introduced into 1000 g of natural rubber latex according to Example 1 «

According to the example. 1 is obtained a transparent elastic film by a stoichiometric mixture of 20 parts of ethylene dialeinic anhydride copolymer and polyvinyl alcohol in 100 parts of natural rubber "

* ■

This mixture, processed on a cylinder mixer, remains transparent · To 120 parts of this mixture «Earth 5 parts zinc oxide, 3 parts sulfur and 1 part. Santocure added · This mixture is left for 30 minutes

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vulcanized at 142 ^° C. "The mechanical properties are much better than with products that were achieved by vulcanizing natural rubber alone under the same conditions." You can also add a reinforcing filler, such as kiss, to the mixture * B, a product with good properties "On the other hand, the products of the same composition, which, however, were only produced by combining the dry substances in a fischer or by coagulation" have very poor properties * The properties of this mixture are summarized in Table 1 "

Example 3

940 g of a solution of ethyl maleic anhydride copolymer and polyvinyl alcohol according to Example 2 become 2000 g of a latex from a 40a emulsion a butadiene-acrylonitrile copolymer, which with Tuton χ 301 is stabilized, added

bene «quietly, a transparent film is prepared that on 909 8277 1627

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100 g of butadiene acrylonitrile copolymer 10.75 g of itnylliialeinic anhydride copolymer and 925 g of polyvinyl alcohol, with about as much hydroxy as Carboxyl groups are present * To be transparent The mass that arises during the processing of de-a films in the Irish gives 5 parts of zinc oxide, 2 parts of ochulphur and 1 part kercaptobenzothiazole added · This mixture.

■ 50 minutes at 142 ⁰ C "erforat; this gives a product with extremely good mechanical properties compared to those of the ethyl-maleic anhydride copolymer »

From table 1 are the mechanical properties of this product compared to those of a mixture? the end Butadiene acrylonitrile copolymer and ethyl-maleic anhydride-polyvinyl alcohol copolymer of the same general composition, which can be seen by simple mechanical introduction of the dry components in a cylinder mixer or by coagulation and

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Failure was won »
Example 4

To 1000 g of latex from a 6Q; Sigen butadiene copolymer _t which is known under the üamen SBH and was polymerized cold, 200 g of a 20; $ aqueous solution τοη 25 S * polyvinyl alcohol was added and then 2400 g of a 10 # solution τοη polymethacrylic acid, which was produced by heating a solution of 500 g methacrylic acid in 4.5 liters of water with 10 g potassium persulfate to 95 ° C. for 5 minutes Further processing, which is optionally carried out with the introduction of τοη crosslinking agents. The mixtures of the same composition from the dry products, on the other hand, are heterogeneous and have poor mechanical properties; the same results are obtained when άε water by coagulating and precipitating the latex and nichi

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is removed by evaporation (see Table 1) · Example 5

To 1000 g of a latex with an emulsion of middle alkylaryl polyether alcohol stabilized polychloroprene 1500 g of a 20% aqueous solution of a copolymer of styrene and maleic anhydride are earthed admitted *

Those made in the same manner above Films are wetter after homogenization and evaporation of the transparent; they develop 50 parts of the copolymer τοη styrene and maleic anhydride to 100 parts of neoprene «.

These films know to be vulcanized when during processing per 150 parts of the transparent till. 5 parts zinc oxide, 4 parts magnesium, 2 parts sulfur and 0.5 parts of a vulcanization accelerator based on τοη 2-lie reap to imidazo lin are added »by Addition of 5 parts of oxallyl chloride starts the crosslinking of the product even better *

909827/1627

ORIGINAL BATHROOM Example 6

One uses an aqueous. ··. Emulsion of a copo-, lymerisats of isobutylene isoprene, which under the liamen "Butyl rubber" is known ·

This stabilized by alkylaryl polyether alcohol, ■; sized emulsion has a dry extract of 30 ^ "600 g of a 20% solution of a copolymer of vinyl chloride and maleic anhydride are added to 2000 g". The transparent films divided in this way give ^: after processing in the mixer, also transparent masses.

Example 7

To 2000 of a g of an aqueous folyvinylchloridemulsion existing latex having a irolyvinylchloridgehait of £ 50 be in the dry matter 250 g of a 20 # aqueous polyvinyl alcohol solution, and then 4000 g of an aqueous solution of 15 $> a 20 ^ aqueous solution of a Ithyl-maleic Anhydride copolymer addition *. ' 9098 27/1627

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The transparent films that result after the water has evaporated can be processed and deformed become * without losing their transparency

Example 8

A mixture of 1000 g of polyvinyl chloride according to Example 7 and 1250 g of latex of 40 # butadiene-acrylonitrile is produced.This mixture is stabilized by alkylaryl-polyether-alcohol, and then 625 g of AQHgQr aqueous solution of low molecular weight polyacrylic acid according to Example 1 are added »The transparent films obtained contain 100 parts of polyvinyl chloride, 100 parts of butadiene-acrylonitrile copolymer and 50 parts of polyacrylic acid * They can be processed without losing their homogeneity and transparency, and by adding 15 parts of zinc oxide to 100 parts of the product, the product is smooth and resistant Hate by lasting 45 minutes curing at 16O ⁰ C *.

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The mixture * which is obtained by introducing 500 g of the dry product from the evaporation of the Vinapol from a mixture of 1000 g of polyvinyl chloride and 1000 g of copolymer of butadiene and acrylonitrile in a cylinder mixer preserved * is opaque, heterogeneous and without usable mechanical properties *

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Claims (1)

? 27 C49 IVd / 39b
Polyplastic SA • · · I Patent claims: 1 «Process for the production of solution belts and water-resistant, rulkania-able or hardenable Plastic masses of at least one hydrophobic and at least one hydrophilic polymer, characterized in that a latex consists of at least one hydrophobic Polymer with more than 2 percent by weight of a hydrophilic polymer consisting of an ethylenically unsaturated monomer with at least 30 percent by weight of Ca- thawed anboxyl, acid, hydride, or acid chloride groups and that is dissolved in nastier, is mixed homogeneously, ■; ■. i and finally the water from the mixture by evaporation removed· 909827/1627 BAO ORIOINAL 2 »Method according to claim 1, characterized! that the mixture of polymers contains a crosslinking agent for at least one of the polymers contained in the mixture or a water-soluble, crosslinking one Folamerisate is added and at the same time or afterwards a crosslinking is effected « 909827/1627 BATH ORIGINAL