DE2262735A1 - CHROME-CONTAINING MASS - Google Patents

Description

Patent attorney »
Dr. Ing.Walter Abite
Dr. Dietician F. Morf

^ '•• ^H ? ^NS " ^A " ^BROWNS - December 21, 1972

Munich 86, Pierainaueratr. 28 gO ^ B

E. I. du Pont de Nemours and Company 10th and Market Streets, Wilmington, Del. I9898, V.St.A.

Chromium-containing compounds

The present patent is an additional patent to P 21 16 (patent application P 21 16 299.2-42), the subject of which is a chromium-containing mass, which is characterized by one or more water-soluble coordination complexes of (a) chromium (III), which consists of a water-soluble Salt derived therefrom with a non-coordinated anion, the salt in water giving 'CriHgO) ^ " ¹ ", with (b) a trans-acid of the formula

E. COOH

σ = σ _ν

HOCC R ₂

where R ^ and R ^, which are the same or different, are hydrogen,

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Alkyl radicals, -CHpCOOH or phenyl radicals mean, with the proviso that the total number of carbon atoms in the trans-acid is an integer ranging from 4 to 10 inclusive, a method of making this mass that characterized in that the trans-acid and a chromium (III) salt, that gives the hexaquochromion, heated at a pH of about 0.2 to 1 or above 1 to 2.4, as well as a Use of this compound to increase the adhesive strength of a substrate made of metal, metal oxide or glass on plastic by bringing the mass into contact with the substrate.

The present invention now relates to a chromium-containing composition which is improved over the chromium-containing composition of the main patent A compound, which is characterized in that said compound is a compound having cations and anions contains, in the said chroin (III,) - coordination complex represents the cation and the anion is uncoordinated and monovalent, and the approximate ratio of chromium (III) to acid (each in the cation complex) to non-coordinated Anion is 2/1/4.

Coordination complexes of chromium (III) with certain dibasic Acids, such as oxalic acid, malonic acid and tartaric acid, are from Gmelin's Handbook of Inorganic Chemistry, Chromium, Part B Verlag Chemie GMBH, 1962, pages 408 to 424 known. From this reference it can be seen that the chemistry of this Complex is complicated. As far as is known, no coordination complexes of chromium (III) with fumaric acid have been found so far produced or reported about it in the literature.

Various organic polymers, such as the polyolefins, are used as assembly adhesives, e.g. B. for the union of metal parts or for the production of permanent protective or decorative coatings on metal or metal oxide substrates

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well suited because the adhesion obtained is not permanent, especially in the presence of moisture under stressful Conditions. So although they have the advantage of low cost and the latent advantages of strength, toughness and chemical .Inertheit is of the olefin polymers, e.g. B. the polyethylenes and polypropylenes, · known that they - Adhere very poorly to metals. It was found that various other polymers have limited use as structural adhesives or as coatings for substrates because the adhesive bonds formed with the substrate are not so good are as desired for many purposes.

It is known to carboxyl groups in polymers by grafting, To introduce copolymerization and the like to improve their adhesion speed, however, this attempt usually the physical strength deteriorates and often the durability of the adhesive bond with such loose ones reactive metals such as steel, iron, copper and the like., Worsened. Various veges have been taken to order to improve the adhesion of polyethylene to metals, For example, according to US Pat. No. 2,838,437, certain ' unsaturated organic acids incorporated or the polyethylene surface or the surface that. should adhere to it, treated with such an acid. According to US Pat. No. 3,038,847, primer coatings are made from various aminoalkyl silicon compounds applied to metal surfaces before organic polymer coatings are applied to them. the. U.S. Patent 3,466,207 describes U.S. Patent No. 3,466,207. Pretreatment of metal substrates with an aqueous solution of an aliphatic Carboxylic acid, preferably after treatment with an aqueous inorganic acid solution, the hexavalent Chromium contains prior to an olefin polymer on the metal substrate is applied. However, they are the result of this; ; Improvements usually involve improvements in the rate of adhesion development (which

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generally by increases in peel and lap shear strengths with reference to freshly prepared test samples,) without any noticeable Improvement in the durability of the adhesion under tension in the presence of moisture. In some cases lead the proposals to improve the peel strength actually lead to a deterioration in the durability of the adhesion under tension in the presence of moisture. Since an assembly adhesive must have the ability to produce a practically continuous Enduring pull in a predictable and dependent manner in our humid environment represents sheer acceleration liability, while useful, is often of limited practical value, if not the problem the poor durability or resistance of the adhesion is also solved or can be solved. In Similarly, protective or decorative polymeric coatings on corrodible metals such as iron or steel are of limited use practical value if the physical forces in the rust increase the coating from a scratch or crack can push away and thereby spread corrosive flaws in the coating.

Aqueous solutions of the Hassen according to the invention are also used provided. The complex is a cation and the anion is monovalent and not coordinated with chromium. That approximate ratio of chromium (III) to acid (each in that Cation complex) to non-coordinated anion is 2/1/4. The preferred trans acid is fumaric acid; the preferred one Anion is nitrate.

A preferred composition is a coordination compound represented by the following general formula:

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Here, X is a non-coordinated anion, preferably nitrate, Z is hydrogen or methyl and X is monovalent. In this preferred composition, the molar ratio of fumaric acid to chromium is 0.5 / 1 »although ratios in the range 0.4 / 1 to 0.6 / 1 are essentially equivalent. This comes to mean that the approximate ratio of Chromium (TII) to acid (each in the cation complex J is 2/1/4 to non-coordinated anion. Each acid group has about two chromium atoms and each chromium atom has about two non-coordinated anions. Aqueous solutions of this preferred composition have a blue color Color and result in a characteristic broadband light absorption spectrum with two maxima at about 4100 Å units and 5700 Å units.

It is believed that all of the products described herein contain mixtures of two or more chromium complexes can and need not be pure chemical species, although a specific species predominates in each product can. Different degrees of polymerization can also be achieved in these by means of the dicarboxylic acid linkages Products occur.

The compositions according to the invention are preferably in an aqueous solution of tetrahydrofuran or an alcohol of 2 to 4 carbon atoms, and preferably the trans acid is fumaric acid. .

ti.

It is particularly preferred if the mass contains less than 10% by weight of water.

Another embodiment of the present invention are Compounds containing polymeric compounds, namely fumarato-chromium (III) nitrate, Aconitato-chromClII ^ -nitrate and Mesaconato-chromClII ^ -nitrate. Such masses are useful for promoting adhesion to metal, metal oxide and

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Glass substrates, in particular on glass substrates. Under polymeric types it is understood that the complex has more than Contains 1 chromium atom. These polymers can be linked through the dicarboxylic acids or through various oxygen linkages as generally reported by Laswick and Plane in the Journal of American Chemical Society, Volume 81, (1959), pages 3564-3567, by Hall and Eyring in the Journal of American Chemical Society, Volume 72 (1950), pages 782 to 790 and by Bailar in Chemistry of the Coordination Compounds, Reinhold Publishing Corporation, New York, (1956) pages 448 to 471.

In the drawings:

Fig. 1 is a graph showing the broadband light absorption spectra shows for solutions of the preferred compositions, and

Figure 2 shows the ultra-red spectra of the preferred composition and various standard compositions.

Compositions according to the invention contain one or more specific, water-soluble chromium (III) coordination complexes described above. They derive from a water-soluble chromium (III) salt with a non-coordinated one Anion (which salt in water gives the hexaquochrome (III) ion) and with a trans acid of the formula

R ₁ COOH

C = C
HOOC R ₂

away. It is essential that the geometry of the acid substituents is trans. R ₁ and R ₂ can have the same or different meanings. However, they are selected from hydrogen, alkyl, phenyl or substituted alkyl or phenyl, for example

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-CHpCOOH, selected. The total number of carbon atoms in these trans acids is an integer in the range of 4 to 10 inclusive. Such acids can be trans-1,2-ethylene-dicarboxylic acids can be described with 4 to 10 carbon atoms.

When reference is made here to complexes of Cr ⁺ ^ and trans acids (e.g. fumaric acid), this "does not mean that in the complex the acid itself is complexed ^{with Cr + ^;} of course, anions of the acid are involved in the complex. In the case of fumaric acid, the anions are the hydrogen fumarate anion (H ^ C ^ O.) "" And the fumarate anion (EpC.Oj ^81. These anions can be added to the reaction mixture as acids or salts containing any of these anions.

It appears that 'that is the gross stoichiometric ratio from chromium atoms to fumarate molecules in solution over the range of about 1: 0.4 to 1 j 0.6. the The nature of the species or mixtures of species in solution is not precisely known, but these are soluble Fumarate coordination complexes or mixtures thereof are all excellently useful for promoting adhesion. Some free chromium nitrate and / or fumaric acid may also be present in these solutions with virtually no unfavorable effect occurs.

In the production of compositions according to the invention, "im the nitrate anion is generally preferred. A fumaric acid to chromium molar ratio of about 0.5 is preferred where highly concentrated solutions are stored or shipped should, because with this relationship such solutions are excellently stable. Complexes or mixtures that contain a have a significantly lower ratio of trans acid to chromium can be produced, but offer none particular advantage in terms of stability and tend

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tend to be somewhat less effective for bonding polymers such as polyethylene to substrates such as glass. In general the range from 0.4 to 0.6 mol of fumaric acid per g atom of chromium is preferred.

Particularly preferred compositions are aqueous solutions which contain about 1 »5 g-atoms of chromium per liter of solution, about 1.2 equivalents of base (preferably alkali) and about 0.5 mol of fumaric acid per g-atom of chromium. These solutions are preferred because they have a high concentration of chromium, because they are stable for extended periods of time at temperatures up to 45 ° C, and because they are very effective for bonding polymers such as polyethylene to glass substrates. These high levels of chromium can only be obtained by carefully controlling the fumaric acid to chromium ratio and the alkali to chromium ratio. These materials contain 1.0 to 1.5 equivalents of base and 0.4 to 0.6 mol of fumaric acid per g-atom of chromium. Preferred compositions contain 1.15 to 1.25 equivalents of alkali per g atom of chromium. Masses containing more than 2 g-atoms of chromium per liter can be produced, but are not as stable and therefore not as preferred. The preferred chromium concentration range is 1.25 to 1.75 g-atom per liter. Lower concentrations can be used, but are more costly in terms of shipping and storage.

The production of fumarate-chromium nitrate complexes according to the invention involves heating an aqueous solution of chromium (III) nitrate, the trans-acid to be used (such as fumaric acid) and its base (preferably an alkali, e.g. a hydroxide, carbonate or bicarbonate Alkali metal or alkaline earth metal) to a temperature of 50 ° C to the reflux temperature long enough for the To allow the reaction to proceed practically to completion. The duration of the reaction takes about 10 minutes to 1 hour. The proportions the starting materials are 1.0 to 1.5 g / equivalent

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a base and 0.4 to 0.6 moles of trans satire per mole of ' Chromium (III) nitrate. The resulting solution contains 1 to -7 % Chromium by weight.

Such masses, which contain about 1.5 g-atoms of chromium per liter of solution and about 1.2 equivalents of alkali and 0.5 mol of fumaric acid per g-atom of chromium, are characterized by the fact that they have the following values of the light absorption maxima, γ ( S units) .. and the molar extinction, A ₁₁₁ ', in the case of freshly prepared solutions.

ν. m

4100 - 4120 & 25-26

5700-5750 £ '25.5-26.5

Minor modifications of the preparative procedure or the presence of impurities can negatively affect these values modify. The molar absorbance generally increases as the sample ages.

The preferred crowd has come in handy for promoting the adhesion of polymers to metal and glass surfaces.

When making preparations of the present complexes as indicated generally above, the reactions to generate the complexes become progressively slower the lower the reaction temperature * at 70 to about 100 ° C. Higher temperatures can be used at pressures above normal pressure. Lower temperatures can also be used, but require longer times, and at temperatures below about 70 ° the reactions are usually too slow to be useful at these temperatures.

PC-3674-B AQ

to be massive. The response time, i.e. H. the total time at the elevated temperature should of course be sufficient, to bring about the desired conversion into the complex. Thus, there is a certain useful conversion in the generally in 5 minutes at 100 ° C. and for somewhat longer times at lower temperatures. Complete conversion of the ChromCIIIj raw material in the desired complex generally a minimum total time * of approx 40 minutes at 100 ° C, but slightly longer total times of 2 to 4 hours are usually used to ensure completeness to ensure the conversion. Even longer times, e.g. B. over 6 hours can be used, but are generally not required.

As an intermediate stage for the high temperature reaction stages reaction steps to neutralize the by-product acid should generally be relatively low Temperatures are carried out, e.g. B. at temperatures not above about 35 ° C »to unwanted coordination reactions avoid which could lead to the precipitation of inactive materials. Temperatures of around room temperature, z. B. 20 to 50 ° C, are very satisfactory and preferred.

Chromium (III) compounds which give hexaquochromion in aqueous solution can be used as chromium (III) raw material or starting material in the production of the complexes according to the invention. Chromium (III) nitrate, Cr ^ NO,) ,. ηΗ _? 0, where η can be 6 to 9, is the preferred salt. Another such salt is chromium (III) perchlorate, but its use is not preferred for reasons of safety. In most other chromium (III) salts, one or more of the six coordination positions can be coordinated with one or more anions instead of water. Some of these can be used. The desired complexes of chromium (III) acetate and formate were thus created

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with enough added nitric acid or sulfamic acid, to adjust the desired pH. However, the use of the acetate or formate salt is not preferred, there, although the fumarate anion is the acetate and I-ormate anions from the internal coordination can replace the reactions referring to using these salts Deviations from exact reaction conditions are much more sensitive, and even result from minor changes the manufacturing conditions often result in insoluble and inactive products. Any appearance of a veil, Cloudiness, precipitate or gel formation in the solutions of these products generally indicates a preparative error, usually leading to complete precipitation and leads to the complete loss of usability.

The reactions for the preparation of the complexes according to the invention are best carried out using fumaric acid GJlJ) ₁ , itself, although the soluble hydrogen fumarates, such as the alkali or ammonium hydrogen fumarates, z. B. NaH (CJrLjOz _1. ) And the soluble fumarates, \ f ± e for example the dialkali or ammonium ■ fumarate, ζ. B. NapCCL ^ O ^), can be used to adjust the pH. The chromium (III) salt and fumaric acid reactants can be used in any desired proportion. However, it is generally preferred that a stoichiometric excess of fumaric acid be used to convert the chromium (III) reactant to the desired complex to promote. A large excess of fumaric acid, e.g. B. up to their solubility limit of about 10 wt. % At 100 ° C is preferred. Once the reaction has ended, the unreacted excess of fumaric acid can be easily recovered; as it is only sparingly soluble in cold solutions at the pH conditions used. If less than one formula weight of fumaric acid per formula weight of chromium (III) reactant salt is used, conversion to the

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desired complex, but is obviously a complete one Transfer of the chromium (III) -Eeaktänten in the 2: 1 chromium ζu-fumarate complex for lack of sufficient fumaric acid not possible.

Oddly, the cis isomer of fumaric acid, i. H. Maleic acid, ineffective for the present purpose and cannot be used in place of fumaric acid. However may optionally be a substituted fumaric acid, e.g. B. methylfumaric acid (mesaconic acid), phenylfumaric acid and the like can be used in place of fumaric acid, provided that the substituent or substituents replace one or both of the hydrogen atoms directly connected to the carbon atoms of the fumaric acid structure, and with the further proviso that the trans configuration is retained. Fumaric acid can be called "trans-1,2-ethylenedicarboxylic acid"

H COOH

C = C
HOOC H

wherein the -1 and 2 positions each have a hydrogen substituent wear, to be designated. Any of these hydrogen substituents can be replaced by a methyl, ethyl, phenyl, -CHoCOOH radical and the like To give fumaric acids, including monosubstitution (in the 1-position ^ and disubstitution (in the 1- and 2-position). Substituted fumaric acids which contain a total of up to 10 carbon atoms can according to of the invention can be used, in particular the acids are represented by the following formula:

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PC ^ - 3674 - B HOOC "" 11 COOH 226 2735 ^v c

wherein R ^ and Rp can be the same or different and for example hydrogen, methyl, ethyl, phenyl radicals ,. -CHpCOOH and the like. Can mean. Since, however, fumaric acid is non-toxic and most readily available, it is preferred over these substituted acids.

Almost any conventional basic material can be used to increase the pH of the reaction solutions.,. As required, e.g. B. in steps between the reaction steps at high temperature, or to increase the pH of the reaction solutions for storage. Examples of such basic materials are the alkali and ammonium hydroxides, carbonates, bicarbonates, hydrogen fumarates and fumarates. Their function is to remove or neutralize the by-product hydrogen ion in a controlled amount. This by-product hydrogen ion can also be removed in a controlled manner by means of a basic ion exchange resin. The use of such a resin may be preferred when it is desired to obtain a product solution which is free of soluble nitrates other than the nitrate salts of the complexes. An example of an anion exchange resin suitable for the above purpose is the hydroxide or carbonate form of commercially available Amberlite IRA-400, which is a resin of the type described in U.S. Patent 2,591,573 in which nitrogen atoms of the quaternary ammonium functional groups are replaced by saturated hydrocarbons - 'groups, for example the methylene group, is connected to the aromatic nucleus of a crosslinked copolymer of styrene and divinylbenz-ol.

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ORIGINAL IMSPEGTED

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Although the use of a base or "basic ion exchange resin" as noted above is usually required to prepare these complexes with an appropriate degree of conversion from the starting hexaaquochrome salt, this is not always so because in some cases the solvent water can also act as a base, ie, to remove hydrogen ions by the reaction H ⁺ + H2O -) ΗχΟ ⁺ . Thus, a reaction can proceed well enough to form a useful concentration of the desired complexes even if no base is added and even if the solution still has a relatively proportionate amount The resulting product solution promotes the adhesion of organic polymers to glass or metal, although not as well as solutions in which a greater degree of conversion to the complex has been ensured through the use of a basic material.

It is understandable that the position of the spectral maxima may shift slightly depending on minor modifications in the procedure for preparing the complexes and on the presence of any minor amounts of impurities. In general, the position of the maxima in carefully prepared fresh samples does not change by more than +30 S-units, and the molar exstrinctions do not change by more than -2. The values for the molar absorbance increase as the solutions age, the amount of increase depending on the pH, the temperature and so on. '

When treating substrates with any of the treatment solutions described above, especially when that For example, the substrate is a mild steel that is easily corroded by solutions of weak acids, it may be desirable be, to the solution a corrosion inhibitor, for example a soluble hexavalent chromium compound, ζ. Β,

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Sodium chromate, add. The addition of a six-valued Chromium compound in about 0.001 to 0.1 g-atom per liter equivalent concentration is used for this purpose.

To substrates that can be effectively used with the one. Or other the. Treated treatment solutions described above include all common base metals or their alloys that are normally used for ^ building purposes be used. Such metals are those that are no higher in the series than magnesium, for example Aluminum, iron, steel, stainless steel, copper, brass, titanium, magnesium, nickel, tin, steel sheet, Zinc and zinc sheet. This also includes metal oxide substrates, such as ceramic aluminum oxide and titanium oxide materials and glass. The substrate can be in any desired physical form, e.g. B. in the form of foils, plates or sheets, rods and the like. or in shredded form, as wire or in fibrous form, which are usually used to reinforce plastic objects be used. In all cases it is preferable that the substrate is clean before treatment, d. that is, that it ...... "i of oily and greasy impurities

and the like.

The treatment of these substrates with the treatment solutions described is generally effective to provide at least some valuable improvement in the Adhesive bonding of any subsequently applied organic polymer to the substrate, the Polymers in its final applied form is solid and applied to the treated substrate in a non-aqueous Form that wets the substrate, e.g. B. in molten form, in solution in a volatile organic solvent or in plastic form; Preferably, the applied to the treated substrate is organic Polymers dispersed therein 0.4 to 10 wt.%, Preferably 1

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up to about 6% by weight, of a finely divided aluminum oxide, that has a bound water content of not more than 9% and a specific surface of at least 5,

ρ
preferably 15 to 700 m / g, measured by the BET nitrogen adsorption method, which is described by Nelson and Eggertsen in Analytical Chemistry, Volume 50, pages 1387 to 1390 (1958). Among the various organic polymers, preferably with aluminum oxide dispersed therein, which can advantageously be applied to the treated substrate according to the invention, those are preferred which include the fusible or thermoplastic polymers, such as, for example, the oleic hydrocarbon polymers, in particular polyethylene with low and high density, polypropylene, ethylene / vinyl acetate copolymers, polyvinylidene fluoride, vinyl chloride / vinyl acetate copolymers, polycarbonates such as bisphenol A polycarbonate (the polycarbonate of 4,4'-isopropylidene diphenol), polysulfones, e.g. B. the poly-bulfone, which is produced by reacting the sodium salt of 4,4'-isopropylidenediphenol with 4,4'-dichlorodiphenylsulfone, polyamides, polyesters, Io] yurethane, Γb] ύ ^ dnylbut3ίrεl and butadicn / styrene copolymers. Suitable polyethylenes include linear high density polyethylene made by high pressure coordination catalysis and linear low density polyethylene made by low pressure coordination catalysis with 1-butene comonomer. If the polymer is to have a high surface area alumina, that is, an alumina dispersed therein with a specific surface area of at least 5 ^ / g, it should of course be stable in the presence of that alumina.

Applying any of the substrate pre-treatments described above usually accelerates the development of the adhesive strength of a subsequently applied organic Polymers considerably and also increases the resistance

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this liability. In order to obtain the greatest possible degree of adhesion resistance in the continued presence of tensile stress and moisture, it is preferred that the polymer applied to the treated substrate has, dispersed therein, an aluminum oxide with a high surface area, as indicated above. The relative improvement in adhesion obtained with the treated glass compared to the untreated glass increases as the moisture content of the polyvinyl butyral resin increases. So this treatment of the glass results in a bond that is much less sensitive to moisture. This property is important in many applications where the effects of high humidity conditions on the resin-glass bond could result in bond failure. Such fields of application are found in applications in the automotive field, examples thereof adhesively mounted Sückspiegelgriffe _s laminated windshield construction, the subject under humid conditions a Kantenentlaminierung laminated glass structure, the metallized glass or metallized resin are included for certain applications in the construction sector, Kantendiohtungssysteme for Building glazes and the like.

Summary:

Disclosed are coordination complexes of chromium (III) and fumaric acid and certain substituted fumaric acids, the preparation of aqueous solutions of such complexes and the use of such solutions for treating metal, metal oxide and glass substrates for the purpose of improving the bonding of subsequently applied organic polymer adhesives These substrates «Preferred coordination compounds of fumaric acid have the approximate formulas ^ r (H ₂ O) ₅ (C ₄ H ₃ O ₄ ] T ₈ X ₂ , ZSr (H ₂ O) ₄ (O ₄ H ₂ O ₄ ^ X and

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et &

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^ on, in which X is a non-coordinated Anion means and a is its value. The preferred anion is nitrate.

The invention is illustrated by the following examples in which all amounts, ratios and compositions are used as Expressed percentages by weight, illustrated.

example 1

This example illustrates the preparation of a preferred complex. 46.2 grams (0.116 moles) of chromium nitrate nonahydrate were dissolved in 38 g of water. While the solution is stirred was 10.9 g (0.136 mol) of 50% aqueous sodium hydroxide added, the temperature being kept below 40 C by using external cooling. Some solids were observed in the solution at this point. The temperature was then raised to the reflux temperature (106 ° C) and held at this temperature for 15 minutes. The precipitate dissolved, and the solution turned green. 6.7 g (0.058 mol) of fumaric acid was added and refluxing was stopped continued for another 15 minutes. The solution was on Chilled 25 ° C and filtered to remove a small amount (less than 0.1 g) of insoluble material. Which resulting solution turned blue and was found by analysis to contain 5-9% chromium. The pH of this solution was 0.06.

A sample of this solution was diluted in water to a 0.05 molar concentration of chromium and the light absorption spectrum was determined on a Carey spectrophotometer (Model 11) at a scanning rate of 100 % per minute. The resulting spectrum showed absorption maxima at 4100 and 5700 2. with molar extinction values of 25.3 and 25.7, respectively.

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After storage for 2 weeks at 4-5 ° C., the product solution was still liquid and free from! solids. The molar absorbances each rose to 26.7.

After 2 months "at room temperature, the molar Extinctions changed to 25 »0 and 25.8, respectively.

The complex described above, when used as a coupling agent, gave borosilicate glass fiber-polyethylene composites having high flexural strength and moisture resistance. Such composites were produced, for example, by immersing borosilicate glass fibers in a chromium complex solution containing 0.05 to 0.2% chromium, letting them dry, producing a multilayer structure from alternating layers of treated fiberglass fabric and polyethylene powder and the structure for a period of about 2 minutes at about 60.46 kg / cm ² C8bO psi) and at 175 ° C. .

Example 2

101 mg (0.001 mol) of CrO were admixed with 3.8 ml of 0.92 normal DNO ^ in D ₂ O (0.35 equivalents of DNO.) With stirring, and then 0.6 mol of 25% DpOp in D ₂ O was added dropwise. The solution was refluxed for 30 minutes to ensure complete conversion as well as the decomposition of excess D ₂ O ₂ . The solution was cooled to room temperature and 1.12 ml of 1.52 normal NaOD in D ₂ O (0.0017 equivalents of NaOD) were added. The solution was refluxed for 15 minutes to ensure complete coordination complex formation (olation) of the chromium nitrate. 59 »4 mg (0.005 mol) of fumaric acid-do was added to the reaction mixture and refluxing was continued for an additional 15 minutes to produce the preferred complex. The infrared spectrum of this solution was on a

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Perkin-Elmer Model 21 ultrared recording spectrophotometer using a slot width of 128 µm, a gain of 6, an automatic barrier adjustment of 3, and a sensitivity level ^of 4 ". The ultra-red cells were a precisely matched pair of windows. of zinc sulfide and a precision pathlength of 0.2 mm. These cells are available as Irtran-2 from Barnes Engineering Co., Stamford, Connecticut.

The ultrared spectrum can be seen in Fig. 2a. It shows that 90 % of the carboxyl (COOHJ groups are directly coordinated to chromium, since only 10% of the carboxyl groups remain unreacted. The amount of non-coraplexed carboxyl groups was determined by comparing the intensity of the} C = 0 band (5 , 92 yes) with that of known standard samples. Fig. 2b shows the spectrum of the fumaric acid do C ^ C = O at 5 »92> u). Fig. 2 shows the spectrum of disodium fumarate (^ C = O at 6.5 / u).

0.1 ml of 0.92 normal DNO in DpO were added to 1 ml of the solution prepared as above. The ultrared spectrum of the resulting solution showed no change in the carboxyl region of the spectrum, indicating that in such Solutions have essentially no free carboxylate (COO "") groups available.

The deuterated reagents used in this example were obtained from Alpha Inorganics, Inc. of Beverly, Massachusetts.

Example 3

Another embodiment of the present invention are Masses which are in an alcoholic (with 2 to 4 carbon atoms) or tetrahydrofuran solution complexes of

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Contain chromium nitrate with fumaric acid, the approximate molar ratio of said acid to chromium nitrate preferably in the range of about O, J? : 1 lies. Compounds with much lower acid to chromium ratios are not as useful as adhesion promoters, and those with much higher ratios are subject to gelation during storage. Such compositions are useful as coupling agents for borosilicate glass fibers and polyethylene. It is possible that the non-aqueous complexes contain more homogeneously complexed ("olated") species than the aqueous complexes; however, it has not been proven that such a difference adversely or favorably affects their usefulness. They are most conveniently produced by mixing chromium nitrate nonahydrate with tetrahydrofuran or an alcohol containing 2 to 4 carbon atoms in such proportions that the resulting solution is less than 10%. Contains water, and that organic acids are added to the resulting solution. The reaction takes place spontaneously in the alcoholic medium or in certain other polar, organic media. On the other hand, one can also assume during the production that a concentrated, aqueous solution of CrO _{7 is added} to a solution of nitric acid in an organic medium; the CrO ^ is initially reduced to CrCIII) nitrate by the organic medium.

This example illustrates the preparation of a non-aqueous complex with 0.6 moles of fumarate per mole of chromium.

231 e (0.58 mol) of chromium nitrate nonahydrate were in 2J80 g Isopropyl alcohol dissolved. The solution was heated to 40 ° C and held at this temperature for 30 minutes, at which point sample A, the coordinated complex Chromium nitrate in isopropanol was taken. Then 33j 5 S (0 * 29 mol) of fumaric acid were added and the

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Solution was stirred an additional 10 minutes and heated at 40 ° C. The solution was
sample B was taken.

heated. The solution was cooled to 25 ° C and it

This product contained 1.14% chromium. Samples for spectrum analysis, by diluting 3 ml samples with water on 25 ml showed the following absorption maxima and molar absorbances.

Sample γ ,. On γ ^ Am

γ ,.

A 4200 2?, 7 5750 18.4

B 4100 27.8 5750 30.3

- 22 309827/1 U3

Claims (1)

PC_3674 ~ B «December 21, 1S72 Claim Chromium-containing compound according to patent. ... ... (patent application P 21 16 299 * 2-42), containing one or more water-soluble coordination complexes from (a) chromium (III), which is derived from a water-soluble salt thereof with a non-coordinated anion, where the salt in water _{gives Cr (H 2} 0) g * ⁺ * with (b) a trans acid. the formula E. COOH C = G, , HOOC ^ E ₂ where E ,. and Eg, which are identical or different, denote hydrogen, alkyl radicals, -CH ₂ COOH or phenyl radicals, with the proviso that the total number of carbon atoms in the Iranian acid is an integer in the range from 4 to 10 inclusive, characterized that said mass contains a compound containing cations and anions, in which the genast " ^I " hrom (III) coordination complex represents the cation and the anion is not coordinated and monovalent, and the approximate ratio of chromium (III) to acid ( 'each in the cation complex) to non-coordinated anion is 2/1/4. - 23 309827 / 1U-3