WO1989009758A1 - Formation of complex compounds and polymers between metals and polyhydroxy organic compounds and additions - Google Patents
Formation of complex compounds and polymers between metals and polyhydroxy organic compounds and additions Download PDFInfo
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- WO1989009758A1 WO1989009758A1 PCT/AU1989/000159 AU8900159W WO8909758A1 WO 1989009758 A1 WO1989009758 A1 WO 1989009758A1 AU 8900159 W AU8900159 W AU 8900159W WO 8909758 A1 WO8909758 A1 WO 8909758A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/28—Compounds containing heavy metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/28—Metal alcoholates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
Definitions
- This invention relates to the formation of new orga ⁇ o-metallic compounds in which the metallic cations become bound through oxygen atoms of particular hydroxyl groups of polyhydroxy alcohols or other polyhydric organic compounds through heat initiated reactions and/or by reactions induced or accelerated by microwave irradiation.
- polyhydric alcohols containing less than four hydroxy groups for example ethylene glycol (ethanediol) are used in various plastic (for example polyurethane) and rubber formulations to confer specific advantages or properties such as for example as an extender or plasticiser.
- plastic for example polyurethane
- Such usage of these lower hydroxy alcohols has not been claimed to include formulations and use of polymers or compounds formed between particular metals and such alcohols.
- the present invention therefore specifically embraces the novel formation of polymers or other such compounds by the use of high temperatures or by other techniques as may be known between certain metal compounds and polyhydric alcohols which contain terminal -CH 2 OH group or groups connected to an adjacent -COH group.
- this invention embraces the formation and use of a new family of chemical polymers or compounds formed between a metal compound and such polyhydric alcohols such as, for example, the alcohols mannitol (six-hydroxy), xylitol (five-hydroxy), erythritol (four-hydroxy) and isomers, and other lower hydroxy alcohols such as, for example, ethane diol or 1 ,2 butane diol or 1 ,2,3, butane triol or substituted compounds such as 2-amino-2(hydroxy-methyl)-propane- 1 :3-diol (tris).
- polyhydric alcohols such as, for example, the alcohols mannitol (six-hydroxy), xylitol (five-hydroxy), erythritol (four-hydroxy) and isomers, and other lower hydroxy alcohols such as, for example, ethane diol or 1 ,2 butane diol or 1 ,2,3, butane triol or
- the intention and claim of the invention is extended to cover the formation and use of polyhydric organic compounds not classified as alcohols but which contain a terminal or unrestrained -CH2OH group adjacent and joined to a -COH group such as, for example, various sacharides.
- these new organo-metal compounds may be formed by reactions between suitable metal compounds and sugars such as, for example, xylose, arabinose, ribose (aldopentoses), ribufose, xylulose (ketopentoses), glucose, galactose and mannose (hexoses) and other such sacharides which may possess this preferred configuration of hydroxyl groups.
- this invention embraces and relates to the formation and use of novel orga ⁇ o-metai polymers or compounds by reacting particular polyhydroxy organic compounds with suitable oxygen-containing metal compounds and which reaction comprises the formation of water by a condensation of hydrogen atoms from the reacting hydroxyl groups and the resultant bonding of the metal cations to the carbon chain via the oxygen residues of these hydroxyl groups. Elimination of the water formed in the reaction allows the reaction to proceed.
- this invention embraces the use of such compounds whether as additives to achieve advantages in the formulation of plastics or rubber or other composites or whether for the purpose of providing an intermediate stage to facilitate further reactions such as, for example, to provide a dispersed form of the metal values contained therein for whatever purpose as may constitute an advantage.
- An object of this invention is to provide an improved organic metal polymer or compound which can be used either as stabilisers or as active reagents or as extenders or fillers or carriers of other active additives for obtaining advantages in the production of plastics and rubber compounds or to provide the slow release of selected metal elements in a dispersed form by the controlled breakdown of these compounds for further chemical reaction such as for example as vehicles for imparting colour or other properties to glasses or ceramics.
- a further object is to provide from these reactions with polyhydric compounds, such as for example sugars, such organo-metal polymers or compounds as might exhibit suitable bioavai lability of the contained metal elements for specific use in agricultural or in human or veterinary pharmacological applications.
- polyhydric compounds such as for example sugars, such organo-metal polymers or compounds as might exhibit suitable bioavai lability of the contained metal elements for specific use in agricultural or in human or veterinary pharmacological applications.
- the advantages of the present invention lie in the chemical nature of the polymer or compound in which the metal values contained therein are dispersed in a compound providing many points for attachment or cross linking when used as an additive in the formation of other polymers or composites such as plastic and rubbers.
- the formation of particular alkoxides of glycerol by a technique comprising microwave irradiation of suitable reactants at a frequency of 2.45 G Hertz or other suitable frequency is already claimed in a separate Patent Application (PCT /AU87/00443 by Reginald Morton Taylor)
- this present application claims and includes the novelty of the use of microwave radiation to initiate the formation of these new metal polyhydroxy polymers or compounds.
- the method of formation of these new compounds in no way limits the scope and intention of this invention.
- metal oxygen-containing compounds which may comprise oxides, hydroxides, organo-metal compounds or the oxy-salts of these metals, for example the carbonate, and particular polyhydroxy compounds, such as, for example, 2-amino-2(hydroxy-methyl)- propane-1 :3-diol [NH 2 .C.-(CH 2 (OH) 3 ], ethylene diol, 1 ,2,3, butane diol, or sugars such as for example xylose, or polyhydric alcohols such as, for example, xylitol or mannitol.
- the compound may be formed very readily from a particular metal compound, for example the acetate salt, whereas preparation from the oxide may require higher temperatures, or extended heating or the addition of a catalyst.
- the intention and claim of the invention is not limited to the above mentioned polyhydric organic compounds but extends to other such compounds and alcohols where the steric arrangement of the associated hydroxyl groups permit the metal to be bonded through the oxygen atoms of these hydroxyl groups with the elimination of the hydrogen of these involved hydroxyl groups as water.
- This invention is also considered and meant to embrace the use of any such metal as may be combined or bonded as described with the hydroxyl groups of suitable poly-hydroxy organic compound, such as, for example, cobalt, iron, zinc, calcium, magnesium, bismuth or chromium.
- suitable poly-hydroxy organic compound such as, for example, cobalt, iron, zinc, calcium, magnesium, bismuth or chromium.
- Figure 1 X-ray diffraction traces of a zinc-mannitol compound/polymer formed by reacting zinc acetate with mannitol by microwave irradiation; 1 a in the presence of initial water and 1 b in the presence of ethylene glycol.
- Figure 2 X-ray diffraction traces of a zinc-xylitol compound/polymer formed by a microwave induced reaction between xylitol and zinc acetate (2a) and between xylitol and zinc carbonate (2b).
- Figure 3 X-ray diffraction trace of a zinc-ethylene glycol compound/polymer formed by irradiating a solution of zinc acetate in glycol with microwaves.
- Figure 6 A and B scan electron-micrographs of polymers according to this invention.
- Figure 6 a zinc-ethylene glycol polymer/compound.
- the mannitol can become molten without charring. After excess water, if present, has been expelled and following the subsequent evolution of acetic acid on further heating or microwave irradiation, the molten mannitol reacts with the zinc residues so as to form Zn-O-C bonds with the elimination of water formed by the condensation of some of the hydroxyl groups of the original polyhydroxy compound.
- Sample Manzin -5 About 5 mmoles zinc acetate powdered crystals (approximately 1g) added to 25 mmoles of powdered mannitol (approximately 4.5g) and mixed. Approximately 0.5-1 ml of water added and the mixture put into glass cup and placed in MW oven on High power setting for 2 min 10 sees. (National model NE8070, 650 watts, 2.45GH). A viscous melt reverted to solid white mass after cooling and the excess mannitol was dissolved out in water - there was no acetate smell. Suspension appeared to stream. It was washed in ETOH and dried at 80° C and examined by X-ray diffraction (XRD).
- XRD X-ray diffraction
- the reaction may also proceed with the same result if the zinc acetate and the mannitol are dissolved in, or reacted in the presence of, some solvent other than water such as for example ethylene glycol or propanetriol. These liquids act only to facilitate the reaction but are not involved or considered to take part in the reaction.
- the zinc-glycol complex is also embraced by the claims of this invention and an example is given of its preparation.
- Zinc acetate was dissolved in ethylene glycol and the clear solution was subjected to microwave irradiation for 2 min at 90% power in a 500 watt domestic oven. A thick gelatinous gel was precipitated. After washing and drying the XRD pattern suggested a well crystalline polymer with a platey particle morphology, see Fig. 3.
- the zinc-mannitol compounds (Manzin) produced by the reactions herein described may contain more than one zinc atom per molecule of mannitol.
- the bonded metal atom may be further bonded to other polyhydric molecules through the oxygens of their hydroxyl groups.
- a polyhydroxy compound such as for example 2-amino- 2(hydroxy-methyl)- propane-1 :3-Diol (Tris) [NH2.C.-(CH2(OH)3]
- Fig 4 gives the XRD pattern of an organo-metal compound formed from heating cobalt acetate in molten Tris.
- the complexes produced by these reactions comprising the essence of this invention may possess varying degrees of crystalline development and/or perfection depending on the nature and composition of the particular compound, the techniques employed for its production and specific properties of the metal cation such as, for example, valence, atomic size, co ⁇ ordination number.
- the intention and scope of the invention is not limited by the degree of crystalline development of the final compound which may result from the further polymerisation or further bonding between the metal- alkoxide or metal polyhydroxy compound exemplified in the schematic equations above or in other examples given within this claim.
- Examples of the application of the invention will naturally depend on the various properties of the individual organo-metal compounds produced by these novel reactions.
- the steric configuration of a zinc- ethylene glycol polymer may make it more suitable for inclusion in a polyethylene formulation than say, for example, a zinc-mannitol compound produced according to the method of the invention.
- the dispersion of the metal values contained within such a metal-organic compound produced by the method of the invention may be of importance in one application whereas the species of metal cation so complexed may exert a greater importance in a different application.
- organo-metal-compound may be seen to have a pharmacological application as a bio-available source for a necessary trace metal, regardless of the mode of administration, toxicological studies or the rates of bioavailability, of the metals from compounds formed with different polyhydric compounds may limit or determine possible applications of the organo-metal compounds which are embraced within this invention.
- a metal-polyol compound embraced by this invention into the formulation of a plastic, for example, polyvinyl chloride, to achieve some modification in properties.
- a zinc-ethylene glycol compound as claimed in this invention may be added and mixed with either the plasticiser (which may also be the carrier for the other additives) or the resin before these two are blended or milled and processed at temperatures generally in the range 160-190°C.
- the optimum quantities of the metal-organic added will be determined by the nature of the compound and the modification to the physical and/or chemical properties that are desired, but generally these quantities should be less than 1 %. This is an example only and is not meant to restrict either in amount or nature the metallic cation or the polyhydric organic compound or the nature of the plastic in which the incorporation may be found to offer an advantage.
- a metal-polyhydric compound/polymer embraced by this invention may be added to and mixed with a natural rubber formulation as an activator to increase the rate of cure of organic accelerators used in vulcanising.
- This addition is seen as a replacement of zinc oxide as an additive in such reactions and to achieve other physical properties such as for example a change in heat conductivity. Because of the more disperse nature of the zinc atoms in the compounds of this invention than in fine grained zinc oxide, the advantages achieved by the addition of zinc oxide should be increased when these new zinc-polyhydric compounds are instead added.
- cobalt polyhydric compound say for example propanetriolato-cobalt, or the cobalt tris compound described herein
- propanetriolato-cobalt or the cobalt tris compound described herein
- cobalt compounds embraced by this invention may offer advantages due to the dispersion of the cobalt and the physical and chemical nature of the organo- cobalt compound.
- polyols with four or more hydroxyl groups which have been shown by steric modelling to be potentially capable of forming these new organo-metal compounds when suitably reacted with appropriate metal compounds, are listed:- ribitol, arabinitol, erythritol, xylitol, lysitol, allitol, altritof, sorbitol (glucitol), mannitol, gulitol, galacticol.
- Related compounds or derivatives of these compounds in which a reaction may be induced to bond the metal moiety to the oxygen residues of two adjacent hydoxyl groups also serve to demonstrate the scope of the claims of this invention.
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Abstract
Polymers and compounds formed between metals and polyhydroxy organic compounds formed by reacting an oxygen containing metal compound with a polyhydric organic compound which contains a terminal -CH2OH group or groups connected to an adjacent -COH group and applying heat to cause the formation of water by a condensation of these adjacent reacting hydroxyl groups, and eliminating the water so formed during the reaction to bond the metal to adjacent carbon atoms of the polyhydric organic compound via the residual oxygens of the reacting hydroxyl groups of the polyhydric organic compound.
Description
FORMATION OF COMPLEX COMPOUNDS AND POLYMERS BETWEEN METALS AND POLYHYDROXY ORGANIC COMPOUNDS AND ADDITIONS
This invention relates to the formation of new orgaπo-metallic compounds in which the metallic cations become bound through oxygen atoms of particular hydroxyl groups of polyhydroxy alcohols or other polyhydric organic compounds through heat initiated reactions and/or by reactions induced or accelerated by microwave irradiation.
It has been claimed by Rhone-Poulenc Industries in their Patent
Specification AU-A1 -59,566/80 entitled "Stabilising compositions for vinyl chloride polymers" that their invention provides a heat stabilising composition for polymers based on vinyl chloride containing amongst other components at least one organic derivative of zinc and at least one polyol (polyhydroxy alcohol). The possible range of compositions of the zinc organic compound was well documented and was defined to be derived from the zinc salts of mono-or di-carboxylic aliphatic acids. Moreover Rhone Poulenc Industries have stated in their claim that polyols containing greater than four hydroxyls are preferred as a further additive with the organo-zinc compound. Thus a polyol such as, for example, the six-hydroxy sorbitol, is particularly effective as one of the desired additives in achieving the benefits of their invention.
It is therefore apparent that the above invention does not embrace the formation or use of polymers or compounds which may be formed directly between particular zinc compounds and a polyhydric alcohol. Moreover, it does not embrace the formation and use of such polymers or compounds made with metals other than zinc, for example cobalt or iron, which may also confer some particular and possibly different advantages by their incorporation into various plastic and rubber composite formulations.
Furthermore polyhydric alcohols containing less than four hydroxy groups, for example ethylene glycol (ethanediol), are used in various plastic (for example polyurethane) and rubber formulations to confer specific advantages or properties such as for example as an extender or plasticiser. Such usage of these lower hydroxy alcohols has not been claimed to include formulations and use of polymers or compounds formed between particular metals and such alcohols.
The present invention therefore specifically embraces the novel formation of polymers or other such compounds by the use of high temperatures or by other techniques as may be known between certain metal compounds and polyhydric alcohols which contain terminal -CH2OH group or groups connected to an adjacent -COH group. Therefore this invention embraces the formation and use of a new family of chemical polymers or compounds formed between a metal compound and such polyhydric alcohols such as, for example, the alcohols mannitol (six-hydroxy), xylitol (five-hydroxy), erythritol (four-hydroxy) and isomers, and other lower hydroxy alcohols such as, for example, ethane diol or 1 ,2 butane diol or 1 ,2,3, butane triol or substituted compounds such as 2-amino-2(hydroxy-methyl)-propane- 1 :3-diol (tris).
The intention and claim of the invention is extended to cover the formation and use of polyhydric organic compounds not classified as alcohols but which contain a terminal or unrestrained -CH2OH group adjacent and joined to a -COH group such as, for example, various sacharides. Thus examples of these new organo-metal compounds may be formed by reactions between suitable metal compounds and sugars such as, for example, xylose, arabinose, ribose (aldopentoses), ribufose, xylulose (ketopentoses), glucose, galactose and mannose (hexoses) and other such sacharides which may possess this preferred configuration of hydroxyl groups.
In particular this invention embraces and relates to the formation and use of novel orgaήo-metai polymers or compounds by reacting particular polyhydroxy organic compounds with suitable oxygen-containing metal compounds and which reaction comprises the formation of water by a condensation of hydrogen atoms from the reacting hydroxyl groups and the resultant bonding of the metal cations to the carbon chain via the oxygen residues of these hydroxyl groups. Elimination of the water formed in the reaction allows the reaction to proceed.
Furthermore, this invention embraces the use of such compounds whether as additives to achieve advantages in the formulation of plastics or rubber or other composites or whether for the purpose of providing an intermediate stage to facilitate further reactions such as, for example, to provide a dispersed form of the metal values contained therein for whatever purpose
as may constitute an advantage. An object of this invention is to provide an improved organic metal polymer or compound which can be used either as stabilisers or as active reagents or as extenders or fillers or carriers of other active additives for obtaining advantages in the production of plastics and rubber compounds or to provide the slow release of selected metal elements in a dispersed form by the controlled breakdown of these compounds for further chemical reaction such as for example as vehicles for imparting colour or other properties to glasses or ceramics.
A further object is to provide from these reactions with polyhydric compounds, such as for example sugars, such organo-metal polymers or compounds as might exhibit suitable bioavai lability of the contained metal elements for specific use in agricultural or in human or veterinary pharmacological applications.
Previous patents describe and embrace the use of the zinc alkoxide of the trihydric alcohol glycerol, zinc glycerolate (CgHgOgZn), as a pharmaceutical compound and method (AU 554 151 ; British Patent 2 101 132 and USA Patent 4 544 761 by Reginald Morton Taylor and Alan James Brock) and as a crystalline modifier of plastics and rubber Patent Application 62872/86; British Patent 2 191 202 and USA Patent 4 789 701 by Reginald Morton Taylor).
Whereas in the above named Patents the large plate-like hexagonal morphology of the very well-crystalline zinc glycerolate was claimed as an advantage of the invention and was described in the first report of this compound (Crystalline cobalt, zinc, manganese and iron alkoxides of glycerol by Radoslovich, Raupach, Slade and Taylor in the Australian J. Chemistry vol 23 1970 p1963), the present invention generally relates to less crystalline metal-polyhydroxy compounds. These novel compounds generally have a non specific particle or crystalline morphology. Therefore it may be claimed that the advantages of the present invention lie in the chemical nature of the polymer or compound in which the metal values contained therein are dispersed in a compound providing many points for attachment or cross linking when used as an additive in the formation of other polymers or composites such as plastic and rubbers.
Whereas the formation of particular alkoxides of glycerol by a technique comprising microwave irradiation of suitable reactants at a frequency of 2.45 G Hertz or other suitable frequency is already claimed in a separate Patent Application (PCT /AU87/00443 by Reginald Morton Taylor), this present application claims and includes the novelty of the use of microwave radiation to initiate the formation of these new metal polyhydroxy polymers or compounds. However the method of formation of these new compounds in no way limits the scope and intention of this invention.
The formation of the members of this new family of chemical compounds may therefore be contrived by any of the several methods disclosed herein from the suitable reactions between certain metal oxygen-containing compounds which may comprise oxides, hydroxides, organo-metal compounds or the oxy-salts of these metals, for example the carbonate, and particular polyhydroxy compounds, such as, for example, 2-amino-2(hydroxy-methyl)- propane-1 :3-diol [NH2.C.-(CH2(OH)3], ethylene diol, 1 ,2,3, butane diol, or sugars such as for example xylose, or polyhydric alcohols such as, for example, xylitol or mannitol. In some cases the compound may be formed very readily from a particular metal compound, for example the acetate salt, whereas preparation from the oxide may require higher temperatures, or extended heating or the addition of a catalyst.
The intention and claim of the invention is not limited to the above mentioned polyhydric organic compounds but extends to other such compounds and alcohols where the steric arrangement of the associated hydroxyl groups permit the metal to be bonded through the oxygen atoms of these hydroxyl groups with the elimination of the hydrogen of these involved hydroxyl groups as water.
This invention is also considered and meant to embrace the use of any such metal as may be combined or bonded as described with the hydroxyl groups of suitable poly-hydroxy organic compound, such as, for example, cobalt, iron, zinc, calcium, magnesium, bismuth or chromium. These elements are given only as an example and in no way limit the scope of the invention, nor is any limitation implied by the valencies or atomic radii of the elements listed.
These reactions occur between the polyhydroxy compounds and metal oxides or hydroxides or metal compounds which may be converted to the oxide or hydroxide using such processes as for example decomposition or transformation achieved by heating or some other suitable technique as may be known.
Moreover the partial substitution of one element for another where such substitution may be considered to offer some advantage does not limit the claims of this invention and the formation and use of such substituted metal- polyhydroxy is thus embraced and included within these claims.
The following are given as examples of the reactions involved in the formation of these new metal-organic polymers or compounds.
The illustrations which form part of this specification are to be read with the examples, Figs, one to five showing x-ray diffraction traces of the polymers or compounds referred to and Fig. 6 showing the particle morphology of two of these new compounds as seen by scanning electron microscopy.
In the illustrations;
Figure 1 X-ray diffraction traces of a zinc-mannitol compound/polymer formed by reacting zinc acetate with mannitol by microwave irradiation; 1 a in the presence of initial water and 1 b in the presence of ethylene glycol.
Figure 2 X-ray diffraction traces of a zinc-xylitol compound/polymer formed by a microwave induced reaction between xylitol and zinc acetate (2a) and between xylitol and zinc carbonate (2b).
Figure 3 X-ray diffraction trace of a zinc-ethylene glycol compound/polymer formed by irradiating a solution of zinc acetate in glycol with microwaves.
Figure 4 X-ray diffraction trace of a cobalt-Tris compound/polymer formed by heating cobalt acetate with molten (2-amino-
2(hydroxy-methyl)-propane-1 :3-diol).
Figure 5 X-ray diffraction trace of zinc-erythritol metal organic compound/polymer formed from slowly heating zinc acetate with erythritol and a little water.
(In the above graphs measurements given against peaks are the d-spacings in Angstom units.)
Figure 6 A and B scan electron-micrographs of polymers according to this invention.
Figure 6a zinc-ethylene glycol polymer/compound.
Figure 6b zinc-xylitol polymer/compound.
Zinc mannitol compound (Manzin..
If zinc acetate is mixed with excess mannitol in an aqueous solution and heated or subjected to controlled microwave irradiation, or if these two compounds are mixed as powders and merely moistened by water, or other suitable liquid, the mannitol can become molten without charring. After excess water, if present, has been expelled and following the subsequent evolution of acetic acid on further heating or microwave irradiation, the molten mannitol reacts with the zinc residues so as to form Zn-O-C bonds with the elimination of water formed by the condensation of some of the hydroxyl groups of the original polyhydroxy compound. On cooling the melt solidifies, and after washing with water to remove excess mannitol a white crystalline metal-organic compound is left as a residue. This product can be characterised by its x-ray diffraction pattern. On heating the compound chars, and burns to give a white zinc oxide.
Example 1.
Sample Manzin -5. About 5 mmoles zinc acetate powdered crystals (approximately 1g) added to 25 mmoles of powdered mannitol (approximately 4.5g) and mixed. Approximately 0.5-1 ml of water added and the mixture put into glass cup and placed in MW oven on High power setting for 2 min 10 sees. (National model NE8070, 650 watts, 2.45GH). A viscous melt reverted to solid white mass after cooling and the excess mannitol was dissolved out in water - there was no acetate smell. Suspension appeared to stream. It was washed in ETOH and dried at 80° C and examined by X-ray
diffraction (XRD). Very weak ZπO diffraction lines in the XRD recording indicated trace amounts of unreacted zinc oxide formed from the decomposition of the zinc acetate. Essentially the same diffraction lines were obtained (see Fig. 1 a) as in previous experiments. .
The reaction may also proceed with the same result if the zinc acetate and the mannitol are dissolved in, or reacted in the presence of, some solvent other than water such as for example ethylene glycol or propanetriol. These liquids act only to facilitate the reaction but are not involved or considered to take part in the reaction.
Example 2.
Sample B1R32. 16 g of zinc acetate (=75 mmole) and 9.1 g mannitol (=50 mmole) were added separately to 10 ml volumes of ethylene glycol. The zinc acetate was dissolved by gentle heating and the mannitol became molten in the glycol also with gentle heating on a hot plate. The solution of the acetate was added to mannitol melt and given 4 minutes at half power in a 500 watt microwave oven. The solution was still clear after two minutes but after four minutes there was a heavy white viscous precipitate. After washing in water and ethanol and drying, the resultant powder gave an XRD pattern similar to that given by sample Manzin 5 (see Fig. 1 b). The small variations in the high XRD spacings between Although ethylene glycol was used as an initial liquid medium to initiate the reaction the XRD pattern was quite distinct from the pattern presented by a zinc-ethylene glycol high temperature compound.
The zinc-glycol complex is also embraced by the claims of this invention and an example is given of its preparation. Zinc acetate was dissolved in ethylene glycol and the clear solution was subjected to microwave irradiation for 2 min at 90% power in a 500 watt domestic oven. A thick gelatinous gel was precipitated. After washing and drying the XRD pattern suggested a well crystalline polymer with a platey particle morphology, see Fig. 3.
Example 3. Sample Zxylin 003 . BIR36)
6.08 g xylitol (=40 mmoles) with 1 ml water was irradiated for 1 min at 80% power in a 500 watt 2.45GH domestic microwave oven The xylitol became molten and was irradiated for a further 1 min at 50% power. Then 5 mmole
zinc acetate added and stirred and given a further 3 min at 50% power with intermittent stirring. When the melt cooled it was washed in water to remove excess xylitol and was further washed in ethanol and dried and examined by X-ray diffraction, see Fig. 2a.
Example 4.
Sample Zxylin.001 (B1R44.
Two part of zinc carbonate (400 mmoles) added slowly to 1 part (200 mmoles) xylitol melted under microwave irradiation after the addition of a small amount of water. The melt was stirred after each addition and given further irradiation until the effervescence initiated with each addition ceased. The final melt after cooling was crushed, washed in water and then dried from ethanol. The resultant well crystalline zinc-organic powder was then , examined by X-Ray diffraction and found to be isostructural with the sample made from the acetate, but was more crystalline, see Fig. 2b.
Where higher zinc/xylitol molar ratios are used, the zinc in the form of acetate gives a structural variation, giving a higher XRD spacing for the first line (a shift from = 8.9A to =13.3A) and a product that becomes very gelatinous and difficult to filter. Heating as opposed to microwave irradiation caused more zinc oxide to be formed as a residual impurity apparently unable to react further with the molten xylitol under the conditions used.
The form of the reactions may be exemplified by the following schematic representations:-
H - C - OH H - C - OH I
OH - C Z -- HH l_OH - C - H
L _ heat 0H _ ci _ H +Wate i +Zn Acetate ■> -
H - C - OH / ave etc. H - C - OH
I
H - C - OH H ~ f °^Zr_
H - C - OH H - C - O-
The above representation of a reaction between zinc contained in the compound zinc acetate and the polyhydric alcohol mannitol does not limit the invention to a reaction involving only the two hydroxyl groups at which the complexation of the zinc is shown to have occurred because it is known
from steric considerations that a similar reaction can be expected to occur between the first and second hydroxyl group ( shown by the dotted connection) and this knowledge is embraced within the claims of this invention. Neither is the above representation seen or meant to limit the reaction to alcohols containing six hydroxyl groups nor is it seen to or meant to infer that the reaction is limited to polyhydric alcohols with the above steric disposition of the hydroxyl groups as an isomer of this alcohol for example sorbitol, is also known from these claims to form a similar organo-metal compound when reacted with suitable metallic compounds.
Thus the zinc-mannitol compounds (Manzin) produced by the reactions herein described may contain more than one zinc atom per molecule of mannitol. Conversely with large excesses of mannitol or other such polyhydric alcohol as may be used the bonded metal atom may be further bonded to other polyhydric molecules through the oxygens of their hydroxyl groups.
As an example of the reaction between oxy-compounds of other elements, the freshly precipitated red-brown Fe(lll) hydroxide (ferrihydrite) when added to molten mannitol under microwave irradiation reacted to form a green iron- organic compound indicating that some reduction must have occurred and the iron was present in the di- and tri-valent state. On heating this compound ferromagnetic maghemite Gamma (Fβ Og) was formed. The XRD pattern was distinctly different to that obtained from the zinc-mannitol reaction.
Suspensions or solutions of cobalt acetate when heated with sorbitol or with a polyhydroxy compound such as for example 2-amino- 2(hydroxy-methyl)- propane-1 :3-Diol (Tris) [NH2.C.-(CH2(OH)3], form compounds further exemplifying this invention. This is exemplified in Fig 4 which gives the XRD pattern of an organo-metal compound formed from heating cobalt acetate in molten Tris.
As a further example 0.3g zinc acetate was added to 1 g erythritol in about 1 ml water. The suspension was slowly heated. The clear solution so formed began fuming and a white precipitate formed. The material was washed and dried from acetone. This zinc-organic compound gave an XRD -pattern similar in some respects to. those of the other compounds exemplified, see Fig. 5.
Further schematic examples are given but they are not meant in any way to limit the types of metal compounds or polyhydric organic compounds that may react in the manner exemplified.
- _ ' Zn o * o o _C* . /
O
**— c . *— s_ c*. o ***** o _— g r= - + ZnCOs > COz + HzO + — — -o- - ϋ- — ϋ — o . !__. - - o— -o - — o -__:
Zinc-xylicol comple
XYLITOL
The complexes produced by these reactions comprising the essence of this invention may possess varying degrees of crystalline development and/or perfection depending on the nature and composition of the particular compound, the techniques employed for its production and specific properties of the metal cation such as, for example, valence, atomic size, co¬ ordination number.
Therefore the intention and scope of the invention is not limited by the degree of crystalline development of the final compound which may result from the further polymerisation or further bonding between the metal- alkoxide or metal polyhydroxy compound exemplified in the schematic equations above or in other examples given within this claim.
Examples of the application of the invention will naturally depend on the various properties of the individual organo-metal compounds produced by these novel reactions. For example, the steric configuration of a zinc- ethylene glycol polymer may make it more suitable for inclusion in a polyethylene formulation than say, for example, a zinc-mannitol compound produced according to the method of the invention. Moreover, the dispersion of the metal values contained within such a metal-organic compound produced by the method of the invention may be of importance in one application whereas the species of metal cation so complexed may exert a greater importance in a different application.
Where the organo-metal-compound may be seen to have a pharmacological application as a bio-available source for a necessary trace metal, regardless of the mode of administration, toxicological studies or the rates of bioavailability, of the metals from compounds formed with different polyhydric
compounds may limit or determine possible applications of the organo-metal compounds which are embraced within this invention.
An example of the application of this invention would be the incorporation of the a metal-polyol compound embraced by this invention into the formulation of a plastic, for example, polyvinyl chloride, to achieve some modification in properties. Thus, for example, a zinc-ethylene glycol compound as claimed in this invention may be added and mixed with either the plasticiser (which may also be the carrier for the other additives) or the resin before these two are blended or milled and processed at temperatures generally in the range 160-190°C. The optimum quantities of the metal-organic added will be determined by the nature of the compound and the modification to the physical and/or chemical properties that are desired, but generally these quantities should be less than 1 %. This is an example only and is not meant to restrict either in amount or nature the metallic cation or the polyhydric organic compound or the nature of the plastic in which the incorporation may be found to offer an advantage.
As a further example of the application, a metal-polyhydric compound/polymer embraced by this invention, say, for example, the zinc- xylitol compound, may be added to and mixed with a natural rubber formulation as an activator to increase the rate of cure of organic accelerators used in vulcanising. This addition is seen as a replacement of zinc oxide as an additive in such reactions and to achieve other physical properties such as for example a change in heat conductivity. Because of the more disperse nature of the zinc atoms in the compounds of this invention than in fine grained zinc oxide, the advantages achieved by the addition of zinc oxide should be increased when these new zinc-polyhydric compounds are instead added.
As a further example of a possible benefit in rubber formulation, the addition of a cobalt polyhydric compound, say for example propanetriolato-cobalt, or the cobalt tris compound described herein, may be added in place of, and at a similar rate to, other cobalt compounds used as additives to increase the metal-rubber bond in metal-reinforced tyres. Again the nature of the cobalt compounds embraced by this invention may offer advantages due to the dispersion of the cobalt and the physical and chemical nature of the organo- cobalt compound.
As an indication only of the scope of this invention examples of polyols with four or more hydroxyl groups, which have been shown by steric modelling to be potentially capable of forming these new organo-metal compounds when suitably reacted with appropriate metal compounds, are listed:- ribitol, arabinitol, erythritol, xylitol, lysitol, allitol, altritof, sorbitol (glucitol), mannitol, gulitol, galacticol. Related compounds or derivatives of these compounds in which a reaction may be induced to bond the metal moiety to the oxygen residues of two adjacent hydoxyl groups also serve to demonstrate the scope of the claims of this invention.
Claims
1. Polymers and compounds formed between metals and polyhydroxy organic compounds (and additives) characterised in that the polymers and compounds are formed by reacting a suitable oxygen containing metal
5 compound with a polyhydric organic compound which contains a terminal - CH2OH group or groups connected to an adjacent -COH group and applying heat to cause the formation of water by a condensation of these adjacent reacting hydroxyl groups, and eliminating the water so formed during the reaction to bond the metal to adjacent carbon atoms of the polyhydric 0 organic compound via the residual oxygens of the reacting hydroxyl groups of the said polyhydric organic compound.
2. The polymers and compounds of Claim 1 wherein the bonding of the metal to the oxygens of adjacent hydroxyl groups and the formation and 5 elimination of water from these reacting hydroxyl groups is contrived through irradiation of the reactants with microwave energy.
3. The polymers and compounds of Claim 1 wherein the said oxygen containing metal compound is reacted with a polyhydric organic compound 0 which is a polyol, with two or more hydroxyl groups.
4. The polymers and compounds of Claim 1 wherein the polymers and compounds are used as additives in plastics and rubber.
5 5. A compound such as zinc-xylitol formulates according to Claim 4 as part of a rubber formation used as an activator to increase the rate of cure of the organic accelerators used in vulcanising.
6. A compound or polymer according to Claim 4 but containing cobalt as 0 part of a rubber formulation used to increase the metal-rubber bond in metal- reinforced tyres.
7. The polymers and compounds of Claim 1 wherein the polymers and compounds are additives in glass and ceramics. D
8. The polymers or compounds of Claim 1 such as formed between a metal and a sacharide which are used in animal or human pharmacological
applications as bio-available source for a necessary or deficient trace element.
9. The polymers and compounds of Claim 1 wherein the polymers and compounds are additives to other metals.
10. The polymers or compounds of Claim 1 wherein the oxygen- containing metal compounds may be taken from the group including metal oxides, metal hydroxides, oxy-salts of the metals or organo-metallic compounds and other such metal compounds which may be readily converted to the oxide by decomposition or transformation.
11. The polymers and compounds of Claim 10 where one metal is partially substituted by another.
12. The polymers and compounds of Claim 1 wherein the polyhydric organic compound is an alcohol.
13. The polymers and compounds of Claim wherein the polyhydric organic compound is a sacharide taken from the group including xylose, arabinose, ribose (aldopentoses) ribuiose, xylulose, (ketopentoses), glucose, galactose, and mannose (hexoses).
14. The polymers and compounds of Claim 1 wherein, the oxygen containing metal compound is mixed with a meltable polyhydric compound and moistened by a liquid and heated or subjected to microwave irradiation whereby to melt the polyhydric compound without charring, and the said heating or microwave irradiation causes bonding between the metal of the said oxygen - containing metal compounds and the said polyhydric organic compound with the elimination of water by condensation of the hydroxyl groups of the original polyhydroxy compound.
15. The polymers and compounds of Claim 3 wherein the said moistening liquid is water.
16- The polymers and compounds of Claim 13 wherein the oxygen- containing metal compound is in powdered crystalline form and the polyhydric organic compound is also in powdered form, and wherein the
said powders are moistened and mixed together and then heated or subjected to microwave irradiation to form a melt, and wherein the melt is reacted and washed to produce a crystalline metal-organo polymer or compound.
17. The polymers and compounds of Claim 13 wherein the said oxygen containing metal and the said polyhydric compound are separately processed to form blendable intergers and are then blended together and subjected to heat or microwave irradiation and then washed to remove impurities to produce a crystalline metal-organo polymer or compound.
18. The method of forming, polymers and compounds from metals and polyhydroxy organic compounds and additives characterised in that polymers and compounds are formed by reacting a mixture of an oxygeπ- containing metal compound and a polyhydric organic compound which contains a terminal -CH2OH group or groups connected to an adjacent -COH group, and applying heat to cause the formation and elimination of water by a condensation of hydrogen atoms from the reacting hydroyxl group and the elimination of water so formed during the reaction to bond the metal action to the carbon chain of the polyhydric organic compound via the oxygen moiety of the said polyhydric organic compound.
19. The method of Claim 18 wherein microwave energy radiation replaces heat in causing the formation.
20. The method of Claim 18 wherein the oxygen containing metals are taken from the group including metal oxides hydroxides, organic-metal compounds, the oxy-salts of the metals, and metal compounds which may be converted to the oxide or hydroxide using decomposition or transformation, and are mixed with the said polyhydric organic compound such as a polyhydric alcohol and heated to form the polymer or compound by reaction as defined in Claim 18.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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AUPI776788 | 1988-04-15 | ||
AUPI7767 | 1988-04-15 | ||
AUPJ039988 | 1988-09-13 | ||
AUPJ0399 | 1988-09-13 |
Publications (1)
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WO1989009758A1 true WO1989009758A1 (en) | 1989-10-19 |
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PCT/AU1989/000159 WO1989009758A1 (en) | 1988-04-15 | 1989-04-13 | Formation of complex compounds and polymers between metals and polyhydroxy organic compounds and additions |
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WO1997008121A1 (en) * | 1995-08-29 | 1997-03-06 | Ferro Corporation | Zinc containing chemical product and method of making same |
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