US3669999A - Storage stability of tetrakis nickel compounds - Google Patents
Storage stability of tetrakis nickel compounds Download PDFInfo
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- US3669999A US3669999A US95325A US3669999DA US3669999A US 3669999 A US3669999 A US 3669999A US 95325 A US95325 A US 95325A US 3669999D A US3669999D A US 3669999DA US 3669999 A US3669999 A US 3669999A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
Definitions
- This invention relates to a method for improving the storage stability of tetrakis nickel compounds. More particularly this invention relates to a method for improving storage stability of tetrakis (triorganophosphite) nickel compounds.
- an organonickel compound can be reacted with a triorganophosphorous compound to yield a tetrakis (triorganophosphite) nickel compound, which can be precipitated and recovered as a solid product, useful as a polymerization catalyst. It has been found that upon storage, the tetrakis nickel compounds tend to decompose badly after periods of more than a few days, even when stored under a blanket of nitrogen.
- a nickel compound in the preparation of a tetrakis (triorganophosphorous) nickel compound, such as described and claimed in US. Pat. Nos 3,152,158 and 3,328,443, a nickel compound can be reacted with a triorganophosphorous compound, and the reaction product comprising complexed zerovalent nickel can be precipitated by pouring the mixture into an inert non-solvent. The precipitated product can be recovered by filtration and is useful as a catalyst.
- US. Pat. No. 3,243,468 describes and claims the use of such tetrakis nickel compounds in the polymerization of various monomers, such as butadiene.
- the tetrakis (triorganophosphite) nickel compounds prepared as described above have been found to be quite sta ble in a completely pure state. It has further been found that when contaminated with relatively small amounts of residual triorganophosphite compounds, the tetrakis nickel compounds tend to be quite unstable during storage, starting to decompose almost immediately, for example within an hour, even when stored under a blanket of nitrogen.
- One way of obviating or overcoming this problem is to work up and purify the tetrakis nickel compounds to a point that there is no remaining residual triorganophosphite material left as a contaminant.
- the improved storage stability can be obtained by storing tetrakis (triorganophosphate) nickel, which is contaminated with triorganophosphite, under a protective blanket consisting essentially of an inert non-solvent for said tetrakis (triorganophosphite) nickel.
- nonsolvent refers to compounds which will dissolve less than about 1 percent by weight of the tetrakis (triorganophosphorous) nickel compound while the term solvent" is meant to include compounds in which more than about 1 percent by weight of the tetrakis nickel compounds are soluble.
- Characteristics of the non-solvents which are useful in the scope of this invention are that they be appreciably miscible with triorganophosphorous contaminant but that the tetrakis nickel product be insoluble therein. Another characteristic of the non-solvent is that it be easily and substantially completely removable from the stored product. Thus, generally, a nonsolvent having a low viscosity is more desirable than one having a high viscosity. Volatility is another factor to be considered in choosing a non-solvent. Since the tetrakis nickel product is generally stored at ambient temperature, the nonsolvent vapor pressure is desirably not excessive at these temperatures. Broadly, the boiling point of the non-solvent can range from about 20 C. to about 300 C.
- the non-solvent will of course be inert with respect to both the reactants and the products and be inert to the surrounding atmosphere. Since this atmosphere is usually air, the non-solvent is desirably not readily oxidized under ambient conditions when the storage container is opened, as for example for the periodic removal of portions of the tetrakis nickel compounds.
- the alcohols are a preferred class of non-solvents.
- the alcohols can be primary, secondary or tertiary, and can be monohydric or polyhydric.
- Preferred alcohols are alkanols having up to about 14 carbon atoms and include for example methanol, ethanol, propanol-l, 2-methylpropanol-l, butanol-l, pentanol-l, 2-ethyl-butanol-l cyclohexanol, octanol-l, dodecanol-l, ethylene glycol and triethylene glycol.
- Liquid alkanols are especially preferred. Mixtures of these alcohols can also be used. Insofar as the liquid alkanols are commercially available and inexpensive, they are especially preferred.
- alkanes are another preferred class of non-solvents.
- the preferred saturated aliphatic hydrocarbons are those which are liquid at ambient temperature. Thus, generally, those saturated aliphatic hydrocarbons having from about five to about 14 carbon atoms are preferred with the c to c, hydrocarbons, such as hexane or heptane, being particularly preferred.
- the saturated aliphatic hydrocarbons can be used either alone or in combination with other saturated aliphatic hydrocarbons and can be either straight or branched chain.
- hydrocarbons other than the saturated aliphatic hydrocarbons, oxygenated hydrocarbons other than the alcohols and alcohol ethers, halogenated hydrocarbons, heterocyclic compounds, aromatic hydrocarbons, etc. can be classified as solvents for the tetrakis nickel compound and are not useful under the conditions set forth herein. These latter compounds can be used as recrystallization solvents, if recrystallization is needed or desired for the crude tetrakis nickel compound. Solvents are not desirable agents for contacting the tetrakis nickel compounds in storage insofar as it has been found that a solution of the tetrakis nickel compound, when exposed to even traces of air or oxygen, decomposes rapidly in a very short time.
- the process of this invention is useful regardless of the structure of the triorganophosphite contaminant or the triorganophosphite ligand in the nickel complex.
- examples of wellknown and useful phosphite contaminants and ligands include tri(2-ethyl-hexyl) phosphite, tri(p-methyoxyphenyl) phosphite, triphenylphosphite, trioctylphosphite, triethylphosphite and tn'( methoxymethyl) phosphite.
- One method of precipitating the tetrakis nickel compound from the reaction mixture and thereafter storing it is to use one non-solvent as a precipitant and another non-solvent as the atmosphere to store the filtered product.
- the preferred practice is to use the same non-solvent for both functions. This, of course, avoids the inconvenience and cost of multiple steps.
- the isolation can be carried out in any convenient manner, such as by filtration using known and accepted methods and equipment.
- the isolated product, in the form of a filter cake can be washed with a fresh portion of the non-solvent.
- the quantity of non-solvent used as an atmosphere to protect the isolated tetrakis nickel compounds is broadly that amount needed to effectively shield the product from an oxidizing atmosphere. Since the catalyst product is substantially insoluble in the non-solvent, a large excess of non-solvent can be used. There is, however, no significant benefit to be derived from the use of a large excess and, in fact, it is preferred to use that amount of non-solvent which just covers the surface of the product.
- Triphenylphosphite Can be Seen from the above that aflfi! eleven y Of p (94.6 lbs., 0.305 mole) was added, with mild agitation. The storage there has been substantial and significant decomposi temperature of the mixture was 8 C. Triethyl aluminum ⁇ ion- (18.75 lbs., 0.165 mole) in 75 lbs. dry benzene was added, EXAMPLE m with mild agltation, over a period of about one hour.
- a precipitate of tetrakis (triphenylphosgram of the ten-abs (mphelwiphosphte) mckel' m phite) nickel was formed
- the product was separated by a Examplelabove, together wrth 0.1 ml. triphenylphosphite and centrifuge filter, and the alcohol-wet filter cake was removed 2 of the test l mdcated
- the i sample from the centrifuge The cake was Smmed with additional bottles were opened twice a week, and the following visual obmethanol, and the mixture was filtered.
- Bottle 1 contained 0.5 ml. water; bottle 2 cony 'p p White l tained 0.5 ml. water plus I ml. triphenylphosphite; bottle 3 fgg ftg contained 1 ml. triphenylphosphite; bottle 4 contained 20 ml. cycloiexanol white w methanol; and bottle 5 contained 20 ml. methanol plus 1 ml. Ethylene glycol White White triphenylphosphite. The capped bottles were opened three Lnahylene glym as?
Abstract
The storage stability of tetrakis nickel compounds, such as tetrakis (triorganophosphite) nickel compounds, can be increased by storing said compounds under a protective blanket selected from alcohols and aliphatic hydrocarbons.
Description
United States Patent Levine [4 1 June 13, 1972 [54] STORAGE STABILITY OF TETRAKIS 3,414,629 12/1968 McCall et al. ..260/666 NICKEL COMPOUNDS FOREIGN PATENTS OR APPLICATIONS 72 I t: RalhLei F hld,N.J. nven or p v ne, f 0 716,072 8/1965 Cana [73] Assignee: Cities Service Company, New York, NY.
R Tl N [22] Filed: Dec. 4, 1970 OTHE PUBLICA O s V al.l 3 1964 .1062-1063 pp No: 95,325 mal et norgamc Chemistry )p Primary Examiner-Tobias E. Levow [52] us. Cl. ..260/439 R, 252/431 P AssislantExaminerA- D me [5 I Int. Cl. ..C07f 75/04 y-J Richard Geaman [58] Field of Search ..260/439 R; 252/431 P ABSTRACT [56] References Cited The storage stability of tetrakis nickel compounds, such as UNITED STATES PATENTS tetrakis (triorganophosphite) nickel compounds, can be increased by storing said compounds under a protective blanket 3,152,158 10/ 1964 Clark ..260/439 R l d f l hol and aliphatic hydrocarbons. 3,243,468 3/1966 Clark et a1. ..260/666 3,328,443 6/1967 Clark et al ..260/439 R 6Claims, No Drawings STORAGE STABILITY OF TETRAKIS NICKEL COMPOUNDS BACKGROUND OF THE INVENTION This invention relates to a method for improving the storage stability of tetrakis nickel compounds. More particularly this invention relates to a method for improving storage stability of tetrakis (triorganophosphite) nickel compounds.
It is known that an organonickel compound can be reacted with a triorganophosphorous compound to yield a tetrakis (triorganophosphite) nickel compound, which can be precipitated and recovered as a solid product, useful as a polymerization catalyst. It has been found that upon storage, the tetrakis nickel compounds tend to decompose badly after periods of more than a few days, even when stored under a blanket of nitrogen.
SUMMARY OF THE INVENTION It has now been found that solid tetrakis (triorganophosphite) nickel compounds, contaminated with residual triorganophosphite compounds, can be stored for extended periods of time when stored in a protective atmosphere selected from alcohols and aliphatic hydrocarbons.
In the preparation of a tetrakis (triorganophosphorous) nickel compound, such as described and claimed in US. Pat. Nos 3,152,158 and 3,328,443, a nickel compound can be reacted with a triorganophosphorous compound, and the reaction product comprising complexed zerovalent nickel can be precipitated by pouring the mixture into an inert non-solvent. The precipitated product can be recovered by filtration and is useful as a catalyst. US. Pat. No. 3,243,468 describes and claims the use of such tetrakis nickel compounds in the polymerization of various monomers, such as butadiene.
The tetrakis (triorganophosphite) nickel compounds prepared as described above have been found to be quite sta ble in a completely pure state. It has further been found that when contaminated with relatively small amounts of residual triorganophosphite compounds, the tetrakis nickel compounds tend to be quite unstable during storage, starting to decompose almost immediately, for example within an hour, even when stored under a blanket of nitrogen. One way of obviating or overcoming this problem is to work up and purify the tetrakis nickel compounds to a point that there is no remaining residual triorganophosphite material left as a contaminant. Unfortunately however, this procedure is time consuming and expensive and yields no real benefit since the presence of small amounts of triorganophosphite material does not effect the utility of the tetrakis (triorganophosphite) nickel compounds as polymerization catalysts. As an alternative to the scrupulous scrubbing of the tetrakis nickel compounds to remove all trace of triorganophosphorous contaminants, it has been found that storage stability of the solid tetrakis (triorganophosphorous) nickel compounds can be improved by storing the material in accordance with this inventron.
Broadly, the improved storage stability can be obtained by storing tetrakis (triorganophosphate) nickel, which is contaminated with triorganophosphite, under a protective blanket consisting essentially of an inert non-solvent for said tetrakis (triorganophosphite) nickel. As used herein, the term nonsolvent" refers to compounds which will dissolve less than about 1 percent by weight of the tetrakis (triorganophosphorous) nickel compound while the term solvent" is meant to include compounds in which more than about 1 percent by weight of the tetrakis nickel compounds are soluble. Characteristics of the non-solvents which are useful in the scope of this invention are that they be appreciably miscible with triorganophosphorous contaminant but that the tetrakis nickel product be insoluble therein. Another characteristic of the non-solvent is that it be easily and substantially completely removable from the stored product. Thus, generally, a nonsolvent having a low viscosity is more desirable than one having a high viscosity. Volatility is another factor to be considered in choosing a non-solvent. Since the tetrakis nickel product is generally stored at ambient temperature, the nonsolvent vapor pressure is desirably not excessive at these temperatures. Broadly, the boiling point of the non-solvent can range from about 20 C. to about 300 C. with a preferred range of from about 50 to about 200 C. The non-solvent will of course be inert with respect to both the reactants and the products and be inert to the surrounding atmosphere. Since this atmosphere is usually air, the non-solvent is desirably not readily oxidized under ambient conditions when the storage container is opened, as for example for the periodic removal of portions of the tetrakis nickel compounds.
As indicated above, the alcohols are a preferred class of non-solvents. The alcohols can be primary, secondary or tertiary, and can be monohydric or polyhydric. Preferred alcohols are alkanols having up to about 14 carbon atoms and include for example methanol, ethanol, propanol-l, 2-methylpropanol-l, butanol-l, pentanol-l, 2-ethyl-butanol-l cyclohexanol, octanol-l, dodecanol-l, ethylene glycol and triethylene glycol. Liquid alkanols are especially preferred. Mixtures of these alcohols can also be used. Insofar as the liquid alkanols are commercially available and inexpensive, they are especially preferred.
In addition to the alcohols, it has been found that alkanes are another preferred class of non-solvents. The preferred saturated aliphatic hydrocarbons are those which are liquid at ambient temperature. Thus, generally, those saturated aliphatic hydrocarbons having from about five to about 14 carbon atoms are preferred with the c to c, hydrocarbons, such as hexane or heptane, being particularly preferred. The saturated aliphatic hydrocarbons can be used either alone or in combination with other saturated aliphatic hydrocarbons and can be either straight or branched chain.
As a general proposition, hydrocarbons other than the saturated aliphatic hydrocarbons, oxygenated hydrocarbons other than the alcohols and alcohol ethers, halogenated hydrocarbons, heterocyclic compounds, aromatic hydrocarbons, etc., can be classified as solvents for the tetrakis nickel compound and are not useful under the conditions set forth herein. These latter compounds can be used as recrystallization solvents, if recrystallization is needed or desired for the crude tetrakis nickel compound. Solvents are not desirable agents for contacting the tetrakis nickel compounds in storage insofar as it has been found that a solution of the tetrakis nickel compound, when exposed to even traces of air or oxygen, decomposes rapidly in a very short time.
The process of this invention is useful regardless of the structure of the triorganophosphite contaminant or the triorganophosphite ligand in the nickel complex. Examples of wellknown and useful phosphite contaminants and ligands include tri(2-ethyl-hexyl) phosphite, tri(p-methyoxyphenyl) phosphite, triphenylphosphite, trioctylphosphite, triethylphosphite and tn'( methoxymethyl) phosphite.
One method of precipitating the tetrakis nickel compound from the reaction mixture and thereafter storing it, is to use one non-solvent as a precipitant and another non-solvent as the atmosphere to store the filtered product. The preferred practice, however is to use the same non-solvent for both functions. This, of course, avoids the inconvenience and cost of multiple steps. When the tetrakis nickel compound is isolated from its reaction mixture, as by precipitation using an inert non-solvent, the isolation can be carried out in any convenient manner, such as by filtration using known and accepted methods and equipment. The isolated product, in the form of a filter cake, can be washed with a fresh portion of the non-solvent. While not essential, this is a desirable inter mediate step insofar as it is useful to remove at least part of the triorganophosphite contaminant from the precipitated tetrakis nickel compound. Additional filtration can, of course, be used to remove the wash liquid.
The quantity of non-solvent used as an atmosphere to protect the isolated tetrakis nickel compounds is broadly that amount needed to effectively shield the product from an oxidizing atmosphere. Since the catalyst product is substantially insoluble in the non-solvent, a large excess of non-solvent can be used. There is, however, no significant benefit to be derived from the use of a large excess and, in fact, it is preferred to use that amount of non-solvent which just covers the surface of the product.
It has been found that moisture frequently can be a contributing factor to the decomposition of the catalyst and it is therefore desirable to maintain a low level of moisture in the stored product and its immediate atmosphere. This can be conveniently accomplished by using a product prepared under conditions minimizing contact with atmospheric moisture,
I methanol, washing several times with methanol and drying at recrystallized by dissolving in benzene, precipitating in such by using an anhydrous non-solvent and by storing the BLE 2 tetrakls nickel compound together with the non-solvent in a substantially airtight container Days of Open Storage N1 *Concentration %Deeompos1t1on DESCRIPTION OF THE PREFERRED EMBODIMENTS 3 5 33 ppm L2 5 1042 ppm 2.3 EXAMPLE I 7 1567 ppm 3.5 2o 11 17,100 ppm 1.71% 38 Tetrakls (triphenylphosphite) nickel was prepared according to the following method: nickel acetylacetonate dihydrate (21.76 lbs., 0.0745 mole) was dissolved in benzene (161.25 The percent decomposition was calculated on the basis that lbs.), and the solution was azeotropically distilled to remove the tetrakis nickel catalyst contained 4.51 percent nickel. lt water. The resultant solution was used. Triphenylphosphite Can be Seen from the above that aflfi! eleven y Of p (94.6 lbs., 0.305 mole) was added, with mild agitation. The storage there has been substantial and significant decomposi temperature of the mixture was 8 C. Triethyl aluminum {ion- (18.75 lbs., 0.165 mole) in 75 lbs. dry benzene was added, EXAMPLE m with mild agltation, over a period of about one hour. During this addition period, the reaction temperature was allowed to A vaflety of llqmd Organic compounds was tested for p rise to 1 1 Then, over a period f 30 minutes the reactor tective activity toward the tetrakls n1ckel compound by the temperature was raised to 40 C. The reactor contents were followmg Procedure: poured, over a period of 30 minutes, into a tank containing In a 1 glass b fitted i h a screw cap, was placedl 401 lbs. of methanol. A precipitate of tetrakis (triphenylphosgram of the ten-abs (mphelwiphosphte) mckel' m phite) nickel was formed The product was separated by a Examplelabove, together wrth 0.1 ml. triphenylphosphite and centrifuge filter, and the alcohol-wet filter cake was removed 2 of the test l mdcated The i sample from the centrifuge The cake was Smmed with additional bottles were opened twice a week, and the following visual obmethanol, and the mixture was filtered. The washed and fil- Servanons were made assummanzedm Table 3 below tered product was then air-dried and stored in a polyethylene 40 TABLE 2 \mdm' a dry nitrogen atmosphere- The P was a Test Liquid Observed sample Observed sample white powder. The product obtained above was determined to color after 2 wks. color after be substantially free of triphenylphosphite. The following 5 evaluations were performed: tetrakis nickel catalyst prepared above (10 grams) was placed in clean 4 oz. flint glass bottle, 212 equipped with a screw cap, and was treated with various addi- 222 whit: Wme tives. All test spec1mens were per1od1cally opened to the atlq white White mosphere. Bottle 1 contained 0.5 ml. water; bottle 2 cony 'p p White l tained 0.5 ml. water plus I ml. triphenylphosphite; bottle 3 fgg ftg contained 1 ml. triphenylphosphite; bottle 4 contained 20 ml. cycloiexanol white w methanol; and bottle 5 contained 20 ml. methanol plus 1 ml. Ethylene glycol White White triphenylphosphite. The capped bottles were opened three Lnahylene glym as? times a week to assure an adequate exposure to air and oxsfi f Ligplnecimy Light Grey ygen. V1sual exammations were made at the end of two weeks acetate white Grey and at the end of four weeks. The results are shown in Table l. Acetone p @9 TABLE 1 Description of bottle contents Bottle Additive At start After 2 weeks After 4 Weeks 1 Water White solid White. solid White solid.
Water plus trlphenylphosphite do Greenlsh paste. Yellow-green paste. Triplienylphosphite d0 Light green solid Yellow-green solid. yetnanolnnflnnl. no.1. .fi. .H down Whitlo solid, with faint supernatant liquid. White solid, with faint supernatant liquid. 5 let ano plus ti'ipienyp osp itm. .(o (0 Do.
i iteeiiheseen rrtinitiiebiei tiits that tier. was essentially gy 'e yt A Light Green Green no difference between the results obtained with methanol and gii zg igg'g 2:3 gl i methanol plus triphenylphosphite. Water, on the other hand, in tetrachloride orange Orange connection with triphenylphosphite, yielded very poor results. Dimethyl sulfoxide White Light Green Dimethyl formamide Light Green Light Green Dark EXAMPLE ll Pyridine Brown Brown Liquid Aniline Grey-Green Dark Green Benzene Green-Brown Green-Brown A portlon of the product prepared in Example I was 5 lyscycloocladiene Brown Brown Pam vent is selected from alcohols and saturated aliphatic hxdwsar q sr. V V w 7 3. A method according to claim 1 in which the alcohols are primary and have a chain length of from one to about 14 carbon atoms.
4. A method according to claim 1 in which the aliphatic hydrocarbons have a chain length of from about five to about 14 carbon atoms.
5. A method according to claim 1 in which the alcohol is methanol.
6. A method according to claim 1 in which the aliphatic hydrocarbon is hexane.
II I I! l l
Claims (5)
- 2. A method according to claim 1 in which the inert non-solvent is selected from alcohols and saturated aliphatic hydrocarbons.
- 3. A method according to claim 1 in which the alcohols are primary and have a chain length of from one to about 14 carbon atoms.
- 4. A method according to claim 1 in which the aliphatic hydrocarbons have a chain length of from about five to about 14 carbon atoms.
- 5. A method according to claim 1 in which the alcohol is methanol.
- 6. A method according to claim 1 in which the aliphatic hydrocarbon is hexane.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US9532570A | 1970-12-04 | 1970-12-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3669999A true US3669999A (en) | 1972-06-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US95325A Expired - Lifetime US3669999A (en) | 1970-12-04 | 1970-12-04 | Storage stability of tetrakis nickel compounds |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4387056A (en) * | 1981-04-16 | 1983-06-07 | E. I. Du Pont De Nemours And Company | Process for separating zero-valent nickel species from divalent nickel species |
| US4557809A (en) * | 1985-04-12 | 1985-12-10 | Borg-Warner Chemicals, Inc. | Electrochemical synthesis of zerovalent transition metal organophosphorus complexes |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3152158A (en) * | 1961-01-23 | 1964-10-06 | Cities Service Res & Dev Co | Method of preparing tetrakis (triorganophosphite) nickel compounds |
| CA716072A (en) * | 1965-08-17 | F. Clark Reginald | Method of preparing tetrakis(triorganophosphite) nickel complexes | |
| US3243468A (en) * | 1962-06-14 | 1966-03-29 | Columbian Carbon | Method of preparing cycloolefins |
| US3328443A (en) * | 1960-12-05 | 1967-06-27 | Columbian Carbon | New tetrakis(organophosphorus) nickel, tetrakis(organoarsenic) nickel, and tetrakis(organoantimony) nickel complexes and methods of preparing the same |
| US3414629A (en) * | 1965-05-13 | 1968-12-03 | Eastman Kodak Co | Cyclooligomerization |
-
1970
- 1970-12-04 US US95325A patent/US3669999A/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA716072A (en) * | 1965-08-17 | F. Clark Reginald | Method of preparing tetrakis(triorganophosphite) nickel complexes | |
| US3328443A (en) * | 1960-12-05 | 1967-06-27 | Columbian Carbon | New tetrakis(organophosphorus) nickel, tetrakis(organoarsenic) nickel, and tetrakis(organoantimony) nickel complexes and methods of preparing the same |
| US3152158A (en) * | 1961-01-23 | 1964-10-06 | Cities Service Res & Dev Co | Method of preparing tetrakis (triorganophosphite) nickel compounds |
| US3243468A (en) * | 1962-06-14 | 1966-03-29 | Columbian Carbon | Method of preparing cycloolefins |
| US3414629A (en) * | 1965-05-13 | 1968-12-03 | Eastman Kodak Co | Cyclooligomerization |
Non-Patent Citations (1)
| Title |
|---|
| Vinal et al. Inorganic Chemistry 3 (1964) p. 1062 1063 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4387056A (en) * | 1981-04-16 | 1983-06-07 | E. I. Du Pont De Nemours And Company | Process for separating zero-valent nickel species from divalent nickel species |
| US4557809A (en) * | 1985-04-12 | 1985-12-10 | Borg-Warner Chemicals, Inc. | Electrochemical synthesis of zerovalent transition metal organophosphorus complexes |
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