GB2032428A – Bimetallic soaps and processes therefor
– Google Patents
GB2032428A – Bimetallic soaps and processes therefor
– Google Patents
Bimetallic soaps and processes therefor
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Publication number
GB2032428A
GB2032428A
GB7931543A
GB7931543A
GB2032428A
GB 2032428 A
GB2032428 A
GB 2032428A
GB 7931543 A
GB7931543 A
GB 7931543A
GB 7931543 A
GB7931543 A
GB 7931543A
GB 2032428 A
GB2032428 A
GB 2032428A
Authority
GB
United Kingdom
Prior art keywords
zinc
calcium
soap
metal
fatty acid
Prior art date
1978-10-20
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
GB7931543A
Other versions
GB2032428B
(en
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dart Industries Inc
Original Assignee
Dart Industries Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
1978-10-20
Filing date
1979-09-11
Publication date
1980-05-08
1979-09-11
Application filed by Dart Industries Inc
filed
Critical
Dart Industries Inc
1980-05-08
Publication of GB2032428A
publication
Critical
patent/GB2032428A/en
1983-01-12
Application granted
granted
Critical
1983-01-12
Publication of GB2032428B
publication
Critical
patent/GB2032428B/en
Status
Expired
legal-status
Critical
Current
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Espacenet
Global Dossier
Discuss
Classifications
C—CHEMISTRY; METALLURGY
C07—ORGANIC CHEMISTRY
C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
C07C53/126—Acids containing more than four carbon atoms
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
C08K5/04—Oxygen-containing compounds
C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
C08K5/098—Metal salts of carboxylic acids
Abstract
Uniformly coformed soaps of calcium and zinc at zinc/calcium atomic ratios of 2/3 to 3/1 are provided having unexpectedly low melting points and outstanding lubricant and anti-stick properties. A method of preparing same is disclosed based upon the simultaneous reaction of calcium and zinc in intimate association, following intensive dispersion in a liquid mass, with available fatty acid groups, the liquid mass being maintained at a suitable reaction temperature so as to form a finely divided pulverulent mixed metal soap of the uniform composition desired.
Description
SPECIFICATION Bimetallic soaps and processes therefor
This invention relates to uniquely alloyed mixed metal soaps of calcium and zinc having
outstanding lubricant qualities, particularly for polymeric resins and plastics, and which melt sharply at
surprisingly low temperatures.
Several metallic soaps of substantially saturated fatty acids such as stearic acid, notably calcium stearate and zinc stearate, have achieved commercial status as lubricants and/or anti-tack agents (abherents) in the plastics and metal working fields. However, to date mixed metal soaps have not
received any special acclaim for such functions or exhibited any unexpected advantages therewith.
Instead, the use of combined metal lubricants has evidently provided only expected levels of
performance pretty much in direct proportion to the amounts of the individual components and their
relative contributions when used separately.
It is a major objective of this invention to provide pulverulent metallic soaps, e.g. stearates, with
superior lubricant and adherent properties. A related object is to provide mixed metal soaps of
exceptional uniformity, homogeneity and suitability for lubricant type uses.
A more specific goal of this invention is to provide mixed metal soaps of calcium and zinc in such
intimate association that they are completely homogeneous even in their finest particulate state of
subdivision. Another specific object is to provide such soaps which are easy to handle, free flowing
powders at normal temperatures and yet melt quickly and uniformly under heat processing operations,
such as the milling and thermo-forming of polymeric resins and similar plastic substances. Still other
objectives and advantages will be obvious from the detailed description of our invention which follows.
In accordance with the present invention such highly desirable lubricant soaps can be obtained by
intensively mixing together a liquid mass containing fatty acid anionic groups and a metal bearing
material the metal content of which consists essentially of zinc and calcium in an anionic ratio of
zinc/calcium of between 2/3 and 3/1, the consistency and uniformity of said metal bearing material
being such that it is readily dispersed by said intensive mixing at a substantially constant Zn/Ca ratio tnroughout said liquid mass and maintaining the temperature of the resultant mixture at a level
sufficient to effect simultaneous reaction of both zinc and calcium with said fatty acid groups but not substantially above 1 000C, thereby effecting simultaneous formation of zinc and calcium soaps with
coprecipitate from the reaction mixture in intimate association as fine solid particulates of substantially
uniform metallic ratio.
The first reactant, namely the liquid mass containing fatty acid anionic groups can be either of two
general types as follows:
1) Molten fatty acids per se or fatty acids liquified with the aid of hot, chemically inert miscible
diluents or solvents such as paraffinic oils like kerosene; and
2) Aqueous solutions of water soluble soaps, usually of alkali metals like sodium and potassium,
but including ammonium soaps or certain organic amine soaps, e.g. those formed by triethanol
amine.
Said second type of liquid mass, i.e. an aqueous solution of water soluble soap, is preferred because of the handling convenience of same as well as the simplicity of providing a suitably
homogeneous, easily dispersible metal bearing coreactant. Thus, aqueous solutions of water soluble
salts of calcium and zinc can be readily prepared of almost any desirable metals content and with very
uniform and precise control of the atomic ratio of zinc/calcium therein. On the other hand, when the fatty acid reactant is supplied as the first type of liquid mass, i.e. in the free acid form, the coreactant
metal bearing material will generally be derived from either the free metals or their oxides or hydroxides.
Special attention is then required to provide such materials in a sufficiently fine state of subdivision to
render same readily dispersible in said liquid mass while simultaneously insuring a correct, uniform ratio
of calcium and zinc throughout said subdivided material.
We have found that the reaction between the free fatty acid type medium and the appropriate
metal bearing coreactant materials therefore can best be carried out at temperatures between about 80 and 1 00C and preferably at temperatures between about 90 and 1 050C. However, when the reaction
is between aqueous soap solution and an aqueous solution of metal salts, somewhat lower reaction temperatures are generally in order with the range of primary interest being from about 500C to about
1 000C and most preferably from about 60 to 900 C.
The coformed calcium and zinc soaps of this invention having zinc/calcium atomic ratios of between 2/3 and 3/1 are exceptionally effective as lubricating and processing aids for plastics or metal working, molding and like operations. This performance appears to be attributable to the intimate
association of zinc and calcium soaps therein, somewhat analogous to the amalgamation of metals in
alloys, as shown by the sharp and surprisingly low melting points possessed by the present soaps. Thus,
although the melting point of calcium stearate is about 1 550C, the melting points of coformed zinc
calcium stearates prepared in accordance with this invention at zinc/calcium atomic ratios of between
2/3 and 3/1 are actually significantly below even the 1 220C melting point of zinc stearate itself.The eutectic among these mixed zinc-calcium stearates appears to occur at a Zn/Ca atomic ratio of about
3/2, exhibiting a melting point of only 1 080C as well as peak abherent properties. In fact, with soap forming fatty acids of greatest interest, i.e. those formed from substantially saturated fatty acids containing from about 12 to 24 carbon atoms, the optimum proportions of Zn/Ca in the coformed soaps of this invention appears to lie between atomic ratios of about 1/1 and about 2/1.
Further details of our invention are illustrated by the specific examples and embodiments which follow.
EXAMPLE 1
Into a jacketed stainless steel reactor equipped with a variabie speed stirrer, eight liters of a dilute aqueous solution of sodium stearate (0.125 molar) is charged and heated to about 800C while stirring slowly. The stirrer speed is then increased and 325 milliliters of a uniform aqueous solution containing 74 grams CaCI2 and 127 g ZnCI2 per liter is added to the sodium stearate solution while mixing rapidly and maintaining the temperature of the mixture at about 800C during addition of said solution of metal chlorides and for an additional 30 minutes thereafter. The resulting fine white powdery precipitate is collected in a filter, washed several times with warm water and dried to constant weight in shallow trays in a forced air oven operated at a temperature of 75 to 850C.About 300 grams of fluffy white product are obtained having a uniform sharp melting point of 1 080C + 10 and possessing the following analytical properties:
Moisture content 0.5% by wt.
Total ash content 11.8% » » Zinc content 6.5%
Calcium content 2.7% » » Atomic Ratio (Zn/Ca) 1.48
EXAMPLES 2-7
A series of runs was made using the equipment described in Example 1 and substantially the same reaction conditions except that the proportions of CaCI2 and ZnCI2 in the uniform aqueous solution added to the sodium stearate solution was varied from run to run. In each run a fine, fluffy, white powdered soap was obtained, the melting points of which varied from run to run as shown in the following table:
ZnC12 CaGI2 Zn/Ca Example Conc. Conc. Atomic Melting Pt.
No. g./l. g./l. Ratio of Product 2 66 124 0.43 120″C 3 87 107 0.67 115″C 4 109 89 1.0 113″C 5 153 53 2.3 113″C 6 164 44 3.0 116″C 7 175 36 4.0 119″C It will be seen from the above results that simultaneously formed and coprecipitated zinc-calcium stearates in which the Zn/Ca ratio is between about 2/3 and 3/1 have surprisingly low melting points, i.e. significantly lower than the melting point of pure zinc stearate even though the melting point of pure calcium stearate is far higher.
Obviously, many substitutions and variations are possible in the above examples within the general guidelines and operating limits already specified for the present invention. For example, potassium stearate or any other sufficiently soluble stearate can be used as the fatty acid group source and other water soluble salts of zinc and calcium, such as the nitrates, can be used informing the uniform aqueous coreactant solution with substantially the same results provided that the zinc and calcium are simultaneously reacted to form particulate bimetallic stearates having uniform atomic metal ratios within the ranges specified.
EXAMPLE 8
The coprecipitated bimetallic stearate produced in Example 1 was tested as an internal lubricant and anti-stick additive in heat curable poiyester resin in direct comparison with pure zinc stearate and pure calcium stearate. The testing was carried out with thermosetting syrups prepared from an unsaturated polyester resin sold under the Trade Name of «Hatco Polyester Resin GR 13037» using the following basic formulation recipe in parts by weight:
Resin syrup 100 pts.
Para-t-butyl perbenzoate 0.6 pts.
Metal stearate powder «X» pts.
The concentration («X») of each of the metal stearate additives in the above recipe was varied from 1 part to 3 parts by weight and casts of the well-mixed syrups were cured on shiny aluminum foils for 5 minutes at 1 630C. The cured films containing the coprecipitated zinc-calcium stearate of Example
1 at concentrations of 2 parts and above released readily from the foil whereas about 3 parts by weight of the pure metal stearates was required for successful parting of the cured sample from the metal support. Furthermore, the parted surfaces of the resin films containing the coprecipitated stearates were noticeabiy smoother and glossier than those containing the pure metal stearate additives.
Because of the intimate state of association of the calcium and zinc species in the coformed bimetallic soaps of this invention and the resulting ease of melting and fusion thereof, these products should prove compatible with a wide variety of resins and serve as versatile processing aids and viscosity control agents as well as adherent additives in many environments.
Claims (12)
1 A coformed mixed metal soap of calcium and zinc with substantially saturated fatty acids of 1 2 to 24 carbon atoms wherein the zinc/calcium atomic ratio is between 2:3 and 3:1 and which melts at temperaturess substantially lower than the pure zinc soap of the corresponding fatty acid(s).
2. A soap according to Claim 1 wherein stearic acid is the prevailing fatty acid.
3. A soap according to Claim 1 or 2 wherein the atomic ratio of zinc/calcium is between 1:1 and 2:1.
4. A soap according to Claim 3 wherein the atomic ratio of zinc/calcium is close to 1.5:1.0.
5. A soap according to Claim 1 substantially as described in any one of Examples 1 and 3 to 6.
6. A process for preparing an intimately coformed, insoluble, mixed metal soap of calcium and zinc which comprises intensively mixing together ( 1 ) a liquid mass containing fatty acid groups and (2) a metal bearing material the metal content of which consists essentially of zinc and calcium in an atomic, ratio of between 2:3 and 3::11 the consistency and uniformity of said metal bearing material being such that it is readily dispersed by said intensive mixing at a substantially constant Zn/Ca ratio throughout said liquid mass and maintaining the temperature of the resultant mixture at a level sufficient to effect simultaneous reaction of both zinc and calcium with fatty acid groups but not substantially above 1 000C, thereby effecting simultaneous formation of zinc and calcium soaps which coprecipitate from the reaction mixture in intimate association as fine solid particles of substantially uniform composition.
7. A process according to Claim 5 wherein said liquid mass comprises free fatty acids of 12 to 24 carbon atoms and said metal bearing material consists essentially of finely divided solid particles containing uniform proportions of zinc and calcium.
8. A process according to Claim 7 wherein said particles are of metallic oxides, metal hydroxides or free metals.
9. A process according to Claim 6, 7 or 8 wherein said liquid mass comprises an aqueous solution of soap formed from substantially saturated fatty acids of 1 2 to 24 carbon atoms, said metal bearing material comprises an aqueous solution of calcium and zinc salts, and said simultaneous reaction is carried out at a temperature of at least 50 C.
1 0. A process according to any one of Claims 6 to 9 wherein stearic acid is the prevailing fatty acid and said simultaneous reaction is carried out at a temperature of between 60 and 900 C.
11. A process according to any one of Claims 6 to 10 wherein the atomic ratio of zinc/calcium is between 1:1 and 2:1.
12. A process according to Claim 6 substantially as described in any one of Examples 1 and 3 to 6.
1 3. The use of a coformed mixed metal soap as ciaimed in any one of Claims 1 to 7 as a lubricant and/or anti-tack agent for plastics or metal working.
GB7931543A
1978-10-20
1979-09-11
Bimetallic soaps and processes therefor
Expired
GB2032428B
(en)
Applications Claiming Priority (1)
Application Number
Priority Date
Filing Date
Title
US95329578A
1978-10-20
1978-10-20
Publications (2)
Publication Number
Publication Date
GB2032428A
true
GB2032428A
(en)
1980-05-08
GB2032428B
GB2032428B
(en)
1983-01-12
Family
ID=25493792
Family Applications (1)
Application Number
Title
Priority Date
Filing Date
GB7931543A
Expired
GB2032428B
(en)
1978-10-20
1979-09-11
Bimetallic soaps and processes therefor
Country Status (9)
Country
Link
JP
(1)
JPS5598299A
(en)
BE
(1)
BE878713A
(en)
CA
(1)
CA1148976A
(en)
DE
(1)
DE2942237A1
(en)
ES
(1)
ES484437A1
(en)
FR
(1)
FR2439231A1
(en)
GB
(1)
GB2032428B
(en)
IT
(1)
IT1207272B
(en)
NL
(1)
NL7907647A
(en)
Cited By (4)
* Cited by examiner, † Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
EP0046073A2
(en)
*
1980-08-08
1982-02-17
E.I. Du Pont De Nemours And Company
Spandex filament and spandex yarn comprising it
EP0150393A1
(en)
*
1983-12-30
1985-08-07
BASF Aktiengesellschaft
Magnetic recording media
EP0330097A2
(en)
*
1988-02-26
1989-08-30
NEYNABER CHEMIE GmbH
Process for the preparation of a pulverulent basic metallic soap
EP2860371B1
(en)
*
2012-06-08
2019-10-30
Toyota Jidosha Kabushiki Kaisha
Liquid coolant composition for internal combustion engines and operating method for internal combustion engines
Families Citing this family (1)
* Cited by examiner, † Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
DE4305944A1
(en)
*
1993-02-26
1994-09-01
Henkel Kgaa
Basic calcium / zinc mixed soaps
Family Cites Families (5)
* Cited by examiner, † Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
NL132018C
(en)
*
1965-06-14
DE1300105C2
(en)
*
1966-03-29
1982-01-28
Akzo Chemie GmbH, 5160 Düren
METHOD FOR PRODUCING NEUTRAL METAL SOAP MIXTURES
JPS565500B2
(en)
*
1971-09-03
1981-02-05
JPS5289612A
(en)
*
1976-01-22
1977-07-27
Iwao Hishida
Granular composite of metallic soap
DE2823002B2
(en)
*
1978-05-26
1981-06-04
Chemische Werke München Otto Bärlocher GmbH, 8000 München
Process for the production of metal soap granules
1979
1979-09-11
GB
GB7931543A
patent/GB2032428B/en
not_active
Expired
1979-09-11
BE
BE0/197092A
patent/BE878713A/en
not_active
IP Right Cessation
1979-09-25
ES
ES484437A
patent/ES484437A1/en
not_active
Expired
1979-10-04
CA
CA000337052A
patent/CA1148976A/en
not_active
Expired
1979-10-10
FR
FR7925262A
patent/FR2439231A1/en
active
Granted
1979-10-16
NL
NL7907647A
patent/NL7907647A/en
not_active
Application Discontinuation
1979-10-18
DE
DE19792942237
patent/DE2942237A1/en
active
Granted
1979-10-18
JP
JP13366579A
patent/JPS5598299A/en
active
Pending
1979-10-19
IT
IT2666479A
patent/IT1207272B/en
active
Cited By (7)
* Cited by examiner, † Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
EP0046073A2
(en)
*
1980-08-08
1982-02-17
E.I. Du Pont De Nemours And Company
Spandex filament and spandex yarn comprising it
EP0046073A3
(en)
*
1980-08-08
1982-03-10
E.I. Du Pont De Nemours And Company
Spandex filament and spandex yarn comprising it
EP0150393A1
(en)
*
1983-12-30
1985-08-07
BASF Aktiengesellschaft
Magnetic recording media
US4647513A
(en)
*
1983-12-30
1987-03-03
Basf Aktiengesellschaft
Magnetic recording media
EP0330097A2
(en)
*
1988-02-26
1989-08-30
NEYNABER CHEMIE GmbH
Process for the preparation of a pulverulent basic metallic soap
EP0330097A3
(en)
*
1988-02-26
1991-06-05
NEYNABER CHEMIE GmbH
Process for the preparation of a pulverulent basic metallic soap
EP2860371B1
(en)
*
2012-06-08
2019-10-30
Toyota Jidosha Kabushiki Kaisha
Liquid coolant composition for internal combustion engines and operating method for internal combustion engines
Also Published As
Publication number
Publication date
FR2439231A1
(en)
1980-05-16
DE2942237C2
(en)
1987-06-25
BE878713A
(en)
1979-12-31
NL7907647A
(en)
1980-04-22
CA1148976A
(en)
1983-06-28
ES484437A1
(en)
1980-05-16
DE2942237A1
(en)
1980-04-24
JPS5598299A
(en)
1980-07-26
IT1207272B
(en)
1989-05-17
GB2032428B
(en)
1983-01-12
FR2439231B1
(en)
1983-06-24
IT7926664D0
(en)
1979-10-19
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Legal Events
Date
Code
Title
Description
1985-10-30
732
Registration of transactions, instruments or events in the register (sect. 32/1977)
1988-05-05
PCNP
Patent ceased through non-payment of renewal fee
