WO2004094351A2

WO2004094351A2 - Novel high metal content intermediates

Info

Publication number: WO2004094351A2
Application number: PCT/US2004/012514
Authority: WO
Inventors: Joseph W. Burley; Rajesh Khattar
Original assignee: Akzo Nobel NV
Current assignee: Akzo Nobel NV
Priority date: 2003-04-23
Filing date: 2004-04-23
Publication date: 2004-11-04
Anticipated expiration: 2005-10-23
Also published as: WO2004094351A3

Abstract

Novel high metal content intermediate compositions, which are useful as driers for paints and as components for the formulation of PVC stabilizers, can be prepared by the reaction of a substantially stoichiometric mixture of: a phenol and an alcohol; a carboxylic acid and an alcohol; or a mixture of a phenol, a carboxylic acid, and an alcohol with a metal oxide or hydroxide.

Description

NOVEL HIGH METAL CONTENT INTERMEDIATES

Solutions of metal organic salts find use in a range of commercial applications, not limited to, but typified by, driers for paints and as components for the formulation of PVC stabilizers . Other end use applications are as thickeners (also termed "gelling agents") in petroleum- containing compositions (such as greases and oils) and in PVC plastisols, as acid scavengers in lubricating oils, and to form surface coatings of the type conventionally formed from metal alkoxides . These compositions are based on metal carboxylates and, in some cases, on alkyl phenolates . They can be either: neutral, containing a stoichiometric quantity of acid; acid-deficient, as in the case of basic zinc octoate or basic aluminum tallate; or carbonated, as in the case of carbonated calcium carboxylates , carbonated barium alkyl phenates , carboxylates and mixed alkylphenate/carboxylates . Typically, neutral salts exhibit a higher viscosity than carbonated intermediates. For example, barium nonylphenate is used at a barium content of about 12%-13%. At metal levels higher than this, the neutral salt is very viscous. Carbonated barium intermediates typically contain 24-34% barium and are of low viscosity.

What are deemed to be new intermediates in accordance with the present invention can be prepared by the reaction of a substantially stoichiometric mixture of either: a phenol and an alcohol ; a carboxylic acid and an alcohol ; or a mixture of a phenol , a carboxylic acid and an alcohol, each with a metal oxide or hydroxide. The products of any of these reactions are of the general formula: M(OC₆H₄R)_a(θ2CR')_b([OR"j_cOR"')₂-_(a+b) where M is a Group II metal selected from Ba, Sr, Cd, Ca, Mg or where M is a monoalkyltin moiety (R^IVSn) _2/3 or a dialkyltin moiety (R^IV ₂Sn) ; R is either H or a saturated or unsaturated alkyl or alkoxy group of up to about 18 carbon atoms, R' is a saturated or unsaturated alkyl group of up to about 18 carbon atoms or an aromatic group which is either unsubstituted or substituted with one or more alkyl or alkoxy groups , each of up to about 18 carbon atoms , R" is an alk lene group of up to about 4 carbon atoms, R"' is either a saturated or unsaturated alkyl group of up to about 18 carbon atoms or an alkyl or alkoxy-substituted or unsubstituted aromatic group, R^IV is an alkyl group of up to about 12 carbon atoms; either a or b can separately be 0, a+b is in the range of from about 0.1 to about 1.9, and c is in the range of 1 to about 10. When the reagent alcohol is a diol the above-described products are represented by the formula:

M(OC₆H₄R)_a(0₂CR')_b([OR"]_dO)₁-,-_+b)/₂, where M, R, R' , R", R^IV, a, and b are defined as above; and d is in the range of from 1 to about 10. Furthermore, it has also been observed that, in contrast to the prior art systems described above, the instant intermediates can be prepared where the total molar equivalence of the "acids" (including phenols) and alcohols is less than that of the metal . Based on the extent of water recovery from their preparative reactions , these products may contain un-reacted hydroxyl or oxide groups and are described as basic" metal organic salts .

With this new approach, for example, non-carbonated barium-containing materials with metal levels as high as 32% have been achieved and with metal levels up to about 27% have been achieved with low viscosity. The advantages of this technology are: lower cost/% barium; good epoxidized oil (e.g., epoxidized soybean oil) compatibility, which is not exhibited by carbonated high metal intermediates; and greater versatility in product formulation based on neutral intermediates since higher barium levels in these products can now be achieved. Additionally, this technology allows the formulation of lower volatility products based on neutral intermediates. The intermediates described above are suited for use in the formulation of liquid mixed-metal stabilizers for PVC but they are prone to hydrolysis . What is further an aspect to the present invention is that this susceptibility can be overcome by combination of these intermediates with an organophosphite to generate metal organic/phosphite intermediates . These materials are equally useful for the preparation of liquid mixed-metal stabilizers for PVC and are inherently more hydrolytically stable.

In one exemplary embodiment of this technology, a stoichiometric amount of barium hydroxide monohydrate can be reacted with an equimolar mixture of nonylphenol and 2- (2-methoxyethoxy) thanol in mineral spirits to give a low viscosity, homogeneous and stable solution containing 21% barium.

In a further exemplary embodiment of this invention, a 25.3% barium-containing intermediate can be combined with triphenyl phosphite to give a product containing 13.1% barium and 4.8% phosphorus.

Within the scope of this invention, the reagent phenols are typified by, but not limited to: phenol, para- nonylphenol , para-octylphenol , para-dodecylphenol , para- cresol, para-t-butylphenol, and para- ethoxyphenol . Also within the scope of this invention, the reagent acids are typified by, but not limited to: acetic acid, propionic acid, n-valeric acid, 2-methylpentanoic acid, 2- ethylbutyric acid, di-n-propylaσetic acid, n-heptanoic acid, isomeric butyric acids, n-octanoic acid, 2- ethylhexanoic acid, isononanoic, isooctanoic acid, versatic acid, tall oil acid, oleic acid, benzoic acid, para-t- butylbenzoic acid, isomeric toluic acids, adipic acid, succinic acid, benzene-1 ,2-dicarboxylic acid, and naphthenic acid. Where dibasic acids are employed, the acid radical in the above formulas is redefined as (0₂CR^vC0₂) __>/2 where R^v is a saturated or unsaturated alkylene group of 2 to about 10 carbon atoms or a benzene radical (CgH) . Reagent alcohols are typified by, but not limited to: 2- (2-methoxyethoxy) ethanol, 2 - (2-ethoxyethoxy)ethanol, 2- (2-butoxyethoxy) ethanol , 1- (2-methoxyisopropoxy) -2- propanol, nonylphenol ethoxylated with six moles of ethylene oxide, lauryl alcohol ethoxylated with three moles of ethylene oxide, and tripropylene glycol .

O ganophosphite esters suitable for combination with the metal organic products of this invention are typified by, but not limited to: triphenyl phosphite, diphenyl isodecyl phosphite, di-isodecyl phenyl phosphite, trideσyl phosphite, diphenyl phosphite, phenyl 2-ethylhexyl phosphite, diphenyl iso-octyl phosphite, tris nonylphenyl phosphite, tetraphenyl dipropyleneglycol diphosphite, dipropylene glycol phenyl phosphite.

Substantially different technology, in regard to this embodiment, is described in U.S. Patent Nos . 3,519,584 and 3,551,530. These patents describe the reaction of barium hydroxide monohydrate with either an alkyl phenol or with a mixture of an alkyl phenol and a carboxylic acid. These reactions are performed in the presence of a mixture of ether alcohols . Reference is made in these patents to the fact that deliberate dehydration of the reaction mixture is not required and that some benefit may actually be obtained from incomplete dehydration. In the present invention substantially complete dehydration of the reaction mixture is desirable. In our hands, heterogeneous products were formed at both stages of the example described in U.S. Patent No. 3,551,530. The above U.S. patents specify only a substantially equimolar ratio of barium to the alkyl phenol or to the mixture of alkyl phenol and carboxylic acid. In the present invention, this ratio can be as large as 1:0.1. The current invention also relates to the reaction of a stoichiometric total quantity, or less, of acid and alcohol with barium hydroxide. The above U.S. patents describe the use of a significant excess of acids and alcohols .

The compositions of this invention have been demonstrated to be useful as constituents for PVC stabilizers. For example, it is possible to use the product of Example 2 (hereinbelow) to replace the neutral barium 12% intermediate that is currently used in commercially significant general purpose products, with no loss of performance and, in some cases, improved performance. These general purpose products may, or may not, contain epoxidized soybean oil as a constituent.

In one further example of the use of this technology: the product of Example 2 (hereinbelow) can be used to replace the 28% barium-containing, carbonated barium constituent of high barium content barium zinc products with the added benefit of use of the such formulated products in PVC plastisol applications. Such use of high metal , carbonated products is normally prohibited by the occurrence of "gassing" (C0₂ elimination) at high gellation temperatures .

The present invention is described by the following Examples , which are intended to merely recite certain potential embodiments of the present invention: Example 1

To a one liter three-neck round-bottom flask equipped with thermometer, mechanical stirrer, heating mantle and distillation condenser was charged 144.75g (0.764 mole) of barium hydroxide monohydrate, 168.50g (0.766 mole) of nonylphenol, 91.90g (0.766 mole) of 2- (2- methoxyethoxy) ethanol , and 136.14g of mineral spirits. The temperature was raised and, over the range of 100°C to

150°C, water was removed (41.3g). The resultant solution analyzed at 21.00% barium. The composition corresponded to a solution of Ba (OC₆HC₉Hι₉) (OC₂H₄OC₂H₄OCH₃) in mineral spirits. The Gardner Holt ("GH") viscosity of this material at 25°C was W-X.

Example 2

To a one liter three-neck round-bottom flask equipped with thermometer, mechanical stirrer, heating mantle and distillation condenser was charged 172.31g (0.910 mole) of barium hydroxide monohydrate, 80.23g (0.365 mole) of nonylphenol, 174.98g (1.458 moles) of 2- (2- methoxyethoxy) ethanol , and 120.63g of mineral spirits. The temperature was raised and, over the range of 100°C to

150°C, water was removed (60. Og). The resultant solution analyzed at 25.3% barium. The composition corresponded to a solution of Ba (OC₆H₄C₉Hι₉) ₀. (OC₂H₄OC₂H₄OCH₃) ι.₆ in mineral spirits . This Ba intermediate was stable at room temperature, at 60°C, and at 4°C for at least six months. The GH viscosity was between Y to Z at 25°C.

Example 3 To a one liter three-neck round-bottom flask equipped with thermometer, mechanical stirrer, heating mantle and distillation condenser was charged 144.7g (0.764 mole) of barium hydroxide monohydrate, 168.5g (0.766 mole) of nonylphenol, 124. Og (0.765 mole) of 2- (2- butoxyethoxy) ethanol , and 104. Og of mineral spirits. The temperature was raised and, over the range of 100°C to 150°C, water was removed (about 40g) . The resultant solution analyzed at 20.3% barium. The composition corresponded to a solution of Ba(OC₆H₄C₉H₁₉) (OC₂H₄θC₂H₄OC₄H₉) in mineral spirits. The GH (Gardner Holt) viscosity of this material at 25°C was S.

Example 4 To a one liter three-neck round-bottom flask equipped with thermometer, mechanical stirrer, heating mantle and distillation condenser, was charged 179.2g (0.946 mole) of barium hydroxide monohydrate, 33.05g (0.150 mole) of nonylphenol, 193.36g (1.611 moles) of 2- (2- ethoxyethoxy) ethanol , 20.48g (0.142 mole) of 2- ethylhexanoic acid, and 129.07g of mineral spirits. The temperature was raised and over, the range of 100°C to 150°C, water was removed (about 66. Og). The resultant solution analyzed at 25.6% barium. The composition corresponded to a solution of Ba(OC₆HC₉Hι₉) ₀.₁₅ (0₂CCH.C₂H₅.C₄Hg)o.i₅(OC₂HOC₂H4θCH₃)ι.₇ in mineral spirits.

Example 5 To a one liter three-neck round-bottom flask equipped with thermometer, mechanical stirrer, heating mantle and distillation condenser, was charged 179.2g (0.946 mole) of barium hydroxide monohydrate, 247.5g (1.527 moles) of 2- (2- butoxyethoxy) ethanol , 51.2g (0.355 mole) of 2-ethylhexanoic acid, and 75.3g of mineral spirits. The temperature was raised and, over the range of 100°C to 150°C, water was removed (about 51.2g). The resultant solution analyzed at 24.2% barium and was a low viscosity liquid. The composition corresponded to a solution of Ba(0₂CCH.C₂H₅.C₄H₉) ₀.₄ (OC₂HOC₂H₄OC₄H₉) ι.₆ in mineral spirits.

Example 6 To a one liter three-neck round-bottom flask equipped with thermometer, mechanical stirrer, heating mantle and distillation condenser, was charged 179.2g (0.946 mole) of barium hydroxide monohydrate, 31.4g of nonylphenol (0.1427 mole), 193.5g (1.6125 mole) of 2- (2-methoxyethoxy) ethanol, 20.5g (0.1424 mole) of 2-ethylhexanoic acid, and 32g of mineral spirits. The temperature was raised and, over the range of 100°C to 150°C, water was removed (about 51.2g) . The resultant solution analyzed at 32% barium and was a viscous liquid. The composition corresponded to a solution of Ba(OC₆H₄C₉H₁₉) ₀.ιs (0₂CCH.C₂H₅.C₄H₉) ₀.ι₅ (OC₂H₄θC₂H₄OCH₃) χ.₇ in mineral spirits .

Example 7 To a one liter three-neck round-bottom flask equipped with thermometer, mechanical stirrer, heating mantle and distillation condenser, was charged 179.2g (0.946 mole) of barium hydroxide monohydrate, 62.6g of nonylphenol (0.2845 mole), 193.4g (1.6116 moles) of 2- (2-methoxyethoxy) ethanol, and 97.5g of aromatic 150 solvent. The temperature was raised and, over the range of 100°C to 150°C, water was removed (about 51. lg) . The resultant solution analyzed at 26.5% barium. The composition corresponded to a solution of Ba(OC₆H₄C₉H₁₉) ₀₃ (OC₂H₄OC₂H₄OCH₃) ι.₇ in aromatic solvent (Aromatic 150 brand from ExxonMobil Chemical) . Example 8 To a one liter three-neck round-bottom flask equipped with thermometer, mechanical stirrer, heating mantle and distillation condenser, was charged 179.2g (0.946 mole) of barium hydroxide monohydrate, 175.7g (1.084 moles) of 2- (2- butoxyethoxy) ethanol , 21.6g (0.1770 mole) of benzoic acid, 25.6g (0.177 mole) of 2-ethylhexanoic acid and 120.5g of mineral spirits. The temperature was raised and, over the range of 100 to 150°C, water was removed (about 43. Og). The resultant solution analyzed at 25.8% barium and represented a 25% basic (acid/alcohol-deficient) barium-containing mixed carboxylate/alkoxide .

Example 9 To a one liter three-neck round-bottom flask equipped with thermometer, mechanical stirrer, heating mantle and distillation condenser was charged 137.85g (0.728 mole) of barium hydroxide monohydrate, 210.61g (0.730 mole) of tall oil acid, 87.49g (0.729 mole) of 2- (2- methoxyethoxy) ethanol , and 103.37g of mineral spirits. The temperature was raised and, over the range of 100°C to 150°C, water was removed (42.6g of water). The resultant solution was of low viscosity and analyzed at 19.5% barium. The composition corresponded to a solution of Ba(tallate) (OC₂H₄OC₂H₄OCH₃) in mineral spirits.

Example 10 To a one liter three-neck round-bottom flask equipped with thermometer, mechanical stirrer, heating mantle and distillation condenser, was charged 171.6g (0.907 mole) of barium hydroxide monohydrate, 79. Og (0.411 mole) of tripropylene glycol, 181.6g (0.826 mole) of nonylphenol, 9.6g (0.16 mole) of acetic acid, and 207.2g of mineral spirits. The temperature was raised and, over the range of 100 to 150°C, water was removed (about 49g) . The resultant solution analyzed at 20.7% barium.

Example 11

To a one liter three-neck round-bottom flask equipped with thermometer, mechanical stirrer, heating mantle and distillation condenser was charged 24.11g (0.198 mole) of strontium hydroxide, 43.68g (0.199 mole) of nonylphenol, 32.17g (0.199 mole) of 2- (2-methoxyethoxy) ethanol, and 57.18g of mineral spirits. The temperature was raised and, over the range of 100°C to 150°C, water was removed (7.2g). The resultant solution was of low viscosity and analyzed at 11.6% strontium. The composition corresponded to a solution of Sr (OC₆HC₉H₁₉) (OC₂H₄θC₂H₄OCH₃) in mineral spirits .

EXAMPLE 12 To a one liter three-neck round-bottom flask equipped with stirrer, thermometer, heating mantle and distillation condenser was charged 224.7g of 2-ethylhexanoic acid, 252.7g of 2- (2-butoxyethoxy) ethanol , 14g of acetic acid, 149. lg of mineral spirits, 87.5g of calcium oxide and l.Og of water. The temperature was raised and, over the range of 100°C to 150°C, water was recovered (29g) . The resulting solution analyzed at 8.5% calcium.

EXAMPLE 13

To a one liter three-neck round-bottom flask equipped with stirrer, heating mantle, thermometer and distillation condenser was charged 294. Og of nonylphenol, 217g of 2- (2- butoxyethoxy) ethanol , 14g of acetic acid and 329g of dibutyltin oxide. The temperature was raised and, over the range of 100°C to 150°C, water was recovered (23.8g). The resulting solution analyzed at 18.8% tin.

Comparative Example 14 5

To a one liter three-neck round-bottom flask equipped with heating mantle, thermometer, mechanical stirrer, and distillation condenser, was charged, 322.3g (1.465 moles) of nonylphenol, 137.5g of 2- (2-butoxyethoxy) ethanol and 10 159.4g of mineral spirits. To this was carefully added

137.5g (0.726 mole) of barium hydroxide monohydrate. , Following the subsidence of the exotherm, the temperature was raised and, over the range of 100°C to 150°C, water was removed (about 39.2g) . The resultant solution analyzed at 15 13.9% barium. The composition corresponded to a solution of Ba(OC6H₄C₉Hι₉) 2 in mineral spirits and 2- (2- butoxyethoxy) ethanol . Solutions with lower barium contents were prepared from this solution by dilution with mineral spirits . Viscosities of these 20 solutions are presented below:

Barium Content (%) GH Viscosity at 25°C 11.9 E

12.9 S

25 13.9 Z2

This data demonstrates the advantage in terms of reduced viscosity with the technology of the present invention .

30

Example 15

To 50. Og of the product of Example 2 above was added 46.2g of commercially available triphenyl phosphite in a 35 stirred reaction vessel initially at 25°C. Substantially immediately thereafter an exothermic reaction occurred.

The product was a homogeneous, stable solution that is useful for the formulation of liquid mixed metal heat stabilizers for PVC.

Example 16 To a one liter three-neck round-bottom flask equipped with thermometer, mechanical stirrer, heating mantle and distillation condenser was charged 178.5g of barium hydroxide monohydrate, 80.25g of nonylphenol, 246.5g of 2- (2-butoxyethoxy) ethanol, 10. Og of acetic acid, and 35.8g of mineral spirits. The temperature was raised and, over the range of 100°C to 150°C, water was removed (51.0g) . After cooling to 85°C, 313g of diphenyl isodecyl phosphite was carefully charged. An exothermic reaction ensued and the resultant mixture analyzed at 15.7% barium and 3.5% phosphorus .

Example 17 To a one liter three-neck round-bottom flask equipped with thermometer, mechanical stirrer, heating mantle and distillation condenser was charged 223.2g of barium hydroxide monohydrate, 61.20g of 2-ethylhexanoiσ acid,

298.2g of 2- (2-butoxyethoxy) ethanol, 12. Og of acetic acid, and 66.6g of mineral spirits. The temperature was raised and over the range of 100°C to 150°C was removed 67. lg of water. After cooling to 85°C was carefully charged 267g of diphenyl isodecyl phosphite. An exothermic reaction ensued and the resultant mixture analyzed at 18.6% barium and 2.6% phosphorus . The efficacy of the aforementioned intermediates produced as the product of this invention is demonstrated by the following Examples .

Examples 18 - 22

Constituent 18 19 2( 21 22

DPIDP 40 40 40 48 36

ZnOct (18%) 7 7 7 10 10 BDK 2 2 2 2 2

Oleic acid 5 5 5 4 4

BNP (12%) 36 36

Product of Example 5 18

Product of Example 8 17 Product of Example 16 27

Mineral Spirits 10 28 29 21

BNP (12%) is a neutral 12% metal barium nonylphenate ZnOct (18%) is an overbased 18% metal 2-ethylhexanoate DPIDP is diphenyl isodecyl phosphite

BDK is a commercially available beta-diketone

These formulations were prepared by sequentially charging ingredients in the order shown to a stirred beaker and, where necessary, applying modest heat to achieve a homogeneous solution .

They were then tested in the PVC test formulations as described below:

PVC Test Formulation A - all amounts in parts per hundred of resin

PVC Suspension grade resin (Geon 30) 100

Dioσtylphthalate 45 Epoxidized Soybean Oil 2.5

Stearic Acid 0.3

Stabilizer 1.5 PVC Test Formulation B - all amounts in parts per hundred of resin

PVC Suspension grade resin (Geon 103EP) 100 Dioctylphthalate 45

Epoxidized Soybean Oil 5.0

Calcium Carbonate 15

Stearic Acid 0.25 Stabilizer 2.5

The PVC test formulations were prepared as follows : The formulations were hand mixed before being placed on an oil heated, two-roll mill and mixed for three minutes at 170°C. The mill conditions were: front roll speed - 28rpm, back roll speed - 20rpm, and nip gap - 0.02". After milling for the specified time, the gelled sheets were removed from the mill and cooled to room temperature. Test specimens were punched from the sheets, mounted on glass slides and subjected to an oven test at 190°C. Test specimens were removed from the oven after specified time intervals , and the color deterioration determined by assessment of the ^ΛHunter' b value (yellowness) . The results of these evaluations are shown in Tables 1 and 2 belo :

TABLE 1 - Formulation A

Example b value after oven heat test in minutes at 190°C

0 10 20 30 40 50 60

18 0.52 1, .36 1.12 1.38 1.86 4.64 10.72 19 -0.53 -0. .18 0.67 0.65 1.31 3.22 9.64 20 -0.66 0, .43 0.60 0.83 1.53 4.42 1.31 21 0.57 1, .26 2.97 3.92 5.90 15.98 22 -0.14 0, .79 1.86 2.79 5.20 18.26 TABLE 2 - Formulation B

Example b value after oven heat test in minutes at 190°C

0 10 20 30 40 50 60 70

18 2.82 1.81 3.89 4.07 6.03 7.63 14.78 24.49

19 1.80 1.55 2.81 3.38 4.44 6.13 12.16 20.79

20 0.59 1.14 2.60 3.41 4.98 6.81 13.15 21.97

Examples 23 - 24

Constituent 23 24

DPIDP 18 10

CdOct (19%) 8 8

Oleic Acid 5 5

ZnOct (14%) 4 4

BNP (12%) 27

Product of Example 16 21

Mineral Spirits 38 52

CdOct (19%) is a neutral 19% metal cadmium octoate ZnOct (14%) is a neutral 14% metal zinc octoate

These formulations were prepared and incorporated into PVC formulation A as described above for Examples 18-22 and subjected to an oven heat stability test in order to determine the efficacy of the formulations . The results of this evaluation are presented below in Table 3.

TABLE 3 - - Formulation A

Example b Value after oven heat test in minutes at 190°C

0 5 10 15 20 25 30 35

23 2.01 2.25 1.54 1.84 3.92 9.05 18.17 6.38 24 2.17 1.33 1.14 1.17 2.27 7.30 16.35 3.05

Examples 25 - 26

Constituent 25 26

BNP (12%) 42

Product of Example 17 27

ZnOct (18%) 4 4

CdNapBenz (13%) 15 15

DPIDP 28 19

Oleic Acid 8 8

Butyl Carbitol 1

Mineral Spirits 2 27

CdNapBenz (13%) is a 13% metal mixed cadmium naphthenate benzoate .

These formulations were prepared and incorporated into PVC formulation A as described above for Examples 18-22 and subjected to an oven heat stability test in order to determine the efficacy of the formulations . The results of this evaluation are presented below in Table 4.

TABLE 4 - Formulation A

Example b value after oven heat test in minutes at 190°C

0 10 20 30 40 50

25 1.60 1.60 3.69 6.00 7.63 15.00 26 1.12 1.53 2.31 4.87 6.06 18.42

Examples 27 - 28

Constituent 27 28

DPIDP 51 44

BDK 1 1

ZnOct (23%) 3 3

Oleic Acid 1 1

Barium BOO (18%) 14

Product of Example 16 16

Mineral Spirits 5

ESO 30 30

Barium BOO (18%) is a 18% metal barium mixed acid octoate, benzoate, oleate

ESO is epoxidized soybean oil These stabilizer formulations were also prepared according to the technique described above for Examples 18- 22.

They were tested in the PVC test formulation as described below:

PVC Test Formulation C - all amounts in parts per hundred of resin

PVC Emulsion grade resin (Geon 121) 100 Dioctylphthalate 60

Stabilizer/Epoxy blend 9.0

The ingredients were initially mixed for ten minutes with a Premier Dispersator. The mixed formulations were spread on a clean glass plate using a plastisol draw-down knife. Films of 0.02" thickness were produced. The films were gelled in an oven preheated to 205°C for a period of five minutes . After cooling to ambient temperature the films were stripped from the glass plates . Test specimens were punched from these sheets and subjected to oven heat stability tests as described above. The results of this evaluation are presented below in Table 5.

TABLE 5 - Formulation C

Example b value after oven heat test in minutes at 250°C

0 2 4 6 8

27 4.14 4.28 4.83 4.74 15.66 28 4.05 4.37 4.72 4.37 12.32

Example 29 To a one liter three-neck round-bottom flask equipped with thermometer, mechanical stirrer, heating mantle and distillation condenser, was charged 182.4g (0.964 moles) of barium hydroxide monohydrate, 184.2g (1.246 moles) of dipropylene glycol methyl ether, 106. Og (0.482 moles) of nonylphenol, 12. Og (0.20 moles) of acetic acid, and 167.4g of mineral spirits . The temperature was raised and over the range of 100 to 150°C was removed about 52g of water. The resultant solution analyzed at 22.0% barium.

Example 30 To a one liter three-neck round-bottom flask equipped with thermometer, mechanical stirrer, heating mantle and distillation condenser, was charged 171.6g (0.907 moles) of barium hydroxide monohydrate, 74.4g (0.827 moles) of 2- ethoxyethanol , 181.6g (0.826 moles) of nonylphenol, 9.6g (0.16 moles) of acetic acid, and 211.8g of mineral spirits. The temperature was raised and over the range of 100 to 150°C was removed about 49g of water. The resultant solution analyzed at 20.7% barium.

Claims

What is Claimed:

1. A chemical composition that is prepared by the reaction of a substantially stoichiometric mixture of: a phenol and an alcohol ; a carboxylic acid and an alcohol ; or a mixture of a phenol, a carboxylic acid, and an alcohol with a metal oxide or hydroxide.

2. The compositions of Claim 1 that are of the formula M(OC₆H₄R) _a(0₂CR' )_b( [OR"]_cOR"' )₂-<a₊b) where M is a Group II metal selected from the group consisting of Ba, Sr, Cd, Ca, and Mg or where M is a monoalkyltin moiety (R^IVSn) ₂/₃ or a dialkyltin moiety (R^IV ₂Sn) ; R is either H or a saturated or unsaturated alkyl or alkoxy group of up to about 18 carbon atoms ; R' is a saturated or unsaturated alkyl group of up to about 18 carbon atoms or an aromatic group which is either unsubstituted or substituted with one or more alkyl or alkoxy groups each of up to about 18 carbon atoms ; R" is an alkylene group of up to about 4 carbon atoms; R"' is either a saturated or unsaturated alkyl group of up to about 18 carbon atoms or an alkyl or alkoxy substituted or unsubstituted aromatic group; R^IV is an alkyl group of u to about 12 carbon atoms ; either a or b can separately be 0 ; a+b is in the range of from about 0.1 to about 1.9; and c is in the range of from about 1 to about 10.

3. A composition as Claimed in Claim 1 where the alcohol is a diol and the products of the reaction are of the formula: M(OC₆H₄R) _a (0₂CR' )_b ( [OR"]_d O) ι-_(a+b)/₂ where M, R,

R' , R", R^IV, a, and b are as defined in Claim 2; and where d is in the range of from about 1 to about 10.

4. A composition as Claimed in Claim 1 where the phenol is selected from the group consisting of phenol, para-nonylphenol , para-octylphenol , para-dodecylphenol , para-cresol , para-t-butylphenol and para-methoxyphenol .

5. A composition as Claimed in Claim 1 where the acid is selected from the group consisting of acetic acid, propionic acid, n-valeric acid, 2-methylpentanoic acid, 2- ethylbutyric acid, di-n-propylacetic acid, n-heptanoic acid, isomeric butyric acids, n-octanoic acid, 2- ethylhexanoiσ acid, isononanoic, isooctanoic acid, versatic acid, tall oil acid, oleic acid, benzoic acid, para-t- butylbenzoic acid, isomeric toluic acids, adipic acid, suσcinic acid and naphthenic acid.

6A composition as Claimed in Claim 1 where the alcohol is selected from the group consisting of 2- (2- methoxyethoxy) ethanol , 2 - (2-ethoxyethoxy) ethanol, 2- (2- butoxyethoxy) ethanol , 1- (2-methoxyisopropoxy) -2-propanol , nonylphenol ethoxylated with six moles of ethylene oxide, and lauryl alcohol ethoxylated with three moles of ethylene oxide and tripropylene glycol .

7. A composition as Claimed in Claim 1 where the metal is selected from the group consisting of barium, strontium, cadmium, calcium, magnesium, monoalkyl substituted tin and dialkyl substituted tin.

8. A composition as Claimed in any of Claims 1-7 that is combined with an organophosphite ester.

9. A composition as claimed in Claim 6 where the organophosphite ester is selected from the group consisting of triphenyl phosphite, diphenyl isodecyl phosphite, di- isodecyl phenyl phosphite, tridecyl phosphite, diphenyl phosphite, phenyl 2ethylhexyl phosphite, diphenyl iso-octyl phosphite, tris nonylphenyl phosphite, tetraphenyl dipropyleneglyσol diphosphite, and dipropylene glycol phenyl phosphite .

10. A chemical composition formed by the reaction of barium hydroxide monohydrate with a mixture of nonylphenol and an ether alcohol in a hydrocarbon solvent.

11. The composition of Claim 8 wherein the ether alcohol is 2- (2-methoxyethoxy) ethanol .

12. A chemical composition according to any of the foregoing Claims that is formed by a substantially complete dehydration of the reaction mixture.

13. A chemical composition according to any of the foregoing Claims that is formed by the reaction of a stoichiometric total quantity, or less, of acid and alcohol with barium hydroxide .

14. A PVC composition comprising the chemical composition of any of Claims 1 to 13 as a stabilizer.

15. A paint composition comprising the chemical composition of any of Claims 1 to 13 as a drier.

16. A petroleum-containing composition or a PVC plastisol comprising the chemical composition of any of Claims 1 to 13 as a thickener.

17. A lubricating oil composition comprising the chemical composition of any of Claims 1 to 13 as an acid scavenger.

18. A surface coating composition formed rom the chemical composition of any of Claims 1 to 13.