Metal salts of malonic acid as nucleating additives for crystalline thermoplastics

Abstract

The present invention provides a metal salt of malonic acid derivative compound having chemical formula (I) as an α-nucleating agent and process for preparing the same. The present invention also provides a polymer additive and thermoplastic composition comprising the metal salt of malonic acid derivative compound having chemical formula (I). ##STR00001##

Claims

1. A metal salt of malonic acid derivative compound having formula (I): ##STR00005## wherein: each of R.sub.1 and R.sub.2 groups are alkyl groups having 2 carbon atoms; each of M.sub.1 and M.sub.2 are selected from monovalent metal and divalent metal; and wherein the compound of formula I is selected from a group consisting of lithium 2,2-diethylmalonate, barium 2,2-diethylmalonate, calcium 2,2-diethylmalonate, and magnesium 2,2-diethylmalonate.

2. A process for preparing a metal salt of malonic acid derivative as claimed in claim 1, wherein the process comprising adding a malonic acid derivative in water and metal hydroxide to obtain a reaction mixture slurry and then heating the reaction mixture slurry to a temperature in the range of 20° C. to 120° C. along with continuous stirring for 5 min. to 10 hours to obtain a metal salt of malonic acid derivative.

3. A polymer additive comprising: (i) a component selected from metal stearate, metal oxide, and mixture thereof; (ii) the metal salt of malonic acid derivative compound having chemical Formula (I) as claimed in claim 1; wherein the component (i) is present in an amount of from 1.0 percent to 90.0 percent by weight based on the total amount of the polymer additive.

4. The polymer additive as claimed in claim 3, wherein the metal stearate is selected from the group comprising of divalent metal stearate having formula C.sub.36H.sub.70MO.sub.4, monovalent metal stearate having formula C.sub.18H.sub.35MO.sub.2, and trivalent metal stearate having formula C.sub.54H.sub.105MO.sub.6, wherein M is a metal and selected from magnesium, calcium, aluminium, lithium, and sodium.

5. The polymer additive as claimed in claim 3, wherein the metal oxides conforming to formula (III)
MO  (III) wherein M is selected from trivalent metal cation, divalent metal cation, and monobasic metal cation.

6. A thermoplastic composition comprising; (i) a polyolefin resin or polyolefin formulation; and (ii) the metal salt of malonic acid derivative compound having chemical Formula (I) as claimed in claim 1, wherein the metal salt of malonic acid derivative is present in an amount from 0.005 percent to 2.0 percent by weight based on the amount of the thermoplastic composition.

7. The thermoplastic composition as claimed in claim 6, optionally comprising the metal stearate and the metal stearate is selected from the group comprising of divalent metal stearate having formula C.sub.36H.sub.70MO.sub.4, monovalent metal stearate having formula C.sub.18H.sub.35MO.sub.2, and trivalent metal stearate having formula C.sub.54H.sub.105MO.sub.6, wherein M is a metal and selected from magnesium, calcium, aluminium, lithium, and sodium.

8. The thermoplastic composition as claimed in claim 6, optionally comprising the metal oxide conforming to formula (III)
MO  (III) wherein M is selected from trivalent metal cation, divalent metal cation, and monobasic metal cation.

9. The thermoplastic composition as claimed in claim 6, wherein the polyolefin resin or polyolefin formulation comprises at least one semi crystalline polyolefin resin.

10. The thermoplastic composition as claimed in claim 6, optionally comprising antioxidant, antimicrobial agent, acid scavenger, antistatic compound, chlorine scavenger, dispersing aid, stabilizer, ultraviolet absorber, and other similar standard thermoplastic additive.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) Accordingly present invention provides a metal salt of malonic acid derivative compound confirming to formula (I) as an α-nucleating agent. The metal salts of malonic acid derivative compounds are represented by chemical Formula (I):

(2) ##STR00003##
wherein:
each of R.sub.1 and R.sub.2 groups are independently selected from hydrogen, alkyl, aryl, alkyl aryl, halogen and cycloalkyls;
provided that R.sub.1 and R.sub.2 are not both hydrogen, and each of M.sub.1 and M.sub.2 are selected from monovalent metal, and divalent metal.

(3) In one of the feature of the present invention, monovalent metal is selected from lithium, sodium, and potassium, and divalent metal is selected from barium, calcium and magnesium.

(4) In one of the feature of the present invention, M.sub.1 and M.sub.2 are same metal. In another feature of the present invention M.sub.1 and M.sub.2 are not same metal.

(5) In another feature of the present invention, wherein each R.sub.1 and R.sub.2 are independently selected from hydrogen, halogen, alkyl having 1 to about 14 carbon atoms, phenyl, arylalkyl having 6 to about 18 carbon atoms or alkyl aryl having 7 to 18 carbon atoms, provided that R.sub.1 and R.sub.2 are not both hydrogen. In one of the feature of the present invention alkyl aryl is selected from ethyl phenyl, propyl phenyl, iso propyl phenyl, tert-butyl phenyl, benzyl or like.

(6) In one of the feature of the present invention, the compound of formula I is selected from the group consisting of sodium 2,2-dimethylmalonate, sodium 2,2-diethylmalonate, sodium 2,2-dipropylmalonate, sodium 2,2-dibutylmalonate, sodium 2,2-dipentylmalonate, sodium 2,2-dihexylmalonate, sodium 2,2-diheptylmalonate, sodium 2,2-dioctylmalonate, sodium 2,2-dinonylmalonate, sodium 2,2-didecylmalonate, sodium 2,2-diundecylmalonate, sodium 2,2-didodecylmalonate, sodium 2-dodecyl-2-undecylmalonate, sodium 2-decyl-2-dodecylmalonate, sodium 2-dodecyl-2-nonylmalonate, sodium 2-dodecyl-2-octylmalonate, sodium 2-dodecyl-2-heptylmalonate, sodium 2-dodecyl-2-hexylmalonate, sodium 2-dodecyl-2-pentylmalonate, sodium 2-butyl-2-dodecylmalonate, sodium 2-dodecyl-2-propylmalonate, sodium 2-dodecyl-2-ethylmalonate, sodium 2-dodecyl-2-methylmalonate, sodium 2-dodecylmalonate, sodium 2-undecylmalonate, sodium 2-decylmalonate, sodium 2-nonylmalonate, sodium 2-octylmalonate, sodium 2-heptylmalonate, sodium 2-hexylmalonate, sodium 2-pentylmalonate, sodium 2-butylmalonate, sodium 2-propylmalonate, sodium 2-ethylmalonate, sodium 2-methylmalonate, sodium 2-phenylmalonate, sodium 2-(p-tolyl)malonate, sodium 2-mesitylmalonate, sodium 2-(4-(tert-butyl)phenyl)malonate, sodium 2-(4-(tert-butyl)-2-methylphenyl)malonate, sodium 2-(4-(tert-butyl)-2,6-dimethylphenyl)malonate, sodium 2,2-diphenylmalonate, sodium 2-methyl-2-phenylmalonate, sodium 2-ethyl-2-phenylmalonate, sodium 2-phenyl-2-propylmalonate, sodium 2-butyl-2-phenylmalonate, sodium 2-pentyl-2-phenylmalonate, sodium 2-hexyl-2-phenylmalonate, sodium 2-heptyl-2-phenylmalonate, sodium 2-octyl-2-phenylmalonate, sodium 2-nonyl-2-phenylmalonate, sodium 2-decyl-2-phenylmalonate, sodium 2-phenyl-2-undecylmalonate, sodium 2-dodecyl-2-phenylmalonate, sodium 2-isopropyl-2-methylmalonate, sodium 2,2-diisopropylmalonate, sodium 2-isopropylmalonate, sodium 2-(tert-butyl)malonate, sodium 2-ditert-butylmalonate, sodium 2-(tert-butyl)-2-methylmalonate, sodium 2-(tert-butyl)-2-ethylmalonate, sodium 2-ethyl-2-isopropylmalonate, sodium 2-isopropyl-2-propylmalonate, sodium 2-butyl-2-isopropylmalonate, sodium 2-isopropyl-2-pentylmalonate, sodium 2-hexyl-2-isopropylmalonate, sodium 2-heptyl-2-isopropylmalonate, sodium 2-isopropyl-2-octylmalonate, sodium 2-isopropyl-2-nonylmalonate, sodium 2-decyl-2-isopropylmalonate, sodium 2-isopropyl-2-undecylmalonate, sodium 2-(tert-butyl)-2-undecylmalonate, sodium 2-(tert-butyl)-2-decylmalonate, sodium 2-(tert-butyl)-2-nonylmalonate, sodium 2-(tert-butyl)-2-octylmalonate, sodium 2-(tert-butyl)-2-heptylmalonate, sodium 2-(tert-butyl)-2-hexylmalonate, sodium 2-(tert-butyl)-2-pentylmalonate, sodium 2-(tert-butyl)-2-butylmalonate, sodium 2-(tert-butyl)-2-propylmalonate, sodium 2-(tert-butyl)-2-ethylmalonate, sodium 2-(tert-butyl)-2-phenylmalonate, sodium 2-isopropyl-2-phenylmalonate, sodium 2-(sec-butyl)malonate, sodium 2-(sec-butyl)-2-methylmalonate, sodium 2-methyl-2-(pentan-2-yl)malonate, sodium 2-(hexan-2-yl)-2-methylmalonate, sodium 2-(heptan-2-yl)-2-methylmalonate, sodium 2-methyl-2-(octan-2-yl)malonate, sodium 2-methyl-2-(nonan-2-yl)malonate, sodium 2-methyl-2-(octan-3-yl)malonate, sodium 2-(octan-3-yl)-2-octylmalonate, sodium 2-benzyl-2-methylmalonate, sodium 2,2-dibenzylmalonate, sodium 2-benzyl-2-ethylmalonate, sodium 2-benzyl-2-isopropylmalonate, sodium 2-benzyl-2-(tert-butyl)malonate, sodium 2-cyclohexylmalonate, sodium 2-cyclohexyl-2-methylmalonate, sodium 2-cyclohexyl-2-ethylmalonate, sodium 2-cyclohexyl-2-isopropylmalonate, sodium 2-(tert-butyl)-2-cyclohexylmalonate, sodium 2,2-dicyclohexylmalonate, sodium 2-cyclohexyl-2-(pentan-3-yl)malonate, sodium 2-ethylmalonate, sodium 2-isopropylmalonate, sodium 2-(tert-butyl)malonate, sodium 2-propylmalonate, sodium 2-butylmalonate, sodium 2-pentylmalonate, sodium 2-(2-methylpentyl)malonate, sodium 2-(2-ethylpentyl)malonate, sodium 2-(3-ethylhexan-2-yl)malonate, sodium 2-hexylmalonate, sodium 2-heptylmalonate, sodium 2-octylmalonate, sodium 2-nonylmalonate, sodium 2-decylmalonate, sodium 2-decyl-2-isopropylmalonate, lithium 2,2-dimethylmalonate, lithium 2,2-diethylmalonate, lithium 2,2-dipropylmalonate, lithium 2,2-dibutylmalonate, lithium 2,2-dipentylmalonate, lithium 2,2-dihexylmalonate, lithium 2,2-diheptylmalonate, lithium 2,2-dioctylmalonate, lithium 2,2-dinonylmalonate, lithium 2,2-didecylmalonate, lithium 2,2-diundecylmalonate, lithium 2,2-didodecylmalonate, lithium 2-dodecyl-2-undecylmalonate, lithium 2-decyl-2-dodecylmalonate, lithium 2-dodecyl-2-nonylmalonate, lithium 2-dodecyl-2-octylmalonate, lithium 2-dodecyl-2-heptylmalonate, lithium 2-dodecyl-2-hexylmalonate, lithium 2-dodecyl-2-pentylmalonate, lithium 2-butyl-2-dodecylmalonate, lithium 2-dodecyl-2-propylmalonate, lithium 2-dodecyl-2-ethylmalonate, lithium 2-dodecyl-2-methylmalonate, lithium 2-dodecylmalonate, lithium 2-undecylmalonate, lithium 2-decylmalonate, lithium 2-nonylmalonate, lithium 2-octylmalonate, lithium 2-heptylmalonate, lithium 2-hexylmalonate, lithium 2-pentylmalonate, lithium 2-butylmalonate, lithium 2-propylmalonate, lithium 2-ethylmalonate, lithium 2-methylmalonate, lithium 2-phenylmalonate, lithium 2-(p-tolyl)malonate, lithium 2-mesitylmalonate, lithium 2-(4-(tert-butyl)phenyl)malonate, lithium 2-(4-(tert-butyl)-2-methylphenyl)malonate, lithium 2-(4-(tert-butyl)-2,6-dimethylphenyl)malonate, lithium 2,2-diphenylmalonate, lithium 2-methyl-2-phenylmalonate, lithium 2-ethyl-2-phenylmalonate, lithium 2-phenyl-2-propylmalonate, lithium 2-butyl-2-phenylmalonate, lithium 2-pentyl-2-phenylmalonate, lithium 2-hexyl-2-phenylmalonate, lithium 2-heptyl-2-phenylmalonate, lithium 2-octyl-2-phenylmalonate, lithium 2-nonyl-2-phenylmalonate, lithium 2-decyl-2-phenylmalonate, lithium 2-phenyl-2-undecylmalonate, lithium 2-dodecyl-2-phenylmalonate, lithium 2-isopropyl-2-methylmalonate, lithium 2,2-diisopropylmalonate, lithium 2-isopropylmalonate, lithium 2-(tert-butyl)malonate, lithium 2-ditert-butylmalonate, lithium 2-(tert-butyl)-2-methylmalonate, lithium 2-(tert-butyl)-2-ethylmalonate, lithium 2-ethyl-2-isopropylmalonate, lithium 2-isopropyl-2-propylmalonate, lithium 2-butyl-2-isopropylmalonate, lithium 2-isopropyl-2-pentylmalonate, lithium 2-hexyl-2-isopropylmalonate, lithium 2-heptyl-2-isopropylmalonate, lithium 2-isopropyl-2-octylmalonate, lithium 2-isopropyl-2-nonylmalonate, lithium 2-decyl-2-isopropylmalonate, lithium 2-isopropyl-2-undecylmalonate, lithium 2-(tert-butyl)-2-undecylmalonate, lithium 2-(tert-butyl)-2-decylmalonate, lithium 2-(tert-butyl)-2-nonylmalonate, lithium 2-(tert-butyl)-2-octylmalonate, lithium 2-(tert-butyl)-2-heptylmalonate, lithium 2-(tert-butyl)-2-hexylmalonate, lithium 2-(tert-butyl)-2-pentylmalonate, lithium 2-(tert-butyl)-2-butylmalonate, lithium 2-(tert-butyl)-2-propylmalonate, lithium 2-(tert-butyl)-2-ethylmalonate, lithium 2-(tert-butyl)-2-phenylmalonate, lithium 2-isopropyl-2-phenylmalonate, lithium 2-(sec-butyl)malonate, lithium 2-(sec-butyl)-2-methylmalonate, lithium 2-methyl-2-(pentan-2-yl)malonate, lithium 2-(hexan-2-yl)-2-methylmalonate, lithium 2-(heptan-2-yl)-2-methylmalonate, lithium 2-methyl-2-(octan-2-yl)malonate, lithium 2-methyl-2-(nonan-2-yl)malonate, lithium 2-methyl-2-(octan-3-yl)malonate, lithium 2-(octan-3-yl)-2-octylmalonate, lithium 2-benzyl-2-methylmalonate, lithium 2,2-dibenzylmalonate, lithium 2-benzyl-2-ethylmalonate, lithium 2-benzyl-2-isopropylmalonate, lithium 2-benzyl-2-(tert-butyl)malonate, lithium 2-cyclohexylmalonate, lithium 2-cyclohexyl-2-methylmalonate, lithium 2-cyclohexyl-2-ethylmalonate, lithium 2-cyclohexyl-2-isopropylmalonate, lithium 2-(tert-butyl)-2-cyclohexylmalonate, lithium 2,2-dicyclohexylmalonate, lithium 2-cyclohexyl-2-(pentan-3-yl)malonate, lithium 2-ethylmalonate, lithium 2-isopropylmalonate, lithium 2-(tert-butyl)malonate, lithium 2-propylmalonate, lithium 2-butylmalonate, lithium 2-pentylmalonate, lithium 2-(2-methylpentyl)malonate, lithium 2-(2-ethylpentyl)malonate, lithium 2-(3-ethylhexan-2-yl)malonate, lithium 2-hexylmalonate, lithium 2-heptylmalonate, lithium 2-octylmalonate, lithium 2-nonylmalonate, lithium 2-decylmalonate, lithium 2-decyl-2-isopropylmalonate, potassium 2,2-dimethylmalonate, potassium 2,2-diethylmalonate, potassium 2,2-dipropylmalonate, potassium 2,2-dibutylmalonate, potassium 2,2-dipentylmalonate, potassium 2,2-dihexylmalonate, potassium 2,2-diheptylmalonate, potassium 2,2-dioctylmalonate, potassium 2,2-dinonylmalonate, potassium 2,2-didecylmalonate, potassium 2,2-diundecylmalonate, potassium 2,2-didodecylmalonate, potassium 2-dodecyl-2-undecylmalonate, potassium 2-decyl-2-dodecylmalonate, potassium 2-dodecyl-2-nonylmalonate, potassium 2-dodecyl-2-octylmalonate, potassium 2-dodecyl-2-heptylmalonate, potassium 2-dodecyl-2-hexylmalonate, potassium 2-dodecyl-2-pentylmalonate, potassium 2-butyl-2-dodecylmalonate, potassium 2-dodecyl-2-propylmalonate, potassium 2-dodecyl-2-ethylmalonate, potassium 2-dodecyl-2-methylmalonate, potassium 2-dodecylmalonate, potassium 2-undecylmalonate, potassium 2-decylmalonate, potassium 2-nonylmalonate, potassium 2-octylmalonate, potassium 2-heptylmalonate, potassium 2-hexylmalonate, potassium 2-pentylmalonate, potassium 2-butylmalonate, potassium 2-propylmalonate, potassium 2-ethylmalonate, potassium 2-methylmalonate, potassium 2-phenylmalonate, potassium 2-(p-tolyl)malonate, potassium 2-mesitylmalonate, potassium 2-(4-(tert-butyl)phenyl)malonate, potassium 2-(4-(tert-butyl)-2-methylphenyl)malonate, potassium 2-(4-(tert-butyl)-2,6-dimethylphenyl)malonate, potassium 2,2-diphenylmalonate, potassium 2-methyl-2-phenylmalonate, potassium 2-ethyl-2-phenylmalonate, potassium 2-phenyl-2-propylmalonate, potassium 2-butyl-2-phenylmalonate, potassium 2-pentyl-2-phenylmalonate, potassium 2-hexyl-2-phenylmalonate, potassium 2-heptyl-2-phenylmalonate, potassium 2-octyl-2-phenylmalonate, potassium 2-nonyl-2-phenylmalonate, potassium 2-decyl-2-phenylmalonate, potassium 2-phenyl-2-undecylmalonate, potassium 2-dodecyl-2-phenylmalonate, potassium 2-isopropyl-2-methylmalonate, potassium 2,2-diisopropylmalonate, potassium 2-isopropylmalonate, potassium 2-(tert-butyl)malonate, potassium 2-ditert-butylmalonate, potassium 2-(tert-butyl)-2-methylmalonate, potassium 2-(tert-butyl)-2-ethylmalonate, potassium 2-ethyl-2-isopropylmalonate, potassium 2-isopropyl-2-propylmalonate, potassium 2-butyl-2-isopropylmalonate, potassium 2-isopropyl-2-pentylmalonate, potassium 2-hexyl-2-isopropylmalonate, potassium 2-heptyl-2-isopropylmalonate, potassium 2-isopropyl-2-octylmalonate, potassium 2-isopropyl-2-nonylmalonate, potassium 2-decyl-2-isopropylmalonate, potassium 2-isopropyl-2-undecylmalonate, potassium 2-(tert-butyl)-2-undecylmalonate, potassium 2-(tert-butyl)-2-decylmalonate, potassium 2-(tert-butyl)-2-nonylmalonate, potassium 2-(tert-butyl)-2-octylmalonate, potassium 2-(tert-butyl)-2-heptylmalonate, potassium 2-(tert-butyl)-2-hexylmalonate, potassium 2-(tert-butyl)-2-pentylmalonate, potassium 2-(tert-butyl)-2-butylmalonate, potassium 2-(tert-butyl)-2-propylmalonate, potassium 2-(tert-butyl)-2-ethylmalonate, potassium 2-(tert-butyl)-2-phenylmalonate, potassium 2-isopropyl-2-phenylmalonate, potassium 2-(sec-butyl)malonate, potassium 2-(sec-butyl)-2-methylmalonate, potassium 2-methyl-2-(pentan-2-yl)malonate, potassium 2-(hexan-2-yl)-2-methylmalonate, potassium 2-(heptan-2-yl)-2-methylmalonate, potassium 2-methyl-2-(octan-2-yl)malonate, potassium 2-methyl-2-(nonan-2-yl)malonate, potassium 2-methyl-2-(octan-3-yl)malonate, potassium 2-(octan-3-yl)-2-octylmalonate, potassium 2-benzyl-2-methyl malonate, potassium 2,2-dibenzylmalonate, potassium 2-benzyl-2-ethylmalonate, potassium 2-benzyl-2-isopropylmalonate, potassium 2-benzyl-2-(tert-butyl)malonate, potassium 2-cyclohexylmalonate, potassium 2-cyclohexyl-2-methylmalonate, potassium 2-cyclohexyl-2-ethylmalonate, potassium 2-cyclohexyl-2-isopropylmalonate, potassium 2-(tert-butyl)-2-cyclohexylmalonate, potassium 2,2-dicyclohexylmalonate, potassium 2-cyclohexyl-2-(pentan-3-yl)malonate, potassium 2-ethylmalonate, potassium 2-isopropylmalonate, potassium 2-(tert-butyl)malonate, potassium 2-propylmalonate, potassium 2-butylmalonate, potassium 2-pentylmalonate, potassium 2-(2-methylpentyl)malonate, potassium 2-(2-ethylpentyl)malonate, potassium 2-(3-ethylhexan-2-yl)malonate, potassium 2-hexylmalonate, potassium 2-heptylmalonate, potassium 2-octylmalonate, potassium 2-nonylmalonate, potassium 2-decylmalonate, potassium 2-decyl-2-isopropylmalonate, barium 2,2-dimethylmalonate, barium 2,2-diethylmalonate, barium 2,2-dipropylmalonate, barium 2,2-dibutylmalonate, barium 2,2-dipentylmalonate, barium 2,2-dihexylmalonate, barium 2,2-diheptylmalonate, barium 2,2-dioctylmalonate, barium 2,2-dinonylmalonate, barium 2,2-didecylmalonate, barium 2,2-diundecylmalonate, barium 2,2-didodecylmalonate, barium 2-dodecyl-2-undecylmalonate, barium 2-decyl-2-dodecylmalonate, barium 2-dodecyl-2-nonylmalonate, barium 2-dodecyl-2-octylmalonate, barium 2-dodecyl-2-heptylmalonate, barium 2-dodecyl-2-hexylmalonate, barium 2-dodecyl-2-pentylmalonate, barium 2-butyl-2-dodecylmalonate, barium 2-dodecyl-2-propylmalonate, barium 2-dodecyl-2-ethylmalonate, barium 2-dodecyl-2-methylmalonate, barium 2-dodecylmalonate, barium 2-undecylmalonate, barium 2-decylmalonate, barium 2-nonylmalonate, barium 2-octylmalonate, barium 2-heptylmalonate, barium 2-hexylmalonate, barium 2-pentylmalonate, barium 2-butylmalonate, barium 2-propylmalonate, barium 2-ethylmalonate, barium 2-methylmalonate, barium 2-phenylmalonate, barium 2-(p-tolyl)malonate, barium 2-mesitylmalonate, barium 2-(4-(tert-butyl)phenyl)malonate, barium 2-(4-(tert-butyl)-2-methylphenyl)malonate, barium 2-(4-(tert-butyl)-2,6-dimethyl phenyl)malonate, barium 2,2-diphenylmalonate, barium 2-methyl-2-phenylmalonate, barium 2-ethyl-2-phenylmalonate, barium 2-phenyl-2-propylmalonate, barium 2-butyl-2-phenylmalonate, barium 2-pentyl-2-phenylmalonate, barium 2-hexyl-2-phenylmalonate, barium 2-heptyl-2-phenylmalonate, barium 2-octyl-2-phenylmalonate, barium 2-nonyl-2-phenylmalonate, barium 2-decyl-2-phenylmalonate, barium 2-phenyl-2-undecylmalonate, barium 2-dodecyl-2-phenylmalonate, barium 2-isopropyl-2-methylmalonate, barium 2,2-diisopropylmalonate, barium 2-isopropylmalonate, barium 2-(tert-butyl)malonate, barium 2-ditert-butylmalonate, barium 2-(tert-butyl)-2-methylmalonate, barium 2-(tert-butyl)-2-ethylmalonate, barium 2-ethyl-2-isopropylmalonate, barium 2-isopropyl-2-propylmalonate, barium 2-butyl-2-isopropylmalonate, barium 2-isopropyl-2-pentylmalonate, barium 2-hexyl-2-isopropylmalonate, barium 2-heptyl-2-isopropylmalonate, barium 2-isopropyl-2-octylmalonate, barium 2-isopropyl-2-nonylmalonate, barium 2-decyl-2-isopropylmalonate, barium 2-isopropyl-2-undecylmalonate, barium 2-(tert-butyl)-2-undecylmalonate, barium 2-(tert-butyl)-2-decylmalonate, barium 2-(tert-butyl)-2-nonylmalonate, barium 2-(tert-butyl)-2-octylmalonate, barium 2-(tert-butyl)-2-heptylmalonate, barium 2-(tert-butyl)-2-hexylmalonate, barium 2-(tert-butyl)-2-pentylmalonate, barium 2-(tert-butyl)-2-butylmalonate, barium 2-(tert-butyl)-2-propylmalonate, barium 2-(tert-butyl)-2-ethylmalonate, barium 2-(tert-butyl)-2-phenylmalonate, barium 2-isopropyl-2-phenylmalonate, barium 2-(sec-butyl)malonate, barium 2-(sec-butyl)-2-methylmalonate, barium 2-methyl-2-(pentan-2-yl)malonate, barium 2-(hexan-2-yl)-2-methylmalonate, barium 2-(heptan-2-yl)-2-methylmalonate, barium 2-methyl-2-(octan-2-yl)malonate, barium 2-methyl-2-(nonan-2-yl)malonate, barium 2-methyl-2-(octan-3-yl)malonate, barium 2-(octan-3-yl)-2-octylmalonate, barium 2-benzyl-2-methylmalonate, barium 2,2-dibenzylmalonate, barium 2-benzyl-2-ethylmalonate, barium 2-benzyl-2-isopropylmalonate, barium 2-benzyl-2-(tert-butyl)malonate, barium 2-cyclohexylmalonate, barium 2-cyclohexyl-2-methylmalonate, barium 2-cyclohexyl-2-ethylmalonate, barium 2-cyclohexyl-2-isopropylmalonate, barium 2-(tert-butyl)-2-cyclohexylmalonate, barium 2,2-dicyclohexylmalonate, barium 2-cyclohexyl-2-(pentan-3-yl)malonate, barium 2-ethylmalonate, barium 2-isopropylmalonate, barium 2-(tert-butyl)malonate, barium 2-propylmalonate, barium 2-butylmalonate, barium 2-pentylmalonate, barium 2-(2-methylpentyl)malonate, barium 2-(2-ethylpentyl)malonate, barium 2-(3-ethylhexan-2-yl)malonate, barium 2-hexylmalonate, barium 2-heptylmalonate, barium 2-octylmalonate, barium 2-nonylmalonate, barium 2-decylmalonate, barium 2-decyl-2-isopropylmalonate, calcium 2,2-dimethylmalonate, calcium 2,2-diethylmalonate, calcium 2,2-dipropylmalonate, calcium 2,2-dibutylmalonate, calcium 2,2-dipentylmalonate, calcium 2,2-dihexylmalonate, calcium 2,2-diheptylmalonate, calcium 2,2-dioctylmalonate, calcium 2,2-dinonylmalonate, calcium 2,2-didecylmalonate, calcium 2,2-diundecylmalonate, calcium 2,2-didodecylmalonate, calcium 2-dodecyl-2-undecylmalonate, calcium 2-decyl-2-dodecylmalonate, calcium 2-dodecyl-2-nonylmalonate, calcium 2-dodecyl-2-octylmalonate, calcium 2-dodecyl-2-heptylmalonate, calcium 2-dodecyl-2-hexylmalonate, calcium 2-dodecyl-2-pentylmalonate, calcium 2-butyl-2-dodecylmalonate, calcium 2-dodecyl-2-propylmalonate, calcium 2-dodecyl-2-ethylmalonate, calcium 2-dodecyl-2-methylmalonate, calcium 2-dodecylmalonate, calcium 2-undecylmalonate, calcium 2-decylmalonate, calcium 2-nonylmalonate, calcium 2-octylmalonate, calcium 2-heptylmalonate, calcium 2-hexylmalonate, calcium 2-pentylmalonate, calcium 2-butylmalonate, calcium 2-propylmalonate, calcium 2-ethylmalonate, calcium 2-methylmalonate, calcium 2-phenylmalonate, calcium 2-(p-tolyl)malonate, calcium 2-mesitylmalonate, calcium 2-(4-(tert-butyl)phenyl)malonate, calcium 2-(4-(tert-butyl)-2-methylphenyl)malonate, calcium 2-(4-(tert-butyl)-2,6-dimethylphenyl)malonate, calcium 2,2-diphenylmalonate, calcium 2-methyl-2-phenylmalonate, calcium 2-ethyl-2-phenylmalonate, calcium 2-phenyl-2-propylmalonate, calcium 2-butyl-2-phenylmalonate, calcium 2-pentyl-2-phenylmalonate, calcium 2-hexyl-2-phenylmalonate, calcium 2-heptyl-2-phenylmalonate, calcium 2-octyl-2-phenylmalonate, calcium 2-nonyl-2-phenylmalonate, calcium 2-decyl-2-phenylmalonate, calcium 2-phenyl-2-undecylmalonate, calcium 2-dodecyl-2-phenylmalonate, calcium 2-isopropyl-2-methylmalonate, calcium 2,2-diisopropylmalonate, calcium 2-isopropylmalonate, calcium 2-(tert-butyl)malonate, calcium 2-ditert-butylmalonate, calcium 2-(tert-butyl)-2-methylmalonate, calcium 2-(tert-butyl)-2-ethylmalonate, calcium 2-ethyl-2-isopropylmalonate, calcium 2-isopropyl-2-propylmalonate, calcium 2-butyl-2-isopropylmalonate, calcium 2-isopropyl-2-pentylmalonate, calcium 2-hexyl-2-isopropylmalonate, calcium 2-heptyl-2-isopropylmalonate, calcium 2-isopropyl-2-octylmalonate, calcium 2-isopropyl-2-nonylmalonate, calcium 2-decyl-2-isopropylmalonate, calcium 2-isopropyl-2-undecylmalonate, calcium 2-(tert-butyl)-2-undecylmalonate, calcium 2-(tert-butyl)-2-decylmalonate, calcium 2-(tert-butyl)-2-nonylmalonate, calcium 2-(tert-butyl)-2-octylmalonate, calcium 2-(tert-butyl)-2-heptylmalonate, calcium 2-(tert-butyl)-2-hexylmalonate, calcium 2-(tert-butyl)-2-pentylmalonate, calcium 2-(tert-butyl)-2-butylmalonate, calcium 2-(tert-butyl)-2-propylmalonate, calcium 2-(tert-butyl)-2-ethylmalonate, calcium 2-(tert-butyl)-2-phenylmalonate, calcium 2-isopropyl-2-phenylmalonate, calcium 2-(sec-butyl)malonate, calcium 2-(sec-butyl)-2-methylmalonate, calcium 2-methyl-2-(pentan-2-yl)malonate, calcium 2-(hexan-2-yl)-2-methylmalonate, calcium 2-(heptan-2-yl)-2-methylmalonate, calcium 2-methyl-2-(octan-2-yl)malonate, calcium 2-methyl-2-(nonan-2-yl)malonate, calcium 2-methyl-2-(octan-3-yl)malonate, calcium 2-(octan-3-yl)-2-octylmalonate, calcium 2-benzyl-2-methylmalonate, calcium 2,2-dibenzylmalonate, calcium 2-benzyl-2-ethylmalonate, calcium 2-benzyl-2-isopropylmalonate, calcium 2-benzyl-2-(tert-butyl)malonate, calcium 2-cyclohexylmalonate, calcium 2-cyclohexyl-2-methylmalonate, calcium 2-cyclohexyl-2-ethylmalonate, calcium 2-cyclohexyl-2-isopropylmalonate, calcium 2-(tert-butyl)-2-cyclohexylmalonate, calcium 2,2-dicyclohexylmalonate, calcium 2-cyclohexyl-2-(pentan-3-yl)malonate, calcium 2-ethylmalonate, calcium 2-isopropylmalonate, calcium 2-(tert-butyl)malonate, calcium 2-propylmalonate, calcium 2-butylmalonate, calcium 2-pentylmalonate, calcium 2-(2-methylpentyl)malonate, calcium 2-(2-ethylpentyl)malonate, calcium 2-(3-ethylhexan-2-yl)malonate, calcium 2-hexylmalonate, calcium 2-heptylmalonate, calcium 2-octylmalonate, calcium 2-nonylmalonate, calcium 2-decylmalonate, calcium 2-decyl-2-isopropylmalonate, potassium sodium 2,2-dimethylmalonate, potassium sodium 2,2-diethylmalonate, potassium sodium 2,2-dipropylmalonate, potassium sodium 2,2-dibutylmalonate, potassium sodium 2,2-dipentylmalonate, potassium sodium 2,2-dihexylmalonate, potassium sodium 2,2-diheptylmalonate, potassium sodium 2,2-dioctylmalonate, potassium sodium 2,2-dinonylmalonate, potassium sodium 2,2-didecylmalonate, potassium sodium 2,2-diundecylmalonate, potassium sodium 2,2-didodecylmalonate, potassium sodium 2-dodecyl-2-undecylmalonate, potassium sodium 2-decyl-2-dodecylmalonate, potassium sodium 2-dodecyl-2-nonylmalonate, potassium sodium 2-dodecyl-2-octylmalonate, potassium sodium 2-dodecyl-2-heptylmalonate, potassium sodium 2-dodecyl-2-hexylmalonate, potassium sodium 2-dodecyl-2-pentylmalonate, potassium sodium 2-butyl-2-dodecylmalonate, potassium sodium 2-dodecyl-2-propylmalonate, potassium sodium 2-dodecyl-2-ethylmalonate, potassium sodium 2-dodecyl-2-methylmalonate, potassium sodium 2-dodecylmalonate, potassium sodium 2-undecylmalonate, potassium sodium 2-decylmalonate, potassium sodium 2-nonylmalonate, potassium sodium 2-octylmalonate, potassium sodium 2-heptylmalonate, potassium sodium 2-hexylmalonate, potassium sodium 2-pentylmalonate, potassium sodium 2-butylmalonate, potassium sodium 2-propylmalonate, potassium sodium 2-ethylmalonate, potassium sodium 2-methylmalonate, potassium sodium 2-phenylmalonate, potassium sodium 2-(p-tolyl)malonate, potassium sodium 2-mesitylmalonate, potassium sodium 2-(4-(tert-butyl)phenyl)malonate, potassium sodium 2-(4-(tert-butyl)-2-methylphenyl)malonate, potassium sodium 2-(4-(tert-butyl)-2,6-dimethylphenyl)malonate, potassium sodium 2,2-diphenylmalonate, potassium sodium 2-methyl-2-phenylmalonate, potassium sodium 2-ethyl-2-phenylmalonate, potassium sodium 2-phenyl-2-propylmalonate, potassium sodium 2-butyl-2-phenylmalonate, potassium sodium 2-pentyl-2-phenylmalonate, potassium sodium 2-hexyl-2-phenylmalonate, potassium sodium 2-heptyl-2-phenylmalonate, potassium sodium 2-octyl-2-phenylmalonate, potassium sodium 2-nonyl-2-phenylmalonate, potassium sodium 2-decyl-2-phenylmalonate, potassium sodium 2-phenyl-2-undecylmalonate, potassium sodium 2-dodecyl-2-phenylmalonate, potassium sodium 2-isopropyl-2-methylmalonate, potassium sodium 2,2-diisopropylmalonate, potassium sodium 2-isopropylmalonate, potassium sodium 2-(tert-butyl)malonate, potassium sodium 2-ditert-butylmalonate, potassium sodium 2-(tert-butyl)-2-methylmalonate, potassium sodium 2-(tert-butyl)-2-ethylmalonate, potassium sodium 2-ethyl-2-isopropylmalonate, potassium sodium 2-isopropyl-2-propylmalonate, potassium sodium 2-butyl-2-isopropylmalonate, potassium sodium 2-isopropyl-2-pentylmalonate, potassium sodium 2-hexyl-2-isopropylmalonate, potassium sodium 2-heptyl-2-isopropylmalonate, potassium sodium 2-isopropyl-2-octylmalonate, potassium sodium 2-isopropyl-2-nonylmalonate, potassium sodium 2-decyl-2-isopropylmalonate, potassium sodium 2-isopropyl-2-undecylmalonate, potassium sodium 2-(tert-butyl)-2-undecylmalonate, potassium sodium 2-(tert-butyl)-2-decylmalonate, potassium sodium 2-(tert-butyl)-2-nonylmalonate, potassium sodium 2-(tert-butyl)-2-octylmalonate, potassium sodium 2-(tert-butyl)-2-heptylmalonate, potassium sodium 2-(tert-butyl)-2-hexylmalonate, potassium sodium 2-(tert-butyl)-2-pentylmalonate, potassium sodium 2-(tert-butyl)-2-butylmalonate, potassium sodium 2-(tert-butyl)-2-propylmalonate, potassium sodium 2-(tert-butyl)-2-ethylmalonate, potassium sodium 2-(tert-butyl)-2-phenylmalonate, potassium sodium 2-isopropyl-2-phenylmalonate, potassium sodium 2-(sec-butyl)malonate, potassium sodium 2-(sec-butyl)-2-methylmalonate, potassium sodium 2-methyl-2-(pentan-2-yl)malonate, potassium sodium 2-(hexan-2-yl)-2-methylmalonate, potassium sodium 2-(heptan-2-yl)-2-methylmalonate, potassium sodium 2-methyl-2-(octan-2-yl)malonate, potassium sodium 2-methyl-2-(nonan-2-yl)malonate, potassium sodium 2-methyl-2-(octan-3-yl)malonate, potassium sodium 2-(octan-3-yl)-2-octylmalonate, potassium sodium 2-benzyl-2-methylmalonate, potassium sodium 2,2-dibenzylmalonate, potassium sodium 2-benzyl-2-ethylmalonate, potassium sodium 2-benzyl-2-isopropylmalonate, potassium sodium 2-benzyl-2-(tert-butyl)malonate, potassium sodium 2-cyclohexylmalonate, potassium sodium 2-cyclohexyl-2-methylmalonate, potassium sodium 2-cyclohexyl-2-ethylmalonate, potassium sodium 2-cyclohexyl-2-isopropylmalonate, potassium sodium 2-(tert-butyl)-2-cyclohexylmalonate, potassium sodium 2,2-dicyclohexylmalonate, potassium sodium 2-cyclohexyl-2-(pentan-3-yl)malonate, potassium sodium 2-ethylmalonate, potassium sodium 2-isopropylmalonate, potassium sodium 2-(tert-butyl)malonate, potassium sodium 2-propylmalonate, potassium sodium 2-butylmalonate, potassium sodium 2-pentylmalonate, potassium sodium 2-(2-methylpentyl)malonate, potassium sodium 2-(2-ethylpentyl)malonate, potassium sodium 2-(3-ethylhexan-2-yl)malonate, potassium sodium 2-hexylmalonate, potassium sodium 2-heptylmalonate, potassium sodium 2-octylmalonate, potassium sodium 2-nonylmalonate, potassium sodium 2-decylmalonate, potassium sodium 2-decyl-2-isopropylmalonate, lithium sodium 2,2-dimethylmalonate, lithium sodium 2,2-diethylmalonate, lithium sodium 2,2-dipropylmalonate, lithium sodium 2,2-dibutylmalonate, lithium sodium 2,2-dipentylmalonate, lithium sodium 2,2-dihexylmalonate, lithium sodium 2,2-diheptylmalonate, lithium sodium 2,2-dioctylmalonate, lithium sodium 2,2-dinonylmalonate, lithium sodium 2,2-didecylmalonate, lithium sodium 2,2-diundecylmalonate, lithium sodium 2,2-didodecylmalonate, lithium sodium 2-dodecyl-2-undecylmalonate, lithium sodium 2-decyl-2-dodecylmalonate, lithium sodium 2-dodecyl-2-nonylmalonate, lithium sodium 2-dodecyl-2-octylmalonate, lithium sodium 2-dodecyl-2-heptylmalonate, lithium sodium 2-dodecyl-2-hexylmalonate, lithium sodium 2-dodecyl-2-pentylmalonate, lithium sodium 2-butyl-2-dodecylmalonate, lithium sodium 2-dodecyl-2-propylmalonate, lithium sodium 2-dodecyl-2-ethylmalonate, lithium sodium 2-dodecyl-2-methylmalonate, lithium sodium 2-dodecylmalonate, lithium sodium 2-undecylmalonate, lithium sodium 2-decylmalonate, lithium sodium 2-nonylmalonate, lithium sodium 2-octylmalonate, lithium sodium 2-heptylmalonate, lithium sodium 2-hexylmalonate, lithium sodium 2-pentylmalonate, lithium sodium 2-butylmalonate, lithium sodium 2-propylmalonate, lithium sodium 2-ethylmalonate, lithium sodium 2-methylmalonate, lithium sodium 2-phenylmalonate, lithium sodium 2-(p-tolyl)malonate, lithium sodium 2-mesitylmalonate, lithium sodium 2-(4-(tert-butyl)phenyl)malonate, lithium sodium 2-(4-(tert-butyl)-2-methylphenyl)malonate, lithium sodium 2-(4-(tert-butyl)-2,6-dimethylphenyl)malonate, lithium sodium 2,2-diphenylmalonate, lithium sodium 2-methyl-2-phenylmalonate, lithium sodium 2-ethyl-2-phenylmalonate, lithium sodium 2-phenyl-2-propylmalonate, lithium sodium 2-butyl-2-phenylmalonate, lithium sodium 2-pentyl-2-phenylmalonate, lithium sodium 2-hexyl-2-phenylmalonate, lithium sodium 2-heptyl-2-phenylmalonate, lithium sodium 2-octyl-2-phenylmalonate, lithium sodium 2-nonyl-2-phenylmalonate, lithium sodium 2-decyl-2-phenylmalonate, lithium sodium 2-phenyl-2-undecylmalonate, lithium sodium 2-dodecyl-2-phenylmalonate, lithium sodium 2-isopropyl-2-methylmalonate, lithium sodium 2,2-diisopropylmalonate, lithium sodium 2-isopropylmalonate, lithium sodium 2-(tert-butyl)malonate, lithium sodium 2-ditert-butylmalonate, lithium sodium 2-(tert-butyl)-2-methylmalonate, lithium sodium 2-(tert-butyl)-2-ethylmalonate, lithium sodium 2-ethyl-2-isopropylmalonate, lithium sodium 2-isopropyl-2-propylmalonate, lithium sodium 2-butyl-2-isopropylmalonate, lithium sodium 2-isopropyl-2-pentylmalonate, lithium sodium 2-hexyl-2-isopropylmalonate, lithium sodium 2-heptyl-2-isopropylmalonate, lithium sodium 2-isopropyl-2-octylmalonate, lithium sodium 2-isopropyl-2-nonylmalonate, lithium sodium 2-decyl-2-isopropylmalonate, lithium sodium 2-isopropyl-2-undecylmalonate, lithium sodium 2-(tert-butyl)-2-undecylmalonate, lithium sodium 2-(tert-butyl)-2-decylmalonate, lithium sodium 2-(tert-butyl)-2-nonylmalonate, lithium sodium 2-(tert-butyl)-2-octylmalonate, lithium sodium 2-(tert-butyl)-2-heptylmalonate, lithium sodium 2-(tert-butyl)-2-hexylmalonate, lithium sodium 2-(tert-butyl)-2-pentylmalonate, lithium sodium 2-(tert-butyl)-2-butylmalonate, lithium sodium 2-(tert-butyl)-2-propylmalonate, lithium sodium 2-(tert-butyl)-2-ethylmalonate, lithium sodium 2-(tert-butyl)-2-phenylmalonate, lithium sodium 2-isopropyl-2-phenylmalonate, lithium sodium 2-(sec-butyl)malonate, lithium sodium 2-(sec-butyl)-2-methylmalonate, lithium sodium 2-methyl-2-(pentan-2-yl)malonate, lithium sodium 2-(hexan-2-yl)-2-methylmalonate, lithium sodium 2-(heptan-2-yl)-2-methylmalonate, lithium sodium 2-methyl-2-(octan-2-yl)malonate, lithium sodium 2-methyl-2-(nonan-2-yl)malonate, lithium sodium 2-methyl-2-(octan-3-yl)malonate, lithium sodium 2-(octan-3-yl)-2-octylmalonate, lithium sodium 2-benzyl-2-methylmalonate, lithium sodium 2,2-dibenzylmalonate, lithium sodium 2-benzyl-2-ethylmalonate, lithium sodium 2-benzyl-2-isopropylmalonate, lithium sodium 2-benzyl-2-(tert-butyl)malonate, lithium sodium 2-cyclohexylmalonate, lithium sodium 2-cyclohexyl-2-methylmalonate, lithium sodium 2-cyclohexyl-2-ethylmalonate, lithium sodium 2-cyclohexyl-2-isopropylmalonate, lithium sodium 2-(tert-butyl)-2-cyclohexylmalonate, lithium sodium 2,2-dicyclohexylmalonate, lithium sodium 2-cyclohexyl-2-(pentan-3-yl)malonate, lithium sodium 2-ethylmalonate, lithium sodium 2-isopropylmalonate, lithium sodium 2-(tert-butyl)malonate, lithium sodium 2-propylmalonate, lithium sodium 2-butylmalonate, lithium sodium 2-pentylmalonate, lithium sodium 2-(2-methylpentyl)malonate, lithium sodium 2-(2-ethylpentyl)malonate, lithium sodium 2-(3-ethylhexan-2-yl)malonate, lithium sodium 2-hexylmalonate, lithium sodium 2-heptylmalonate, lithium sodium 2-octylmalonate, lithium sodium 2-nonylmalonate, lithium sodium 2-decylmalonate, lithium sodium 2-decyl-2-isopropylmalonate, lithium potassium 2,2-dimethylmalonate, lithium potassium 2,2-diethylmalonate, lithium potassium 2,2-dipropylmalonate, lithium potassium 2,2-dibutylmalonate, lithium potassium 2,2-dipentylmalonate, lithium potassium 2,2-dihexylmalonate, lithium potassium 2,2-diheptylmalonate, lithium potassium 2,2-dioctylmalonate, lithium potassium 2,2-dinonylmalonate, lithium potassium 2,2-didecylmalonate, lithium potassium 2,2-diundecylmalonate, lithium potassium 2,2-didodecylmalonate, lithium potassium 2-dodecyl-2-undecylmalonate, lithium potassium 2-decyl-2-dodecylmalonate, lithium potassium 2-dodecyl-2-nonylmalonate, lithium potassium 2-dodecyl-2-octylmalonate, lithium potassium 2-dodecyl-2-heptylmalonate, lithium potassium 2-dodecyl-2-hexylmalonate, lithium potassium 2-dodecyl-2-pentylmalonate, lithium potassium 2-butyl-2-dodecylmalonate, lithium potassium 2-dodecyl-2-propylmalonate, lithium potassium 2-dodecyl-2-ethylmalonate, lithium potassium 2-dodecyl-2-methylmalonate, lithium potassium 2-dodecylmalonate, lithium potassium 2-undecylmalonate, lithium potassium 2-decylmalonate, lithium potassium 2-nonylmalonate, lithium potassium 2-octylmalonate, lithium potassium 2-heptylmalonate, lithium potassium 2-hexylmalonate, lithium potassium 2-pentylmalonate, lithium potassium 2-butylmalonate, lithium potassium 2-propylmalonate, lithium potassium 2-ethylmalonate, lithium potassium 2-methylmalonate, lithium potassium 2-phenylmalonate, lithium potassium 2-(p-tolyl)malonate, lithium potassium 2-mesitylmalonate, lithium potassium 2-(4-(tert-butyl)phenyl)malonate, lithium potassium 2-(4-(tert-butyl)-2-methylphenyl)malonate, lithium potassium 2-(4-(tert-butyl)-2,6-dimethylphenyl)malonate, lithium potassium 2,2-diphenylmalonate, lithium potassium 2-methyl-2-phenylmalonate, lithium potassium 2-ethyl-2-phenylmalonate, lithium potassium 2-phenyl-2-propylmalonate, lithium potassium 2-butyl-2-phenylmalonate, lithium potassium 2-pentyl-2-phenylmalonate, lithium potassium 2-hexyl-2-phenylmalonate, lithium potassium 2-heptyl-2-phenylmalonate, lithium potassium 2-octyl-2-phenylmalonate, lithium potassium 2-nonyl-2-phenylmalonate, lithium potassium 2-decyl-2-phenylmalonate, lithium potassium 2-phenyl-2-undecylmalonate, lithium potassium 2-dodecyl-2-phenylmalonate, lithium potassium 2-isopropyl-2-methylmalonate, lithium potassium 2,2-diisopropylmalonate, lithium potassium 2-isopropylmalonate, lithium potassium 2-(tert-butyl)malonate, lithium potassium 2-ditert-butylmalonate, lithium potassium 2-(tert-butyl)-2-methylmalonate, lithium potassium 2-(tert-butyl)-2-ethylmalonate, lithium potassium 2-ethyl-2-isopropylmalonate, lithium potassium 2-isopropyl-2-propylmalonate, lithium potassium 2-butyl-2-isopropylmalonate, lithium potassium 2-isopropyl-2-pentylmalonate, lithium potassium 2-hexyl-2-isopropylmalonate, lithium potassium 2-heptyl-2-isopropylmalonate, lithium potassium 2-isopropyl-2-octylmalonate, lithium potassium 2-isopropyl-2-nonylmalonate, lithium potassium 2-decyl-2-isopropylmalonate, lithium potassium 2-isopropyl-2-undecylmalonate, lithium potassium 2-(tert-butyl)-2-undecylmalonate, lithium potassium 2-(tert-butyl)-2-decylmalonate, lithium potassium 2-(tert-butyl)-2-nonylmalonate, lithium potassium 2-(tert-butyl)-2-octylmalonate, lithium potassium 2-(tert-butyl)-2-heptylmalonate, lithium potassium 2-(tert-butyl)-2-hexylmalonate, lithium potassium 2-(tert-butyl)-2-pentylmalonate, lithium potassium 2-(tert-butyl)-2-butylmalonate, lithium potassium 2-(tert-butyl)-2-propylmalonate, lithium potassium 2-(tert-butyl)-2-ethylmalonate, lithium potassium 2-(tert-butyl)-2-phenylmalonate, lithium potassium 2-isopropyl-2-phenylmalonate, lithium potassium 2-(sec-butyl)malonate, lithium potassium 2-(sec-butyl)-2-methylmalonate, lithium potassium 2-methyl-2-(pentan-2-yl)malonate, lithium potassium 2-(hexan-2-yl)-2-methylmalonate, lithium potassium 2-(heptan-2-yl)-2-methylmalonate, lithium potassium 2-methyl-2-(octan-2-yl)malonate, lithium potassium 2-methyl-2-(nonan-2-yl)malonate, lithium potassium 2-methyl-2-(octan-3-yl)malonate, lithium potassium 2-(octan-3-yl)-2-octylmalonate, lithium potassium 2-benzyl-2-methylmalonate, lithium potassium 2,2-dibenzylmalonate, lithium potassium 2-benzyl-2-ethylmalonate, lithium potassium 2-benzyl-2-isopropylmalonate, lithium potassium 2-benzyl-2-(tert-butyl)malonate, lithium potassium 2-cyclohexylmalonate, lithium potassium 2-cyclohexyl-2-methylmalonate, lithium potassium 2-cyclohexyl-2-ethylmalonate, lithium potassium 2-cyclohexyl-2-isopropylmalonate, lithium potassium 2-(tert-butyl)-2-cyclohexylmalonate, lithium potassium 2,2-dicyclohexylmalonate, lithium potassium 2-cyclohexyl-2-(pentan-3-yl)malonate, lithium potassium 2-ethylmalonate, lithium potassium 2-isopropylmalonate, lithium potassium 2-(tert-butyl)malonate, lithium potassium 2-propylmalonate, lithium potassium 2-butylmalonate, lithium potassium 2-pentylmalonate, lithium potassium 2-(2-methylpentyl)malonate, lithium potassium 2-(2-ethylpentyl)malonate, lithium potassium 2-(3-ethylhexan-2-yl)malonate, lithium potassium 2-hexylmalonate, lithium potassium 2-heptylmalonate, lithium potassium 2-octylmalonate, lithium potassium 2-nonylmalonate, lithium potassium 2-decylmalonate, lithium potassium 2-decyl-2-isopropylmalonate, magnesium 2,2-dimethylmalonate, magnesium 2,2-diethylmalonate, magnesium 2,2-dipropylmalonate, magnesium 2,2-dibutylmalonate, magnesium 2,2-dipentylmalonate, magnesium 2,2-dihexylmalonate, magnesium 2,2-diheptylmalonate, magnesium 2,2-dioctylmalonate, magnesium 2,2-dinonylmalonate, magnesium 2,2-didecylmalonate, magnesium 2,2-diundecylmalonate, magnesium 2,2-didodecylmalonate, magnesium 2-dodecyl-2-undecylmalonate, magnesium 2-decyl-2-dodecylmalonate, magnesium 2-dodecyl-2-nonylmalonate, magnesium 2-dodecyl-2-octylmalonate, magnesium 2-dodecyl-2-heptylmalonate, magnesium 2-dodecyl-2-hexylmalonate, magnesium 2-dodecyl-2-pentylmalonate, magnesium 2-butyl-2-dodecylmalonate, magnesium 2-dodecyl-2-propylmalonate, magnesium 2-dodecyl-2-ethylmalonate, magnesium 2-dodecyl-2-methylmalonate, magnesium 2-dodecylmalonate, magnesium 2-undecylmalonate, magnesium 2-decylmalonate, magnesium 2-nonylmalonate, magnesium 2-octylmalonate, magnesium 2-heptylmalonate, magnesium 2-hexylmalonate, magnesium 2-pentylmalonate, magnesium 2-butylmalonate, magnesium 2-propylmalonate, magnesium 2-ethylmalonate, magnesium 2-methylmalonate, magnesium 2-phenylmalonate, magnesium 2-(p-tolyl)malonate, magnesium 2-mesitylmalonate, magnesium 2-(4-(tert-butyl)phenyl)malonate, magnesium 2-(4-(tert-butyl)-2-methylphenyl)malonate, magnesium 2-(4-(tert-butyl)-2,6-dimethylphenyl)malonate, magnesium 2,2-diphenylmalonate, magnesium 2-methyl-2-phenylmalonate, magnesium 2-ethyl-2-phenylmalonate, magnesium 2-phenyl-2-propylmalonate, magnesium 2-butyl-2-phenylmalonate, magnesium 2-pentyl-2-phenylmalonate, magnesium 2-hexyl-2-phenylmalonate, magnesium 2-heptyl-2-phenylmalonate, magnesium 2-octyl-2-phenylmalonate, magnesium 2-nonyl-2-phenylmalonate, magnesium 2-decyl-2-phenylmalonate, magnesium 2-phenyl-2-undecylmalonate, magnesium 2-dodecyl-2-phenylmalonate, magnesium 2-isopropyl-2-methylmalonate, magnesium 2,2-diisopropylmalonate, magnesium 2-isopropylmalonate, magnesium 2-(tert-butyl)malonate, magnesium 2-ditert-butylmalonate, magnesium 2-(tert-butyl)-2-methylmalonate, magnesium 2-(tert-butyl)-2-ethylmalonate, magnesium 2-ethyl-2-isopropylmalonate, magnesium 2-isopropyl-2-propylmalonate, magnesium 2-butyl-2-isopropylmalonate, magnesium 2-isopropyl-2-pentylmalonate, magnesium 2-hexyl-2-isopropylmalonate, magnesium 2-heptyl-2-isopropylmalonate, magnesium 2-isopropyl-2-octylmalonate, magnesium 2-isopropyl-2-nonylmalonate, magnesium 2-decyl-2-isopropylmalonate, magnesium 2-isopropyl-2-undecylmalonate, magnesium 2-(tert-butyl)-2-undecylmalonate, magnesium 2-(tert-butyl)-2-decylmalonate, magnesium 2-(tert-butyl)-2-nonylmalonate, magnesium 2-(tert-butyl)-2-octylmalonate, magnesium 2-(tert-butyl)-2-heptylmalonate, magnesium 2-(tert-butyl)-2-hexylmalonate, magnesium 2-(tert-butyl)-2-pentylmalonate, magnesium 2-(tert-butyl)-2-butylmalonate, magnesium 2-(tert-butyl)-2-propylmalonate, magnesium 2-(tert-butyl)-2-ethylmalonate, magnesium 2-(tert-butyl)-2-phenylmalonate, magnesium 2-isopropyl-2-phenylmalonate, magnesium 2-(sec-butyl)malonate, magnesium 2-(sec-butyl)-2-methylmalonate, magnesium 2-methyl-2-(pentan-2-yl)malonate, magnesium 2-(hexan-2-yl)-2-methylmalonate, magnesium 2-(heptan-2-yl)-2-methylmalonate, magnesium 2-methyl-2-(octan-2-yl)malonate, magnesium 2-methyl-2-(nonan-2-yl)malonate, magnesium 2-methyl-2-(octan-3-yl)malonate, magnesium 2-(octan-3-yl)-2-octylmalonate, magnesium 2-benzyl-2-methylmalonate, magnesium 2,2-dibenzylmalonate, magnesium 2-benzyl-2-ethylmalonate, magnesium 2-benzyl-2-isopropylmalonate, magnesium 2-benzyl-2-(tert-butyl)malonate, magnesium 2-cyclohexylmalonate, magnesium 2-cyclohexyl-2-methylmalonate, magnesium 2-cyclohexyl-2-ethylmalonate, magnesium 2-cyclohexyl-2-isopropylmalonate, magnesium 2-(tert-butyl)-2-cyclohexylmalonate, magnesium 2,2-dicyclohexylmalonate, magnesium 2-cyclohexyl-2-(pentan-3-yl)malonate, magnesium 2-ethylmalonate, magnesium 2-isopropylmalonate, magnesium 2-(tert-butyl)malonate, magnesium 2-propylmalonate, magnesium 2-butylmalonate, magnesium 2-pentylmalonate, magnesium 2-(2-methylpentyl)malonate, magnesium 2-(2-ethylpentyl)malonate, magnesium 2-(3-ethylhexan-2-yl)malonate, magnesium 2-hexylmalonate, magnesium 2-heptylmalonate, magnesium 2-octylmalonate, magnesium 2-nonylmalonate, magnesium 2-decylmalonate, magnesium 2-decyl-2-isopropylmalonate.

(7) In one of the feature of the present invention, the compound of formula I is selected from the group consisting of calcium 2,2-di-methylmalonate, magnesium 2,2-di-methylmalonate, barium 2,2-di-methylmalonate, lithium 2,2-di-methylmalonate, calcium 2,2-di-ethylmalonate, calcium 2-ethylmalonate, calcium 2-benzyl malonate, and calcium 2-methylmalonate.

(8) According to the further feature, the present invention also encompasses metal stearates conforming to formula (II),

(9) ##STR00004##

(10) In one of the feature of the present invention, the metal stearate is selected from divalent metal stearate having formula C.sub.36H.sub.70MO.sub.4, monovalent metal stearate having formula C.sub.18H.sub.35MO.sub.2, and trivalent metal stearate having formula C.sub.54H.sub.105MO.sub.6, wherein M is a metal and selected from magnesium, calcium, aluminium, lithium, and sodium.

(11) In another feature of the present invention, formula (II) is selected from calcium stearate (C.sub.36H.sub.70CaO.sub.4), magnesium stearate (C.sub.36H.sub.70MgO.sub.4), lithium stearate (C.sub.18H.sub.35LiO.sub.2), zinc stearate (C.sub.36H.sub.70ZnO.sub.4), sodium stearate (C.sub.18H.sub.35NaO.sub.2), and barium stearate (C.sub.36H.sub.70BaO.sub.4).

(12) According to the further feature, the present invention also encompasses metal oxides conforming to formula (III).
MO  (III)
wherein:
M can be trivalent metal cation of aluminium and similar; divalent metal cation of calcium, magnesium and similar; monobasic metal cation of sodium and similar. O represents oxide. In one of the feature of the present invention, formula (III) is selected from calcium oxide, magnesium oxide, lithium oxide, barium oxide, sodium oxide, aluminium oxide, potassium oxide, iron oxide, and zinc oxide.

(13) In preferred feature of the present invention, the metal stearate or metal oxide is added individually or as a mixture in the formulation with the above mentioned nucleator in an amount from about 1.0 percent to 90.0 percent by weight, in order to achieve desired results or characteristics. More preferably, the metal stearate or metal oxide is added individually or as a mixture in the formulation with the above mentioned nucleator in an amount from about 5.0 to about 70.0 percent by weight. Most preferably, the metal stearate or metal oxide is added individually or as a mixture in the formulation with the above mentioned nucleator in an amount from about 10.0 to 50.0 percent by weight.

(14) The inventive metal salts of malonic acid derivatives are thus added within the target thermoplastic in an amount from about 0.005 percent to 2.0 percent by weight in order to achieve desired results or characteristics. More preferably, metal salts of malonic acid derivatives are added within the target thermoplastic in an amount from about 0.01 to about 1.5 percent by weight. Most preferably, metal salts of malonic acid derivatives are added within the target thermoplastic in an amount from about 0.02 to 1.0 percent by weight.

(15) Metal salts of malonic acid derivatives may also be added in a polymer formulation in form of master-batch where it is desirable to include up to 50% or more of the active compound in a master-batch, although this is not a restriction.

(16) Within the formulation or the final thermoplastic article made containing metal salts of malonic acid derivatives, other additives may be included like antioxidant, antimicrobial agent, acid scavengers, antistatic compounds, chlorine scavengers, dispersing aids, stabilizers, ultraviolet absorbers, and other similar standard thermoplastic additives. These co-additives along with metal salts of malonic acid derivatives may be present as admixture in powder, liquid, or in compressed/pellet form for easy feeding.

(17) In one of the feature of the present invention, the antioxidant is selected from pentaerthrityl-tetrakis(3-(3,5′-di-tert-butyl-4-hydroxyphenyl)-propionate and tris(2,4-di-t-butyl-phenyl) phosphate.

(18) In another feature of the present invention, the antimicrobial agent is selected from 10,10′-oxybisphenoxarsine and n-octyl-isothiazolinone.

(19) In yet another feature of the present invention, the acid scavenger is selected from calcium stearates, hydrotalcites (Mg.sub.4Al.sub.2(OH).sub.12CO.sub.3.nH.sub.2O) and Mg.sub.6Al.sub.2 (OH).sub.16CO.sub.3.4H.sub.2O (supplied asDHT-4A, Kisuma). In one of the preferred feature of the present invention, the acid scavenger is Mg.sub.6Al.sub.2 (OH).sub.16CO.sub.3.4H.sub.2O.

(20) In yet another feature of the present invention, the antistatic compounds is selected from glycerol monostearate, and ethoxylated fatty acid amines.

(21) In yet another feature of the present invention, the dispersing aid is selected from polyolefin waxes, mineral oils, and stearate esters of glycerin.

(22) The compound thus obtained in accordance with the present invention may be added to polyolefin resin or formulation comprised of at least one semi crystalline polyolefin resin preferred examples include isotactic and syndiotactic polypropylene, polyethylene, poly(4-methyl-1-pentene), polybutylene, and any blends or copolymers thereof, whether high or low density in composition. The polyolefin polymers of the present invention may include aliphatic polyolefins and copolymers made from at least one aliphatic olefin and one or more ethylenically unsaturated co-monomers. Other polymers or rubber (such as ethylene propylene diene monomer (EPDM) or ethylene propylene rubber (EPR)) may also be compounded with the polyolefin. Other co-monomer examples include acrylic acid and vinyl acetate, etc. Formulation may include polymer such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), as well as polyamides such as Nylon 6, Nylon 66, and others.

(23) The present invention also provides a process for preparing a metal salt of malonic acid derivative, wherein the process comprising adding a malonic acid derivative in water and metal hydroxide to obtain a reaction mixture slurry and then heating the reaction mixture slurry to a temperature in the range of 20° C. to 120° C. along with continuous stirring for 5 min. to 10 hours to obtain a metal salt of malonic acid derivative.

(24) The present invention also provides a polymer additive comprising:

(25) (i) a component selected from metal stearate, metal oxide, and mixture thereof; and

(26) (ii) the metal salt of malonic acid derivative compound having chemical Formula (I),

(27) wherein the component (i) is present in an amount of from 1.0 percent to 90.0 percent by weight based on the total amount of the polymer additive.

(28) In one of the feature of the polymer additive of the present invention, the metal stearate is selected from the group comprising of divalent metal stearate having formula C.sub.36H.sub.70MO.sub.4, monovalent metal stearate having formula C.sub.18H.sub.35MO.sub.2, and trivalent metal stearate having formula C.sub.54H.sub.105MO.sub.6, wherein M is a metal and selected from magnesium, calcium, aluminium, lithium, and sodium.

(29) In one of the feature of the polymer additive of the present invention, the metal oxides conforming to formula (III)
MO  (III)
wherein M is selected from trivalent metal cation, divalent metal cation, and monobasic metal cation and O is oxide.

(30) The present invention also provides a thermoplastic composition comprising;

(31) (i) a polyolefin resin or polyolefin formulation; and

(32) (ii) the metal salt of malonic acid derivative compound having chemical formula (I),

(33) wherein the metal salt of malonic acid derivative is present in an amount from 0.005 percent to 2.0 percent by weight based on the amount of the thermoplastic composition.

(34) In one of the feature of the present invention, the thermoplastic composition optionally comprising the metal stearate and the metal stearate is selected from the group comprising of divalent metal stearate having formula C.sub.36H.sub.70MO.sub.4, monovalent metal stearate having formula C.sub.18H.sub.35MO.sub.2, and trivalent metal stearate having formula C.sub.54H.sub.105MO.sub.6, wherein M is a metal and selected from magnesium, calcium, aluminium, lithium, and sodium.

(35) In another feature of the present invention, the thermoplastic composition optionally comprising the metal oxide conforming to formula (III)
MO  (III)
wherein M is selected from trivalent metal cation, divalent metal cation, and monobasic metal cation and O is oxide.

(36) In one of the feature of the thermoplastic composition of the present invention, the polyolefin resin or polyolefin formulation comprises at least one semi crystalline polyolefin resin.

(37) In another feature of the present invention, the thermoplastic composition optionally comprising antioxidant, antimicrobial agent, acid scavenger, antistatic compound, chlorine scavenger, dispersing aid, stabilizer, ultraviolet absorber, and other similar standard thermoplastic additive.

(38) Generally, any thermoplastic composition having some degree of crystalline content may be improved with the nucleating agents of the present invention.

(39) The following non-limiting examples illustrate in details about the invention. However, they are not intended to be limiting the scope of present invention in any way.

General Synthesis Procedure of Metal Salt of Malonic Acid Derivative

(40) In a 2-neck flask with equipped with magnetic stirrer and was added malonic acid derivative in distilled water and metal hydroxide was added to the reaction mixture and then reaction mixture slurry was heated to 70° C. The stirring was continued for 5 hours. The white product was collected by suction filtration, washed thrice with water, and dried in a vacuum oven overnight at 90° C.

Example-1

General Synthesis Procedure of Calcium Salt of di-methyl malonic Acid (Calcium 2,2-di-methylmalonate)

(41) To a 500 mL 2-neck flask with equipped with magnetic stirrer and was added di-methylmalonic acid (5.0 g, 0.037 mol) in 250 ml of distilled water and calcium hydroxide (2.8 g, 0.038 mol) was added to the reaction mixture and then reaction mixture slurry was heated to 70° C. The stirring was continued for 5 hours, the mixture became quite thick, at which time the pH of the aqueous phase was found to be about 7. The white product was collected by suction filtration, washed thrice with water, and dried in a vacuum oven overnight at 90° C. Yield 98%.

Example-2

General Synthesis Procedure of Magnesium Salt of di-methyl malonic Acid (Magnesium 2,2-di-methylmalonate)

(42) To a 500 mL 2-neck flask with equipped with magnetic stirrer and was added di-methylmalonic acid (5.0 g, 0.037 mol) in 250 ml of distilled water and magnesium hydroxide (2.16 g, 0.038 mol) was added to the reaction mixture and then reaction mixture slurry was heated to 70° C. The stirring was continued for another 5 hours, the solvent was removed from rotoevaporator. After removal of the solvent, the final product obtained as white powder and dried in a vacuum oven overnight at 90° C. Yield 99%.

Example-3

General Synthesis Procedure of Barium Salt of di-methyl malonic Acid (Barium 2,2-di-methylmalonate)

(43) To a 500 mL 2-neck flask with equipped with magnetic stirrer and was added di-methylmalonic acid (5.0 g, 0.037 mol) in 250 ml of distilled water and barium hydroxide octahydrate (11.93 g, 0.038 mol) was added to the reaction mixture and then reaction mixture slurry was heated to 70° C. The stirring was continued for 5 hours, the mixture became quite thick, at which time the pH of the aqueous phase was found to be about 7. The white product was collected by suction filtration, washed thrice with water, and dried in a vacuum oven overnight at 90° C. Yield 95%.

Example-4

General Synthesis Procedure of Lithium Salt of di-methyl malonic Acid (Lithium 2,2-di-methylmalonate)

(44) To a 500 mL 2-neck flask with equipped with magnetic stirrer and was added di-methyl malonic acid (5.0 g, 0.037 mol) in 250 ml of distilled water and lithium hydroxide monohydrate (3.18 g, 0.075 mol) was added to the reaction mixture and then reaction mixture slurry was heated to 70° C. The stirring was continued for another 5 hours, the solvent was removed from rotoevaporator. After removal of the solvent, the final product obtained as white powder and dried in a vacuum oven overnight at 90° C. Yield 95%.

Example-5

General Synthesis Procedure of Calcium Salt of Malonic Acid (Comparative)

(45) To a 500 mL 2-neck flask with equipped with magnetic stirrer and was added malonic acid (5.0 g, 0.048 mol) in 250 ml of distilled water and calcium hydroxide (3.55 g, 0.048 mol) was added to the reaction mixture and then reaction mixture slurry was heated to 70° C. The stirring was continued for 5 hours, the mixture became quite thick, at which time the pH of the aqueous phase was found to be about 7. The white product was collected by suction filtration, washed thrice with water, and dried in a vacuum oven overnight at 90° C. Yield 98%.

Example-6

General Synthesis Procedure of Magnesium Salt of Malonic Acid (Comparative)

(46) To a 500 mL 2-neck flask with equipped with magnetic stirrer and was added malonic acid (5.0 g, 0.048 mol) in 250 ml of distilled water and magnesium hydroxide (2.8 g, 0.048 mol) was added to the reaction mixture and then reaction mixture slurry was heated to 70° C. The stirring was continued for another 5 hours at 70° C., the solvent was removed from rotoevaporator. After removal of the solvent, the final product obtained as white powder and dried in a vacuum oven overnight at 90° C. Yield 99%.

Example-7

General Synthesis Procedure of Reaction Between Calcium Salt of Malonic Acid and Pimelic Acid (Comparative)

(47) In a 250 mL 2-neck flask with equipped with magnetic stirrer and pimelic acid (dicarboxylic acid) 5.0 g was added in 50 ml of acetone and stirred for 1 hours to obtain clear solution. 5.0 g of calcium salt of malonic acid (5.0 g) was added to the solution and then reaction mixture slurry was heated to 40° C. The stirring was continued for 5 hours, the mixture became milky. The white product was collected by suction filtration, washed thrice with acetone to remove unreacted pimelic acid, and dried in a vacuum oven overnight at 90° C.

Example-8

General Synthesis Procedure of Reaction Between Calcium Salt of di-methyl Malonic Acid and Pimelic Acid (Comparative)

(48) In a 250 mL 2-neck flask with equipped with magnetic stirrer and pimelic acid (dicarboxylic acid) 5.0 g was added in 50 ml of acetone and stirred for 1 hours to obtain clear solution. 5.0 g of calcium salt of di-methyl malonic acid (5.0 g) was added to the solution and then reaction mixture slurry was heated to 40° C. The stirring was continued for 5 hours, the mixture became milky. The white product was collected by suction filtration, washed thrice with acetone to remove unreacted pimelic acid, and dried in a vacuum oven overnight at 90° C.

Example-9

General Synthesis Procedure of Calcium Salt of di-ethyl Malonic Acid (Calcium 2,2-di-ethylmalonate)

(49) To a 500 mL 2-neck flask with equipped with magnetic stirrer and was added di-ethyl malonic acid (4.0 g, 0.025 mol) in 200 ml of distilled water and calcium hydroxide (1.85 g, 0.025 mol) was added to the reaction mixture and then reaction mixture slurry was heated to 70° C. The stirring was continued for 5 hours, the mixture became quite thick, at which time the pH of the aqueous phase was found to be about 7. The white product was collected by suction filtration, washed thrice with water, and dried in a vacuum oven overnight at 90° C. Yield 95%.

Example-10

General Synthesis Procedure of Calcium Salt of Ethyl Malonic Acid (Calcium 2-ethylmalonate)

(50) To a 500 mL 2-neck flask with equipped with magnetic stirrer and was added ethyl malonic acid (1.5 g, 0.0114 mol) in 100 ml of distilled water and calcium hydroxide (0.85 g, 0.0114 mol) was added to the reaction mixture and then reaction mixture slurry was heated to 70° C. The stirring was continued for another 5 hours. The solvent was removed from rotoevaporator. After removal of the solvent, the final product obtained as white powder and dried in a vacuum oven overnight at 90° C. Yield 95%.

Example-11

General Synthesis Procedure of Calcium Salt of Benzyl Malonic Acid (Calcium 2-benzyl malonate)

(51) To a 500 mL 2-neck flask with equipped with magnetic stirrer and was added benzyl malonic acid (2.0 g, 0.010 mol) in 100 ml of distilled water and calcium hydroxide (0.76 g, 0.010 mol) was added to the reaction mixture and then reaction mixture slurry was heated to 70° C. The stirring was continued for another 5 hours. The solvent was removed from rotoevaporator. After removal of the solvent, the final product obtained as white powder and dried in a vacuum oven overnight at 90° C. Yield 95%.

Example-12

General Synthesis Procedure of Calcium Salt of Methyl Malonic Acid (Calcium 2-methylmalonate)

(52) To a 500 mL 2-neck flask with equipped with magnetic stirrer and was added methyl malonic acid (3.0 g, 0.0254 mol) in 150 ml of distilled water and calcium hydroxide (1.88 g, 0.0254 mol) was added to the reaction mixture and then reaction mixture slurry was heated to 70° C. The stirring was continued for another 5 hours, the mixture became quite thick, at which time the pH of the aqueous phase was found to be about 7. The white product was collected by suction filtration, washed thrice with water, and dried in a vacuum oven overnight at 90° C. Yield 95%.

(53) Recipes:

(54) All the mixtures were prepared of batch size of 2000 g (2 Kg), polypropylene was 1996.65 g whereas rest amounts constitutes all the additives (antioxidants, acid scavenger and metal salt of malonic acid derivates). Prior to extrusion, polymer and additives were homogeneous mixed using high speed mixer for 2 minutes. Mixtures 1-8 were prepared using polypropylene homopolymer (PP-HP) having WI (15 g/10 min) mixed with 0.35% pentaerthrityl-tetrakis(3-(3′,5′-di-tert-butyl-4-hydroxyphenyl)-propionate (supplied as Irganox 1010, Ciba SC), 0.70% tris(2,4-di-t-butyl-phenyl) phosphate (supplied as Irgafos 168, Ciba SC) and 0.375% calcium stearate (CaSt). In mixture 3, 0.375% of (Mg.sub.6Al.sub.2 (OH).sub.16CO.sub.3.4H.sub.2O) (supplied as DHT-4A, Kisuma) was added instead of calcium stearate. DHT-4A or calcium stearates are commonly used as acid scavengers in polyolefins. Various metal salts of malonic acid derivatives were added as in mixture 2-6 (synthesized as per procedure described above). Mixtures 7-8 were prepared for comparative purpose containing commercial nucleating agents HPN-20E (metal salt of Hexahydropthalic acid, supplied by Milliken Corporation) and sodium benzoate (NaBz) used in polyolefin industry. Mixtures 1-8 were extruded using a extruder (M/s. Labtech make twin screw extruder) at a melt temperature of 230° C. and injection molded at 230° C. (M/s. Toshiba Machine (India) Pvt. Ltd. make ASWA Injection molding machine). The obtained products were evaluated for their thermal-mechanical properties. Injection molded specimens were conditioned for 48 hrs at 55° C. and 23° C. prior to testing.

(55) TABLE-US-00001 EXPERIMENTAL TABLE 1 Inventive Nucleator performance in Homo polypropylene (15 MFI) @ 1000 ppm concentration Nucleator added Flexural Flexural Mixture (Example No. Nucleator Acid Haze Tc Tm.sub.α modulus modulus No. from above) Dosage scavenger (%) (° C.) (° C.) (Mpa) (std. dev.) 1 PP — CaSt 94.5 121.5 165.2 1220 18 2 1 1000 CaSt 72.1 131.8 166.3 1526 25 3 1 1000 DHT-4A 66.4 132.0 166.6 1557 13 4 2 1000 CaSt 78.8 130.0 165.8 1460 22 5 3 1000 CaSt 81.8 127.2 167.1 1379 07 6 4 1000 CaSt 73.7 130.3 165.8 1509 23 7 HPN-20E 1000 CaSt 73.8 129.4 167.0 1454 20 8 NaBz 1000 CaSt 82.4 127.1 166.0 1374 13

(56) From table above, inventive salts of malonic acid derivatives (mixture 2-4 & 6), exhibited higher peak crystallization temperature and flexural modulus. The haze values were relatively on lower side as compared to commercial nucleator sodium benzoate (NaBz). Thus the metal salts of malonic acid derivatives acts as effective α-nucleating agents.

(57) Mixtures 9-13 were prepared using polypropylene homopolymer (PP-HP) having MFI (15 g/10 min) mixed with 0.35% pentaerthrityl-tetrakis(3-(3′,5′-di-tert-butyl-4-hydroxyphenyl)-propionate (supplied as Irganox 1010, Ciba SC), 0.70% tris(2,4-di-t-butyl-phenyl) phosphate (supplied as Irgafos 168, Ciba SC) and 0.375% calcium stearate (CaSt). 2000 ppm of Calcium salt of di-methyl malonic acid (derivate of malonic acid) was added as part of mixture 10-11. Mixtures 12-13 were prepared for comparative purpose containing commercial nucleating agents used in polyolefin industry (HPN-20E and NA-27 supplied by M/s. Milliken Corporation and M/s. Adeka Corporation). In mixture 11, 0.375% of (Mg.sub.6Al.sub.2 (OH).sub.16CO.sub.3.4H.sub.2O) (supplied as DHT-4A, Kisuma) was added instead of calcium stearate.

(58) TABLE-US-00002 EXPERIMENTAL TABLE 2 Inventive Nucleator performance in Homo polypropylene (15 MFI) @ 2000 ppm concentration Nucleator added Nucleator Mixture (Example No. Dosage Acid Tc Tm.sub.α No. from above) (ppm) scavenger (° C.) (° C.) 9 PP — CaSt 121.5 165.2 10 1 2000 CaSt 133.1 165.4 11 1 2000 DHT-4A 131.5 166.5 12 HPN-20E 2000 CaSt 128.1 165.7 13 NA-27 2000 CaSt 130.9 166.5

(59) The peak crystallization temperature of polypropylene nucleated with inventive compound was found to be higher as compared to the commercial α-nucleating agents. Higher crystallization temperature corresponds to lower cycle time and higher productivity during molding or any other related process.

(60) Mixtures 14-17 were prepared using polypropylene homopolymer (PP-HP) having MFI (15 g/10 min) mixed with 0.35% pentaerthrityl-tetrakis(3-(3′,5′-di-tert-butyl-4-hydroxyphenyl)-propionate (supplied as Irganox 1010, Ciba SC), 0.70% tris(2,4-di-t-butyl-phenyl) phosphate (supplied as Irgafos 168, Ciba SC) and 0.375% calcium stearate (CaSt) containing calcium salt of different malonic acid derivatives. 2000 ppm of each inventive compound were added as part of each formulation. The peak crystallization temperature of polypropylene increased significantly when nucleated with inventive metal salts as mentioned in table-3.

(61) TABLE-US-00003 EXPERIMENTAL TABLE 3 Inventive Nucleator performance (metal salts of other malonic acid derivatives) in Homo polypropylene (15 MFI) @ 2000 ppm concentration Nucleator added Nucleator Mixture (Example No. Dosage Acid Tc Tm.sub.α No. from above) (ppm) scavenger (° C.) (° C.) 14  9 2000 CaSt 132.1 165.1 15 10 2000 CaSt 126.1 165.5 16 11 2000 CaSt 126.7 164.6 17 12 2000 CaSt 126.7 165.4

(62) Mixtures 18-20 were prepared using polypropylene homopolymer (PP-HP) having MFI (03 g/10 min) mixed with 0.35% pentaerthrityl-tetrakis(3-(3,5′-di-tert-butyl-4-hydroxyphenyl)-propionate (supplied as Irganox 1010, Ciba SC), 0.70% tris(2,4-di-t-butyl-phenyl) phosphate (supplied as Irgafos 168, Ciba SC) and 0.375% calcium stearate (CaSt). Calcium salt of di-methyl malonic acid was varied as 250 ppm, 500 ppm and 1000 ppm in respective mixtures as mentioned in table-4.

(63) TABLE-US-00004 EXPERIMENTAL TABLE 4 Inventive Nucleator performance in Homo polypropylene (03 MFI) @ 2000 ppm concentration Nucleator added Nucleator Mixture (Example No. Dosage Acid Tc Tm.sub.α No. from above) (ppm) scavenger (° C.) (° C.) 18 1 250 CaSt 132.0 166.2 19 1 500 CaSt 132.2 165.7 20 1 1000 CaSt 133.1 165.3

(64) The significant increase in the peak crystallization temperature of polypropylene having 03 MFI nucleated with varying concentration of inventive compound shows effectiveness as good α-nucleating agent.

(65) Mixtures 21-27 were prepared using polypropylene homopolymer (PP-HP) having MFI (15 g/10 min) mixed with 0.35% pentaerthrityl-tetrakis(3-(3,5′-di-tert-butyl-4-hydroxyphenyl)-propionate (supplied as Irganox 1010, Ciba SC), 0.70% tris(2,4-di-t-butyl-phenyl) phosphate (supplied as Irgafos 168, Ciba SC) and 0.375% calcium stearate (CaSt). 250 ppm of Calcium salt of di-methyl malonic acid was added as part of each mixture 21-27. Zinc stearate (metal stearate) and Zinc oxide (metal oxide) were varied as 10% to 30% as mentioned in table-5 below. Mixture 27 contain 50% each of zinc stearate and zinc oxide by wt. % of total 30%.

(66) TABLE-US-00005 EXPERIMENTAL TABLE 5 Inventive Nucleator performance (metal salts of malonic acid derivatives containing metal stearates and oxides) in Homo polypropylene (15 MFI) @ 250 ppm concentration Nucleator added Nucleator (Example No. from Dosage Acid Metal stearate/ Tc Tm.sub.α Mixture No. above) (ppm) scavenger oxide (%) (° C.) (° C.) 21 1 250 CaSt ZnSt (10%) 132.3 167.5 22 1 250 CaSt ZnSt (20%) 131.6 166.7 23 1 250 CaSt ZnSt (30%) 132.4 167.6 24 1 250 CaSt ZnO (10%) 132.4 168.3 25 1 250 CaSt ZnO (20%) 132.2 167.3 26 1 250 CaSt ZnO (30%) 132.5 167.6 27 1 250 CaSt ZnO: 50%::50% ZnSt 131.3 166.8 (30%)

(67) From table-5, with addition of metal stearate or metal oxide or their blend as part of the inventive compound concentration in polymer does not hinder the nucleation ability of the inventive compounds but acts as a dispersing agent.

(68) Mixtures 28-32 were prepared for comparison purpose using polypropylene homopolymer (PP-HP) having MFI (15 g/10 min) mixed with 0.35% pentaerthrityl-tetrakis(3-(3′,5′-di-tert-butyl-4-hydroxyphenyl)-propionate (supplied as Irganox 1010, Ciba SC), 0.70% tris(2,4-di-t-butyl-phenyl) phosphate (supplied as Irgafos 168, Ciba SC) and 0.375% calcium stearate (CaSt) containing 1000 ppm of calcium salt of different compounds as mentioned in table-6.

(69) TABLE-US-00006 COMPARATIVE EXPERIMENTAL TABLE 6 Nucleator performance in Homo polypropylene (15 MFI) @ 1000 ppm concentration Flexural Nucleator added Nucleator Flexural modulus Mixture (Example No. from Dosage Acid Haze Tc Tm.sub.α modulus (std. No. above) (ppm) scavenger (%) (° C.) (° C.) (Mpa) dev.) 28 PP — CaSt 94.5 121.5 165.2 1220 18 29 5 1000 CaSt 88.7 126.0 166.4 1193 10 30 6 1000 CaSt 96.3 123.1 166.0 1082 19 31 7 1000 CaSt — 125.1 165.6 — — 32 8 1000 CaSt — 129.4 165.1 — —

(70) As reported in J. Macromolecular science, Part B: Physics (47:900-912,2008), various metal salts of malonic acid acts as β-nucleating agent at 3000 ppm (0.3%) concentration in polypropylene matrix however the compounds 5-6 (calcium and magnesium salt of malonic acid, table-6) at 1000 ppm did not show any beta nucleation effect. No significant increase in flexural modulus and peak crystallization temperature was observed. The reason may be due to lower concentration being used or lower extrusion time as it was 2 min as mentioned in the research article. Calcium salts of malonic and di-methyl malonic acid were reacted with di-carboxylic acid (synthesis procedure described above). No beta nucleation effect was observed in polypropylene however there was improvement in the peak crystallization temperature (Tm.sub.α).

(71) Two gram of each compound as mentioned in table-7 were vacuum dried for 12 hrs and later placed in humidity chamber set at 60% for 05 days. Compounds were evenly spread on watch glass to give maximum surface area for moisture intake. Weight gained is reported as % moisture uptake in 05 days.

(72) TABLE-US-00007 EXPERIMENTAL TABLE 7 Hygroscopicity of Compounds Mixture Nucleator added % Water No. (Example No. from above) absorbed 33 1 0.37 34 NaBz (comparative) 0.83

(73) From table-7, it is clear that the inventive compound showed lower hygroscopicity.

(74) A mixture 36 containing 5000 ppm of calcium salt of di-methyl malonic acid was prepared for comparison purpose using Nylon-6 supplied by UBE industries (Grade-101-3B).

(75) TABLE-US-00008 EXPERIMENTAL TABLE 8 Inventive Nucleator performance in Nylon-6 @ 5000 ppm concentration Nucleator Mixture No. Nucleator added Dosage Tc Tm.sub.α above) (Example No. from (ppm) (° C.) (° C.) 35 Nylon-6 — 169.4 220.5 36 1 5000 188.0 220.7

(76) Nylon-6 nucleated with the inventive compound exhibited significant increase in peak crystallization temperature as compared to non-nucleated Nylon-6.

(77) From the inventive examples it has been found and confirmed that metal salts of malonic acid derivatives acts as efficient α-nucleating agent or Nucleator thereby increasing peak crystallization temperature by several degrees and flexural modulus and lower haze.

Abbreviations

(78) PP Polypropylene PP-HP Polypropylene Homopolymer DMMA Di-Methyl malonic acid MFI Melt flow index/rate Tm Melting temperature Tc Crystallization temperature NaBz Sodium Benzoate 9999ZnSt Zinc stearate ZnO Zinc Oxide CaSt Calcium stearate