General purpose plasticizers based on naphthalic acid diesters

Abstract

A diester of a fused ring compound of the formula (I): ##STR00001##
wherein: the fused rings are both aromatic; R1 and R4 to R6 substituents are H or ester moieties having C1 to C20 linear or branched alkyl chains; R2 and R3 are C(O)OCxHy, wherein x is from 10 to 12 and y is from 21 to 25; two adjacent R1 to R4 substituents are C(O)OCxHy, wherein x is from 10 to 12 and y is from 21 to 25; and when R3 and R4 are ester moieties, the alkyl chains of R4 are not C5 or C8; and polymer compositions containing the fused ring compound.

Claims

1. A diester of a fused ring compound of the formula (I): ##STR00033## wherein: the fused rings are both aromatic; R.sub.1 and R.sub.4 to R.sub.6 substituents are H or ester moieties having C.sub.1 to C.sub.20 linear or branched alkyl chains; R2 and R3 are C(O)OCxHy, wherein x is from 10 to 12 and y is from 21 to 25; two adjacent R.sub.1 to R.sub.4 substituents are C(O)OC.sub.xH.sub.y, wherein x is from 10 to 12 and y is from 21 to 25; and when R.sub.3 and R.sub.4 are ester moieties, the alkyl chains of R4 are not C.sub.5 or C.sub.8.

2. The diester of claim 1, wherein R.sub.1 is C(O)OC.sub.xH.sub.y, wherein x is from 10 to 12 and y is from 21 to 25.

3. The diester of claim 1, wherein R.sub.2 and R.sub.5 are C(O)OC.sub.xH.sub.y, wherein x is from 3 to 12 and y is from 7 to 25.

4. The diester of claim 1, wherein is C(O)OC.sub.xH.sub.y, wherein x is from 3 to 12 and y is from 7 to 25.

5. A method of making a naphthalic acid based diester having adjacent ester substituents, comprising: supplying a di-substituted naphthalene of the formula: ##STR00034## oxidizing the di-substituted naphthalene to form an anhydride intermediate of the formula: ##STR00035## and esterifying the anhydride intermediate with an alcohol, ROH, wherein R is a C.sub.1 to C.sub.20 linear or branched alkyl group, to form adjacent napthalic diesters of the formula: ##STR00036##

6. The method of claim 5, further comprising hydrogenating at least one of the fused rings to form diesters of the formula: ##STR00037##

7. A polymer composition comprising a thermoplastic polymer and at least one diester of a fused ring compound of claim 1, wherein the thermoplastic polymer is selected from the group consisting of vinyl chloride resins, polyesters, polyurethanes, ethylene-vinyl acetate copolymer, rubbers, and poly(meth)acrylics.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a graph showing the relative volatility of commercial plasticizers and the compound of Example 1.

(2) FIG. 2 is a graph displaying the flex onset for PVC blends made using the listed plasticizers.

(3) FIG. 3 is a graph displaying the relative efficiency of the tested plasticizers in PVC blends.

DETAILED DESCRIPTION

(4) All numerical values within the detailed description and the claims herein are modified by about or approximately the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.

(5) There is an increased interest in developing new plasticizers that are non-phthalates and which possess good plasticizer performance characteristics but are still competitive economically. The present disclosure is directed towards non-phthalate ester plasticizers, particularly OXO-ester plasticizers, that can be made from low cost feeds and employ fewer manufacturing steps in order to meet economic targets.

Definitions

(6) An OXO-ester is a compound having at least one functional ester moiety within its structure derived from esterification of either an acid or alcohol compound with an OXO-alcohol or OXO-acid, respectively.

(7) An OXO-alcohol is an organic alcohol, or mixture of organic alcohols, which is prepared by hydroformylating an olefin, followed by hydrogenation to form the alcohols. Typically, the olefin is formed by light olefin oligomerization over heterogenous acid catalysts, which olefins are readily available from refinery processing operations. The reaction results in mixtures of longer-chain, branched olefins, which subsequently form longer chain, branched alcohols, as described in U.S. Pat. No. 6,274,756, incorporated herein by reference in its entirety. The OXO-alcohols consist of multiple isomers of a given chain length due to the various isomeric olefins obtained in the oligomerization process, in tandem with the multiple isomeric possibilities of the hydroformylation step.

(8) An OXO-acid is an organic acid, or mixture of organic acids, which is prepared by hydroformylating an olefin, followed by oxidation to form the acids. Typically, the olefin is formed by light olefin oligomerization over heterogenous acid catalysts, which olefins are readily available from refinery processing operations. The reaction results in mixtures of longer-chain, branched olefins, which subsequently form longer-chain, branched acids. The OXO-acids similarly consist of multiple isomers of a given chain length.

(9) The purpose of the presently disclosed plasticizers is to replace the currently used, phthalate-based plasticizers with a non-phthalate alternative for the global general purpose plasticizer market. Esters of naphthalic acid are described and tested as general purpose plasticizers with properties rivaling commercially used DINP (diisononyl phthalate). The molecules presented are non-phthalates, yet show performance comparable to the currently deployed commercial technology. These plasticizers utilize di-esters of naphthalene as the base architecture for the plasticizer which offer good physical properties such as miscibility with PVC, clarity, non-volatility and low viscosity.

(10) The structures and positional numbering of the naphthalene-based plasticizers is shown below.

(11) ##STR00010##

(12) The ester substitutions can be located at any two positions on the rings, such as at the 1,4- or 2,6-positions, but adjacent positions are advantageous (e.g. 1,2-; 1,8-; 2,3-) with the 1,8-substitution being most advantageous. The core can be (N) naphthalene-based, partially hydrogenated to a tetralin-like core (T), or fully-hydrogenated to a decalin-like structure (D). Further, the ester functionality can be made from any alcohol from C.sub.1 to C.sub.20. The general structure of a 1,8-naphthalene diester is shown below:

(13) ##STR00011##
Advantageously, the low volatility of these naphthalene-based structures allows for the use of shorter-chain alcohols, such as isopropyl alcohol, to form the ester moiety. It has been found that shorter alcohol chains on these naphthalene-based structures actually result in more viscous materials.

(14) A preferred starting structure for the presently disclosed plasticizers is a di-methyl substituted naphthalene, which methyl groups are subsequently oxidized to form carboxylic acid substituents. It is advantageous if the methyl substituents are located at adjacent positions on the naphthalene core. The potential dimethyl naphthalenes useful for forming the naphthalene diester plasticizers of the present application are shown below, which are the 1,2-, 2,3- and 1,8-dimethyl substituted naphthalenes respectively.

(15) ##STR00012##

(16) The oxidation process of making the esters is less-complex and more cost-effective if the hydrocarbon feed proceeds through an anhydride intermediate rather than having to complete two sequential oxidations.

(17) ##STR00013##

(18) The multiple oxidation process is more difficult and requires special processing. As an example, the oxidation of para-xylene is more challenging than ortho-xylene for the same reason.

(19) ##STR00014##

(20) Further, the 1,8-diester substitution is interesting because each functionality is located on a different ring via a peri-substitution, which may significantly affect the toxicological behavior relative to phthalate-like ortho-type substitutions. Likewise, the 2,6-diester substitution has each functionality on different rings.

(21) An additional variation on this family of molecules is related to the aromatic core. The original naphthalene-based ester (N) can be hydrogenated such that only one ring becomes saturated (T) or both rings are saturated (D), so that all aromaticity is removed. Analogously to the change in performance observed in going from DINP to 1,2-cyclohexane dicarboxylic acid diisononyl esters (DINCH), ring hydrogenation improves toxicology and allows for tuning of plasticizer performance.

(22) ##STR00015##

(23) For example, the diesters of the present application can be those of the formula (I) below:

(24) ##STR00016##
wherein the R.sub.1 to R.sub.6 substituents are H or ester moieties having C.sub.1 to C.sub.20 linear or branched alkyl chains, but when both fused rings are aromatic and R.sub.3 and R.sub.4 are ester moieties, the alkyl chains are not C.sub.5 or C.sub.8. The diesters of formula (I) can be those wherein both rings are aromatic rings, such as naphthalene.

(25) Alternatively, the diesters can be those of formula (II) below:

(26) ##STR00017##
wherein the R.sub.1 to R.sub.6 substituents are H or ester moieties having C.sub.1 to C.sub.20 linear or branched alkyl chains.

(27) In another form, the diesters of the present application can be those of formula (III) below:

(28) ##STR00018##
wherein the R.sub.1 to R.sub.6 substituents are H or ester moieties having C.sub.1 to C.sub.20 linear or branched alkyl chains.

(29) Advantageously, the alkyl chains can be C.sub.1 to C.sub.20 alkyl chains, or even C.sub.3 to C.sub.18 alkyl chains, or even C.sub.3 to C.sub.12 alkyl chains. In all instances, the alkyl chains can be linear or branched alkyls. The ester moieties are formed by reacting the carboxylic acid substituents on the rings with linear or branched alcohols, such as OXO-alcohols, under esterification conditions.

(30) In one form, R.sub.1 and R.sub.2 are C(O)OC.sub.xH.sub.y, wherein x is from 3 to 12 and y is from 7 to 25, or R.sub.2 and R.sub.3 are C(O)OC.sub.xH.sub.y, wherein x is from 3 to 12 and y is from 7 to 25, or R.sub.3 and R.sub.4 are C(O)OC.sub.xH.sub.y, wherein x is from 3 to 12 and y is from 7 to 25, or wherein R.sub.2 and R.sub.5 are C(O)OC.sub.xH.sub.y, wherein x is from 3 to 12 and y is from 7 to 25, or wherein R.sub.3 and R.sub.6 are C(O)OC.sub.xH.sub.y, wherein x is from 3 to 12 and y is from 7 to 25, except when both fused rings are aromatic, x is not 5 or 8. It can be advantageous if two adjacent R.sub.1 to R.sub.4 substituents are ester moieties.

(31) In another form the present application discloses a method of making a naphthalic acid based diester having adjacent ester substituents, comprising supplying a di-substituted naphthalene of the formula:

(32) ##STR00019##

(33) oxidizing the di-substituted naphthalene over a catalyst to form an anhydride intermediate of the formula:

(34) ##STR00020##
and
esterifying the anhydride intermediate with an alcohol, ROH, wherein R is a C.sub.1 to C.sub.20 linear or branched alkyl group, to form adjacent napthalic diesters of the formula:

(35) ##STR00021##

(36) In another form, 1,8-naphthalic anhydride can be prepared by oxidizing acenaphthene or acenaphthylene, which occur naturally in coal tar, as follows:

(37) ##STR00022##

(38) The method can further comprise hydrogenating at least one of the fused rings to form diesters of the formula:

(39) ##STR00023##

(40) In another form the application is directed to a polymer composition comprising a thermoplastic polymer and at least one plasticizer of the formula (I):

(41) ##STR00024##
wherein the R.sub.1 to R.sub.6 substituents are H or ester moieties having C.sub.1 to C.sub.20 linear or branched alkyl chains, but when both fused rings are aromatic and R.sub.3 and R.sub.4 are ester moieties, the alkyl chains are not C.sub.5 or C.sub.8. Suitable thermoplastic polymers include vinyl chloride resins, polyesters, polyurethanes, ethylene-vinyl acetate copolymer, rubbers, poly(meth)acrylics and combinations thereof.

EXAMPLES

Example 1: Preparation of 1,8-Naphthalenedicarboxylic Acid, Didecyl Ester

(42) A 1000-mL 3-neck round bottom fitted with a Dean-Stark apparatus was charged with 1,8-naphthalic anhydride (10.0 g, 50.46 mmol), 1-decanol (300 mL, 1571 mmol), xylenes (200 mL), and p-toluenesulfonic acid monohydrate (0.96 g, 5.05 mmol). The solution was refluxed under a dry nitrogen atmosphere for 48 h after which only a trace of anhydride was detected by TLC (20% EtOAc/hexanes). The reaction was concentrated under high vacuum (<1 Torr) to 27.73 g crude product as an amber colored oil that was 85% pure by GC (approx. 94% yield). Impurities identified by .sup.1H NMR were didecyl ether (major) and decyl p-toluenesulfonate. The crude material was combined with other preparations and purified by automated column chromatography (2) in 3-5 g batches producing approximately 1.5-3 g of purified material (99+% by .sup.1H NMR) each run as a light yellow oil (Biotage, 100 g SNAP ultra, 0-5% EtOAc/hexanes). To further reduce color the accumulated purified product (23.5 g) was dissolved in hexane (200 mL), stirred with decolorizing carbon (2 g) for 2 h, filtered through a silica gel plug, and concentrated under high vacuum (<1 Torr) at 105 C. for 2 h to remove all volatiles.

(43) The 1,8-naphthalenedicarboxylic acid, didecyl ester was blended into PVC and tested in several primary screens (viscosity, volatility, flex onset, thermal stability and efficiency). The viscosity, volatility and thermal stability of this complex was measured to be better than the industry standard (DOP and DINP). The Table below compares the viscosities of various commercially available plasticizers and of the Example 1 plasticizer.

(44) TABLE-US-00001 Plasticizer Viscosity @ 334.4 sec.sup.1 Diisononylphthalate (DINP) 81.3 Diisononylcyclohexane (DINCH) 50.5 Dioctylphthalate (DOP) 86 1,8-naphthalenedicarboxylic acid, didecyl 75.1 ester (Ex. 1)

(45) FIG. 1 is a graph showing the relative volatility of the commercial plasticizers and the compound of Example 1. The larger-sized core of Example 1 (C.sub.10) compared to the commercial plasticizers (C.sub.6) is likely the reason for the significant reduction in volatility. This is a very important feature in commercial applications and the very low value for 1,8-naphthalenedicarboxylic acid, didecyl ester permits optimizing structural changes, such as use of shorter side-chains to improve other properties while maintaining an attractive low volatility. For example, butyl or isopropyl alcohols are too short for the conventional phthalate-based plasticizers but the low volatility of 1,8-naphthalenedicarboxylic acid, didecyl ester allows for significant give-away and should allow the use of cheaper alcohol feedstocks.

(46) In accelerated thermal testing the blended Example 1/PVC bars did not exhibit any exudation during testing. This implies that the Example 1 plasticizer has good miscibility with PVC and does not phase segregate. Further, it was found that that the molecule does not thermally decompose (i.e. 50 wt. % loss) until 279 C.; as compared to 299 C. for DINP.

(47) FIG. 2 is a graph displaying the flex onset for PVC blends made using the listed plasticizers. The flex onset is a measure of the low temperature performance of the PVC blends. A lower value is better as the blends can be used in colder applications without any degradation of product performance. The Example 1 plasticizer slightly under performs the commercial controls, but optimization with other alcohols, such as OXO-alcohols, could achieve better low temperature flex.

(48) FIG. 3 is a graph displaying the relative efficiency of the tested plasticizers in PVC blends. The efficiency is a relative measure of how much material is required to achieve a flexible PVC blend. The efficiency of DOP is set as 1.0.

(49) PCT/EP Clauses

(50) 1. A diester of a fused ring compound of the formula (I):

(51) ##STR00025##
wherein the R.sub.1 to R.sub.6 substituents are H or ester moieties having C.sub.1 to C.sub.20 linear or branched alkyl chains, but when both fused rings are aromatic and R.sub.3 and R.sub.4 are ester moieties, the alkyl chains are not C.sub.5 or C.sub.8.

(52) 2. The diester of clause 1, wherein the fused rings are both aromatic, or wherein only one of the fused rings is aromatic, or wherein neither fused ring is aromatic.

(53) 3. The diester of either one of clauses 1 or 2, wherein R.sub.1 and R.sub.2 are C(O)OC.sub.xH.sub.y, wherein x is from 3 to 12 and y is from 7 to 25, or wherein R.sub.2 and R.sub.3 are

(54) C(O)OC.sub.xH.sub.y, wherein x is from 3 to 12 and y is from 7 to 25, or wherein R.sub.3 and R.sub.4 are

(55) C(O)OC.sub.xH.sub.y, wherein x is from 3 to 12 and y is from 7 to 25, or wherein R.sub.2 and R.sub.5 are

(56) C(O)OC.sub.xH.sub.y, wherein x is from 3 to 12 and y is from 7 to 25, or wherein R.sub.3 and R.sub.6 are

(57) C(O)OC.sub.xH.sub.y, wherein x is from 3 to 12 and y is from 7 to 25, except that when both fused rings are aromatic, x is not 5 or 8.

(58) 4. The diester of any one of clauses 1 to 3, wherein two adjacent R.sub.1 to R.sub.4 substituents are said ester moieties.

(59) 5. A diester of a fused ring compound of the formula (II):

(60) ##STR00026##
wherein the R.sub.1 to R.sub.6 substituents are H or ester moieties having C.sub.1 to C.sub.20 linear or branched alkyl chains.

(61) 6. The diester of clause 5, wherein R.sub.1 and R.sub.2 are

(62) C(O)OC.sub.xH.sub.y, wherein x is from 3 to 12 and y is from 7 to 25, or wherein R.sub.2 and R.sub.3 are

(63) C(O)OC.sub.xH.sub.y, wherein x is from 3 to 12 and y is from 7 to 25, or wherein R.sub.3 and R.sub.4 are

(64) C(O)OC.sub.xH.sub.y, wherein x is from 3 to 12 and y is from 7 to 25, or wherein R.sub.2 and R.sub.5 are

(65) C(O)OC.sub.xH.sub.y, wherein x is from 3 to 12 and y is from 7 to 25, or wherein R.sub.3 and R.sub.6 are

(66) C(O)OC.sub.xH.sub.y, wherein x is from 3 to 12 and y is from 7 to 25.

(67) 7. The diester of either of clauses 5 or 6, wherein two adjacent R.sub.1 to R.sub.4 substituents are said ester moieties.

(68) 8. A diester of a fused ring compound of the formula (III):

(69) ##STR00027##
wherein the R.sub.1 to R.sub.6 substituents are H or ester moieties having C.sub.1 to C.sub.20 linear or branched alkyl chains.

(70) 9. The diester of clause 8, wherein R.sub.1 and R.sub.2 are

(71) C(O)OC.sub.xH.sub.y, wherein x is from 3 to 12 and y is from 7 to 25, or wherein R.sub.2 and R.sub.3 are

(72) C(O)OC.sub.xH.sub.y, wherein x is from 3 to 12 and y is from 7 to 25, or wherein R.sub.3 and R.sub.4 are

(73) C(O)OC.sub.xH.sub.y, wherein x is from 3 to 12 and y is from 7 to 25, or wherein R.sub.2 and R.sub.5 are

(74) C(O)OC.sub.xH.sub.y, wherein x is from 3 to 12 and y is from 7 to 25, or wherein R.sub.3 and R.sub.6 are

(75) C(O)OC.sub.xH.sub.y, wherein x is from 3 to 12 and y is from 7 to 25.

(76) 10. The diester of either of clauses 8 or 9, wherein two adjacent R.sub.1 to R.sub.4 substituents are said ester moieties.

(77) 11. A method of making a naphthalic acid based diester having adjacent ester substituents, comprising:

(78) supplying a di-substituted naphthalene of the formula:

(79) ##STR00028##

(80) oxidizing the di-substituted naphthalene to form an anhydride intermediate of the formula:

(81) ##STR00029##
and
esterifying the anhydride intermediate with an alcohol, ROH, wherein R is a C.sub.1 to C.sub.20 linear or branched alkyl group, to form adjacent napthalic diesters of the formula:

(82) ##STR00030##

(83) 12. The method of clause 11, further comprising hydrogenating at least one of the fused rings to form diesters of the formula:

(84) ##STR00031##

(85) 13. A polymer composition comprising a thermoplastic polymer and at least one plasticizer of the formula (I):

(86) ##STR00032##
wherein the R.sub.1 to R.sub.6 substituents are H or ester moieties having C.sub.1 to C.sub.20 linear or branched alkyl chains, but when both fused rings are aromatic and R.sub.3 and R.sub.4 are ester moieties, the alkyl chains are not C.sub.5 or C.sub.8.

(87) 14. The polymer composition of clause 13, wherein the thermoplastic polymer is selected from the group consisting of vinyl chloride resins, polyesters, polyurethanes, ethylene-vinyl acetate copolymer, rubbers, poly(meth)acrylics and combinations thereof.

INDUSTRIAL APPLICABILITY

(88) The systems and methods disclosed herein are applicable to the polymer industry. It is believed that the disclosure set forth above encompasses multiple distinct inventions with independent utility. While each of these inventions has been disclosed in its preferred form, the specific embodiments thereof as disclosed and illustrated herein are not to be considered in a limiting sense as numerous variations are possible. The subject matter of the inventions includes all novel and non-obvious combinations and subcombinations of the various elements, features, functions and/or properties disclosed herein. Similarly, where the claims recite a or a first element or the equivalent thereof, such claims should be understood to include incorporation of one or more such elements, neither requiring nor excluding two or more such elements.

(89) It is believed that the following claims particularly point out certain combinations and subcombinations that are directed to one of the disclosed inventions and are novel and non-obvious. Inventions embodied in other combinations and subcombinations of features, functions, elements and/or properties may be claimed through amendment of the present claims or presentation of new claims in this or a related application. Such amended or new claims, whether they are directed to a different invention or directed to the same invention, whether different, broader, narrower, or equal in scope to the original claims, are also regarded as included within the subject matter of the inventions of the present disclosure.