Glycerin triester plasticizer

Details Glycerin triester plasticizer Glycerin triester plasticizer

2002-12-09

2004-05-25

Anthony, Joseph D. (Department: 1714)

Compositions

Compositions containing a single chemical reactant or plural...

Organic reactant

C252S182130, C560S008000, C560S055000, C560S124000, C560S174000, C560S189000

Reexamination Certificate

active

06740254

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of Invention
The present invention provides a plasticizer for polymer resins, and more particularly, a phthalate-free plasticizer for polymer resins comprising a mixture of different triesters of glycerin, and a method of making the same.
2. Description of Related Art
Plasticizers are compounds or mixtures of compounds that are added to polymer resins to impart softness and flexibility. Phthalic acid diesters, which are also called phthalates, are the primary plasticizers for most flexible polymer products, especially polymer products formed from polyvinyl chloride (PVC) and other vinyl polymers. Examples of common phthalate plasticizers include, for example, di-isononyl phthalate (DINP), diallyl phthalate (DAP), and di-2-ethylhexyl-phthalate (DEHP).
Although phthalate plasticizers have been tested for more than 40 years and are among the most studied and best understood compounds in the world from a health and environmental perspective, phthalate plasticizers have recently come under intense scrutiny by public interest groups that are concerned about the potential of adverse health effects in children exposed to these chemicals. Consequently, there is a demand for phthalate-free plasticizers that provide the same properties when added to polymer resins such as, for example, vinyl polymers, rubbers, polyurethanes, and acrylics.
BRIEF SUMMARY OF THE INVENTION
The present invention provides a phthalate-free plasticizer for polymer resins and a method of making the same. A phthalate-free plasticizer according to the present invention comprises a mixture of different triesters of glycerin, at least one of which meets the formula:
 CH
2
(OOR
1
)CH(OOR
2
)CH
2
(OOR
3
)
wherein at least two of R
1
, R
2
, and R
3
are different alkyl or aryl groups. In a preferred embodiment, R
1
, R
2
, and R
3
each contain up to about 11 carbon atoms, and more preferably from about 2 to about 11 carbon atoms each.
The phthalate-free plasticizer according to the present invention is very compatible with a wide variety of polymers including vinyl polymers, rubbers, polyurethanes, and acrylics. In addition, the phthalate-free plasticizer according to the invention has superb thermostability and low volatility.
The phthalate-free plasticizer according to the invention can be made by heating glycerin and a mixture of at least two different acids in the presence of a catalyst to form a mixture of different triesters of glycerin, at least one of which meets the formula:
CH
2
(OOR
1
)CH(OOR
2
)CH
2
(OOR
3
)
wherein at least two of R
1
, R
2
, and R
3
are different alkyl or aryl groups. In a preferred embodiment, the glycerin and mixture of acids are heated while under a partial vacuum to assist in the removal of water.
The foregoing and other features of the invention are hereinafter more fully described and particularly pointed out in the claims, the following description setting forth in detail certain illustrative embodiments of the invention, these being indicative, however, of but a few of the various ways in which the principles of the present invention may be employed.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a phthalate-free plasticizer for polymer resins. As used in the instant specification in the appended claims, the term “phthalate-free” means that the plasticizer does not contain any phthalate diesters, which are also known in the art simply as phthalates.
A phthalate-free plasticizer according to the invention comprises a mixture of different triesters of glycerin, at least one of which meets the formula:
CH
2
(OOR
1
)CH(OOR
2
)CH
2
(OOR
3
)
wherein at least two of R
1
, R
2
, and R
3
are different alkyl or aryl groups. In other words, R
1
and R
2
can be the same but R
3
must be different, or R
1
and R
3
can be the same but R
2
must be different, or R
2
and R
3
can be the same but R
1
must be different. Preferably, R
1
, R
2
, and R
3
each contain up to about 11 carbon atoms, and more preferably from about 2 to about 9 carbon atoms each.
A phthalate-free plasticizer according to the invention can be formed by the process of esterifying glycerin with a mixture comprising at least two different acids to form a mixture of different triesters of glycerin. The acids comprising the mixture are preferably a mixture of alkyl acids and aryl acids.
The alkyl carboxylic acids used in the mixture can (but need not) be halogenated. Such acids can be linear, branched, or have cyclic moieties. Preferably, the alkyl carboxylic acids contain up to about 11 carbon atoms, or from about 2 to about 11 carbon atoms, or more preferably from about 4 to about 9 carbon atoms. Suitable alkyl acids include, for example, acetic acid, bromoacetic acid, propanoic acid, 2-chloropropanoic acid, 3-chloropropanoic acid, butanoic acid, 2-methylpropanoic acid, 2-ethylpropanoic acid, pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, 2-ethylbutanoic acid, 2,2-dimethylbutanoic acid, 2,3-dimethylbutanoic acid, 3,3-dimethylbutanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid, 4-methylpentanoic acid, hexanoic, cyclopentyl acetic acid, cyclopentyl propanoic acid, cyclopentyl hexanoic acid, cyclohexane carboxylic acid, cyclohexane acetic acid, 2-ethylhexanoic acid, nonadecafluorodecanoic acid, decanoic acid, and undecanoic acid.
The aryl carboxylic acids used in the mixture have one are more aromatic rings. Such acids can (but need not) be substituted, with one or more aromatic hydrogens being replaced by alkyl, halogen, ether, and/or ketone substituent groups. Suitable aryl acids include, for example, benzoic acid, 2-methylbenzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, 2-ethylbenzoic acid, 3-ethylbenzoic acid, 4-ethylbenzoic acid, 4-isopropylbenzoic acid, 4-tertiary butylbenzoic acid, 4-(1-methylpropyl)benzoic acid, 2-ethoxybenzoic acid, 3,4-dimethoxybenzoic acid, 4-methoxy-2-methylbenzoic acid, 4-acetylbenzoic acid, acetylmandelic acid, 2-chlorobenzoic acid, 3-chlorobenzoic acid, 4-chlorobenzoic acid, 2,3-dibromobenzoic acid, 2,4-di-iodobenzoic acid, 2,6-dibrombenzoic acid, 3,4-dibromobenzoic acid, 3,5-dichlorobenzoic acid, 2,3,5-tribromobenzoic acid, 2,4,6-trichlorobenzoic acid, 2,3,4,5,6-pentabromobenzoic acid, 1-naphthoic acid, 2-naphthoic acid, 4-biphenyl carboxylic acid, 2-biphenyl carboxylic acid, 4-biphenyl acetic acid, furfuryl carboxylic acid, and 3-pyridinecarboxylic acid.
In order to fully esterify one mole of gylcerin, three moles of acids are needed. In the preferred embodiment of the invention, for every mole of gylcerin that is esterified, a three mole mixture of different acids is used. Preferably, the three mole mixture of different acids comprises from about 0.5 to about 2.5 moles of an alkyl acid and from about 0.5 to about 2.5 moles of an aryl acid. It will be appreciated that in excess of three moles of different acids can be charged to the reactor for every mole of glycerin to be esterified, but only three moles of acids per mole of glycerin will actually participate in the reaction. A particularly preferable mixture of acids comprises 1.25 moles an alkyl acid (e.g., butanoic acid) and 1.75 moles of an aryl acid (e.g., benzoic acid) per mole of gylcerin esterified.
It will be appreciated that when the mixture of acids comprises a blend of only two different acids (e.g., R
1
OOH and R
2
OOH), as many as six different glycerin triesters may be present in the resulting product: (e.g., CH
2
(OOR
1
)CH(OOR
1
)CH
2
(OOR
1
); CH
2
(OOR
1
)CH(OOR
1
)CH
2
(OOR
2
); CH
2
(OOR
1
)CH(OOR
2
)CH
2
(OOR
1
); CH
2
(OOR
2
)CH(OOR
2
)CH
2
(OOR
1
); CH
2
(OOR
2
)CH(OOR
1
)CH
2
(OOR
2
); and CH
2
(OOR
2
)CH(OOR
2
)CH
2
(OOR
2
). And, when the mixture of acids comprises a blend of three different acids (e.g., R
1
OOH, R
2
OOH, and R
3
OOH), as many as eighteen different glycerin triesters may be present in the resulting product: (e.g., CH
2
(OOR
1
)CH(OOR
1
)CH
2
(OOR
1
); CH
2
(OOR
1
)CH(OOR
1
)CH
2
(OOR
2
); CH
2
(OOR
1
)CH(OOR
2
)CH
2
(OOR
1
); CH
2
(OOR
2
)CH(OOR
2
)CH
2
(OOR
1
); CH
2
(OOR
2
)CH(OOR
1
)CH
2
(OOR
2

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