Polytrimethylene ether ester amide and use thereof

Details Polytrimethylene ether ester amide and use thereof Polytrimethylene ether ester amide and use thereof

2002-02-11

2003-07-08

Hightower, P. Hampton (Department: 1711)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

From carboxylic acid or derivative thereof

C528S271000, C528S272000, C528S288000, C528S292000, C528S301000, C528S323000, C525S411000, C525S419000, C525S420000, C428S221000, C428S357000, C428S364000, C428S394000, C428S395000, C428S474400, C428S480000, C442S327000, C442S181000, C442S324000

Reexamination Certificate

active

06590065

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The field of this invention is polyether ester amides and their use.
2. Description of Related Art
Thermoplastic elastomers (TPE) are a class of polymers which combine the properties of two other classes of polymers, namely thermoplastics which may be reformed upon heating, and elastomers which are rubber-like polymers. One form of TPE is a block polymer, usually containing some blocks whose polymer properties usually resemble those of thermoplastics, and some blocks whose properties usually resemble those of elastomers. Those blocks whose properties resemble thermoplastics are often referred to as “hard” segments, while those blocks whose properties resemble elastomers are often referred to as “soft” segments. In such TPEs, the hard segments are believed to take the place of chemical crosslinks in traditional thermosetting elastomers, while the soft segments provide the rubber-like properties. Improved thermoplastic elastomers, particularly those with improved elastomeric properties such as high tenacity, elongation and unload power, and low tensile set, have been desired for use in fibers and other shaped articles.
Polyether ester amide block polymers prepared from polyether glycol and polyamide with carboxyl end groups are known. These polymers have been prepared using polyethylene glycol, polypropylene glycol, polytetramethylene glycol, copolyethers derived therefrom, and copolymers of THF and 3-alkylTHF as shown by U.S. Pat. Nos. 4,230,838, 4,252,920, 4,349,661, 4,331,786 and 6,300,463, all of which are incorporated herein by reference. The general structure may be represented by the following formula (I):
represents a polyamide segment containing terminal carboxyl groups or acid equivalents thereof (e.g., diacid anhydrides, diacid chlorides or diesters) and
—O—G—O—  (III)
is a polyether segment.
Poly ether ester amides prepared using poly(ethylene glycol) have the disadvantage that they absorb considerable amounts of moisture. Polypropylene glycol as described in the aforementioned patents refers to the polyether glycol derived from 1,2-propylene oxide. Polymerizations using polypropylene glycol generally proceed slowly due to the presence of sterically-hindered secondary hydroxyl groups. The extended periods of time for which these polymers are held at elevated temperatures can lead to thermal decomposition and discoloration. Polytetramethylene ether ester amide block polymers are easy to prepare, and thus they have been used to prepare fibers with elastomeric properties. Polyether ester amide elastomers derived from copolymers of tetrahydrofuran (THF) and 3-methylTHF are relatively new and have been found to have excellent physical properties, particularly high unload power and elastic recovery (lower tensile set) after stretching.
None of the aforementioned patents describe preparing polyether ester amide elastomers from polytrimethylene ether glycol. It has unexpectedly been found that polytrimethylene ether ester amides provide improved elastomeric properties over polytetramethylene ether ester amide block polymers and polyether ester amide elastomers derived from copolymers of tetrahydrofuran (THF) and 3-methylTHF. Particularly noteworthy are improvements in elongation and tensile set.
SUMMARY OF THE INVENTION
The invention is directed to polytrimethylene ether ester amide and its use.
The polyamide segment preferably has an average molar mass of at least about 300, more preferably at least about 400. Its average molar mass is preferably up to about 5,000, more preferably up to about 4,000 and most preferably up to about 3,000.
The polytrimethylene ether segment has an average molar mass of at least about 800, more preferably at least about 1,000 and more preferably at least about 1,500. Its average molar mass is preferably up to about 5,000, more preferably up to about 4,000 and most preferably up to about 3,500.
The polytrimethylene ether ester amide preferably comprises 1 up to an average of up to about 60 polyalkylene ether ester amide repeat units. Preferably it averages at least about 5, more preferably at least about 6, polyalkylene ether ester amide repeat units. Preferably it averages up to about 30, more preferably up to about 25, polyalkylene ether ester amide repeat units.
At least 40 weight % of the polyalkylene ether repeat units are polytrimethylene ether repeat units. Preferably at least 50 weight %, more preferably at least about 75 weight %, and most preferably about 85 to 100 weight %, of the polyether glycol used to form the soft segment is polytrimethylene ether glycol.
The weight percent of polyamide segment, also sometimes referred to as hard segment, is preferably at least about 10% and most preferably at least about 15% and is preferably up to about 60%, more preferably up to about 40%, and most preferably up to about 30%. The weight percent of polytrimethylene ether segment, also sometimes referred to as soft segment, is preferably up to about 90%, more preferably up to about 85%, and is preferably at least about 40%, more preferably at least about 60% and most preferably at least about 70%.
The polytrimethylene ether ester amide comprises polyamide hard segments joined by ester linkages to polytrimethylene ether soft segments and is prepared by reacting carboxyl terminated polyamide or diacid anhydride, diacid chloride or diester acid equivalents thereof and polyether glycol under conditions such that ester linkages are formed. Preferably it is prepared by reacting carboxyl terminated polyamide and polyether glycol comprising at least 50 weight %, more preferably at least 75 weight %, and most preferably about 85 to 100 weight %, polytrimethylene ether glycol.
In one preferred embodiment the carboxyl terminated polyamide is the polycondensation product of lactam, amino-acid or a combination thereof with dicarboxylic acid. Preferably, the carboxyl terminated polyamide is the polycondensation product of C
4
-C
14
lactam with C
4
-C
14
dicarboxylic acid. More preferably, the carboxyl terminated polyamide is the polycondensation product of lactam selected from the group consisting of lauryl lactam, caprolactam and undecanolactam, and mixtures thereof, with dicarboxylic acid selected from the group consisting of succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, and isophthalic acid, and mixtures thereof. Alternatively, the carboxyl terminated polyamide is the polycondensation product of amino-acid with dicarboxylic acid, preferably C
4
-C
14
amino-acid and preferably C
4
-C
14
dicarboxylic acid. More preferably, the carboxyl terminated polyamide is the polycondensation product of amino-acid selected from the group consisting of 1 -amino-undecanoic acid and 12-aminododecanoic acid, and mixtures thereof, with dicarboxylic acid selected from the group consisting of succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, and isophthalic acid, and mixtures thereof.
In another preferred embodiment, the carboxyl terminated polyamide is the condensation product of a dicarboxylic acid and diamine. Preferably, the carboxyl terminated polyamide is the condensation product of a C
4
-C
14
alkyl dicarboxylic acid and C
4-14
diamine. More preferably, the polyamide is selected from the group consisting of nylon 6-6, 6-9, 6-10, 6-12 and 9-6.
Preferably the polytrimethylene ether ester amide has a general structure represented by the following formula (I):
represents a polyamide segment containing terminal carboxyl groups or acid equivalents thereof, and
—O—G—O—  (III)
is a polyether segment, and X is 1 up to an average of about 60, and wherein at least 40 weight % of the polyether segments comprise polytrimethylene ether units. (A and G are used to depict portions of the segments which are ascertained from the description of the polytrimethylene ether ester amide and starting materials.)
Preferably the polytrimethylene ether este

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