Polymers made from telechelic N-alkylated polyamides

Patent metadata

Field	Value
Publication number	US-9809675-B2
Application number	US-201414767157-A
Country	US
Kind code	B2
Filing date	Feb 4, 2014
Priority date	Feb 13, 2013
Publication date	Nov 7, 2017
Grant date	Nov 7, 2017

Abstract

This invention relates to polymers made from low molecular weight polyamide oligomers and telechelic polyamides (including copolymers) containing N-alkylated amide groups in the backbone structure. The described telechelic polyamides are used as the soft segment in the described TPU. These telechelic polyamides are unique in that they have an unexpectedly low glass-transition (desirably 30 degrees C. or lower) which makes them suitable for further reaction and polymerization, allowing for the formation of the described TPU. The resulting TPU can provide improved hydrolytic, oxidative and/or thermal stability as well as improved adhesion to other materials, especially polar materials.

First claim

What is claimed is:

1. A thermoplastic polyurethane composition comprising the reaction product of: (i) a polyol component containing a telechelic polyamide; and (ii) a polyisocyanate component; and optionally (iii) a chain extender component;
wherein the telechelic polyamide:
(a) has repeat units connected by linkages, wherein the linkages comprise heteroatom containing linkages, and has functional end groups selected from carboxyl or primary or secondary amine, wherein at least 70 mole percent of the telechelic polyamide has exactly two functional end groups of the same functional type selected from the group consisting of amine or carboxyl functional end groups;
(b) has a polyamide segment comprising at least two amide linkages derived from reacting an amine with a carboxyl group, wherein said polyamide segment comprises repeat units derived from two or more monomers selected from lactams, aminocarboxylic acids, dicarboxylic acids, and diamines;
(c) wherein at least 10 percent of the total number of the heteroatom containing linkages are amide linkages; and
(d) wherein at least 50 percent of the amide linkages are tertiary amide linkages.

2. The thermoplastic polyurethane composition of claim 1 wherein said polyamide segment of feature (b) has at least one of the following conditions:
(i) where said amide linkages are derived from polymerizing amide forming monomers and at least 90 mole percent of said monomers are selected from the group consisting of lactams and aminocarboxylic acid monomers such that said polyamide is a copolymer of at least two different monomers; or
(ii) where said amide linkages are derived from polymerizing amide forming monomers and at least 90 mole percent of said monomers are combined amounts of dicarboxylic acid and diamine monomers such that said polyamide is a copolymer of at least three different monomers; or
(iii) where said amide linkages are derived from polymerizing a combination of dicarboxylic acid, diamine and either lactam and/or aminocarboxylic acid monomers such that the total dicarboxylic acid monomer(s) and the diamine monomer(s) are present at 10 mole percent or more and the total lactam and/or aminocarboxylic acid monomers are present in the monomer blend at 10 mole percent or more.

3. The thermoplastic polyurethane composition of claim 1 wherein at least 50 weight percent of said telechelic polyamide is made up of repeating units derived from monomers selected from the group of lactam monomers, aminocarboxylic acid monomers, dicarboxylic acid monomers, and diamine monomers.

4. The thermoplastic polyurethane composition of claim 1 wherein at least 10 weight percent of said telechelic polyamide is made up of repeating units derived from monomers selected from the group of lactam monomers, aminocarboxylic acid monomers, dicarboxylic acid monomers, and diamine monomers.

5. The thermoplastic polyurethane composition of claim 1 wherein at least 50 weight percent of said polyamide segment comprises repeat units of the structure:

wherein R a is the alkylene portion of the dicarboxylic acid and is a cyclic, linear, or branched alkylene of 2 to 36 carbon atoms, optionally including up to 1 heteroatom per 3 or 10 carbon atoms of the diacid; and
wherein R b is a direct bond or a linear or branched alkylene group of 2 to 60 carbon atoms and R c and R d are individually a linear or branched alkyl group of 1 to 8 carbon atoms, or R c and R d connect together to form a single linear or branched alkylene group of 1 to 8 carbon atoms.

6. The thermoplastic polyurethane composition of claim 5 wherein said unit:

within the repeat unit structure of said polyamide segment is derived from polymerizing diamine monomers including piperazine.

7. The thermoplastic polyurethane composition of claim 1 wherein at least 50 weight percent of said polyamide segment comprises repeat units of the structure:

wherein said repeat units are derived from monomers selected from the group consisting of lactams monomers and amino carboxylic acid monomers; wherein each R e is independently a linear or branched alkyl containing 5 to 12 carbon atoms, and each R f is independently a linear or branched alkyl containing 1 to 8 carbon atoms.

8. The thermoplastic polyurethane composition of claim 1 wherein at least 80 percent of the functional end groups of the telechelic polyamide of component (i) are secondary amine groups.

9. The thermoplastic polyurethane composition of claim 1 wherein at least 80 percent of the functional end groups of the telechelic polyamide of component (i) are terminal primary or secondary carboxyl end groups.

10. The thermoplastic polyurethane composition of claim 1 wherein the telechelic polyamide has a weight average molecular weight from about 200 to 10,000 g/mole; and
wherein said telechelic polyamide, free of any solvents, has a viscosity of less than 100,000 cps at 70° C. as measured by a Brookfield circular disc viscometer with the circular disc spinning at 5 rpm.

11. The thermoplastic polyurethane composition of claim 1 wherein said telechelic polyamide further comprises at least one oligomer segment selected from the group consisting of a polyester segment, a polyether segment, a polycarbonate segment, or a combination thereof.

12. The thermoplastic polyurethane composition of claim 1 wherein component (ii), the polyisocyanate component, comprises an aromatic diisocyanate, an aliphatic diisocyanate, or a mixture thereof.

13. The thermoplastic polyurethane composition of claim 1 wherein component (ii), the polyisocyanate component, comprises diphenyl methane-4, 4′-diisocyanate (MDI), H 12 MDI, m-xylylene diisocyanate (XDI), m-tetramethyl xylylene diisocyanate (TMXDI), phenylene-1, 4-diisocyanate (PPDI), 1,5-naphthalene diisocyanate (NDI), diphenylmethane-3, 3′-dimethoxy-4, 4′-diisocyanate (TODI), isophorone diisocyanate (IPDI), 1,4-cyclohexyl diisocyanate (CHDI), hexamethylene diisocyanate (HDI), 1,6-diisocyanato-2,2,4,4-tetramethyl hexane (TMDI), 1,10-decane diisocyanate, trans-dicyclohexylmethane diisocyanate (HMDI), or any combination thereof.

14. The thermoplastic polyurethane composition of claim 1 wherein component (iii), the chain extender component, comprises one or more short chain glycols having from about 2 to about 10 carbon atoms.

15. The thermoplastic polyurethane composition of claim 1 wherein component (iii), the chain extender component, comprises ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, triethylene glycol, cis-trans-isomers of cyclohexyl dimethylol, neopentyl glycol, 1,4-butanediol, 1,6-hexandiol, 1,3-butanediol, and 1,5-pentanediol, benzene glycol (HQEE), xylylene glycols, resorcinol, bis(beta -hydroxyethyl) ether, catechol, or any combinations thereof.

16. The thermoplastic polyurethane composition of claim 1 , wherein at least 75 percent of the amide linkages are tertiary amide linkages.

17. The thermoplastic polyurethane composition of claim 1 , wherein at least 85 percent of the amide linkages are tertiary amide linkages.

Assignees

• Lubrizol Advanced Mat Inc

Inventors

• Pourahmady Naser
• Makal Umit G
• Erdodi Gabor
• Lai John Ta-Yuan

Classifications

• C08G69/44

  Polyester-amides · CPC title

• C08G18/7671

  containing only one alkylene bisphenyl group · CPC title

• C08G18/6511

  compounds of group C08G18/3203 · CPC title

• C08G18/603 Primary

  Polyamides · CPC title

• C08G69/40

  Polyamides containing oxygen in the form of ether groups (C08G69/12, C08G69/32 take precedence) · CPC title