Carbodiimides, method for the production and use thereof

Patent metadata

Field	Value
Publication number	US-10065925-B2
Application number	US-201515524118-A
Country	US
Kind code	B2
Filing date	Nov 3, 2015
Priority date	Nov 4, 2014
Publication date	Sep 4, 2018
Grant date	Sep 4, 2018

Abstract

The invention relates to novel carbodiimides having terminal urea and/or urethane groups, to processes for the production thereof and to the use thereof as a stabilizer in ester-based polymers especially in films for protection from hydrolytic degradation.

First claim

What is claimed is:

1. A carbodiimide of formula (I) having terminal urea and/or urethane groups

wherein:
each R may be Identical or different, and is selected from the group of —NHCONHR I , —NHCONR I R II and —NHCOOR III radicals, wherein
R I and R II are identical or different and represent a C 1 -C 22 -alkyl, C 8 -C 12 -cycloalkyl, C 6 -C 18 -aryl, or C 7 -C 18 -aralkyl radical, and
R III represents a C 1 -C 22 -alkyl, C 6 -C 12 -cycloalkyl, C 6 -C 16 -aryl, C 7 -C 18 -aralkyl radical, an unsaturated alkyl radical having 2-22 carbon atoms, or an alkoxypolyoxyalkylene radical, and

n=0 to 20.

2. The carbodiimide as claimed in claim 1 , wherein:
R is an —NHCOOR III radical where R III is an alkoxypolyoxyalkylene or an unsaturated alkyl radical having 18 carbon atoms, and
n=0 to 20.

3. The carbodiimide as claimed in claim 1 , wherein:
R is an —NHCOOR III radical, wherein R III is C 1 -C 22 -alkyl, C 6 -C 12 -cycloalkyl, and
n=0 to 15.

4. The carbodiimide as claimed in claim 2 , wherein the NCN content in the carbodiimide is 2-8 wt %.

5. The carbodiimide as claimed in claim 3 , wherein the NCN content in the carbodimide is 2-10 wt %.

6. The carbodiimide as claimed in claim 1 , wherein the carbodiimide has an average molar mass (Mw) of 1000-10,000 g/mol.

7. A process for producing the carbodiimides as claimed in claim 1 , the process comprising:
carbodiimidizing diisocyanates of formula (II)

 to eliminate carbon dioxide at temperatures of 80° C. to 200° C. in the presence of catalysts and optionally solvent, and
subsequently, end-functionalizing free NCO functionalities with primary or secondary amines and/or alcohols.

8. A process for producing the carbodiimides as claimed in claim 1 , the process comprising:
end-functionalizing a portion of free NCO groups of aromatic diisocyanates of formula (II)

 with primary or secondary amines and/or alcohols and/or alkoxypolyoxyalkylene alcohols, and
subsequently, carbodiimidizing to eliminate carbon dioxide at temperatures of 80° C. to 200° C. in the presence of catalysts and optionally solvent.

9. A process for producing the carbodiimides as claimed in claim 3 , the process comprising end-functionalizing and carbodiimidizing aromatic diisocyanates of formula (II)

to produce a carbodiimide melt, and, after production of the melt, pelletizing the melt on pelletizing belts.

10. A composition comprising:
at least one carbodiimide as claimed in claim 1 ; and
at least one ester-based polymer selected from the group of polyester polyols, ester-based thermoplastic polyurethanes, polyurethane elastomers, PU adhesives, PU casting resins, polyamides (PA), polyethylene terephthalates (PET), polybutylene terephthalates (PBT), polytrimethylene terephthalates (PTT), copolyesters, thermoplastic polyester elastomers (TPE E), ethylene vinyl acetates (EVA), polylactic acids (PLA), polybutylene adipate terephthalates (PBAT), polybutylene succinates (PBS), PLA derivatives, and/or polyhydroxyalkanoates (PHA).

11. The composition as claimed in claim 10 , wherein the concentration of the carbodiimide is 0.1-10 wt %.

12. A process for producing the compositions as claimed in claim 10 , the process comprising adding the carbodiimides by means of solids metering units to the ester-based polymers, wherein
for the carbodiimides, R is an —NHCOOR III radical, wherein Rd is C 1 -C 22 -alkyl, or C 6 -C 12 -cycloalkyl, and n=0 to 15; and
the ester-based polymer is selected from the group consisting of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyamides (PA), thermoplastic polyurethanes (TPU), copolyesters, modified polyester made of cyclohexanediol and terephthalic acid (PCTA), thermoplastic polyester elastomers (TPE E), ethylene vinyl acetate (EVA), polylactic acid (PLA), polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), PLA derivatives and/or polyhydroxyalkanoates (PHA).

13. A method for protecting ester-based polymers from hydrolytic degradation, the method comprising adding the carbodiimides as claimed in claim 1 to ester-based polymers, wherein the ester-based Polymers are selected from the group consisting of polyols, polyamides (PA), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), copolyesters, thermoplastic polyester elastomers (TPE E), ethylene vinyl acetate (EVA), polylactic acid (PLA), PLA derivatives, polybutylene adipate terephthalates (PBAT), polybutylene succinates (PBS), polyhydroxyalkanoates (PHA), PA/PET or PHA/PLA blends, thermoplastic polyurethanes (TPU), polyurethane elastomers, PU adhesives, PU casting resins, PU foams, and PU coatings for wood, leather, synthetic leather and textiles.

14. A method for protecting polyester films, from hydrolytic degradation, the method comprising adding the carbodiimides as claimed in claim 1 to polyester, and extruding the polyester into films.

15. A film comprising at least one polyester selected from the group polyethylene terephthalate (PET), ethylene vinyl acetate (EVA), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT) and/or polycyclohexanedimethanol terephthalate (PCT) and 1.0-3.0 wt % of at least one carbodiimide as claimed in claim 1 based on the polyester.

16. A molding material made of polyamide (PA) and comprising:
1.0-3.0 wt % of the carbodiimide as claimed in claim 1 based on the polyamide, and optionally further additives, fillers and/or reinforcers.

17. The carbodiimide as claimed in claim 1 , wherein:
R is an —NHCOOR III radical where R III is an alkoxypolyoxyalkylene or an unsaturated alkyl radical having 18 carbon atoms, and
n=1 to 10;
the NCN content in the carbodiimide is 3-6 wt %; and
the carbodiimide has an average molar mass (Mw) of 2000-8000 g/mol.

18. The carbodiimide as claimed in claim 1 , wherein:
R is an —NHCOOR III radical where R III is an alkoxypolyoxyalkylene or an unsaturated alkyl radical having 18 carbon atoms;
n=3 to 6;
the NCN content in the carbodiimide is 4-5 wt %; and
the carbodiimide has an average molar mass (Mw) of 3000-6000 g/mol.

19. The carbodiimide as claimed in claim 1 , wherein:
R is an —NHCOOR III radical, wherein R III is C 1 -C 6 -alkyl, or C 6 -C 12 -cycloalkyl;
n=1 to 15; and
the NCN content in the carbodiimide is 3-10 wt %; and
the carbodimide has an average molar mass (Mw) of 2000-8000 g/mol.

20. The carbodiimide as claimed in claim 1 , wherein:
R is an —NHCOOR III radical, wherein R III is methyl, ethyl, 1-propyl, or C 6 -cycloalkyl;
n=3 to 8; and
the NCN content in the carbodiimide is 4-5 wt %; and
the carbodiimide has an average molar mass (Mw) of 3000-6000 g/mol.

Assignees

• Lanxess Deutschland Gmbh

Inventors

• Laufer Wilhelm
• Wenzel Volker

Classifications

• C08L67/00

  Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain (of polyester-amides C08L77/12; of polyester-imides C08L79/08); Compositions of derivatives of such polymers · CPC title

• C08K5/29

  Compounds containing {one or more} carbon-to-nitrogen double bonds · CPC title

• C07C2601/14

  The ring being saturated · CPC title

• C07C271/28 Primary

  to a carbon atom of a non-condensed six-membered aromatic ring · CPC title

• C07C275/40 Primary

  being further substituted by nitrogen atoms not being part of nitro or nitroso groups · CPC title