STABLE EMULSIONS AND THEIR USE IN THE PRODUCTION OF FOAMS BASED ON ISOCYANATE

• US 20140323605A1
• Filed: 08/22/2012
• Published: 10/30/2014
• Est. Priority Date: 08/26/2011
• Status: Abandoned Application

• Current Assignee: Bayer Materialscience AG (Covestro AG)
• Original Assignee: Bayer Intellectual Property GmbH (Bayer AG)
• Inventors: Albers, Reinhard, Heinemann, Torsten, Vogel, Stephanie, Otto, Frank, Nefzger, Hartmut
• Application Number:
  US14/240,770
• Publication Number:
  US 20140323605A1
• Time in Patent Office: Days
• US Class Current: 521/128
• CPC Class Codes: C08G 18/4018 Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
• CPC Class Codes: C08G 18/4216 from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
• CPC Class Codes: C08G 18/425 the polyols containing one or two ether groups
• CPC Class Codes: C08G 18/48 Polyethers
• CPC Class Codes: C08G 18/4829 Polyethers containing at least three hydroxy groups C08G18/4833 - C08G18/5096 take precedence
• CPC Class Codes: C08G 18/5033 containing carbocyclic groups C08G18/5024 takes precedence
• CPC Class Codes: C08L 71/02 Polyalkylene oxides
• CPC Class Codes: C08L 75/08 from polyethers

Abstract

The invention relates to stable emulsions for the production of foams based on isocyanate, at least comprising three polyols A1a, A1b and A1c as well as at least one physical blowing agent T, wherein A1a is a polyether polyol obtained by addition of epoxides to starter compounds selected from carbohydrates and di- or higher-functional alcohols, A1b is a polyether polyol started on an aromatic amine, and A1c is a polyester polyol obtained by esterification of a polycarboxylic acid component and a polyalcohol component, wherein the total amount of aromatic dicarboxylic acid derivatives used in the esterification, calculated on the basis of the free aromatic dicarboxylic acids and based on the total mass of polyalcohol component and polycarboxylic acid component, is less than or equal to 48.5% by mass.

Claims

1-17. -17. (canceled)

18. An emulsion comprising

(I) an isocyanate-reactive composition A comprising a polyol mixture A1 of at least three polyols A1a, A1b and A1e as the continuous phase

and

(II) at least one physical blowing agent T as the disperse phase,

wherein:

A1a is a polyether polyol having a hydroxyl number of from 15 mg KOH/g to 550 mg KOH/g and having a functionality of from 1.5 to 6.0, obtained by addition of an epoxide to one or more starter compound(s) selected from the group consisting of carbohydrates and di- or higher-functional alcohols;

(ii) A1b is a polyether polyol having a hydroxyl number of from 100 mg KOH/g to 550 mg KOH/g and having a functionality of from 1.5 to 5.0, obtained by addition of an epoxide to an aromatic amine;

(iii) A1e is a polyester polyol having a hydroxyl number of from 100 mg KOH/g to 450 mg KOH/g and having a functionality of from 1.5 to 3.5, obtained by esterification of a polycarboxylic acid component and a polyalcohol component, wherein the total content of aromatic dicarboxylic acid derivatives used in the esterification, calculated on the basis of the free aromatic dicarboxylic acids. is less than or equal to 48.5% by mass, based on the total mass of polyalcohol component and polycarboxylic acid component.

19. The emulsion according to claim 18, wherein the the average size of the droplets of the physical blowing agent T is ≧

0.1 μ

m to ≦

20 μ

m, the droplet size being determined by using an optical microscope operating in bright field transmission mode.

20. The emulsion according to claim 18, wherein the average size of the droplets of the physical blowing agent T is ≧

0.1 μ

m to ≦

15 μ

m, the droplet size being determined by using an optical microscope operating in bright field transmission mode.

21. The emulsion according to claim 18, in which the polyether polyol A1a is a polyether polyol started on sucrose, mixtures of sucrose and propylene glycol, mixtures of sucrose and ethylene glycol, mixtures of sucrose, propylene glycol and ethylene glycol, sorbitol or mixtures of sorbitol and glycerol.

22. The emulsion according to claim 18, in which the polyether polyol A1b is a polyether polyol started on ortho-, meta- or para-toluylenediamine or a mixture of the isomeric toluylenediamines.

23. The emulsion according to claim 18, in which the polyester polyol A1e is a polyester polyol obtained by esterification of

a polycarboxylic acid component selected from the group consisting of

succinic acid, fumaric acid, maleic acid, maleic anhydride, glutaric acid, adipic acid, sebacic acid, suberic acid, azelaic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, pyromellitic acid and trimellitic acid

and

a polyalcohol component selected from the group consisting of

ethylene glycol and diethylene glycol including their higher homologues, 1,2-propanediol, dipropylene glycol and its higher homologues, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol including their higher homologues, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, glycerol, pentaerythritol, 1,1,1-trimethylolpropane and carbohydrates having from 5 to 12 carbon atoms.

24. The emulsion according to claim 18, in which the polyol mixture A1 additionally comprises:

(iv) a polyether polyol A1d started on an aliphatic amine or a polyhydric alcohol and having a hydroxyl number of from 500 mg KOH/g to 1000 mg KOH/g and a functionality of from 1.5 to 5.0.

25. The emulsion according to claim 18, in which the polyol mixture A1 additionally comprises:

(v) a di- to tetra-functional aminic or alcoholic chain extender or crosslinker.

26. The emulsion according to claim 18, in which the physical blowing agent T is selected from at least one member of the group consisting of

hydrocarbons, halogenated ethers and perfluorinated hydrocarbons having from 1 to 8 carbon atoms.

27. The emulsion according to claim 18, in which the isocyanate-reactive composition A additionally comprises

(vi) water A2;

(vii) at least one stabiliser A3 selected from the group of the polyether-polydimethylsiloxane copolymers;

and

(viii) at least one catalyst A4 selected from the group consisting of

triethylenediamine, N,N-dimethylcyclohexylamine, dicyclohexylmethylamine, tetramethylenediamine, 1-methyl-4-dimethylaminoethylpiperazine, triethylamine, tributylamine, dimethylbenzylamine, N,N′

,N″

-tris-(dimethylaminopropyl)-hexahydrotriazine, tris-(dimethylaminopropyl)amine, tris-(dimethylaminomethyl)phenol, dimethylaminopropyl formamide, N,N,N′

,N′

-tetramethylethylenediamine, N,N,N′

,N′

-tetramethylbutanediamine, tetramethylhexanediamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, tetramethyldiaminoethyl ether, dimethylpiperazine, 1,2-dimethylimidazole, 1-azabicyclo[3.3.0]octane, bis-(dimethylaminopropyl)-urea, N-methylmorpholine, N-ethylmorpholine, sodium N-[(2-hydroxy-5-nonylphenyl)methyl]-N-methylaminoacetate, N-cyclohexylmorpholine, 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, triethanolamine, diethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyl diethanolamine and dimethyl ethanolamine.

28. The emulsion according to claim 18, wherein the mass ratio of A1:

T is ≧

5;

1 to ≦

12;

1.

29. The emulsion according to claim 18, wherein the polyol component A1 has a viscosity according to EN ISO 3219 at 25°

C. of ≧

1000 mPas to ≦

18000 mPas.

30. A process for the production of a polyurethane-containing polymer C, in which an isocyanate component B is reacted with the emulsion according to claim 18.

31. The process according to claim 30, in which the isocyanate component B is

a) at least one isocyanate B1 selected from the group consisting of

toluylene diisocyanate, diphenylmethane diisocyanate, polyphenylpolymethylene polyisocyanate, xylylene diisocyanate, naphthylene diisocyanate, hexamethylene diisocyanate, diisocyanatodicyclohexylmethane and isophorone diisocyanate

or

b) an isocyanate-terminated prepolymer B2 prepared from at least one polyisocyanate B1 and at least one isocyanate-reactive compound selected from at least one of the following polyols

b1) polyether polyol having a hydroxyl number of from 15 mg KOH/g to 550 mg KOH/g and having a functionality of from 1.5 to 6.0, obtained by addition of an epoxide to one or more starter compound(s) selected from the group consisting of carbohydrates and di- or higher-functional alcohols;

b2) polyether polyol having a hydroxyl number of from 100 mg KOH/g to 550 mg KOH/g and having a functionality of from 1.5 to 5.0, obtained by addition of an epoxide to an aromatic amine (A1b);

b3) polyester polyol having a hydroxyl number of from 100 mg KOH/g to 450 mg KOH/g and having a functionality of from 1.5 to 3.5, obtained by esterification of a polycarboxylic acid component and a polyalcohol component, wherein the total amount of aromatic dicarboxylic acid derivatives used in the esterification, calculated on the basis of the free aromatic dicarboxylic acids, is less than or equal to 48.5% by mass, based on the total mass of polyalcohol component and polycarboxylic acid component (A1c);

b4) polyether polyol having a hydroxyl number of from 500 mg KOH/g to 1000 mg KOH/g and having a functionality of from 1.5 to 5.0 (A1d);

b5) polyether carbonate polyol having a functionality of from >

1.0 to 8.0 and a number-average molar mass of from 400 g/mol to 10,000 g/mol (A1f)

or

c) a mixture of B1 and B2.

32. The process according to claim 30, in which the reaction of the isocyanate component B with the emulsion is carried out at indexes of from 95 to 130.

33. A polyurethane-containing polymer C, obtained by a process according to claim 30.

34. A method comprising utilizing the polyurethane-containing polymer C according to claim 33 as insulating material.