Insulation moulding and method for its manufacture

• US 9,713,886 B2
• Filed: 02/20/2014
• Issued: 07/25/2017
• Est. Priority Date: 02/25/2013
• Status: Active Grant

• Current Assignee: Covestro Deutschland AG
• Original Assignee: Covestro Deutschland AG
• Inventors: Otto, Frank, Albers, Reinhard, Loof, Michael, Vogel, Stephanie
• Primary Examiner(s): AUGHENBAUGH, WALTER
• Application Number:
  US14/185,270
• Publication Number:
  US 20140242313A1
• Time in Patent Office: 1,251 Days
• CPC Class Codes: B29B 7/7471 Mixers in which the mixing takes place at the inlet of a mould, e.g. mixing chambers situated in the mould opening
• CPC Class Codes: B29C 44/02 for articles of definite length, i.e. discrete articles
• CPC Class Codes: B29C 44/3403 Foaming under special conditions, e.g. in sub-atmospheric pressure, in or on a liquid
• CPC Class Codes: B29C 44/383 using spreading devices mounted in the mould, in front of the feed opening
• CPC Class Codes: B29C 44/42 using pressure difference, e.g. by injection or by vacuum
• CPC Class Codes: B32B 5/18 characterised by features of a layer of foamed material
• CPC Class Codes: B32B 5/20 foamed in situ
• CPC Class Codes: C08G 18/4018 Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
• CPC Class Codes: C08G 18/42 Polycondensates having carboxylic or carbonic ester groups in the main chain
• CPC Class Codes: C08G 18/4261 prepared by oxyalkylation of polyesterpolyols
• CPC Class Codes: C08G 18/482 Mixtures of polyethers containing at least one polyether containing nitrogen
• CPC Class Codes: C08G 2101/00 Manufacture of cellular products
• CPC Class Codes: C08G 2110/0025 rigid
• CPC Class Codes: C08J 2375/04 Polyurethanes
• CPC Class Codes: C08J 2375/06 from polyesters
• CPC Class Codes: C08J 2375/08 from polyethers
• CPC Class Codes: C08J 2375/12 from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
• CPC Class Codes: C08J 9/08 developing carbon dioxide
• CPC Class Codes: C08J 9/12 by a physical blowing agent
• CPC Class Codes: C08J 9/14 organic
• CPC Class Codes: C08J 9/141 : Hydrocarbons
• CPC Class Codes: C08J 9/143 : Halogen containing compounds
• CPC Class Codes: C08J 9/148 : perfluorinated
• CPC Class Codes: F25D 23/064 : formed by moulding, e.g. moulding in situ
• CPC Class Codes: Y10T 428/1376 : Foam or porous material containing

Abstract

A cavity between inner and outer walls of an open-box-shaped mold is filled with a polyurethane reaction mixture, containing an isocyanate and an emulsion of an isocyanate-reactive composition with three polyols and a blowing agent, which is cured to a polyurethane containing polymer. The inner and outer wall are a fixed distance from one another and each wall comprises a bottom and sides. The mixture is fed through an inlet in the bottom of the outer wall. Before filling the cavity, the mold is turned downwards so that the mixture foams upwards, filling the cavity. The three polyols are polyether polyol obtained by adding an epoxy to carbohydrates or difunctional or higher-functional alcohols; polyether polyol obtained by adding an epoxy to an aromatic amine; and polyester polyether polyol obtained by adding an epoxy to the esterification product of an aromatic dicarboxylic acid derivative and a difunctional or higher-functional alcohol.

Claims

1. A method for manufacturing an insulation moulding comprising

filling a cavity between an inner and an outer wall of an open-box-shaped mould with a polyurethane reaction mixture and

allowing the polyurethane reaction mixture to cure to a polyurethane comprising polymer C,

wherein the inner and outer wall being arranged a fixed distance from one another and each wall comprising a bottom face and a plurality of side faces, wherein the fixed distance between the inner and outer wall can be the same or different for each face,

wherein the polyurethane reaction mixture is fed through an inlet opening positioned in a middle area of the bottom face of the outer wall,

wherein before filling the cavity, the mould is turned with the bottom face of the outer wall downwards so that the polyurethane reaction mixture is foaming upwards to fill the cavity,

wherein the polyurethane reaction mixture comprises an isocyanate component B, which is reacted with an emulsion comprising

(I) an isocyanate-reactive composition A, comprising a polyol mixture A1 comprising at least three polyols A1a, A1b and A1c as a continuous phase and

(II) at least one physical blowing agent T as a disperse phase, wherein:

(i) Ala is a polyether polyol having a hydroxyl value from 15 mg KOH/g to 550 mg KOH/g and an OH functionality from 1.5 to 6.0, obtained by addition of an epoxy to at least one starter compound selected from the group consisting of carbohydrates, difunctional alcohols, and higher-functional alcohols;

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

(iii) A1c is a polyester polyether polyol having a hydroxyl value from 100 mg KOH/g to 450 mg KOH/g and an OH functionality from 1.5 to 3.5, obtained by addition of an epoxy to an esterification product of an aromatic dicarboxylic acid derivative and a difunctional and/or higher-functional alcohol.

2. The method according to claim 1, wherein the physical blowing agent T has an average droplet size of ≧

0.1 μ

m to ≦

20 μ

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

3. The method according to claim 1, wherein the starter compound for polyether polyol Ala is at least one of sucrose, a mixture of sucrose and propylene glycol, a mixture of sucrose and ethylene glycol, a mixture of sucrose, propylene glycol and ethylene glycol, sorbitol or a mixture of sorbitol and glycerol.

4. The method according to claim 1, wherein the aromatic amine is ortho-, meta- or para-toluoylene diamine or a mixture of isomeric toluoylene diamines;

and/or wherein the polyester polyether polyol Ale is a polyester polyether polyol obtained by addition of an epoxy to an esterification product of a phthalic acid derivative with a difunctional or higher-functional alcohol selected from the group consisting of 1,2-propanediol, dipropylene glycol and higher homologues thereof, 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 higher homologues thereof, 2-methyl propanediol-1,3, neopentyl glycol, 3-methyl pentanediol-1,5, glycerol, pentaerythritol, 1,1, 1-trimethylolpropane and carbohydrates having 5 to 12 carbon atoms; and

/or wherein the polyol mixture AI additionally comprises;

(iv) a polyether polyol Aid based on an aliphatic amine or a polyhydric alcohol and having a hydroxyl value from 500 mg KOH/g to 1000 mg KOH/g and a functionality from 1.5 to 5.0; and

/or wherein the polyol mixture AI additionally comprises a polyether polyol A1g based on a polyhydric alcohol and having a hydroxyl value from 15 mg KOH/g to 550 mg KOH/g and a functionality from 1.5 to 5.0.

5. The method according to claim 1, wherein the polyol mixture A1 additionally comprises:

(v) a difunctional to tetrafunctional amine-type or alcoholic chain extender or crosslinker.

6. The method according to claim 1, wherein the physical blowing agent T is selected from at least one member of the group consisting of hydrocarbons, halogenated ethers and perfluorinated hydrocarbons having 1 to 8 carbon atoms.

7. The method according to claim 1, wherein the isocyanate-reactive composition A additionally comprises

(vi) water A2;

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

(viii) at least one catalyst A4 selected from the group consisting of triethylenediamine, N,N-dimethylcyclohexylamine, dicyclohexylmethylamine, tetramethy 1 enediamine, 1-methy 1-4-dimethylaminoethy 1 piperazine, triethylamine, tributylamine, dimethylbenzylamine, N,N′

,N″

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

,N′

tetramethyl ethylenediamine, N,N,N′

,N′

-tetramethyl butanediamine, tetramethyl hexanediamine, pentamethyl-diethylenetriamine, pentamethyl dipropylenetriamine, tetramethyl diaminoethyl ether, dimethyl piperazine, 1,2-dimethyl imidazole, 1-azabicyclo[3.3.0]octane, bis-(dimethylaminopropyl) urea, N-methylmorpholine, N-ethylmorpholine, sodium-N-[(2-hydroxy-5-nonylphenyl) methyl]-N-methylaminoacetate, N-cyclohexyl morpholine, 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, triethanolamine, diethanolamine, triisopropanolamine, N-methyl diethanolamine, N-ethyl diethanolamine.

8. The method according to claim 1, wherein the mass ratio of A1:

T is ≧

5;

1 to ≦

12;

1.

9. The method according to claim 1, wherein the polyol component A1 has a viscosity according to EN ISO 3219 at 25°

C. of ≧

1000 mPas to ≦

18000 mPas.

10. The method according to claim 1, wherein the isocyanate component B is

a) at least one isocyanate B 1 selected from the group consisting of toluoylene diisocyanate, diphenylmethane diisocyanate, polyphenyl polymethylene polyisocyanate, xylylene diisocyanate, naphthylene diisocyanate, hexamethylene diisocyanate, diisocyanatodicyclohexylmethane and isophorone diisocyanate, or

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

b. 1) polyether polyol having a hydroxyl value from 15 mg KOH/g to 550 mg KOH/g and a functionality from 1.5 to 6.0, obtained by addition of an epoxy to at least one starter compound selected from carbohydrates and difunctional or higher-functional alcohols (A1a);

b.2) polyether polyol having a hydroxyl value from 100 mg KOH/g to 550 mg KOH/g and a functionality from 1.5 to 5.0, obtained by addition of an epoxy to an aromatic amine (A1b);

b.3) polyester polyether polyol having a hydroxyl value from 100 mg KOH/g to 450 mg KOH/g and a functionality from 1.5 to 3.5, obtained by addition of an epoxy to an esterification product of an aromatic dicarboxylic acid derivative and a difunctional or higher-functional alcohol (A1c);

b.4) polyether polyol having a hydroxyl value from 500 mg KOH/g to 1000 mg KOH/g and a functionality from 1.5 to 5.0 (A1d);

b.5) polyether carbonate polyol having a functionality of ≧

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

b.6) polyether polyol having a functionality of 1.5 to 5.0 and a hydroxyl value from 15 mg KOH/g to 550 mg KOH/g (A1 g)

or

c) a mixture of B1 and B2.

11. The method according to claim 1, wherein reaction of the isocyanate component B with the emulsion is performed at an isocyanate index of 95 to 130.

12. The method according to claim 1, wherein the middle area of the bottom face of the outer wall is arranged concentrically in a two-dimensional projection of the bottom face and/or wherein the middle area of the bottom face of the outer wall is defined by a segment of the bottom face which extends from a centroid of a two-dimensional projection of the bottom face to not more than 10% of a longitudinal extent of a two-dimensional projection in each direction.

13. The method according to claim 1, wherein the mould is provided with at least one ventilation hole and/or wherein the cavity is evacuated to a pressure lower than ambient pressure.

14. The method according to claim 1, wherein the polyurethane reaction mixture is injected into the cavity through an injection nozzle being arranged at the inlet opening, wherein the inlet opening and/or the injection nozzle is provided with a baffle plate and/or a distributor head, wherein the distributor head is provided with a plurality of discharge outlets and/or wherein a plurality of discharge outlets are formed between the distributor head and a bottom face of the outer wall, the polyurethane reaction mixture being injected through the discharge outlets into the cavity in a substantially laminar manner, wherein the discharge outlets are in the shape of slits.

15. The method according to claim 14, wherein the distributor head is arranged at the inlet opening, fixed to the bottom face of the outer wall and supported on the bottom face of the inner wall, and/or wherein the discharge outlets are arranged in such a way that the polyurethane reaction mixture is injected into the cavity substantially parallel to the bottom face of the outer wall.

16. The method according to claim 1, wherein the physical blowing agent T has an average droplet size of ≧

0.1 μ

m to ≦

15 μ

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

17. The method according to claim 4, wherein the polyol mixture A1 additionally comprises a polyether polyol A1g based on a polyhydric alcohol and having a hydroxyl value from 20 mg KOH/g to 530 mg KOH/g and a functionality from 1.5 to 4.0.

18. The method according to claim 4, wherein the polyol mixture A1 additionally comprises a polyether polyol A1g based on a polyhydric alcohol and having a hydroxyl value from 25 mg KOH/g to 515 mg KOH/g and a functionality from 1.5 to 4.0.

19. The method according to claim 12, wherein the middle area of the bottom face of the outer wall is defined by a segment of the bottom face which extends from a centroid of the two-dimensional projection of the bottom face to not more than 5% of the longitudinal extent of a two-dimensional projection in each direction.

20. The method according to claim 13, wherein the pressure is reduced by ≧

1 mbar to ≦

900 mbar.

21. The method according to claim 13, wherein the pressure is reduced by ≧

20 mbar to ≦

600 mbar.

22. The method according to claim 13, wherein the pressure is reduced by ≧

50 mbar to ≦

300 mbar.