Process for the production of brominated polyether polyols

Abstract

The present invention relates to brominated polyether polyols, processes for the production as well as intermediates useful in the production of the same and to processes for the preparation of flame-retardant blends, premixes as well as polyurethane foams.

Claims

1. A process for the production of a compound or a mixture of compounds according to general formula (I): ##STR00014## wherein R.sup.1 and R.sup.4 are independently selected from the group consisting of H, methyl, Cl and Br; R.sup.2, R.sup.3, R.sup.5 and R.sup.6 are independently selected from the group consisting of H, methyl, or ethyl; and n and m are independently 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; the process comprising a step wherein a compound or a mixture of compounds of general formula (II): ##STR00015## wherein R.sup.1, R.sup.4, m and n have the meaning as given above; is reacted with a mixture of water and methanol in a weight/weight ratio of 90/10, 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, 20/80 or 10/90; or a mixture of water, methanol, and ethanol in a weight/weight/weight ratio of 30/60/10, 20/60/20, 20/70/10 or 10/70/20 to obtain the compound or the mixture of compounds of general structure (I); or comprising a step wherein a compound or a mixture of compounds of general formula (III): ##STR00016## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, m and n have the meaning as given above; is reacted with bromine, a bromide ion or a bromonium ion, to obtain the compound or a mixture of compounds of general structure (I); and obtaining the compound or the mixture of compounds of general structure (III) in a step wherein a compound or a mixture of compounds of general formula (VI): ##STR00017## wherein R.sup.1 and R.sup.4 are independently selected from the group consisting of H, methyl, Cl and Br; and n and m are independently 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; is reacted with a mixture of water and methanol in a weight/weight ratio of 90/10, 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, 20/80 or 10/90; or a mixture of water, methanol and ethanol in a weight/weight/weight ratio of 30/60/10, 20/60/20, 20/70/10 or 10/70/20.

2. The process according to claim 1 comprising the step wherein the compound or the mixture of compounds of general formula (II): ##STR00018## wherein R.sup.1 and R.sup.4 are independently selected from the group consisting of H, methyl, Cl and Br; and n and m are independently 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 is reacted with a mixture of water and methanol in a weight/weight ratio of 90/10, 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, 20/80 or 10/90; or a mixture of water, methanol, and ethanol in a weight/weight/weight ratio of 30/60/10, 20/60/20, 20/70/10 or 10/70/20, to obtain the compound or the mixture of compounds of general structure (I); and further comprising obtaining the compound or the mixture of compounds of general formula (II) in a step wherein a compound or a mixture of compounds of general formula (IV): ##STR00019## wherein R.sup.1 and R.sup.4 are independently selected from the group consisting of H, methyl and Cl; X.sup.1, X.sup.2, Y.sup.2 are independently selected from OH, Cl and Br, with the proviso that at least one substituent selected from X.sup.1 and Y.sup.1 is OH and at least one substituent selected from X.sup.2 and Y.sup.2 is OH; and n and m are independently 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; is reacted with an acid or a base.

3. The process according to claim 2 further comprising obtaining the compound or the mixture of compounds of general formula (IV) in a step wherein a compound or a mixture of compounds of general formula (V): ##STR00020## wherein R.sup.1 and R.sup.4 are independently selected from the group consisting of H, methyl, Cl and Br; X.sup.1, X.sup.2, Y.sup.1, Y.sup.2 are independently selected from OH, Cl and Br, with the proviso that at least one substituent selected from X.sup.1 and Y.sup.1 is OH and at least one substituent selected from X.sup.2 and Y.sup.2 is OH; and n and m are independently 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; is reacted with bromine, a bromide ion or a bromonium ion.

4. The process according to claim 3 further comprising obtaining the compound or the mixture of compounds of general formula (V) in a step wherein epichlorohydrin is reacted with but-2-yne-1,4-diol.

5. The process according to claim 4 wherein epichlorohydrin is reacted with but-2-yne-1,4-diol in presence of an acid or a base.

6. The process according to claim 5 wherein epichlorohydrin is reacted with but-2-yne-1,4-diol in presence of an acid.

7. The process of claim 3, wherein the compound or the mixture of compounds of general formula (V) is reacted with bromine.

8. The process according to claim 1 further comprising obtaining the compound or the mixture of compounds of general formula (VI) in a step wherein a compound or a mixture of compounds of general formula (V): ##STR00021## wherein R.sup.1 and R.sup.4 are independently selected from the group consisting of H, methyl, Cl and Br; X.sup.1, X.sup.2, Y.sup.1, Y.sup.2 are independently selected from OH, Cl and Br, with the proviso that at least one substituent selected from X.sup.1 and Y.sup.1 is OH and at least one substituent selected from X.sup.2 and Y.sup.2 is OH; and n and m are independently 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; is reacted with an acid or a base.

9. The process according to claim 8 further comprising obtaining the compound or the mixture of compounds of general formula (V) in a step wherein epichlorohydrin is reacted with but-2-yne-1,4-diol.

10. The process according to claim 9 wherein epichlorohydrin is reacted with but-2-yne-1,4-diol in presence of an acid or a base.

11. The process according to claim 10 wherein epichlorohydrin is reacted with but-2-yne-1,4-diol in presence of an acid.

12. The process according to claim 1 wherein R.sup.1 and R.sup.4 are Cl.

13. The process according to claim 1 wherein R.sup.1, R.sup.3, R.sup.5 and R.sup.6 are independently selected from H and methyl.

14. The process according to claim 1 wherein m is 0.

15. A mixture of compounds of general formula (I): ##STR00022## wherein R.sup.1 and R.sup.4 are independently selected from the group consisting of H, methyl, Cl, and Br; R.sup.2, R.sup.3, R.sup.5 and R.sup.6 are independently selected from the group consisting of H, methyl, or ethyl; and n and m are independently 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; produced by the process of claim 1.

16. A process for the preparation of a flame-retardant blend, the process comprising a step of blending the product of the process according to claim 1 with a further flame-retardant.

17. A process for the preparation of a premix comprising a step of blending the product of the step or the steps according to claim 1 with a blowing agent and optionally one or more further components selected from the list consisting of further polyol compounds, foam stabilizer, further blowing agents, further flame retardants, catalysts, cross-linking agents and surfactants.

18. A process for the preparation of a polyurethane foam comprising a step of reacting the product of the step or the steps according to claim 1 with one or more isocyanate compounds.

19. The process of claim 1, wherein the compound or the mixture of compounds of general formula (III) is reacted with bromine.

Description

EXAMPLES

Example 1a

(1) Condensation with Brnsted Acid

(2) A reactor is charged with 2.0 kg but-2-yne-1,4-diol. The reactor is heated by pumping water at 95 C. through the heating coils. At an inner temperature of 90 C., stirring is started and 2.7 g 65% HClO.sub.4 is added to the melted but-2-yne-1,4-diol followed by the addition of 5.3 kg epichlorohydrin over the course of 300 min. During the addition, the temperature is maintained at 90 C. Subsequently, the mixture is cooled to 65 C. and 1.3 kg methanol is added to allow transferring the crude reaction mixture to the reactor for the next reaction step.

Example 1b

(3) Condensation with Lewis Acid

(4) A reactor is charged with 2.0 kg but-2-yne-1,4-diol. The reactor is heated by pumping water at 95 C. through the heating coils. At an inner temperature of 80 C., stirring is started and 4.0 g BF.sub.3.Math.OEt.sub.2 is added to the melted but-2-yne-1,4-diol. The temperature is raised to 90 C. followed by the addition of 5.3 kg epichlorohydrin over the course of 300 min. During the addition, the temperature is maintained at 90 C. Subsequently, the mixture is cooled to 65 C. and 1.3 kg methanol is added to allow transferring the crude reaction mixture to the reactor for the next reaction step.

Example 1c

(5) Condensation with Base

(6) A reactor is charged with 2.0 kg but-2-yne-1,4-diol. The reactor is heated by pumping water at 95 C. through the heating coils. At an inner temperature of 90 C., stirring is started and 5.3 g KOH pellets is added to the melted but-2-yne-1,4-diol. The mixture is stirred for 30 min followed by the addition of 5.3 kg epichlorohydrin over the course of 300 min. During the addition, the temperature is maintained at 90 C. Subsequently, the mixture is cooled to 65 C. and 1.3 kg methanol is added to allow transferring the crude reaction mixture to the reactor for the next reaction step.

Example 2a

(7) Bromination Procedure 1

(8) The crude mixture from example 1a, 1b or 1c as well as 1.0 mol-equivalents Br.sub.2 are fed to a stirred reactor simultaneously at a rate allowing the internal temperature in the reactor to be around 49 C. After complete addition of Br.sub.2 (usually around 3 h), 0.13 kg of a 35% H.sub.2O.sub.2 solution is added to the mixture over the course of 40 min. Subsequently, the mixture is allowed to cool and directly used for the next step.

Example 2b

(9) Bromination Procedure 2

(10) The crude mixture from example 1a, 1b or 1c is placed in a stirred reactor. To this mixture, 1.0 mol-equivalents Br.sub.2 and 0.13 kg of a 35% H.sub.2O.sub.2 solution are fed simultaneously at a rate allowing the internal temperature in the reactor to be around 19 C. After complete addition of the H.sub.2O.sub.2/Br.sub.2 mixture (usually around 1.5 h), the reaction mixture is allowed to cool to room temperature and directly used for the next step.

Example 3a

(11) Epoxidation with Strong Base

(12) A reactor is charged with the mixture from example 2a or 2b and 1.2 kg dichloromethane. 1.5 kg of a 50% aqueous solution of NaOH is fed to the reaction mixture at a rate so as to maintain the internal temperature at 45 C. After stirring for another 40 min, 2.5 kg water is added and the mixture is stirred for another 20 min. After decanting, the two phases formed are separated and the organic phase is directly used for the next step.

Example 3b

(13) Epoxidation with Strong Acid

(14) A reactor is charged with the mixture from example 2a or 2b and 1.2 kg dichloromethane. To this mixture, 0.73 kg concentrated H.sub.2SO.sub.4 is added slowly and the internal temperature is subsequently raised to 65 C. After stirring at this temperature for 90 min, the mixture is neutralized by addition of 20% aqueous NaOH solution. The mixture is stirred for another 10 min and subsequently decanted. The two phases formed are separated and the organic phase is directly used for the next step.

Example 4a

(15) Ring Opening Procedure 1

(16) A stirred reactor equipped with a condenser is charged with 5.5 kg crude product from example 3a or 3b. A mixture of 1.2 kg methanol, 2.1 kg water, 1.2 kg ethanol and 0.02 kg concentrated HCl is added. The reactor is heated to 85 C. and the reaction mixture is stirred under reflux conditions for 60 min. The mixture is allowed to cool to room temperature and neutralized by addition of 20% aqueous NaOH solution. After decanting from the solids formed, the volatiles are removed by evaporation at 90 C. under vacuum (300 to 30 mbar) to yield the desired product.

Example 4b

(17) Ring-Opening Procedure 2

(18) An autoclave is charged with 1.3 kg methanol, 3.3 kg water and 0.02 kg 65% HClO.sub.4. The autoclave is kept at a pressure of 1.9 bar and heated to 65 C., after which 5.5 kg of the crude product from example 3a or 3b is added. During the addition, the temperature is allowed to rise to 75 C. After complete addition, the temperature is raised to 85 C. and the reaction is allowed to stir for another 30 min. The reaction mixture is neutralized by addition of 20% aqueous NaOH solution. The volatiles are removed by evaporation at 90 C. under vacuum (300 to 30 mbar) to yield the desired product.

Example 5a

(19) Epoxidation with Strong Base

(20) A reactor is charged with the mixture from example 1a, 1b or 1c and 1.2 kg dichloromethane. 1.5 kg of a 50% aqueous solution of NaOH is fed to the reaction mixture at a rate so as to maintain the internal temperature at 45 C. After stirring for another 40 min, 2.5 kg water is added and the mixture is stirred for another 20 min. After decanting, the two phases formed are separated and the organic phase is directly used for the next step.

Example 5b

(21) Epoxidation with Strong Acid

(22) A reactor is charged with the mixture from example 1a, 1b or 1c and 1.2 kg dichloromethane. To this mixture, 0.73 kg concentrated H.sub.2SO.sub.4 is added slowly and the internal temperature is subsequently raised to 65 C. After stirring at this temperature for 90 min, the mixture is neutralized by addition of 20% aqueous NaOH solution. The mixture is stirred for another 10 min and subsequently decanted. The two phases formed are separated and the organic phase is directly used for the next step.

Example 6a

(23) Ring Opening Procedure 1

(24) A stirred reactor equipped with a condenser is charged with 5.5 kg crude product from example 5a or 5b. A mixture of 1.2 kg methanol, 2.1 kg water, 1.2 kg ethanol and 0.02 kg concentrated HCl is added. The reactor is heated to 85 C. After the dichloromethane from the previous step is distilled off, the reaction mixture is stirred under reflux conditions for 60 min. The mixture is allowed to cool to room temperature and neutralized by addition of 20% aqueous NaOH solution.

Example 6b

(25) Ring-Opening Procedure 2

(26) An autoclave is charged with 1.3 kg methanol, 3.3 kg water and 0.02 kg 65% HClO.sub.4. The autoclave is kept at a pressure of 1.9 bar and heated to 65 C., after which 5.5 kg of the crude product from example 3a or 3b is added. During the addition, the temperature is allowed to rise to 75 C. After complete addition, the temperature is raised to 85 C. and the reaction is allowed to stir for another 30 min. The reaction mixture is neutralized by addition of 20% aqueous NaOH solution and decanted from the solids formed.

Example 7a

(27) Bromination Procedure 1

(28) The crude mixture from example 6a or 6b as well as 1.05 mol-equivalents Br.sub.2 dissolved in 1.0 kg dichloromethane (optionally recycled from the previous step) are fed to a stirred reactor simultaneously at a rate allowing the internal temperature in the reactor to be around 49 C. After complete addition of the Br.sub.2 solution (usually around 3 h), 0.13 kg 35% H.sub.2O.sub.2 solution is added to the mixture over the course of 40 min. After cooling to room temperature and decanting, the phases are separated. To the organic phase, 0.5 kg water is added and the mixture is stirred for 15 min. The phases are separated and the organic phase is evaporated at 90 C. under vacuum (300 to 30 mbar) to yield the desired product.

Example 7b

(29) Bromination Procedure 2

(30) The crude mixture from example 6a or 6b as well as 1.0 kg dichloromethane (optionally recycled from the previous step) are placed in a stirred reactor. To this mixture, 1.05 mol-equivalents Br.sub.2 and 0.13 kg 35% H.sub.2O.sub.2 solution are fed simultaneously at a rate allowing the internal temperature in the reactor to be around 19 C. After complete addition of the H.sub.2O.sub.2/Br.sub.2 mixture (usually around 1.5 h), the mixture is cooled to room temperature and decanted. The phases are separated. To the organic phase, 0.5 kg water is added and the mixture is stirred for 15 min. The phases are separated and the organic phase is evaporated at 90 C. under vacuum (300 to 30 mbar) to yield the desired product.

Example 8

(31) Preparation of a Premix

(32) A premix was prepared by blending the following components using conventional means:

(33) TABLE-US-00001 Compound Type Part by weight Product of example 4a, 4b, 6 7a or 7b Stepanpol PS2412 Aromatic Polyester polyol 45 Voranol RN490 Polyether polyol 30 TEP Physical flame retardant 5 DMCHA Amine based catalyst 2.3 Struksilon 8006 Surfactant 1.5 Solkane 365 Blowing agent (physical) 18.4 Water Blowing agent (chemical) 1.4 Voranol RN 490 (Dow chemicals), Struksilon 8006 (Schill + Seilacher Struktol GmbH), triethylphosphat (TEP), Stepanpol PS 2412, HFC 365mfc (Solkane 365) and 1 wt % N,N-dimethylcyclohexylamine (DMCHA, Lupragen N100).

Example 9

(34) Preparation of a Polyurethane Foam

(35) A polyurethane foam was prepared by conventional means using the premix from example 8 and

(36) TABLE-US-00002 Compound Type Part by weight Methylendiphenyldiisocyanat (MDI) Isocyanate 143.4

(37) An isocyanate MDI index of 115 was applied to prepare the polyurethane foams.