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EP-4056615-B1 - NOVEL IN-SITU FORMED POLYOLS, A PROCESS FOR THEIR PREPARATION, FOAMS PREPARED FROM THESE IN-SITU FORMED POLYOLS AND A PROCESS FOR THEIR PREPARATION

EP4056615B1EP 4056615 B1EP4056615 B1EP 4056615B1EP-4056615-B1

Inventors

  • LEWIS, SHARLENE
  • REESE, JACK
  • BARKSBY, NIGEL
  • NEAL, BRIAN

Dates

Publication Date
20260513
Application Date
20220308

Claims (15)

  1. An in-situ formed polyol blend having an overall functionality of 2 to 3, an overall hydroxyl number of 50 mg KOH/g to 150 mg KOH/g, and comprising: (a) a monol initiated oxyalkylene ether having a calculated hydroxyl number of less than or equal to 56 mg KOH/g, and containing less than or equal to 20% by weight of copolymerized oxyethylene, based on the total weight of monol initiated oxyalkylene ether (a); (b) a polyether polyol having a calculated hydroxyl number of 80 mg KOH/gto 220 mg KOH/g, a nominal functionality of 2, and containing from 5 to 45% by weight of copolymerized oxyethylene, based on the total weight of polyether polyol (b); (c) a polyether polyol having a calculated hydroxyl number of 80 mg KOH/gto 220 mg KOH/g, a nominal functionality of greater than 2 to 8, and containing from 5 to 45% by weight of copolymerized oxyethylene, based on the total weight of polyether polyol (c); and (d) a polyether polyol having a calculated hydroxyl number of 80 mg KOH/g to 220 mg KOH/g, a nominal functionality of 2 to 8, and containing 100% by weight of polyoxypropylene, based on the total weight of polyoxyalkylene in polyether polyol (d); wherein said in-situ formed polyol blend comprises from 10 to 40% by weight of said monol initiated oxyalkylene ether (a), from 10 to 30% by weight of said polyether polyol (b), from 20 to 65% by weight of said polyether polyol (c), and from 5 to 20% by weight of said polyether polyol (d), with the sum of the %'s by weight of (a), (b), (c) and (d) totaling 100% by weight of said in-situ formed polyol blend.
  2. The in-situ formed polyol blend of Claim 1, wherein (d) the polyether polyol has a functionality of at least 3 and a calculated hydroxyl number of 100 mg KOH/g to 180 mg KOH/g.
  3. The in-situ formed polyol blend of Claim 1 or claim 2, wherein the monol initiated oxyalkylene ether (a) comprises an oxypropylene block next to the monofunctional starter followed by a mixed oxyalkylene block at the end of the chain which comprises copolymerized oxypropylene and copolymerized oxyethylene, wherein the mixed oxyalkylene block at the end of the chain which comprises copolymerized oxypropylene and copolymerized oxyethylene contains 20% by weight or less of copolymerized oxyethylene, based on 100% by weight of the mixed oxyalkylene block.
  4. The in-situ formed polyol blend of one of Claim 1 to claim 3, wherein the polyether polyol (b) has an initial mixed oxyalkylene block which comprises copolymerized oxypropylene and copolymerized oxyethylene containing 20% by weight or less of copolymerized oxyethylene, based on 100% by weight of the mixed oxyalkylene block, which is followed by a second mixed oxyalkylene block which comprises copolymerized oxypropylene and copolymerized oxyethylene containing at least 40% by weight of copolymerized oxyethylene, based on 100% by weight of the second mixed oxyalkylene block.
  5. The in-situ formed polyol blend of one of Claim 1 to claim 4, wherein the polyether polyol (c) has an initial mixed oxyalkylene block which comprises copolymerized oxypropylene and copolymerized oxyethylene containing 20% by weight or less of copolymerized oxyethylene, based on 100% by weight of the mixed oxyalkylene block, which is followed by a second mixed oxyalkylene block which comprises copolymerized oxypropylene and copolymerized oxyethylene containing at least 40% by weight of copolymerized oxyethylene, based on 100% by weight of the second mixed oxyalkylene block.
  6. The in-situ formed polyol blend of one of Claim 1 to claim 5, which comprises from 25 to 35% by weight of said monol initiated oxyalkylene ether (a); from 15 to 25% of said polyether polyol (b); from 30 to 55% by weight of said polyether polyol (c); and from 5 to 15% by weight of said polyether polyol (d), with the sum of the %'s by weight of (a), (b), (c) and (d) totaling 100% by weight of the in-situ formed polyol blend.
  7. A process of preparing the in-situ formed polyol blend having an overall functionality of 2 to 3, and an overall hydroxyl number of 50 mg KOH/g to 150 mg KOH/g, comprising: I) introducing into a reaction vessel a mixture comprising: (1) an initially charged starter (S i ) comprising a monofunctional compound having a calculated hydroxyl number of less than or equal to 80 mg KOH/g, and (2) a DMC (double metal cyanide) catalyst; II) feeding (1) an epoxide comprising propylene oxide and ethylene oxide in a weight ratio of 100:0 to 80:20, into the reaction vessel; III) allowing the epoxide mixture and the initially charged starter (S i ) to react and to polymerize by feeding the epoxide until the equivalent weight of the monofunctional compound is increased by at least 10% by weight and reaches a value between 1,500 g/mol and 6,000 g/mol; IV) continuously adding (1) a continuously added starter (S c ) having a nominal functionality of greater than 2 to 6, and an equivalent weight of 28 g/mol to 400 g/mol into the reaction vessel while continuing to feed epoxide; V) completing addition of the continuously added starter (S c ); VI) allowing the mixture to continue to polymerize in the reaction vessel thereby forming (1) an intermediate in-situ formed polyol blend which has an overall calculated hydroxyl number of 50 mg KOH/g to 150 mg KOH/g, an overall functionality of 2 to 3, and which comprises (a) a monol initiated oxyalkylene ether having a calculated hydroxyl number of less than or equal to 56 mg KOH/g, and containing less than or equal to 20% by weight of copolymerized oxyethylene, based on 100% by weight of (a), (b) a polyether polyol having a calculated hydroxyl number of 80 mg KOH/g to 220 mg KOH/g, a nominal functionality of 2 and containing from 5 to 45% by weight of copolymerized oxyethylene, based on the total weight of the polyether polyol (b), and (c) a polyether polyol having a calculated hydroxyl number of 80 mg KOH/g to 220 mg KOH/g, a nominal functionality of greater than 2 to 8, and containing from 5 to 45% by weight of copolymerized oxyethylene, based on the total weight of the polyether polyol (c); VII) feeding (1) an epoxide comprising propylene oxide while continuously adding (2) a continuously added starter (S c ) having a nominal functionality of 2 to 8, and an equivalent weight of 28 g/mol to 400 g/mol into the reaction vessel; VIII) completing addition of the continuously added starter (S c ) and epoxide thereby forming in addition to (a), (b) and (c); (d) a polyether polyol having a calculated hydroxyl number of 80 to 220 mg KOH/g, a nominal functionality of 2 to 8, and containing 100% of polyoxypropylene, based on the total weight of polyoxyalkylene in polyether polyol (d); wherein said in-situ formed polyol blend comprises from 10 to 40% by weight of said monol initiated oxyalkylene ether (a), from 10 to 30% by weight of said polyether polyol (b), from 20 to 65% by weight of said polyether polyol (c), and from 5 to 20% by weight of said polyether polyol (d), with the sum of the %'s by weight of (a), (b), (c) and (d) totaling 100% by weight of said in-situ formed polyol blend.
  8. The process of Claim 7, wherein the monol initiated oxyalkylene ether (a) comprises an oxypropylene block next to the monofunctional starter followed by a mixed oxyalkylene block at the end of the chain which comprises copolymerized oxypropylene and copolymerized oxyethylene, wherein the mixed oxyalkylene block at the end of the chain which comprises copolymerized oxypropylene and copolymerized oxyethylene contains 20% by weight or less of copolymerized oxyethylene, based on 100% by weight of the mixed oxyalkylene block.
  9. The process of Claim 7 or claim 8, wherein the polyether polyol (b) has an initial mixed oxyalkylene block which comprises copolymerized oxypropylene and copolymerized oxyethylene containing 20% by weight or less of copolymerized oxyethylene, based on 100% by weight of the mixed oxyalkylene block, which is followed by a second mixed oxyalkylene block which comprises copolymerized oxypropylene and copolymerized oxyethylene containing at least 40% by weight of copolymerized oxyethylene, based on 100% by weight of the second mixed oxyalkylene block.
  10. The process of one of claim 7 to Claim 9, wherein the polyether polyol (c) has an initial mixed oxyalkylene block which comprises copolymerized oxypropylene and copolymerized oxyethylene containing 20% by weight or less of copolymerized oxyethylene, based on 100% by weight of the mixed oxyalkylene block, which is followed by a second mixed oxyalkylene block which comprises copolymerized oxypropylene and copolymerized oxyethylene containing at least 40% by weight of copolymerized oxyethylene, based on 100% by weight of the second mixed oxyalkylene block.
  11. The process of one of Claim 7 to claim 10, wherein said initially charged starter (S i ) has a calculated hydroxyl number of less than 56 mg KOH/g.
  12. The process of one of Claim 7 to claim 11, wherein said initially charged starter (S i ) comprises a monol initiated oxyalkylene ether which comprises the reaction product of a monofunctional starter and an epoxide.
  13. The process of one of Claim 7 to claim 12, wherein said in-situ formed polyol blend comprises from 25 to 35% by weight of said monol initiated oxyalkylene ether (a); from 15 to 25% of said polyether polyol (b); from 30 to 55% by weight of said polyether polyol (c); and from 5 to 15% by weight of said polyether polyol (d), with the sum of the %'s by weight of (a), (b), (c) and (d) totaling 100% by weight of said in-situ formed polyol blend.
  14. An isocyanate-reactive component comprising (1) said in-situ formed polyol blend of one of Claim 1 to claim 6, and (2) at least one of (2)(a) a polyether polyol having a calculated hydroxyl number of 20 to 240 mg KOH/g, an average functionality of 2 to 8, and containing at least 50% of copolymerized oxyethylene, based on 100% by weight of component (2)(a), and (2)(b) a filled polyol.
  15. A viscoelastic flexible polyurethane foam comprising the reaction product of: (A) a diisocyanate and/or polyisocyanate component, (B) an isocyanate-reactive component comprising: (1) an in-situ formed polyol blend having an overall functionality of 2 to 3, an overall hydroxyl number of 50 mg KOH/g to 150 mg KOH/g, which comprises: (a) a monol initiated oxyalkylene ether having a calculated hydroxyl number of less than or equal to 56 mg KOH/g, and containing less than or equal to 20% by weight of copolymerized oxyethylene, based on the total weight of monol initiated oxyalkylene ether (a), (b) a polyether polyol having a calculated hydroxyl number of 80 to 220 mg KOH/g, a nominal functionality of 2, and containing from 5 to 45% by weight of copolymerized oxyethylene, based on the total weight of polyether polyol (b), (c) a polyether polyol having a calculated hydroxyl number of 80 to 220 mg KOH/g, a nominal functionality of greater than 2 to 8, and containing from 5 to 45% by weight of copolymerized oxyethylene, based on the total weight of polyether polyol (c), and (d) a polyether polyol having a calculated hydroxyl number of 80 to 220 mg KOH/g, a nominal functionality of 2 to 8, and containing 100% of polyoxypropylene, based on the total weight of polyoxyalkylene in polyether polyol (d); wherein said in-situ formed polyol blend comprises from 10 to 40% by weight of said monol initiated oxyalkylene ether (a), from 10 to 30% by weight of said polyether polyol (b), from 20 to 65% by weight of polyether polyol (c), and from 5 to 20% by weight of polyether polyol (d), with the sum of the %'s by weight of (a), (b), (c) and (d) totaling 100% by weight of said in-situ formed polyol blend; in the presence of: (C) a blowing agent; (D) a catalyst; and (E) a surfactant.

Description

FIELD The invention relates to novel in-situ formed polyol blends, a process for preparing these novel in-situ formed polyol blends, viscoelastic flexible polyurethane foams comprising these in-situ formed polyol blends, and a process for preparing these viscoelastic polyurethane foams from these in-situ formed polyol blends. The novel in-situ formed polyol blends provide simpler formulation processes by eliminating the need for blending two or more polyols while maintaining good physical properties in foams comprising these in-situ formed polyol blends. BACKGROUND In-situ formed polyol blends are important and/or highly desirable because they eliminate the need to blend two or more polyols. This helps to simplify formulation processes and also makes polyol blend formulations accessible when there is no capacity to separately store and/or blend together individual components. Foams prepared from these in-situ formed blends maintain good physical properties. The popularity of viscoelastic polyurethane foam, also referred to as memory foam or low resilience foam, has significantly increased in recent years as pillows, toppers or layers in mattresses and bed in a box foams. It is also used in other home and office furnishings as well as automotive applications. This increased use has created a demand for better quality viscoelastic foams with high air flows and improved physical properties such as reduced compression sets and better tear strength. US 9 951 174 B2 is related to a novel polyol composition and a process for preparing these polyol compositions. These polyol compositions comprise (a) an in-situ formed polyol blend which comprises (i) one or more polyether monols and (ii) one or more polyether polyols, and (b) a polyether polyol. This prior art is also related to a process for preparing an open celled, flexible polyurethane foam in which the isocyanate-reactive component comprises this polyol composition, and to a viscoelastic polyurethane foam wherein the isocyanate-reactive comprise the latter polyol composition. In US 6 491 846 B1 a process for the in-situ production of a blend of a polyether monol and a polyether polyol is disclosed, wherein the process comprises introducing a monol and a double metal cyanide catalyst into a reaction vessel, feeding an epoxide mixture into the vessel and allowing the epoxide to react with the initial starter and continuing to polymerize by feeding epoxide until the equivalent weight of the monol reaches the desired level, then continuously adding a polyfunctional starter to the reaction vessel while continuing to feed an epoxide mixture, completing addition of the starter, and allowing the mixture to continue to polymerize until the resultant blend of the monol and polyether polyol has an equivalent weight of from 350 to 750, and an average functionality of from 2 to 4. SUMMARY The novel in-situ formed polyol blends have an overall functionality of 2 to 3 and an overall hydroxyl number of 50 mg KOH/g to 150 mg KOH/g. These polyol blends comprise: (a) a monol initiated oxyalkylene ether having a calculated hydroxyl number of less than or equal to 56 mg KOH/g, and containing less than or equal to 20% by weight of copolymerized oxyethylene, based on the total weight of monol initiated oxyalkylene ether (a),(b) a polyether polyol having a calculated hydroxyl number of 80 mg KOH/g to 220 mg KOH/g, a nominal functionality of 2, and containing from 5 to 45% by weight of copolymerized oxyethylene, based on the total weight of polyether polyol (b),(c) a polyether polyol having a calculated hydroxyl number of 80 mg KOH/g to 220 mg KOH/g, a nominal functionality of greater than 2 to 8, and containing from 5 to 45% by weight of copolymerized oxyethylene, based on the total weight of polyether polyol (c), and(d) a polyether polyol having a calculated hydroxyl number of 80 mg KOH/g to 220 mg KOH/g, a nominal functionality of 2 to 8, and containing 100% of polyoxypropylene, based on the total weight of polyoxyalkylene in polyether polyol (d); wherein the in-situ formed polyol blend comprises from 10 to 40% by weight of (a) the monol initiated oxyalkylene ether, from 10 to 30% by weight of (b) the polyether polyol, from 20 to 65% by weight of (c) the polyether polyol, and from 5 to 20% by weight of (d) the polyether polyol, with the sum of the %'s by weight of components (a), (b), (c) and (d) totaling 100% by weight of the in-situ formed polyol blend. The process of preparing the in-situ formed polyol blend having an overall functionality of 2 to 3, and an overall hydroxyl number of 50 to 150 mg KOH/g, comprises: I) introducing into a reaction vessel a mixture comprising: (1) an initially charged starter (Si) comprising a monofunctional compound having a calculated hydroxyl number of less than or equal to 80 mg KOH/g, and(2) a DMC (double metal cyanide) catalyst;II) feeding (1) an epoxide comprising propylene oxide and ethylene oxide in a weight ratio of 100:0 to 80:20, into th