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EP-3904421-B1 - MODIFIED POLYETHER POLYOL AND USE THEREOF IN POLYURETHANE FOAM MATERIALS

EP3904421B1EP 3904421 B1EP3904421 B1EP 3904421B1EP-3904421-B1

Inventors

  • LI, Fuguo
  • LIU, YANG
  • JU, Changxun
  • JIANG, Naihua
  • LIU, BIN
  • QIN, Chengqun
  • WANG, LUNPENG

Dates

Publication Date
20260506
Application Date
20181226

Claims (10)

  1. A method for preparing a modified polyether polyol, comprising the following steps: (1) contacting and reacting a compound A with a polyether polyol, at a reaction temperature of 80-160 °C; wherein the compound A is an anhydride and/or a dicarboxylic acid compound containing a polymerizable double bond; and (2) reacting the product obtained in step (1) with an epoxy compound containing a polymerizable double bond in the presence of a catalyst, at a reaction temperature of 60-150 °C, to produce the modified polyether polyol; wherein the catalyst used in step (2) comprises a catalyst A and a catalyst B; wherein the catalyst A is an oxidized tertiary amine compound, and the catalyst B is a halide.
  2. The method according to claim 1, wherein a molar ratio of the compound A to the polyether polyol is 0.5-1.5: 1, preferably 0.9-1: 1; and a molar ratio of the compound A to the epoxy compound is 0.2-4: 1, preferably 0.5-1.5: 1.
  3. The method according to claim 1 or 2, wherein in step (1), the compound A is reacted with the polyether polyol in the presence or absence of a catalyst, preferably in the presence of a catalyst, wherein the catalyst is used in an amount of preferably 0.1‰ to 3‰ of the mass of the polyether polyol; preferably, the catalyst used in step (1) is one or a combination of two or more of carbonates, bicarbonates, and hydroxides of alkali metals or alkaline earth metals, more preferably one or a combination of two or more of hydroxides of alkali metals.
  4. The method according to any one of claims 1 to 3, wherein the epoxy compound containing a polymerizable double bond is 1,2-epoxide containing an olefinic double bond, preferably one or a combination of two or more of glycidyl methacrylate, glycidyl acrylate, and derivatives thereof, further preferably one or a combination of two or more of allyl glycidyl ether, glycidyl methacrylate, and glycidyl acrylate, more preferably glycidyl methacrylate.
  5. The method according to any one of claims 1 to 4, wherein the catalyst A is one or a combination of two or more selected from oxidized aryl tertiary amines, oxidized alkyl tertiary amines, oxidized cycloalkyl tertiary amines, oxidized acyl tertiary amines, and oxidized hydroxyl-substituted tertiary amines; further preferably, the catalyst A is selected from oxidized alkyl methyl tertiary amines containing 8-22 carbon atoms; the catalyst B is one or a combination of two or more of an organic bromide, a bromide salt, an iodide salt, and an organic iodide; further preferably one or a combination of two or more of divalent or trivalent metal bromide salts and divalent or trivalent metal iodide salts; more preferably, the bromide salt and the iodide salt are each one or a combination of two or more of calcium salts or barium salts; preferably, the oxidized aryl tertiary amines are selected from oxidized dimethylanilines; the oxidized alkyl tertiary amines are one or a combination of two or more selected from oxidized dimethyl benzyl tertiary amines, oxidized dimethyl decyl tertiary amines, oxidized dimethyl dodecyl tertiary amines, oxidized dimethyl octyl tertiary amines, and oxidized dimethyl nonyl tertiary amines; and the oxidized hydroxyl-substituted tertiary amines are at least one selected from oxidized dihydroxymethylbutylamines and oxidized dihydroxyethyldodecyltertiary amines; preferably, a mass ratio of the catalyst A to the catalyst B is 0.5-4: 1, preferably 1.5-2.5: 1; preferably, a total amount of the catalyst used in step (2) is 0.01% to 3% of the mass of the polyether polyol in step (1).
  6. The method according to any one of claims 1 to 5, wherein step (1) or step (2) is performed in the presence or absence of a solvent which is preferably a proton-free polar solvent; and/or optionally, an polymerization inhibitor is further added in step (2), wherein an amount of the polymerization inhibitor is 0% to 1.5% of a total mass of reductants in step (2), preferably 30-2000 ppm.
  7. A modified polyether polyol, which is prepared by the method according to any one of claims 1 to 6, comprising a polyether segment, an active group A, and an active group B, wherein the active group A is linked to the polyether segment by an ester group, the active group B is linked to the active group A by a linking group which is an organic segment with a molecular weight of less than 200; and the active group A and the active group B are each independently an alkenyl group containing a polymerizable unsaturated double bond; preferably, the linking group is one or a combination of two or more selected from an ester group, an ether group, an alkyl group, an amide group, and a thioether group, preferably, the linking group contains at least one of a sulfhydryl group and/or a hydroxyl group; further preferably, the linking group contains an ester group and a hydroxyalkyl group.
  8. A method for preparing a copolymer polyol, comprising: polymerizing a base polyether polyol with at least one olefinic unsaturated monomer in the presence of an initiator and a dispersion stabilizer to obtain the copolymer polyol; wherein the dispersion stabilizer is the modified polyether polyol according to claim 7; preferably, the copolymer polyol is prepared at a reaction temperature of 80-140 °C; preferably, the olefinic unsaturated monomer is a vinyl monomer, preferably selected from a combination of a vinyl aromatic compound and an olefinic unsaturated nitrile; more preferably a combination of styrene and acrylonitrile with a mass ratio of preferably 10: 90 to 90: 10, more preferably 60: 40 to 90: 10; preferably, a mass ratio of the olefinic unsaturated monomer to the base polyether polyol is 0.1% to 200%, preferably 30% to 140%; preferably, the dispersion stabilizer occupies 0.3% to 10%, preferably 2% to 5% of a total mass of the base polyether polyol and the olefinic unsaturated monomer; preferably, an amount of the initiator is 0.01 wt% to 5 wt% of the total mass of the base polyether polyol and the olefinic unsaturated monomer.
  9. A polyurethane foam material, which is obtained through foaming of a composition of the copolymer polyol prepared by the method according to claim 8 and a polyisocyanate.
  10. A product containing the polyurethane foam material according to claim 9.

Description

TECHNICAL FIELD The present disclosure relates to a synthesis of a modified polyether polyol and the use thereof and, in particular, to a synthesis of a modified polyether polyol with multiple active sites and the use thereof as a dispersion stabilizer in a synthesis of a copolymer polyol. BACKGROUND Polyurethane foam is prepared by reacting a polyisocyanate with a polyol in the presence of a foaming agent. Various modified polyol products have been developed by those skilled in the art in order to improve a bearing property and other properties. Common types are dispersions of polymer particles in polyols, such as vinyl polymer particle polyols (styrene-acrylonitrile dispersions), polyurea particle dispersions (PHD polyols), and polyisocyanate addition polymers (PIPA polyols and polyurethane-polyurea particle dispersions). Currently, the dispersions of styrene/acrylonitrile copolymers in polyols (simply referred to as copolymer polyols or polyol polymer dispersions) are widely commercialized. Their stability is mostly achieved by the stabilizing effect of grafting or addition products formed between the polymers of unsaturated compounds and polyol molecules. There are numerous methods known in the art. In addition to the unsaturation inherent to polyoxyalkylene polyols for forming dispersions, these methods generally introduce a small amount of unsaturation into the polyols. A typical molecular design is shown in FIG. 1, with one active site such as a polymerizable unsaturated double bond attached to an end of the multi-branched polyether. As described in previously published patent documents such as US4550194 and US4998857, a polyether polyol starting from sorbitol or pentaerythritol is reacted with maleic anhydride in the presence of a catalyst to perform a ring-opening reaction, followed by a reaction with alkylene oxide such as ethylene oxide or propylene oxide. Unsaturation is introduced by maleic anhydride. The process is concise, the reaction is complete, and the device is low in cost. US 6 403 667 describes a process for the preparation of a macromer suitable as a stabilizer precursor in a polymer polyol. However, a polymeric polyol synthesized with a stabilizer prepared with maleic anhydride has high viscosity. EP02253584 has disclosed a stabilizer prepared by reacting phthalic anhydride with glycidyl methacrylate in the presence of a catalyst. The synthesis takes a long time and uses an organotin catalyst which remains in the copolymer polyol and affects a subsequent reaction of a hydroxyl compound with an isocyanate, causing a foam product to fall back, irregular foam pores, and pore collapse in an extreme formulation. SUMMARY In view of this, the present disclosure provides a method for preparing a modified polyether polyol. The modified polyether polyol prepared by the method has more active sites, and has the characteristics of good dispersion stability, good filterability and low viscosity when served as a dispersion stabilizer in synthesis of a copolymer polyol. To achieve the preceding object, the present disclosure adopts technical solutions described below. One aspect of the present disclosure provides a method for preparing a modified polyether polyol, comprising the following steps: (1) contacting and reacting a compound A with a polyether polyol to perform an esterification ring-opening or an esterification reaction, preferably at a reaction temperature of 80-160 °C, more preferably 120-140 °C; wherein the compound A is an anhydride and/or a dicarboxylic acid compound containing a polymerizable double bond, preferably one or two selected from maleic anhydride and itaconic anhydride, preferably maleic anhydride; and(2) reacting the product obtained in step (1) with an epoxy compound containing a polymerizable double bond in the presence of a catalyst to perform ring-opening addition, preferably at a reaction temperature of 60-150 °C, more preferably 80-130 °C, to produce the modified polyether polyol. The catalyst used in step (2) comprises a catalyst A and a catalyst B, wherein the catalyst A is an oxidized tertiary amine compound, and the catalyst B is a halide. In some preferred embodiments, a molar ratio of the compound A to the polyether polyol is 0.5-1.5: 1, preferably 0.9-1: 1; and a molar ratio of the compound A to the epoxy compound is 0.2-4: 1, preferably 0.5-1.5: 1. In some preferred embodiments, in step (1), the reaction temperature is 80-160 °C, preferably 120-140 °C; and in step (2), the reaction temperature is 60-150 °C, preferably 80-130 °C. In some preferred embodiments, in step (1), the compound A may be reacted with the polyether polyol in the presence or absence of a catalyst. Preferably, the reaction is performed in the presence of a catalyst, where the catalyst is used in an amount of preferably 0.1%o to 3‰, for example 0.1‰ of the mass of the polyether polyol. In a case where the reaction in step (1) is performed in the presence of a catalyst, the catalyst used m