Modified polyether polyol and use thereof in polyurethane foam materials

Abstract

Provided are a modified polyether polyol and the use thereof in polyurethane foam materials. The method for preparing a modified polyether polyol comprises the following steps: 1) reacting a compound A with a polyether polyol, wherein the compound A is an anhydride and/or dicarboxylic acid compound containing a polymerizable double bond, preferably selected from one or two of 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, in order to prepare the modified polyether polyol. The modified polyether polyol obtained by means of the preparation method has more active sites, uses the polymerizable double bond for blocking, is used as a dispersion stabilizer for the synthesis of copolymer polyols, and has the characteristics of a better dispersion stability, filterability and a low viscosity.

Claims

1. A method for preparing a modified polyether polyol, comprising the following steps: (1) contacting and reacting a compound A with a polyether polyol; 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, 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; and a molar ratio of the compound A to the epoxy compound is 0.2-4:1.

3. The method according to claim 1, wherein in step (1), the compound A is reacted with the polyether polyol in the presence of a catalyst.

4. The method according to claim 1, wherein the epoxy compound containing a polymerizable double bond is 1,2-epoxide containing an olefinic double bond.

5. The method according to claim 1, wherein the polyether polyol used in step (1) has an average molecular weight of 2500-15000.

6. A modified polyether polyol, which is prepared by the method according to claim 1.

7. A polyurethane foam material, which is obtained through foaming of a composition of a copolymer polyol and polyisocyanate, wherein the copolymer polyol is prepared by a method 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 6.

8. The method according to claim 1, 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 one or two selected from maleic anhydride and itaconic 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 at a reaction temperature of 60-150° C. to produce the modified polyether polyol.

9. The method according to claim 8, comprising the following steps: (1) contacting and reacting a compound A with a polyether polyol at a reaction temperature of 120-140° C.; wherein the compound A is 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 at a reaction temperature of 80-130° C., to produce the modified polyether polyol.

10. The method according to claim 9, wherein a molar ratio of the compound A to the polyether polyol is 0.9-1:1; and a molar ratio of the compound A to the epoxy compound is 0.5-1.5:1.

11. The method according to claim 3, wherein in step (1), the compound A is reacted with the polyether polyol in the presence of a catalyst, wherein the catalyst is used in an amount of 0.1% to 3% of the mass of the polyether polyol.

12. The method according to claim 11, whereon 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.

13. The method according to claim 1, wherein the oxidized tertiary amine compound is selected from the group consisting of oxidized aryl tertiary amines, oxidized alkyl tertiary amines, oxidized cycloalkyl tertiary amines, oxidized acyl tertiary amines, and oxidized hydroxyl-substituted tertiary amines.

14. The method according to claim 1, wherein the oxidized tertiary amine compound comprises an oxidized alkyl methyl tertiary amine containing 8-22 carbon atoms.

15. The method according to claim 1, wherein the halide is selected from the group consisting of an organic bromide, a bromide salt, an iodide salt and an organic iodide.

16. The method according to claim 1, wherein a mass ratio of the catalyst A to the catalyst B is 0.5-4:1.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a structure diagram of an existing polyether polyol.

(2) FIG. 2 is a structure diagram of a modified polyether polyol in some embodiments of the present disclosure.

(3) FIGS. 3 to 5 show results of observation of foam microstructures of polyurethane foams 1# to 3#, respectively.

DETAILED DESCRIPTION

(4) For a better understanding of technical solutions of the present disclosure, the content of the present disclosure is further described below in conjunction with examples and is not limited to the examples set forth below.

(5) Some raw materials involved in examples and comparative example are described below.

(6) Polyether polyol A: A reaction was carried out using sorbitol as a starter and using KOH as a catalyst in an amount of 0.3% of the mass of propylene oxide (PO) at a reaction temperature of 110±5° C. under a pressure of lower than 0.15 MPa. After PO was fed, the reaction system was aged for 2 h and degassed for 1 h. After degassing, ethylene oxide (EO) was fed, and a reaction was carried out at a reaction temperature of 110±5° C. under a pressure of lower than 0.15 MPa. After materials were fed, the reaction system was aged for 2 h and degassed for 1 h. At this time, the reaction stage ended. With the temperature controlled at 85-90° C., the reaction product was neutralized by soft water and phosphoric acid added thereto, dehydrated, filtered and cooled to 25° C. for output. The mass ratio of sorbitol, EO, and PO was 1.08:4.95:93.97. The polyether polyol A was obtained. After measurement, the polyether polyol had a hydroxyl value of about 28 mgKOH/g, an average molecular weight of 11400 g/mol, and an average functionality of 5.7.

(7) Base polyol B: a polyether polyol for high-resilience and flexible foam, prepared by reacting glycerol with propylene oxide and ethylene oxide, available from Wanhua Chemical Group Co., Ltd., WANOL®F3135.

(8) Base polyether polyol: a polyether polyol for ordinary flexible foam, prepared by reacting glycerol with propylene oxide and ethylene oxide, available from Wanhua Chemical Group Co., Ltd., WANOL®F3136. OA-12: an oxidized dimethyl dodecyl tertiary amine, which is dehydrated and dried to obtain a viscous liquid. WANNATE®8001: modified diphenylmethane diisocyanate (MDI) from Wanhua Chemical Group Co., Ltd. BiCAT®8106: an organic bismuth catalyst from Shepherd Chemical Company. B-8715 LF2: a foam stabilizer from TMG Chemicals Co., Ltd.

(9) Other raw materials involved in examples set forth below were purchased from Aladdin Biochemical Technology Co., Ltd unless otherwise specified.

(10) Detection methods involved in examples and comparative examples are described below. Hydroxyl value: GB 12008.3-2009 Plastics—Polyether Polyols—Part 3: Determination of hydroxyl value Viscosity: GB 12008.7-2010 Plastics—Polyether Polyols—Part 7: Determination of viscosity Unsaturation: GB 12008.6-2010 Plastics—Polyether polyols—Part 6: Determination of unsaturation Solid content: GB/T 31062-2014 Polymeric polyols

Example 1

Preparation of Dispersion Stabilizer 1

(11) 3000 g of polyether polyol A, 24.2 g of maleic anhydride, and 3 g of KOH were mixed uniformly, heated to 120° C., and reacted for 5 h.

(12) Then, 5.0 g of OA-12 and 3.1 g of calcium bromide were added, stirred uniformly, then 22.8 g of glycidyl acrylate and 1.78 g of hydroquinone were added, and reacted at 100° C. for 5 h to obtain a transparent brown-yellow liquid with a viscosity of 2520 mPa.Math.s and a measured unsaturation of 0.095 meq/g.

Example 2

Preparation of Dispersion Stabilizer 2

(13) 3000 g of polyether polyol A, 22.5 g of itaconic anhydride, and 3 g of KOH were mixed uniformly, heated to 130° C., and reacted for 3 h.

(14) Then, 6 g of OA-12 and 2.6 g of barium bromide were added, stirred uniformly, then 37.3 g of glycidyl methacrylate and 1.78 g of p-hydroxyanisole were added, and reacted at 130° C. for 4 h to obtain a transparent light-yellow liquid with a viscosity of 2850 mPa.Math.s and a measured unsaturation of 0.103 meq/g.

Example 3

Preparation of Copolymer Polyol 1

(15) A 500 mL four-necked bottle equipped with a stirrer, a heating device, a temperature control device, and a feeder was used as a reactor. 55.4 g of base polyol B and 5.6 g of dispersion stabilizer 1 were added to the reactor. After purged with nitrogen, the reaction system was stirred and slowly heated to 110° C., top materials (a mixed solution of 10.47 g of isopropanol, 85.71 g of base polyether polyol WANOL®F3156, 46.55 g of acrylonitrile, 69.83 g of styrene, and 1.21 g of azobisisobutyronitrile) were continuously added, and the temperature was controlled at 115° C. to 120° C. The above mixed solution was added dropwise within 100 min. After the materials were fed completely, the reaction system was aged for 1 h and heated to 160° C. The unreacted monomers were removed under vacuum for 2 h to obtain a product. The indexes of the product were measured. The solid content was 44.6% and the viscosity was 4950 cp (25° C.).

Example 4

Preparation of Copolymer Polyol 2

(16) A 500 mL four-necked bottle equipped with a stirrer, a heating device, a temperature control device, and a feeder was used as a reactor. 55.4 g of base polyol B and 5.6 g of dispersion stabilizer 2 were added to the reactor. After purged with nitrogen, the reaction system was stirred and slowly heated to 110° C., top materials (a mixed solution of 10.47 g of isopropanol, 85.71 g of base polyether polyol WANOL®F3156, 46.55 g of acrylonitrile, 69.83 g of styrene, and 1.21 g of azobisisobutyronitrile) were continuously added, and the temperature was controlled at 115° C. to 120° C. The above mixed solution was added dropwise within 100 min. After the materials were fed completely, the reaction system was aged for 1 h and heated to 160° C. The unreacted monomers were removed under vacuum for 2 h to obtain a product with a solid content of 44.5% and a viscosity of 5018 cp (25° C.).

Comparative Example

(17) Preparation of dispersion stabilizer 3: 3000 g of polyether polyol A and 30.6 g of maleic anhydride were heated to 120° C. and reacted for 12 h under nitrogen protection. Then, 50 g of ethylene oxide (EO) were added and the reaction was continued for 4 h at 130° C. Unreacted EO was removed to obtain a product as a transparent brown-yellow liquid with a viscosity of 5500 mPa.Math.s and a measured unsaturation of 0.045 meq/g. The modified polyether polyols prepared in Examples 1 and 2 had higher unsaturation and more active sites than this comparative example.

(18) A 500 mL four-necked bottle equipped with a stirrer, a heating device, a temperature control device, and a feeder was used as a reactor. 55.4 g of base polyol B and 5.6 g of comparative dispersion stabilizer 3 were added to the reactor. After purged with nitrogen, the reaction system was stirred and slowly heated to 110° C., top materials (a mixed solution of 10.47 g of isopropanol, 85.71 g of base polyether polyol WANOL®F3156, 46.55 g of acrylonitrile, 69.83 g of styrene, and 1.21 g of azobisisobutyronitrile) were continuously added, and the temperature was controlled at 115° C. to 120° C. The above mixed solution was added dropwise within 100 min. After the materials were fed completely, the reaction system was aged for 1 h. Subsequently, the unreacted monomers were removed under vacuum for 2 h to obtain a product with a solid content of 45.0% and a viscosity of 5783 cp (25° C.).

Example 6

(19) Method for Preparing Polyurethane Foam:

(20) Premixes were prepared according to raw materials and their parts by weight in Table 1. The premixes and an isocyanate were placed at a constant temperature of 22° C. for 3 h, separately. Then, 100 g of each premix and 60 g of isocyanate WANNATE®8001 were stirred to be mixed in a stirrer (with rotational speed of 3000 rpm) for 6 s. The stirred mixture was quickly poured into an aluminum open mold (size: 300 mm length, 300 mm width, and 50 mm thickness) previously heated to 60° C. so that the mixture was allowed to foam. After 7 min, the foam was taken out to obtain the polyurethane foam.

(21) TABLE-US-00001 TABLE 1 Formulation of premixes Polyurethane Foam No. Material 1# 2# 3# Copolymer polyol 33.70 33.70 33.70 WANOL ® F3156 59.46 59.46 59.46 (base polyether polyol) Diethanolamine 0.50 0.50 0.50 Water 4.16 4.16 4.16 N,N-bis(dimethylaminopropyl) 0.40 0.40 0.40 isopropanolamine N,N,N′-trimethyl-N′-hydroxyethyl 0.50 0.50 0.50 diaminoethyl ether BiCAT ® 08106 0.10 0.10 0.10 (an organic bismuth catalyst) B-8715 LF2 (a foam stabilizer) 1.19 1.19 1.19

(22) In Table 1, polyurethane foams 1#, 2#, and 3# were prepared using the copolymer polyols prepared in Comparative Example, Example 3, and Example 4, respectively.

(23) The tested performance indexes of the prepared polyurethane foams and the corresponding test criteria are shown in Table 2.

(24) TABLE-US-00002 TABLE 2 Performance of polyurethane foams Polyurethane Foam No. Item Test Criteria 1# 2# 3# VOC VDA 278 50 45 35 90° C./0.5 h Odor (μgC/g) VDA 270B3 5 3 4 80° C./2 h Tensile IS01798 95 110 115 strength (Kpa) Elongation at IS01798 80 85 90 break (Kpa)

(25) The foam microstructures of polyurethane foams 1#, 2#, and 3# were observed using an Olympus IX73 microscope. The results are shown in FIGS. 3 to 5, respectively. Foam 1# had many large and coarse pores, with pores being messy; foams 2# and 3# had few coarse pores, with pores being fine. From test results, the copolymer polyols prepared with the modified polyether polyols of the present disclosure in the embodiments of the present disclosure had lower viscosity and good filterability; and the polyurethane foam prepared with the obtained copolymer polyols had better comprehensive performance.

(26) Those skilled in the art will appreciate that some modifications or adaptations may be made to the present disclosure based on the teachings of the description. These modifications or adaptations should fall within the scope of the present disclosure as defined by the claims.