Vegetable Oil Polyol for Flexible Polyurethane Foam and Preparation Method and Application Thereof

Abstract

A vegetable oil polyol for flexible polyurethane foam, a preparation method and application thereof. The method includes the following steps: (1) subjecting an epoxidized vegetable oil, a benzoylformic acid, a basic catalyst, and an inert solvent to a ring-opening reaction in a first microchannel reactor of a microchannel reaction device to obtain a vegetable oil polyol; and (2) subjecting the vegetable oil polyol obtained in the step (1), a propylene oxide and an inert solvent to an addition polymerization reaction in a second microchannel reactor of the microchannel reaction device to obtain the vegetable oil polyol for flexible polyurethane foam.

Claims

1. A method for preparing a vegetable oil polyol for flexible polyurethane foam, which is characterized by comprising the following steps: (1) subjecting an epoxidized vegetable oil, a benzoylformic acid, a basic catalyst, and an inert solvent to a ring-opening reaction in a first microchannel reactor of a microchannel reaction device to obtain a vegetable oil polyol; (2) subjecting the vegetable oil polyol obtained in the step (1), a propylene oxide and an inert solvent to an addition polymerization reaction in a second microchannel reactor of the microchannel reaction device to obtain the vegetable oil polyol for flexible polyurethane foam.

2. The method of claim 1, which is characterized by comprising the following steps: (1) simultaneously pumping a mixed solution prepared by dissolving the epoxidized vegetable oil and the basic catalyst in the inert solvent and a mixed solution prepared by dissolving the benzoylformic acid in the inert solvent into the first microchannel reactor in the microchannel reaction device and making a ring-opening reaction to obtain a reaction solution containing the vegetable oil polyol; (2) pumping a mixed solution prepared by dissolving the reaction solution containing the vegetable oil polyol and obtained in the step (1) and propylene oxide in the inert solvent into the second microchannel reactor of the microchannel reaction device, and making an addition polymerization reaction to obtain the vegetable oil polyol for flexible polyurethane foam.

3. The method of claim 1, which is characterized in that the epoxidized vegetable oil in the step (1) is any one or more of epoxidized olive oil, epoxidized peanut oil, epoxidized rapeseed oil, epoxidized cotton seed oil, epoxidized soybean oil, epoxidized coconut oil, epoxidized palm oil, epoxidized sesame oil, epoxidized corn oil or epoxidized sunflower oil, wherein a molar ratio of epoxy group in the epoxidized vegetable oil to benzoylformic acid is 1: (0.8-1.5), and the basic catalyst is any one or more of sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, sodium n-butoxide, sodium tert-butoxide, sodium carbonate, sodium bicarbonate, potassium methoxide, potassium ethoxide, potassium isopropoxide, potassium tert-butoxide, potassium carbonate and potassium bicarbonate, wherein the mass percentage of the basic catalyst in the epoxidized vegetable oil is 0.02-0.10%.

4. The method of claim 1, which is characterized in that the reaction temperature of the ring-opening reaction in the step (1) is 80 C. to 150 C., the reaction time is 5 min to 20 min, and the volume of the first microchannel reactor is 5 mL to 15 mL.

5. The method of claim 1, which is characterized in that a molar ratio of epoxy group in the epoxidized vegetable oil in the step (1) to the propylene oxide in the step (2) is 1: (10-20), the reaction temperature of the addition polymerization reaction in the step (2) is 80 C. to 150 C., the reaction time is 10 min to 25 min, and the volume of the second microchannel reactor is 20 mL to 70 mL.

6. The method of claim 1, which is characterized in that reaction effluent of the second microchannel reactor in the step (2) is separated, and an organic phase is acid washed, neutralized, separated, rotary-evaporated, and dried to obtain the vegetable oil polyol for flexible polyurethane foam.

7. The method of claim 1, which is characterized in that the inert solvent is any one or more of dichloromethane, benzene, dichloroethane, chloroform, n-hexane, carbon tetrachloride, and xylene.

8. The method of claim 1, which is characterized in that the microchannel reaction device comprises a first micromixer, a first microchannel reactor, a second micromixer and a second microchannel reactor which are sequentially connected by a pipe, and the reaction raw materials are input into the micromixers and subsequent equipment via a pump with precise and low pulsation.

9. A vegetable oil polyol for flexible polyurethane foam, wherein the vegetable oil polyol is prepared by a method of claim 1.

10. A process for utilizing for a vegetable oil polyol of claim 9, wherein the process for use the vegetable oil polyol for preparing a flexible polyurethane foam.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0035] FIG. 1 is a schematic diagram of a microchannel reaction device.

DETAILED DESCRIPTION OF THE INVENTION

[0036] The present invention is further below in conjunction with specific examples.

[0037] Related determination methods for the vegetable oil polyol for flexible polyurethane foam and flexible polyurethane foam as prepared according to the present invention are as follows: [0038] determining a hydroxyl value according to GB/T 12008.3-2009; [0039] determining the viscosity according to GB/T 12008.7-2010; [0040] determining the density of foam plastic according to GB/T 6343-2009XX; [0041] determining the indentation strength of the foam plastic according to GB/T 20467-2006XX; [0042] determining the tensile strength of the foam plastic according to GB/T 6344-2008XX; and [0043] determining the tear strength of foam according to GB/T 10808-2006.

[0044] A microchannel reaction device in the following examples, as shown in FIG. 1, includes a first micromixer, a first microchannel reactor, a second micromixer, and a second microchannel reactor which are sequentially connected by a pipe. Reaction raw materials are input into the micromixers and subsequent equipment via a pump with precise and low pulsation. Among them, a first raw material storage tank (benzoylformic acid solution storage tank) is connected to a feed port of the first micromixer through the pump, a second raw material storage tank (epoxidized vegetable oil and basic catalyst solution storage tank) is connected to a feed port of the first micromixer through the pump, and a third raw material storage tank (propylene oxide solution storage tank) is connected to a feed port of the second micromixer through the pump.

[0045] The first micromixer and the second micromixer are both Y-type mixers. The first microchannel reactor and the second microchannel reactor are both polytetrafluoroethylene coils having an inner diameter of 1.0 mm and connected to a back pressure valve. The temperatures of the first microchannel reactor and the second microchannel reactor are both controlled by heating in an oil bath.

Example 1

[0046] 50.57 g of benzoylformic acid was dissolved in 600 mL of dichloromethane to obtain a mixed solution A, 100 g of epoxidized soybean oil and 0.08 g of sodium carbonate were dissolved in 600 mL of dichloroethane to obtain a solution B, and 91.58 g of propylene oxide was dissolved in 1200 mL of dichloroethane to obtain a solution C. A molar ratio of epoxy group in the epoxidized soybean oil to benzoylformic acid was 1:1.2, the mass percentage of sodium carbonate in the epoxidized soybean oil was 0.08%, and a molar ratio of epoxy group in the epoxidized soybean oil to propylene oxide was 1:15. The mixed solution A and the solution B were separately and simultaneously pumped into the first micromixer in the microchannel reaction device, fully mixed, then passed into the first microchannel reactor and subjected to a ring-opening reaction to obtain a reaction solution containing a vegetable oil polyol. The obtained reaction solution containing the vegetable oil polyol and the solution C were pumped into the second micromixer in the microchannel reaction device, fully mixed, then passed into the second microchannel reactor and subjected to an addition polymerization reaction. The volume of the first microchannel reactor was 10 mL, the reaction temperature was 100 C., and the reaction time was 8 min; and the volume of the second microchannel reactor was 50 mL, the reaction temperature was 130 C., and the reaction time was 20 min. The flow rates of the solutions A, B, and C were 0.625 mL/min, 0.625 mL/min, and 1.25 mL/min, respectively. After the completion of the reaction, a product was introduced into a separator and allowed to stand for layering to remove an aqueous solution in a lower layer. An upper organic phase was neutralized with 5 wt % hydrochloric acid to a pH value of 6.5-7.5 and separated. The organic phase was rotary-evaporated and dried to obtain a vegetable oil polyol for flexible polyurethane foam.

Example 2

[0047] 75.82 g of benzoylformic acid was dissolved in 600 mL of dichloromethane to obtain a mixed solution A, 100 g of epoxidized soybean oil and 0.02 g of sodium carbonate were dissolved in 600 mL of dichloroethane to obtain a solution B, and 61.05 g of propylene oxide was dissolved in 1200 mL of dichloroethane to obtain a solution C. A molar ratio of epoxy group in the epoxidized soybean oil to benzoylformic acid was 1:0.8, the mass percentage of sodium carbonate in the epoxidized soybean oil was 0.02%, and a molar ratio of epoxy group in the epoxidized soybean oil to propylene oxide was 1:10. The mixed solution A and the solution B were separately and simultaneously pumped into the first micromixer in the microchannel reaction device, fully mixed, then passed into the first microchannel reactor and subjected to a ring-opening reaction to obtain a reaction solution containing a vegetable oil polyol. The obtained reaction solution containing the vegetable oil polyol and the solution C were pumped into the second micromixer in the microchannel reaction device, fully mixed, then passed into the second microchannel reactor and subjected to an addition polymerization reaction. The volume of the first microchannel reactor was 10 mL, the reaction temperature was 100 C., and the reaction time was 5 min; and the volume of the second microchannel reactor was 40 mL, the reaction temperature was 80 C., and the reaction time was 10 min. The flow rates of the solutions A, B, and C were 1.0 mL/min, 1.0 mL/min, and 2.0 mL/min, respectively. After the completion of the reaction, a product was introduced into a separator and allowed to stand for layering to remove an aqueous solution in a lower layer. An upper organic phase was neutralized with 5 wt % hydrochloric acid to a pH value of 6.5-7.5 and separated. The organic phase was rotary-evaporated and dried to obtain a vegetable oil polyol for flexible polyurethane foam.

Example 3

[0048] 94.81 g of benzoylformic acid was dissolved in 600 mL of dichloromethane to obtain a mixed solution A, 100 g of epoxidized soybean oil and 0.1 g of sodium carbonate were dissolved in 600 mL of dichloroethane to obtain a solution B, and 122.11 g of propylene oxide was dissolved in 1200 mL of dichloroethane to obtain a solution C. The molar ratio of epoxy group in the epoxidized soybean oil to benzoylformic acid was 1:1.5, the mass percentage of sodium carbonate in the epoxidized soybean oil was 0.1%, and a molar ratio of epoxy group in the epoxidized soybean oil to propylene oxide was 1:20. The mixed solution A and the solution B were separately and simultaneously pumped into the first micromixer in the microchannel reaction device, fully mixed, then passed into the first microchannel reactor and subjected to a ring-opening reaction to obtain a reaction solution containing a vegetable oil polyol. The obtained reaction solution containing the vegetable oil polyol and the solution C were pumped into the second micromixer in the microchannel reaction device, fully mixed, then passed into the second microchannel reactor and subjected to an addition polymerization reaction. The volume of the first microchannel reactor was 10 mL, the reaction temperature was 150 C., and the reaction time was 20 min; and the volume of the second microchannel reactor was 25 mL, the reaction temperature was 150 C., and the reaction time was 25 min. The flow rates of the solutions A, B, and C were 0.25 mL/min, 0.25 mL/min, and 0.5 mL/min, respectively. After the completion of the reaction, a product was introduced into a separator and allowed to stand for layering to remove an aqueous solution in a lower layer. An upper organic phase was neutralized with 5 wt % hydrochloric acid to a pH value of 6.5-7.5 and separated. The organic phase was rotary-evaporated and dried to obtain a vegetable oil polyol for flexible polyurethane foam.

Example 4

[0049] Different from Example 1, the epoxidized vegetable oil was epoxidized cottonseed oil, and a molar ratio of epoxy group in the epoxidized cottonseed oil to benzoylformic acid was 1:1.5, a molar ratio of epoxy group in the epoxidized cottonseed oil to propylene oxide was 1:12, and the mass percentage of sodium carbonate in the epoxidized cottonseed oil was 0.05%.

Example 5

[0050] Different from Example 1, the epoxidized vegetable oil was epoxidized palm oil, a molar ratio of epoxy group in the epoxidized palm oil to benzoylformic acid was 1:1.3, a molar ratio of epoxy group in the epoxidized palm oil to propylene oxide was 1:15, and the mass percentage of sodium carbonate in the epoxidized palm oil was 0.06%.

Example 6 Preparation of Flexible Polyurethane Foam

[0051] A formula of flexible polyurethane foam includes the following components in parts by weight: 100 parts of vegetable oil polyol for flexible polyurethane foam; 8 parts of ethylene glycol; 0.5 part of B8681 (stabilizer); 1 part of water; 1 part of triethylene diamine; and 1.0 part of toluene diisocyanate.

[0052] A preparation method includes the following steps: weighing the above components in parts by weight, mixing thoroughly and uniformly at 25 C. (except for toluene diisocyanate), adding the stoichiometric toluene diisocyanate, stirring for 10 s, pouring into a foaming box to freely foam, and aging to obtain a conventional flexible polyurethane foam.

[0053] Table 1 shows performance indexes of the vegetable oil polyol for flexible polyurethane foam prepared in Examples 1 to 5. The flexible polyurethane foams were prepared using the vegetable oil polyol for flexible polyurethane foam obtained in Examples 1 to 5, and performance indexes of the obtained products are shown in Table 2.

TABLE-US-00001 TABLE 1 Performance indexes of vegetable oil polyol for flexible polyurethane foam Performance indexes Example 1 Example 2 Example 3 Example 4 Example 5 Hydroxyl 31 38 42 38 46 value mgKOH/g Viscosity 860 812 648 960 760 mPas/25 C.

TABLE-US-00002 TABLE 2 Performance indexes of polyurethane foam Test item Example 1 Example 2 Example 3 Example 4 Example 5 Density 41.5 38.5 52.2 33 30.2 (kg/m.sup.3) Indentation 136 113 85 106 105.5 strength (25% IFD, N) Tensile 116 108 120 103 121 strength kPa Elongation at 127 115 131 135 144 break % Resilience 61 43 51 58 39 by ball rebound % Tear strength 412 372 351 364 410 N/m Surface 46 51 45 48 60 hardness

Example 7

[0054] Example 7 was carried out in the same way as Example 1, except that the epoxidized soybean oil was replaced with an epoxidized olive oil, the sodium carbonate was replaced with sodium hydroxide, the dichloromethane was replaced with chloroform, and dichloroethane was replaced with n-hexane. The obtained vegetable oil polyol for flexible polyurethane foam was detected to have similar properties to the vegetable oil polyol for flexible polyurethane foam and obtained in Example 1.

Example 8

[0055] Example 8 was carried out in the same way as Example 1, only except that the epoxidized soybean oil was replaced with epoxidized peanut oil, and the sodium carbonate was replaced with sodium methoxide. A product obtained was detected to have similar properties to the product obtained in Example 1. The obtained vegetable oil polyol for flexible polyurethane foam was detected to have similar properties to the vegetable oil polyol for flexible polyurethane foam and obtained in Example 1.

Example 9

[0056] Example 9 was carried out in the same way as Example 1, only except that the epoxidized soybean oil was replaced with epoxidized rapeseed oil, and the sodium carbonate was replaced with sodium tert-butoxide. A product obtained was detected to have similar properties to the product obtained in Example 1. The obtained vegetable oil polyol for flexible polyurethane foam was detected to have similar properties to the vegetable oil polyol for flexible polyurethane foam and obtained in Example 1.

Example 10

[0057] Example 10 was carried out in the same way as Example 1, only except that the epoxidized soybean oil was replaced with epoxidized corn oil, and the sodium carbonate was replaced with sodium bicarbonate. A product obtained was detected to have similar properties to the product obtained in Example 1. The obtained vegetable oil polyol for flexible polyurethane foam was detected to have similar properties to the vegetable oil polyol for flexible polyurethane foam and obtained in Example 1.

Example 11

[0058] Example 11 was carried out in the same way as Example 1, only except that the epoxidized soybean oil was replaced with epoxidized sesame oil, and the sodium carbonate was replaced with potassium ethoxide. A product obtained was detected to have similar properties to the product obtained in Example 1. The obtained vegetable oil polyol for flexible polyurethane foam was detected to have similar properties to the vegetable oil polyol for flexible polyurethane foam and obtained in Example 1.