A slow-rebound bio-based polyether polyol, preparation method and application

Abstract

The present invention discloses a slow-rebound bio-based polyether polyol, a preparation method and an application thereof, wherein the polyether polyol has a hydroxyl value of 105-135 mgKOH / g and a bio-based content of 25-70%; the polyether polyol comprises a monofunctional polyether a and a multifunctional polyether b in a weight ratio of (1-4):(6-9); the monofunctional polyether a has a hydroxyl value of 10-60 mgKOH / g and contains 5-50 wt% of copolymerized ethylene oxide, based on the total weight of the monofunctional polyether a; the multifunctional polyether b has a hydroxyl value of 105-210 mgKOH / g, an average functionality of 2.1-8, and contains ≤50 wt% of copolymerized ethylene oxide, based on the total weight of the multifunctional polyether b; the bio-based in the polyether polyol is derived from the monofunctional polyether a and / or the multifunctional polyether b. The slow-rebound bio-based polyether polyol provided by the present invention can significantly improve the bio-based content in the foam while ensuring the slow rebound performance of the foam.

Description

Technical Field

[0001] The invention relates to a polyether polyol, in particular to a slow-rebound bio-based polyether polyol, a preparation method and application thereof. Background Art

[0002] Slow-rebound foam, also known as viscoelastic foam or memory foam, is widely used in furniture, bedding, auto parts, medical equipment and other fields due to its shape memory, sound absorption, energy absorption and other functions. With the advancement of the dual-carbon policy, both domestic and foreign countries have put forward requirements for the bio-based content of foam. Some countries require the bio-based content of slow-rebound foam to be higher than 25%.

[0003] At present, the main raw materials of slow-rebound foam are some highly active polyethers (such as 330N, F3135) and small molecule polyethers (3-guan 700 molecular weight polyether, 3-guan 500 molecular weight polyether). This slow-rebound foam prepared by polyether combination has serious closed-cell property and poor air permeability, and usually needs to add additional pore-opening agent in the formula to improve the closed-cell problem. In addition, this type of foam has poor low-temperature resistance. The foam will harden in a low-temperature environment, affecting the comfort of the product. Patent CN105315449A and Patent 110402263A prepare slow-rebound foam with good air permeability and low-temperature resistance by adjusting the polyether structure, but these polyethers are non-biobased polyether polyols. CN101121784B discloses a method for preparing castor oil polyether polyol, which can be used for the preparation of soft foam, but when used for slow-rebound foam, the polyether has similar properties to 330N products and has problems such as closed cells. Developing new bio-based polyether polyols is an effective way to increase the bio-based content of slow-rebound foam, but how to maintain the excellent slow-rebound elasticity of slow-rebound foam at the same time is a difficult point in development within the industry. Summary of the invention

[0004] In order to solve the above technical problems, the present invention proposes a slow-rebound bio-based polyether polyol, a preparation method and an application thereof.

[0005] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0006] A slow-rebound bio-based polyether polyol having a hydroxyl value of 105-135 mgKOH / g and a bio-based content of 25-70%, preferably 40-65%;

[0007] The polyether polyol comprises a monofunctional polyether a and a multifunctional polyether b in a weight ratio of (1-4):(6-9);

[0008] The monofunctional polyether a has a hydroxyl value of 10-60 mgKOH / g and contains 5-50 wt % of copolymerized ethylene oxide, based on the total weight of the monofunctional polyether a;

[0009] The multifunctional polyether b has a hydroxyl value of 105-210 mgKOH / g, an average functionality of 2.1-8, and contains ≤50 wt% of copolymerized ethylene oxide, based on the total weight of the multifunctional polyether b; the bio-based materials in the polyether polyol are derived from the monofunctional polyether a and / or the multifunctional polyether b.

[0010] In some examples, the initiator of the monofunctional polyether a is a bio-based monofunctional alcohol, preferably a natural fatty alcohol, more preferably C 12 -C 14 Fatty alcohol, C 16 -C 18 Fatty alcohol, C8-C 10 Fatty alcohol, C 10 One or more of alcohols.

[0011] In some examples, the initiator of the multifunctional polyether b is a bio-based multifunctional alcohol, preferably one or more of castor oil, soybean oil polyol, 1,3-propylene glycol, 1,4-butanediol, sorbitol, sucrose, and glucose, more preferably castor oil or a mixture of castor oil and 1,4-butanediol.

[0012] The present invention also provides a method for preparing the slow-rebound bio-based polyether polyol as described above, comprising the following steps:

[0013] 1) Add bio-based monofunctional alcohol and catalyst into the reactor, replace with nitrogen until the oxygen content is ≤50ppm, raise the temperature to 125-150°C, control the pressure in the reactor to be lower than 0.5MPa, and continuously add epoxy compound a into the reactor. When the designed amount of epoxy compound a is reached, stop adding and continue the aging reaction for 0.5-2h;

[0014] 2) After aging, the pressure in the reactor is controlled to be lower than 0.5MPa, the temperature in the reactor is 125-150°C, and bio-based multifunctional alcohol and epoxy compound b are continuously introduced into the reactor. When the designed amount of bio-based multifunctional alcohol is reached, the addition of bio-based multifunctional alcohol is stopped, and when the designed amount of epoxy compound b is reached, the addition of epoxy compound b is stopped, and the aging reaction is continued for 0.5-2h; the monomer is removed, the temperature is lowered and the material is discharged to obtain a slow-rebound bio-based polyether polyol.

[0015] In some examples, the catalyst is a bimetallic catalyst DMC, and the amount used is 0.002-0.005% of the designed mass of the slow-rebound bio-based polyether polyol.

[0016] In some examples, the epoxy compound a is one or both of propylene oxide and ethylene oxide, preferably a mixture of propylene oxide and ethylene oxide in a mass ratio of (50-95):(5-50).

[0017] In some examples, the epoxy compound b is one or both of propylene oxide and ethylene oxide, preferably a mixture of propylene oxide and ethylene oxide in a mass ratio of (10-100):(0-90).

[0018] The present invention also provides a bio-based slow-rebound foam, which comprises, by weight, a component A and a component B of the following compositions:

[0019] Component A:

[0020]

[0021] Wherein, the total weight parts of polyether polyol a and bio-based polyether polyol are 100 parts;

[0022] Component B: modified MDI.

[0023] In some examples, the polyether polyol a is a polyether polyol having a hydroxyl value of 26-42 mgKOH / g, preferably at least one of F3140, F3150, and F3135;

[0024] Preferably, the catalyst is one or more of polyurethane catalyst A-33, polyurethane catalyst A-300, polyurethane catalyst NE300, and polyurethane catalyst A-1;

[0025] Preferably, the silicone oil is one or more of B8002, B8409, and L-580;

[0026] Preferably, the foaming agent is one or both of water and dichloromethane;

[0027] Preferably, the modified MDI is selected from one or more of modified MDI 8019, modified MDI 8223B, and modified MDI 2412.

[0028] In some examples, the mixing ratio of the A component to the B component is 60-115 in terms of isocyanate index.

[0029] Optionally, the preparation method of the bio-based slow-rebound foam is, for example: after component A is prepared, component A and component B are evenly mixed at room temperature, and then quickly poured into a mold preheated to 40-60° C. and matured for 3-5 minutes to obtain the bio-based slow-rebound foam.

[0030] The beneficial effects of the present invention are:

[0031] (1) The present invention provides a bio-based polyether polyol that can be used to prepare slow-rebound foam, which can significantly increase the bio-based content in the foam while ensuring the slow-rebound performance of the foam.

[0032] (2) The foam prepared using the polyether prepared by the present invention without using a cell-opening agent has excellent air permeability and low-temperature resistance, and the product has good comfort under low-temperature conditions.

[0033] (3) The bio-based polyether is suitable for foaming under high index conditions and can effectively reduce the amine residue in the foam. DETAILED DESCRIPTION

[0034] The present invention is further described below by means of specific examples. The examples described in the present invention are only used to illustrate the present invention and do not limit the scope of the present invention.

[0035] 1. The main test methods used in the present invention are as follows:

[0036] 1. Hydroxyl value: The hydroxyl value test reference standard GB / T 12008.3-2009 Plastic polyether polyols Part 3: Determination of hydroxyl value;

[0037] 2. Biobased content: Biobased content test refers to ASTM D6866-18;

[0038] 3. Air permeability test: refer to the standard method "GB / T 5453-1997";

[0039] 4. Slow rebound time: compress the foam to the lowest height with force, and record the foam recovery time after removing the external force;

[0040] 5. Glass transition temperature Tg: refer to GB / T 40396-2021

[0041] 2. Information on the main raw materials of the present invention:

[0042] All materials involved in the examples are from commercial sources unless otherwise specified, and the purity of the products is analytical grade unless otherwise specified.

[0043] The following examples 1-4 are used to prepare different bio-based polyether polyols:

[0044] [Example 1]

[0045] 82.6 g C 12 -C 14 Fatty alcohol and 0.08 g of bimetallic catalyst DMC were added to the reactor, and nitrogen was replaced until the oxygen content was ≤50 ppm. The temperature was raised to 150°C, and the pressure in the reactor was controlled to be lower than 0.5 MPa. The epoxy mixture (15.9 g of ethylene oxide and 302 g of propylene oxide) was continuously introduced into the reactor while maintaining the temperature at 150°C. After the feeding was completed, the reactor was aged at 150°C for 0.5 h.

[0046] After the aging, the pressure in the kettle was controlled below 0.5 MPa, and 2444.4 g of castor oil and an epoxy mixture (347 g of ethylene oxide and 809 g of propylene oxide) were introduced into the kettle while maintaining the temperature at 150°C. The feed rate ratio of castor oil to epoxy mixture was 4:1. After the epoxy mixture was fed, the temperature was maintained at 150°C for 0.5 h, vacuum degassing was performed, and the temperature was lowered by 50°C to discharge the material, thereby obtaining 3993 g of bio-based polyether polyol A (hydroxyl value 105 mgKOH / g, bio-based content 65.3%).

[0047] [Example 2]

[0048] 103.6 g C 16 -C 18 Fatty alcohol and 0.12g of bimetallic catalyst DMC were added to the reactor, and nitrogen was replaced until the oxygen content was ≤50ppm. The temperature was raised to 135°C, and the pressure in the reactor was controlled to be lower than 0.5MPa. The epoxy mixture (219g of ethylene oxide and 877g of propylene oxide) was continuously introduced into the reactor while maintaining the temperature in the reactor at 135°C. After the feeding was completed, the reactor was aged at 135°C for 1h.

[0049] After the aging, the pressure in the kettle was controlled below 0.5 MPa. The temperature in the kettle was maintained at 135°C. A multifunctional alcohol mixture (1280 g of castor oil and 142.2 g of 1,3-propylene glycol) and an epoxy mixture (689 g of ethylene oxide and 689 g of propylene oxide) were introduced into the kettle at the same time. The feeding rate ratio of the multifunctional alcohol mixture to the epoxy mixture was 2:1. After the epoxy mixture was fed, the temperature was maintained at 135°C for 1 hour. The mixture was vacuumed for degassing, cooled by 50°C and discharged to obtain 3995 g of bio-based polyether polyol B (hydroxyl value: 110 mgKOH / g, bio-based content: 41.5%).

[0050] [Example 3]

[0051] 80.6 g C8-C 10 Fatty alcohol and 0.16 g of bimetallic catalyst DMC were added to the reactor, and nitrogen was replaced until the oxygen content was ≤50 ppm. The temperature was raised to 140°C, and the pressure in the reactor was controlled to be lower than 0.5 MPa. The epoxy mixture (215.8 g of ethylene oxide and 504 g of propylene oxide) was continuously introduced into the reactor while maintaining the temperature in the reactor at 140°C. After the feeding was completed, the reactor was aged at 140°C for 1 hour;

[0052] After the aging, the pressure in the kettle was controlled below 0.5 MPa. The temperature in the kettle was maintained at 140°C. A multifunctional alcohol mixture (816 g of castor oil, 102 g of sorbitol, and 102 g of 1,4-butanediol) and an epoxy mixture (436 g of ethylene oxide and 1744 g of propylene oxide) were introduced into the kettle at the same time. The feeding rate ratio of the multifunctional alcohol to the epoxy mixture was 1:1. After the feeding of the epoxy mixture was completed, the kettle was aged at 135°C for 1 hour, vacuumed for degassing, cooled by 50°C and discharged to obtain 3994 g of bio-based polyether polyol C (hydroxyl value 120 mgKOH / g, bio-based content 28.5%).

[0053] [Example 4]

[0054] 45.2 g C 10 Fatty alcohol and 0.20 g of bimetallic catalyst DMC were added to the reactor, and nitrogen was replaced until the oxygen content was ≤50 ppm. The temperature was raised to 125° C., and the pressure in the reactor was controlled to be lower than 0.5 MPa. The epoxy mixture (ethylene oxide 777.4 g, propylene oxide 777.4 g) was continuously introduced into the reactor while maintaining the temperature in the reactor at 125° C. After the feeding was completed, the reactor was aged at 125° C. for 2 h.

[0055] After the aging, the pressure in the kettle was controlled below 0.5 MPa. The temperature in the kettle was maintained at 125°C. A multifunctional alcohol mixture (687.7 g soybean oil polyol, 294.7 g 1,4-butanediol) and 1417.5 g propylene oxide were introduced into the kettle at the same time. The feeding rate ratio of the multifunctional alcohol to the epoxy mixture was 1.4:1. After the feeding of the epoxy mixture was completed, the aging was maintained at 125°C for 2 hours. The mixture was vacuumed for degassing, cooled by 50°C and discharged to obtain 993 g of bio-based polyether polyol D3 (hydroxyl value 135 mgKOH / g, bio-based content 26.1%).

[0056] [Comparative Example 1]

[0057] 2444.4 g of castor oil and 0.08 g of a bimetallic catalyst were added into a reactor, and nitrogen was replaced until the oxygen content was ≤50 ppm. The temperature was raised to 150° C., the pressure in the reactor was controlled to be lower than 0.5 MPa, and an epoxy mixture (347 g of ethylene oxide and 809 g of propylene oxide) was continuously introduced into the reactor while maintaining the temperature at 150° C. After the feeding was completed, the temperature was maintained at 150° C. for aging for 0.5 h; vacuum degassing was performed, and the temperature was lowered by 50° C. to discharge the material, thereby obtaining 3596 g of bio-based polyether polyol E (hydroxyl value 110 mgKOH / g, bio-based content 69.4%).

[0058] [Comparative Example 2] Bio-based polyether polyol F

[0059] 826g C 12 -C 14Fatty alcohol and 0.08 g of bimetallic catalyst DMC were added to the reactor, and nitrogen was replaced until the oxygen content was ≤50 ppm. The temperature was raised to 150° C., the pressure in the reactor was controlled to be lower than 0.5 MPa, and the epoxy mixture (159 g of ethylene oxide and 3020 g of propylene oxide) was continuously introduced into the reactor while maintaining the temperature in the reactor at 150° C. After the feeding was completed, the temperature was maintained at 150° C. for aging for 0.5 h, vacuum degassing was performed, and the temperature was lowered by 50° C. to discharge the material, thereby obtaining 3994 g of bio-based polyether polyol F (hydroxyl value 58 mgKOH / g, bio-based content 24.7%).

[0060] The following examples are used to prepare different bio-based slow-rebound foams:

[0061] [Example 5]

[0062] Prepare component A and component B according to the following formula:

[0063] Component A:

[0064] Polyether polyol a F3135 20g, bio-based polyether polyol A 80g, catalyst A-33 0.5g and catalyst A-1 0.5g, silicone oil B8409 1.5g, water 2.5g.

[0065] Component B: modified MDI 8223B.

[0066] The mixing ratio of component A to component B is 60 according to the isocyanate index.

[0067] The above-mentioned component A and component B are mixed uniformly at room temperature, and then quickly poured into a mold preheated to 50° C. and cured for 5 minutes to obtain a bio-based slow-rebound foam.

[0068] [Example 6-8, Comparative Example 3-6]

[0069] The bio-based slow-rebound foam was prepared in substantially the same manner as in Example 5, except that the components A and B and their amounts were respectively referred to the formula in Table 1.

[0070] The air permeability, slow resilience and Tg tests were performed on the foams prepared in Examples 5-8 and Comparative Examples 3-6, respectively. The test results are shown in Table 2.

[0071] It can be seen from the test results that the slow-rebound bio-based foam provided by the present invention not only has a high bio-based content, but also has a good slow-rebound effect, and also has high air permeability and low-temperature resistance.

[0072] Table 1, Foam formulations in Examples 5-8 and Comparative Examples 3-6

[0073]

[0074] Table 2. Foam performance test results

[0075]

Claims

1. A slow-rebound bio-based polyether polyol, characterized in that: The polyether polyol has a hydroxyl value of 105-135 mgKOH / g and a biobased content of 25-70%; The polyether polyol comprises a monofunctional polyether a and a multifunctional polyether b in a weight ratio of (1-4):(6-9); The monofunctional polyether a has a hydroxyl value of 10-60 mgKOH / g and contains 5-50 wt % of copolymerized ethylene oxide, based on the total weight of the monofunctional polyether a; The multifunctional polyether b has a hydroxyl value of 105-210 mgKOH / g, an average functionality of 2.1-8, and contains ≤50 wt% of copolymerized ethylene oxide, based on the total weight of the multifunctional polyether b; The bio-based groups in the polyether polyol are derived from the monofunctional polyether a and / or the multifunctional polyether b.

2. The slow-rebound bio-based polyether polyol according to claim 1, characterized in that: The bio-based content of the polyether polyol is 40-65%.

3. The slow-rebound bio-based polyether polyol according to claim 1, characterized in that: The initiator of the monofunctional polyether a is a bio-based monofunctional alcohol.

4. The slow-rebound bio-based polyether polyol according to claim 3, characterized in that: The initiator of the monofunctional polyether a is a natural fatty alcohol.

5. The slow-rebound bio-based polyether polyol according to claim 3, characterized in that: The initiator of the monofunctional polyether a is C 12 -C 14 Fatty alcohol, C 16 -C 18 Fatty alcohol, C8-C 10 Fatty alcohol, C 10 One or more of alcohols.

6. The slow-rebound bio-based polyether polyol according to any one of claims 1 to 5, characterized in that: The initiator of the multifunctional polyether b is a bio-based multifunctional alcohol.

7. The slow-rebound bio-based polyether polyol according to claim 6, characterized in that: The initiator of the multifunctional polyether b is one or more of castor oil, soybean oil polyol, 1,3-propylene glycol, 1,4-butanediol, sorbitol, sucrose and glucose.

8. The slow-rebound bio-based polyether polyol according to claim 6, characterized in that: The initiator of the multifunctional polyether b is castor oil or a mixture of castor oil and 1,4-butanediol.

9. A method for preparing the slow-rebound bio-based polyether polyol according to any one of claims 1 to 8, characterized in that: The following steps are involved: 1) Add bio-based monofunctional alcohol and catalyst into the reactor, replace with nitrogen until the oxygen content is ≤50ppm, raise the temperature to 125-150°C, control the pressure in the reactor to be lower than 0.5MPa, and continuously add epoxy compound a into the reactor. When the designed amount of epoxy compound a is reached, stop adding and continue the aging reaction for 0.5-2h; 2) After aging, the pressure in the reactor is controlled to be lower than 0.5 MPa, the temperature in the reactor is 125-150°C, and bio-based multifunctional alcohol and epoxy compound b are continuously introduced into the reactor. When the designed amount of bio-based multifunctional alcohol is reached, the addition of bio-based multifunctional alcohol is stopped, and when the designed amount of epoxy compound b is reached, the addition of epoxy compound b is stopped, and the aging reaction is continued for 0.5-2h; the monomer is removed, the temperature is lowered and the material is discharged to obtain a slow-rebound bio-based polyether polyol.

10. The method for preparing the slow-rebound bio-based polyether polyol according to claim 9, characterized in that: The catalyst is a bimetallic catalyst DMC, and the dosage is 0.002-0.005% of the designed mass of the slow-rebound bio-based polyether polyol.

11. The method for preparing the slow-rebound bio-based polyether polyol according to claim 9 or 10, characterized in that: The epoxy compound a is one or both of propylene oxide and ethylene oxide.

12. The method for preparing the slow-rebound bio-based polyether polyol according to claim 11, characterized in that: The epoxy compound a is a mixture of propylene oxide and ethylene oxide in a mass ratio of (50-95):(5-50).

13. The method for preparing the slow-rebound bio-based polyether polyol according to claim 9 or 10, characterized in that: The epoxy compound b is one or both of propylene oxide and ethylene oxide.

14. The method for preparing the slow-rebound bio-based polyether polyol according to claim 13, characterized in that: The epoxy compound b is a mixture of propylene oxide and ethylene oxide in a mass ratio of (10-100):(0-90).

15. A bio-based slow-rebound foam, characterized in that: The composition comprises the following components A and B by weight: Component A: Polyether polyol a 20-50 parts, 50-80 parts of bio-based polyether polyol, Catalyst 0.5-1 part, Silicone oil 0.5-1.5 parts, 2.5-5 parts of foaming agent, Wherein, the total weight of polyether polyol a and bio-based polyether polyol is 100 parts; the bio-based polyether polyol is the slow-rebound bio-based polyether polyol described in any one of claims 1 to 8 or the slow-rebound bio-based polyether polyol prepared by the method described in any one of claims 9 to 14; Component B: modified MDI.

16. The bio-based slow-rebound foam according to claim 15, characterized in that: The polyether polyol a is a polyether polyol having a hydroxyl value of 26-42 mgKOH / g.

17. The bio-based slow-rebound foam according to claim 16, characterized in that: The polyether polyol a is at least one of F3140, F3150, and F3135.

18. The bio-based slow-rebound foam according to claim 16, characterized in that: The catalyst is one or more of polyurethane catalyst A-33, polyurethane catalyst A-300, polyurethane catalyst NE300, and polyurethane catalyst A-1.

19. The bio-based slow-rebound foam according to claim 16, characterized in that: The silicone oil is one or more of B8002, B8409, and L-580.

20. The bio-based slow-rebound foam according to claim 16, characterized in that: The foaming agent is one or both of water and dichloromethane.

21. The bio-based slow-rebound foam according to claim 16, characterized in that: The modified MDI is selected from one or more of modified MDI8019, modified MDI 8223B, and modified MDI 2412.

22. The bio-based slow-rebound foam according to any one of claims 15 to 21, characterized in that: The mixing ratio of component A to component B is 60-115 according to the isocyanate index.

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