CN111825827A - Synthetic process and application of vegetable oil-based modified isocyanate - Google Patents
Synthetic process and application of vegetable oil-based modified isocyanate Download PDFInfo
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Abstract
The invention relates to a synthetic process of vegetable oil-based modified isocyanate and application thereof, wherein vegetable oil modified isocyanate is adopted, the isocyanate is reacted with hydroxylated vegetable oil, the content of TDI isocyanate after modification is 30-42%, the content of MDI isocyanate after modification is 15-25%, and the content of TDI/MD mixed isocyanate after modification is 18-35%. The isocyanate comprises: TDI, MDI, or a mixture of TDI and MDI. Hydroxylated vegetable oil, petroleum-based polyether polyol and petroleum-based polymer polyol are mixed with a catalyst, a silicone oil surfactant and a foaming agent, and then react with vegetable oil-based isocyanate to obtain the high vegetable oil-based flexible polyurethane foam. The method has the advantages that the proportion of the vegetable oil-based material in the soft polyurethane foam is 30-50%, the dependence on petroleum-based polyurethane raw materials is reduced, the degradation rate of the soft polyurethane foam is improved, and the method has strong support on national environmental protection policies.
Description
Technical Field
The invention relates to the technical field of vegetable oil-based modified isocyanate, in particular to a synthesis process and application of vegetable oil-based modified isocyanate.
Background
The Flexible Polyurethane Foam (Polyurethane Foam for short) refers to a kind of Flexible Polyurethane Foam with certain elasticity, which is a Polyurethane product with the largest usage amount. The product mainly comprises High Resilience Foam (HRF), block sponge, slow resilience foam, self-skinning foam (ISF), semi-rigid foam and the like. The cell structure of the polyurethane flexible foam is mostly open-celled. Generally has the performances of low density, good elastic recovery, sound absorption, ventilation, heat preservation and the like, and is mainly used as furniture cushion materials, vehicle seat cushion materials and various soft liner laminated composite materials. The soft foam is also used as a filter material, a sound insulation material, a shockproof material, a decorative material, a packaging material, a heat insulation material and the like in industry and civilian use.
The dependence on petroleum-based polyurethane raw materials in the production process of the existing soft polyurethane sponge is large, so that the produced soft polyurethane foam is not easy to degrade, and the later-stage waste soft polyurethane sponge is not easy to be chemically recovered; in order to improve the environmental protection effect, in the production of soft polyurethane foam by adopting a bio-based material, at present, in the production, the bio-based material is adopted to replace petroleum-based polyurethane raw materials, and a large amount of bio-based material is added, theoretically, but in the actual reaction process, other raw materials are fast in reaction speed and are cured quickly, the bio-based material is not reacted completely, so that the product is not shaped, only part of the bio-based material participates in the reaction, so that the use ratio of the bio-based material in the soft polyurethane foam at present is generally not more than 20 percent, even less, the content of the bio-based material cannot be further improved, and.
Disclosure of Invention
In order to solve the technical problems, the invention provides a synthesis process and application of vegetable oil-based modified isocyanate, which adopts vegetable oil modified isocyanate and matches with hydroxylated vegetable oil to be used in soft polyurethane foam to improve the proportion of vegetable oil-based biological materials in the soft polyurethane foam; the method has great help for reducing the dependence on petroleum-based polyurethane raw materials and improving the degradation rate of the flexible polyurethane foam, and has strong support for the national environmental protection policy.
The technical scheme of the invention is as follows:
the synthetic process of the vegetable oil-based modified isocyanate comprises the following steps,
1) the isocyanate is first placed in a reaction vessel and the reaction vessel is heated to 75-90 ℃.
2) Adding the hydroxylated vegetable oil into a reaction container, and dropwise adding for 1 hour in a dropwise adding mode, wherein the temperature in the reaction container is kept at 80-95 ℃ in the dropwise adding process.
3) After the dropwise addition, the temperature in the reaction container is raised to 90-100 ℃, and the temperature is kept for 2-4 hours.
4) After the heat preservation is finished, cooling the temperature in the reaction container to 40-60 ℃, and discharging; obtaining the vegetable oil-based modified isocyanate.
The weight ratio of the isocyanate to the hydroxylated vegetable oil is 2-3.5: 1.
the hydroxylated vegetable oil is hydroxylated vegetable oil A or hydroxylated vegetable oil B; the hydroxylated vegetable oil A: hydroxyl value: 60, viscosity: 2540 cps; the hydroxylated vegetable oil B is a hydroxyl value: 110, viscosity: 1840 cps.
The isocyanate is one or a mixture of more than two of Toluene Diisocyanate (TDI) with the isocyanate content of 48 percent, diphenylmethane diisocyanate (MDI) with the isocyanate content of 33 percent or polyphenyl polymethylene isocyanate (MDI) with the isocyanate content of 33 percent.
The content of the isocyanate in the vegetable oil-based modified isocyanate is 30-42% of that of the TDI isocyanate after modification; the content of modified MDI isocyanate is 15-25%; the content of the modified TDI/MDI mixed isocyanic acid radical is 18-35%; the viscosity is 450 to 1000 cps/25 ℃; the content of the vegetable oil base is 21-32%.
The application of the vegetable oil-based modified isocyanate produced by adopting the synthetic process of the vegetable oil-based modified isocyanate in any one of the claims to the production of high vegetable oil-based polyurethane soft foam,
the formula process of the high vegetable oil-based polyurethane flexible foam comprises the following raw materials in percentage by weight,
55-68% of a mixture of hydroxylated vegetable oil and petroleum-based polyether polyol, 0.5-1% of silicone oil L-580, 0.1-0.2% of 33% triethylene diamine D-33Lv, 0.05-0.15% of stannous octoate T-9 with 28.5% of tin, 1.5-2% of water, 0-2% of a pore-opening agent and 25-40% of vegetable oil-based modified isocyanate.
The mixture of the hydroxylated vegetable oil and the petroleum-based polyether polyol is 59.26-66.93%, the silicone oil L-580 is 0.59-0.8%, the 33% triethylene diamine D-33Lv is 0.12-0.15%, the 28.5% tin stannous octoate T-9 is 0.07-0.09%, the water is 1.78-1.87%, the pore-opening agent is 0-1.67%, and the vegetable oil-based modified isocyanate is 28.51-38.16%.
The mixture of the hydroxylated vegetable oil and the petroleum-based polyether polyol is hydroxylated vegetable oil A, polyether polyol SC56-23 and polymer polyol POP-2045, and the weight ratio of the hydroxylated vegetable oil A to the polyether polyol SC56-23 to the polymer polyol POP-2045 is 7: 9: 4.
the mixture of the hydroxylated vegetable oil and the petroleum-based polyether polyol is hydroxylated vegetable oil B, polyether polyol SC56-23, polyether polyol HF3070 and polymer polyol HFP-2045, and the weight ratio of the hydroxylated vegetable oil B, the polyether polyol SC56-23, the polyether polyol HF3070 and the polymer polyol HFP-2045 is 5: 1: 3: 1.
the production method adopting the formula of the high vegetable oil-based polyurethane flexible foam comprises the following specific steps,
1) firstly, the vegetable oil modified isocyanate is kept at 20-23 ℃ and the other materials are kept at 20-26 ℃.
2) The other materials are put into a stirring container for stirring, premixed for 4 minutes at a low speed, stirred at a speed of 300 revolutions per minute and then stood for 2 minutes.
3) Then adding the vegetable oil-based modified isocyanate rapidly and stirring at 2000 rpm for 10-20 s.
4) Then quickly pouring the mixture into a foaming box; curing and curing requirements: 20-36 hours; obtaining the high vegetable oil-based polyurethane flexible foam.
The hydroxylated vegetable oil A: hydroxyl value: 60, viscosity: 2540 cps; the hydroxylated vegetable oil B is the hydroxyl value: 110, viscosity: 1840 cps; the silicone oil L-580 is produced by German Ma chart company; polyether polyol SC56-23 is produced by Zhonghai Shell petrochemical Co., Ltd, and has a hydroxyl value of 56; the polymer polyol POP-2045 is a New Zhejiang Hengfeng material Co., Ltd, and has a hydroxyl value of 27.5; polyether polyol HF3070 is a hydroxyl value of 240 from Zhejiang Hengfeng New Material Co; polymer polyol HFP-2045 is Zhejiang Hengfeng New Material Co., Ltd, and has a hydroxyl value of 27.5.
The invention has the advantages that the hydroxylated vegetable oil is used for modifying isocyanate, so that the content of bio-based in the soft polyurethane foam is improved, the proportion of the vegetable oil-based material in the soft polyurethane foam is 30-50%, the dependence on petroleum-based polyurethane raw materials is reduced, the degradation rate of the soft polyurethane foam is improved, and the invention has strong support for the national environmental protection policy.
Drawings
FIG. 1 is a block flow diagram of the present invention.
Detailed Description
Referring to the attached figure 1, a synthetic process of vegetable oil-based modified isocyanate and application thereof are as follows:
the first step is the preparation of hydroxyl-valued vegetable oil:
modifying the epoxy vegetable oil into hydroxylated vegetable oil with hydroxyl value of 50-120mgKOH/g, refer to CN101186694(CN 101186694B);
the second step is the vegetable oil modified isocyanate:
reacting isocyanate with hydroxylated vegetable oil, wherein the content of modified TDI isocyanate is 30-42%, the content of modified MDI isocyanate is 15-25%, and the content of modified TDI/MD mixed isocyanate is 18-35%.
The isocyanate comprises: TDI, MDI, or a mixture of TDI and MDI.
The third step is the technology of the flexible polyurethane foam:
hydroxylated vegetable oil, petroleum-based polyether polyol and petroleum-based polymer polyol are mixed with a catalyst, a silicone oil surfactant and a foaming agent, and react with vegetable oil-based isocyanate to obtain the high vegetable oil-based flexible polyurethane foam plastic containing 30-50%.
The production method comprises the following specific production steps:
1. preparing hydroxylated vegetable oil:
the method for synthesizing hydroxylated vegetable oil according to the prior patent CN101186694(CN101186694B) obtains the following hydroxylated vegetable oil, the main indexes of which are as follows.
Hydroxylated vegetable oil a: hydroxyl value: 60, viscosity: 2540 cps.
Hydroxylated vegetable oil B: hydroxyl value: 110, viscosity: 1840 cps.
Vegetable oil-modified isocyanate:
TDI 80/20: isocyanate 48% (including TDI100, TDI65/35) toluene diisocyanate, TDI generally referring to toluene diisocyanate; there are two isomers of 2, 4-toluene diisocyanate and 2, 6-Toluene Diisocyanate (TDI).
MDI: isocyanate 33% (including diphenylmethane diisocyanate, polyphenyl polymethylene isocyanate).
The following method and steps are used for synthesizing the vegetable oil-based modified isocyanate:
the first embodiment is as follows:
a500 ml three-neck flask with a dropping funnel was used, and TDI: 350g, adding 100g of hydroxylated vegetable oil A into a dropping funnel, heating the three-neck flask to 90-95 ℃, opening a switch of the dropping funnel, slowly adding the hydroxylated vegetable oil A, adding the hydroxylated vegetable oil A one hour later, keeping the temperature at 85-95 ℃, heating to 95-100 ℃, preserving the temperature for 2-4 hours, cooling to 40-60 ℃ and discharging. Obtaining vegetable oil-based modified isocyanate JS-01, and testing the content of isocyanate groups: 36.4%, viscosity (cps): 471/25 ℃ and the content of vegetable oil base is 21.1 percent.
Example two:
a500 ml three-neck flask with a dropping funnel was used, and TDI: 200g, adding 100g of hydroxylated vegetable oil A into a dropping funnel, heating a three-neck flask to 90-95 ℃, opening a switch of the dropping funnel, slowly adding the hydroxylated vegetable oil A, adding the hydroxylated vegetable oil A one hour later, keeping the temperature at 85-95 ℃, heating to 95-100 ℃, preserving the temperature for 2-4 hours, cooling to 40-60 ℃, and discharging to obtain the vegetable oil-based modified isocyanate JS-02. Testing the content of isocyanate groups: 30.4%, viscosity (cps): 556/25 degrees, vegetable oil content 31.7%.
Example three:
using a 500ml three-neck flask with a dropping funnel, MDI was added to the three-neck flask: 250g, adding 100g of hydroxylated vegetable oil A into a dropping funnel, heating the three-neck flask to 85-90 ℃, opening a switch of the dropping funnel, slowly adding the hydroxylated vegetable oil A, adding the hydroxylated vegetable oil A one hour later, keeping the temperature at 80-90 ℃, heating to 90-95 ℃ after adding the hydroxylated vegetable oil A, keeping the temperature for 2-4 hours, cooling to 40-60 ℃, and discharging to obtain the vegetable oil-based modified isocyanate JS-03. Testing the content of isocyanate groups: 22.6%, viscosity (cps): 989/25 deg.C. The content of vegetable oil base is 27.5%
Example four:
using a 500ml three-neck flask with a dropping funnel, MDI was added to the three-neck flask: 250g, adding 100g of hydroxylated vegetable oil B into a dropping funnel, heating the three-neck flask to 85-90 ℃, opening a switch of the dropping funnel, slowly adding the hydroxylated vegetable oil B, adding the hydroxylated vegetable oil B one hour later, keeping the temperature at 85-95 ℃, heating to 90-95 ℃ after adding the hydroxylated vegetable oil B, keeping the temperature for 2-4 hours, cooling to 40-60 ℃, and discharging to obtain the vegetable oil-based modified isocyanate JS-04. Testing the content of isocyanate groups: 17.6%, viscosity (cps): 964/25 deg.C. The content of the vegetable oil base is 27.1 percent
Example five:
using a 500ml three-necked flask with a dropping funnel, TDI/MDI (1: 1 by weight) was added to the three-necked flask: 350g, adding 100g of hydroxylated vegetable oil A into a dropping funnel, heating the three-neck flask to 90 ℃, opening a switch of the dropping funnel, slowly adding the hydroxylated vegetable oil A, adding the hydroxylated vegetable oil A one hour later, keeping the temperature at 80-90 ℃, heating to 90-95 ℃, keeping the temperature for 2-4 hours, cooling to 40-60 ℃, and discharging to obtain the vegetable oil-based modified isocyanate JS-06. Testing the content of isocyanate groups: 30.4%, viscosity (cps): 749/25 deg.C. The content of the vegetable oil base is 21.1 percent
3. Synthesis of high vegetable oil-based flexible polyurethane foam
The high vegetable oil-based flexible foam is synthesized by foaming and molding the hydroxylated vegetable oil, the petroleum-based polyether polyol, the petroleum-based polymer polyol and the vegetable oil-based modified isocyanate under the conditions of a catalyst, silicone oil and a crosslinking agent.
The production steps of the high vegetable oil-based flexible polyurethane foam technology are as follows:
3.1 common vegetable oil-based Soft polyurethane sponge
1) The formula and the weight portion are as follows:
hydroxylated vegetable oil a 35.0.
SC56-23 (Zhonghai Shell brand, hydroxyl number 56) 45.0.
POP-2045 (Zhejiang Hengfeng, hydroxyl value 27.5) 20.0.
Silicone oil (L-580) (produced by Meiji Kogyo) 1.0.
D-33Lv (triethylene diamine content: 33%) 0.20.
T-9 (stannous octoate-tin content 28.5%) 0.15.
And 3.0 of water.
Vegetable oil-based modified isocyanate JS-01 (Nco-content 30.4%): 64.4.
2) the process requirements are as follows:
the vegetable oil modified isocyanate is kept at 20-23 ℃ and the other materials are kept at 20-26 ℃.
Premixing other materials at low speed (the mechanical speed of a stirring blade is 300 r/min) for 4 min, standing for 2 min, rapidly adding vegetable oil-based modified isocyanate, stirring at 2000 r/min for 10-20 s; then quickly pouring the mixture into a foaming box; curing and curing requirements: 20-30 hours.
3) And (3) performance testing:
the polyurethane soft foam of the prepared vegetable oil is subjected to related physical property tests according to the standard of GBT 10802-2006 general soft polyether polyurethane foam, and the test data are as follows:
25% indentation hardness: 82.5N.
And (3) indentation ratio: 1.98.
75% compression set: 4.2 percent.
The rebound resilience: 38 percent.
Tensile strength: 105 KPa.
Elongation at break: 145 percent.
Tear strength: 2.1N/cm.
40% indentation hardness loss rate after fatigue: 28.5 percent.
The soft polyurethane foam contains 32.6 percent of vegetable oil base.
Slow-resilience type plant oil-based soft polyurethane sponge
1) The formula and the weight portion are as follows:
hydroxylated vegetable oil B (hydroxyl number 110) 50.0.
SC56-23 (Zhonghai Shell brand, hydroxyl number 56) 10.0.
HF3070 (Zhejiang Hengfeng, hydroxyl value 240) 30.0.
HFP-2045 (Zhejiang Hengfeng, hydroxyl value 27.5) 10.0.
Silicone oil (L-580) (produced by Meiji Kogyo) 1.2.
33Lv (triethylene diamine content: 33%) 0.22.
T-9 (stannous octoate-content 28.5%) 0.10.
And 2.8 of water.
Cell opener Y1900 (Korea SKC chemical Co., Ltd.) 2.5.
Vegetable oil-based modified isocyanate JS-01 (Nco-content 36.1%): 42.6.
2) the process requirements are as follows:
the temperature of the vegetable oil modified isocyanate is 20-23 ℃, and the temperature of other materials is controlled to be 20-26 ℃.
Other materials are premixed for 5 minutes at low speed (the mechanical speed of a stirring blade is 300 rpm), then are stood for 2 minutes, and then vegetable oil-based modified isocyanate is added rapidly and stirred for 10 to 20 seconds at 2000 rpm. Then quickly pouring the mixture into a foaming box, and curing and solidifying the mixture according to the following requirements: 24-36 hours.
3) And (3) performance testing:
the polyurethane soft foam of the prepared vegetable oil is subjected to related physical property tests according to the standard of GBT 10802-2006 general soft polyether polyurethane foam, and the test data are as follows:
40% indentation hardness: 40.5N.
Recovery time: 8.5 s.
75% compression set: 2.5 percent.
The rebound resilience: 2.5 percent.
Tensile strength: 75 kpa.
Elongation at break: 155 percent.
Tear strength: 1.8N/cm.
40% indentation hardness loss rate after fatigue: 21.5 percent.
The soft polyurethane foam contains 41.9 percent of vegetable oil base.
The method for testing the content of the vegetable oil base in the vegetable oil base soft polyurethane foam comprises the following steps:
the instrument comprises the following steps: model number of 400MHz nuclear magnetic resonance spectrometer: DDR 2400-MR.
The manufacturer: agilent technologies, Inc. (USA).
Reagent: n, N-Dimethylformamide (DMF): reagent grade (or reagent grade acetone may also be used).
The testing steps are as follows:
1. 1.0000g of vegetable oil (same raw material as that used for the production of vegetable oil-based isocyanate and hydroxylated vegetable oil) and 99.0000g of DMF were sampled and completely dissolved, and then used as sample A.
2. 1.0000g of sponge and 99.0000g of DMF were sampled and, after complete dissolution, used as sample B.
3. Debugging a nuclear magnetic resonance spectrometer until a base line is stable, taking 10ul of sample A, injecting into the instrument, and repeating for five times; also 10ul of sample B was taken and injected into the instrument.
4. The calculation method comprises the following steps: and (4) obtaining the area of the sample A, and then calculating the area of the same region of the sample B and the sample A.
5. Calculating the formula: the area of sample B divided by the area of sample a in the same area multiplied by 100 equals the percentage of vegetable oil based.
By adopting the detection instrument and the detection method, the following results are obtained by detecting the samples of the traditional non-plant oil-based soft polyurethane sponge, the traditional plant oil-based soft polyurethane sponge and the samples of the two products in the invention on the market, and the following results are obtained as shown in the following table:
through the data displayed in the table, the content of the vegetable oil base in the product is obviously improved, the industrial problems are overcome, the vegetable oil base is adopted to carry out modification reaction on isocyanate firstly, part of hydroxyl vegetable oil is subjected to advanced reaction, the isocyanate containing the vegetable oil base is used for replacing the original isocyanate, the total content of the vegetable oil base in the final vegetable oil base soft polyurethane sponge is improved, the vegetable oil base soft polyurethane sponge is more environment-friendly and easy to degrade, and the waste vegetable oil base soft polyurethane sponge is convenient to recover by adopting a chemical mode in the later period.
Claims (10)
1. The synthesis process of the vegetable oil-based modified isocyanate is characterized by comprising the following steps,
1) firstly, putting isocyanate into a reaction vessel, heating the reaction vessel to 75-90 ℃,
2) adding the hydroxylated vegetable oil into a reaction container, dropwise adding for 1 hour in a dropwise adding mode, keeping the temperature in the reaction container at 80-95 ℃ in the dropwise adding process,
3) after the dropwise adding is finished, the temperature in the reaction container is raised to 90-100 ℃, and the temperature is kept for 2-4 hours;
4) after the heat preservation is finished, cooling the temperature in the reaction container to 40-60 ℃, and discharging; obtaining the vegetable oil-based modified isocyanate.
2. The synthesis process of the vegetable oil-based modified isocyanate according to claim 1, wherein the weight ratio of the isocyanate to the hydroxylated vegetable oil is 2-3.5: 1.
3. the process for synthesizing the vegetable oil-based modified isocyanate according to claim 1, wherein the hydroxylated vegetable oil is a hydroxylated vegetable oil A or a hydroxylated vegetable oil B; the hydroxylated vegetable oil A: hydroxyl value: 60, viscosity: 2540 cps; the hydroxylated vegetable oil B is a hydroxyl value: 110, viscosity: 1840 cps.
4. The process for synthesizing the vegetable oil-based modified isocyanate according to claim 1, wherein the isocyanate is one or a mixture of two or more of Toluene Diisocyanate (TDI) with an isocyanate content of 48% or diphenylmethane diisocyanate (MDI) with an isocyanate content of 33% or polyphenyl polymethylene isocyanate (MDI) with an isocyanate content of 33%.
5. The process for synthesizing the vegetable oil-based modified isocyanate according to claim 1, 2, 3 or 4, wherein the isocyanate content of the vegetable oil-based modified isocyanate is 30-42% of the modified TDI isocyanate content; the content of modified MDI isocyanate is 15-25%; the content of the modified TDI/MDI mixed isocyanic acid radical is 18-35%; the viscosity is 450 to 1000 cps/25 ℃; the content of the vegetable oil base is 21-32%.
6. The application of the vegetable oil-based modified isocyanate is characterized in that the vegetable oil-based modified isocyanate produced by adopting the synthesis process of the vegetable oil-based modified isocyanate in any claim is applied to the production of high vegetable oil-based polyurethane soft foam,
the formula process of the high vegetable oil-based polyurethane flexible foam comprises the following raw materials in percentage by weight,
55-68% of a mixture of hydroxylated vegetable oil and petroleum-based polyether polyol, 0.5-1% of silicone oil L-580, 0.1-0.2% of 33% triethylene diamine D-33Lv, 0.05-0.15% of stannous octoate T-9 with 28.5% of tin, 1.5-2% of water, 0-2% of a pore-opening agent and 25-40% of vegetable oil-based modified isocyanate.
7. The use of the vegetable oil-based modified isocyanate according to claim 6, wherein the mixture of the hydroxylated vegetable oil and the petroleum-based polyether polyol is hydroxylated vegetable oil A, polyether polyol SC56-23 and polymer polyol POP-2045, and the weight ratio of the hydroxylated vegetable oil A, the polyether polyol SC56-23 and the polymer polyol POP-2045 is 7: 9: 4.
8. the use of the vegetable oil-based modified isocyanate according to claim 6, wherein the mixture of the hydroxylated vegetable oil and the petroleum-based polyether polyol is hydroxylated vegetable oil B, polyether polyols SC56-23, polyether polyol HF3070 and polymer polyol HFP-2045, and the weight ratio of the hydroxylated vegetable oil B, the polyether polyols SC56-23, the polyether polyol HF3070 and the polymer polyol HFP-2045 is 5: 1: 3: 1.
9. the use of the vegetable oil-based modified isocyanate according to claim 6, 7 or 8, wherein the formulation of the flexible polyurethane foam with high vegetable oil-based content is produced by the following steps,
1) firstly, keeping the temperature of vegetable oil modified isocyanate at 20-23 ℃, and keeping the temperature of other materials at 20-26 ℃;
2) other materials are put into a stirring container to be stirred, and are premixed for 4 minutes at a low speed, the stirring speed is 300 r/min, and then the mixture is kept still for 2 minutes;
3) then quickly adding the vegetable oil-based modified isocyanate and stirring at 2000 r/min for 10-20 s;
4) then quickly pouring the mixture into a foaming box; curing and curing requirements: 20-36 hours; obtaining the high vegetable oil-based polyurethane flexible foam.
10. The use of a vegetable oil-based modified isocyanate according to claim 7 or 8, wherein the hydroxylated vegetable oil A: hydroxyl value: 60, viscosity: 2540 cps; the hydroxylated vegetable oil B is the hydroxyl value: 110, viscosity: 1840 cps; the silicone oil L-580 is produced by German Ma chart company; polyether polyol SC56-23 is produced by Zhonghai Shell petrochemical Co., Ltd, and has a hydroxyl value of 56; the polymer polyol POP-2045 is a New Zhejiang Hengfeng material Co., Ltd, and has a hydroxyl value of 27.5; polyether polyol HF3070 is a hydroxyl value of 240 from Zhejiang Hengfeng New Material Co; polymer polyol HFP-2045 is Zhejiang Hengfeng New Material Co., Ltd, and has a hydroxyl value of 27.5.
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