Curtain foaming material composition and preparation process thereof
By using bio-based polyols and plant oil-based non-isocyanates to prepare polyurethane foam, the limited resource and environmental protection problems of traditional polyurethane materials are solved, and the preparation of renewable, low-energy and environmentally friendly polyurethane foam is achieved, which has good mechanical properties and degradability.
Patent Information
- Application Number
- CN202511121765.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-12
- Publication Date
- 2025-10-10
AI Technical Summary
Traditional polyurethane materials rely on petroleum-based materials, which have limited resources and fluctuating prices. Foaming agents are destructive to the ozone layer, and there is a need to find renewable alternative materials and environmentally friendly foaming agents.
Polyurethane foam is prepared using bio-based polyol and vegetable oil-based non-isocyanate as raw materials, combined with water as a foaming agent. Composite catalysts, foam stabilizers and flame retardants are used to prepare curtain foam materials through mixing in a foaming machine and oven aging.
It has achieved the goal of reducing dependence on oil, lowering energy consumption and carbon emissions. Polyurethane foam has good mechanical properties, thermal insulation properties and biodegradability, and the foaming process does not consume ozone and has low global warming potential.
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of foaming material, in particular to a curtain foaming material composition and a preparation process thereof. BACKGROUND
[0002] Polyurethane (PU) is a polymer with a urethane chain segment repeat unit prepared by the polymerization of isocyanate and polyol, and polyurethane foam is widely concerned due to its wide application range and good performance, wherein the polyurethane foam is a foam material formed by the addition of a foaming agent, a surfactant and a catalyst during the reaction of polyol and isocyanate, and then cured after foaming.
[0003] However, one of the raw materials required for the traditional synthesis of polyurethane products is mainly provided by petroleum-based materials, and with the gradual depletion of traditional petroleum resources such as oil and natural gas, petroleum-based materials as non-renewable resources have continuously reduced reserves under the condition of long-term exploitation, and the price has been fluctuating, which has caused great obstacles to the production and development of polyurethane materials, and the foaming agent as the main raw material for preparing polyurethane hard foam has a great influence on the performance of polyurethane foam, and the physical foaming agent HCFC-141B is used to achieve the requirement of reducing the density, which still has a destructive effect on the ozone layer. SUMMARY
[0004] In order to overcome the above-mentioned shortcomings, the present application provides a curtain foaming material composition and a preparation process thereof.
[0005] To achieve the above-mentioned purpose, the curtain foaming material composition provided by the present application comprises the following raw material components in parts by weight:
[0006] 100 parts of bio-based polyol, 140-150 parts of vegetable oil-based non-isocyanate, 0.05-0.4 parts of composite catalyst, 1.0-1.5 parts of foam stabilizer, 0.5-2 parts of crosslinking agent, 10-12 parts of distilled water and 15-20 parts of flame retardant.
[0007] Preferably, the bio-based polyol is any one of lignin-based polyol, starch-based polyol and vegetable oil polyol.
[0008] Preferably, the vegetable oil-based non-isocyanate is any one of rapeseed oil-based cyclic carbonate and castor oil-based cyclic carbonate.
[0009] Preferably, the composite catalyst is a compound of delayed amine catalyst and stannous octoate.
[0010] Preferably, the foam stabilizer is an organic silicon surfactant.
[0011] Preferably, the crosslinking agent is triethanolamine.
[0012] Preferably, the flame retardant is one or more of dimethyl methyl phosphate, quartz sand or aluminum hydroxide.
[0013] Preferably, the present invention further provides a method for preparing a curtain foam material composition, comprising the following steps:
[0014] A preparation process of a curtain foam material composition comprises the following steps:
[0015] S1. Preparation of lignin-based polyols
[0016] Weigh the solvent-based lignin into a three-necked flask, add glycerol and stir evenly with a glass rod, then add concentrated sulfuric acid and place in an oil bath for reaction. After cooling, add polyethylene glycol and seal the mixture for storage to obtain lignin-based polyol:
[0017] S2. Preparation of rapeseed oil-based cyclic carbonate
[0018] Weigh rapeseed oil, thiol-containing cyclic carbonate, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and chloroform into a 50 ml round-bottom flask. Irradiate with ultraviolet light and stir magnetically. Distill off the chloroform to obtain a yellow-green viscous liquid rapeseed oil-based cyclic carbonate.
[0019] S3. Preparation of bio-based polyurethane foam
[0020] The lignin-based polyol, composite catalyst, foam stabilizer, cross-linking agent, distilled water and flame retardant are weighed in parts and added to a dry beaker. After stirring and mixing, the mixture is sealed and allowed to stand for degassing to obtain a premixed polyol component; the weighed rapeseed oil-based cyclic carbonate and the premixed polyol component are poured into the mixing head of a foaming machine in proportion and mixed; after mixing, the mixture is quickly injected into a mold, placed in an oven for aging to complete the polymerization reaction, and cooled to room temperature to obtain a polyurethane foam sample.
[0021] Preferably, the preparation of lignin-based polyol in step S1 specifically comprises the following steps: weighing 60-100 g of solvent-processed lignin into a three-necked flask, then adding glycerol in a mass ratio of 3:(5-5.5) of solvent-processed lignin to glycerol, stirring evenly with a glass rod, adding 5% concentrated sulfuric acid (relative to the mass of lignin), and reacting in an oil bath. The reaction conditions are: 75-95° C., 200-300 r / min, and reacting for 2.5-3 hours. After cooling, polyethylene glycol is added in a mass ratio of 3:(5-5.5):1 of solvent-processed lignin, glycerol, and polyethylene glycol, and the mixture is sealed and stored to obtain a lignin-based polyol.
[0022] Preferably, the preparation of rapeseed oil-based cyclic carbonate in step S2 specifically comprises the following steps: weighing 2.6-3 g of rapeseed oil, 2.8-3.2 g of thiol-containing cyclic carbonate, 0.135-0.14 g of 2-hydroxy-2-methyl-1-phenyl-1-propanone and 7-8 g of chloroform into a 50 ml round-bottom flask, irradiating with an ultraviolet lamp (1700 μW / cm2, 365 nm) with magnetic stirring for 24-26 h, and evaporating the chloroform to obtain a yellow-green viscous liquid rapeseed oil-based cyclic carbonate (CCAO).
[0023] Preferably, the preparation of bio-based polyurethane foam in step S3 comprises the following steps:
[0024] S3.1. Weigh the lignin-based polyol, composite catalyst, foam stabilizer, cross-linking agent, distilled water, and flame retardant in proportion to the amount in the beaker, stir and mix for 5-10 minutes, seal and allow to stand for 30-60 minutes to degas, and obtain a premixed polyol component.
[0025] S3.2. Pour rapeseed oil-based cyclic carbonate and premixed polyol components into the mixing head of the foaming machine according to the proportions and mix them; after mixing, quickly inject into the mold, mature in an oven at 45-80℃ for 4-5h to complete the polymerization reaction, and cool to room temperature to obtain a polyurethane (PU) foam sample.
[0026] Preferably, the mixing parameters of the foaming machine mixing head are pressure ≥ 120 bar, mixing time 3-7 s, and high-speed stirring (2000-3000 rpm).
[0027] Beneficial effects: Bio-based polyols and vegetable oil-based non-isocyanates are renewable raw materials that can reduce dependence on petroleum, reduce energy consumption and carbon emissions, and have significant advantages. Bio-based polyols are rich in active hydroxyl groups. Using bio-based polyols and vegetable oil-based non-isocyanates as base materials for the synthesis of polyurethane foam can make the polyurethane foam not only have good mechanical properties and thermal insulation properties, but also have good biodegradability. Water is used as a foaming agent to react with polyisocyanates to generate CO2 for foaming, achieving zero ozone depletion potential (ODP) and low global warming potential (GWP). DETAILED DESCRIPTION
[0028] The curtain foam material composition and its preparation process provided by the present invention are described in detail below with reference to specific embodiments.
[0029] Example 1: A curtain foam material composition, comprising the following raw material components in parts by weight:
[0030] Lignin-based polyol 100 parts, rapeseed oil-based cyclic carbonate 140 parts, composite catalyst 0.05 parts, silicone surfactant 1.0 parts, triethanolamine crosslinking agent 0.5 parts, distilled water 10 parts, methyl phosphonate dimethyl ester flame retardant 15 parts.
[0031] Further, the composite catalyst is a compound of delayed amine catalyst and stannous octoate.
[0032] Further, a preparation method of a curtain foaming material composition comprises the following steps:
[0033] S1, preparing lignin-based polyol
[0034] Take 60 g of solvent lignin in a three-necked flask, then add glycerol according to the mass ratio of solvent lignin to glycerol 3:5, stir uniformly with a glass rod, then add 5% concentrated sulfuric acid (relative to the mass of lignin) and place in an oil bath for reaction, the reaction conditions are 75℃, 200 r / min for 2.5 h, after cooling, add polyethylene glycol according to the mass ratio of solvent lignin, glycerol and polyethylene glycol 3:5:1, seal and store, to obtain lignin-based polyol;
[0035] S2, preparing rapeseed oil-based cyclic carbonate
[0036] Take 2.6 g of rapeseed oil, 2.8 g of thiol-containing cyclic carbonate, 0.135 g of 2-hydroxy-2-methyl-1-phenyl-1-propanone and 7 g of chloroform into a 50 ml round-bottom flask, irradiate under a UV lamp (1700 μW / cm2, 365 nm) and magnetically stir for 24 h, then spin-evaporate the chloroform to obtain yellow-green viscous liquid rapeseed oil-based cyclic carbonate (CCAO);
[0037] S3, preparing bio-based polyurethane foam
[0038] S3.1, take the lignin-based polyol, composite catalyst, foam stabilizer, crosslinking agent, distilled water and flame retardant according to the parts and add them into a dry beaker, stir and mix for 7 min, seal and stand for 45 min to degas, to obtain a premixed polyol component;
[0039] S3.2, pour the rapeseed oil-based cyclic carbonate and the premixed polyol component into the mixing head of a foaming machine according to the parts, the mixing parameters are pressure 120 bar, mixing time 5 s and high-speed stirring 2000; after mixing, quickly inject into a mold, and cure in a 60℃ oven for 4 h to complete the polymerization reaction, cool to room temperature to obtain a polyurethane foam sample.
[0040] Example 2: a curtain foaming material composition, comprising the following raw material components in parts by weight:
[0041] 100 parts of lignin-based polyol, 150 parts of rapeseed oil-based cyclic carbonate, 0.3 parts of composite catalyst, 1.5 parts of organosilicon surfactant, 2 parts of triethanolamine cross-linking agent, 12 parts of distilled water, and 20 parts of dimethyl methyl phosphate flame retardant.
[0042] Furthermore, the composite catalyst is a compound of a delayed amine catalyst and stannous octoate.
[0043] Furthermore, a method for preparing a curtain foam material composition comprises the following steps:
[0044] S1. Preparation of lignin-based polyols
[0045] Weigh 100 g of solvent-based lignin into a three-necked flask, then add glycerol at a mass ratio of 3:5.5 between solvent-based lignin and glycerol, stir evenly with a glass rod, add 5% concentrated sulfuric acid (relative to the mass of lignin), and react in an oil bath. The reaction conditions are: 75-95°C, 200-300 rpm, and react for 2.5-3 hours. After cooling, polyethylene glycol is added at a mass ratio of 3:5.5:1 between solvent-based lignin and glycerol, and the mixture is sealed and stored to obtain a lignin-based polyol.
[0046] S2. Preparation of rapeseed oil-based cyclic carbonate
[0047] 3 g of rapeseed oil, 3.2 g of thiol-containing cyclic carbonate, 0.14 g of 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 8 g of chloroform were weighed and added to a 50 ml round-bottom flask. The mixture was magnetically stirred under ultraviolet light (1700 μW / cm2, 365 nm) for 24-26 h, and the chloroform was evaporated to obtain a yellow-green viscous liquid rapeseed oil-based cyclic carbonate (CCAO).
[0048] S3. Preparation of bio-based polyurethane foam
[0049] S3.1. Weigh the lignin-based polyol, composite catalyst, foam stabilizer, cross-linking agent, distilled water, and flame retardant in proportion to the amount in the beaker, stir and mix for 5-10 minutes, seal and allow to stand for 30-60 minutes to degas, and obtain a premixed polyol component.
[0050] S3.2. Pour the rapeseed oil-based cyclic carbonate and the premixed polyol components into the mixing head of the foaming machine according to the proportions and mix them. The mixing parameters are pressure ≥ 120 bar, mixing time 3-7 seconds, and high-speed stirring (2000-3000 rpm). After mixing, quickly inject into the mold and mature in an oven at 45-80°C for 4-5 hours to complete the polymerization reaction. Cool to room temperature to obtain a polyurethane foam sample.
[0051] Example 3: A curtain foam material composition, comprising the following raw material components in parts by weight:
[0052] lignin-based polyol 100 parts, rapeseed oil-based cyclic carbonate 140-150 parts, composite catalyst 0.05-0.4 parts, silicone surfactant 1.0-1.5 parts, triethanolamine crosslinking agent 0.5-2 parts, distilled water 10-12 parts, dimethyl methylphosphonate flame retardant 15-20 parts.
[0053] Further, the composite catalyst is a compound of delayed amine catalyst and stannous octoate.
[0054] Further, a preparation method of a curtain foaming material composition, comprising the following steps:
[0055] S1, preparing lignin-based polyol
[0056] 60-100g of solvent method lignin is weighed in a three-necked flask, then 5-5.5g of glycerol is added according to the mass ratio of solvent method lignin to glycerol 3: (5-5.5), stirred uniformly with a glass rod, then 5% concentrated sulfuric acid (relative to the mass of lignin) is added, and the reaction is carried out in an oil bath at 80℃ and 300r / min for 3h. After cooling, 1g of polyethylene glycol is added according to the mass ratio of solvent method lignin, glycerol and polyethylene glycol 3: (5-5.5): 1, and the mixture is sealed and stored to obtain lignin-based polyol.
[0057] S2, preparing rapeseed oil-based cyclic carbonate
[0058] 2.6-3g of rapeseed oil, 2.8-3.2g of thiol-containing cyclic carbonate, 0.135-0.14g of 2-hydroxy-2-methyl-1-phenyl-1-propanone and 7-8g of chloroform are weighed into a 50ml round-bottomed flask, and magnetically stirred under the irradiation of a UV lamp (1700μW / cm2, 365nm) for 26h. The chloroform is removed by rotary evaporation to obtain yellow-green viscous liquid rapeseed oil-based cyclic carbonate;
[0059] S3, preparing bio-based polyurethane foam
[0060] S3.1, the lignin-based polyol, composite catalyst, foam stabilizer, crosslinking agent, distilled water and flame retardant are weighed according to the fraction and added to a dry beaker, stirred and mixed for 10min, sealed and left for 60min to remove bubbles, and a premixed polyol component is obtained;
[0061] S3.2, the rapeseed oil-based cyclic carbonate is poured into the mixing head of the foaming machine according to the fraction and mixed with the premixed polyol component, and the mixing parameters are pressure > 120bar, mixing time 7s and high-speed stirring 3000rpm; after mixing, the mixture is quickly injected into a mold, and the polymeric reaction is completed in an 80℃ oven for 5h, and the polyurethane foam sample is obtained after cooling to room temperature.
[0062] Comparative Example 1: Compared with Example 1, the difference of Comparative Example 1 is that in step S3.1, the lignin-based polyol is replaced by a polyurethane rigid foam combination polyether, and the rapeseed oil-based cyclic carbonate is replaced by diphenylmethane diisocyanate. The other steps remain unchanged, specifically:
[0063] S3.1. Weigh the polyurethane rigid foam composite polyether, composite catalyst, foam stabilizer, cross-linking agent, distilled water, and flame retardant in proportion to the amount in the beaker, stir and mix for 7 minutes, seal and allow to stand for 45 minutes to degas, and obtain a premixed polyol component.
[0064] S3.2. Pour diphenylmethane diisocyanate and premixed polyol components into the mixing head of the foaming machine according to the proportions and mix them. The mixing parameters are pressure 120 bar, mixing time 5 s, and high-speed stirring 2000. After mixing, quickly inject into the mold and mature in an oven at 60°C for 4 h to complete the polymerization reaction. Cool to room temperature to obtain a polyurethane foam sample.
[0065] The bio-based polyurethane foam prepared in step S3 of Example 1-3 is recorded as Example 1-3.
[0066] The polyurethane foams prepared in Examples 1-3 and Comparative Example 1 were subjected to performance testing. Degradation performance was characterized using an outdoor soil burial degradation test: The polyurethane foams prepared in Examples 1-3 and Comparative Example 1 were numbered A, B, C, and D, and their weights were measured as m0. The foams were then buried approximately 10 cm below ordinary horticultural soil at regular intervals and allowed to degrade under natural conditions for 90 days. Afterward, the bio-based polyurethane foam samples were removed, rinsed with deionized water, and dried in a 50°C forced air drying oven for 24 hours. Finally, the foams were allowed to equilibrate at room temperature for 24 hours and weighed again as m1. The weight loss rate of the foams was calculated (weight loss rate = (m0 - m1) / m0 × 100%).
[0067] Testing standards: Tensile strength: ISO527; Impact strength: ISO180; Flexural strength and flexural modulus: ISO178.
[0068] The foaming material compositions prepared in Examples 1-3 and Comparative Example 1 were respectively added to the barrel of an injection molding machine. After heating to a molten state, the melt was injected into the mold cavity by a screw. After the melt was cooled and solidified in the mold, the mold was opened and the sample was taken out. The sample length was 150 mm ± 1 mm, the width of the narrow parallel part was 6 mm ± 0.4 mm, and the thickness was 2 mm ± 0.2 mm for testing.
[0069] The performance test results are shown in Table 1.
[0070] Table 1 Test results of polyurethane foam properties of Examples 1-3 and Comparative Example 1
[0071] Performance indicators Example 1 Example 2 Example 3 Comparative Example 1 <![CDATA[泡沫芯密度,kg / m 3 ]]> 40.2 39.7 39.5 38.2 Foam open cell rate, % 82 77 80 66 Foam water absorption, % 679 697 581 342 Weight loss rate, % (90 days) 13.1 12.6 13 6.7 Tensile strength, MPa 40.1 36.6 39.9 28.7 <![CDATA[冲击强度,J / m 2 ]]> 36.8 38.3 36.1 27.4 Flexural strength, MPa 42.3 39.9 41.8 30.6 Flexural modulus, MPa 1860 1845 1865 1553
[0072] The above embodiments are provided to persons skilled in the art to implement or use the present application, and the persons skilled in the art can make various modifications or changes to the above embodiments without departing from the inventive idea of the present application, and thus the protection scope of the present application is not limited by the above embodiments, but should be the maximum scope of the innovative features mentioned in the claims.
Claims
1. A curtain foam material composition, characterized in that: The raw material components include the following parts by weight: 100 parts of bio-based polyol, 140-150 parts of vegetable oil-based non-isocyanate, 0.05-0.4 parts of composite catalyst, 1.0-1.5 parts of foam stabilizer, 0.5-2 parts of cross-linking agent, 10-12 parts of distilled water, 15-20 parts of flame retardant; The bio-based polyol is any one of lignin-based polyol, starch-based polyol and vegetable oil polyol; The vegetable oil-based non-isocyanate is any one of rapeseed oil-based cyclic carbonate and castor oil-based cyclic carbonate.
2. A curtain foam material composition according to claim 1, characterized in that: The composite catalyst is a compound of a delayed amine catalyst and stannous octoate.
3. A curtain foam material composition according to claim 1, characterized in that: The foam stabilizer is a silicone surfactant.
4. A curtain foam material composition according to claim 1, characterized in that: The cross-linking agent is triethanolamine.
5. A curtain foam material composition according to claim 1, characterized in that: The flame retardant is one or more of dimethyl methyl phosphate, quartz sand or aluminum hydroxide.
6. The process for preparing a curtain foam material composition according to claim 1, characterized in that: The following steps are involved: S1. Preparation of lignin-based polyols Weigh the solvent-based lignin into a three-necked flask, add glycerol and stir evenly with a glass rod, then add concentrated sulfuric acid and place in an oil bath for reaction. After cooling, add polyethylene glycol and seal the mixture for storage to obtain lignin-based polyol. S2. Preparation of rapeseed oil-based cyclic carbonate Weigh rapeseed oil, thiol-containing cyclic carbonate, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and chloroform into a 50 ml round-bottom flask. Irradiate with ultraviolet light and stir magnetically. Distill off the chloroform to obtain a yellow-green viscous liquid rapeseed oil-based cyclic carbonate. S3. Preparation of bio-based polyurethane foam The bio-based polyol, composite catalyst, foam stabilizer, cross-linker, distilled water and flame retardant are weighed in parts and added to a dry beaker. After stirring and mixing, the mixture is sealed and allowed to stand for degassing to obtain a premixed polyol component; the weighed rapeseed oil-based cyclic carbonate and the premixed polyol component are poured into the mixing head of a foaming machine in proportion and mixed; after mixing, the mixture is quickly injected into a mold, placed in an oven for curing to complete the polymerization reaction, and cooled to room temperature to obtain a polyurethane foam sample.
7. The process for preparing the curtain foam material composition according to claim 6, wherein: Step S1 is to prepare a lignin-based polyol, specifically comprising the following steps: weighing 60-100 g of solvent-processed lignin into a three-necked flask, then adding glycerol in a mass ratio of 3:(5-5.5) of solvent-processed lignin to glycerol, stirring evenly with a glass rod, adding 5% concentrated sulfuric acid (relative to the mass of lignin), and reacting in an oil bath. The reaction conditions are: 75-95° C., 200-300 r / min, and reacting for 2.5-3 hours. After cooling, polyethylene glycol is added in a mass ratio of 3:(5-5.5):1 of solvent-processed lignin, glycerol, and polyethylene glycol, and the mixture is sealed and stored to obtain a lignin-based polyol.
8. The process for preparing the curtain foam material composition according to claim 7, wherein: Step S2 is to prepare rapeseed oil-based cyclic carbonate, specifically comprising the following steps: weighing 2.6-3 g of rapeseed oil, 2.8-3.2 g of thiol-containing cyclic carbonate, 0.135-0.14 g of 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 7-8 g of chloroform into a 50 ml round-bottom flask, and magnetically stirring the mixture under ultraviolet light (1700 μW / cm2, 365 nm) for 24-26 hours, and then evaporating the chloroform to obtain a yellow-green viscous liquid rapeseed oil-based cyclic carbonate.
9. The process for preparing the curtain foam material composition according to claim 8, wherein: The preparation of bio-based polyurethane foam in step S3 comprises the following specific steps: S3.
1. Weigh the lignin-based polyol, composite catalyst, foam stabilizer, cross-linking agent, distilled water, and flame retardant in proportion to the amount in the beaker, stir and mix for 5-10 minutes, seal and allow to stand for 30-60 minutes to degas, and obtain a premixed polyol component. S3.
2. Pour rapeseed oil-based cyclic carbonate and premixed polyol components into the mixing head of the foaming machine according to the proportions and mix them; after mixing, quickly inject into the mold, mature in an oven at 45-80℃ for 4-5h to complete the polymerization reaction, and cool to room temperature to obtain a polyurethane (PU) foam sample.
10. The process for preparing the curtain foam material composition according to claim 9, wherein: The mixing parameters of the foaming machine mixing head are pressure ≥120 bar, mixing time 3-7 s, and high-speed stirring (2000-3000 rpm).