CN112266463B - Flame-retardant lignin-based rigid polyurethane foam for automotive interior and preparation method thereof - Google Patents
Flame-retardant lignin-based rigid polyurethane foam for automotive interior and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention belongs to the technical field of automotive interior materials, and particularly relates to a flame-retardant lignin-based polyurethane rigid foam for automotive interior and a preparation method thereof. The flame-retardant lignin-based polyurethane rigid foam comprises the following raw materials: polyether polyol, polymeric MDI and flame retardant; wherein the flame retardant is a mixture of nano titanium dioxide and tris (2-hydroxypropyl) phosphate. The lignin-based polyurethane rigid foam has good flame retardance and mechanical property, few volatile harmful substances and easy degradation, and the preparation method is simple and feasible and is suitable for industrial popularization and application.
Description
Technical Field
The invention belongs to the technical field of automotive interior materials, and particularly relates to a flame-retardant lignin-based polyurethane rigid foam for automotive interior and a preparation method thereof.
Background
In recent years, the rapid development of automobile technology worldwide has led to a rise in automobile inventory, which has led to human problems such as global warming, shortage of petroleum resources, air pollution and water pollution. With the change of consumer's needs and concepts, the interior materials of automobiles not only need to satisfy the requirements of practicability, economy and durability, but also should be developed towards humanization, comfort, beauty, environmental protection, etc.
At present, the first three most used plastics in automobiles are respectively: polypropylene, polyurethane and polyvinyl chloride. The polyurethane material is named as polyurethane, is a novel organic polymer material, is widely applied to automotive interior, and can well meet the requirements of modern automotive interior on comfort, safety, light weight, environmental protection and the like. Taking rigid polyurethane foam as an example, most of traditional automotive ceilings and interior parts are compounded by fabrics or polyvinyl chloride and the like, and are basically replaced by rigid polyurethane foam materials at present, and the adoption of the directly molded rigid foam not only improves the assembly efficiency of a vehicle, but also can meet the use requirements on strength, dimensional stability, heat insulation and sound absorption. However, most of polyurethane materials used in the traditional automobiles are petroleum-based polyurethane, and have the problems of poor thermal stability, poor mechanical property, more volatile harmful substances, difficult degradation and the like; bio-based polyurethanes prepared using biomass such as starch, rosin, vegetable oil, etc. as a hydroxyl source or directly as a filler have been desired to solve the above problems.
Meanwhile, the polyurethane material is extremely easy to burn, the Limiting Oxygen Index (LOI) of the polyurethane material is below 18 percent, the polyurethane material is extremely easy to ignite in air, and a large amount of toxic smoke is generated after the polyurethane material is burnt, so that the application range of the polyurethane material in the automotive interior material is greatly limited. Taking rigid polyurethane foam as an example, the rigid polyurethane foam has low density, a cellular structure and a large specific surface area, and is easier to burn than common polyurethane materials, so that the flame retardant property of the rigid polyurethane foam used in automobiles is urgently needed to be improved.
Therefore, it is particularly important to research the application of the bio-based polyurethane hard foam which has good application performance, excellent flame retardant performance, low content of harmful substances and easy degradation in the automotive interior.
Disclosure of Invention
In order to overcome the technical problems, the invention provides the flame-retardant lignin-based polyurethane rigid foam for the automotive interior, the lignin-based polyurethane has better flame retardance and mechanical property, and meanwhile, the lignin-based polyurethane has less volatile harmful substances and is easy to degrade, the preparation method is simple and feasible, and the preparation method is suitable for industrial popularization and application.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
the flame-retardant lignin-based polyurethane rigid foam comprises the following raw materials: polyether polyol, polymeric MDI and flame retardant;
preferably, the flame retardant is a mixture of nano titanium dioxide and tris (2-hydroxypropyl) phosphate;
the mass ratio of the nano titanium dioxide to the tris (2-hydroxypropyl) phosphate is 3-5: 1.
preferably, the preparation method of the tris (2-hydroxypropyl) phosphate comprises the following steps:
taking phosphoric acid, adding epoxypropane, heating at 70-80 ℃, stirring at 500-;
wherein the mass ratio of phosphoric acid to propylene oxide is 1: 3-4.
Preferably, the polyether polyol is a mixture of lignin-based polyether polyol, polyether polyol 4110 and polyether polyol 403;
preferably; the mass ratio of the mixture of the lignin-based polyether polyol, the polyether polyol 4110 and the polyether polyol 403 is 5-7: 2-4: 1.
preferably, the flame-retardant lignin-based rigid polyurethane foam further comprises the following raw materials: silicone oil, triethylene diamine, dibutyl tin dilaurate, cyclopentane and water;
preferably, the flame-retardant lignin-based rigid polyurethane foam comprises the following raw materials in parts by weight: 50-100 parts of polyether polyol, 100-200 parts of polymeric MDI, 4-12 parts of flame retardant, 5-10 parts of silicone oil, 0.5-5 parts of triethylene diamine, 0.5-1 part of dibutyl tin dilaurate, 5-20 parts of cyclopentane and 1-5 parts of water;
preferably, the flame-retardant lignin-based rigid polyurethane foam comprises the following raw materials in parts by weight: 80-100 parts of polyether polyol, 150 parts of polymeric MDI, 4-6 parts of flame retardant, 6-8 parts of silicone oil, 1-2 parts of triethylene diamine, 0.5-0.6 part of dibutyl tin dilaurate, 7-15 parts of cyclopentane and 2-3 parts of water;
preferably, the polymeric MDI is polymeric MDI with NCO content of 30-32%;
preferably, the preparation method of the lignin-based polyether polyol comprises the following steps:
adding a solid acid catalyst and an alcoholization reagent into lignin, heating, and stirring for reaction to obtain lignin-based polyether polyol;
preferably, the lignin is at least one of alkali lignin, enzymatic lignin and lignosulfonate;
preferably, the lignin alcoholization solid acid catalyst consists of alumina and a molecular sieve in a mass ratio of 2-3: 1; wherein the alumina is gamma-alumina; the molecular sieve is at least one of HY molecular sieve, H-beta molecular sieve and HZSM-5 molecular sieve;
preferably, the amount of the solid acid catalyst is 1-5% of the mass of the lignin;
preferably, the dosage of the alcoholizing reagent is 6-9 times of the mass of the lignin;
preferably, the alcoholizing agent is a mixture of polyethylene glycol and ethylene glycol;
the mass ratio of the mixture of the polyethylene glycol and the ethylene glycol is 3-4: 1-2;
the polyethylene glycol is a mixture of polyethylene glycol 400 and polyethylene glycol 800;
the mass ratio of the polyethylene glycol 400 to the polyethylene glycol 800 is 5-10: 1.
Preferably, the heating temperature is 140-160 ℃, preferably 150 ℃.
Preferably, the reaction time is 1-2 h.
Further preferably, the lignin-based polyether polyol is a flame-retardant modified lignin-based polyether polyol;
the preparation method of the flame-retardant modified lignin-based polyether polyol comprises the following steps:
(1) mixing lignin-based polyether polyol and triethanolamine, adding the mixture into trichloromethane, dropwise adding phosphorus oxychloride, heating, and stirring for reaction;
(2) and adding ethylene glycol, and heating for reaction to obtain the flame-retardant modified lignin-based polyether polyol.
Preferably, in the step (1), the amount of the triethanolamine is 2-3 times of the mass of the lignin-based polyether polyol;
preferably, in the step (1), the trichloromethane is used in an amount of 10-20ml per unit mass (in g) of the lignin-based polyether polyol;
preferably, in the step (1), the mass of the phosphorus oxychloride is 1-3 times of that of the lignin-based polyether polyol;
preferably, in the step (1), the heating temperature is 60-80 ℃; preferably 75 ℃;
preferably, in the step (1), the rotation speed of the stirring is 500-1000 rpm;
preferably, in step (1), the reaction time is 8-12 h.
Preferably, in the step (2), the heating temperature is 60-90 ℃; preferably 90 ℃;
preferably, in the step (2), the reaction time is 12-20 h;
preferably, in the step (2), the mass of the ethylene glycol is 2-4 times that of the lignin-based polyether polyol;
the invention also aims to provide a preparation method of the flame-retardant lignin-based polyurethane rigid foam, which comprises the following steps:
mixing the flame-retardant modified lignin-based polyether polyol with polyether polyol, adding a flame retardant, silicone oil, triethylene diamine, dibutyl tin dilaurate, cyclopentane and water, polymerizing MDI, stirring, foaming, drying and curing to obtain the flame-retardant lignin-based polyurethane rigid foam.
Preferably, the rotation speed of the stirring is 2000-3000 rpm;
the drying and curing are carried out for curing for 16-30h at the temperature of 60-80 ℃.
The invention also aims to provide application of the flame-retardant lignin-based polyurethane rigid foam in automotive interior.
Compared with the prior art, the invention has the technical advantages that:
(1) the flame retardant system is a halogen-free flame retardant, and meanwhile, the titanium dioxide is used due to better optical performance, so that the decomposition of nitrogen oxides and formaldehyde can be promoted, and the quality of air in the car can be obviously improved.
(2) According to the invention, the flame-retardant modified lignin-based polyether polyol is used, so that the obtained polyurethane foam has better degradation resistance and improved flame retardant property.
(3) The flame-retardant modified lignin-based polyether polyol is used, and the nano titanium dioxide and the tris (2-hydroxypropyl) phosphate composite flame retardant are used, so that the three are synergistic, and the flame retardant property of the automotive polyurethane foam is better improved.
(4) The thermal stability and the compressive strength are obviously improved, and the impact resistance is increased.
Detailed Description
The present invention will be described below with reference to specific examples to make the technical aspects of the present invention easier to understand and grasp, but the present invention is not limited thereto. The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
Preparation of lignin-based polyether polyol:
adding a solid acid catalyst accounting for 5% of the mass of lignin and an alcoholization reagent accounting for 6 times of the mass of the lignin into sodium lignosulfonate, heating to 140 ℃, and stirring for reacting for 1 hour to obtain lignin-based polyether polyol;
wherein the lignin alcoholization solid acid catalyst is prepared from the following components in a mass ratio of 2: 1, wherein the alumina is gamma-alumina; the molecular sieve is an HY molecular sieve;
the alcoholizing reagent is prepared from the following components in a mass ratio of 3: 2 a mixture of polyethylene glycol and ethylene glycol;
wherein the mass ratio of the polyethylene glycol is 5: 1, a mixture of polyethylene glycol 400 and polyethylene glycol 800;
preparing the flame-retardant modified lignin-based polyether polyol:
(1) mixing lignin-based polyether polyol with triethanolamine in an amount which is 2 times (calculated by the mass of the lignin-based polyether polyol, the same below) to obtain 10ml/g (10 ml of trichloromethane is used in each g of the lignin-based polyether polyol, the same below) of trichloromethane, dropwise adding phosphorus oxychloride in an amount which is 1 time (calculated by the mass of the lignin-based polyether polyol, the same below) of the trichloromethane, heating the mixture to 60 ℃, and stirring the mixture at 1000rpm for reaction for 8 hours;
(2) and adding 4 times of glycol by mass (calculated by the mass of the lignin-based polyether polyol), heating to 90 ℃, and reacting for 12 hours to obtain the flame-retardant modified lignin-based polyether polyol.
Example 2
Preparation of lignin-based polyether polyol:
adding a solid acid catalyst with the mass of 1% of that of lignin and an alcoholization reagent with the mass of 9 times of that of the lignin into sodium lignosulfonate, heating to 160 ℃, and stirring for reacting for 2 hours to obtain lignin-based polyether polyol;
wherein the lignin alcoholization solid acid catalyst is prepared from the following components in a mass ratio of 3:1, wherein the alumina is gamma-alumina; the molecular sieve is HZSM-5 molecular sieve;
the alcoholizing reagent is prepared from the following components in a mass ratio of 4:1, a mixture of polyethylene glycol and ethylene glycol;
wherein the mass ratio of the polyethylene glycol is 10:1, a mixture of polyethylene glycol 400 and polyethylene glycol 800;
the preparation method of the flame-retardant modified lignin-based polyether polyol comprises the following steps:
(1) mixing lignin-based polyether polyol with triethanolamine with the mass of 3 times, adding the mixture into chloroform with the mass of 20ml/g, dropwise adding phosphorus oxychloride with the mass of 3 times, heating to 80 ℃, and stirring and reacting for 12 hours at 500 rpm;
(2) and adding 2 times of glycol by mass, heating to 60 ℃, and reacting for 20 hours to obtain the flame-retardant modified lignin-based polyether polyol.
Example 3
In this example, the flame-retardant lignin-based rigid polyurethane foam comprises the following raw materials in parts by weight: 100 parts of polyether polyol, 150 parts of polymeric MDI, 12 parts of flame retardant, 6 parts of silicone oil, 1 part of triethylene diamine, 0.5 part of dibutyl tin dilaurate, 15 parts of cyclopentane and 2 parts of water;
wherein the polyether polyol is prepared from the following components in a mass ratio of 5: 2: 1 (using the flame retardant modified lignin-based polyether polyol of example 1), polyether polyol 4110 and polyether polyol 403.
The flame retardant is a mixture of nano titanium dioxide and tris (2-hydroxypropyl) phosphate; wherein the mass ratio of the nano titanium dioxide to the tris (2-hydroxypropyl) phosphate is 3: 1.
the preparation method of the tris (2-hydroxypropyl) phosphate comprises the following steps:
taking phosphoric acid, adding 3 times of propylene oxide by mass, heating at 70 ℃, stirring at 500rpm, and reacting for 12 hours to obtain the tris (2-hydroxypropyl) phosphate.
The preparation method of the flame-retardant lignin-based rigid polyurethane foam comprises the following steps:
mixing the flame-retardant modified lignin-based polyether polyol with polyether polyol, adding a flame retardant, silicone oil, triethylene diamine, dibutyl tin dilaurate, cyclopentane and water, and polymerizing MDI; rapidly and uniformly stirring the mixture under the stirring of 2000r/min, then pouring the mixture into a preheating mould, and freely rising and foaming at room temperature; after the foaming is stopped, curing the mixture in an oven at the temperature of 80 ℃ for 16h to obtain the flame-retardant lignin-based polyurethane rigid foam.
Example 4
In this embodiment, the flame-retardant lignin-based rigid polyurethane foam comprises the following raw materials in parts by weight: 80 parts of polyether polyol, 120 parts of polymeric MDI, 4 parts of flame retardant, 8 parts of silicone oil, 2 parts of triethylene diamine, 0.6 part of dibutyl tin dilaurate, 7 parts of cyclopentane and 3 parts of water;
wherein the polyether polyol is prepared from the following components in a mass ratio of 7: 4:1 (using the flame retardant modified lignin-based polyether polyol of example 1), polyether polyol 4110 and polyether polyol 403.
The flame retardant is a mixture of nano titanium dioxide and tris (2-hydroxypropyl) phosphate; wherein the mass ratio of the nano titanium dioxide to the tris (2-hydroxypropyl) phosphate is 5: 1.
the preparation method of the tris (2-hydroxypropyl) phosphate comprises the following steps:
adding 4 times of propylene oxide into phosphoric acid, heating at 80 ℃, stirring at 1000rpm, and reacting for 8h to obtain tris (2-hydroxypropyl) phosphate.
The preparation method of the flame-retardant lignin-based rigid polyurethane foam comprises the following steps:
mixing the flame-retardant modified lignin-based polyether polyol with polyether polyol, adding a flame retardant, silicone oil, triethylene diamine, dibutyl tin dilaurate, cyclopentane and water, and polymerizing MDI; rapidly and uniformly stirring the mixture under the stirring of 3000r/min, then pouring the mixture into a preheating mould, and freely rising and foaming at room temperature; after the foaming is stopped, putting the mixture into an oven at 60 ℃ for curing for 30h to obtain the flame-retardant lignin-based polyurethane rigid foam.
Example 5
In this embodiment, the flame-retardant lignin-based rigid polyurethane foam comprises the following raw materials in parts by weight: 50 parts of polyether polyol, 100 parts of polymeric MDI, 6 parts of flame retardant, 10 parts of silicone oil, 5 parts of triethylene diamine, 1 part of dibutyl tin dilaurate, 20 parts of cyclopentane and 1 part of water;
wherein the polyether polyol is prepared from the following components in a mass ratio of 7: 2: 1 (using the flame retardant modified lignin-based polyether polyol of example 2), polyether polyol 4110 and polyether polyol 403.
The flame retardant is a mixture of nano titanium dioxide and tris (2-hydroxypropyl) phosphate; wherein the mass ratio of the nano titanium dioxide to the tris (2-hydroxypropyl) phosphate is 4: 1.
the preparation method of the tris (2-hydroxypropyl) phosphate comprises the following steps:
adding 4 times of propylene oxide into phosphoric acid, heating at 75 ℃, stirring at 800rpm, and reacting for 10h to obtain tris (2-hydroxypropyl) phosphate.
The preparation method of the flame-retardant lignin-based rigid polyurethane foam comprises the following steps:
mixing the flame-retardant modified lignin-based polyether polyol with polyether polyol, adding a flame retardant, silicone oil, triethylene diamine, dibutyl tin dilaurate, cyclopentane and water, and polymerizing MDI; rapidly and uniformly stirring the mixture under the stirring of 2000r/min, then pouring the mixture into a preheating mould, and freely rising and foaming at room temperature; after foaming is stopped, placing the mixture in an oven at the temperature of 60-80 ℃ for curing for 16-30h to obtain the flame-retardant lignin-based rigid polyurethane foam.
Comparative example 1
Compared with example 3, the difference is only that: lignin-based polyether polyol from example 1, which was not flame retardant modified, was used.
In this example, the flame-retardant lignin-based rigid polyurethane foam comprises the following raw materials in parts by weight: 100 parts of polyether polyol, 150 parts of polymeric MDI, 12 parts of flame retardant, 6 parts of silicone oil, 1 part of triethylene diamine, 0.5 part of dibutyl tin dilaurate, 15 parts of cyclopentane and 2 parts of water;
wherein the polyether polyol is prepared from the following components in a mass ratio of 5: 2: 1 lignin-based polyether polyol, polyether polyol 4110 and polyether polyol 403.
The flame retardant is a mixture of nano titanium dioxide and tris (2-hydroxypropyl) phosphate; wherein the mass ratio of the nano titanium dioxide to the tris (2-hydroxypropyl) phosphate is 3: 1.
the preparation method of the tris (2-hydroxypropyl) phosphate comprises the following steps:
taking phosphoric acid, adding 3 times of propylene oxide by mass, heating at 70 ℃, stirring at 500rpm, and reacting for 12 hours to obtain the tris (2-hydroxypropyl) phosphate.
The preparation method of the flame-retardant lignin-based rigid polyurethane foam comprises the same steps as in example 3.
Comparative example 2
The composition of the flame retardant was different compared to example 3.
In this example, the flame-retardant lignin-based rigid polyurethane foam comprises the following raw materials in parts by weight: 100 parts of polyether polyol, 150 parts of polymeric MDI, 12 parts of flame retardant, 6 parts of silicone oil, 1 part of triethylene diamine, 0.5 part of dibutyl tin dilaurate, 15 parts of cyclopentane and 2 parts of water;
wherein the polyether polyol is prepared from the following components in a mass ratio of 5: 2: 1 (using the flame retardant modified lignin-based polyether polyol of example 1), polyether polyol 4110 and polyether polyol 403.
The flame retardant is nano titanium dioxide.
The preparation steps of the flame retardant lignin-based rigid polyurethane foam are the same as those of example 3.
Comparative example 3
The composition of the flame retardant was different compared to example 3.
In this example, the flame-retardant lignin-based rigid polyurethane foam comprises the following raw materials in parts by weight: 100 parts of polyether polyol, 150 parts of polymeric MDI, 12 parts of flame retardant, 6 parts of silicone oil, 1 part of triethylene diamine, 0.5 part of dibutyl tin dilaurate, 15 parts of cyclopentane and 2 parts of water;
wherein the polyether polyol is prepared from the following components in a mass ratio of 5: 2: 1 (using the flame retardant modified lignin-based polyether polyol of example 1), polyether polyol 4110 and polyether polyol 403.
The flame retardant is tris (2-hydroxypropyl) phosphate; the preparation method of the tris (2-hydroxypropyl) phosphate comprises the following steps:
taking phosphoric acid, adding 3 times of propylene oxide by mass, heating at 70 ℃, stirring at 500rpm, and reacting for 12 hours to obtain the tris (2-hydroxypropyl) phosphate.
The preparation steps of the flame retardant lignin-based rigid polyurethane foam are the same as those of example 3.
Comparative example 4
The composition of the polyether polyol was different compared to example 3.
In this example, the flame-retardant lignin-based rigid polyurethane foam comprises the following raw materials in parts by weight: 100 parts of polyether polyol, 150 parts of polymeric MDI, 12 parts of flame retardant, 6 parts of silicone oil, 1 part of triethylene diamine, 0.5 part of dibutyl tin dilaurate, 15 parts of cyclopentane and 2 parts of water;
wherein the polyether polyol is prepared from the following components in a mass ratio of 5: 1 (using the flame retardant modified lignin-based polyether polyol of example 1) and polyether polyol 403.
The flame retardant was the same as that of example 3.
The preparation steps of the flame retardant lignin-based rigid polyurethane foam are the same as those of example 3.
Comparative example 5
The alcoholizing reagent during the preparation of the lignin-based polyether polyol was different compared to example 3.
Preparing lignin-based polyether polyol:
adding a solid acid catalyst accounting for 5% of the mass of lignin and an alcoholization reagent accounting for 6 times of the mass of the lignin into sodium lignosulfonate, heating to 140 ℃, and stirring for reacting for 1 hour to obtain lignin-based polyether polyol;
wherein the lignin alcoholization solid acid catalyst is prepared from the following components in a mass ratio of 2: 1, wherein the alumina is gamma-alumina; the molecular sieve is an HY molecular sieve;
the alcoholizing reagent is prepared from the following components in a mass ratio of 3: 2 a mixture of polyethylene glycol and ethylene glycol;
wherein the polyethylene glycol is polyethylene glycol 400;
the obtained lignin-based polyether polyol is used for preparing the flame-retardant modified lignin-based polyether polyol, and the preparation steps are the same as those of example 1.
The obtained flame-retardant modified lignin-based polyether polyol is used for preparing the flame-retardant lignin-based rigid polyurethane foam, and the steps of preparing other components and the flame-retardant lignin-based rigid polyurethane foam are the same as the steps in the example 3.
Effect test
The experimental method comprises the following steps:
(1) the flame retardant property of the polyurethane rigid foam is measured by GB/T2406.2-2009 part 2 room temperature test for measuring combustion behavior by oxygen index method for plastics;
(2) the compression strength of the polyurethane rigid foam is measured by GB/T8813-2008 'determination of compression performance of rigid foam plastic'; sample size 50X 30mm3. The compression rate is 3mm/min, and the compression set is 15%; the direction of application of pressure is parallel to the cell elongation direction.
(3) Biodegradation test: the composite material is placed in moist soil, the field is well ventilated, the composite material is buried for 180 days, and the percentage of mass loss is calculated and is counted as the biodegradation rate.
TABLE 1 Properties of the rigid polyurethane foams
| Test group | Oxygen index (%) | Compressive Strength (MPa) | Biodegradation Rate (%) |
| Example 3 | 29 | 0.87 | 22.6 |
| Example 4 | 28 | 0.92 | 23.9 |
| Example 5 | 29 | 0.88 | 22.4 |
| Comparative example 1 | 24 | 0.51 | 19.3 |
| Comparative example 2 | 20 | 0.68 | 22.6 |
| Comparative example 3 | 19 | 0.46 | 20.5 |
| Comparative example 4 | 26 | 0.33 | 22.3 |
| Comparative example 5 | 22 | 0.54 | 18.6 |
Therefore, the polyurethane rigid foam provided by the application has better flame retardant property, and simultaneously has better mechanical property and biodegradability; the type of the flame retardant in the preparation process of the polyurethane rigid foam and the preparation process of the flame-retardant modified lignin-based polyether polyol have important influence on the performance of the polyurethane rigid foam.
The above detailed description is specific to one possible embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, and all equivalent implementations or modifications without departing from the scope of the present invention should be included in the technical scope of the present invention.
Claims (5)
1. The flame-retardant lignin-based polyurethane rigid foam comprises the following raw materials: polyether polyol, polymeric MDI and flame retardant; wherein the flame retardant is a mixture of nano titanium dioxide and tris (2-hydroxypropyl) phosphate; the mass ratio of the nano titanium dioxide to the tris (2-hydroxypropyl) phosphate is 3-5: 1;
the preparation method of the tris (2-hydroxypropyl) phosphate comprises the following steps: taking phosphoric acid, adding epoxypropane, heating at 70-80 ℃, stirring at 500-; wherein the mass ratio of phosphoric acid to propylene oxide is 1: 3-4;
the polyether polyol is a mixture of lignin-based polyether polyol, polyether polyol 4110 and polyether polyol 403; the mass ratio of the mixture of the lignin-based polyether polyol, the polyether polyol 4110 and the polyether polyol 403 is 5-7: 2-4: 1;
the preparation method of the lignin-based polyether polyol comprises the following steps: adding a solid acid catalyst and an alcoholization reagent into lignin, heating, and stirring for reaction to obtain lignin-based polyether polyol;
the solid acid catalyst consists of alumina and a molecular sieve in a mass ratio of 2-3:1, wherein the alumina is gamma-alumina; the molecular sieve is at least one of HY molecular sieve, H-beta molecular sieve and HZSM-5 molecular sieve;
the dosage of the solid acid catalyst is 1-5% of the mass of the lignin;
the lignin-based polyether polyol is flame-retardant modified lignin-based polyether polyol;
the preparation method of the flame-retardant modified lignin-based polyether polyol comprises the following steps:
mixing lignin-based polyether polyol and triethanolamine, adding the mixture into trichloromethane, dropwise adding phosphorus oxychloride, heating, and stirring for reaction;
and adding ethylene glycol, and heating for reaction to obtain the flame-retardant modified lignin-based polyether polyol.
2. The flame retarded lignin-based rigid polyurethane foam according to claim 1, wherein said flame retarded lignin-based rigid polyurethane foam further comprises: silicone oil, triethylene diamine, dibutyl tin dilaurate, cyclopentane and water.
3. The flame-retardant lignin-based rigid polyurethane foam according to claim 2, wherein the flame-retardant lignin-based rigid polyurethane foam comprises the following raw materials in parts by weight: 50-100 parts of polyether polyol, 100-200 parts of polymeric MDI, 4-12 parts of flame retardant, 5-10 parts of silicone oil, 0.5-5 parts of triethylene diamine, 0.5-1 part of dibutyl tin dilaurate, 5-20 parts of cyclopentane and 1-5 parts of water.
4. The method for preparing the flame-retardant lignin-based rigid polyurethane foam according to claim 3, comprising the steps of:
mixing polyether polyol, adding a flame retardant, silicone oil, triethylene diamine, dibutyl tin dilaurate, cyclopentane and water, polymerizing MDI, stirring, foaming, drying and curing to obtain the flame-retardant lignin-based polyurethane rigid foam.
5. The use of the flame retardant lignin-based rigid polyurethane foam according to any one of claims 1 to 3 or the flame retardant lignin-based rigid polyurethane foam produced by the method for producing a flame retardant lignin-based rigid polyurethane foam according to claim 4 for automotive interior.
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| CN102850507A (en) * | 2012-07-30 | 2013-01-02 | 华南理工大学 | Reinforced lignin-base polyurethane hard foam and preparation method thereof |
| CN111171264A (en) * | 2018-11-12 | 2020-05-19 | 天津市嘉美特自行车有限公司 | Preparation method of lignin polyurethane |
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| CN102850507A (en) * | 2012-07-30 | 2013-01-02 | 华南理工大学 | Reinforced lignin-base polyurethane hard foam and preparation method thereof |
| CN111171264A (en) * | 2018-11-12 | 2020-05-19 | 天津市嘉美特自行车有限公司 | Preparation method of lignin polyurethane |
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