CN112194784A - Preparation method of starch-based flame-retardant polyether polyol - Google Patents
Preparation method of starch-based flame-retardant polyether polyol Download PDFInfo
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- CN112194784A CN112194784A CN202011013649.9A CN202011013649A CN112194784A CN 112194784 A CN112194784 A CN 112194784A CN 202011013649 A CN202011013649 A CN 202011013649A CN 112194784 A CN112194784 A CN 112194784A
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- polyether polyol
- starch
- based flame
- retardant polyether
- retardant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
Abstract
The invention relates to a method for preparing flame-retardant polyether polyol by catalyzing and liquefying pregelatinized starch by using boron phosphate as a catalyst, belonging to the technical field of efficient utilization of chemical material biomass. The flame-retardant polyether polyol is prepared by reacting pregelatinized starch serving as a raw material, a mixed solvent of diethylene glycol, diethanol amine and glycerol serving as a liquefying agent and boron phosphate serving as a catalyst in a hydrothermal kettle. The hydroxyl value of the obtained flame-retardant polyether polyol is 360.5-436.5mgKOH/g, and the liquefaction rate of starch is as high as 96.4%. The limit oxygen index of the foam prepared from the liquefied product reaches 28.9, the thermal conductivity coefficient is 0.019W/m.K, the compressive strength is 206.0 kPa, and the apparent density is 62.8 kg/m3The flame retardant property can be self-extinguished after being away from fire. The mechanical property is equivalent to that of polyurethane rigid foam prepared from petrochemical raw materials, and the indexes meet the industrial standard (JG/T314-2012) and the national standard (GB) of polyurethane rigid foam composite insulation boards10800-1989, GBT8813-2008, GBT 6343-2009).
Description
Technical Field
The invention relates to the technical field of high-quality utilization of new chemical materials and biomass, in particular to a preparation method of starch-based flame-retardant polyether polyol.
Background
Polyurethanes are a general term for macromolecular compounds containing repeating urethane groups in the main chain, obtained by reacting polyisocyanates with dihydroxy or polyhydroxy compounds. In recent years, with the increasing shortage of petroleum resources, a polyether polyol, which is one of main raw materials for synthesizing polyurethane, is coming to be on the market at an explosive price. And because the traditional polyurethane raw materials are completely from the petroleum industry, the products are difficult to degrade and recycle after being discarded, and the environment is seriously polluted. In order to relieve the excessive dependence on the increasingly exhausted petroleum resources and reduce the environmental pollution caused by the abandoned traditional polyurethane, the renewable natural plant polyol is used in the polyurethane industry, and the development of degradable biomass polyurethane materials becomes a hot point of domestic and foreign research. Starch is a renewable natural resource and has become an extremely important industrial raw material, and corn starch contains a large amount of hydroxyl groups and is one of the most ideal raw materials for producing polyols.
Starch liquefaction is an important way for converting starch into liquid polyol, and the wood and the starch are co-liquefied at normal pressure by adopting a catalytic liquefaction method, a Yao Guang method and the like at present. The reaction is carried out at 150 ℃ by using a mixture (volume ratio is 4: 1) of polyethylene glycol (PEG) and glycerol as a liquefying agent and sulfuric acid as a catalyst, and the obtained polyether polyol has a hydroxyl value of 434.6 mgKOH/g and a viscosity of 412.8 mPa & s.
Yao et al use corn starch as raw material, polypropylene glycol with relative molecular mass of 200 and hydroxyl value of 560 mgKOH/g as liquefier, and H2SO4As a catalyst, glycerol is an auxiliary liquefying agent. In the liquid-solid ratio of 1: 2, reacting for 30-60min, and preparing polyether polyol with hydroxyl value of 420 mgKOH/g and viscosity of 302.1-412.5 mPa.s under the process condition that the catalyst dosage is 0.3-2.8%, wherein the obtained polyether polyol can be mixed with other polyols, and the closed cell rate of the polyurethane foam prepared by the reaction is more than 80%.
Carr et al liquefy starch with concentrated sulfuric acid as a catalyst, then react with propylene oxide to obtain a polyol having a hydroxyl value of 470 mgKOH/g, and react the reaction product with isocyanate to obtain foam having good insulation properties, compressive strength and dimensional stability.
The Zhang Long topic group of Changchun university successfully developed a patent technology (CN 201510577286.4) for preparing biomass-based polyether polyol by using solid acid as a catalyst, starch or glucose as a raw material and polyol as a liquefying agent, and the obtained product is successfully used for preparing polyurethane rigid foam materials (CN 201510577071.2).
The problems of catalyst treatment, equipment corrosion and the like exist in the liquefaction process taking liquid mineral acid such as sulfuric acid and the like as a catalyst by integrating the existing polyol preparation technology; the problems of catalyst separation and repeated use exist in the liquefaction process with the solid acid as the catalyst, and the foam material prepared from the liquefied product has no flame retardant property, so that the popularization and application of the product are limited, and therefore, the development of more effective starch-based flame retardant polyether polyol has more important practical value.
Disclosure of Invention
Aiming at the problems, the invention provides a method for preparing polyether polyol by catalytic liquefaction of pregelatinized starch, which adopts a catalytic solvothermal method to directly liquefy the pregelatinized starch and then dehydrates the pregelatinized starch to prepare the polyether polyol. Therefore, the catalyst does not need to be removed by neutralization or other methods, the process is simple to operate, and the obtained biomass-based flame-retardant polyether polyol meets the requirement of preparing the flame-retardant rigid polyurethane thermal insulation material. In order to achieve the above object, the present invention adopts the following technical solutions:
a method for preparing flame-retardant polyether polyol by catalytic liquefaction of starch adopts a catalytic solvent thermal synthesis method, starch, a liquefying agent and a catalyst are sequentially added into a hydrothermal reaction kettle according to a proportion, the mixture is uniformly mixed, the reaction kettle is sent into an oven with a temperature control device, the reaction is carried out for 2-9 hours at the temperature of 130-190 ℃, then the temperature is reduced, and the product is subjected to reduced pressure distillation and dehydration until the water content is lower than 0.2%, so as to obtain the biomass-based flame-retardant polyether polyol.
Preferably, a catalytic solvothermal synthesis method is adopted, and the raw materials are various starches or pregelatinized starches.
Preferably, the liquefying agent is a mixture of a liquefying agent and a catalyst in a mass ratio of 5: 2: 3 of diethylene glycol, diethanolamine and glycerol, the mass ratio of the liquefying agent to the starch being 3-5:1, preferably 2.5-3: 1.
Preferably, the liquefaction reaction temperature is 130-190 ℃, preferably 150-170 ℃.
Preferably, the catalyst is boron phosphate, added in an amount of 1.0-15.0%, preferably 5-10%, by mass of the liquefier.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
1) the invention adopts a catalytic solvothermal method and takes the boron phosphate as the catalyst, thereby avoiding the problems of corrosion and side reaction caused by using sulfuric acid, realizing the high-efficiency liquefaction of the starch raw material without removing the catalyst and having simple process.
2) According to the invention, boron phosphate with a flame-retardant function is used as a catalyst, so that the prepared polyol has flame retardancy, the prepared hard polyurethane foam has flame retardancy, the addition of a flame retardant in a foaming process is avoided, the process operation is simple, and the production cost is low.
3) The rigid polyurethane foam product prepared from the liquefied product shows excellent flame retardant performance without an additional flame retardant, and the limited oxygen index reaches 29%; and other performance indexes of the foam completely meet the requirements for preparing the flame-retardant rigid polyurethane thermal insulation material.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
Example 1.
Adding 5.0g of pregelatinized starch into a 50mL hydrothermal reaction kettle, adding 15.0g of mixed liquefier, adding 1.5g of boron phosphate, uniformly mixing, putting the reaction kettle into a drying oven with a temperature control device, reacting for 8 hours at 170 ℃, taking out the reaction kettle, cooling, and carrying out reduced pressure distillation on a product to remove water to obtain polyether polyol, wherein the liquefaction rate of the pregelatinized starch is determined to be 96.4%, the hydroxyl value is 352.5mgKOH/g, and the viscosity is determined to be 418.5 mPa.
Example 2.
Adding 5.0g of corn starch into a 50mL hydrothermal reaction kettle, adding 20g of mixed liquefier, adding 1.0g of boron phosphate, uniformly mixing, putting the reaction kettle into an oven with a temperature control device, reacting for 8 hours at 170 ℃, taking out the reaction kettle, cooling, and carrying out reduced pressure distillation on a product to remove water to obtain polyether polyol, wherein the liquefaction rate of the corn starch is determined to be 90.2%, the hydroxyl value is 343.7mgKOH/g, and the viscosity is determined to be 420.3 mPa.
Example 3.
Adding 5.0g of potato starch into a 50mL hydrothermal reaction kettle, adding 10.5g of mixed liquefier, adding 0.525g of boron phosphate, uniformly mixing, putting the reaction kettle into an oven with a temperature control device, reacting for 6 hours at 160 ℃, taking out the reaction kettle, cooling, and carrying out reduced pressure distillation on a product to remove water to obtain polyether polyol, wherein the liquefaction rate of the starch is determined to be 92.2%, the hydroxyl value is 383.7mgKOH/g, and the viscosity is determined to be 350.3 mPa.
Example 4.
Adding 5.0g of cassava starch into a 50mL hydrothermal reaction kettle, adding 15.0g of mixed liquefier solution, adding 1.5g of boron phosphate, uniformly mixing, putting the reaction kettle into an oven with a temperature control device, reacting for 6 hours at 160 ℃, taking out the reaction kettle, cooling, and carrying out reduced pressure distillation on a product to remove water to obtain polyether polyol, wherein the liquefaction rate of the corn starch is determined to be 96.2%, the hydroxyl value is 375.8mgKOH/g, and the viscosity is determined to be 345.7 mPa.
Example 5 preparation of rigid polyurethane foams from the liquefied products mechanical and flame retardant Properties
Respectively weighing 20.0g of the liquefied product of the embodiment 1-4, 0.6g of silicone oil L-580, 1.6g of water and 0.65g of dibutyltin dilaurate serving as a catalyst, uniformly mixing in a 500mL beaker, adding 30.0g of MDI, fully stirring until the system is uniform and foam rises, stopping stirring, allowing the system to freely foam at room temperature, and curing the foam to obtain the flame-retardant rigid polyurethane foam. The compression strength of the obtained flame-retardant polyurethane rigid foam is measured to be 0.16-0.25MPa, the bending strength is 332-508kPa, and the average apparent density is 60-63kg/m3The thermal conductivity coefficient is 0.018-0.022W/m.K, and the limiting oxygen index of the foam is 26.7-28.9. The performance of the rigid polyurethane foam prepared by the liquefied product meets the requirements of national standards (GB/T6343-2009 and GB/T8813-2008), and the flame retardance can achieve self-extinguishing after fire.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (9)
1. A method for preparing starch-based flame-retardant polyether polyol comprises the following steps: adding a certain mass of starch raw material into a hydrothermal kettle, then adding a liquefying agent with the mass being 3-5 times that of the raw material and a catalyst with the mass being 1-15% that of the liquefying agent into the hydrothermal kettle, uniformly mixing, putting the hydrothermal kettle into an oven for reaction for 2-9 hours, cooling a liquefied product to room temperature, carrying out suction filtration, putting a liquefied residue into an oven with the temperature of 105 ℃ for drying for 24 hours, and carrying out reduced pressure distillation on the liquefied product to remove water, thus obtaining the starch-based flame-retardant polyether polyol.
2. The preparation method of the pregelatinized starch-based flame retardant polyether polyol as claimed in claim, wherein: the method adopts a catalytic solvent thermal synthesis method, and the raw materials are various starches or pregelatinized starches.
3. The method for preparing starch-based flame-retardant polyether polyol according to the claim, wherein the method comprises the following steps: the liquefying agent is prepared from the following components in percentage by mass: 2: 3, the mass ratio of the liquefying agent to the starch is 3-5: 1.
4. The method for preparing starch-based flame-retardant polyether polyol according to the claim, wherein the method comprises the following steps: the temperature of the catalytic liquefaction reaction is 130-190 ℃.
5. The method for preparing starch-based flame-retardant polyether polyol according to the claim, wherein the method comprises the following steps: the water is removed by reduced pressure distillation, specifically, the reaction product is dehydrated under reduced pressure under the conditions of 105 ℃ and-0.1 MP until the water content of the product is lower than 0.2 percent.
6. The method for preparing starch-based flame-retardant polyether polyol according to the claim, wherein the method comprises the following steps: the hydroxyl value of the pregelatinized starch-based flame-retardant polyether polyol is 360.5-436.5 mgKOH/g.
7. The method for preparing starch-based flame-retardant polyether polyol according to the claim, wherein the method comprises the following steps: and the unreacted raw material obtained by filtering is recycled as the raw material for the next reaction.
8. The method for preparing starch-based flame-retardant polyether polyol according to claim, wherein the catalyst is dissolved in the reaction system and has a flame-retardant function, so that the catalyst is not required to be removed by neutralization or other means.
9. Use of a pregelatinized starch-based flame retardant polyether polyol prepared according to the preparation method of any one of claims 1 to 8, wherein: is suitable for preparing the flame-retardant rigid polyurethane thermal insulation material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113717374A (en) * | 2021-09-24 | 2021-11-30 | 长春工业大学 | Preparation method and application of bio-based flame-retardant polyether polyol |
| CN113929858A (en) * | 2021-10-20 | 2022-01-14 | 长春工业大学 | Preparation method of bio-based polyurethane material |
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| CN106279634A (en) * | 2016-09-06 | 2017-01-04 | 南京大学 | A kind of high-strength anti-flaming hard polyaminoester insulation material for building and preparation method thereof |
| CN106459353A (en) * | 2014-06-24 | 2017-02-22 | 路博润先进材料公司 | Integrated polyurethane article |
| CN107129570A (en) * | 2017-05-18 | 2017-09-05 | 长春工业大学 | A kind of preparation method of starch based polyether polyol |
| CN110172143A (en) * | 2019-04-16 | 2019-08-27 | 吉林市福创节能建材有限公司 | A kind of method of starch catalytic liquefaction preparation polyether polyol |
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- 2020-09-24 CN CN202011013649.9A patent/CN112194784A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106459353A (en) * | 2014-06-24 | 2017-02-22 | 路博润先进材料公司 | Integrated polyurethane article |
| CN106279634A (en) * | 2016-09-06 | 2017-01-04 | 南京大学 | A kind of high-strength anti-flaming hard polyaminoester insulation material for building and preparation method thereof |
| CN107129570A (en) * | 2017-05-18 | 2017-09-05 | 长春工业大学 | A kind of preparation method of starch based polyether polyol |
| CN110172143A (en) * | 2019-04-16 | 2019-08-27 | 吉林市福创节能建材有限公司 | A kind of method of starch catalytic liquefaction preparation polyether polyol |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113717374A (en) * | 2021-09-24 | 2021-11-30 | 长春工业大学 | Preparation method and application of bio-based flame-retardant polyether polyol |
| CN113929858A (en) * | 2021-10-20 | 2022-01-14 | 长春工业大学 | Preparation method of bio-based polyurethane material |
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