CN112646161B - Full sucrose type flame-retardant polyether polyol and preparation method thereof - Google Patents
Full sucrose type flame-retardant polyether polyol and preparation method thereof Download PDFInfo
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- CN112646161B CN112646161B CN202011465460.3A CN202011465460A CN112646161B CN 112646161 B CN112646161 B CN 112646161B CN 202011465460 A CN202011465460 A CN 202011465460A CN 112646161 B CN112646161 B CN 112646161B
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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
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5006—Polyethers having heteroatoms other than oxygen having halogens having chlorine and/or bromine atoms
- C08G18/5009—Polyethers having heteroatoms other than oxygen having halogens having chlorine and/or bromine atoms having chlorine atoms
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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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5006—Polyethers having heteroatoms other than oxygen having halogens having chlorine and/or bromine atoms
- C08G18/5012—Polyethers having heteroatoms other than oxygen having halogens having chlorine and/or bromine atoms having bromine atoms
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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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5018—Polyethers having heteroatoms other than oxygen having halogens having iodine atoms
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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
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2639—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of polyether polyol synthesis, and particularly relates to full sucrose type flame-retardant polyether polyol and a preparation method thereof. Firstly, a large amount of halogen elements are introduced into sucrose molecules through methylation reaction to obtain a body flame-retardant effect, then an intermediate product and alkylene oxide are subjected to polymerization reaction to prepare flame-retardant polyether polyol, the prepared full sucrose type flame-retardant polyether polyol product has both structural flame retardance and ultrahigh functionality, and the prepared polyurethane hard foam product has excellent dimensional stability and flame retardant property.
Description
Technical Field
The invention belongs to the technical field of polyether polyol synthesis, and particularly relates to full sucrose type flame-retardant polyether polyol and a preparation method thereof.
Background
The rigid polyurethane foam plastic has the advantages of excellent heat insulation performance, high strength, excellent electrical performance, chemical resistance and sound insulation performance, convenient processing and forming and the like, and is widely applied to various fields of building heat insulation, petrochemical engineering pipeline transportation, household appliances and the like. However, in practical application of polyurethane materials, since the materials are very susceptible to temperature, severe temperature changes or long-term low and high temperature conditions may cause dimensional shrinkage of the materials, and further cause cracking, falling off and other phenomena, which inevitably affect normal use of the materials. Therefore, the dimensional stability of rigid polyurethane foams is a common concern in the industry.
Meanwhile, polyurethane foam belongs to flammable organic polymer materials, and has a porous structure and a large specific surface, so that the flame retardance of polyurethane foam is always a focus of people. However, the additive flame retardant has the problems of poor flame retardant migration and durability, large influence on material performance and the like, so that embedding flame-retardant elements into molecules for structural flame retardance is a more effective way for preparing efficient flame-retardant materials.
In the traditional polyether production process, the problem that the initial stirring of a reaction kettle is difficult to open or even stop as solid sucrose serving as a reaction material usually occurs, so that great process safety hidden dangers and period waste are caused in the production process.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the defects of the prior art are overcome, the full sucrose type flame-retardant polyether polyol is provided, and the full sucrose type flame-retardant polyether polyol has structural flame retardance and ultrahigh functionality at the same time, so that the prepared polyurethane rigid foam product has excellent dimensional stability and flame retardance; meanwhile, the invention also provides a preparation method of the solid material, solves the problem that stirring is difficult to open commonly occurring in the actual polyether production process of the solid material sucrose, and has excellent application significance.
The full sucrose type flame-retardant polyether polyol is prepared from the following raw materials in parts by weight:
wherein:
the solvent is one or two of anhydrous dimethyl sulfoxide or pyridine, and preferably anhydrous dimethyl sulfoxide.
The strong base catalyst is one or two of potassium hydroxide or sodium hydroxide, and potassium hydroxide is preferred.
The halogenated methane is one or more of bromodichloromethane, dibromo-chloromethane, dichloromethane, trichloromethane, tribromomethane or iodomethane.
The alkylene oxide is one or more of ethylene oxide, butylene oxide, propylene oxide or epichlorohydrin.
According to the preparation method of the full sucrose flame-retardant polyether polyol, firstly, a large amount of halogen elements are introduced into sucrose molecules through methylation reaction to obtain a body flame-retardant effect, then the flame-retardant polyether polyol is prepared through polymerization reaction with alkylene oxide, the prepared full sucrose flame-retardant polyether polyol product has both structural flame retardance and ultrahigh functionality, so that the prepared polyurethane rigid foam product is excellent in size stability and flame retardance, meanwhile, a polar organic solvent used in the methylation reaction can dissolve sucrose, the problem that stirring of solid sucrose in the actual polyether production process is difficult to start is solved, and the preparation method has excellent application significance.
The preparation method of the full sucrose type flame-retardant polyether polyol specifically comprises the following steps:
(1) Sequentially adding a solvent, sucrose and a strong base catalyst into a reaction kettle, stirring and heating to a specified temperature, sequentially adding methyl halide into the reaction kettle, carrying out methylation reaction, and keeping the temperature until the reaction time is over to obtain a methylated polysaccharide derivative;
(2) And (2) introducing alkylene oxide into the methylated polysaccharide derivative obtained in the step (1), carrying out polymerization reaction, controlling the temperature and the reaction pressure until the reaction time is over, and refining the obtained crude full sucrose flame-retardant polyether polyol to obtain the full sucrose flame-retardant polyether polyol.
In the step (1), the methylation reaction temperature is 40-60 ℃, and the reaction time is 1-3h.
In the step (2), the polymerization reaction temperature is 80-120 ℃, the reaction time is 1-5h, and the reaction pressure is-0.08-0.15 MPa.
The refining treatment process in the step (2) comprises the following specific steps: adding acid into the crude full sucrose type flame retardant polyether polyol, stirring for 05-1h at 80-90 ℃ for neutralization treatment, adding an adsorbent after neutralization, stirring for 05-1h at 80-90 ℃ for adsorption treatment, dehydrating and drying after adsorption, and performing reduced pressure suction filtration to obtain the full sucrose type flame retardant polyether polyol.
Preferably, the acid is phosphoric acid, and the adsorbent is one or two of magnesium silicate or aluminum silicate.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention introduces a large amount of halogen elements into sucrose molecules through methylation reaction to obtain the bulk flame retardant effect.
(2) The invention only takes sucrose as an initiator, the functionality of the prepared polyether polyol product can reach 7-8, and the polyether polyol has excellent dimensional stability under the condition of large special temperature difference change and in the application field of extreme temperature.
(3) The polar organic solvent used in the methylation reaction can dissolve sucrose, so that the problem that stirring of solid sucrose is difficult to start in the actual polyether production process is solved, and the method has excellent application significance.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
All the raw materials used in the examples are commercially available unless otherwise specified.
Example 1
Adding 75g of anhydrous dimethyl sulfoxide, 300g of sucrose and 4.35g of solid KOH into a reaction kettle in sequence, starting stirring, pressurizing, leakage testing and nitrogen replacement, raising the temperature of the reaction kettle to 50 ℃, adding 10g of methyl iodide into the reaction kettle for 3 times, reacting for 1 hour at the temperature, pumping the pressure of the reaction kettle to negative pressure (-0.08 MPa), heating to 105 ℃, slowly introducing 855g of ethylene oxide, maintaining the pressure at 0.15MPa, continuously reacting for 3 hours at the temperature and the pressure, finally adding a mixed solution of 10g of phosphoric acid and 86g of pure water at 85 ℃ for neutralization reaction, adding 1.2g of magnesium silicate and 0.6g of aluminum silicate adsorbent after reacting for 1 hour, stirring for 30 minutes, dehydrating and drying for 2.5 hours, and performing suction filtration to obtain the full sucrose type flame-retardant polyether polyol after drying, wherein the performance indexes are shown in Table 1.
Example 2
Adding 60g of pyridine, 300g of sucrose and 3.6g of solid KOH into a reaction kettle in sequence, starting stirring, pressurizing, leak testing and nitrogen replacement, raising the temperature of the reaction kettle to 50 ℃, adding 7.5g of trichloromethane into the reaction kettle for 3 times, reacting for 1.5h at the temperature, pumping the pressure of the reaction kettle to negative pressure (-0.05 MPa), raising the temperature to 110 ℃, slowly introducing 705g of ethylene oxide, maintaining the pressure to be 0.15MPa, continuously reacting for 4h at the temperature, finally adding a mixed solution of 9g of phosphoric acid and 60g of pure water at 85 ℃ for neutralization reaction, adding 1g of magnesium silicate and 0.5g of aluminum silicate adsorbent after reacting for 1h, stirring for 30min, dehydrating and drying for 2.5h to obtain the full sucrose type flame-retardant polyether polyol after drying, wherein the performance index is shown in Table 1.
Example 3
Adding 90g of pyridine, 350g of cane sugar and 6.5g of solid KOH into a reaction kettle in sequence, starting stirring, pressurizing, leakage testing and nitrogen replacement, raising the temperature of the reaction kettle to 40 ℃, adding 15g of dibromo-monochloromethane into the reaction kettle for 3 times, reacting for 1 hour at the temperature, pumping the pressure of the reaction kettle to negative pressure (-0.05 MPa), raising the temperature to 105 ℃, slowly introducing 920g of propylene oxide, maintaining the pressure at 0.15MPa, continuously reacting for 3 hours at the temperature and the pressure, finally adding a mixed solution of 15.21g of phosphoric acid and 100g of pure water at 85 ℃ for neutralization reaction, adding 1.5g of magnesium silicate and 0.8g of aluminum silicate adsorbent after reacting for 1 hour, stirring for 30 minutes, dehydrating and drying for 3 hours, drying and filtering to obtain the full sucrose type flame-retardant polyether polyol, wherein the performance indexes are shown in Table 1.
Comparative example 1
Adding 130g of diethylene glycol, 300g of sucrose and 4.35g of solid KOH into a reaction kettle in sequence, starting stirring, pumping the pressure of the reaction kettle to negative pressure (-0.08 MPa) after pressurization leakage testing and nitrogen replacement, heating to 105 ℃, slowly introducing 855g of propylene oxide, maintaining the pressure to be 0.15MPa, continuously reacting for 3 hours at the temperature and the pressure, finally adding a mixed solution of 10g of phosphoric acid and 86g of pure water at 85 ℃ for neutralization reaction, adding 1.2g of magnesium silicate and 0.6g of aluminum silicate adsorbent after reacting for 1 hour, stirring for 30 minutes, dehydrating and drying for 2.5 hours, and performing suction filtration to obtain the conventional polyether polyol, wherein the performance indexes are shown in Table 1.
Comparative example 2
300g of sucrose and 4.35g of solid KOH are sequentially added into the reaction kettle, and stirring is difficult to open.
Articles were made using the materials of examples 1-3 and comparative examples 1-2 using the same formulation system and the same conditions and were tested for oxygen index and dimensional stability, the results of which are shown in table 1.
The formula system is as follows:
polyol:100 parts of a binder;
H2O:1.5 parts;
cyclohexylamine: 1 part;
141b:25 parts of a binder;
silicone oil: and 2 parts of the raw materials.
The preparation method comprises the following steps:
accurately weighing the formula materials, preparing the formula materials into a 500mL beaker to prepare a combined material, fully stirring 50 parts of the combined material and 50 parts of PM200, stopping stirring when the system is uniform and foam rises, allowing the combined material to foam freely at room temperature, and curing the foam to obtain the polyurethane rigid foam. The polyurethane rigid foam obtained above was subjected to an oxygen index test.
TABLE 1 test results
Of course, the foregoing is merely exemplary of the invention and is not to be construed as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit of the present invention should be included in the scope of the present invention.
Claims (8)
1. The full sucrose type flame-retardant polyether polyol is characterized in that: the feed is prepared from the following raw materials in parts by mass:
2.5-15 parts of a solvent;
10-60 parts of cane sugar;
0.3-8 parts of a strong base catalyst;
0.5-20 parts of halogenated methane;
15-80 parts of alkylene oxide;
the solvent is one or two of anhydrous dimethyl sulfoxide or pyridine;
the preparation method of the full sucrose type flame-retardant polyether polyol comprises the following steps:
(1) Sequentially adding a solvent, sucrose and a strong base catalyst into a reaction kettle, stirring and heating to a specified temperature, sequentially adding methyl halide into the reaction kettle, carrying out methylation reaction, and keeping the temperature until the reaction time is over to obtain a methylated polysaccharide derivative;
(2) And (2) introducing alkylene oxide into the methylated polysaccharide derivative obtained in the step (1), carrying out polymerization reaction, controlling the temperature and the reaction pressure until the reaction time is over, and refining the obtained crude full sucrose flame-retardant polyether polyol to obtain the full sucrose flame-retardant polyether polyol.
2. The all-sucrose flame-retardant polyether polyol according to claim 1, characterized in that: the strong base catalyst is one or two of potassium hydroxide or sodium hydroxide.
3. The all-sucrose-type flame-retardant polyether polyol according to claim 1, characterized in that: the halogenated methane is more than one of monobromo dichloromethane, dibromo monochloromethane, dichloromethane, trichloromethane, tribromomethane or iodomethane.
4. The all-sucrose flame-retardant polyether polyol according to claim 1, characterized in that: the alkylene oxide is more than one of ethylene oxide, butylene oxide, propylene oxide or epichlorohydrin.
5. The all-sucrose flame-retardant polyether polyol according to claim 1, characterized in that: in the step (1), the methylation reaction temperature is 40-60 ℃, and the reaction time is 1-3h.
6. The all-sucrose-type flame-retardant polyether polyol according to claim 1, characterized in that: in the step (2), the polymerization reaction temperature is 80-120 ℃, the reaction time is 1-5h, and the reaction pressure is-0.08-0.15 MPa.
7. The all-sucrose flame-retardant polyether polyol according to claim 1, characterized in that: the refining treatment process in the step (2) is specifically as follows: adding acid into the crude full sucrose type flame retardant polyether polyol, stirring for 1h at 80-90 ℃ for neutralization treatment, adding an adsorbent after neutralization, stirring for 1h at 80-90 ℃ for adsorption treatment, dehydrating and drying after adsorption, and performing reduced pressure suction filtration to obtain the full sucrose type flame retardant polyether polyol.
8. The all-sucrose flame-retardant polyether polyol of claim 7, wherein: the acid is phosphoric acid, and the adsorbent is one or two of magnesium silicate or aluminum silicate.
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CN112011045A (en) * | 2020-08-31 | 2020-12-01 | 荆晓东 | Method for synthesizing flame-retardant polyether polyol |
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2020
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JPH01313543A (en) * | 1988-06-10 | 1989-12-19 | Toyo Tire & Rubber Co Ltd | Production of rigid polyurethane foam by using mixed blowing aid |
CN101899160A (en) * | 2010-07-15 | 2010-12-01 | 山东兄弟科技股份有限公司 | Preparation method of oligomerization phosphate polyalcohol |
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