CN112851901A - High-activity flame-retardant polymer polyol and preparation method thereof - Google Patents
High-activity flame-retardant polymer polyol and preparation method thereof Download PDFInfo
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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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/6795—Unsaturated polyethers
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4027—Mixtures of compounds of group C08G18/54 with other macromolecular compounds
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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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
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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
- C08G18/54—Polycondensates of aldehydes
- C08G18/544—Polycondensates of aldehydes with nitrogen compounds
Abstract
The invention discloses a high-activity flame-retardant polymer polyol and a preparation method thereof, belonging to the technical field of polyether polyol and comprising the following components: 48-60 parts of 6000-molecular-weight polyether; 10-20 parts of melamine; 1-5 parts of dicyandiamide; 0.1-1 part of urea; 0.1-0.4 part of triethylamine; 1-5 parts of paraformaldehyde; 10-25 parts of pure water; 0.5-1.5 parts of block polyether using amine as initiator. Uniformly mixing melamine, dicyandiamide, paraformaldehyde and water, heating to 75-85 ℃, and reacting under normal pressure for 1-2 hours to obtain a precursor; adding the precursor into 6000 molecular weight polyether, urea, triethylamine and amine as block polyether of an initiator, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours; and introducing inert gas under a high vacuum state to remove moisture to prepare the polymer polyol. The product does not contain harmful components such as halogen, phosphate ester and the like, has stable structure and good flame retardant property, and provides a new idea for the research of environment-friendly flame retardant polyether polyol.
Description
Technical Field
The invention relates to the technical field of polyether polyol, and particularly relates to high-activity flame-retardant polymer polyol and a preparation method thereof.
Background
Zhouyanxin and the like synthesize a bromine-containing flame-retardant polyether polyol, and under the condition of not using a flame retardant, the oxygen index of a polyurethane product reaches 24.1 percent. However, halogen-containing polyether polyols produce a large amount of smoke when burned, and the released hydrogen halide is a corrosive, toxic gas, often causing secondary damage.
Plum blossom and the like use trihydroxymethyl oxyphosphorus and epoxypropane to synthesize phosphorus-containing flame-retardant polyether polyol, and under the condition of not using a flame retardant, the oxygen index of a polyurethane product reaches 25.6 percent. However, the phosphorus-containing flame-retardant polyether polyol is easy to decompose, has high volatility and poor heat resistance.
Melamine and epoxy chloropropane are synthesized into polyether polyol MNFRP (MNFRP), and under the condition of not using a flame retardant, the oxygen index of a polyurethane product is 24.2 percent; the Shuguangjun takes N, N-dimethylacetamide as a solvent, melamine and propylene oxide are synthesized into melamine polyether polyol, and under the condition that a flame retardant is not used, the oxygen index of a polyurethane product is 25%.
Lijian, etc. the melamine is first mixed with organic solvent to prepare slurry, which is then reacted with olefin oxide to produce serial polyether polyol containing imido triazine amine structure unit in different molecular weights and hydroxyl values.
The existing polyether polyol products generally have the problems of low flame retardant efficiency, pollution caused by corrosive gas, halogen-containing, phosphate ester and other harmful components, and the like, so that the research on the flame retardant performance, the stability and the use safety performance is the key point of the research in the field of polyether polyol.
Disclosure of Invention
Aiming at the problems of insufficient flame retardant efficiency, easy volatilization, corrosive gas generation, pollution and the like of polyether polyol products in the prior art, the invention provides high-activity flame-retardant polymer polyol which is prepared from the following components in parts by weight:
preferably, the composition is prepared from the following components in parts by weight:
preferably, the composition is prepared from the following components in parts by weight:
preferably, the composition is prepared from the following components in parts by weight:
preferably, the water content of the polymer polyol is less than or equal to 0.15%, the viscosity is greater than or equal to 1500mPa.s/25 ℃, the nitrogen content is greater than or equal to 1%, and the oxygen index of the synthesized polyurethane product is more than 25%.
Preferably, the water content of the polymer polyol is less than or equal to 0.14%, the viscosity is greater than 5000mPa.s/25 ℃, the nitrogen content is greater than or equal to 5%, and the oxygen index of the synthesized polyurethane product is more than 25%.
The invention also provides a preparation method of the high-activity flame-retardant polymer polyol, which is characterized by comprising the following steps:
uniformly mixing melamine, dicyandiamide, paraformaldehyde and water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding the product obtained in the step two into 6000 molecular weight polyether, urea, triethylamine and segmented polyether taking amines as initiators, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required high-activity flame-retardant polymer polyol.
Has the advantages that:
the technical scheme of the invention has the following beneficial effects:
(1) the dicyandiamide and the melamine are selected mainly to improve the flame retardance of the product, and meanwhile, the molecular weight and the solid content of the product can be controlled, the stability of the product is improved, the viscosity of the product is higher when the melamine is used alone, and the molecular weight of the product is lower when the dicyandiamide is used alone. And the raw material contains nitrogen, so that toxic gas like halogen flame-retardant products can not be generated when the product is burnt, and the environment is protected.
(2) Paraformaldehyde (compared with formaldehyde) is selected, firstly, the content of free formaldehyde in the product is reduced; and secondly, the formaldehyde is generally 38% aqueous solution, so that excessive wastewater is easily generated in the production process, and the environmental protection pressure is caused. The addition of cyanamide when reacting aldehydes with urea reduces the water absorption of the product. The introduction of dicyandiamide can improve the product decolorization rate.
(3) The 6000 molecular weight polyether is introduced to the polyether and is capped by ethylene oxide, so that the reaction activity is high, and the free radical grafted nitrogen-containing group is easy to initiate. The block polyether taking amines with hydroxyl and unsaturated bond structures as an initiator is used as one of reaction monomers to react with dicyandiamide, melamine and urea together, so that the synthesized polymer polyol dispersed phase particles have the functions of a dispersing agent and reactive hydroxyl, and the problem of stability of the polymer polyol at high solid content is solved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the embodiments of the present invention will be described in detail and completely with reference to the examples of the present invention, and it is apparent that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. Thus, the following detailed description of the embodiments of the present invention, provided in the examples, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The dicyandiamide and the melamine are selected mainly to improve the flame retardance of the product, the molecular weight and the solid content of the product can be controlled, the stability of the product can be improved, the viscosity of the product is higher when the melamine is used alone, and the molecular weight of the product is lower when the dicyandiamide is used alone. And the raw material contains nitrogen, so that toxic gas like halogen flame-retardant products can not be generated when the product is burnt, and the environment is protected. The method comprises the following specific steps:
a high-activity flame-retardant polymer polyol is prepared from the following components in parts by weight:
the composition is prepared from the following components in parts by weight:
the composition is prepared from the following components in parts by weight:
the composition is prepared from the following components in parts by weight:
in a preferred embodiment, the water content of the polymer polyol is less than or equal to 0.15%, the viscosity is greater than or equal to 1500mPa.s/25 ℃, the nitrogen content is greater than or equal to 1%, and the oxygen index of the synthesized polyurethane product is more than 25%.
In a preferred embodiment, the water content of the polymer polyol is less than or equal to 0.14%, the viscosity is greater than 5000mPa.s/25 ℃, the nitrogen content is greater than or equal to 5%, and the oxygen index of the synthesized polyurethane product is more than 25%.
The embodiment also provides a preparation method of the high-activity flame-retardant polymer polyol, which is characterized by comprising the following steps:
uniformly mixing melamine, dicyandiamide, paraformaldehyde and water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding the product obtained in the step two into 6000 molecular weight polyether, urea, triethylamine and segmented polyether taking amines as initiators, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required high-activity flame-retardant polymer polyol.
The beneficial effects of the polymer polyol obtained by the technical solution of the present embodiment are further illustrated by several sets of examples and comparative examples.
The first embodiment is as follows:
the preparation method of the polymer polyol in this example includes the following steps:
step one, uniformly mixing 19 parts by weight of melamine, 1.5 parts by weight of dicyandiamide, 5 parts by weight of paraformaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 58 parts by weight of 6000 molecular weight polyether, 0.5 part by weight of urea, 0.1 part by weight of triethylamine and 0.9 part by weight of block polyether taking amine as an initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Example two:
the preparation method of the polymer polyol in this example includes the following steps:
uniformly mixing 20 parts by weight of melamine, 4 parts by weight of dicyandiamide, 4 parts by weight of paraformaldehyde and 20 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 55 parts by weight of 6000 molecular weight polyether, 0.2 part by weight of urea, 0.2 part by weight of triethylamine and 1 part by weight of block polyether taking amine as initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Example three:
the preparation method of the polymer polyol in this example includes the following steps:
step one, uniformly mixing 17 parts by weight of melamine, 2 parts by weight of dicyandiamide, 4 parts by weight of paraformaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 56 parts by weight of 6000 molecular weight polyether, 0.5 part by weight of urea, 0.1 part by weight of triethylamine and 1 part by weight of block polyether taking amine as an initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example one:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
uniformly mixing 10 parts by weight of melamine, 2.5 parts by weight of dicyandiamide, 4 parts by weight of paraformaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 48 parts by weight of 5000 molecular weight polyether, 0.5 part by weight of urea, 0.4 part by weight of triethylamine and 0.5 part by weight of block polyether taking amine as an initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example two:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
step one, uniformly mixing 19 parts by weight of melamine, 1.5 parts by weight of dicyandiamide, 5 parts by weight of paraformaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 58 parts by weight of 7000 parts of polyether with molecular weight, 0.5 part by weight of urea, 0.1 part by weight of triethylamine and 0.9 part by weight of block polyether taking amine as initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example three:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
step one, uniformly mixing 19 parts by weight of melamine, 1.5 parts by weight of dicyandiamide, 5 parts by weight of paraformaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 58 parts by weight of 8000 parts by weight of molecular weight polyether, 0.5 part by weight of urea, 0.1 part by weight of triethylamine and 0.9 part by weight of block polyether taking amine as initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example four:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
step one, uniformly mixing 19 parts by weight of melamine, 1.5 parts by weight of dicyandiamide, 5 parts by weight of formaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 58 parts by weight of 6000 molecular weight polyether, 0.5 part by weight of urea, 0.1 part by weight of triethylamine and 0.9 part by weight of block polyether taking amine as an initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example five:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
uniformly mixing 20 parts by weight of melamine, 5 parts by weight of paraformaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 58 parts by weight of 6000 molecular weight polyether, 0.5 part by weight of urea, 0.1 part by weight of triethylamine and 0.9 part by weight of block polyether taking amine as an initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example six:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
step one, uniformly mixing 5 parts by weight of dicyandiamide, 5 parts by weight of paraformaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 58 parts by weight of 6000 molecular weight polyether, 0.5 part by weight of urea, 0.1 part by weight of triethylamine and 0.9 part by weight of block polyether taking amine as an initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example seven:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
step one, uniformly mixing 19 parts by weight of melamine, 1.5 parts by weight of dicyandiamide, 5 parts by weight of paraformaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 45 parts by weight of 6000-molecular-weight polyether, 0.5 part by weight of urea, 0.1 part by weight of triethylamine and 0.9 part by weight of block polyether taking amine as an initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example eight:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
step one, uniformly mixing 19 parts by weight of melamine, 1.5 parts by weight of dicyandiamide, 5 parts by weight of paraformaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 70 parts by weight of 6000-molecular-weight polyether, 0.5 part by weight of urea, 0.1 part by weight of triethylamine and 0.9 part by weight of block polyether taking amine as an initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example nine:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
step one, uniformly mixing 7 parts by weight of melamine, 1.5 parts by weight of dicyandiamide, 5 parts by weight of paraformaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 58 parts by weight of 6000 molecular weight polyether, 0.5 part by weight of urea, 0.1 part by weight of triethylamine and 0.9 part by weight of block polyether taking amine as an initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example ten:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
uniformly mixing 25 parts by weight of melamine, 1.5 parts by weight of dicyandiamide, 5 parts by weight of paraformaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 58 parts by weight of 6000 molecular weight polyether, 0.5 part by weight of urea, 0.1 part by weight of triethylamine and 0.9 part by weight of block polyether taking amine as an initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example eleven:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
step one, uniformly mixing 19 parts by weight of melamine, 0.5 part by weight of dicyandiamide, 5 parts by weight of paraformaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 58 parts by weight of 6000 molecular weight polyether, 0.5 part by weight of urea, 0.1 part by weight of triethylamine and 0.9 part by weight of block polyether taking amine as an initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example twelve:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
uniformly mixing 19 parts by weight of melamine, 7 parts by weight of dicyandiamide, 5 parts by weight of paraformaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 58 parts by weight of 6000 molecular weight polyether, 0.5 part by weight of urea, 0.1 part by weight of triethylamine and 0.9 part by weight of block polyether taking amine as an initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example thirteen:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
step one, uniformly mixing 19 parts by weight of melamine, 1.5 parts by weight of dicyandiamide, 5 parts by weight of paraformaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 58 parts by weight of 6000 molecular weight polyether, 0.1 part by weight of triethylamine and 0.9 part by weight of block polyether taking amine as initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example fourteen:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
step one, uniformly mixing 19 parts by weight of melamine, 1.5 parts by weight of dicyandiamide, 5 parts by weight of paraformaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 58 parts by weight of 6000 molecular weight polyether, 1.2 parts by weight of urea, 0.1 part by weight of triethylamine and 0.9 part by weight of block polyether taking amine as an initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example fifteen:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
step one, uniformly mixing 19 parts by weight of melamine, 1.5 parts by weight of dicyandiamide, 5 parts by weight of paraformaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 58 parts by weight of 6000 molecular weight polyether, 0.5 part by weight of urea and 0.9 part by weight of block polyether taking amine as initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example sixteen:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
step one, uniformly mixing 19 parts by weight of melamine, 1.5 parts by weight of dicyandiamide, 5 parts by weight of paraformaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 58 parts by weight of 6000 molecular weight polyether, 0.5 part by weight of urea, 0.6 part by weight of triethylamine and 0.9 part by weight of block polyether taking amine as an initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example seventeen:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
step one, uniformly mixing 19 parts by weight of melamine, 1.5 parts by weight of dicyandiamide, 0.5 part by weight of paraformaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 58 parts by weight of 6000 molecular weight polyether, 0.5 part by weight of urea, 0.1 part by weight of triethylamine and 0.9 part by weight of block polyether taking amine as an initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example eighteen:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
step one, uniformly mixing 19 parts by weight of melamine, 1.5 parts by weight of dicyandiamide, 7 parts by weight of paraformaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 58 parts by weight of 6000 molecular weight polyether, 0.5 part by weight of urea, 0.1 part by weight of triethylamine and 0.9 part by weight of block polyether taking amine as an initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example nineteen:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
step one, uniformly mixing 19 parts by weight of melamine, 1.5 parts by weight of dicyandiamide, 5 parts by weight of paraformaldehyde and 7 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 58 parts by weight of 6000 molecular weight polyether, 0.5 part by weight of urea, 0.1 part by weight of triethylamine and 0.9 part by weight of block polyether taking amine as an initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example twenty:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
step one, uniformly mixing 19 parts by weight of melamine, 1.5 parts by weight of dicyandiamide, 5 parts by weight of paraformaldehyde and 30 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 58 parts by weight of 6000 molecular weight polyether, 0.5 part by weight of urea, 0.1 part by weight of triethylamine and 0.9 part by weight of block polyether taking amine as an initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example twenty one:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
step one, uniformly mixing 19 parts by weight of melamine, 1.5 parts by weight of dicyandiamide, 5 parts by weight of paraformaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 58 parts by weight of 6000 molecular weight polyether, 0.5 part by weight of urea, 0.1 part by weight of triethylamine and 0.2 part by weight of block polyether taking amine as an initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example twenty-two:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
step one, uniformly mixing 19 parts by weight of melamine, 1.5 parts by weight of dicyandiamide, 5 parts by weight of paraformaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 58 parts by weight of 6000 molecular weight polyether, 0.5 part by weight of urea, 0.1 part by weight of triethylamine and 2 parts by weight of block polyether taking amine as initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example twenty-three:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
step one, uniformly mixing 19 parts by weight of melamine, 1.5 parts by weight of dicyandiamide, 5 parts by weight of paraformaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 65 ℃, and reacting at normal pressure for 1-2 hours to obtain a precursor;
step three, adding 58 parts by weight of 6000 molecular weight polyether, 0.5 part by weight of urea, 0.1 part by weight of triethylamine and 0.9 part by weight of block polyether taking amine as an initiator into the product obtained in the step two, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
Comparative example twenty-four:
the preparation method of the polymer polyol in the comparative example comprises the following steps:
step one, uniformly mixing 19 parts by weight of melamine, 1.5 parts by weight of dicyandiamide, 5 parts by weight of paraformaldehyde and 15 parts by weight of water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding 58 parts by weight of 6000 molecular weight polyether, 0.5 part by weight of urea, 0.1 part by weight of triethylamine and 0.9 part by weight of block polyether taking amine as an initiator into the product obtained in the step two, uniformly mixing, heating to 80 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required polymer polyol.
The polymer polyols prepared in the three groups of examples and the twenty-four groups of comparative examples are tested for water content, viscosity, oxygen index and nitrogen content, and the specific data are as follows:
TABLE 1 sets of examples and comparative examples Polymer polyol test data
As can be seen from Table 1, the polyether polyol prepared by the formula and the preparation method can obtain higher nitrogen content and oxygen index while keeping lower water content, and can control the viscosity within a proper range.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The high-activity flame-retardant polymer polyol is characterized by being prepared from the following components in parts by weight:
2. the high-activity flame-retardant polymer polyol as claimed in claim 1, which is prepared from the following components in parts by weight:
3. the high-activity flame-retardant polymer polyol as claimed in claim 2, which is prepared from the following components in parts by weight:
4. the high-activity flame-retardant polymer polyol as claimed in claim 2, which is prepared from the following components in parts by weight:
5. the high-activity flame-retardant polymer polyol according to any one of claims 1 to 4, wherein the water content of the polymer polyol is less than or equal to 0.15%, the viscosity is greater than or equal to 1500mPa.s/25 ℃, the nitrogen content is greater than or equal to 1%, and the oxygen index of a synthetic polyurethane product is more than 25%.
6. The polymer polyol of claim 5, wherein the polymer polyol has a water content of 0.14% or less, a viscosity of greater than 5000mPa.s/25 ℃, a nitrogen content of 5% or more, and an oxygen index of the resultant polyurethane product of 25% or more.
7. The method for preparing the highly reactive flame retardant polymer polyol according to any of claims 1 to 4, comprising the steps of:
uniformly mixing melamine, dicyandiamide, paraformaldehyde and water;
step two, heating the mixed solution in the step one to 75-85 ℃ to react under normal pressure for 1-2 hours to prepare a precursor;
step three, adding the product obtained in the step two into 6000 molecular weight polyether, urea, triethylamine and segmented polyether taking amines as initiators, uniformly mixing, heating to 90-110 ℃, maintaining the pressure at normal pressure, and continuously reacting for 4-8 hours;
and step four, introducing inert gas in a high vacuum state, and removing moisture to prepare the required high-activity flame-retardant polymer polyol.
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