CN112679722A - Preparation method of polyether polyol for all-water flame-retardant system - Google Patents
Preparation method of polyether polyol for all-water flame-retardant system Download PDFInfo
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- CN112679722A CN112679722A CN202011579216.XA CN202011579216A CN112679722A CN 112679722 A CN112679722 A CN 112679722A CN 202011579216 A CN202011579216 A CN 202011579216A CN 112679722 A CN112679722 A CN 112679722A
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Abstract
The invention relates to a preparation method of polyether polyol for an all-water flame-retardant system, belonging to the technical field of polyether polyol modification. The preparation method of the polyether polyol for the all-water flame-retardant system takes trihydroxyethyl isocyanurate, methylol melamine and micromolecule alcohol as composite initiators, and the polyether polyol is obtained by polymerization reaction with alkylene oxide under the catalysis of alkali. The invention has scientific and reasonable design and reduced cost, and the prepared polyether has low viscosity, good compatibility with water and auxiliaries and good flame retardant effect.
Description
Technical Field
The invention relates to a preparation method of polyether polyol for an all-water flame-retardant system, belonging to the technical field of polyether polyol modification.
Background
The full-water rigid foam polyurethane takes water as a foaming agent, does not contain substances damaging the ozone layer, and is the most environment-friendly polyurethane heat-insulating material. The principle of water foaming is that water reacts with polyisocyanate to generate CO2，C02Left in the cells as a blowing agent for the foam. The ODP value of the system is zero, and the system is non-toxic, environment-friendly, simple and convenient in process, free of special requirements on equipment and low in cost, and is one of the main directions for replacing the foaming agent at present.
The all-water foaming body is not added with a physical foaming agent, and needs to adopt polyether polyol which has lower viscosity and can be well mixed and dissolved with water and an auxiliary agent. Most products in the market at present are limited by basic raw materials such as sucrose, sorbitol and the like, have the conditions of high viscosity and low intersolubility with auxiliaries, and generally have the conditions of poor storage stability or low flame retardant property and the like.
Disclosure of Invention
The invention aims to provide a preparation method of polyether polyol for an all-water flame-retardant system, which has scientific and reasonable design and reduced cost, and the prepared polyether has low viscosity, good compatibility with water and auxiliaries and good flame-retardant effect.
The preparation method of the polyether polyol for the full-water flame-retardant system comprises the steps of taking trihydroxyethyl isocyanurate, hydroxymethyl melamine and micromolecular alcohol as composite initiators, and carrying out polymerization reaction with alkylene oxide under the catalysis of alkali to obtain the polyether polyol;
the preparation method of the methylol melamine comprises the following steps: putting melamine and formaldehyde into a reaction kettle, adding an alkaline catalyst at the same time, after leakage test and replacement in the reaction kettle, heating to 60-70 ℃ in the nitrogen atmosphere, keeping the pressure in the reaction kettle within the range of 0.1-0.15MPa, and stirring for reaction for 1-1.5h to synthesize the hydroxymethyl melamine. Preferably, the small molecule alcohol is propylene glycol or diethylene glycol.
The methylol melamine is used as an initiator, and is different from a commercial product in that etherification is not generated, raw materials purchased from the market cannot be used as the initiator, and the proportion is different.
The methylol melamine is synthesized by taking melamine and formaldehyde as raw materials through a hydroxymethylation reaction.
Preferably, the formaldehyde is polyformaldehyde with a polymerization degree of 3-100 or more or a formaldehyde solution with a mass content of 37%.
Preferably, the molar ratio of melamine to formaldehyde is from 1:2 to 4.
Preferably, the base is potassium hydroxide, sodium hydroxide, triethylamine or dimethylcyclohexylamine.
Preferably, the alkylene oxide is one or both of ethylene oxide and propylene oxide.
Preferably, the tris (hydroxyethyl) isocyanurate is 26 to 90 wt% of the methylolmelamine.
Preferably, the small molecular alcohol accounts for 3.5-6.5 per mill of the total mass of the composite initiator.
The synthesis and preparation method of the polyether polyol for the all-water flame-retardant system preferably comprises the following steps:
1) preparation of methylol melamine: putting 34-58% by mass of melamine and 42-66% by mass of formaldehyde into a 2.5L reaction kettle, simultaneously adding 1 per mill of alkaline catalyst, after leakage test and replacement of the reaction kettle, heating to 60-70 ℃ in a nitrogen atmosphere, stirring and reacting for 1-1.5h in the kettle under the pressure of 0.1-0.15MPa, and synthesizing the methylol melamine.
2) On the basis of synthesizing the trimethylol melamine in the step 1), 26-90% of the trihydroxy ethyl isocyanurate of the trimethylol melamine is added into a reaction kettle, about 3.5-6.5 per thousand of propylene glycol or diethylene glycol is added, 3 per thousand of alkaline catalyst is added, after the temperature is raised to 80 ℃ by stirring, an epoxy olefin compound valve is opened, an epoxy olefin compound is slowly dripped to carry out ring opening reaction, and the weight of the dripped epoxy olefin compound is 10-15% of the weight of the initiator after dehydration.
3) After the pre-dripping in the step 2) is finished, continuously heating and stirring. When the temperature rises to 105-115 ℃, the bubbling dehydration is started for 2-3 h.
4) And 3) after the dehydration is finished, continuously heating and stirring. And opening the epoxy olefin compound valve when the temperature is raised to 115-135 ℃, and continuously dropwise adding the epoxy olefin compound to carry out ring-opening reaction. The weight of the epoxy olefin compound is 36-45% of the weight of the dehydrated initiator, the pressure is controlled at 0.35MPa in the dropping process, the temperature is controlled at 135 ℃ at 120 ℃, and after the dropping is finished, the internal pressure reaction is continued for 2-3h within the range of 0.2-0.4 MPa.
5) And 4) cooling to about 100 ℃ after the internal pressure reaction is finished, carrying out nitrogen bubbling, removing residual micromolecule substances in the product, cooling after bubbling for 1-2h, and discharging to obtain the polyether polyol.
Compared with the prior art, the invention has the following beneficial effects:
1) in the synthesized polyether product, the hydroxymethyl melamine and the trihydroxyethyl isocyanurate in the compound initiator have the same triazine nitrogen-containing heterocyclic structure, so that the polyether product has excellent flame retardance and better intersolubility, and simultaneously, the functionality and the molecular weight are controlled, so that the product has lower viscosity and hydroxyl value, better intersolubility with water, good compatibility with a conventional polyether product and more stability in a full-water combined material system;
2) the raw materials used in the invention are melamine and trihydroxyethyl isocyanurate, the comprehensive cost is low, and meanwhile, the high-content triazine nitrogen-containing heterocyclic structure provides better strength and better flame retardance for polyurethane foam;
3) the invention has simple and easy-to-implement process and wide industrial utilization value.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
The starting materials used in the examples are all commercial products.
Example 1
Adding 94g of melamine and 181g of formaldehyde solution into a reaction kettle, simultaneously adding 0.2g of triethylamine catalyst, after leakage test and replacement of the reaction kettle, heating to 65 +/-5 ℃ under the nitrogen atmosphere, keeping the pressure of the nitrogen atmosphere in the reaction kettle within the range of 0.12 +/-0.02 MPa, and reacting for 1h to prepare the hydroxymethyl melamine.
146g of trihydroxyethyl isocyanurate is pumped into a reaction kettle in vacuum, 10.2g of propylene glycol and 1g of triethylamine catalyst are pumped into the reaction kettle simultaneously, the reaction kettle is stirred and heated to 80 ℃, and 65g of propylene oxide is dripped in the reaction kettle after the temperature is reached. After the pre-dripping is finished, the temperature is raised to 110 +/-5 ℃, and the dehydration is started, and the bubbling dehydration is carried out for 1.5 h.
After dehydration, the temperature is raised to about 125 +/-5 ℃, after reaching the temperature, propylene oxide is continuously dripped, the mass is 109g, the temperature is kept near 125 +/-5 ℃ in the dripping process, and the pressure in the kettle is controlled to be 0.2 MPa. After the dropwise addition, nitrogen is filled to pressurize to 0.2MPa, the temperature is kept between 128 +/-2 ℃, and the internal pressure reaction is continued for 2 hours until the pressure in the kettle is not reduced any more. Then cooling to about 80 ℃, discharging to obtain the polyether polyol with the hydroxyl value of 172mgKOH/g and the viscosity of 90 MPa.s.
Example 2
Adding 94g of melamine and 89.5g of paraformaldehyde into a reaction kettle, simultaneously adding 0.5g of dimethylcyclohexylamine catalyst, closing the kettle, performing leakage test and replacement, heating to 65 +/-5 ℃ under the nitrogen atmosphere, keeping the pressure of the nitrogen atmosphere in the kettle within the range of 0.12 +/-0.02 MPa, and reacting for 1.5h to prepare the hydroxymethyl melamine.
73g of trihydroxyethyl isocyanurate is pumped into a reaction kettle in vacuum, 14.2g of diethylene glycol and 1g of triethylamine catalyst are simultaneously pumped and added, the temperature is heated to 75 ℃ by stirring, and 131.3g of ethylene oxide is dripped in advance after the temperature is reached. After the pre-dripping is finished, the temperature is raised to 110 +/-5 ℃, and the dehydration is started, and the bubbling dehydration is carried out for 2 h.
After dehydration, the temperature is raised to about 125 +/-5 ℃, propylene oxide is continuously dripped after the temperature is reached, the mass is 116g, the temperature is kept near 125 +/-5 ℃ in the dripping process, and the pressure in the kettle is controlled to be 0.1 MPa. After the dropwise addition, nitrogen is filled to pressurize to 0.2MPa, the temperature is kept between 128 +/-2 ℃, and the internal pressure reaction is continued for 3 hours until the pressure in the kettle is not reduced any more. Then cooling to about 80 ℃, discharging to obtain polyether polyol with hydroxyl value of 197mgKOH/g and viscosity of 230 MPa.s.
Example 3
Adding 94g of melamine and 120.9g of formaldehyde solution into a reaction kettle, simultaneously adding 0.3g of dimethylcyclohexylamine catalyst, after leakage test and replacement of the reaction kettle, heating to 65 +/-5 ℃ under the nitrogen atmosphere, keeping the pressure of the nitrogen atmosphere in the reaction kettle within the range of 0.12 +/-0.02 MPa, and reacting for 1.5h to prepare the hydroxymethyl melamine.
42g of trihydroxyethyl isocyanurate is pumped into a reaction kettle in vacuum, 28g of diethylene glycol and 0.7g of triethylamine catalyst are simultaneously pumped and added, the temperature is heated to 75 ℃ by stirring, and 88g of ethylene oxide is dripped in advance after the temperature is reached. After the pre-dripping is finished, the temperature is raised to 110 +/-5 ℃, and the dehydration is started, and the bubbling dehydration is carried out for 2 h.
After dehydration, the temperature is raised to about 125 +/-5 ℃, propylene oxide is continuously dripped after the temperature is reached, the mass is 58g, the temperature is kept near 125 +/-5 ℃ in the dripping process, and the pressure in the kettle is controlled to be 0.1 MPa. After the dropwise addition, nitrogen is filled to pressurize to 0.2MPa, the temperature is kept between 128 +/-2 ℃, and the internal pressure reaction is continued for 3 hours until the pressure in the kettle is not reduced any more. Then cooling to about 80 ℃, discharging to obtain the polyether polyol with the hydroxyl value of 200mgKOH/g and the viscosity of 212 MPa.s.
Comparative example 1
Adding 63g of melamine, 122g of formaldehyde solution and 315g of diethanolamine into a reaction kettle, simultaneously adding 5g of dimethylcyclohexylamine catalyst, after leakage test and replacement of the reaction kettle, heating to 65 +/-5 ℃ under negative pressure, reacting for 1h, stirring and heating to 75 ℃, and beginning to drop 264g of ethylene oxide after the temperature is reached. After the pre-dripping is finished, the temperature is raised to 110 +/-5 ℃, and the dehydration is started, and the bubbling dehydration is carried out for 1.5 h.
After dehydration, the temperature is raised to about 125 +/-5 ℃, propylene oxide is continuously dripped after the temperature is reached, the mass is 198g, the temperature is kept near 125 +/-5 ℃ in the dripping process, and the pressure in the kettle is controlled to be 0.1 MPa. After the dropwise addition, nitrogen is filled to pressurize to 0.2MPa, the temperature is kept between 128 +/-2 ℃, and the internal pressure reaction is continued for 2.5 hours until the pressure in the kettle is not reduced any more. Then cooling to about 80 ℃, discharging to obtain the polyether polyol with the hydroxyl value of 583mgKOH/g and the viscosity of 9000 MPa.s.
Comparative example 2
Adding 265g of sucrose, 140g of diethylene glycol and 10g of organic amine catalyst into a reaction kettle, slowly dropwise adding 690g of propylene oxide into the reaction kettle through a pressure container, carrying out polymerization reaction at 106 ℃, discharging materials after the reaction is finished, and obtaining the polyether polyol with the appearance of light yellow transparent liquid, the hydroxyl value of 440mgKOH/g and the viscosity of 3400 MPa.s.
The following table compares the example to comparative example indices:
TABLE 1 indices of products prepared in examples and comparative examples
| Hydroxyl value (mgKOH/g) | Viscosity (MPa.s) | Water soluble (100 parts) | |
| Example 1 | 174 | 90 | More than 25 hair turbid |
| Example 2 | 197 | 230 | More than 17 hair turbid |
| Example 3 | 200 | 212 | More than 10 turbid hair |
| Comparative example 1 | 583 | 9000 | More than 3 hair turbid |
| Comparative example 2 | 440 | 3600 | Mutual solubility in any proportion |
Wherein, the comparative example 1 is the flame-retardant polyether with the same type structure, and the comparative example 2 is the conventional hard bubble polyether in the market. The water solubility is compared to how much of the 100 parts polyether dissolves in water.
TABLE 2 comparison of flame retardancy of examples and comparative examples
| Raw material (M) | Example 1 | Example 2 | Comparative example 1 | Comparative example 2 |
| Polyether compounding | 100 | 100 | 100 | 100 |
| Foam homogenizing agent | 2 | 2 | 2 | 2 |
| Catalyst and process for preparing same | 1.5 | 1.5 | 1.5 | 1.5 |
| Water (W) | 5 | 5 | 3.5 | 4 |
| TCPP | 20 | 20 | 20 | 20 |
| NCO index | 1.15 | 1.15 | 1.15 | 1.15 |
| Oxygen index | 25.2 | 24.3 | 22.7 | 19.5 |
As can be seen from Table 2, the oxygen index of examples 1-2 is significantly increased, and it is confirmed by comparing examples 1-2 that the flame retardancy of polyether itself is increased as the triazine structure is increased with the increase of the triethyolisocyanurate.
Claims (9)
1. A preparation method of polyether polyol for an all-water flame-retardant system is characterized by comprising the following steps: taking trihydroxyethyl isocyanurate, methylol melamine and micromolecule alcohol as a composite initiator, and carrying out polymerization reaction with alkylene oxide under the catalysis of alkali to obtain the polyether polyol;
the preparation method of the methylol melamine comprises the following steps: putting melamine and formaldehyde into a reaction kettle, adding an alkaline catalyst at the same time, after leakage test and replacement in the reaction kettle, heating to 60-70 ℃ in the nitrogen atmosphere, keeping the pressure in the reaction kettle within the range of 0.1-0.15MPa, and stirring for reaction for 1-1.5h to synthesize the hydroxymethyl melamine.
2. The method of preparing polyether polyol for all-water flame retardant system according to claim 1, characterized in that: the small molecular alcohol is propylene glycol or diethylene glycol.
3. The method of preparing polyether polyol for all-water flame retardant system according to claim 1, characterized in that: the methylol melamine is synthesized by taking melamine and formaldehyde as raw materials through a hydroxymethylation reaction.
4. A process for preparing a polyether polyol for an all-water flame retardant system according to claim 3, characterized in that: the formaldehyde is polyformaldehyde with polymerization degree of 3-100 or above or formaldehyde solution with mass content of 37%.
5. A process for preparing a polyether polyol for an all-water flame retardant system according to claim 3, characterized in that: the mol ratio of the melamine to the formaldehyde is 1: 2-4.
6. The method of preparing polyether polyol for all-water flame retardant system according to claim 1, characterized in that: the base is potassium hydroxide, sodium hydroxide, triethylamine or dimethylcyclohexylamine.
7. The method of preparing polyether polyol for all-water flame retardant system according to claim 1, characterized in that: the alkylene oxide is one or two of ethylene oxide or propylene oxide.
8. The method of preparing polyether polyol for all-water flame retardant system according to claim 1, characterized in that: the trihydroxyethyl isocyanurate accounts for 26-90 wt% of the hydroxymethyl melamine.
9. The method of preparing polyether polyol for all-water flame retardant system according to claim 1, characterized in that: the small molecular alcohol accounts for 3.5-6.5 per mill of the total mass of the composite initiator.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116042007A (en) * | 2022-12-29 | 2023-05-02 | 上海汇得科技股份有限公司 | Flame-retardant insulating coating for power battery and preparation method thereof |
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Patent Citations (5)
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| CN116042007A (en) * | 2022-12-29 | 2023-05-02 | 上海汇得科技股份有限公司 | Flame-retardant insulating coating for power battery and preparation method thereof |
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