CN110527079A - Add the flame retardant polyether polyol and preparation method thereof of hydramine - Google Patents
Add the flame retardant polyether polyol and preparation method thereof of hydramine Download PDFInfo
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- CN110527079A CN110527079A CN201910815886.8A CN201910815886A CN110527079A CN 110527079 A CN110527079 A CN 110527079A CN 201910815886 A CN201910815886 A CN 201910815886A CN 110527079 A CN110527079 A CN 110527079A
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- Prior art keywords
- flame retardant
- polyether polyol
- retardant polyether
- preparation
- hydramine
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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
- C08G18/5075—Polyethers having heteroatoms other than oxygen having phosphorus
- C08G18/509—Polyethers having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
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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
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to organic synthesis fields, and in particular to add the flame retardant polyether polyol and its synthetic method of hydramine.The present invention prepares flame retardant polyether polyol using hydramine and PhosphorodichloridicAcid Acid Phenyl Ester as starting material, through two-step reaction, and reaction yield is up to 90%, and reaction process is simple, reaction condition is mild, easily controllable；And flame retardant polyether polyol prepared by this preparation method has midium-viscosity, has good compatibility and lasting anti-flammability with other polyalcohols, has biggish economic results in society.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to the flame retardant polyether polyol of addition hydramine and its preparation side
Method.
Background technique
Fire retardant, assigns the functional aid of combustible polymers flame retardancy, and fire-retardant primarily directed to high molecular material sets
Meter；There are many types for fire retardant, are divided into additive flame retardant and reactive flame retardant by application method.
Additive flame retardant is added in polymer by mechanical mix techniques, and polymer is made to have anti-flammability, mesh
The main organic fire-retardant of preceding additive flame retardant and inorganic fire retardants, halogenated flame retardant and non-halogen.Organic is with bromine system, phosphorus nitrogen
System, nitrogen system and red phosphorus and compound are some fire retardants of representative, inorganic mainly antimony oxide, magnesium hydroxide, hydroxide
Aluminium, the flame-retardant systems such as silicon systems.
Reactive flame retardant is then to participate in polymerization reaction as a kind of monomer, therefore make polymer itself to contain flame-retardant composition
, its advantage is that smaller on the influence of polymer material service performance, anti-flammability is lasting.Common reactive flame retardant is to pass through fluorine
The ignition-proof elements such as chlorine bromine iodine realize flame retardant effect, but the burning of this reactive flame retardant can generate harmful substance, Bu Nengman
Demand of the sufficient material at environmentally protective aspect, and the preparation process of this reactive flame retardant often complicated cumbersome, operation difficulty
Greatly.Therefore, the preparation method for studying the small reactive flame retardant of environmentally protective one kind, simple process, operation difficulty becomes the general trend of events
Become.
Summary of the invention
The present invention is in view of the deficiencies of the prior art, and it is an object of the present invention to provide the flame retardant polyether polyol and its system of addition hydramine
Preparation Method.
For achieving the above object, the technical scheme adopted by the invention is as follows:
The flame retardant polyether polyol for adding hydramine, includes the following steps:
(1) hydramine and triethylamine are added in organic solvent, heating up and stirring to all dissolutions obtains mixed liquor a；
(2) it is poured into three-necked flask after PhosphorodichloridicAcid Acid Phenyl Ester being dissolved in organic solvent；
(3) it stirs at a certain temperature and is slowly dropped to mixed liquor a in three-necked flask by dropping funel, drip
By reaction, temperature reaction obtains product b under nitrogen protection after；
(4) product b is obtained into flame retardant polyether polyol product by vacuum distillation removal organic solvent.
In above scheme, the hydramine and triethylamine molar ratio are 6:1~8:1.
In above scheme, the molar ratio of the PhosphorodichloridicAcid Acid Phenyl Ester and hydramine is 1:0.8~1:1.
In above scheme, the organic solvent is Isosorbide-5-Nitrae-dioxane.
In above scheme, the temperature of agitation and dropping mixed liquor a described in step (3) is 25~35 DEG C, the temperature of the reaction
Degree is 58~78 DEG C, and the reaction time is 5~8h.
In above scheme, the vacuum distillation temperature is 58~78 DEG C.
Above-mentioned preparation method prepares obtained flame-retardant polyether polyol product.
Beneficial effects of the present invention: the present invention is using hydramine and PhosphorodichloridicAcid Acid Phenyl Ester as starting material, through two-step reaction system
Standby flame retardant polyether polyol out, reaction yield is up to 90%, and reaction process is simple, reaction condition is mild, easily controllable；And
Flame retardant polyether polyol prepared by this preparation method has midium-viscosity, has good compatibility with other polyalcohols, with
The resistance combustion polyurethane foam that expanded graphite packing is prepared jointly has the anti-flammability of high-efficient and lasting, has biggish social economy effect
Benefit.
Detailed description of the invention
Fig. 1 is Examples 1 to 5 synthesis flame retardant polyether polyol and then the limit oxygen index for preparing flame retarded polyurethane-foam
Coefficient.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
A kind of flame retardant polyether polyol synthesizes as follows:
(1) 28g diethanol amine and 2g triethylamine are added in 115ml Isosorbide-5-Nitrae-dioxane, are warming up to 28 DEG C and stirred extremely
All dissolution obtains mixed liquor a；
(2) 20g PhosphorodichloridicAcid Acid Phenyl Ester is dissolved in Isosorbide-5-Nitrae-dioxane of 110ml, is warming up to 25 DEG C and stirred extremely
All dissolutions, pour into and keep the temperature 25min in three-necked flask；
(3) under nitrogen protection, under 30 DEG C of stirring conditions, mixed liquor a is slowly dropped to three mouthfuls of burnings by dropping funel
In bottle, 65 DEG C of heating water bath mechanical stirring 6h of three-necked flask heating are obtained into product b after being added dropwise to complete；
(4) product b is removed into unreacted ingredient and organic solvent by vacuum distillation (vacuum distillation temperature is 60 DEG C),
Obtain flame retardant polyether polyol product.
Use acetylation method measurement hydroxyl value for 33mg KOH/g, yield 91%；Into 50g flame retardant polyether polyol product
Reacting its limit oxygen index of polyurethane foam obtained after addition 10g expansible graphite with isocyanates is 31.2, vertical combustion
Experiment reaches the grade of V~0.
Embodiment 2
A kind of flame retardant polyether polyol synthesizes as follows:
(1) 28g N methyldiethanol amine and 2g triethylamine are added in 130ml Isosorbide-5-Nitrae-dioxane, are warming up to 34 DEG C
And it stirs to all dissolutions and obtains mixed liquor a；
(2) 20g PhosphorodichloridicAcid Acid Phenyl Ester is dissolved in Isosorbide-5-Nitrae-dioxane of 110ml, is warming up to 27 DEG C and stirred extremely
All dissolutions, pour into and keep the temperature 32min in three-necked flask；
(3) under nitrogen protection, under 30 DEG C of stirring conditions, mixed liquor a is slowly dropped to three mouthfuls of burnings by dropping funel
In bottle, 65 DEG C of heating water bath mechanical stirring 7h of three-necked flask heating are obtained into product b after being added dropwise to complete；
(4) product b is removed into unreacted ingredient and organic solvent by vacuum distillation (vacuum distillation temperature is 71 DEG C),
Obtain flame retardant polyether polyol product.
Use acetylation method measurement hydroxyl value for 34mg KOH/g, yield 91%；Into 50g flame retardant polyether polyol product
Reacting its limit oxygen index of polyurethane foam obtained after addition 10g expansible graphite with isocyanates is 31.0, vertical combustion
Experiment reaches the grade of V~0.
Embodiment 3
A kind of flame retardant polyether polyol synthesizes as follows:
(1) 24g N butyl diethanol amine and 2g triethylamine are added in 110ml Isosorbide-5-Nitrae-dioxane, are warming up to 25 DEG C
And it stirs to all dissolutions and obtains mixed liquor a；
(2) 17g PhosphorodichloridicAcid Acid Phenyl Ester is dissolved in Isosorbide-5-Nitrae-dioxane of 105ml, is warming up to 25 DEG C and stirred extremely
All dissolutions, pour into and keep the temperature 30min in three-necked flask；
(3) under nitrogen protection, under 31 DEG C of stirring conditions, mixed liquor a is slowly dropped to three mouthfuls of burnings by dropping funel
In bottle, 72 DEG C of heating water bath mechanical stirring 5.5h of three-necked flask heating are obtained into product b after being added dropwise to complete；
(4) product b is removed into unreacted ingredient and organic solvent by vacuum distillation (vacuum distillation temperature is 65 DEG C),
Obtain flame retardant polyether polyol product.
Use acetylation method measurement hydroxyl value for 34mg KOH/g, yield 95%；Into 50g flame retardant polyether polyol product
Reacting its limit oxygen index of polyurethane foam obtained after addition 10g expansible graphite with isocyanates is 33.4, vertical combustion
Experiment reaches the grade of V~0.
Embodiment 4
A kind of flame retardant polyether polyol synthesizes as follows:
(1) 23gN, N- dihydroxy ethyl-para-totuidine and 3.3g triethylamine are added in 100ml Isosorbide-5-Nitrae-dioxane, are risen
Temperature is to 31 DEG C and stirring to all dissolutions obtain mixed liquor a；
(2) 20g PhosphorodichloridicAcid Acid Phenyl Ester is dissolved in Isosorbide-5-Nitrae-dioxane of 105ml, is warming up to 26 DEG C and stirred extremely
All dissolutions, pour into and keep the temperature 23min in three-necked flask；
(3) under nitrogen protection, under 34 DEG C of stirring conditions, mixed liquor a is slowly dropped to three mouthfuls of burnings by dropping funel
In bottle, 29 DEG C of heating water bath mechanical stirring 7h of three-necked flask heating are obtained into product b after being added dropwise to complete；
(4) product b is removed into unreacted ingredient and organic solvent by vacuum distillation (vacuum distillation temperature is 58 DEG C),
Obtain flame retardant polyether polyol product.
Use acetylation method measurement hydroxyl value for 36mg KOH/g, yield 91%；Into 50g flame retardant polyether polyol product
Reacting its limit oxygen index of polyurethane foam obtained after addition 10g expansible graphite with isocyanates is 31.8, vertical combustion
Experiment reaches the grade of V~0.
The performance indicator of 1 flame retardant polyether polyol of table
| Performance indicator | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Hydroxyl value MgKOH/g | 33 | 34 | 34 | 36 |
| Yield | 91% | 91% | 95% | 91% |
Obviously, above-described embodiment is only intended to clearly illustrate made example, and is not the limitation to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And the obvious variation or change therefore amplified
It moves within still in the protection scope of the invention.
Claims (8)
1. a kind of preparation method for the flame retardant polyether polyol for adding hydramine, which comprises the steps of:
(1) hydramine and triethylamine are added in organic solvent, heating up and stirring to all dissolutions obtains mixed liquor a；
(2) it is poured into three-necked flask after PhosphorodichloridicAcid Acid Phenyl Ester being dissolved in organic solvent；
(3) it stirs at a certain temperature and is slowly dropped to mixed liquor a in three-necked flask by dropping funel, after being added dropwise to complete
By reaction, temperature reaction obtains product b under nitrogen protection；
(4) product b is obtained into flame retardant polyether polyol product by vacuum distillation removal organic solvent.
2. the preparation method of flame retardant polyether polyol according to claim 1, which is characterized in that the hydramine is diethanol
Amine, N methyldiethanol amine, N butyl diethanol amine or N, N- dihydroxy ethyl-para-totuidine.
3. the preparation method of flame retardant polyether polyol according to claim 1, which is characterized in that the hydramine and triethylamine rub
You are than being 6:1 ~ 8:1.
4. the preparation method of flame retardant polyether polyol according to claim 1, which is characterized in that the PhosphorodichloridicAcid Acid Phenyl Ester
Molar ratio with hydramine is 1:0.8 ~ 1:1.
5. the preparation method of flame retardant polyether polyol according to claim 1, which is characterized in that the organic solvent is Isosorbide-5-Nitrae-
Dioxane.
6. the preparation method of flame retardant polyether polyol according to claim 1, which is characterized in that stirred described in step (3)
The temperature that mixed liquor a is added dropwise is 25 DEG C ~ 35 DEG C, and the temperature of the reaction is 58 DEG C ~ 78 DEG C, and the reaction time is 5h ~ 8h.
7. the preparation method of flame retardant polyether polyol according to claim 1, which is characterized in that the vacuum distillation temperature is
58℃~78℃。
8. any preparation method of claim 1 ~ 7 prepares obtained flame-retardant polyether polyol product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910815886.8A CN110527079B (en) | 2019-08-30 | 2019-08-30 | Fire-retardant polyether polyol added with alcohol amine and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910815886.8A CN110527079B (en) | 2019-08-30 | 2019-08-30 | Fire-retardant polyether polyol added with alcohol amine and preparation method thereof |
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| Publication Number | Publication Date |
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| CN110527079A true CN110527079A (en) | 2019-12-03 |
| CN110527079B CN110527079B (en) | 2022-12-06 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201910815886.8A Active CN110527079B (en) | 2019-08-30 | 2019-08-30 | Fire-retardant polyether polyol added with alcohol amine and preparation method thereof |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106432740A (en) * | 2016-09-08 | 2017-02-22 | 四川大学 | Hydroxyl polyphosphoester-containing flame retardant as well as preparation method and application thereof |
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2019
- 2019-08-30 CN CN201910815886.8A patent/CN110527079B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106432740A (en) * | 2016-09-08 | 2017-02-22 | 四川大学 | Hydroxyl polyphosphoester-containing flame retardant as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| RAMAZAN BENRASHID1 ET AL: "Synthesis of Phosphate-Urethane Block Copolymers: Effect of Bound Phosphorus in the Soft Moiety of Block Copolymers on Thermal and Flame Retardant Characteristics of Polyphosphate Polyurethane Block Copolymers", 《IN FIRE AND POLYMERS VI: NEW ADVANCES IN FLAME RETARDANT CHEMISTRY AND SCIENCE》 * |
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| CN110527079B (en) | 2022-12-06 |
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