CN108341946A - A kind of phosphorus base block flame retarding polyether and preparation method thereof and the application in hard polyurethane foams - Google Patents
A kind of phosphorus base block flame retarding polyether and preparation method thereof and the application in hard polyurethane foams Download PDFInfo
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- CN108341946A CN108341946A CN201810100968.XA CN201810100968A CN108341946A CN 108341946 A CN108341946 A CN 108341946A CN 201810100968 A CN201810100968 A CN 201810100968A CN 108341946 A CN108341946 A CN 108341946A
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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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
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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
- C08G18/5078—Polyethers having heteroatoms other than oxygen having phosphorus having phosphorus bound to carbon and/or to hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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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
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
Abstract
The present invention relates to a kind of phosphorus base block flame retarding polyethers and preparation method thereof, this method is reacted with low molecular polyether dihydric alcohol or polyethers diamine according to certain mol proportion by containing two P Cl key compounds, it is big to obtain a kind of molecular weight, it is good with polyurethane compatibility, it is not easy to migrate, and the block type phosphorus-based flame-retardant polyethers blocked with hydroxyl or amido with highly effective flame-retardant efficiency.And as part material, with polyethers（Ester）Polyalcohol, isocyanates, expansible graphite, metal hydroxides, foaming agent, catalyst and foam stabiliser pass through mechanical agitation according to a certain percentage at normal temperatures, prepare a kind of flame retarded rigid polyurethane foams, the foam is not easy to shrink, good stability of the dimension, and there is excellent flame retardant property and mechanical property.
Description
Technical field
The present invention relates to flame retardant polyurethane foam material fields, and in particular to a kind of phosphorus base block flame retarding polyether and its preparation
Method and the application in hard polyurethane foams.
Background technology
Hard polyurethane foams are widely used as building and are protected because having many advantages, such as that thermal coefficient is low, density is low, intensity is high
The uses such as warm outer wall material, thermal insulation board material or ornament materials.But pure hard polyurethane foams with external heat source after contacting
It easily burns, limit oxygen index is only 18% or so.Therefore the flame retardant property of raising hard polyurethane foams is needed.
Due to the requirement of environmental protection, the fire retardant fire-retardant currently used for polyurethane foam is mainly phosphorus flame retardant, including liquid
The organophosphorus compounds of body, such as TEP, RDP, BDP etc. and solid-state phosphorus-containing compound, such as ammonium polyphosphate, red phosphorus.But it is answering
With finding in the process, when using the powdery types additive flame retardant such as such as ammonium polyphosphate, there is that dispersibility is poor, flame retarding efficiency is low,
The big problem of additive amount；And when using the liquid based flame retardant such as organophosphorus compounds, that there are flame retardant molecule amounts is small, easily from matrix
In move out, the problem of foam easily shrinks, poor dimensional stability, the application of hard polyurethane foams is had an impact.
Invention content
For the deficiency of existing flame retarded rigid polyurethane foams method, the present invention provides a kind of phosphorus base block flame retarding polyethers
Preparation method, and be prepared for flame retarded rigid polyurethane foams as raw material.
The structural formula of phosphorus base block flame retarding polyether of the present invention is：
Wherein R is the average mark of polyether polyol segment or polyether polyamine segment, the polyether polyol or polyether polyamine
Son amount is that 100~1000, degree of functionality 2, R ' is to remove the remaining part of P=O keys containing two P-Cl key compounds.
The preparation method of the phosphorus base block flame retarding polyether of the present invention is as follows：
Aprotic organic solvent containing two P-Cl key compounds is added drop-wise to low molecular polyether polyalcohol or gathered by step (1)
In the aprotic organic solvent of ether polyamine, and acid binding agent is added in system, dropwise addition process is completed simultaneously under -5 °C~30 °C
Stirring；
Described is diphenylphosphoryl dichloro, PhosphorodichloridicAcid Acid Phenyl Ester, vinyl phosphonyl chloride, dichloro phosphorus containing two P-Cl key compounds
One kind in sour methyl esters, dichloro etherophosphoric acid；
The low molecular polyether polyalcohol or polyether polyamine, average molecular weight is 100~1000, degree of functionality 2；
In the aprotic organic solvent containing two P-Cl key compounds containing two P-Cl key compounds a concentration of 0.6~
2.5 mol/L；What is be added rubs containing two P-Cl key compounds, low molecular polyether polyalcohol or polyether polyamine, acid binding agent
Your ratio is 1：1：1~1：2：2；
The acid binding agent is triethylamine, potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, sodium bicarbonate, saleratus, pyrrole
Pyridine, 4-dimethylaminopyridine, N, one kind in N- diisopropylethylamine；
The non-proton organic solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, tetrahydrofuran, dioxy six
One kind in ring, acetone, butanone, ethyl acetate；
After step (2) is added dropwise, adjustment temperature is persistently stirred to react 4~15 hours to 30 °C~70 °C；
Step (3) obtains phosphorus base block flame retarding polyether after reaction, by vacuum distillation.
The preparation method of the flame retarded rigid polyurethane foams of the present invention is as follows：
Step (1) hinders expansible graphite, metal hydroxides, foaming agent, catalyst, foam stabiliser and phosphorus base block
Fire polyethers and polyethers（Ester）Polyol blends mix, and stir evenly at normal temperatures；
Polyisocyanates is added to step by step (2) at normal temperatures（1）In the system of acquisition, at 1000-3000 revs/min
Mixing speed under stir 5 seconds, pour into mold, flame retarded rigid polyurethane foams prepared using free foaming mode；
The raw material of the flame retarded rigid polyurethane foams includes mainly：100 parts of phosphorus base block flame retarding polyethers and polyethers（Ester）It is more
First alcohol mixture, 100-160 parts of polyisocyanates, 1-10 parts of catalyst, 10-35 parts of foaming agents, 1-15 parts of foam stabilisers, 2-
100 parts of expansible graphites, 2-100 parts of metal hydroxides；
100 parts of phosphorus base block flame retarding polyethers and polyethers（Ester）Polyol blends, phosphorus base block flame retarding polyether and polyethers
（Ester）The ratio of polyalcohol is 1:9~9:1；
The polyethers（Ester）Polyalcohol is the polyethers that hydroxyl value is 350~400mgKOH/g（Ester）One kind or several in polyalcohol
Kind, polyisocyanates is polyphenyl polymethylene isocyanates；
The catalyst is double dimethylamino ethyl ethers, N- methyldicyclohexyls amine, N, N- dimethyl cyclohexyl amines, N, N- bis-
Methylaminoethyl-N- methyl amino ethanols, pentamethyl-diethylenetriamine, 30% oleic acid potassium solution, 30% liquor kalii acetici
Middle one or more, foaming agent are water, pentane, pentamethylene, isopentane, CFC-11, HFC-152a, HCFC-141b, HCFC-
One or more of 142b, HFC-245fa, foam stabiliser are organic silicon surfactant, specially AK-8801, AK-
8803, one or more of AK-8808, AK-8812, AK-8818；
The metal hydroxides is one or both of magnesium hydroxide, aluminium hydroxide.
The patent of invention has the advantages that：(1) phosphorus-containing groups are introduced into polyether polyols by the invention
In alcohol or polyether polyols amine structure, a kind of phosphor-containing flame-proof polyethers is obtained, molecular weight is big, good with polyurethane compatibility, is not easy to move
It moves, flame retarding efficiency is high；(2) present invention prepares a kind of poly- ammonia of flame retarded rigid using the phosphor-containing flame-proof polyethers prepared as raw material
Ester foam, the foam are not easy to shrink, good stability of the dimension；With excellent flame retardant property and mechanical property.
Specific implementation mode
Embodiment 1
Step（1）：By 11.21g（0.0575mol）Diphenylphosphoryl dichloro be dissolved in 35ml tetrahydrofuran solvents be slowly dropped to it is molten
There is 23g（0.0575mol）Average molecular weight is 400 polyethers（Ester）Polyalcohol and 5.82g（0.0575mol）The 35ml of triethylamine
In tetrahydrofuran solvent, the stirring completion dropwise addition process under 0 °C；
Step（2）：After being added dropwise, temperature is increased to 40 °C, is persistently stirred to react 6 hours；
Step（3）：After reaction, phosphorus base block flame retarding polyether is obtained by vacuum distillation；
Step（4）：By 20 parts of expansible graphites, 60 parts of magnesium hydroxides, 10 parts of water, 6 parts of catalyst, 10 parts of foam stabilisers and
100 parts of phosphorus base block flame retarding polyethers and polyethers（Ester）Polyol blends mix（10 parts of phosphorus base block flame retarding polyether, polyethers（Ester）
90 parts of polyalcohol）, and stir evenly at normal temperatures；
Step（5）：140 parts of polyisocyanates are added to step at normal temperatures（1）In the system of acquisition, 1000-3000 turn/
It is stirred 5 seconds under the mixing speed of minute, pours into mold, flame retarded rigid polyurethane foams are prepared using free foaming mode.
Embodiment 2
Step（1）：By 12.13g（0.0575mol）PhosphorodichloridicAcid Acid Phenyl Ester is dissolved in 30ml1,4- dioxane solvents and slowly dripping
It is added to dissolved with 23g（0.115mol）Average molecular weight is 200 polyether polyol and 11.64g（0.115mol）Triethylamine
In 35ml1,4- dioxane solvent, the stirring completion dropwise addition process under 20 °C；
Step（2）：After being added dropwise, temperature is increased to 65 °C, is persistently stirred to react 12 hours；
Step（3）：After reaction, phosphorus base block flame retarding polyether is obtained by vacuum distillation；
Step（4）：By 50 parts of expansible graphites, 60 parts of aluminium hydroxides, 20 parts of water, 10 parts of catalyst, 12 parts of foam stabilisers with
And 100 parts of phosphorus base block flame retarding polyethers and polyethers（Ester）Polyol blends mix（20 parts of phosphorus base block flame retarding polyether, polyethers
（Ester）80 parts of polyalcohol）, and stir evenly at normal temperatures；
Step（5）：160 parts of polyisocyanates are added to step at normal temperatures（1）In the system of acquisition, 1000-3000 turn/
It is stirred 5 seconds under the mixing speed of minute, pours into mold, flame retarded rigid polyurethane foams are prepared using free foaming mode.
Embodiment 3
Step（1）：By 8.70g（0.06mol）Vinyl phosphonyl chloride is dissolved in 20mlN, is slowly dripped in dinethylformamide solvent
It is added to dissolved with 7.2g（0.072mol）Average molecular weight is 100 polyether polyol and 8.29g（0.06mol）Potassium carbonate
25mlN, in dinethylformamide solvent, under 30 °C stirring complete dropwise addition process；
Step（2）：After being added dropwise, temperature remains at 30 °C, is persistently stirred to react 4 hours；
Step（3）：After reaction, phosphorus base block flame retarding polyether is obtained by vacuum distillation；
Step（4）：By 100 parts of expansible graphites, 15 parts of aluminium hydroxides, 15 parts of magnesium hydroxides, 25 parts of pentanes, 1 part of catalyst,
15 parts of foam stabilisers and 100 parts of phosphorus base block flame retarding polyethers and polyethers（Ester）Polyol blends mix（Phosphorus base block hinders
Fire 30 parts of polyethers, polyethers（Ester）70 parts of polyalcohol）, and stir evenly at normal temperatures；
Step（5）：100 parts of polyisocyanates are added to step at normal temperatures（1）In the system of acquisition, 1000-3000 turn/
It is stirred 5 seconds under the mixing speed of minute, pours into mold, flame retarded rigid polyurethane foams are prepared using free foaming mode.
Embodiment 4
Step（1）：By 7.45g（0.05mol）Dichloro methyl orthophosphoric acid is dissolved in 40mlN, is slowly dripped in N- dimethylacetamide solvents
It is added to dissolved with 7.2g（0.075mol）Average molecular weight is 300 polyether polyol and 7.95g（0.075mol）Sodium carbonate
In 40mlN, N- dimethylacetamide solvent, the stirring completion dropwise addition process under 25 °C；
Step（2）：After being added dropwise, temperature remains at 45 °C, is persistently stirred to react 10 hours；
Step（3）：After reaction, phosphorus base block flame retarding polyether is obtained by vacuum distillation；
Step（4）：By 90 parts of expansible graphites, 2 parts of aluminium hydroxides, 35 parts of pentamethylene, 4 parts of catalyst, 6 parts of foam stabilisers with
And 100 parts of phosphorus base block flame retarding polyethers and polyethers（Ester）Polyol blends mix（50 parts of phosphorus base block flame retarding polyether, polyethers
（Ester）50 parts of polyalcohol）, and stir evenly at normal temperatures；
Step（5）：150 parts of polyisocyanates are added to step at normal temperatures（1）In the system of acquisition, 1000-3000 turn/
It is stirred 5 seconds under the mixing speed of minute, pours into mold, flame retarded rigid polyurethane foams are prepared using free foaming mode.
Embodiment 5
Step（1）：By 8.15g（0.05mol）Dichloro etherophosphoric acid, which is dissolved in 25ml acetone solvents, to be slowly dropped to dissolved with 7.2g
（0.08mol）Average molecular weight is 500 polyether polyol and 6.72g（0.08mol）In the 35ml acetone solvents of sodium bicarbonate,
Dropwise addition process is completed in stirring under 5 °C；
Step（2）：After being added dropwise, temperature remains at 25 °C, is persistently stirred to react 8 hours；
Step（3）：After reaction, phosphorus base block flame retarding polyether is obtained by vacuum distillation；
Step（4）：By 2 parts of expansible graphites, 100 parts of magnesium hydroxides, 16 parts of pentamethylene, 4 parts of catalyst, 1 part of foam stabiliser
And 100 parts of phosphorus base block flame retarding polyethers and polyethers（Ester）Polyol blends mix（60 parts of phosphorus base block flame retarding polyether, polyethers
（Ester）40 parts of polyalcohol）, and stir evenly at normal temperatures；
Step（5）：120 parts of polyisocyanates are added to step at normal temperatures（1）In the system of acquisition, 1000-3000 turn/
It is stirred 5 seconds under the mixing speed of minute, pours into mold, flame retarded rigid polyurethane foams are prepared using free foaming mode.
Embodiment 6
Step（1）：By 11.21g（0.0575mol）Diphenylphosphoryl dichloro be dissolved in 35ml tetrahydrofuran solvents be slowly dropped to it is molten
There is 57,5g（0.0575mol）Average molecular weight is 1000 polyether polyol and 5.82g（0.0575mol）The 60ml of triethylamine
In tetrahydrofuran solvent, the stirring completion dropwise addition process under -5 °C；
Step（2）：After being added dropwise, temperature is increased to 40 °C, is persistently stirred to react 12 hours；
Step（3）：After reaction, phosphorus base block flame retarding polyether is obtained by vacuum distillation；
Step（4）：By 80 parts of expansible graphites, 5 parts of aluminium hydroxides, 25 parts of magnesium hydroxides, 16 parts of water, 2 parts of catalyst, 6 parts of bubbles
Foam stabilizers and 100 parts of phosphorus base block flame retarding polyethers and polyethers（Ester）Polyol blends mix（Phosphorus base block flame retarding polyether
90 parts, polyethers（Ester）10 parts of polyalcohol）, and stir evenly at normal temperatures；
Step（5）：140 parts of polyisocyanates are added to step at normal temperatures（1）In the system of acquisition, 1000-3000 turn/
It is stirred 5 seconds under the mixing speed of minute, pours into mold, flame retarded rigid polyurethane foams are prepared using free foaming mode.
A part of polyethers is replaced to the phosphorus base block flame retarding polyether prepared in the embodiment described 1-6（Ester）Polyalcohol
For raw material, obtained flame retarded rigid polyurethane foams carry out limit oxygen index test, and specific test result is shown in Table 1.
The limit oxygen index test result of 1 pure polyurethane of table and flame retarded rigid polyurethane foams.
| Sample | Pure RPUF | RPUF-1 | RPUF-2 | RPUF-3 | RPUF-4 | RPUF-5 | RPUF-6 |
| Oxygen index (OI) LOI | 19.8% | 31.1% | 29.6% | 30.7% | 29.4% | 26.1% | 28.8% |
| Heat release rate peak value（Irradiation power 50kW） | 317kW/m2 | 219kW/m2 | 322kW/m2 | 259kW/m2 | 267kW/m2 | 228kW/m2 | 294kW/ m2 |
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
The specific implementation of the present invention is confined to these explanations.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, several equivalent substitute or obvious modifications is made, and performance or use is identical, all should
It is considered as belonging to protection scope of the present invention.
Claims (9)
1. a kind of phosphorus base block flame retarding polyether, which is characterized in that its structural formula is
Wherein R is polyether polyol segment or polyether polyamine segment, and R ' is to remove P=O keys containing two P-Cl key compounds to remain
Remaining part.
2. the method for preparing phosphorus base block flame retarding polyether as described in claim 1, which is characterized in that this method includes following step
Suddenly：
Aprotic organic solvent containing two P-Cl key compounds is added drop-wise to low molecular polyether polyalcohol or polyether polyamine
Aprotic organic solvent in, and acid binding agent is added in system, dropwise addition process is completed under -5 °C~30 °C and is stirred；
Described is diphenylphosphoryl dichloro, PhosphorodichloridicAcid Acid Phenyl Ester, vinyl phosphonyl chloride, dichloro phosphorus containing two P-Cl key compounds
One kind in sour methyl esters, dichloro etherophosphoric acid；
The low molecular polyether polyalcohol or polyether polyamine, average molecular weight is 100~1000, degree of functionality 2；
In the aprotic organic solvent containing two P-Cl key compounds containing two P-Cl key compounds a concentration of 0.6~
2.5 mol/L；What is be added rubs containing two P-Cl key compounds, low molecular polyether polyalcohol or polyether polyamine, acid binding agent
Your ratio is 1：1：1~1：2：2；
After being added dropwise, adjustment temperature is persistently stirred to react 4~15 hours to 30 °C~70 °C；
After reaction, phosphorus base block flame retarding polyether is obtained by vacuum distillation.
3. the preparation method of phosphorus base block flame retarding polyether according to claim 2, which is characterized in that the acid binding agent is
Triethylamine, potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, sodium bicarbonate, saleratus, pyridine, 4-dimethylaminopyridine,
One kind in N, N- diisopropylethylamine.
4. the preparation method of phosphorus base block flame retarding polyether according to claim 2, which is characterized in that the aprotic
Organic solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, tetrahydrofuran, dioxane, acetone, butanone, acetic acid
One kind in ethyl ester.
5. a kind of flame retarded rigid polyurethane foams, which is characterized in that being obtained such as claim 2-4 any one of them methods
Phosphorus base block flame retarding polyether replaces a part of polyethers（Ester）Polyalcohol is raw material, and is made of the raw material of following mass fraction：
100 parts of phosphorus base block flame retarding polyethers and polyethers（Ester）Polyol blends, phosphorus base block flame retarding polyether and polyethers
（Ester）The ratio of polyol blends is 1:9~9:1.
6. a kind of flame retarded rigid polyurethane foams according to claim 5, which is characterized in that polyethers（Ester）Polyalcohol is hydroxyl
Value is the polyethers of 350~400mgKOH/g（Ester）One or more of polyalcohol, polyisocyanates are polyphenyl polymethylene
Isocyanates.
7. a kind of flame retarded rigid polyurethane foams according to claim 5, it is characterised in that catalyst is double dimethylamino
Ethylether, N- methyldicyclohexyls amine, N, N- dimethyl cyclohexyl amines, N, N- dimethylaminoethyl-N- methyl amino ethanols, five
One or more of in methyl diethylenetriamine, 30% oleic acid potassium solution, 30% liquor kalii acetici, foaming agent is water, positive penta
One kind or several in alkane, pentamethylene, isopentane, CFC-11, HFC-152a, HCFC-141b, HCFC-142b, HFC-245fa
Kind, foam stabiliser is organic silicon surfactant, specially AK-8801, AK-8803, AK-8808, AK-8812, AK-8818
One or more of.
8. a kind of flame retarded rigid polyurethane foams according to claim 5, it is characterised in that metal hydroxides is hydrogen-oxygen
Change one or both of magnesium, aluminium hydroxide.
9. the method for preparing flame retarded rigid polyurethane foams as claimed in claim 5, which is characterized in that this method includes following
Step：
By expansible graphite, metal hydroxides, foaming agent, catalyst, foam stabiliser and phosphorus base block flame retarding polyether and
Polyethers（Ester）Polyol blends mix, and stir evenly at normal temperatures；
Polyisocyanates is added to step at normal temperatures（1）In the system of acquisition, in 1000-3000 revs/min of stirring speed
The lower stirring of degree 5 seconds, pours into mold, flame retarded rigid polyurethane foams is prepared using free foaming mode.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810100968.XA CN108341946A (en) | 2018-02-01 | 2018-02-01 | A kind of phosphorus base block flame retarding polyether and preparation method thereof and the application in hard polyurethane foams |
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| CN201810100968.XA CN108341946A (en) | 2018-02-01 | 2018-02-01 | A kind of phosphorus base block flame retarding polyether and preparation method thereof and the application in hard polyurethane foams |
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| CN201810100968.XA Pending CN108341946A (en) | 2018-02-01 | 2018-02-01 | A kind of phosphorus base block flame retarding polyether and preparation method thereof and the application in hard polyurethane foams |
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| CN109181255A (en) * | 2018-08-24 | 2019-01-11 | 安徽汇创新材料有限公司 | A kind of flame-retarded unsaturated polyester resin glass reinforced plastic |
| CN110157042A (en) * | 2019-04-28 | 2019-08-23 | 北京工商大学 | The application of novel surface inorganic agent, preparation method and the nano particle being processed in resistance combustion polyurethane foam |
| KR20200111298A (en) * | 2019-03-18 | 2020-09-29 | 한국화학연구원 | Crosslinked reactive phosphorus polyol and method for producing the same, and flame retardant thermoplastic polyurethane made from crosslinked reactive phosphorus polyol |
| CN112250858A (en) * | 2020-08-31 | 2021-01-22 | 万华化学集团股份有限公司 | Method for preparing flame-retardant polymer polyol, application and polyurethane foam plastic prepared by using flame-retardant polymer polyol |
| CN112585185A (en) * | 2018-08-23 | 2021-03-30 | 美国圣戈班性能塑料公司 | Polyurethane foam and method of forming same |
| CN112851909A (en) * | 2021-01-14 | 2021-05-28 | 万华化学（宁波）有限公司 | Storage-stable polyisocyanate composition |
| CN115403759A (en) * | 2022-11-02 | 2022-11-29 | 山东一诺威聚氨酯股份有限公司 | Halogen-free flame-retardant polyether ester polyol and preparation method and application thereof |
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| CN112585185A (en) * | 2018-08-23 | 2021-03-30 | 美国圣戈班性能塑料公司 | Polyurethane foam and method of forming same |
| US11851521B2 (en) | 2018-08-23 | 2023-12-26 | Saint-Gobain Performance Plastics Corporation | Polyurethane foam and methods of forming the same |
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| KR20200111298A (en) * | 2019-03-18 | 2020-09-29 | 한국화학연구원 | Crosslinked reactive phosphorus polyol and method for producing the same, and flame retardant thermoplastic polyurethane made from crosslinked reactive phosphorus polyol |
| KR102163340B1 (en) * | 2019-03-18 | 2020-10-12 | 한국화학연구원 | Crosslinked reactive phosphorus polyol and method for producing the same, and flame retardant thermoplastic polyurethane made from crosslinked reactive phosphorus polyol |
| CN110157042A (en) * | 2019-04-28 | 2019-08-23 | 北京工商大学 | The application of novel surface inorganic agent, preparation method and the nano particle being processed in resistance combustion polyurethane foam |
| CN112250858A (en) * | 2020-08-31 | 2021-01-22 | 万华化学集团股份有限公司 | Method for preparing flame-retardant polymer polyol, application and polyurethane foam plastic prepared by using flame-retardant polymer polyol |
| CN112250858B (en) * | 2020-08-31 | 2022-07-12 | 万华化学集团股份有限公司 | Method for preparing flame-retardant polymer polyol, application and polyurethane foam plastic prepared by using flame-retardant polymer polyol |
| CN112851909A (en) * | 2021-01-14 | 2021-05-28 | 万华化学（宁波）有限公司 | Storage-stable polyisocyanate composition |
| CN112851909B (en) * | 2021-01-14 | 2022-08-05 | 万华化学（宁波）有限公司 | Storage-stable polyisocyanate composition |
| CN115403759A (en) * | 2022-11-02 | 2022-11-29 | 山东一诺威聚氨酯股份有限公司 | Halogen-free flame-retardant polyether ester polyol and preparation method and application thereof |
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Application publication date: 20180731 |