CN108192089A - A kind of preparation method of high functionality flame retardant polyether polyol - Google Patents
A kind of preparation method of high functionality flame retardant polyether polyol Download PDFInfo
- Publication number
- CN108192089A CN108192089A CN201810019010.8A CN201810019010A CN108192089A CN 108192089 A CN108192089 A CN 108192089A CN 201810019010 A CN201810019010 A CN 201810019010A CN 108192089 A CN108192089 A CN 108192089A
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- CN
- China
- Prior art keywords
- flame retardant
- polyether polyol
- acid
- high functionality
- retardant polyether
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/263—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing heterocyclic amine groups
-
- 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
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5054—Polyethers having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/5063—Polyethers having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
-
- 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
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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)
Abstract
The invention discloses a kind of methods for preparing high functionality flame retardant polyether polyol.Include following steps：Melamine methylol is reacted with binary acid (or its acid anhydrides), generates multi-hydroxy ester constituents；Multi-hydroxy ester constituents react again with epoxyalkane, obtain high functionality flame retardant polyether polyol.The flame retardant polyether polyol degree of functionality of the present invention is high, nitrogen content is high, thermal stability is good, can be used to prepare rigid poly urethanes, semi-rigid foam.Its foamed product flame retardant effect is notable, and oxygen index (OI) is more than 30%, and smoke amount is low during burning.
Description
Technical field
The invention belongs to the preparation method of organic high molecular compound, the high function of specifically a kind of polyurethane foam
Spend the preparation method of flame retardant polyether polyol.
Background technology
Polyether polyol is by initiator（Compound containing active hydrogen group）With epoxyalkane is aggregated reacts, be system
Make the primary raw material of polyurethane foam plastics.Polyurethane foam plastics is widely used in the fields such as household, building, traffic, sport.
Polyether polyol can be divided into two classes by its fire-retardant mode：Additive flame combustible polyether glycol and reaction-type flame-retarding polyethers
Polyalcohol.Additive flame combustible polyether glycol reaches fire-retardant mesh by adding inorganic or organic fire-retardant into polyether polyol
's.But addition these fire retardants usually there are easy to migrate, flame retardant effect it is not lasting and destroy foam physics performance the shortcomings of.Instead
The characteristics of answering type flame retardant polyether polyol is to be bonded with fire-retardant group on polyol molecule main chain or side chain, to the object of foamed product
Property influences small, and flame retarding efficiency is high.
Invention content
The object of the present invention is to provide a kind of methods for preparing high functionality flame retardant polyether polyol.The resistance that the present invention obtains
Combustible polyether glycol degree of functionality is high, nitrogen content is high, thermal stability is good, can be used to prepare rigid poly urethanes, semi-rigid foam.It is steeped
Foam fire block articles significant effect, oxygen index (OI) are more than 30%, and smoke amount is low during burning.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of high functionality flame retardant polyether polyol, it is characterised in that this method includes the following steps：
1) melamine methylol and binary acid or its anhydride reaction, generate multi-hydroxy ester constituents；
2) multi-hydroxy ester constituents are reacted with epoxyalkane, generate high functionality flame retardant polyether polyol.
Step 1 of the present invention）In multi-hydroxy ester constituents have the following structure：
Wherein, R is alkane, cycloalkane or the aromatic hydrocarbon of C1-C10, and n is between 1 and 3.Step 1）In binary acid (or acid anhydrides)
It may be selected from malonic acid, succinic acid, adipic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), maleic anhydride, O-phthalic
One or more of acid anhydrides, tetrahydrophthalic anhydride, methyl tetrahydro phthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride.
The molar ratio of melamine methylol and binary acid (or its acid anhydrides) is 1.2:1-2:Between 1.Methylol melamine
The preparation method of amine is no longer described in detail, and any available scheme may be selected.
Generation multi-hydroxy ester constituents comprise the concrete steps that：Melamine methylol is mixed with binary acid or its acid anhydrides to anti-
It answers in kettle, adds in n-butyl titanate catalyst, warming while stirring, temperature rises to 130-150oStart to be discharged between C, continue
It is warming up to 180-200oC, and in 180-200oIt is reacted 3-5 hours under C.N-butyl titanate catalyst addition is methylol three
The 0.1% of poly cyanamid and binary acid or its acid anhydrides total amount.
Generation high functionality flame retardant polyether polyol comprises the concrete steps that in step 2)：Potassium hydroxide catalyst is added in,
100-130 oEpoxyalkane is passed through under C, after epoxyalkane adds, in 100-130oIt is stirred 3-6 hours under C, fills system
Divide reaction；The addition of epoxyalkane is 1-2 times of multi-hydroxy ester constituents；Potassium hydroxide catalyst addition is multi-hydroxy ester
Constituents total amount 0.2%.Obtain high functionality flame retardant polyether polyol.Epoxyalkane is selected from ethylene oxide, propylene oxide or epoxy fourth
One or more of alkane.
The functionality polyols prepared using the multi-hydroxy ester constituents in the present invention are between 4-6.The present invention's is fire-retardant
Polyether polyols alcohol functionalities are high, nitrogen content is high, thermal stability is good, can be used to prepare rigid poly urethanes, semi-rigid foam.Its foam
Fire block articles significant effect, oxygen index (OI) are more than 30%, and smoke amount is low during burning.
Specific embodiment
Below by specific embodiment, the present invention is further illustrated, but each embodiment is not the tool to the present invention
Body limits.
Embodiment 1
A kind of method for preparing high functionality flame retardant polyether polyol adds in 700 g of melamine methylol into reaction kettle,
300 g of adipic acid, 1 g of n-butyl titanate catalyst, under nitrogen protection warming while stirring, temperature rise to 150oC starts
Water outlet, is continuously heating to 190oC, and 190oIt is reacted 4 hours under C, obtains melamine methylol adipate ester.Then it puts into
2 g of potassium hydroxide catalyst, 120 oCUnder be passed through 1500 g of propylene oxide, after propylene oxide adds, 120 oCTemperature
Lower stirring 3 hours, makes system fully react, and filters, obtains high functionality flame retardant polyether polyol.
Embodiment 2
The preparation method of another high functionality flame retardant polyether polyol, using tetrabutyl titanate as catalyst, 180oUnder C, hydroxyl
Methyl melamine (450 g) reacts 5 hours with phthalic anhydride (150 g), obtains melamine methylol phthalic acid
Ester.Again 110o1000 g of propylene oxide is passed through under C, after propylene oxide feeds intake, 110oIt is stirred to react under C 4 hours,
Filtering, obtains high functionality flame retardant polyether polyol.
Embodiment 3
The application of flame retardant polyether polyol made from a kind of above-mentioned preparation method.70 parts of polyether polyol for polyurethane foam is taken,
30 parts of flame retardant polyether polyol prepared by the present invention, 1 part of foam stabiliser, 0.2 part of catalyst, 2 parts of water, 110 parts of isocyanates,
It foams after high-speed stirred mixing and polyurethane foam product, oxygen index (OI) 31.0% is made.
Claims (7)
1. a kind of preparation method of high functionality flame retardant polyether polyol, it is characterised in that this method includes the following steps：
1) melamine methylol and binary acid or its anhydride reaction, generate multi-hydroxy ester constituents；
2) multi-hydroxy ester constituents are reacted with epoxyalkane, generate high functionality flame retardant polyether polyol.
2. the preparation method of high functionality flame retardant polyether polyol according to claim 1, it is characterised in that：Step 1）In
Multi-hydroxy ester constituents have the following structure：
Wherein, R is alkane, cycloalkane or the aromatic hydrocarbon of C1-C10, and n is between 1 and 3.
3. the preparation method of high functionality flame retardant polyether polyol according to claim 1, it is characterised in that：Step 1）In
Binary acid or its acid anhydrides include：Malonic acid, succinic acid, adipic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), horse
Carry out one kind or several in acid anhydrides, phthalic anhydride, tetrahydrophthalic anhydride, methyl tetrahydro phthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride
Kind.
4. the preparation method of high functionality flame retardant polyether polyol according to claim 1, it is characterised in that：Step 1）
In, melamine methylol is 1.2 with the molar ratio of binary acid or its acid anhydrides:1-2:Between 1.
5. the preparation method of high functionality flame retardant polyether polyol according to claim 1, it is characterised in that：Step 1）Tool
Body is as follows：Melamine methylol is mixed with binary acid or its acid anhydrides into reaction kettle, n-butyl titanate catalyst is added in, while stirring
Side heating is mixed, temperature rises to 130-150oStart to be discharged between C, be continuously heating to 180-200oC, and in 180-200oUnder C
Reaction 3-5 hours;N-butyl titanate catalyst addition is melamine methylol and binary acid or the 0.1% of its acid anhydrides total amount.
6. the preparation method of high functionality flame retardant polyether polyol according to claim 1, it is characterised in that：Step 2）Tool
Body is as follows：Potassium hydroxide catalyst is added in into the multi-hydroxy ester constituents of generation, in 100-130oEpoxyalkane is passed through under C,
After epoxyalkane adds, in 100-130oIt is stirred 3-6 hours under C, system is made fully to react；The addition of epoxyalkane
It is 1-2 times of multi-hydroxy ester constituents；Potassium hydroxide catalyst addition is multi-hydroxy ester constituents total amount 0.2%.
7. the preparation method of high functionality flame retardant polyether polyol according to claim 1, it is characterised in that：Step 2）In
The epoxyalkane is one or more of ethylene oxide, propylene oxide or epoxy butane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201810019010.8A CN108192089A (en) | 2018-01-09 | 2018-01-09 | A kind of preparation method of high functionality flame retardant polyether polyol |
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| CN201810019010.8A CN108192089A (en) | 2018-01-09 | 2018-01-09 | A kind of preparation method of high functionality flame retardant polyether polyol |
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| CN108192089A true CN108192089A (en) | 2018-06-22 |
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| CN201810019010.8A Pending CN108192089A (en) | 2018-01-09 | 2018-01-09 | A kind of preparation method of high functionality flame retardant polyether polyol |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796750A (en) * | 2018-12-29 | 2019-05-24 | 广州市聚科聚氨酯有限公司 | A kind of polyurethane rigid foam combined polyether |
| CN111499828A (en) * | 2020-04-15 | 2020-08-07 | 黎明化工研究设计院有限责任公司 | Resin composition for low-density high-flame-retardant polyurethane material and application thereof |
| CN112225887A (en) * | 2020-10-20 | 2021-01-15 | 北京理工大学 | Hyperbranched polyester carbonizing agent prepared from terephthalic acid, melamine and formaldehyde and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504244A (en) * | 2011-10-28 | 2012-06-20 | 山东理工大学 | Synthesis and preparation method of melamine modified non-halogen inflaming retarding polyether |
| CN107082876A (en) * | 2017-05-24 | 2017-08-22 | 黄山市向荣新材料有限公司 | A kind of flame retardant type polyester resin, its preparation method and the powdery paints comprising it |
-
2018
- 2018-01-09 CN CN201810019010.8A patent/CN108192089A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504244A (en) * | 2011-10-28 | 2012-06-20 | 山东理工大学 | Synthesis and preparation method of melamine modified non-halogen inflaming retarding polyether |
| CN107082876A (en) * | 2017-05-24 | 2017-08-22 | 黄山市向荣新材料有限公司 | A kind of flame retardant type polyester resin, its preparation method and the powdery paints comprising it |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796750A (en) * | 2018-12-29 | 2019-05-24 | 广州市聚科聚氨酯有限公司 | A kind of polyurethane rigid foam combined polyether |
| CN111499828A (en) * | 2020-04-15 | 2020-08-07 | 黎明化工研究设计院有限责任公司 | Resin composition for low-density high-flame-retardant polyurethane material and application thereof |
| CN111499828B (en) * | 2020-04-15 | 2022-04-12 | 黎明化工研究设计院有限责任公司 | Resin composition for low-density high-flame-retardant polyurethane material and application thereof |
| CN112225887A (en) * | 2020-10-20 | 2021-01-15 | 北京理工大学 | Hyperbranched polyester carbonizing agent prepared from terephthalic acid, melamine and formaldehyde and preparation method thereof |
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