CN101967228A - Method for synthesizing highly active flame-resistant polyether polyol - Google Patents
Method for synthesizing highly active flame-resistant polyether polyol Download PDFInfo
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- CN101967228A CN101967228A CN 201010295881 CN201010295881A CN101967228A CN 101967228 A CN101967228 A CN 101967228A CN 201010295881 CN201010295881 CN 201010295881 CN 201010295881 A CN201010295881 A CN 201010295881A CN 101967228 A CN101967228 A CN 101967228A
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- polyether polyol
- flame retardant
- synthetic method
- glycol
- reactive flame
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Abstract
The invention relates to a method for synthesizing highly active flame-resistant polyether polyol, comprising the following steps of: mixing polyol compound, epoxy compound and halogenated epoxide; and synthesizing halogenated polyether polyol by the reaction of catalyst under a temperature of 80-130 DEG C. A substitution reaction is performed between the polyether polyol prepared through the method and tribromphenol salt under a temperature of 60-100 DEG C. The highly active flame-resistant polyether polyol prepared through the method can be widely applied to the preparation of high performance polyamine soft foam. After bromine is introduced in the polyether polyol, the flame-resistant performance of the prepared foam plastic products is obviously improved. The product prepared in such a way has high flame-resistant rate and no influence to other performances, and can obviously reduce the content of hydrogen chloride in the fuel. The invention has the advantages of cheap materials, good flame-resistant performance and simple and easy synthetic technique route and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of synthetic method of High Reactive Flame Retardant Polyether Polyol.
Background technology
Along with the raising that country requires for security against fire, the fire resistance that polyurethane material is used in each field is also strengthened gradually, and soft bubble industries such as furniture, automobile require more and more higher for flame retardant properties.The foam materials that the tradition polyether glycol makes requires lower for fp, belong to inflammable material.Widely used porous plastics is extremely urgent for the requirement of fire resistance in these lives and the production.Therefore need seek a new way realizing that foam is fire-retardant.
Summary of the invention
According to the prior art deficiency, technical problem to be solved by this invention is: the synthetic method that a kind of High Reactive Flame Retardant Polyether Polyol is provided, the polyether glycol that this method prepares can be used for the preparation of the soft bubble of high performance polyurethane, and the synthetic technology route is simple and easy to do, and product has lighter color, viscosity is low, small molecular weight impurity is few.
The technical solution adopted for the present invention to solve the technical problems is: a kind of synthetic method of High Reactive Flame Retardant Polyether Polyol is provided, it is characterized in that may further comprise the steps:
(1) multicomponent alcoholics compound, epoxy compounds and halogenated epoxide are mixed, under 80～130 ℃, synthesizing halogen polyether glycol under the katalysis of catalyzer;
(2) polyether glycol that makes with (1) and tribromophenol salt are under catalyst action, 60～100 ℃ of generation substitution reactions.
Preferred 85～120 ℃ of the described temperature of reaction of the synthetic method of above-mentioned High Reactive Flame Retardant Polyether Polyol.
Described multicomponent alcoholics compound is selected from the mixture that one or more arbitrary proportions in ethylene glycol, Diethylene Glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerine, tetramethylolmethane, Xylitol, sorbyl alcohol, N.F,USP MANNITOL, sucrose or the glycoside are formed.
Described multicomponent alcoholics compound is glycerine or propylene glycol.
Described epoxy compounds is oxyethane, propylene oxide or butylene oxide ring.
Described halogenated epoxide is epoxy chloropropane or epoxy bromopropane.
Described halogenated epoxide account for amount of the mixture amount of substance 10%～40%.
Catalysts described in the step (1) is potassium hydroxide, boron trifluoride tetrahydrofuran solution or bimetal complex catalyst, and catalyst levels is the 2-4% of total mixture quality.
Tribromophenol salt described in the step (2) is tribromophenol sodium or tribromophenol potassium.
Catalyzer described in the step (2) is benzyltriethylammoinium chloride, iron(ic) chloride or sodium iodide, and catalyzer is the 2-4% of total quality of material.
Tribromophenol salt quality described in the step (2) accounts for 20～50% of tribromophenol salt and polyether glycol total mass.
The invention has the beneficial effects as follows: the High Reactive Flame Retardant Polyether Polyol that makes with present method can be widely used in the preparation of the soft bubble of high performance polyurethane, after in polyether glycol, introducing bromo element, the foam article flame retardant properties that it makes obviously improves, the product flame retarding efficiency height that makes by this approach, almost not influence of other performances to the product that makes, can significantly reduce simultaneously the content of hydrogenchloride in the combustion gas, raw materials used cheap, be suitable for industrial production, fire resistance is good, and this synthetic technology route is simple and easy to do, and product has lighter color, viscosity is low, characteristics such as small molecular weight impurity is few.
Embodiment
Embodiment 1
Taking by weighing 60g initiator glycerine drops in the polymerization reaction kettle, feed nitrogen temperature to 80 ℃, under agitation drip the mixture of 2.8g bimetal complex catalyst and 590g propylene oxide and epoxy bromopropane (propylene oxide 406g, epoxy chloropropane 184g), after this at the bottom of polymerization reaction kettle, slowly be pressed into 84g oxyethane, sustained reaction 2h.Obtain product after the washing underpressure distillation.
Take by weighing the product 700g input reactor that the first step obtains, add Catalysts Cu Cl 3.3g, stirred 10 minutes.Drop into tribromophenol sodium 300g.Heat up nitrogen replacement.Temperature rises to 60 ℃ and keeps stirring reaction 6h.Reaction finishes the back cooling and obtains product.
Embodiment 2
Taking by weighing 33g initiator propylene glycol drops in the polymerization reaction kettle, feed nitrogen temperature to 90 ℃, under agitation drip the mixture of 1.2g boron trifluoride tetrahydrofuran solution and 512g oxyethane and epoxy chloropropane (propylene oxide 406g, epoxy chloropropane 60g), after this at the bottom of polymerization reaction kettle, slowly be pressed into 84g oxyethane, sustained reaction 2h.Obtain product after the washing underpressure distillation.
Take by weighing the product 600g input reactor that the first step obtains, add catalyzer benzyltriethylammoinium chloride 2.4g, stirred 10 minutes.Drop into tribromophenol sodium 600g.Heat up nitrogen replacement.Temperature rises to 80 ℃ and keeps stirring reaction 6h.Reaction finishes the back cooling and obtains product.
Embodiment 3
Taking by weighing initiator 30g glycerine and 30g dipropylene glycol drops in the polymerization reaction kettle, feed nitrogen temperature to 130 ℃, under agitation drip the mixture of 2.4g potassium hydroxide and 578g butylene oxide ring and epoxy chloropropane (propylene oxide 398g, epoxy chloropropane 320g), after this at the bottom of polymerization reaction kettle, slowly be pressed into 84g oxyethane, sustained reaction 2h.Obtain product after the washing underpressure distillation.
Take by weighing the product 800g input reactor that the first step obtains, add catalyst n aI4.0g, stirred 10 minutes.Drop into tribromophenol potassium 200g.Heat up nitrogen replacement.Temperature rises to 100 ℃ and keeps stirring reaction 6h.Reaction finishes the back cooling and obtains product.
Product detects the index summary sheet
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Outward appearance | Translucent thick liquid | Translucent thick liquid | Light yellow viscous liquid |
| Viscosity (25 ℃), mPas | 0.92? | 0.76? | 1.35? |
| Hydroxyl value (mgKOH/g) | 145? | 76? | 133? |
| Bromine massfraction/% | 22.5? | 18.2? | 20.2? |
Remarks: according to this patent method synthetic High Reactive Flame Retardant Polyether Polyol, lighter color, viscosity is low, small molecular weight impurity is few, and performance index such as the outward appearance of product, viscosity, hydroxyl value and brominated massfraction can satisfy the manufacturing requirement of the soft bubble of PU.
Claims (10)
1. the synthetic method of a High Reactive Flame Retardant Polyether Polyol is characterized in that may further comprise the steps:
(1) multicomponent alcoholics compound, epoxy compounds and halogenated epoxide are mixed, under 80～130 ℃, synthesizing halogen polyether glycol under the katalysis of catalyzer;
(2) polyether glycol that makes with (1) and tribromophenol salt are under catalyst action, 60～100 ℃ of generation substitution reactions.
2. the synthetic method of High Reactive Flame Retardant Polyether Polyol according to claim 1, it is characterized in that described multicomponent alcoholics compound is selected from the mixture that one or more arbitrary proportions in ethylene glycol, Diethylene Glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerine, tetramethylolmethane, Xylitol, sorbyl alcohol, N.F,USP MANNITOL, sucrose or the glycoside are formed, and multicomponent alcoholics compound accounts for 5～8% of amount of the mixture.
3. the synthetic method of High Reactive Flame Retardant Polyether Polyol according to claim 1 is characterized in that described multicomponent alcoholics compound is glycerine or propylene glycol.
4. the synthetic method of High Reactive Flame Retardant Polyether Polyol according to claim 1 is characterized in that described epoxy compounds is oxyethane, propylene oxide or butylene oxide ring.
5. the synthetic method of High Reactive Flame Retardant Polyether Polyol according to claim 1 is characterized in that described halogenated epoxide is epoxy chloropropane or epoxy bromopropane.
6. the synthetic method of High Reactive Flame Retardant Polyether Polyol according to claim 1, it is characterized in that described halogenated epoxide account for amount of the mixture amount of substance 10%～40%.
7. the synthetic method of High Reactive Flame Retardant Polyether Polyol according to claim 1, it is characterized in that catalysts described in the step (1) is potassium hydroxide, boron trifluoride tetrahydrofuran solution or bimetal complex catalyst, catalyst levels is the 2-4% of total mixture quality.
8. the synthetic method of High Reactive Flame Retardant Polyether Polyol according to claim 1 is characterized in that tribromophenol salt described in the step (2) is tribromophenol sodium or tribromophenol potassium.
9. the synthetic method of High Reactive Flame Retardant Polyether Polyol according to claim 1 it is characterized in that the catalyzer described in the step (2) is benzyltriethylammoinium chloride, iron(ic) chloride or sodium iodide, and catalyzer is the 2-4% of total quality of material.
10. the synthetic method of High Reactive Flame Retardant Polyether Polyol according to claim 1 is characterized in that the tribromophenol salt quality described in the step (2) accounts for 20～50% of tribromophenol salt and polyether glycol total mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010295881 CN101967228A (en) | 2010-09-28 | 2010-09-28 | Method for synthesizing highly active flame-resistant polyether polyol |
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| CN 201010295881 CN101967228A (en) | 2010-09-28 | 2010-09-28 | Method for synthesizing highly active flame-resistant polyether polyol |
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| CN101967228A true CN101967228A (en) | 2011-02-09 |
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| CN 201010295881 Pending CN101967228A (en) | 2010-09-28 | 2010-09-28 | Method for synthesizing highly active flame-resistant polyether polyol |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875794A (en) * | 2012-10-16 | 2013-01-16 | 山东蓝星东大化工有限责任公司 | Hard bubble polyether polyol and preparation method thereof |
| CN103497322A (en) * | 2013-09-09 | 2014-01-08 | 江苏雅克科技股份有限公司 | Preparation method and application for reaction-type halogen-containing flame-retardant polyether polyol |
| CN104497296A (en) * | 2014-12-09 | 2015-04-08 | 淄博德信联邦化学工业有限公司 | Permanent flame retardant high-activity polyether polyol and preparation method thereof |
| CN107602794A (en) * | 2017-09-15 | 2018-01-19 | 山东诺威聚氨酯股份有限公司 | Polyurethane chair configuration material and preparation method thereof |
| CN109467690A (en) * | 2018-09-17 | 2019-03-15 | 佳化化学科技发展（上海）有限公司 | A kind of flame-retardant polyether glycol and its preparation method and application |
-
2010
- 2010-09-28 CN CN 201010295881 patent/CN101967228A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 《聚氨酯工业》 20031231 张田林等 高活性阻燃聚醚多元醇的合成 第14-17页，第1.3、1.4和2.2节，表3 1-10 第18卷, 第2期 2 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875794A (en) * | 2012-10-16 | 2013-01-16 | 山东蓝星东大化工有限责任公司 | Hard bubble polyether polyol and preparation method thereof |
| CN103497322A (en) * | 2013-09-09 | 2014-01-08 | 江苏雅克科技股份有限公司 | Preparation method and application for reaction-type halogen-containing flame-retardant polyether polyol |
| CN103497322B (en) * | 2013-09-09 | 2015-05-27 | 江苏雅克科技股份有限公司 | Preparation method and application for reaction-type halogen-containing flame-retardant polyether polyol |
| CN104497296A (en) * | 2014-12-09 | 2015-04-08 | 淄博德信联邦化学工业有限公司 | Permanent flame retardant high-activity polyether polyol and preparation method thereof |
| CN107602794A (en) * | 2017-09-15 | 2018-01-19 | 山东诺威聚氨酯股份有限公司 | Polyurethane chair configuration material and preparation method thereof |
| CN107602794B (en) * | 2017-09-15 | 2020-03-20 | 山东一诺威聚氨酯股份有限公司 | Polyurethane seat composite material and preparation method thereof |
| CN109467690A (en) * | 2018-09-17 | 2019-03-15 | 佳化化学科技发展（上海）有限公司 | A kind of flame-retardant polyether glycol and its preparation method and application |
| US11401375B2 (en) | 2018-09-17 | 2022-08-02 | Jiahua Science & Technology Development (Shanghai) Ltd. | Flame-retardant polyether polyol as well as preparation method and application thereof |
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Application publication date: 20110209 |