CN104327304A - Fire retardant for polyolefin high polymers and epoxy resin and preparation method of fire retardant - Google Patents
Fire retardant for polyolefin high polymers and epoxy resin and preparation method of fire retardant Download PDFInfo
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- CN104327304A CN104327304A CN201410580357.1A CN201410580357A CN104327304A CN 104327304 A CN104327304 A CN 104327304A CN 201410580357 A CN201410580357 A CN 201410580357A CN 104327304 A CN104327304 A CN 104327304A
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Abstract
The invention provides a fire retardant for polyolefin high polymers and epoxy resin and a preparation method of the fire retardant, relating to a fire retardant and a preparation method thereof. The preparation method comprises the following synthesis steps: at room temperature, weighing a certain amount of an intermediate II (PDCEPE) and melamine, grinding together and uniformly mixing; then putting into a 250ml three-necked flask provided with an electric stirrer, a thermometer and a condenser pipe, then adding 40-80ml of water and starting the electric stirrer; increasing the temperature to 70-100 DEG C, wherein in the temperature increasing process, a reaction liquid becomes sticky and is prone to caking; then reacting for 3-6h; and filtering, washing and drying to finally obtain white blocky solid which is the fire retardant. The prepared phosphorus-and-nitrogen-containing fire retardant is halogen-free, has the advantages of good carbonizing property and obvious fire retardant effect and wide application scope and can be applied to fire retardance for polyolefin materials.
Description
Technical field
The present invention relates to a kind of fire retardant and preparation method thereof, particularly relate to a kind of fire retardant for polyolefine superpolymer and epoxy resin and preparation method thereof.
Background technology
In the last hundred years, the large synthetic material industry of plastics, rubber and fiber three obtains very fast development, and chemical building material, organic polymer polymeric material are applied to all respects of people's life more and more widely, the fields such as such as building, traffic, electrical equipment, communication.But the experience of life tells us, because these materials are red label goods mostly, and thermal discharge is large, combustionvelocity is very fast, and be difficult to put out, the disaster hidden-trouble brought thus has become the social concern of global concern, therefore people more and more pay much attention to change material inflammableness, and fire retardant arises at the historic moment.
It is found that charcoal oxygen index reaches 65%, is kind a material for difficult combustion, thus expects the fire-retardant object that makes organic materials superficiality become the method for layer of charcoal to reach.Again come into one's own afterwards and obtain and develop rapidly.In fact, the Gay-Lussac epoch just occurred making material surface form the flame resistant method of layer of charcoal, but had just had the patent of first intumescent fire-retardant coating material by 1938.Utilize the molecular weight of phosphor-nitrogen expansion type combustion inhibitor own comparatively large, have that the low cigarette of low toxicity, consistency are good, the not easily advantage such as migration, have thermotolerance height and the stable feature of hydrolysis, more lasting flame retardant effect.Phosphor-nitrogen expansion type combustion inhibitor overcome traditional fire retardant its to there is addition large, the critical defect such as produce poisonous, corrosive gases and the amount of being fuming is large.Cause environmental problem because new halogen flame produces toxic gas, and phosphorus nitrogen expansion type combustion inhibitor is the environmentally friendly fire retardant of a class, toxicity is little, pollutes little, and development in recent years speed is very fast, and market is extensive.From the eighties in 20th century till now, this Intumescent Retardant System receive fire-retardant boundary height favor.
This based flame retardant mainly develops towards following several respects in recent years:
1, the macromole of phosphor-nitrogen expansion type combustion inhibitor is brought up to a certain degree, thus overcome poor heat resistance, shortcoming that volatility is large, to multifunction future development.
2, by phosphor-nitrogen expansion type combustion inhibitor super-refinement and micro encapsulation, these two kinds of methods can improve the consistency of fire retardant and material, improve the consumption of the mechanical property of material, flame retardant properties and reduction fire retardant.
3, contain phosphorus, nitrogen element and silicon, sulphur, one or more elements of boron with in a part, or carried out composite, studying the cooperative flame retardant effect between them, providing foundation for preparing new and effective type fire retardant.
Summary of the invention
The object of the present invention is to provide a kind of fire retardant for polyolefine superpolymer and epoxy resin and preparation method thereof, fire retardant contains phosphorus, nitrogen element, the effect of cooperative flame retardant can be played, and there is the advantage of Halogen, can not to environment, and preparation method is simple, mild condition, is easy to control, without other additives, the product purity of gained is high, convenient post-treatment.
The object of the invention is to be achieved through the following technical solutions:
For a fire retardant for polyolefine superpolymer and epoxy resin, described flame retardant polymer structural formula is as follows:
。
A kind of fire retardant preparation method for polyolefine superpolymer and epoxy resin, the synthesis step of the method is as follows: at room temperature, take intermediate II (PDCEPE) and trimeric cyanamide, put together grinding, make it mix, then put in the 250ml there-necked flask being equipped with electric mixer, thermometer, prolong, add the water of 40-80ml afterwards, start electric stirring; Increase the temperature to 70-100 DEG C, in the process of raised temperature, reaction solution becomes glutinous, easily lumps, reacts 3-6h afterwards, and the solid obtaining white chunks after filtration, washing, drying is fire retardant.
Described a kind of fire retardant preparation method for polyolefine superpolymer and epoxy resin, the ratio of described intermediate II (PDCEPE) and trimeric cyanamide is 1:2-1:2.5.
Described a kind of fire retardant preparation method for polyolefine superpolymer and epoxy resin, described solvent is the mixture of any one or its arbitrary proportion in Isosorbide-5-Nitrae dioxane, acetonitrile.
Described a kind of fire retardant preparation method for polyolefine superpolymer and epoxy resin, described temperature of reaction is 70-100 DEG C; Reaction times is 3-6h.
Described a kind of fire retardant preparation method for polyolefine superpolymer and epoxy resin, described solvent load is 40-80mL.
Described a kind of fire retardant preparation method for polyolefine superpolymer and epoxy resin, described cleaning solvent is the mixing of any one or its arbitrary proportion in distilled water, acetonitrile, dehydrated alcohol.
Advantage of the present invention and effect are:
1, fire retardant provided by the invention contains phosphorus, nitrogen element, can play the effect of cooperative flame retardant, and has the advantage of Halogen, can not to environment.
2, preparation method provided by the invention is simple, mild condition, is easy to control, and without other additives, the product purity of gained is high, convenient post-treatment.
3, phosphorous, nitrogen combustion inhibitor applied range provided by the invention, can be used for the fire-retardant of the polymerization system such as epoxy resin and polyolefine.
Accompanying drawing explanation
Fig. 1 is flame retardant polymer structural formula of the present invention.
Embodiment
Below in conjunction with accompanying drawing illustrated embodiment, the invention will be further described.
Embodiment 1:
To being equipped with magnetic stirring apparatus, thermometer, (upper end is through CaCl for prolong
2drying tower) and constant pressure funnel 100ml there-necked flask in add 5.023g(0.022mol) dihydroxyphenyl propane, 2.226g(0.022mol) triethylamine and 10ml acetonitrile.Start magnetic agitation, make it dissolve.1.950g phosphenyl oxychloride (DCPPO) and 10ml acetonitrile is added in constant pressure funnel.When the temperature in there-necked flask is between 5 DEG C-10 DEG C, starts slowly to drip, within about 1.5 hours, drip off, and continue reaction 4 hours at such a temperature, then locate each reaction 1.5 hours at 25 DEG C, 50 DEG C and backflow point respectively.Have white mist (cigarette) to generate when starting to drip DCPPO, reaction solution slowly becomes micro white by colourless, along with the rising of temperature becomes oyster white, finally becomes intimate transparent micro-yellow.Through repeatedly washing after reaction terminates, at 60 DEG C, vacuum-drying 12 hours, obtains white powdery solids after grinding.Be intermediate I (PDPPE).
At room temperature, in the 100ml there-necked flask being equipped with magnetic stirring apparatus, thermometer, prolong (upper end is through CaCl2 drying tower and HCl device for absorbing tail gas) and N2 charging device, 5.786g(0.01mol is added) PDPPE, 4.290(0.022mol) phosphenyl oxychloride and 20ml acetonitrile.Start magnetic agitation (comparatively fast), be then warmed up to backflow point, about need 0.5 hour, now reaction solution is water white transparency.React 10 hours when refluxing point, reaction solution becomes oyster white by water white transparency in reaction process, stirs layering if stop.Through repeatedly washing after reaction terminates, at 60 DEG C, vacuum-drying 12 hours, obtains white powdery solids after grinding.Be intermediate II (PDCEPE).
At room temperature, take 5.374g(0.006mol) intermediate II (PDCEPE) and 1.589g(0.0126mol) trimeric cyanamide, put together grinding, make it mix, then put in the 250ml there-necked flask being equipped with electric mixer, thermometer, prolong, add the water of 60ml afterwards, start electric stirring.Increase the temperature to 90 DEG C, in the process of raised temperature, reaction solution becomes glutinous, easily lumps, and reacts 4 hours afterwards.The solid obtaining white chunks after filtration, washing, drying is fire retardant.
Embodiment 2:
Wherein the synthetic method of intermediate I (PDPPE) and intermediate II (PDCEPE) is with example 1.
At room temperature, take 5.374g(0.006mol) intermediate II (PDCEPE) and 1.665g(0.0132mol) trimeric cyanamide, put together grinding, make it mix, then put in the 250ml there-necked flask being equipped with electric mixer, thermometer, prolong, add the water of 60ml afterwards, start electric stirring.Increase the temperature to 95 DEG C, in the process of raised temperature, reaction solution becomes glutinous, easily lumps, and reacts 5 hours afterwards.The solid obtaining white chunks after filtration, washing, drying is fire retardant.
Embodiment 3:
Wherein the synthetic method of intermediate I (PDPPE) and intermediate II (PDCEPE) is with example 1.
At room temperature, take 5.374g(0.006mol) intermediate II (PDCEPE) and 1.741g(0.0138mol) trimeric cyanamide, put together grinding, make it mix, then put in the 250ml there-necked flask being equipped with electric mixer, thermometer, prolong, add the water of 60ml afterwards, start electric stirring.Increase the temperature to 95 DEG C, in the process of raised temperature, reaction solution becomes glutinous, easily lumps, and reacts 4 hours afterwards.The solid obtaining white chunks after filtration, washing, drying is fire retardant.
Claims (7)
1., for a fire retardant for polyolefine superpolymer and epoxy resin, it is characterized in that, described flame retardant polymer structural formula is as follows:
。
2. the fire retardant preparation method for polyolefine superpolymer and epoxy resin, it is characterized in that, the synthesis step of the method is as follows: at room temperature, take intermediate II (PDCEPE) and trimeric cyanamide, put together grinding, make it mix, then put in the 250ml there-necked flask being equipped with electric mixer, thermometer, prolong, add the water of 40-80ml afterwards, start electric stirring; Increase the temperature to 70-100 DEG C, in the process of raised temperature, reaction solution becomes glutinous, easily lumps, reacts 3-6h afterwards, and the solid obtaining white chunks after filtration, washing, drying is fire retardant.
3. a kind of fire retardant preparation method for polyolefine superpolymer and epoxy resin according to claim 2, it is characterized in that, the ratio of described intermediate II (PDCEPE) and trimeric cyanamide is 1:2-1:2.5.
4. a kind of fire retardant preparation method for polyolefine superpolymer and epoxy resin according to claim 2, is characterized in that, described solvent is the mixture of any one or its arbitrary proportion in Isosorbide-5-Nitrae dioxane, acetonitrile.
5. a kind of fire retardant preparation method for polyolefine superpolymer and epoxy resin according to claim 2, it is characterized in that, described temperature of reaction is 70-100 DEG C; Reaction times is 3-6h.
6. a kind of fire retardant preparation method for polyolefine superpolymer and epoxy resin according to claim 2, it is characterized in that, described solvent load is 40-80mL.
7. a kind of fire retardant preparation method for polyolefine superpolymer and epoxy resin according to claim 2, is characterized in that, described cleaning solvent is the mixing of any one or its arbitrary proportion in distilled water, acetonitrile, dehydrated alcohol.
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| Application Number | Priority Date | Filing Date | Title |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801471A (en) * | 2016-04-06 | 2016-07-27 | 沈阳化工大学 | Bisphenol containing pyridine side groups and synthesis method of bisphenol |
| CN113214454A (en) * | 2021-06-28 | 2021-08-06 | 西华大学 | Transparent halogen-free flame-retardant epoxy resin, material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1721423A (en) * | 2004-07-16 | 2006-01-18 | 中国石油天然气集团公司 | Process for synthesis of melamine salt of pentaerythritol bis (dihydrogen phosphate) |
| CN103224599A (en) * | 2013-01-21 | 2013-07-31 | 苏州科技学院 | Preparation method of resorcinol formaldehyde resin-based macromolecular fire retardant |
| CN103408837A (en) * | 2013-07-30 | 2013-11-27 | 大禹节水（天津）有限公司 | Composite intumescent flame retardant for polypropylene |
-
2014
- 2014-10-27 CN CN201410580357.1A patent/CN104327304A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1721423A (en) * | 2004-07-16 | 2006-01-18 | 中国石油天然气集团公司 | Process for synthesis of melamine salt of pentaerythritol bis (dihydrogen phosphate) |
| CN103224599A (en) * | 2013-01-21 | 2013-07-31 | 苏州科技学院 | Preparation method of resorcinol formaldehyde resin-based macromolecular fire retardant |
| CN103408837A (en) * | 2013-07-30 | 2013-11-27 | 大禹节水（天津）有限公司 | Composite intumescent flame retardant for polypropylene |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801471A (en) * | 2016-04-06 | 2016-07-27 | 沈阳化工大学 | Bisphenol containing pyridine side groups and synthesis method of bisphenol |
| CN113214454A (en) * | 2021-06-28 | 2021-08-06 | 西华大学 | Transparent halogen-free flame-retardant epoxy resin, material and preparation method thereof |
| CN113214454B (en) * | 2021-06-28 | 2022-06-07 | 西华大学 | Transparent halogen-free flame-retardant epoxy resin, material and preparation method thereof |
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Application publication date: 20150204 |