CN105482096B - A kind of reactive phosphorus flame retardant and preparation method thereof - Google Patents
A kind of reactive phosphorus flame retardant and preparation method thereof Download PDFInfo
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- CN105482096B CN105482096B CN201510878385.6A CN201510878385A CN105482096B CN 105482096 B CN105482096 B CN 105482096B CN 201510878385 A CN201510878385 A CN 201510878385A CN 105482096 B CN105482096 B CN 105482096B
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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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- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/22—Halogen free composition
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Abstract
A kind of reactive phosphorus flame retardant and preparation method thereof, it is related to a kind of synthesis fire retardant and preparation method thereof, preparing raw material includes：PEPA（1 epoxide phospha, 4 methylol 2,6,7 trioxa-l-phosphabicyclo [2.2.2] octane）, POCl3 (POCl3), polyethylene glycol and epoxychloropropane.The step of preparing the fire retardant is divided into three steps and carried out, the first step, and, first reaction generates a kind of intermediate by PEPA and POCl3 under certain condition；Second step：This intermediate and polyethylene glycol of synthesis are reacted to a kind of new polymer of generation under certain condition.3rd step：Epoxychloropropane and polymer reaction generation final product.Product is filtered, washing, the processing such as dry, obtains white solid.The phosphorus content of the compound has good fire resistance more than 10%.The simple production process of this product, post processing is easy, has development potentiality.
Description
Technical field
The present invention relates to a kind of phosphorus flame retardant and preparation method thereof, more particularly to a kind of reactive phosphorus flame retardant and
Its preparation method.
Background technology
With the extensive use of high polymer material in daily life, therewith it is all come the problem of be also just exposed, from
Since the 50's of last century, high polymer material and its product based on the synthetic materials such as plastics, rubber, fiber are inflammable because of its
Property and the fire incident that triggers causes great casualties and property loss to society.Flame retarded polymeric material, which has, to be difficult to a little
Combustion, from fiery self-extinguishment the features such as, even if catching fire, can also slow down the rate of propagation of flame, it is catastrophic can to prevent that small fire from developing into
Big fire, people are made to obtain more times to withdraw or stamp out a fire, so as to play a part of reducing the harm of fire.
Therefore, necessary flame-retardant modified research is carried out to high polymer material turns into the great research class to involve the interests of the state and the people
Topic, wherein most crucial is the research on fire retardant and flame-retarded technology.
Traditional halogenated flame retardant is because of its environmental hazard in use, recovery and combustion process and by more and more
Limitation.It is difficult to find to incite somebody to action in terms of performance, price and Environmental Safety because halogenated flame retardant applicating history is longer, in the short time
Its product substituted completely, therefore, halogenated flame retardant will not withdraw from the market in a short time.But caused environmental protection organization and
The great attention of national governments and the people and vigilant.
Scientific progress improves with environmental consciousness, it is desirable to which people not only develop the more preferable fire retardant of performance, also to fire retardant
Itself proposes more strict requirements, the non-halogen of fire retardant, less toxicization, Composite, suppression with the environmental issue during use
Fuming has become 21 century fire retardant overall development trend.Fire retardant development and application business both domestic and external is adjusting fire-retardant always
The product structure of agent, reduces the use of halogenated flame retardant, and increases the developmental research to the halogen-free type fire retardant of high-efficiency environment friendly.
But the kind for the halogen-free flame retardants that can be applied to market at present is also seldom, it would be highly desirable to which exploitation is suitable for industrialized new product.
Efficiently, less toxic or nontoxic, environmental type fire retardant research and application are exploitation high-performance refractory macromolecule materials
The key link of material and important scientific problems most urgently to be resolved hurrily, flame-retarded technology will further develop as advanced high polymer material
Important support.
The content of the invention
It is an object of the invention to provide a kind of reactive phosphorus flame retardant and preparation method thereof.Its phosphorus element content compared with
Height, there is flame retarding efficiency high and Halogen, low cigarette, less toxic, meet the requirement that current people preserve the ecological environment, this resistance
Combustion agent greatly reduces the generation of toxic gas and corrosive gas in combustion, is a kind of preferably environmental type resistance
Fire agent.
The purpose of the present invention is achieved through the following technical solutions：
A kind of reactive phosphorus flame retardant, described phosphorus flame retardant raw material include：PEPA（1- epoxide phospha -4- hydroxyl first
Base -2,6,7- trioxa-l-phosphabicyclos [2.2.2] octane）, POCl3 (POCl3), polyethylene glycol and epoxychloropropane, fire retardant tool
There is following structure：
Said process is expressed as with chemical equation：
A kind of described reactive phosphorus flame retardant preparation method, in the first step, intermediate and polyethylene glycol feed intake and rubbed
You are than being 1:1 to 1:.2 between；Solvent for use is the mixture of any one or its arbitrary proportion in acetonitrile, DMF and DMSO.
A kind of described reactive phosphorus flame retardant preparation method, in the first step, reaction temperature are controlled at 60-120 DEG C
；Reaction time is 20-40 h.
A kind of described reactive phosphorus flame retardant preparation method, in the first step, used catalyst AlCl3Or
The mixture of any one or its arbitrary proportion in DMAP.
A kind of described reactive phosphorus flame retardant preparation method, in the first step, it is deionization to wash required solvent
The mixture of any one or its arbitrary proportion in water, ethanol, acetonitrile, acetone and toluene.
A kind of described reactive phosphorus flame retardant preparation method, in the first step, drying temperature are 60-80 DEG C.
A kind of described reactive phosphorus flame retardant preparation method, in second step, the throwing of polymer and epoxychloropropane
Material is than being 1:1 to 1:Between 2；Solvent for use is any one solvent or its arbitrary proportion in DMSO, acetonitrile, DMF and chloroform
Mixture conditions under carry out.
A kind of described reactive phosphorus flame retardant preparation method, in second step, reaction temperature is 60-120 DEG C
A kind of described reactive phosphorus flame retardant preparation method, in second step, in second step, the reaction time is
20-40 h。
A kind of described reactive phosphorus flame retardant preparation method, in second step, cleaning solvent is deionized water, second
The mixture of any one or its arbitrary proportion in alcohol, acetone and toluene.
A kind of described reactive phosphorus flame retardant preparation method, in second step, drying temperature is 60-80 DEG C.
Advantages of the present invention is with effect：
1. aggretion type phosphorus flame retardant provided by the invention is as a kind of addition type or PBT reactive flame retardant curing agent,
Improving can also be increased by the facile hydrolysis of ignition resistant substrate, toughness, not easy to migrate in the polymer, have excellent durable
Property.
2. the main phosphorus element-containing of aggretion type fire retardant provided by the invention, there is the advantages of low toxicity, high-efficiency environment friendly, favorably
In sustainable development.
3. preparation method provided by the invention is simple, mild condition is easily controllable, without other additives, the product of gained
Purity is high, convenient post-treatment.
Embodiment
With reference to embodiment, the present invention is described in detail.
Embodiment 1：
The first step：The g of PEPA 16.24 are added into the 250 ml there-necked flasks equipped with reflux condensing tube, thermometer and magneton
With the ml of POCl3 5, the ml of solvent acetonitrile 50 is added, raises reaction temperature, when temperature rises to 80 DEG C, adds catalyst
DMAP, controlling reaction temperature is between 80-82 DEG C, after the h of sustained response 25, there is a white solid precipitation, product acetone or
After acetonitrile washing, the white powder obtained after 60 DEG C of dryings is intermediate.
Second step：2.63 g intermediates are added into the 100 ml there-necked flasks equipped with reflux condensing tube, thermometer and magneton
With 1.53 g polyethylene glycol, 40 ml acetonitrile as solvents are added, after being warming up to 80 DEG C, 0.1 g DMAP are added to three mouthfuls
In bottle, control temperature is in 80-82 DEG C of reaction.Reaction time 25, h was down to room temperature after terminating, and the sediment of white was obtained, by it
Suction filtration, washing, after drying, obtain white solid powder.
3rd step：In the 100 ml there-necked flasks equipped with magnetic agitation, thermometer and magneton, the g of addition polymerization compound 4 and 0.55
G epoxychloropropane, after being warming up to 90 DEG C, 0.2 g DMAP are added in there-necked flask, control temperature is in 90-95 DEG C of reaction.
Reaction time 30, h was down to room temperature after terminating, and obtains settled solution and the sediment of white, is filtered, washed, obtained white
Drying can obtain fire retardant at 70 DEG C of color solid powder.
Embodiment 2：
The first step：A kind of synthetic method of reactive phosphorus flame retardant intermediate is the same as embodiment 1.
Second step：2.60 g intermediates are added into the 100 ml there-necked flasks equipped with reflux condensing tube, thermometer and magneton
With 1.7 g polyethylene glycol, add 25 ml DMSO and make solvent, after being warming up to 80 DEG C, add acid binding agent：0.52 g pyridines；Again
Add catalyst：0.1 g DMAP are added in there-necked flask, and control temperature is in 80-82 DEG C of reaction.After the h of reaction time 20 terminates
Room temperature is down to, obtains yellow solution and sediment, is filtered, washed, after drying, obtaining white solid powder.
3rd step：3rd step：In the 100 ml there-necked flasks equipped with magnetic agitation, thermometer and magneton, addition polymerization compound
4.31 g and 0.75 g epoxychloropropane, after being warming up to 90 DEG C, 0.1 g DMAP and 0.50 g pyridines are added to there-necked flask
In, control temperature is in 90-95 DEG C of reaction.Reaction time 30, h was down to room temperature after terminating, and obtained the heavy of settled solution and white
Starch, filtered, washed, fire retardant can be obtained by obtaining drying at 70 DEG C of white solid powder.
Embodiment 3：
The first step：A kind of synthetic method of reactive phosphorus flame retardant intermediate is the same as embodiment 1.
Second step：2.55 g intermediates are added into the 100 ml there-necked flasks equipped with reflux condensing tube, thermometer and magneton
With 1.8 g polyethylene glycol, add 30 ml DMSO and make solvent, after being warming up to 90 DEG C, add acid binding agent：0.71 g triethylamines；
Add catalyst：0.1 g DMAP are added in there-necked flask, and control temperature is in 90-95 DEG C of reaction.Reaction time 25, h terminated
After be down to room temperature, obtain yellow solution and sediment, filtered, washed, dry after, obtain white solid powder.
3rd step：In the 100 ml there-necked flasks equipped with magnetic agitation, thermometer and magneton, the g of addition polymerization compound 4 and 0.8 g
Epoxychloropropane, after being warming up to 90 DEG C, 0.1 g DMAP and 0.72 g triethylamines are added in there-necked flask, control temperature
In 90-95 DEG C of reaction.Reaction time 30, h was down to room temperature after terminating, and obtains settled solution and the sediment of white, is taken out
Filter, washing, fire retardant can be obtained by obtaining drying at 70 DEG C of white solid powder.
Claims (9)
1. a kind of reactive phosphorus flame retardant, it is characterised in that described flame retardant mechanism is as follows：
Wherein n is 5-7 positive integer.
2. a kind of reactive phosphorus flame retardant preparation method, it is characterised in that the preparation method of the fire retardant is that two steps are entered
OK, the first step：A kind of intermediate that PEPA and POCl3 are synthesized, it is a kind of to react generation under certain condition with polyethylene glycol
New polymer；Second step：With this polymer and epichlorohydrin reaction generation final product；Product is filtered, washs, and does
Dry processing, obtains white solid；
Said process is expressed as with chemical equation：
。
A kind of 3. preparation method of reactive phosphorus flame retardant according to claim 2, it is characterised in that in the first step,
Intermediate and polyethylene glycol molar ratio are 1:1 to 1:Between 2；Solvent for use is any one in acetonitrile, DMF and DMSO
Or the mixture of its arbitrary proportion.
4. the preparation method of a kind of reactive phosphorus flame retardant according to claim 2, it is characterised in that closed in the first step
During into polymer, reaction temperature is controlled at 60-120 DEG C；Reaction time is 20-40 h.
5. the preparation method of a kind of reactive phosphorus flame retardant according to claim 2, it is characterised in that in the first step
In, used catalyst AlCl3Or the mixture of any one or its arbitrary proportion in DMAP.
6. the preparation method of a kind of reactive phosphorus flame retardant according to claim 2, it is characterised in that in the first step
In, required solvent is washed as the mixed of any one in deionized water, ethanol, acetonitrile, acetone and toluene or its arbitrary proportion
Compound.
7. the preparation method of a kind of reactive phosphorus flame retardant according to claim 2, it is characterised in that in the first step
In, drying temperature is 60-80 DEG C.
8. the preparation method of a kind of reactive phosphorus flame retardant according to claim 2, it is characterised in that in second step
In, the rate of charge of polymer and epoxychloropropane is 1:1 to 1:Between 2；Solvent for use is in DMSO, acetonitrile, DMF and chloroform
Carried out under the mixture conditions of any one solvent or its arbitrary proportion.
9. the preparation method of a kind of reactive phosphorus flame retardant according to claim 2, it is characterised in that in second step
In, reaction temperature is 60-120 DEG C, and the reaction time is 20-40 h, and cleaning solvent is in deionized water, ethanol, acetone and toluene
Any one or its arbitrary proportion mixture, drying temperature is 60-80 DEG C.
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| CN201510878385.6A CN105482096B (en) | 2015-12-04 | 2015-12-04 | A kind of reactive phosphorus flame retardant and preparation method thereof |
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| CN201510878385.6A CN105482096B (en) | 2015-12-04 | 2015-12-04 | A kind of reactive phosphorus flame retardant and preparation method thereof |
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| CN109897224A (en) * | 2017-12-11 | 2019-06-18 | 广东广山新材料股份有限公司 | A kind of reactive flame retardant and its preparation method and application |
| CN109988335B (en) * | 2019-04-12 | 2021-03-23 | 深圳市通产丽星股份有限公司 | Ferrocenyl Schiff base and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0126491A2 (en) * | 1983-05-23 | 1984-11-28 | Great Lakes Chemical Corporation | Amine salts of phosphoric acid, a process for their preparation, their use and flame-retardant polymer compositions |
| CN103254466A (en) * | 2013-05-24 | 2013-08-21 | 华南理工大学 | Spiro-cage-structure-containing phosphate halogen-free flame retardant and preparation method thereof |
-
2015
- 2015-12-04 CN CN201510878385.6A patent/CN105482096B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0126491A2 (en) * | 1983-05-23 | 1984-11-28 | Great Lakes Chemical Corporation | Amine salts of phosphoric acid, a process for their preparation, their use and flame-retardant polymer compositions |
| CN103254466A (en) * | 2013-05-24 | 2013-08-21 | 华南理工大学 | Spiro-cage-structure-containing phosphate halogen-free flame retardant and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 4种PEPA衍生物阻燃剂的合成;房晓敏 等;《精细化工》;20070430;第24卷(第4期);401-403,412 * |
| Influence of molecular weight of PEG on thermal and fire protection properties of PEPA-containing polyether flame retardants with high water solubility;Yanchao Shi et al.;《Progress in Organic Coatings》;20150828;第90卷;390-398 * |
| 含季戊四醇磷酸酯阻燃剂的合成与表征;钟柳 等;《化学研究与应用》;20120131;第24卷(第1期);127-132 * |
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