CN102558225B - Aryl phosphatide high-efficiency flame retardant and synthesis method thereof - Google Patents
Aryl phosphatide high-efficiency flame retardant and synthesis method thereof Download PDFInfo
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- CN102558225B CN102558225B CN201110412562.3A CN201110412562A CN102558225B CN 102558225 B CN102558225 B CN 102558225B CN 201110412562 A CN201110412562 A CN 201110412562A CN 102558225 B CN102558225 B CN 102558225B
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Abstract
The invention relates to an aryl phosphatide flame retardant which has the advantages of high purity, no halogen, environmental protection and high molecular weight. The preparation method comprises the following steps: reacting derivatives of monohydric phenols, dihydric phenols and phenols containing two phenolic hydroxyl groups, and phosphorus oxychloride, which are used as raw materials, at 100-200 DEG C in the presence of catalyst and solvent under inert gas conditions, thereby obtaining a crude product; and carrying out acid washing, alkali washing, draining, and drying under reduced pressure to obtain the finished product. The aryl phosphatide flame retardant provided by the invention can be produced under simple equipment conditions and requirements, and the subsequent purification and separation are simple to implement and convenient to operate.
Description
Technical field
The present invention relates to a class aromatic base phosphate synthesis method, what it related to a simple building-up process and highly purified product obtains method; This product uses mainly as fire retardant.
Background technology
The history of phosphorus type flame retardant is of long standing and well established, and kind is numerous, of many uses, and prosperity does not wane.Nearly phosphorus type flame retardant development decades rapidly, fire retardant market is occupied very large proportion.Particularly in recent years, outside the shortcoming such as produce corrosive gases when burning due to halogenated flame retardant and the amount of being fuming is large, fire retardant material manufacturers of various countries is made to start with the careful application of Attitude Towards bromide fire retardant in superpolymer, thus non-halogen fire retardant is a dark horse, particularly inorganic oxide and phosphorus type flame retardant are subject to increasing attention.Along with the proposition of various engineering plastics flame-retardancy requirements in recent years, the research of phosphorus type flame retardant also becomes increasingly active.Because phosphorus type flame retardant major part is low-molecular-weight phosphoric acid ester and chlorinated phosphate ester, its molecular weight is low, volatility large, poor heat resistance, and flame retardant resistance is not enough, and thus its development trend improves thermostability and flame retarding efficiency.Phosphorus flame retardant-Halogen aromatic base the phosphoric acid ester of exploitation macromolecule improves the developing direction of phosphorus content and thermostability.The aromatic base phosphoric acid ester in molecule with two or more phosphorus atom has good thermostability and good flame retardant resistance (Hua Jinlong, Li Wenxia, the present situation of organophosphorous fire retardant and progress. dye and fuel, 2009, Vol.46., No.6, P38).It is reported, aromatic base phosphoric acid ester is used as fire retardant can provide excellent flame retardant properties, and thermal stability is good, and possesses good processing characteristics and can not reduce resin treatment characteristic, and therefore it is used as the added ingredients of various kinds of resin composition;
But in most industry is produced, obtain the product of aromatic base phosphoric acid ester, be wherein inevitable containing analogue or by product; How to improve the purity of product, yield, Cheng Liao enterprise faces an another difficult problem.
Summary of the invention
The invention provides a class and there is high purity, the aromatic base phosphide fire retardant of halogen-free environmental and synthetic method thereof.
Concrete summary of the invention is:
A kind of aromatic base phosphide flame-retardant compound, is characterized in that having following structure:
Wherein R
1, R
2, R
3and R
4can be identical or different; X is one and connects component, and m is any one integer in 0-4, and n is any one integer in 0-1.
Wherein, described R
1, R
2, R
3and R
4be selected from hydrogen, or following low alkyl group and derivative thereof: methyl, N-methyl, ethyl, propyl group, isopropyl ester, positive butyl ester, isobutyl ester, secondary butyl ester, the tertiary butyl, N-amyl group, isopentyl, tert-pentyl and neo-pentyl, preferable methyl or hydrogen.
Wherein, described X is selected from-CH
2-,-C (CH
3)
2-,-S-,-SO
2-, the one in-O-,-CO-or-N=N-.
Wherein, with monohydric phenol, dihydric phenol and the phenol derivatives containing two phenolic hydroxyl groups, phosphorus oxychloride for main raw material, at 100-200 DEG C, under the existence of catalyzer, solvent, inert gas conditions, obtained crude product, divides water through overpickling, alkali cleaning, drying under reduced pressure, can obtain finished product.
When material purity all reaches more than 95% purity, above-mentioned aromatic base phosphide flame-retardant compound can be produced.
A synthetic method for Aryl phosphatide high-efficiency flame retardant, comprises following 3 steps:
(1) monohydric phenol and phosphorus oxychloride are by a certain percentage, are generally mol ratio 2: 1-1.05, and under catalyzer, solvent existence, protection of inert gas condition, 100-190 DEG C of reaction 4-10 hour, obtains intermediate A;
(2) dihydric phenol or phenol derivatives and phosphorus oxychloride containing two hydroxyls by a certain percentage, are generally mol ratio 3: 1-1.05, exist, under protection of inert gas condition, 110-190 DEG C is reacted 4-10 hour, obtain intermediate B at catalyzer, solvent;
(3) intermediate A and intermediate B in molar ratio 3-3.5: 1, under catalyzer, solvent existence condition, 120-200 DEG C of reaction 4-10 hour, obtains crude product; Crude product adds solvent, divides water, drying under reduced pressure through overpickling, alkali cleaning, can obtain finished product; Finished product detects purity through high performance liquid chromatography and reaches 92-99%, and yield reaches 85-95%.
Wherein, synthesis used catalyst is selected from the one in Magnesium Chloride Anhydrous, Calcium Chloride Powder Anhydrous, Aluminum chloride anhydrous, Manganese chloride anhydrous, Zinc Chloride Anhydrous.
Wherein, described solvent is hexanaphthene, dimethylbenzene;
Wherein, this type of material, when synthesizing, relates to pyroreaction, and easily cause phenols be oxidized and cause yield to decline, side reaction increases, and reaction process adopts protection of inert gas, as nitrogen etc.;
Wherein, building-up reactions is thermopositive reaction, and reaction process adopts a kind of material dropping mode to control to react the speed of carrying out.
The described application of aromatic base phosphide flame-retardant compound in fire retardant.
Excellent results of the present invention: products obtained therefrom of the present invention is powder form, is convenient to packaging and transport; Production can complete at a simple appointed condition with under requiring, and subsequent purification is separated simple, is convenient to industrial production.
Embodiment
The synthetic method of one class Aryl phosphatide high-efficiency flame retardant, it is characterized in that, with monohydric phenol, dihydric phenol and the phenol derivatives containing two phenolic hydroxyl groups, phosphorus oxychloride for main raw material, mainly comprise 3 steps: (1) monohydric phenol and phosphorus oxychloride are by a certain percentage, be generally mol ratio 2: (1-1.05), under catalyzer, solvent existence, protection of inert gas condition, 100-190 DEG C of reaction 4-10 hour, obtains intermediate A; (2) dihydric phenol or containing the phenol derivatives of two hydroxyls and phosphorus oxychloride by a certain percentage, be generally mol ratio 3: (1-1.05), under catalyzer, solvent existence, protection of inert gas condition, 110-190 DEG C of reaction 4-10 hour, obtains intermediate B; (3) intermediate A and intermediate B are by a certain percentage, general mol ratio (3-3.5): 1, and under catalyzer, solvent existence condition, 120-200 DEG C of reaction 4-10 hour, obtains crude product; Crude product adds a certain amount of solvent, divides water, drying under reduced pressure through overpickling, alkali cleaning, can obtain finished product; Structural formula is:
Embodiment 1
R
1, R
2, R
3, R
4for hydrogen atom; N=0; During m=0, reaction is as follows:
Phenol 286.7g (3.05mol) is added successively at 1000ml there-necked flask, catalyzer Magnesium Chloride Anhydrous 3.84g, dimethylbenzene 50ml, (object: get rid of the air in reaction vessel after nitrogen replacement air 10min, prevent raw material oxidation by air), under condensing reflux condition, be warming up to 100-190 DEG C, start to drip phosphorus oxychloride 238.85g (1.556mol), time is 2 hours, after dripping, reaction 4-8 hour, react 2 hours under the above vacuum condition of-0.08MPa, obtain intermediate A 1;
Resorcinol 165g (1.5mol) is added successively in 500ml there-necked flask, catalyzer aluminum chloride 1.58g, dimethylbenzene 30ml, nitrogen replacement air is after 10 minutes, under condensing reflux condition, be warming up to 110-190 DEG C, start to drip phosphorus oxychloride 79.05g (0.515mol), the time is 1 hour, after dripping, reaction 4-8 lab scale, reacts 2 hours under the above vacuum condition of-0.08MPa, obtains intermediate B 1;
In 1000ml there-necked flask, add disposable for intermediate B 1, add dimethylbenzene 100ml, catalyzer magnesium chloride 1.93g, nitrogen replacement air is after 10 minutes, under condensing reflux condition, be warming up to 120-200 DEG C to start to drip intermediate A 1, the time is 2 hours, is added dropwise to complete rear reaction 4-8 lab scale, react 2 hours under the above vacuum condition of-0.08MPa, obtain crude product;
Be cooled to room temperature, proceed in 2000ml there-necked flask, add 500ml dimethylbenzene, 150ml10% hydrochloric acid stirs 30min, proceed to separating funnel, after leaving standstill 30 minutes points of water, collected organic layer is to 2000ml there-necked flask, adds 6% sodium hydroxide 350ml, and 70 DEG C are stirred 30 minutes, proceed to separating funnel, divide water, collected organic layer after leaving standstill 30min, underpressure distillation obtains finished product 505.2g, through liquid chromatographic detection purity 98.86%, yield 93.35%
Embodiment 2
R
1, R
2for-CH
3; R
3, R
4for hydrogen atom; N=0; During m=0, reaction is as follows:
2,6-xylenol 372.1g (3.05mol) is added successively, catalyzer Magnesium Chloride Anhydrous 3.84g at 1000ml there-necked flask, dimethylbenzene 50ml, after nitrogen replacement air 10min, under condensing reflux condition, be warming up to 100-190 DEG C, start to drip phosphorus oxychloride 238.85g (1.556mol), time is 2 hours, after dripping, reaction 4-8 hour, react 2 hours under the above vacuum condition of-0.08MPa, obtain intermediate A 2;
Resorcinol 165g (1.5mol) is added successively in 500ml there-necked flask, catalyzer aluminum chloride 1.58g, dimethylbenzene 30ml, nitrogen replacement air is after 10 minutes, under condensing reflux condition, be warming up to 110-190 DEG C, start to drip phosphorus oxychloride 79.05g (0.515mol), the time is 1 hour, after dripping, reaction 4-8 lab scale, reacts 2 hours under the above vacuum of-0.08MPa, obtains intermediate B 1;
In 1000ml there-necked flask, add disposable for intermediate B 1, add dimethylbenzene 100ml, catalyzer magnesium chloride 1.93g, under condensing reflux condition, is warming up to 120-200 DEG C and starts to drip intermediate A 2, time is 2 hours, be added dropwise to complete rear reaction 4-8 lab scale, react 2 hours under the above vacuum condition of-0.08MPa, obtain crude product;
Be cooled to room temperature, proceed in 2000ml there-necked flask, add 500ml dimethylbenzene, 150ml10% hydrochloric acid stirs 30min, proceed to separating funnel, leaving standstill after 30 minutes divides water collected organic layer to 2000ml there-necked flask, add 6% sodium hydroxide 350ml, 70 DEG C are stirred 30 minutes, proceed to separating funnel, water collected organic layer is divided after leaving standstill 30min, underpressure distillation obtains finished product 553.9g, through liquid chromatographic detection purity 98.65%, and yield 94.21%.
Embodiment 3
R
1, R
2, for-CH
3; R
3, R
4for hydrogen atom; X is-C (CH
3)
2-; N=1; During m=0, reaction is as follows:
2,6-xylenol 372.1g (3.05mol) is added successively, catalyzer Magnesium Chloride Anhydrous 3.84g at 1000ml there-necked flask, dimethylbenzene 50ml, after nitrogen replacement air 10min, under condensing reflux condition, be warming up to 100-190 DEG C, start to drip phosphorus oxychloride 238.85g (1.556mol), time is 2 hours, after dripping, reaction 4-8 hour, react 2 hours under the above vacuum condition of-0.08MPa, obtain intermediate A 1;
Dihydroxyphenyl propane 342g (1.5mol) is added successively in 1000ml there-necked flask, catalyzer aluminum chloride 1.58g, dimethylbenzene 30ml, nitrogen replacement air is after 10 minutes, under condensing reflux condition, be warming up to 140-190 DEG C, start to drip phosphorus oxychloride 79.05g (0.515mol), the time is 1 hour, after dripping, reaction 4-8 lab scale, reacts 2 hours under the above vacuum condition of-0.08MPa, obtains intermediate B 1;
In 1000ml there-necked flask, add disposable for intermediate B 1, add dimethylbenzene 100ml, catalyzer magnesium chloride 1.93g, under condensing reflux condition, is warming up to 120-200 DEG C and starts to drip intermediate A 1, time is 2 hours, be added dropwise to complete rear reaction 4-8 lab scale, react 2 hours under the above vacuum condition of-0.08MPa, obtain crude product;
Be cooled to room temperature, proceed in 2000ml there-necked flask, add 500ml dimethylbenzene, 150ml10% hydrochloric acid stirs 30min, proceed to separating funnel, leaving standstill after 30 minutes divides water collected organic layer to 2000ml there-necked flask, add 6% sodium hydroxide 350ml, 70 DEG C are stirred 30 minutes, proceed to separating funnel, water collected organic layer is divided after leaving standstill 30min, underpressure distillation obtains finished product 678.1g, and liquid chromatographic detection purity is 97.76%, and yield is 93.11%.
Embodiment 1 ~ 3 finished product structure and hydrogen nuclear magnetic resonance spectrum analysis:
The structural formula of embodiment 1 finished product:
H NMR characterization result is: chemical shift δ=6.21 (H1,3), δ=6.27-6.30 (H2,6), δ=6.75 (H3,12), δ=6.81-6.93 (H4,12), δ=7.08-7.13 (H5,12).
The structural formula of embodiment 2 finished product:
H NMR characterization result is: chemical shift δ=2.33 (H1,36), δ=6.19 (H2,3), δ=6.27 ~ 6.36 (H3,6), δ=6.55-6.65 (H4,6), δ=6.72 (H5,12), δ=6.90-6.98 (H6,3).
The structural formula of embodiment 3 finished product
H NMR characterization result is: chemical shift δ=1.77 (H1,18), δ=2.35 (H2,36), δ=6.53 ~ 6.59 (H3,6), δ=6.65-6.73 (H4,24), δ=7.01-7.08 (H5,12).
Flammability test:
The embodiment of the present invention 1 gained, test batten is made according to mass ratio interpolation 20% this flame-retardant compound and ABS resin (acrylonitrile-butadiene-styrene copolymer) 80%, survey its oxygen index with oxygen index instrument and reach 29, surveying its burning rank with vertical combustion instrument is V-0 rank.
The embodiment of the present invention 2 obtained flame-retardant compound, adds this flame-retardant compound 20% according to mass ratio, makes test batten with ABS resin 80%, surveys its oxygen index reach 31 with oxygen index instrument, and surveying its burning rank with vertical combustion instrument is V-0 rank.
The embodiment of the present invention 3 obtained flame-retardant compound, adds this flame-retardant compound 20% according to mass ratio and make test batten together with the ABS resin of 80%, survey its oxygen index reach 35 with oxygen index instrument, and surveying its burning rank with vertical combustion instrument is V-0 rank.
Claims (1)
1. an aromatic base phosphide flame-retardant compound, is characterized in that, has following structure:
Described aromatic base phosphide flame-retardant compound adopts following methods synthesis: add 2,6-xylenol 372.1g successively at 1000ml there-necked flask, catalyzer Magnesium Chloride Anhydrous 3.84g, dimethylbenzene 50ml, after nitrogen replacement air 10min, under condensing reflux condition, be warming up to 100-190 DEG C, start to drip phosphorus oxychloride 238.85g, time is 2 hours, after dripping, reaction 4-8 hour, react 2 hours under the above vacuum condition of-0.08MPa, obtain intermediate A 1;
Dihydroxyphenyl propane 342g is added successively in 1000ml there-necked flask, catalyzer aluminum chloride 1.58g, dimethylbenzene 30ml, nitrogen replacement air is after 10 minutes, under condensing reflux condition, be warming up to 140-190 DEG C, start to drip phosphorus oxychloride 79.05g, the time is 1 hour, after dripping, under the above vacuum condition of reaction 4-8 hour ,-0.08MPa, reaction 2 hours, obtains intermediate B 1;
In 1000ml there-necked flask, add disposable for intermediate B 1, add dimethylbenzene 100ml, catalyzer magnesium chloride 1.93g, under condensing reflux condition, is warming up to 120-200 DEG C and starts to drip intermediate A 1, time is 2 hours, react 2 hours under being added dropwise to complete the above vacuum condition of rear reaction 4-8 hour ,-0.08MPa, obtain crude product;
Be cooled to room temperature, proceed in 2000ml there-necked flask, add 500ml dimethylbenzene, 150ml 10% hydrochloric acid stirs 30min, proceed to separating funnel, leave standstill point water collected organic layer after 30 minutes and, to 2000ml there-necked flask, add 6% sodium hydroxide 350ml, 70 DEG C are stirred 30 minutes, proceed to separating funnel, divide water collected organic layer after leaving standstill 30min, underpressure distillation obtains finished product 678.1g, liquid chromatographic detection purity is 97.76%, and yield is 93.11%.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1110976A (en) * | 1994-03-14 | 1995-11-01 | 东丽株式会社 | Flame-retardant polymer composition and shaped article thereof |
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| CN1110976A (en) * | 1994-03-14 | 1995-11-01 | 东丽株式会社 | Flame-retardant polymer composition and shaped article thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Flame retardant epoxy polymers based on all phosphorus-containing components";Ru-Jong Jeng et al.;《European Polymer Journal》;20021231;第38卷;第683-693页 * |
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