CN107674240A - A kind of preparation method of compound phosphonium flame retardant - Google Patents
A kind of preparation method of compound phosphonium flame retardant Download PDFInfo
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- CN107674240A CN107674240A CN201710928928.XA CN201710928928A CN107674240A CN 107674240 A CN107674240 A CN 107674240A CN 201710928928 A CN201710928928 A CN 201710928928A CN 107674240 A CN107674240 A CN 107674240A
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- flame retardant
- spiro
- phosphonium flame
- preparation
- diacid chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
Abstract
The present invention relates to a kind of preparation method of compound phosphonium flame retardant, belong to technical field of flame retardant.The present invention takes pentaerythrite, POCl3 is fitted into heating stirring in four-hole boiling flask, filter residue is filtered to obtain after being cooled to room temperature, after washing filter residue with absolute ethyl alcohol filter residue is washed with dichloromethane, it is transferred to after filter residue is washed with deionized again in drying box, dry spiro-phosphate diacid chloride, take spiro-phosphate diacid chloride, mixed with deionized water and be fitted into water bath with thermostatic control in four-hole boiling flask, sodium sulfanilate solution is added dropwise again, amino silicone, heated after being added dropwise, continue insulated and stirred, it is placed in after being cooled to room temperature on Rotary Evaporators, it is evaporated to dryness under reduced pressure, it is placed in drying box and dries after being washed with deionized again, obtain compound phosphonium flame retardant, volatility of the present invention is small, low toxicity, stability is good, have broad application prospects, it is worth of widely use.
Description
Technical field
The present invention relates to a kind of preparation method of compound phosphonium flame retardant, belong to technical field of flame retardant.
Background technology
Fire retardant is a kind of to improve the auxiliary agent of high polymer material fire resistance, and material can be prevented to be ignited or support
Flame processed is further propagated.At present, fire retardant is generally used for synthesizing in high polymer material or natural macromolecular material, such as：
Plastics, rubber, timber, fiber, coating etc..The material of addition fire retardant, which has, to be not easy to ignite, and it is excellent can to suppress flame propagation etc.
Point, so as to reduce the harm that fire is brought, reduce the harm of the economic loss caused by fire and life security.Fire-retardant work
One of elementary tactics for disaster reduction and prevention, the benefit brought to society can not be underestimated.Currently, severe fire hazard situation and tight
The fire-retardant and environmental regulation of lattice, even more promote the further development of fire-retardant science.
With the rise of the industries such as oil, chemical industry, high polymer material is also increasingly valued by people and then obtained fluffy
Vigorous development.Especially after the 1930s, three big synthetic materials, as plastics, fiber and rubber gradually instead of timber,
Some traditional materials such as steel and bafta, and progressively it is applied to each department in people's daily life.High polymer material
There is light weight, heat-resist, high mechanical strength and easily mass produce, be widely used in space flight, electronics, partly lead
The fields such as body, building and automobile.
But high polymer material is inflammable and flammable, the mankind are made to be encountered by the fire threat of sternness.At present, fire retardant has been
Through as one of most important auxiliary agent of high polymer material.For dosage, it is only second to plasticizer and occupy second.In recent years
Come, research and development, production and the application of fire retardant and fire proofing have obtained quick development.With the U.S., Europe, Japan and other
The Asian-Pacific area（It is mainly Chinese）For this four big fire-retardant market, 2005~2008 years, the average annual growth rate of the total dosage of fire retardant
Rate is 4.1%, 2008~2014, and the annual average rate of increase of the total dosage of fire retardant is up to 5% or so.In the world, fire retardant
Demand it is still in rising trend, according to Freedonia research report, global retardant requirement with annual 4.8% speed increase
It is long, reach 2,300,000 tons within 2010.Wherein, the demand average annual growth rate of EU market fire retardant is about 3%, and 2010 are about 520,000
Ton.North America market average annual growth rate about 3.4%, reach 740,000 tons within 2010, and Asia-Pacific market average annual growth rate is about 7%, is reached within 2010 years
860000 tons, turn into global maximum fire retardant consumption market.This trend uses more and more mainly due to developing country
Fire retardant caused by because these countries are just progressively using stricter flammability standard and to plastics demand itself
The increase of amount.In addition, the fire retardant market in the U.S. and West Europe also can further expand.Freedonia represents that the Asian-Pacific area turns into
The maximum consumption market of fire retardant, and fastest-rising area in world wide, and increase of the China to retardant requirement amount
Major part therein will be accounted for.Meanwhile other countries and area such as TaiWan, China and Korea S will also show to be higher than average level
Growth rate, the market motive force of the Asian-Pacific area mostly come to implementing high fire-retardance standard national outlet manufactured goods.
At present, it is about 16300 to be engaged in fire retardant and fire proofing production of articles, the enterprise of trade in China.Wherein, it is raw
Chan Lei enterprises are about 11770, account for the 72% of enterprise's total quantity.Chinese fire proofing passes through the hair of nearly 30 years with product industry
Exhibition, product category very abundant, including flame-proof PVC tubing, flame-retardant plywood, flame retardant type floor, polyethylene anti-flaming pipe, fire-retardant aluminium
Plastic clad plate, flame retardant type wallpaper, Fire-retarded carpet, flame retardant type medium density fibre board (MDF), polyvinyl chloride insulation flame-retardant electric wire and cable etc. produce
Product.With the continuous enhancing of people's environmental consciousness and continually strengthening for fire retardant industry laws, the exploitation of fire retardant is also more next
More develop towards efficient, environmentally friendly, less toxic, multi-functional direction, some also shows some new dynamics, for example develops big point
The fire retardant of son amount.Macromolecular technology is newly risen in recent years, is still study hotspot at present.Organophosphorous fire retardant typically has
The advantages that low toxicity, few cigarette, Halogen, meet the development trend of fire retardant, there is good development prospect.
The content of the invention
The technical problems to be solved by the invention：Have that volatility is big, production process is malicious for presently commercially available fire retardant
A kind of the problem of property is larger, there is provided preparation method of compound phosphonium flame retardant.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of preparation method of compound phosphonium flame retardant, it is characterised in that concretely comprise the following steps：
（1）Pentaerythrite is mixed with POCl3 and is fitted into four-hole boiling flask, is heated to 70 ~ 80 DEG C of 1 ~ 2h of stirring reaction, is cooled down
Filtering after to room temperature, alcohol is washed, dichloromethane wash, the washing of 0 ~ 20 DEG C of deionized water, drying, obtain spiro-phosphate diacid chloride；
（2）Spiro-phosphate diacid chloride is mixed with deionized water and is fitted into four-hole boiling flask, under 80 ~ 90 DEG C of waters bath with thermostatic control, is stirred
2 ~ 3h of reaction is mixed, obtains hydrolyzate；
（3）Sodium sulfanilate solution and amino silicone are added dropwise into hydrolyzate, 60 ~ 70 DEG C are heated to after being added dropwise,
Insulated and stirred reacts 3 ~ 5h, washs drying with 0 ~ 20 DEG C of deionized water after being evaporated to dryness under reduced pressure, obtains compound phosphonium flame retardant.
Step（1）The mol ratio of the pentaerythrite and POCl3 is 1：4.
Step（2）The deionized water dosage is the 10 ~ 20% of spiro-phosphate diacid chloride quality.
Step（3）The mol ratio of the sodium sulfanilate and spiro-phosphate diacid chloride is 1：1, drop rate be 1 ~
2mL/min。
Step（3）The mol ratio of the amino silicone and spiro-phosphate diacid chloride is 1：1, drop rate is 1 ~ 2mL/
min。
Beneficial effects of the present invention：
（1）For the present invention by introducing silicon, nitrogen, element sulphur in phosphonium flame retardant, synthesis is a kind of simultaneously new containing 4 kinds of elements
Fire retardant, it can generate a kind of polyphosphoric acid film in burning using P elements and be coated on material surface, play a part of heat-insulated anoxybiotic,
Element silicon can generate fine and close solid Si-C layers when heated, effectively prevent the heated molten drop that produces of material so as to trigger second-time burning,
Element sulphur can change the decomposition course of polymer, play condensed phase fire retardation, and nitrogen decomposes heat absorption and generation noninflammability gas
Body plays fire retardation to dilute combustible, while preferably fire-retardant synergy can be produced with P elements；
（2）Tetra- kinds of element combinations of Si, P, S, N together, can be played good cooperative flame retardant effect by the present invention, at the same by this four
The fire retardant that kind element compounds to obtain also has good compatibility with high polymer material, and is solid product, and volatility is small, low
Poison, stability are good, have broad application prospects, are worth of widely use.
Embodiment
0.5 ~ 1.0mol pentaerythrites are taken, 2 ~ 4mol POCl3s are fitted into four-hole boiling flask, are heated to 70 ~ 80 DEG C, and with
300 ~ 400r/min stirs 1 ~ 2h, and filter residue is filtered to obtain after being cooled to room temperature, and dichloromethane is used after washing filter residue 2 ~ 3 times with absolute ethyl alcohol
Alkane washing filter residue 2 ~ 3 times, then be transferred to after wash filter residue 2 ~ 3 times with 0 ~ 20 DEG C of deionized water in drying box, the drying at 70 ~ 80 DEG C
3 ~ 5h, spiro-phosphate diacid chloride is obtained, take 0.5 ~ 1.0mol spiro-phosphate diacid chlorides, loading is mixed with 15 ~ 30g deionized waters
In four-hole boiling flask, under 80 ~ 90 DEG C of waters bath with thermostatic control, with 300 ~ 400r/min stir 2 ~ 3h, then with 1 ~ 2mL/min be added dropwise 100 ~
200mL molar concentrations are 5mol/L sodium sulfanilate solution, and 0.5 ~ 1.0mol amino silica is added dropwise with 1 ~ 2mL/min
Alkane, 60 ~ 70 DEG C are heated to after being added dropwise, continue 3 ~ 5h of insulated and stirred, be placed in after being cooled to room temperature on Rotary Evaporators, depressurized
It is evaporated to dryness, then is placed in after washing 2 ~ 3 times with 0 ~ 20 DEG C of deionized water in drying box, 2 ~ 4h is dried at 80 ~ 100 DEG C, must be answered
Mould assembly phosphonium flame retardant.
Example 1
0.5mol pentaerythrites are taken, 2mol POCl3s are fitted into four-hole boiling flask, are heated to 70 DEG C, and stir with 300r/min
1h, filter residue is filtered to obtain after being cooled to room temperature, filter residue is washed 2 times with dichloromethane after washing filter residue 2 times with absolute ethyl alcohol, then with 0
It is transferred to after DEG C deionized water washing filter residue 2 times in drying box, 3h is dried at 70 DEG C, spiro-phosphate diacid chloride is obtained, takes
0.5mol spiro-phosphate diacid chlorides, mix with 15g deionized waters and are fitted into four-hole boiling flask, under 80 DEG C of waters bath with thermostatic control, with
300r/min stirs 2h, then sodium sulfanilate solution of the 100mL molar concentrations as 5mol/L is added dropwise using 1mL/min, with
0.5mol amino silicones are added dropwise in 1mL/min, and 60 DEG C are heated to after being added dropwise, and continue insulated and stirred 3h, after being cooled to room temperature
It is placed on Rotary Evaporators, is evaporated to dryness under reduced pressure, then be placed in after washing 2 times with 0 DEG C of deionized water in drying box, is done at 80 DEG C
Dry 2h, obtain compound phosphonium flame retardant.
Example 2
0.8mol pentaerythrites are taken, 3mol POCl3s are fitted into four-hole boiling flask, are heated to 75 DEG C, and stir with 350r/min
1h, filter residue is filtered to obtain after being cooled to room temperature, filter residue is washed 2 times with dichloromethane after washing filter residue 2 times with absolute ethyl alcohol, then with 10
It is transferred to after DEG C deionized water washing filter residue 2 times in drying box, 4h is dried at 75 DEG C, spiro-phosphate diacid chloride is obtained, takes
0.8mol spiro-phosphate diacid chlorides, mix with 20g deionized waters and are fitted into four-hole boiling flask, under 85 DEG C of waters bath with thermostatic control, with
350r/min stirs 2h, then sodium sulfanilate solution of the 150mL molar concentrations as 5mol/L is added dropwise using 1mL/min, with
0.8mol amino silicones are added dropwise in 1mL/min, and 65 DEG C are heated to after being added dropwise, and continue insulated and stirred 4h, after being cooled to room temperature
It is placed on Rotary Evaporators, is evaporated to dryness under reduced pressure, then be placed in after washing 2 times with 10 DEG C of deionized waters in drying box, at 80 DEG C
3h is dried, obtains compound phosphonium flame retardant.
Example 3
1.0mol pentaerythrites are taken, 4mol POCl3s are fitted into four-hole boiling flask, are heated to 80 DEG C, and stir with 400r/min
2h, filter residue is filtered to obtain after being cooled to room temperature, filter residue is washed 3 times with dichloromethane after washing filter residue 3 times with absolute ethyl alcohol, then with 20
It is transferred to after DEG C deionized water washing filter residue 3 times in drying box, 5h is dried at 80 DEG C, spiro-phosphate diacid chloride is obtained, takes
1.0mol spiro-phosphate diacid chlorides, mix with 30g deionized waters and are fitted into four-hole boiling flask, under 90 DEG C of waters bath with thermostatic control, with
400r/min stirs 3h, then sodium sulfanilate solution of the 200mL molar concentrations as 5mol/L is added dropwise using 2mL/min, with
1.0mol amino silicones are added dropwise in 2mL/min, and 70 DEG C are heated to after being added dropwise, and continue insulated and stirred 5h, after being cooled to room temperature
It is placed on Rotary Evaporators, is evaporated to dryness under reduced pressure, then be placed in after washing 3 times with 20 DEG C of deionized waters in drying box, at 100 DEG C
4h is dried, obtains compound phosphonium flame retardant.
Reference examples：The fire retardant of Hefei company production.
The fire retardant of example and reference examples is detected, specific detection is as follows：
Vertical burn test：Vertical burn test method refers under certain experimental condition, to being disposed vertically and with certain
The method that the batten of size is detected by flame combustion behavior.Testing vertical flammability herein is to use CZF-3 type water
Flat vertical combustion analyzer, is detected with reference to GB/T2408-2008 standards, and batten size is：129mm×12.8mm×
3.1mm, one group of ten batten, put before batten test in the environment of temperature is (23 ± 2) degree Celsius, relative humidity is 50 ± 5%
Put 48h.
Limited oxygen index（LOI）Test：Limited oxygen index（LOI）Refer under prescribed conditions, batten mixes in oxygen and nitrogen
The minimum oxygen concentration required for its burning can be supported in gas, it is the finger for evaluating high polymer material burning behavior
Number, represent the complexity of material relative combustion.This detection method operation it is very easy, and the reappearance of data also compared with
It is good, therefore application is more universal.It is generally acknowledged that limited oxygen index belongs to combustible material less than 22%, belong to flammable between 22~27%
Material, and then it is regarded as nonflammable material more than 27%.Carried out in this experiment oxygen index (OI) test bars sizes be 130mm ×
6.6mm × 3.1mm, one group of 15 batten will be by batten in 23 ± 2 DEG C of temperature, wet according to GB/T2406-2008 standards before test
40h is placed under 50 ± 5% environment of degree.
Specific testing result such as table 1.
Table 1
| Detection project | Example 1 | Example 2 | Example 3 | Reference examples |
| UL94 | V-1 | V-2 | V-2 | Nothing |
| LOI% | 29.2 | 29.9 | 30.8 | 27.3 |
As shown in Table 1, the fire retardant that prepared by the present invention has certain fire retardation, has preferable flame retardant effect, Ke Yigai
The fire resistance of kind material, there is certain effect for reducing fire risk.
Claims (5)
1. a kind of preparation method of compound phosphonium flame retardant, it is characterised in that concretely comprise the following steps：
（1）Pentaerythrite is mixed with POCl3 and is fitted into four-hole boiling flask, is heated to 70 ~ 80 DEG C of 1 ~ 2h of stirring reaction, is cooled down
Filtering after to room temperature, alcohol is washed, dichloromethane wash, the washing of 0 ~ 20 DEG C of deionized water, drying, obtain spiro-phosphate diacid chloride；
（2）Spiro-phosphate diacid chloride is mixed with deionized water and is fitted into four-hole boiling flask, under 80 ~ 90 DEG C of waters bath with thermostatic control, is stirred
2 ~ 3h of reaction is mixed, obtains hydrolyzate；
（3）Sodium sulfanilate solution and amino silicone are added dropwise into hydrolyzate, 60 ~ 70 DEG C are heated to after being added dropwise,
Insulated and stirred reacts 3 ~ 5h, washs drying with 0 ~ 20 DEG C of deionized water after being evaporated to dryness under reduced pressure, obtains compound phosphonium flame retardant.
A kind of 2. preparation method of compound phosphonium flame retardant as claimed in claim 1, it is characterised in that step（1）It is described
The mol ratio of pentaerythrite and POCl3 is 1：4.
A kind of 3. preparation method of compound phosphonium flame retardant as claimed in claim 1, it is characterised in that step（2）It is described
Deionized water dosage is the 10 ~ 20% of spiro-phosphate diacid chloride quality.
A kind of 4. preparation method of compound phosphonium flame retardant as claimed in claim 1, it is characterised in that step（3）It is described
The mol ratio of sodium sulfanilate and spiro-phosphate diacid chloride is 1：1, drop rate is 1 ~ 2mL/min.
A kind of 5. preparation method of compound phosphonium flame retardant as claimed in claim 1, it is characterised in that step（3）It is described
The mol ratio of amino silicone and spiro-phosphate diacid chloride is 1：1, drop rate is 1 ~ 2mL/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710928928.XA CN107674240A (en) | 2017-10-09 | 2017-10-09 | A kind of preparation method of compound phosphonium flame retardant |
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| CN201710928928.XA CN107674240A (en) | 2017-10-09 | 2017-10-09 | A kind of preparation method of compound phosphonium flame retardant |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114950272A (en) * | 2022-06-06 | 2022-08-30 | 宿州汉泰化工有限公司 | Automatic dropping equipment for phosphorus oxychloride |
| CN116589777A (en) * | 2023-06-16 | 2023-08-15 | 高尚蓉 | Halogen-free flame-retardant crosslinked polyethylene cable material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671568A (en) * | 2009-09-06 | 2010-03-17 | 青岛科技大学 | Phosphorus-contained organic silicon resin fire retardant and preparation method thereof |
| CN103073725A (en) * | 2013-02-08 | 2013-05-01 | 苏州大学 | Swelling flame retardant and preparation method thereof |
| CN103073889A (en) * | 2013-02-08 | 2013-05-01 | 苏州大学 | Flame retardant thermosetting resin and preparation method thereof |
| CN106279884A (en) * | 2016-08-12 | 2017-01-04 | 杨秀枝 | A kind of manufacture method of protecting film PE master batch |
-
2017
- 2017-10-09 CN CN201710928928.XA patent/CN107674240A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671568A (en) * | 2009-09-06 | 2010-03-17 | 青岛科技大学 | Phosphorus-contained organic silicon resin fire retardant and preparation method thereof |
| CN103073725A (en) * | 2013-02-08 | 2013-05-01 | 苏州大学 | Swelling flame retardant and preparation method thereof |
| CN103073889A (en) * | 2013-02-08 | 2013-05-01 | 苏州大学 | Flame retardant thermosetting resin and preparation method thereof |
| CN106279884A (en) * | 2016-08-12 | 2017-01-04 | 杨秀枝 | A kind of manufacture method of protecting film PE master batch |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114950272A (en) * | 2022-06-06 | 2022-08-30 | 宿州汉泰化工有限公司 | Automatic dropping equipment for phosphorus oxychloride |
| CN116589777A (en) * | 2023-06-16 | 2023-08-15 | 高尚蓉 | Halogen-free flame-retardant crosslinked polyethylene cable material and preparation method thereof |
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Effective date of registration: 20180418 Address after: 213000 Room 102, unit 2, Taoyuan 2 village, Tianning District, Changzhou, Jiangsu Applicant after: Wang Min Address before: 213102 room 1106, Guanghua Street, Zhong Lou District, Changzhou, Jiangsu, China, 20 Applicant before: Changzhou Jian Xuan Textile Co., Ltd. |
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