CN101161659A - Method for preparing tetraphenyl diphenol A diphosphonate - Google Patents

Method for preparing tetraphenyl diphenol A diphosphonate Download PDF

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CN101161659A
CN101161659A CNA2007101684747A CN200710168474A CN101161659A CN 101161659 A CN101161659 A CN 101161659A CN A2007101684747 A CNA2007101684747 A CN A2007101684747A CN 200710168474 A CN200710168474 A CN 200710168474A CN 101161659 A CN101161659 A CN 101161659A
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phenol
dihydroxyphenyl propane
hydrogenchloride
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高山俊
侯占伟
沈春晖
郭金明
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Wuhan University of Technology WUT
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Abstract

The present invention relates to a preparation method to produce tetraphenyl-[diphenyl phosphate]- diphosphate, which is characterized in that the following procedures are involved: firstly the condensation is carried out, in which a mixture of diphenyl phosphate, POCl3 and AlCl3 and PdCl2 is added into a four-neck flask provided inside with the condensation device, then heated under agitation to circumfluence at 105 DEG C to 110DEG C, until no hydrogen chloride is released, and then the reaction is ended, secondly the distillation device is substituted, distillation is carried out under nitrogen, and then the unreacted phosphorus oxychloride is collected, thirdly the end-capping reaction is performed, in which the distillation device is removed, and a polymerization device is substituted, then phenol is added for 3-4 times to the reactant as above under 80 DEG C to 85 DEG C, the temperature is raised to 115 DEG C to 120 DEG C after hour an hour, and the reaction ends when no hydrogen chloride is produced obviously, fourthly decompressed distillation is performed to eliminate the excessive phenol and the produced hydrogen chloride to obtain the crude ester and, fifthly the crude ester is filtrated to obtain the tetraphenyl-[diphenyl phosphate]- diphosphate. The preparation method has simple technics and low cost. When burnt, the product obtained through the method is characterized in low fume, low toxicity but high flame resistance and high stability.

Description

The preparation method of tetraphenyl diphenol A diphosphonate
Technical field
The present invention relates to a kind of halogen-free refractory fire retardant preparation method of tetraphenyl diphenol A diphosphonate (BDP) one by one.
Background technology
Fire retardant (flame retardant) is in order to improve the material of material non-flame properties, promptly stop material to be ignited and suppress the auxiliary agent of propagation of flame, fire retardant is mainly used in the fire-retardant of natural and synthesized polymer material (comprising plastics, rubber, fiber, timber, paper, coating etc.).
The organic halogen of present fire retardant commonly used system (bromine system and chlorine system), organophosphorus are and are inorganic is three major types.The market scale of bromide fire retardant and Application Areas rank first of each based flame retardant for a long time, its excellent cost performance be other fire retardants can't be equal to.But generate more cigarette, corrosive gases and some toxic products when halogenated flame retardant when burning or hot tearing, so the non-halogen of product is people's ultimate aim, be that product will not abandoned by people owing to reaching environment protection requirement thereby can cause a part of halogen.Because the environmental hazard that bromide fire retardant may cause in production and use, European Union has announced to stop using bromide fire retardant since on July 1st, 2006 in electronic product.In addition because corrodibility, Toxic be seldom in the thermo-cracking of phosphorus flame retardant degradation production and fire-retardant superpolymer thereof and the products of combustion, a lot of kinds also have plasticising, effect such as thermally-stabilised simultaneously, the over-all properties that improves macromolecular material there is crucial effect, therefore, organophosphorous fire retardant will become one of research focus of fire-retardant science.The whole world three tame topmost bromide fire retardant production company also begins to turn to the exploitation of Halogen phosphorus flame retardant as Albemarle Corporation, big lake company and Dead Sea bromide company, and existing supply of commodities, and the domestic development that still is in does not have industrialization product.At present mainly from company's imports such as the refined treasured of the U.S., big by eight, the U.S. Aksu of Japan.
In the current macromolecular material fire retardant, metal oxide and oxyhydroxide are inexpensive nontoxic, but bad with the consistency of material, can reduce the thermomechanical property of material; Halogenated flame retardant (particularly brominated flame-retardant) is though there is the good flame effect, but the toxic smoke and the corrosive gases that produce during burning pollute the environment, and phosphorus flame retardant particularly the phosphorus series non-halogen fire retardant do not have above shortcoming, and good flame retardation effect is so enjoy investigator's favor.Phosphoric acid ester is existing historical for many years as flame retardant of polymer, and general phosphoric acid ester fire retardant has following shortcoming: relative molecular mass is little, is prone to the bloom phenomenon, heat decomposition temperature is lower, poor heat resistance, and the processing temperature of engineering plastics is generally very high, poor with the engineering plastics consistency in addition.
Tetraphenyl diphenol A diphosphonate or claim dihydroxyphenyl propane two (diphenyl phosphoester), molecular formula: C 39H 34O 4P 2, be called for short BDP, be a kind of novel additive type fire retardant, domestic still do not have a volume production, and quality reaches import like product level, can be used in multiple thermoplasticity, elastomerics, the thermoset copolymer material, as: HIPS, PBT, PP, PE, PA, PS, ABS, PC, PU or the like also is applicable to tackiness agent, coating etc.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of preparation technology tetraphenyl diphenol A diphosphonate simple, with low cost, low cigarette, low toxicity, flame retarding efficiency height, stability height when the product that this method obtains burns.
To achieve these goals, technical scheme of the present invention is: the preparation method of tetraphenyl diphenol A diphosphonate is characterized in that it comprises the steps:
1) polycondensation: to middle adding dihydroxyphenyl propane, the POCl of the four-hole boiling flask that poly-unit is housed 3, AlCl 3And PdCl 2Mixture, stir down said mixture to be heated to and reflux 105～110 ℃ stopped reaction when no hydrogenchloride is emitted; Poly-unit is thermometer, agitator, prolong and HCl absorption unit;
Wherein, dihydroxyphenyl propane and POCl 3Mass ratio be 1: 3.0-4.5, AlCl 3And PdCl 2Quality be dihydroxyphenyl propane quality 2～2.5%, AlCl 3With PdCl 2Mass ratio is 2: 1;
2) pull down poly-unit then, change water distilling apparatus, under the condition of logical nitrogen, distill, reclaim unreacted phosphorus oxychloride;
3) end capping: pull down water distilling apparatus, change poly-unit, in the time of 80～85 ℃, in above-mentioned reactant, divide to add phenol for 3～4 times, be warming up to 115～120 ℃ after half an hour, stopped reaction when not having obvious hydrogenchloride and produce;
Wherein, dihydroxyphenyl propane and phenol mass ratio are 1: 1.6～1.7;
4) under the condition of logical nitrogen, carry out underpressure distillation then to remove the excessive phenol and the hydrogenchloride of generation, get thick ester;
5) the thick ester that reaction is obtained filters, and obtains tetraphenyl diphenol A diphosphonate (product).
Its reaction mechanism is:
Figure S2007101684747D00021
In the preparation feedback process of the present invention, the temperature of polyreaction and end capping has very big influence to product thermally-stabilised, shows that mainly the molecular weight by impact polymer influences the thermally-stabilised of product.The polymerization process temperature is low excessively to help taking place substitution reaction, and the polymerization degree is increased, and is unfavorable for the carrying out of end capping, thereby influences the thermostability of result product; The too high meeting of polymerization process temperature causes the volatilization of phosphorus oxychloride, is unfavorable for the carrying out of polyreaction.The temperature in end-blocking stage is low can to cause polymer poly right not high, influences the thermostability of product; Temperature is too high, then can cause phenol volatilization and oxidation, thus artificial increase impurity.So the temperature of polymerization stage is controlled at about 105 ℃～110 ℃, and the temperature of end capping is controlled at 80～85 ℃ earlier, wait temperature to be raised to 115～120 ℃ after adding phenol in batches.
In order to guarantee the substitution value of product, the proportion relation of raw material is in the method for the invention: dihydroxyphenyl propane and POCl 3Mass ratio is 3.0-4.5, and adds the AlCl that is equivalent to dihydroxyphenyl propane quality 2～2.5% 3And PdCl 2Mixture (AlCl 3: PdCl 2Mass ratio is 2: 1), in the end capping process, add phenol (dihydroxyphenyl propane and phenol mass ratio are 1: 1.6～1.7).
The invention has the beneficial effects as follows:
1, preparation technology is simple.
2, low production cost is low than the interpolation cost of conventional flame retardant.
Low cigarette, low toxicity when 3, product burns; The flame retarding efficiency height, consumption is low, can make flame very fast from putting out, and not produce drippage; Do not produce paramorphogen to human body cell; Stability is high, and good consistency is arranged in polyolefine, migrates to the fire retardant material surface for a short time, and is low by fire retardant material density, and non-blooming, and goodish stability is arranged in the reprocessing process simultaneously; To less by the mechanical property of fire retardant material, electric property, uvioresistant and processing characteristics influence.
Description of drawings
The TG graphic representation of the tetraphenyl diphenol A diphosphonate that Fig. 1 obtains for embodiment 1.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
The preparation method of tetraphenyl diphenol A diphosphonate (BDP), it comprises the steps:
1) to middle adding 28g dihydroxyphenyl propane, the 60mlPOCl of the four-hole boiling flask that poly-unit (thermometer, agitator, prolong and HCl absorption unit) is housed 3The AlCl of (phosphorus oxychloride), 0.56g 3And PdCl 2Mixture (AlCl 3: PdCl 2Mass ratio is 2: 1), stir down above-mentioned material to be heated to and reflux about 105 ℃ stopped reaction when no hydrogenchloride is emitted.
2) pull down poly-unit (thermometer, agitator, prolong and HCl absorption unit), change water distilling apparatus, under the condition of logical nitrogen, distill, reclaim unreacted phosphorus oxychloride.
3) pull down water distilling apparatus, change polymerizing reactor (thermometer, agitator, prolong and HCl absorption unit), in the time of 80 ℃, in above-mentioned reactant, divide to add 45g phenol 3 times, after half an hour it is warming up to 120 ℃, stopped reaction when not having obvious hydrogenchloride and produce.
4) under the condition of logical nitrogen, carry out underpressure distillation then to remove the excessive phenol and the hydrogenchloride of generation.
5) the thick ester that reaction is obtained filters and can obtain tetraphenyl diphenol A diphosphonate (final product).Polymerization degree n=1 ~ 10, it is yellowish near neutral liquid phase phosphate compound; The TG curve of tetraphenyl diphenol A diphosphonate as shown in Figure 1.Its basic physicals test result such as table 1.
Embodiment 2:
The preparation method of tetraphenyl diphenol A diphosphonate, it comprises the steps:
1) to middle adding 28g dihydroxyphenyl propane, the 70mlPOCl of the four-hole boiling flask that poly-unit (thermometer, agitator, prolong and HCl absorption unit) is housed 3, 0.56g AlCl 3And PdCl 2Mixture (AlCl 3: PdCl 2Mass ratio is 2: 1), stir down above-mentioned material to be heated to and reflux about 105 ℃ stopped reaction when no hydrogenchloride is emitted.
2) pull down poly-unit (thermometer, agitator, prolong and HCl absorption unit), change water distilling apparatus, under the condition of logical nitrogen, distill, reclaim unreacted phosphorus oxychloride.
3) pull down water distilling apparatus, change polymerizing reactor (thermometer, agitator, prolong and HCl absorption unit), in the time of 80 ℃, in above-mentioned reactant, divide to add 45g phenol 4 times, after half an hour it is warming up to 120 ℃, stopped reaction when not having obvious hydrogenchloride and produce.
4) under the condition of logical nitrogen, carry out underpressure distillation then to remove the excessive phenol and the hydrogenchloride of generation.
5) the thick ester that reaction is obtained filters and can obtain tetraphenyl diphenol A diphosphonate (final product.Polymerization degree n=1～10, its basic physicals test result such as table 1.
Embodiment 3:
The preparation method of tetraphenyl diphenol A diphosphonate, it comprises the steps:
(1) to middle adding 28g dihydroxyphenyl propane, the 60mlPOCl of the four-hole boiling flask that poly-unit (thermometer, agitator, prolong and HCl absorption unit) is housed 3, 0.56g AlCl 3And PdCl 2Mixture (AlCl 3: PdCl 2Mass ratio is 2: 1), stir down above-mentioned material to be heated to and reflux about 105 ℃ stopped reaction when no hydrogenchloride is emitted.
(2) pull down poly-unit (thermometer, agitator, prolong and HCl absorption unit), change water distilling apparatus, under the condition of logical nitrogen, distill, reclaim unreacted phosphorus oxychloride.
(3) pull down water distilling apparatus, change polymerizing reactor (thermometer, agitator, prolong and HCl absorption unit), in the time of 80 ℃, in above-mentioned reactant, divide to add 45g phenol 3 times, after half an hour it is warming up to 120 ℃ approximately, stopped reaction when not having obvious hydrogenchloride and produce.
(4) under the condition of logical nitrogen, carry out underpressure distillation then to remove the excessive phenol and the hydrogenchloride of generation.
(5) the thick ester that reaction is obtained filters and can obtain final product.Polymerization degree n=1 ~ 10, its basic physicals test result such as table 1.
Embodiment 4:
The preparation method of tetraphenyl diphenol A diphosphonate, it comprises the steps:
1) polycondensation: to middle adding dihydroxyphenyl propane, the POCl of the four-hole boiling flask that poly-unit is housed 3, AlCl 3And PdCl 2Mixture, stir down said mixture to be heated to and reflux 105 ℃ stopped reaction when no hydrogenchloride is emitted; Poly-unit is thermometer, agitator, prolong and HCl absorption unit;
Wherein, dihydroxyphenyl propane and POCl 3Mass ratio be 1: 3.0, AlCl 3And PdCl 2Quality be dihydroxyphenyl propane quality 2%, AlCl 3With PdCl 2Mass ratio is 2: 1;
2) pull down poly-unit then, change water distilling apparatus, under the condition of logical nitrogen, distill, reclaim unreacted phosphorus oxychloride;
3) end capping: pull down water distilling apparatus, change poly-unit, in the time of 80 ℃, in above-mentioned reactant, divide 3 times and add phenol, be warming up to 115 ℃ after half an hour, stopped reaction when not having obvious hydrogenchloride and produce;
Wherein, dihydroxyphenyl propane and phenol mass ratio are 1: 1.6;
4) under the condition of logical nitrogen, carry out underpressure distillation then to remove the excessive phenol and the hydrogenchloride of generation, get thick ester;
5) the thick ester that reaction is obtained filters, and obtains tetraphenyl diphenol A diphosphonate.
Embodiment 5:
The preparation method of tetraphenyl diphenol A diphosphonate, it comprises the steps:
1) polycondensation: to middle adding dihydroxyphenyl propane, the POCl of the four-hole boiling flask that poly-unit is housed 3, AlCl 3And PdCl 2Mixture, stir down said mixture to be heated to and reflux 110 ℃ stopped reaction when no hydrogenchloride is emitted; Poly-unit is thermometer, agitator, prolong and HCl absorption unit;
Wherein, dihydroxyphenyl propane and POCl 3Mass ratio be 1: 4.5, AlCl 3And PdCl 2Quality be dihydroxyphenyl propane quality 2.5%, AlCl 3With PdCl 2Mass ratio is 2: 1;
2) pull down poly-unit then, change water distilling apparatus, under the condition of logical nitrogen, distill, reclaim unreacted phosphorus oxychloride;
3) end capping: pull down water distilling apparatus, change poly-unit, in the time of 85 ℃, in above-mentioned reactant, divide 4 times and add phenol, be warming up to 120 ℃ after half an hour, stopped reaction when not having obvious hydrogenchloride and produce;
Wherein, dihydroxyphenyl propane and phenol mass ratio are 1: 1.7;
4) under the condition of logical nitrogen, carry out underpressure distillation then to remove the excessive phenol and the hydrogenchloride of generation, get thick ester;
5) the thick ester that reaction is obtained filters, and obtains tetraphenyl diphenol A diphosphonate.
Comparative example (AlCl 3And PdCl 2Quality less than dihydroxyphenyl propane quality 2%):
The preparation method of tetraphenyl (dihydroxyphenyl propane) bisphosphate, it comprises the steps:
(1) to middle adding 28g dihydroxyphenyl propane, the 60mlPOCl of the four-hole boiling flask that poly-unit (thermometer, agitator, prolong and HCl absorption unit) is housed 3AlCl with 0.3g 3And PdCl 2Mixture (AlCl 3: PdCl 2Mass ratio is 2: 1), stir down above-mentioned material to be heated to and reflux about 105 ℃ stopped reaction when no hydrogenchloride is emitted.
(2) pull down poly-unit, change water distilling apparatus, under the condition of logical nitrogen, distill, reclaim unreacted phosphorus oxychloride.
(3) pull down water distilling apparatus, change polymerizing reactor, in the time of 80 ℃, in above-mentioned reactant, divide 3 times and add 45g phenol, after half an hour it is warming up to 120 ℃ approximately, stopped reaction when not having obvious hydrogenchloride and produce.
(4) under the condition of logical nitrogen, carry out underpressure distillation then to remove the excessive phenol and the hydrogenchloride of generation.
(5) the thick ester that reaction is obtained filters and can obtain tetraphenyl diphenol A diphosphonate.Its basic physicals test result such as table 1.
Table 1, the basic physicals test result of tetraphenyl diphenol A diphosphonate
Figure S2007101684747D00051

Claims (1)

1. the preparation method of tetraphenyl diphenol A diphosphonate is characterized in that it comprises the steps:
1) polycondensation: to middle adding dihydroxyphenyl propane, the POCl of the four-hole boiling flask that poly-unit is housed 3, AlCl 3And PdCl 2Mixture, stir down said mixture to be heated to and reflux 105～110 ℃ stopped reaction when no hydrogenchloride is emitted; Poly-unit is thermometer, agitator, prolong and HCl absorption unit;
Wherein, dihydroxyphenyl propane and POCl 3Mass ratio be 1: 3.0-4.5, AlCl 3And PdCl 2Quality be dihydroxyphenyl propane quality 2～2.5%, AlCl 3With PdCl 2Mass ratio is 2: 1;
2) pull down poly-unit then, change water distilling apparatus, under the condition of logical nitrogen, distill, reclaim unreacted phosphorus oxychloride;
3) end capping: pull down water distilling apparatus, change poly-unit, in the time of 80～85 ℃, in above-mentioned reactant, divide to add phenol for 3～4 times, be warming up to 115～120 ℃ after half an hour, stopped reaction when not having obvious hydrogenchloride and produce;
Wherein, dihydroxyphenyl propane and phenol mass ratio are 1: 1.6～1.7;
4) under the condition of logical nitrogen, carry out underpressure distillation then to remove the excessive phenol and the hydrogenchloride of generation, get thick ester;
5) the thick ester that reaction is obtained filters, and obtains tetraphenyl diphenol A diphosphonate.
CN2007101684747A 2007-11-27 2007-11-27 Method for preparing tetraphenyl diphenol A diphosphonate Expired - Fee Related CN101161659B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101284982B (en) * 2008-05-30 2010-10-27 天津天石带压密封有限公司 EPDM baseband press plugging sealant
CN108178935A (en) * 2018-03-13 2018-06-19 烟台启程德瑞新型建材科技股份有限公司 A kind of quantum bed board of efficient release anion
CN109912646A (en) * 2019-03-08 2019-06-21 南通江山农药化工股份有限公司 The preparation method of bis- (diphenyl phosphoester) fire retardants of bisphenol-A-

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101284982B (en) * 2008-05-30 2010-10-27 天津天石带压密封有限公司 EPDM baseband press plugging sealant
CN108178935A (en) * 2018-03-13 2018-06-19 烟台启程德瑞新型建材科技股份有限公司 A kind of quantum bed board of efficient release anion
CN109912646A (en) * 2019-03-08 2019-06-21 南通江山农药化工股份有限公司 The preparation method of bis- (diphenyl phosphoester) fire retardants of bisphenol-A-
CN109912646B (en) * 2019-03-08 2021-02-09 南通江山农药化工股份有限公司 Preparation method of bisphenol A-bis (diphenyl phosphate) flame retardant

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