CN101434619B - Method for producing high quality triarylphosphate - Google Patents
Method for producing high quality triarylphosphate Download PDFInfo
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- CN101434619B CN101434619B CN2007101570337A CN200710157033A CN101434619B CN 101434619 B CN101434619 B CN 101434619B CN 2007101570337 A CN2007101570337 A CN 2007101570337A CN 200710157033 A CN200710157033 A CN 200710157033A CN 101434619 B CN101434619 B CN 101434619B
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- temperature
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- esterification
- distillation
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- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000005886 esterification reaction Methods 0.000 claims abstract description 17
- 230000032050 esterification Effects 0.000 claims abstract description 16
- 238000004821 distillation Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 230000009183 running Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 238000005804 alkylation reaction Methods 0.000 claims description 4
- 239000003039 volatile agent Substances 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 abstract description 3
- ANVREEJNGJMLOV-UHFFFAOYSA-N tris(4-propan-2-ylphenyl) phosphate Chemical compound C1=CC(C(C)C)=CC=C1OP(=O)(OC=1C=CC(=CC=1)C(C)C)OC1=CC=C(C(C)C)C=C1 ANVREEJNGJMLOV-UHFFFAOYSA-N 0.000 abstract 3
- 238000005516 engineering process Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 3
- 230000002950 deficient Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 239000010730 cutting oil Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000010731 rolling oil Substances 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Fireproofing Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a producing method of tri(4-isopropylphenyl)phosphate. In the exisint method, the acid value of the finished product is not qualified, an extra post treatment procedure is often needed, and the tri(4-isopropylphenyl)phosphate products with high yield, high purity and high quality are hard to be obtained. The producing method comprises the following steps in sequence: melt phenol is put into a reaction kettle; propylene is pumped into the reaction kettle and the reaction temperature is kept between 115 DEG C to 125 DEG C; the materials treated with the action are put into an esterification kettle, the temperature is kept between 60 DEG C to 80 DEG C and phosphorus oxychloride is dripped in; the materials after being esterified is pumped into a distillation kettle for distillation; the front cut fraction and the after cut fraction obtained from the distillation are returned to the esterification kettle for esterification reaction, and the middle fraction is the finished tri(4-isopropylphenyl)phosphate product.
Description
Technical field
The invention discloses a kind of production method of high quality triarylphosphate.
Background technology
High quality triarylphosphate is mainly as the fire retardant of elastomeric flame-retardant plasticizers such as rubber item, PVC plastics fire retarding conveying band, leather, paulin, agricultural mulching, flooring material, electric wire, cable, chloroprene rubber, nitrile rubber, epoxy resin, also can be used as the resistance to compression additive of cutting oil, gear oil, rolling oil etc.In the conventional method, only collect front-end volatiles during distillation and carry out esterification again, cause the acid number of finished product defective, often to increase by one postprocessing working procedures, promptly to substandard product wash again, dehydration etc., thereby increased production time and production unit, a certain amount of waste water is arranged simultaneously.In addition, reaction obtains high yield, high purity, high-quality triaryl phosphate product than difficulty inadequately completely.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defective that above-mentioned prior art exists, and a kind of production method of optimizing the triaryl phosphate of technology is provided, and to save aftertreatment technology, obtains high yield, high purity, high-quality product.
For this reason, the present invention adopts following technical scheme: the production method of high quality triarylphosphate, and its step is as follows: a, alkylation reaction, in the phenol input reactor with fusing, feed propylene again, temperature of reaction remains on 115～125 ℃; B, esterification will change over to through the material of above-mentioned reaction in the esterifying kettle, and temperature remains on 60～80 ℃, splashes into phosphorus oxychloride; C, distillation will be through distilling in the material suction still kettle after the esterification, and the forward and backward cut that distillation obtains turns back to and carries out esterification in the esterifying kettle, and middle runnings is finished product.The collected forward and backward cut of the present invention is a tart, turns back to and carries out esterification in the esterifying kettle, has both made the acid number of finished product qualified, saves aftertreatment technology, has reduced facility investment, has reduced environmental pollution; Again the product look number is had greatly improved, improved the output capacity and the quality product of product.
As the further of technique scheme improved and replenish, the present invention takes following technical measures:
Above-mentioned method is equipped with outer refrigerating unit of still and hydrogen chloride gas absorption unit on the esterifying kettle, utilize the outer refrigerating unit of still that the material in the still is cooled off, and utilizes the hydrogen chloride gas that produces in the hydrogen chloride gas absorption unit absorption reaction.
Above-mentioned method, forward and backward distillate flow enters in the esterifying kettle behind the refrigerating unit outside still again, the forward and backward cut of this moment is as cooling fluid, material temperature in the still is lowered, the temperature of self is risen, and then enter in the esterifying kettle and react, make full use of heat energy, greatly reduce energy consumption.
Above-mentioned method, the vacuum tightness during distillation remains on 〉=0.098MPa, when temperature is 195-210 ℃, collects front-end volatiles; In temperature is more than 270 ℃ the time, collects after cut; When temperature was 210-270 ℃, the cut of collection was middle runnings.
Stir after dropping into phenol in the above-mentioned method, reactor, and in reacting kettle jacketing, add steam; when making the interior temperature of reactor be raised to 115-125 ℃; feeding propylene to the mass ratio of phenol and propylene is 1: 0.1-0.2, reaction should be cooled off under nitrogen protection after finishing.
Above-mentioned method, drip off phosphorus oxychloride in the esterifying kettle after, deepen reaction with 16-20 ℃ heat-up rate per hour, the time is 0.5-1 hour, terminal temperature is 195-200 ℃.
Above-mentioned method, during esterification, the still internal pressure when producing hydrogen chloride gas is controlled at the 0-5mm mercury column.
The present invention optimizes technology, has following beneficial effect: 1) operational condition is relatively gentleer, and reaction parameter is controlled easily; 2) material that obtains after the esterification enters in the esterifying kettle with forward and backward cut cooling and with forward and backward cut, can guarantee complete reaction, reduced technology (washing, dehydration), reduced facility investment, reduced environmental pollution simultaneously, also solve the cooling problem of electrically heated still, reduced raw material and energy consumption again, but also improved quality product and yield; 3) save aftertreatment technology, shortened nearly 6 hours of explained hereafter cycle, reduced production cost.
The invention will be further described below in conjunction with embodiment.
Embodiment
Concrete steps of the present invention are as follows:
A, alkylation reaction, phenol after the 600Kg fusing put in 1000 liters the reactor, open and stir, and in reacting kettle jacketing injecting steam, when making temperature in the reactor be raised to 115 ℃, beginning to feed propylene to the mass ratio of phenol and propylene is that whole feeding process is measured control reaction temperature with feeding till 1: 0.16, temperature of reaction remains on 115-125 ℃, and the reaction times is 9-10 hour; Deepen reaction afterwards, time 0.5-1 hour,, and maintain the temperature at 50-55 ℃ towards the nitrogen cooling.
B, esterification, the material that alkylation reaction is finished is drawn in the reaction kettle of the esterification, open and stir, open the electrically heated switch, make temperature of reaction be raised to 60 ℃, begin to drip phosphorus oxychloride, whole dropping process is with the rate of addition control reaction temperature, temperature of reaction remains on 60-80 ℃, rate of addition is about 3 kilograms of per minutes, and the time that drips phosphorus oxychloride is 2.5-3.5 hour, to the mass ratio of phosphorus oxychloride and phenol be till 1: 0.5, vacuum tightness in the reactor is exceeded can drip phosphorus oxychloride, generally at the 0-0.5MM mercury column; After dripping off phosphorus oxychloride, 16-20 ℃ the speed that continue to keep per hour heating up reached terminal temperature 195-200 ℃ in 8 hours, and the in-depth reaction is 0.5-1 hour then, and vacuum tightness slowly raises during temperature reaction, and vacuum tightness is in the 0.098-1.05 MPa; The temperature of reaction terminal point is 195-200 ℃, continue to stir 0.5 hour, treat that HCl gas in the still sucks substantially after, reaction finishes, and obtains the triaryl phosphate raw product.
C, distillation, the triaryl phosphate raw product is extracted in the still kettle distills, vacuum tightness during distillation remains on 0.098-1.05MPa, heating wants slow when getting rid of the leading portion cut, after the equal vacuum degree is stable, when 210 ℃ of temperature, get rid of front-end volatiles, when 270 ℃ of temperature, get rid of after cut, forward and backward cut enters esterifying kettle esterification again after returning the outer refrigerating unit of the still of flowing through again, and middle runnings is finished product.
The above only is preferred embodiment of the present invention.Every foundation technical spirit of the present invention all falls within the scope of protection of the present invention any simple modification, equivalent variations and modification that above embodiment did.
Claims (6)
1. the production method of triaryl phosphate, its step is as follows: a, alkylation reaction, the phenol of fusing is dropped in the reactor, feed propylene again, temperature of reaction remains on 115～125 ℃; B, esterification will change in the esterifying kettle through the material of reaction of last step, and temperature remains on 60～80 ℃, splashes into phosphorus oxychloride; C, distillation will be through distilling in the material suction still kettle after the esterification, and the forward and backward cut that distillation obtains turns back to and carries out esterification in the esterifying kettle, and middle runnings is finished product;
Vacuum tightness during distillation remains on 〉=0.098MPa, when temperature is 195-210 ℃, collects front-end volatiles; In temperature is more than 270 ℃ the time, collects after cut; When temperature was 210-270 ℃, the cut of collection was middle runnings.
2. method according to claim 1 is characterized in that being equipped with on the esterifying kettle outer refrigerating unit of still and hydrogen chloride gas absorption unit.
3. method according to claim 2 is characterized in that forward and backward distillate flow enters in the esterifying kettle behind the refrigerating unit again outside still.
4. method according to claim 1; stir after it is characterized in that in reactor, dropping into phenol; and in reacting kettle jacketing, add steam; when making the interior temperature of reactor be raised to 115-125 ℃; feeding propylene to the mass ratio of phenol and propylene is 1: 0.1-0.2; reaction is cooled off under nitrogen protection after finishing.
5. method according to claim 1 after it is characterized in that dripping off phosphorus oxychloride in the esterifying kettle, is deepened reaction with 16-20 ℃ heat-up rate per hour, and the time is 0.5-1 hour, and terminal temperature is 195-200 ℃.
6. method according to claim 1, when it is characterized in that esterification, the still internal pressure when producing hydrogen chloride gas is controlled at the 0-5mm mercury column.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101570337A CN101434619B (en) | 2007-11-16 | 2007-11-16 | Method for producing high quality triarylphosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101570337A CN101434619B (en) | 2007-11-16 | 2007-11-16 | Method for producing high quality triarylphosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101434619A CN101434619A (en) | 2009-05-20 |
| CN101434619B true CN101434619B (en) | 2011-07-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101570337A Active CN101434619B (en) | 2007-11-16 | 2007-11-16 | Method for producing high quality triarylphosphate |
Country Status (1)
| Country | Link |
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| CN (1) | CN101434619B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2159264A1 (en) * | 1971-11-08 | 1973-06-22 | Koppers Co Inc | |
| US4351780A (en) * | 1980-12-09 | 1982-09-28 | Stauffer Chemical Company | Process for preparing isopropylphenyl/phenyl phosphate |
| CN1248260A (en) * | 1997-10-29 | 2000-03-22 | Fmc(英国)有限公司 | Production of phosphate esters |
| CN1257075A (en) * | 1998-12-14 | 2000-06-21 | 旭化成工业株式会社 | Method for preparing phosphate ester |
| CN1339039A (en) * | 1999-02-16 | 2002-03-06 | 大八化学工业株式会社 | Process for producing phosphorohalidate |
| CN1512997A (en) * | 2001-06-08 | 2004-07-14 | ��Ԩ��ѧ��ҵ��ʽ���� | Process for preparation of phosphoric esters |
| CN1517353A (en) * | 2002-12-26 | 2004-08-04 | ������������ʽ���� | Manufacturing method of phosphate ester |
| US20050137425A1 (en) * | 2003-12-23 | 2005-06-23 | Abramson Alan J. | Alkylation of triphenylphosphate |
-
2007
- 2007-11-16 CN CN2007101570337A patent/CN101434619B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2159264A1 (en) * | 1971-11-08 | 1973-06-22 | Koppers Co Inc | |
| US4351780A (en) * | 1980-12-09 | 1982-09-28 | Stauffer Chemical Company | Process for preparing isopropylphenyl/phenyl phosphate |
| CN1248260A (en) * | 1997-10-29 | 2000-03-22 | Fmc(英国)有限公司 | Production of phosphate esters |
| CN1257075A (en) * | 1998-12-14 | 2000-06-21 | 旭化成工业株式会社 | Method for preparing phosphate ester |
| CN1339039A (en) * | 1999-02-16 | 2002-03-06 | 大八化学工业株式会社 | Process for producing phosphorohalidate |
| CN1512997A (en) * | 2001-06-08 | 2004-07-14 | ��Ԩ��ѧ��ҵ��ʽ���� | Process for preparation of phosphoric esters |
| CN1517353A (en) * | 2002-12-26 | 2004-08-04 | ������������ʽ���� | Manufacturing method of phosphate ester |
| US20050137425A1 (en) * | 2003-12-23 | 2005-06-23 | Abramson Alan J. | Alkylation of triphenylphosphate |
Non-Patent Citations (1)
| Title |
|---|
| 周杰兴 等.三异丙苯基磷酸酯的合成工艺改进.《上海化工》.1999,第24卷(第19期),第21-22页. * |
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| CN101434619A (en) | 2009-05-20 |
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