CN110066398A - A kind of preparation method of polyphosphate - Google Patents
A kind of preparation method of polyphosphate Download PDFInfo
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- CN110066398A CN110066398A CN201910356390.9A CN201910356390A CN110066398A CN 110066398 A CN110066398 A CN 110066398A CN 201910356390 A CN201910356390 A CN 201910356390A CN 110066398 A CN110066398 A CN 110066398A
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- phenol
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- polyphosphate
- dialkyl group
- phosphorus oxychloride
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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
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
Abstract
The present invention is a kind of preparation method of polyphosphate, and this method obtains polyphosphate by phosphorus oxychloride, dialkyl group phenol and hydroquinone one-step method, finally blocked by phenol；This method first generates monomer monophenyl by phosphorus oxychloride and dialkyl group phenol, is then polymerize to obtain poly- phosphatide intermediate by hydroquinone, then blocked by phenol；The degree of polymerization is 1-20；Progress, simple process, safety coefficient are high under normal pressure for the method for the present invention synthesis condition, and polyphosphate has many uses: can be used as solid flame retardant, its advantage is that resistance to volatilization, resistance to migration, radiation hardness, heat resistance is high, compatibility is good, toxicity is low, flame retardant effect is lasting；It can be used as the plasticizer of material, its advantage is that toughness is strong, brittleness is small, can solve the mechanical property etc. including material notch impact strength.
Description
Technical field
The present invention relates to a kind of preparation method of fire retardant, especially a kind of preparation method of polyphosphate.
Background technique
With social progress, people increasingly pay attention to environmental protection, especially propose strict requirements to chemical industry,
Need to accomplish safe and environment-friendly, energy-saving and emission-reduction etc., thus it is low to safety coefficient, pollution is big, production technology complexity product is sought to replace
For product or carry out process modification.Many about phosphate preparations report, phosplate is mostly liquid, because of its molecule
Measure small, vapour pressure is high, decomposition temperature is low, it is easy be precipitated, thermal stability it is poor, therefore it is volatile in plastic processes, decompose, make
The mechanical performance of plastic products is a greater impact.These all hamper phosplate based flame retardant in the higher work of processing temperature
Application in engineering plastics and the resistance to persistently fire-retardant plastic products of needs.In order to avoid the above-mentioned defect of phosplate, carry out
The synthesis of polyphosphate.It is by three if US publication document US4382042 discloses this kind of low polyphosphate preparation method
Alkyl phosphate or three alkylhalide group phosphates or trialkyl phosphite or three alkylhalide group phosphite esters are reacted with phosphorus pentoxide,
The condensate of bond structure containing P-O-P (polyphosphate and poly- phosphite ester) is obtained, then obtains low polyphosphate with reacting ethylene oxide.
However this method, because using ethylene oxide for raw material, not only cost of material is high, but also production security is poor；In addition phosphorus pentoxide is rotten
Corrosion is big, thus high to equipment requirement, and especially to make to prevent volatility losses of ethylene oxide, reaction must increase pressure
Lower progress has even more increased the risk of preparation.
The big bright synthesis for reporting polyphenylene oxide quinol phosphate of class, Beijing Institute of Technology, characterization and its thermal stability
Research, has prepared solid flame retardant, polymer thermogravimetric curve shows: initial decomposition temperature (Tonset) it is 364.31 DEG C, most fastly
Decomposition temperature (TMAX) it is 545.53 DEG C, decompose 50% temperature (T50%) it is 547.84 DEG C.Residual quantity of the polymer at 700 DEG C
WResidIt is 36.39%, research shows that the thermal stability of polymer is fine, but synthesis process uses two-step method, and synthesis technology is multiple
It is miscellaneous.
Fire-resistant engineering plastics include bromine system product and fire retardant of polyphosphate, and bromide fire retardant is carcinogenic because that can generate when burning
Property substance dioxin, does not meet environmental requirement.Fire retardant of polyphosphate is because of its high thermal decomposition temperature, low volatility
And good material compatibility and obtained a large amount of application.
In the prior art, the preparation process of conventional condensed phosphoric esters is usually: first by bisphenol compound and excessive
Phosphorus oxychloride is reacted in the presence of a catalyst；Then distillation removes excessive phosphorus oxychloride；It is reacted again with unit phenolic compound
Condensed phosphoric esters crude product is made；After further to condensed phosphoric esters crude product by pickling, alkali cleaning, washing, desolventizing and water are distilled,
Condensed phosphoric esters product is obtained by filtration.
The condensed phosphoric esters usually use at a high temperature of 200-300 DEG C as fire retardant, and in preparation polycondensation phosphorus
During acid esters, since raw material contain a certain amount of moisture, it can make to contain hydroxyl phosphate in reactor product, the hydroxyl phosphorus
Acid esters will be greatly reduced the thermal decomposition temperature of condensed phosphoric esters in acidity, limit condensed phosphoric esters in the application in many fields,
It thus must be by carrying out the post-processing such as washing to condensed phosphoric esters crude product, to effectively remove hydroxyl phosphate.
Chinese patent literature CN1257075A describes the preparation process of condensed phosphoric esters and is gone by controlling wash conditions
Except containing all kinds of impurity, including hydrophily phosphate (hydroxy-containig phosphonate) in condensed phosphoric esters crude product.Patent is pointed out due to parent
Aqueous phosphate ester easily forms emulsion in washing process, not easy to wash, need to repeatedly carry out the flushing of water.The patent, which does not refer to, to be subtracted
The method that few hydrophily phosphate is formed.
Chinese patent literature CN1633441A describes a kind of method of purification of phosphate esters, in phosphate after washing
The acid phosphoric acid ester (hydroxy-containig phosphonate) contained makes its acid phosphoric acid ester be converted into neutral phosphoric acid by the way that epoxide is added
Ester.But the thermal decomposition temperature for the product that this method obtains does not get a promotion.The same patent does not refer to reduction acid phosphatase yet
The method that ester is formed.
Summary of the invention
The technical problem to be solved by the present invention is in view of the deficiencies of the prior art, provide a kind of not only production safety, work
Skill is simple, and product compatibility is good, the preparation method of the high polyphosphate of thermal stability.
The technical problem to be solved by the present invention is to what is realized by technical solution below.The present invention is a kind of poly- phosphorus
The preparation method of acid esters, its main feature is that: polyphosphate is obtained by phosphorus oxychloride, dialkyl group phenol and hydroquinone one-step method, most
It is blocked afterwards by phenol；The general formula of dialkyl group phenol is shown in formula I:
In Formulas I: R1, R2For identical or different straight chain C1-C 5Alkyl.
The preparation method of polyphosphate of the present invention, further preferred technical side decide on a verdict and are: the R1, R2
Selected from 2,3- dialkyl group phenol, 2,4- dialkyl group phenol, 2,5- dialkyl group phenol or 2,6- dialkyl group phenol.
The preparation method of polyphosphate of the present invention, further preferred technical side decide on a verdict and are: this method first by
Phosphorus oxychloride and dialkyl group phenol generate monomer monophenyl, are then polymerize to obtain poly- phosphatide intermediate by hydroquinone, then by benzene
Phenol sealing end；The degree of polymerization is 1-20；Phosphorus oxychloride and dialkyl group phenol molar ratio are 0.5-1.5: 1；Hydroquinone and phosphorus oxychloride
Molar ratio be 0.8-5: 1.
The preparation method of polyphosphate of the present invention, further preferred technical side decide on a verdict and are: urging used in reaction
Agent is lewis acid catalyst.
The preparation method of polyphosphate of the present invention, further preferred technical side decide on a verdict and are: the Louis
This acid catalyst is selected from AlCl3、MgCl2、ZnCl2Or TiCl4。
The preparation method of polyphosphate of the present invention, further preferred technical side decide on a verdict and are: the use of catalyst
Amount is the 0.05%-1% of dialkyl group phenol quality.
The preparation method of polyphosphate of the present invention, further preferred technical side decide on a verdict and be: reaction is used
Solvent be carbon tetrachloride, chloroform or dichloroethanes.
The preparation method of polyphosphate of the present invention, further preferred technical side decide on a verdict and are: solvent used
Dosage is 1-20 times of dialkyl group phenol quality.
The preparation method of polyphosphate of the present invention, further preferred technical side decide on a verdict and are: product alcohols
Precipitating reagent is purified, the preferred methanol of alcohol precipitating agent, ethyl alcohol, propyl alcohol or butanol.
The preparation method of polyphosphate of the present invention, further preferred technical side decide on a verdict and be: reaction is lazy
It is carried out under property gas shield.
Compared with prior art, the invention has the following advantages:
The preparation method of polyphosphate of the present invention is obtained by phosphorus oxychloride, dialkyl group phenol and hydroquinone one-step method, is saved
Go the intermediate link for preparing polyphosphate technique in the past, i.e., obtain intermediate monomer with phosphorus oxychloride and phenol etc. first, then into
Row, which condenses and separates, to be proposed, obtains the higher intermediate monomer of purity, then carry out second step with hydroquinone and react to obtain polymer.This
Invention is in reaction process further to be gathered by using control reaction rate of feeding and reaction temperature and reaction time
Phosphate, degree of polymerization 1-20.It is chemically identical in reaction principle, but operation technique is improved, it is anti-
Answer equation are as follows:
Reaction process of the present invention is common synthesis under normal pressure, is carried out at a proper temperature, easy to operate, and safety coefficient is high.
In order to reduce the generation of side reaction, a kind of better method is to be reacted under inert gas protection, can be to avoid trichlorine oxygen
Phosphorus causes side reaction to increase with oxygen in air and water, help to obtain purer product.
The method of the present invention is that solvent is added, and reactant can be made preferably to disperse, and is adequately reacted.In addition, by being added one
Quantitative lewis acid catalyst can promote reaction to carry out, and to keep reaction more thorough, while shorten the reaction time.Reaction
After, washing removes catalyst, distilling off solvent, and solvent can reuse.
Polyphosphate preparation method raw material of the present invention is not dangerous material, and synthesis under normal pressure is highly-safe, saves intermediate point
From purification, simple process can reduce the production cost of 20%-40%.And acquired product polyphosphate is as fire retardant,
With good, heat-resisting, the resistance to volatilization of other materials compatibility, resistance to migration, radiation hardness, toxicity is low, flame retardant effect is lasting the advantages that.
Specific example mode
Below in conjunction with specific example, the main case of technology of the invention is further illustrated, without constituting the limit to right of the present invention
System.
Embodiment 1, a kind of preparation method of polyphosphate: by phosphorus oxychloride, dialkyl group phenol and hydroquinone one-step method
Polyphosphate is obtained, is finally blocked by phenol；The general formula of dialkyl group phenol is shown in formula I:
In Formulas I: the R1, R2Selected from 2,3- dialkyl group phenol, 2,4- dialkyl group phenol, 2,5- dialkyl group phenol or
2,6- dialkyl group phenol.
This method first generates monomer monophenyl by phosphorus oxychloride and dialkyl group phenol, is then polymerize by hydroquinone
Phosphatide intermediate, then blocked by phenol；The degree of polymerization is 1-20；Phosphorus oxychloride and dialkyl group phenol molar ratio are 0.5: 1；To benzene two
The molar ratio of phenol and phosphorus oxychloride is 0.8: 1.
Reaction used catalyst is AlCl3, the dosage of catalyst is the 0.05% of dialkyl group phenol quality.Reaction is used
Solvent be carbon tetrachloride.Solvent usage used is 5 times of dialkyl group phenol quality.Product is mentioned with alcohol precipitating agent
Pure, alcohol precipitating agent is methanol.Reaction is carrying out under inert gas protection.
Embodiment 2, a kind of preparation method of polyphosphate: by phosphorus oxychloride, dialkyl group phenol and hydroquinone one-step method
Polyphosphate is obtained, is finally blocked by phenol；The general formula of dialkyl group phenol is shown in formula I:
In Formulas I: R1, R2For identical or different straight chain C1-C 5Alkyl.
The R1, R2Selected from 2,3- dialkyl group phenol, 2,4- dialkyl group phenol, 2,5- dialkyl group phenol or 2,6- bis-
Alkylphenol.
This method first generates monomer monophenyl by phosphorus oxychloride and dialkyl group phenol, is then polymerize by hydroquinone
Phosphatide intermediate, then blocked by phenol；The degree of polymerization is 1-20；Phosphorus oxychloride and dialkyl group phenol molar ratio are 1.5: 1；To benzene two
The molar ratio of phenol and phosphorus oxychloride is 5: 1.
Reaction used catalyst is MgCl2.The dosage of catalyst is the 1% of dialkyl group phenol quality.Used in reaction
Solvent is chloroform.Solvent usage used is 1 times of dialkyl group phenol quality.Product is purified with alcohol precipitating agent, alcohols
Precipitating reagent is ethyl alcohol.Reaction is carrying out under inert gas protection.
Embodiment 3, a kind of preparation method of polyphosphate: by phosphorus oxychloride, dialkyl group phenol and hydroquinone one-step method
Polyphosphate is obtained, is finally blocked by phenol；The general formula of dialkyl group phenol is shown in formula I:
In Formulas I: R1, R2For identical or different straight chain C1-C 5Alkyl.
The R1, R2Selected from 2,3- dialkyl group phenol, 2,4- dialkyl group phenol, 2,5- dialkyl group phenol or 2,6- bis-
Alkylphenol.
This method first generates monomer monophenyl by phosphorus oxychloride and dialkyl group phenol, is then polymerize by hydroquinone
Phosphatide intermediate, then blocked by phenol；The degree of polymerization is 15；Phosphorus oxychloride and dialkyl group phenol molar ratio are 1: 1；Hydroquinone with
The molar ratio of phosphorus oxychloride is 2: 1.
Reaction used catalyst is lewis acid catalyst.The lewis acid catalyst is ZnCl2.The use of catalyst
Amount is the 0.1% of dialkyl group phenol quality.Solvent used in reacting is dichloroethanes.Solvent usage used is dialkyl benzene
20 times of phenol quality.Product is purified with alcohol precipitating agent, and alcohol precipitating agent is butanol.Reaction is under inert gas protection
It carries out.
Embodiment 4, a kind of preparation method of polyphosphate: by phosphorus oxychloride, dialkyl group phenol and hydroquinone one-step method
Polyphosphate is obtained, is finally blocked by phenol；The general formula of dialkyl group phenol is shown in formula I:
In Formulas I: R1, R2For identical or different straight chain C1-C 5Alkyl.
The R1, R2Selected from 2,3- dialkyl group phenol, 2,4- dialkyl group phenol, 2,5- dialkyl group phenol or 2,6- bis-
Alkylphenol.
This method first generates monomer monophenyl by phosphorus oxychloride and dialkyl group phenol, is then polymerize by hydroquinone
Phosphatide intermediate, then blocked by phenol；The degree of polymerization is 1-20；Phosphorus oxychloride and dialkyl group phenol molar ratio are 0.8: 1；To benzene two
The molar ratio of phenol and phosphorus oxychloride is 3: 1.
Reaction used catalyst is lewis acid catalyst.The lewis acid catalyst ZnCl2Or TiCl4.Catalyst
Dosage be the 0.5% of dialkyl group phenol quality.Solvent used in reacting is carbon tetrachloride, chloroform or dichloroethanes.It is used
Solvent usage be 10 times of dialkyl group phenol quality.Product is purified with alcohol precipitating agent, the preferred methanol of alcohol precipitating agent,
Ethyl alcohol, propyl alcohol or butanol.Reaction is carrying out under inert gas protection.
Embodiment 5, polyphosphate preparation method experiment one:
The addition 1.2g aluminum trichloride (anhydrous), 200g dichloroethanes, 120g2 in the four-hole boiling flask of 1L, 6- xylenol,
Use N2Then gas shielded is warming up to 80 DEG C, stirring makes aluminum trichloride (anhydrous) and 2, and 6- xylenol all dissolves, at this time slowly
Phosphorus oxychloride is added dropwise into flask, discovery has a small amount of HCL gas (to be absorbed with water) when emerging, is continuously heating to 100 DEG C of Shi You great
Amount HCL gas is emerged, and continues that phosphorus oxychloride is added dropwise, and with the progress of reaction, it is found that HCL gas flow is reduced, until not having gas
It releases, stops plus phosphorus oxychloride (be added about 150g phosphorus oxychloride), be warming up to 120 the reaction was continued 2h.At this point, stop heating,
70 DEG C are cooled to, 132g hydroquinone is added in flask in three batches, reacts 3h.Be warming up to 120 DEG C later, maintain this temperature after
Continuous reaction, when finding that no gas is emerged, then reacts 1h.The phenol of 10g is added, is warming up to 170-200 DEG C of reaction 2h, stops
Heating, is cooled to 120 DEG C for reaction solution, and heat filtering obtains solid product, all dissolves product with chloroform, is then with methanol
Precipitating reagent is polymer precipitation and separation, and the solid product being obtained by filtration is dried in vacuo for 24 hours at 80 DEG C, and it is poly- to obtain white solid product
2,6- dimethyl phenoxy quinol phosphates.Weighing, yield 93% (in terms of hydroquinone).Gel permeation chromatography point
Analysis, molecular weight 3965, the degree of polymerization about 15.Thermogravimetric analysis is as follows: 1% decomposition temperature (T1%) it is 225.8 DEG C, 5% decomposition temperature
(T5%) it is 294.0 DEG C, most fast decomposition temperature (TMAX) it is 511 DEG C, decompose 50% temperature (T50%) it is 513.3 DEG C, which exists
Residual quantity W at 700 DEG CResidIt is 38.89%.
Embodiment 6, polyphosphate preparation method experiment two:
2g zinc chloride, 200g chloroform, 120g 2 are added in the four-hole boiling flask of 1L, 5- xylenol uses N2Gas shielded,
Then 65 DEG C are warming up to, stirring dissolves 2,5- xylenol all, and phosphorus oxychloride is slowly added dropwise into flask at this time, finds
There is a small amount of HCL gas (to be absorbed with water) when emerging, be continuously heating to there are a large amount of HCL gases to emerge at 80 DEG C, continues that trichlorine is added dropwise
Oxygen phosphorus finds the reduction of HCL gas flow with the progress of reaction, until releasing without gas, stops adding phosphorus oxychloride (about
150g phosphorus oxychloride is added dropwise the speed control of phosphorus oxychloride and completes in 3-4h), the reaction was continued 2h.By 132g hydroquinone point three
It criticizes and is added in flask, react 3h.It is warming up to 120 DEG C later, maintaining this temperature, the reaction was continued, when finding that no gas is emerged,
1h is reacted again.The phenol of 10g is added, is warming up to 170-200 DEG C of reaction 2h, stops heating, reaction solution is cooled to 80 DEG C.Then
Be precipitating reagent with ethyl alcohol be polymer precipitation and separation, the solid product being obtained by filtration 80 DEG C of vacuum drying for 24 hours, it is solid to obtain white
Poly- 2, the 5- dimethyl phenoxy quinol phosphate of body product.Weighing, yield 86% (in terms of hydroquinone).Gel seeps
Saturating chromatography, molecular weight 2655, the degree of polymerization about 10.Thermogravimetric analysis is as follows: 1% decomposition temperature (T1%) it is 235.6 DEG C, 5% point
Solve temperature (T5%) it is 304.0 DEG C, most fast decomposition temperature (TMAX) it is 506 DEG C, decompose 50% temperature (T50%) it is 515.6 DEG C, it should
Residual quantity W of the product at 700 DEG CResidIt is 34.65%.
Embodiment 7, polyphosphate preparation method three:
1.8g magnesium chloride, 200g carbon tetrachloride, 120g 2 are added in the four-hole boiling flask of 1L, 4- xylenol uses N2
Then gas shielded is warming up to 80 DEG C, stirring dissolves 2,4- xylenol all, and trichlorine oxygen is slowly added dropwise into flask at this time
Phosphorus, discovery have a small amount of HCL gas (to be absorbed with water) when emerging, are continuously heating to have a large amount of HCL gases to emerge at 100 DEG C, continue
Phosphorus oxychloride is added dropwise, with the progress of reaction, finds the reduction of HCL gas flow, until releasing without gas, stops adding phosphorus oxychloride
(be added about 150g phosphorus oxychloride) is warming up to 120 the reaction was continued 2h.At this point, stopping heating, 70 DEG C are cooled to, by 132g pairs
Benzenediol is added in flask in three batches, reacts 3h.It is warming up to 120 DEG C later, maintaining this temperature, the reaction was continued, when the no gas of discovery
When body is emerged, then react 1h.The phenol of 10g is added, is warming up to 170-200 DEG C of reaction 2h, stops heating, reaction solution is cooled to
Then it is polymer precipitation and separation that 100 DEG C are precipitating reagent with butanol, and the solid product being obtained by filtration is dried in vacuo at 100 DEG C
For 24 hours, poly- 2, the 4- dimethyl phenoxy quinol phosphate of white solid product is obtained.Weighing, yield 65% is (to benzene
Diphenol meter).Gel osmoticing chromatogram analysis, molecular weight 1305, the degree of polymerization about 5.Thermogravimetric analysis is as follows: 1% decomposition temperature (T1%) be
197.8 DEG C, 5% decomposition temperature (T5%) it is 265.4 DEG C, most fast decomposition temperature (TMAX) it is 465.2 DEG C, decompose 50% temperature
(T50%) it is 197.8 DEG C, residual quantity W of the product at 700 DEG CResidIt is 17.74%.
Claims (10)
1. a kind of preparation method of polyphosphate, it is characterised in that: by phosphorus oxychloride, dialkyl group phenol and hydroquinone one-step method
Polyphosphate is obtained, is finally blocked by phenol；The general formula of dialkyl group phenol is shown in formula I:
In Formulas I: R1, R2For identical or different straight chain C1-C5Alkyl.
2. the preparation method of polyphosphate according to claim 1, it is characterised in that: the R1, R2Selected from 2,3- dioxane
Base phenol, 2,4- dialkyl group phenol, 2,5- dialkyl group phenol or 2,6- dialkyl group phenol.
3. the preparation method of polyphosphate according to claim 1, it is characterised in that: this method is first by phosphorus oxychloride and two
Alkylphenol generates monomer monophenyl, is then polymerize to obtain poly- phosphatide intermediate by hydroquinone, then blocked by phenol；The degree of polymerization
For 1-20；Phosphorus oxychloride and dialkyl group phenol molar ratio are 0.5-1.5: 1；The molar ratio of hydroquinone and phosphorus oxychloride is 0.8-
5∶1。
4. the preparation method of polyphosphate according to claim 1 or 2 or 3, it is characterised in that: reacting used catalyst is
Lewis acid catalyst.
5. the preparation method of polyphosphate according to claim 4, it is characterised in that: the lewis acid catalyst choosing
From AlCl3、MgCl2、ZnCl2Or TiCl4。
6. the preparation method of polyphosphate according to claim 4, it is characterised in that: the dosage of catalyst is dialkyl benzene
The 0.05%-1% of phenol quality.
7. the preparation method of polyphosphate according to claim 1 or 2 or 3, it is characterised in that: solvent used in reacting
For carbon tetrachloride, chloroform or dichloroethanes.
8. the preparation method of polyphosphate according to claim 7, it is characterised in that: solvent usage used is dialkyl group
1-20 times of phenol quality.
9. the preparation method of polyphosphate according to claim 1 or 2 or 3, it is characterised in that: product alcohol precipitating agent
It is purified, the preferred methanol of alcohol precipitating agent, ethyl alcohol, propyl alcohol or butanol.
10. the preparation method of polyphosphate according to claim 1 or 2 or 3, it is characterised in that: reaction is in indifferent gas
Body protection is lower to be carried out.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111205652A (en) * | 2020-03-18 | 2020-05-29 | 临海市奇升橡塑制品有限公司 | Modified flame retardant, high-temperature-resistant flame-retardant silicone rubber using flame retardant and application of silicone rubber |
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|---|---|---|---|---|
| US4134876A (en) * | 1976-01-16 | 1979-01-16 | Imperial Chemical Industries Limited | Phosphorus and linear polyester compositions and products containing them |
| EP0509506B1 (en) * | 1991-04-16 | 1997-06-25 | Daihachi Chemical Industry Co., Ltd. | Crystalline powders of aromatic diphosphates, their preparation and use |
| CN101293896A (en) * | 2007-04-29 | 2008-10-29 | 江苏雅克化工有限公司 | Preparation of low polyphosphate |
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| CN101671439A (en) * | 2009-09-24 | 2010-03-17 | 浙江万盛化工有限公司 | Preparation method of macromolecular bisphenol A tetraphenyl diphosphate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111205652A (en) * | 2020-03-18 | 2020-05-29 | 临海市奇升橡塑制品有限公司 | Modified flame retardant, high-temperature-resistant flame-retardant silicone rubber using flame retardant and application of silicone rubber |
| CN111205652B (en) * | 2020-03-18 | 2022-02-18 | 临海市奇升橡塑制品有限公司 | Modified flame retardant, high-temperature-resistant flame-retardant silicone rubber using flame retardant and application of silicone rubber |
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Application publication date: 20190730 |