CN105037418B - A kind of industrialized process for preparing of the bisphenol-A phenyl condensed phosphoric esters of low triphenyl content - Google Patents
A kind of industrialized process for preparing of the bisphenol-A phenyl condensed phosphoric esters of low triphenyl content Download PDFInfo
- Publication number
- CN105037418B CN105037418B CN201510517984.5A CN201510517984A CN105037418B CN 105037418 B CN105037418 B CN 105037418B CN 201510517984 A CN201510517984 A CN 201510517984A CN 105037418 B CN105037418 B CN 105037418B
- Authority
- CN
- China
- Prior art keywords
- bisphenol
- phosphorus oxychloride
- phosphoric esters
- condensed phosphoric
- phenyl condensed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The present invention relates to the industrialized process for preparing of the bisphenol-A phenyl condensed phosphoric esters of a kind of low triphenyl content, bisphenol-A phenyl condensed phosphoric esters is called for short BDP, and the phosphorus oxychloride of part bisphenol-A and excess is first reacted the bisphenol-A phosphoryl chloride phosphorus oxychloride condensation polymer generated containing excess phosphorus oxychloride by the presence of a catalyst；Phosphorus oxychloride removed by vacuum distilling；Under vacuum, more remaining bisphenol-A is added in the bisphenol-A phosphoryl chloride phosphorus oxychloride condensation polymer containing a small amount of phosphorus oxychloride obtained；The bisphenol-A phosphoryl chloride phosphorus oxychloride condensation polymer containing trace phosphorus oxychloride obtained and phenol reactant make BDP crude product, and after BDP crude product is dissolved in solvent, then pickling, alkali cleaning, washing, decompression distillation obtains BDP product.The present invention is not increasing and on the premise of change equipment, assists vacuum to blow down the phosphorus oxychloride remained by the creative hydrogen chloride gas utilizing reactant reaction to produce, obtains the bisphenol-A phenyl condensed phosphoric esters of low triphenyl content.
Description
Technical field
The present invention relates to the industrialized process for preparing of a kind of bisphenol-A phenyl phosphorus contracting phosphorus polyacids ester, more specifically to arrive
The industrialized process for preparing of the bisphenol-A phenyl phosphorus contracting phosphorus polyacids ester BDP of a kind of low triphenyl content, this product is a kind of
Excellent fire retardant for various engineering plastics.
Background technology
Use the fire proofings such as flame retardant plastics to improve goods fire savety, be the most increasingly subject at each department of national economy
To paying close attention to and paying attention to.Each application of engineering plastics all fire resistances to material propose more and more strict requirements,
Particularly electronic information industry.In recent years the application industry of fire-resistant engineering plastics is just at expanding day, in five large-engineering plastics, past
Toward needing to carry out flame-retardant modified to it, the needs of all types of user could be met.
Before 1986, fire-resistant engineering plastics is nearly all bromine system product, although up to this point, fire-resistant engineering plastics
Industrialization product in also have the most most use bromide fire retardant such as deca-BDE, TDE and tetrabromobisphenol A
Deng, also have phosphorus compound such as phosphate toluene diphenyl ester and the triphenyl phosphate etc. of some low-molecular-weights simultaneously.Bromide fire retardant because of
Carcinogenecity material dioxin can be produced during burning, and incompatible with environmental protection, and the phosphorus compound fire retardant of low-molecular-weight is low because of it
Decomposition temperature and high volatility, produce big impact to the performance of engineering plastics.Therefore from the beginning of the nineties in last century, based on ring
Protecting and the requirement of sustainable development, the non-halogen cry of fire-resistant engineering plastics is with increasing intensity daily, and some bromide fire retardants are the most disabled,
Also having some also to treat for the discretion of people institute, application is restricted.Based on above-mentioned factor, condensation polymer type phosphorus flame retardant oneself start
To extensive concern.In condensation polymer type phosphorus flame retardant, bisphenol-A phenyl condensed phosphoric esters (being called for short BDP) fire retardant is at engineering plastics
As in PC/ABS alloy and PPE/HIPS Alloyapplication because of its efficiently, environmental protection and little and made in a large number on material property impact
With.But, engineering plastics are typically machine-shaping under the high temperature more than 200 DEG C, thus processed at fire-resistant engineering plastics
Cheng Zhonghui produces following problems: when use low-molecular-weight phosphate flame retardant such as triphenyl phosphate (TPP) etc., in processing and forming
Period low-molecular-weight phosphate flame retardant is decomposed because of its low heat decomposition temperature, catabolite can pollute mould again thus
Produce bad moulding article, the most even can decomposite corrosive substance and make mould generation corrosion-damaged, moreover because it is low
Molecular weight, therefore easily volatilize, the problem such as ooze out, affect anti-flammability and other physical property of goods.And BDP is big because of it
Molecular weight, high heat decomposition temperature and low volatility and overcome use low-molecular-weight phosphorus with the good compatibility of material
Ester flame-proof agent such as TPP and the problems referred to above of producing.
Current technological improvement in terms of the industrialized process for preparing and production thereof of BDP oneself have very in-depth study,
Such as: US5281741, US5750756, CN1414968A, CN01821930, CN1361786 etc., its production process is as follows: first
The phosphorus oxychloride of bisphenol-A and excess is reacted under catalyst such as anhydrous magnesium chloride participates in;Then the trichlorine of excess is removed in distillation
Oxygen phosphorus;Make BDP crude product again with proper amount of phenol reactant, further to BDP crude product by after pickling, alkali cleaning, washing, distill
Desolventizing and water, be filtrated to get BDP product.The BDP that generally commercial scale produces is generally possibly together with the triphenyl phosphorus of about 1-3%
Acid esters TPP, and the existence of TPP can cause the defect of mechanograph, pollute and corrode mould, easily volatilizees, oozes after entering material
The problem such as go out, affect anti-flammability and other physical property of goods.
Summary of the invention
The present inventor finds after actively research, and in BDP, the main source of TPP is in bisphenol-A and the phosphorus oxychloride of excess
After after reaction, the phosphorus oxychloride of excess is removed in distillation, the phosphorus oxychloride of residual generates TPP with phenol reactant, therefore fully reduces residual
The amount staying phosphorus oxychloride becomes the key factor of preparation of industrialization low TPP content BDP.Typically require for effectively removing phosphorus oxychloride
Improve vacuum during distillation, or utilize nitrogen bubble under vacuum, it is possible to by increasing some particularly efficient steamings
Evaporate equipment such as membrane evaporator etc. and improve the removal effect of phosphorus oxychloride, yet with in Distallation systm containing phosphorus oxychloride,
The highly acid materials such as hydrogen chloride, have the strongest anti-corrosive properties to the equipment of general material, thereby through improving vacuum or using it
Its efficient distillation equipment all can be greatly increased cost of investment, can improve follow-up cost of equipment maintenance simultaneously, finally makes production become
This rising.
For the above-mentioned problems in the prior art, it is desirable to provide a kind of low triphenyl content is double
The industrialized process for preparing of phenol A phenyl condensed phosphoric esters, to overcome problem present in existing preparation of industrialization technology.The present invention
People finds, the phosphorus oxychloride reaction in part bisphenol-A and excess generates the bisphenol-A phosphoryl chloride phosphorus oxychloride condensation polymer containing phosphorus oxychloride, so
After the phosphorus oxychloride of overwhelming majority excess is removed in final vacuum distillation, then utilize twin screw solid charger under maintaining vacuum state
It is continuously added to remaining bisphenol-A, utilizes bisphenol-A and the bisphenol-A phosphoryl chloride phosphorus oxychloride condensation polymer containing a small amount of phosphorus oxychloride to react generation
A large amount of hydride hydrogen gases, after collaborative vacuum condition blows down the phosphorus oxychloride of residual, then with phenol reactant, the final TPP that reduces is at BDP
In content.
The industrialized process for preparing of the bisphenol-A phenyl condensed phosphoric esters of described a kind of low triphenyl content, mistake
Journey is as follows:
1) bisphenol-A is divided into two parts, is initially charged wherein part bisphenol-A and phosphorus oxychloride and reacts raw in the presence of a catalyst
Become containing the bisphenol-A phosphoryl chloride phosphorus oxychloride condensation polymer of phosphorus oxychloride, there is following structure:
, wherein: n=1,2,3 ...；
2) big portion in the bisphenol-A phosphoryl chloride phosphorus oxychloride condensation polymer containing phosphorus oxychloride that distillation removal step 1 obtains under vacuum
Part excess phosphorus oxychloride, obtains the bisphenol-A phosphoryl chloride phosphorus oxychloride condensation polymer still containing a small amount of phosphorus oxychloride；
3) under vacuum, continuously to step 2) in the bisphenol-A phosphoryl chloride phosphorus oxychloride condensation polymer that obtains adds remaining bis-phenol
A, obtains the bisphenol-A phosphoryl chloride phosphorus oxychloride condensation polymer containing trace phosphorus oxychloride；
4) it is thick that bisphenol-A phosphoryl chloride phosphorus oxychloride condensation polymer and phenol reactant step 3) obtained makes bisphenol-A phenyl condensed phosphoric esters
Product；
5) bisphenol-A phenyl condensed phosphoric esters crude product step 4) obtained is dissolved in organic solvent, by pickling, alkali cleaning,
After washing, decompression distillation desolventizing and water, finally it is filtrated to get bisphenol-A phenyl condensed phosphoric esters product, its chemical structural formula is such as
Shown in lower:
Wherein: n=0,1,2,3 ...,
As n=0, for triphenyl TPP, there is following structure:
As n=1, referred to as bisphenol-A phenyl condensed phosphoric esters list aggressiveness, as n=2, referred to as bisphenol-A phenyl condensed phosphoric esters
Dimer, during n=n, for bisphenol-A phenyl condensed phosphoric esters n aggressiveness.
The industrialized process for preparing of the bisphenol-A phenyl condensed phosphoric esters of described low triphenyl content, its feature
It is that bisphenol-A is 1:4-10 with the molar ratio of phosphorus oxychloride.
The industrialized process for preparing of the bisphenol-A phenyl condensed phosphoric esters of described low triphenyl content, its feature
It is that the bisphenol-A added in step 1) reaction accounts for the 90-99% of bisphenol-A total amount.
The industrialized process for preparing of the bisphenol-A phenyl condensed phosphoric esters of described low triphenyl content, its feature
It is that the bisphenol-A added in step 3) reaction accounts for the 1-10% of bisphenol-A total amount.
The industrialized process for preparing of the bisphenol-A phenyl condensed phosphoric esters of described low triphenyl content, its feature
It is that catalyst described in step 1) is anhydrous magnesium chloride, aluminum trichloride (anhydrous) or anhydrous titanium tetrachloride.
The commercial process of the present invention described in detail below.
1) to equipped with bisphenol-A solid Double-screw feeder, phosphorus oxychloride backflow and vacuum distillation plant and hydrogen chloride gas
The reactor of body absorption plant puts into phosphorus oxychloride and catalyst, is warmed up to 90-100 DEG C, use Double-screw feeder continuous
Adding bisphenol-A to feed intake the bisphenol-A of total amount 90-99%, after adding, at 100-110 DEG C, insulation is to reaction completely；
2) reactor system is transformed into be furnished with phosphorus oxychloride distillate velocity determination equipment phosphorus oxychloride backflow and vacuum
Distilling apparatus, gradually promotes reactor vapo(u)rizing temperature and vacuum, phosphorus oxychloride is evaporated off, when temperature is 130-140 DEG C, and vacuum
For 0.093-0.097Mpa, and when phosphorus oxychloride distillated speed less than 10ML/ minute, complete phosphorus oxychloride distillation process；
3) continue to keep step 2) vacuum distilling state, maintain temperature 130-140 DEG C, even with Double-screw feeder simultaneously
The remaining 1-10% bisphenol-A of continuous addition, is incubated to bisphenol-a reaction complete after adding material；
4) in step 3), add phenol reactant and make BDP crude product；
5) BDP crude product step 4) obtained is dissolved in organic solvent, by pickling, alkali cleaning, washing, decompression distillation removing
The processes such as solvent and water, are finally filtrated to get BDP product.
The present invention is not increasing and on the premise of change equipment, by the creative chlorination utilizing reactant reaction to produce
Hydrogen assists vacuum to blow down the phosphorus oxychloride of residual, solves the problems referred to above.
Accompanying drawing explanation
Fig. 1 is the HPLC analysis chart of the BDP that the embodiment of the present invention 1 obtains；
Fig. 2 is the HPLC analysis chart of the BDP that comparative example of the present invention obtains.
Detailed description of the invention
Further illustrating the present invention by following embodiment, comparing embodiment, they are not to be construed as protecting the present invention
The restriction of scope.
The industrialized process for preparing of the bisphenol-A phenyl condensed phosphoric esters of the low triphenyl content of the present invention, including
Following steps:
1) to equipped with bisphenol-A solid Double-screw feeder, phosphorus oxychloride backflow and vacuum distillation plant and hydrogen chloride gas
The reactor of body absorption plant puts into the phosphorus oxychloride relative to bisphenol-A mole 4-10 times, adds phosphorus oxychloride weight
The catalyst of 0.2-1%, is warmed up to 90-100 DEG C, uses Double-screw feeder to be continuously added to account for total bisphenol-A inventory 90-99% double
Phenol A, after adding, at 100-110 DEG C, insulation is complete to reaction；Described catalyst is anhydrous magnesium chloride, aluminum trichloride (anhydrous) or nothing
Water titanium tetrachloride；
2) system is transformed into it is furnished with phosphorus oxychloride and distillates the phosphorus oxychloride distilling apparatus of velocity determination equipment, gradually promote
Vapo(u)rizing temperature and vacuum, when temperature to 130-140 DEG C, vacuum reaches 0.093-0.097Mpa, and phosphorus oxychloride distillates speed
Degree is less than a certain when determining value, completes phosphorus oxychloride distillation process；
3) continue to keep vacuum distilling state, maintain temperature 130-140 DEG C, be continuously added to remain with Double-screw feeder simultaneously
Remaining 1-10% bisphenol-A, is incubated to bisphenol-a reaction complete after adding material；
4) product utilizing technology well-known in the art step 3) to be obtained makes BDP with proper amount of phenol reactant
Crude product；
5) utilize technology well-known in the art that BDP crude product is dissolved in toluene equal solvent, by pickling, alkali cleaning, washing,
The processes such as decompression distillation desolvation and water, are finally filtrated to get BDP product.
The detection method of TPP content in the BDP that the present invention obtains, uses liquid chromatograph (HPLC) to analyze, uses area normalization
Method determines content.
Detecting instrument:
Chromatograph of liquid: LC-10AT；Chromatographic column: VP-ODS 150L*4.6；Detector: SPA-10A
Test condition is:
Eluent: methanol: water=9:1；Temperature: 25 DEG C；Flow velocity: 1.0mL/ minute；Volume injected: 10 μ L；Detection ripple
Long: 254nm
Embodiment 1:
1) equipped with bisphenol-A solid Double-screw feeder, phosphorus oxychloride backflow and vacuum distillation plant and hydrogen chloride gas
The 6300L reactor of body absorption plant puts into phosphorus oxychloride 6060 kilograms (39.48 kilomol), adds the anhydrous chlorination of catalyst
20 kilograms of magnesium, is warmed up to 97 DEG C, uses Double-screw feeder to be continuously added to account for total bisphenol-A inventory 95% bisphenol-A 1425 kilograms
(6.25 kilomol), adds for about 6 hours, then is incubated about 2 hours at 100-110 DEG C to reaction completely；
2) system is transformed into it is furnished with phosphorus oxychloride and distillates the phosphorus oxychloride distilling apparatus of velocity determination equipment, gradually promote
Vapo(u)rizing temperature and vacuum, after about 5 hours, temperature is raised to about 135 DEG C, and vacuum reaches 0.096Mpa, and phosphorus oxychloride evaporates
When going out speed less than 10ML/ minute, complete phosphorus oxychloride distillation process；
3) continue to keep vacuum distilling state, maintain temperature 130-140 DEG C, be continuously added to Double-screw feeder remaining
5% bisphenol-A 150 kilograms (0.658 kilomol), after about 20 minutes add material, more under vacuo insulation 1 hour complete to bisphenol-a reaction
Entirely；
4) step 3) reactant is proceeded to equipped with hydrogen chloride absorption device, phenol dropping equipment, phenol reflux condenser
Another 6300L reactor in, logical nitrogen, control temperature 130-140 DEG C, about 5 hours, be continuously added to phenol 2350 kilogram (25
Kilomol), the hydrogen chloride gas that reaction generates absorbs through absorption plant, after adding phenol, is incubated 1 hour at continuing 135 DEG C, then
Evacuation 1 hour under vacuum 0.096Mpa, makes BDP crude product；
5) being proceeded to by BDP crude product in the washing kettle of 20000L, the toluene solvant adding 10000 kilograms is warmed up to 65-75 DEG C,
Respectively washed once with the hydrochloric acid of 3000L5% concentration, the sodium hydroxide solution of 3000L5% concentration respectively, more respectively with 3000L go from
Sub-water washes twice, then is proceeded to by washed solution in precipitation still, after decompression Distillation recovery toluene, refilters and obtains BDP product
Product, detect through HPLC, and its HPLC spectrogram is as it is shown in figure 1, the content of triphenyl TPP is: 0.39%.
Embodiment 2:
1) equipped with bisphenol-A solid Double-screw feeder, phosphorus oxychloride backflow and vacuum distillation plant and hydrogen chloride gas
The 6300L reactor of body absorption plant puts into phosphorus oxychloride 6060 kilograms (39.48 kilomol), adds the anhydrous trichlorine of catalyst
Change 20 kilograms of aluminum, be warmed up to 100 DEG C, use Double-screw feeder to be continuously added to account for total bisphenol-A inventory 90% bisphenol-A 1350 public
Jin (5.92 kilomol), adds for about 6 hours, then is incubated 2 hours at 100-110 DEG C to reaction completely；
2) system is transformed into it is furnished with phosphorus oxychloride and distillates the phosphorus oxychloride distilling apparatus of velocity determination equipment, gradually promote
Vapo(u)rizing temperature and vacuum, after about 5 hours, temperature is raised to 140 DEG C, and vacuum reaches 0.093Mpa, and phosphorus oxychloride distillates speed
When degree was less than 10ML/ minute, complete phosphorus oxychloride distillation process；
3) continue to keep vacuum distilling state, maintain temperature 130-140 DEG C, be continuously added to Double-screw feeder remaining
10% bisphenol-A 75 kilograms (0.329 kilomol), after about 20 minutes add material, then is incubated 1 hour to bisphenol-a reaction under vacuo
Completely.
4) step 3) reactant is proceeded to equipped with hydrogen chloride absorption device, phenol dropping equipment, phenol reflux condenser
Another 6300L reactor in, logical nitrogen, control temperature 130-140 DEG C, about 5 hours, be continuously added to phenol 2350 kilogram (25
Kilomol), the hydrogen chloride gas that reaction generates absorbs through absorption plant, after adding phenol, is incubated 1 hour at continuing 135 DEG C, then
Evacuation 1 hour under vacuum 0.096Mpa, makes BDP crude product；
5) being proceeded to by BDP crude product in the washing kettle of 20000L, the toluene solvant adding 10000 kilograms is warmed up to 65-75 DEG C,
Respectively washed once with the hydrochloric acid of 3000L5% concentration, the sodium hydroxide solution of 3000L5% concentration respectively, more respectively with 3000L go from
Sub-water washes twice, then is proceeded to by washed solution in precipitation still, after decompression Distillation recovery toluene, refilters and obtains BDP product
Product.The content detecting triphenyl TPP through HPLC is: 0.28%.
Embodiment 3:
Operation is with embodiment 1, and wherein before and after bisphenol-A, twice rate of charge is 99:1, obtains in BDP product, detects through HPLC
The content of triphenyl TPP is: 0.45%.
Comparing embodiment:
1) similar with above-described embodiment, simply use Double-screw feeder to add whole bisphenol-As 1500 kilograms continuously
(6.579 kilomol).
2) similar with above-described embodiment, after 5h, temperature is raised to about 135 degree, and vacuum reaches 0.096Mpa, and
When phosphorus oxychloride distillated speed less than 10ML/ minute, continue to extend distillation time 3 hours, complete phosphorus oxychloride distillation process.
3) operating process of embodiment is not carried out
4) equally operate with above-described embodiment
5) equally operating with above-described embodiment, detect through HPLC, its HPLC spectrogram is as in figure 2 it is shown, triphenyl TPP
Content be: 2.84%.
Show from Fig. 1, Fig. 2 data and learn, compared with comparative example, by TPP in the BDP product prepared by the present invention
Content is significantly reduced.
Claims (5)
1. an industrialized process for preparing for the bisphenol-A phenyl condensed phosphoric esters of low triphenyl content, process is as follows:
Bisphenol-A is divided into two parts by step 1), is initially charged wherein part bisphenol-A and phosphorus oxychloride and reacts raw in the presence of a catalyst
Becoming the bisphenol-A phosphoryl chloride phosphorus oxychloride condensation polymer containing phosphorus oxychloride, described catalyst is anhydrous magnesium chloride, aluminum trichloride (anhydrous) or anhydrous tetrachloro
Changing titanium, bisphenol-A phosphoryl chloride phosphorus oxychloride condensation polymer has a following structure:
, wherein: n=1,2,3 ...；
Step 2) distill big portion in the bisphenol-A phosphoryl chloride phosphorus oxychloride condensation polymer containing phosphorus oxychloride that removal step 1 obtains under vacuum
Part excess phosphorus oxychloride, obtains the bisphenol-A phosphoryl chloride phosphorus oxychloride condensation polymer still containing a small amount of phosphorus oxychloride；
Step 3) under vacuum, continuously to step 2) in the bisphenol-A phosphoryl chloride phosphorus oxychloride condensation polymer that obtains adds remaining bis-phenol
A, obtains the bisphenol-A phosphoryl chloride phosphorus oxychloride condensation polymer containing trace phosphorus oxychloride；
It is thick that bisphenol-A phosphoryl chloride phosphorus oxychloride condensation polymer and the phenol reactant that step 3) is obtained by step 4) makes bisphenol-A phenyl condensed phosphoric esters
Product；
The bisphenol-A phenyl condensed phosphoric esters crude product that step 4) is obtained by step 5) is dissolved in organic solvent, by pickling, alkali cleaning,
After washing, decompression distillation desolventizing and water, finally it is filtrated to get bisphenol-A phenyl condensed phosphoric esters product, its chemical structural formula is such as
Shown in lower:
Wherein: n=0,1,2,3 ...,
As n=0, for triphenyl TPP, there is following structure:
As n=1, referred to as bisphenol-A phenyl condensed phosphoric esters list aggressiveness, as n=2, referred to as bisphenol-A phenyl condensed phosphoric esters dimerization
Body, during n=n, for bisphenol-A phenyl condensed phosphoric esters n aggressiveness.
The preparation of industrialization of the bisphenol-A phenyl condensed phosphoric esters of low triphenyl content the most according to claim 1
Method, it is characterised in that bisphenol-A is 1:4-10 with the molar ratio of phosphorus oxychloride.
The industrialization system of the bisphenol-A phenyl condensed phosphoric esters of low triphenyl content the most according to claim 1 and 2
Preparation Method, it is characterised in that bisphenol-A participates in reaction in step 1) with step 3) the most respectively.
The industrialization system of the bisphenol-A phenyl condensed phosphoric esters of low triphenyl content the most according to claim 1 and 2
Preparation Method, it is characterised in that the bisphenol-A added in step 1) reaction accounts for the 90-99% of bisphenol-A total amount.
The industrialization system of the bisphenol-A phenyl condensed phosphoric esters of low triphenyl content the most according to claim 1 and 2
Preparation Method, it is characterised in that the bisphenol-A added in step 3) reaction accounts for the 1-10% of bisphenol-A total amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510517984.5A CN105037418B (en) | 2015-08-21 | 2015-08-21 | A kind of industrialized process for preparing of the bisphenol-A phenyl condensed phosphoric esters of low triphenyl content |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510517984.5A CN105037418B (en) | 2015-08-21 | 2015-08-21 | A kind of industrialized process for preparing of the bisphenol-A phenyl condensed phosphoric esters of low triphenyl content |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105037418A CN105037418A (en) | 2015-11-11 |
| CN105037418B true CN105037418B (en) | 2016-09-21 |
Family
ID=54444436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510517984.5A Active CN105037418B (en) | 2015-08-21 | 2015-08-21 | A kind of industrialized process for preparing of the bisphenol-A phenyl condensed phosphoric esters of low triphenyl content |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105037418B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4039689A4 (en) * | 2020-12-07 | 2023-05-10 | Zhejiang Wansheng Co., Ltd | Continuous industrial production method for high-purity bisphenol a-bis(diphenyl phosphate) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317108B (en) * | 2016-08-24 | 2017-08-01 | 浙江万盛股份有限公司 | A kind of preparation method of the condensed phosphoric esters of bis-phenol in high yield |
| CN107629086B (en) * | 2017-09-25 | 2019-10-01 | 浙江万盛股份有限公司 | A kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants |
| CN112409404B (en) * | 2020-12-07 | 2022-08-09 | 浙江万盛股份有限公司 | Continuous industrial production method of high-purity bisphenol A-bis (diphenyl phosphate) |
| CN112607946B (en) * | 2020-12-17 | 2023-03-24 | 浙江万盛股份有限公司 | Method for recycling organic waste in BDP wastewater |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5661446A (en) * | 1979-10-24 | 1981-05-26 | Ajinomoto Co Inc | Stabilizer for halogen-containing resin |
| CN101565431A (en) * | 2008-04-22 | 2009-10-28 | 东莞市柏百顺石油化工有限公司 | Process for synthetizing phosphoester oligopolymer BDP |
-
2015
- 2015-08-21 CN CN201510517984.5A patent/CN105037418B/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4039689A4 (en) * | 2020-12-07 | 2023-05-10 | Zhejiang Wansheng Co., Ltd | Continuous industrial production method for high-purity bisphenol a-bis(diphenyl phosphate) |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105037418A (en) | 2015-11-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105037418B (en) | A kind of industrialized process for preparing of the bisphenol-A phenyl condensed phosphoric esters of low triphenyl content | |
| CN101157670A (en) | Method for synthesizing epichlorohydrin | |
| CN106317108B (en) | A kind of preparation method of the condensed phosphoric esters of bis-phenol in high yield | |
| CN105061499B (en) | A kind of industrialized process for preparing of the resorcinol phenyl condensed phosphoric esters of low triphenyl content | |
| CN106008592A (en) | Industrial synthesis method of tris(butoxyethyl)phosphate and device thereof | |
| CN103408460B (en) | Recovery method of secondary products of iminodiacetonitrile and mother liquid treatment method | |
| CN110317228A (en) | A kind of preparation method of bisphenol-A-bis- (diphenyl phosphoesters) | |
| JPH06316586A (en) | Production of poly(hydrocarbylenearylphosphate) composition | |
| CN108148089A (en) | A kind of preparation method of four (dimethylamino) titaniums | |
| CN101899064B (en) | Preparation method of dihydric phenol di(dialkyl phenyl organic phosphate) | |
| CN108164393B (en) | Preparation method of deuterated tert-butyl alcohol | |
| CN102264747B (en) | Water miscible solvent based process for purifying bisphosphate | |
| CN105272827A (en) | Catalysis method for synthesizing bisphenol F | |
| US20160137520A1 (en) | Method of making sodium carbonate and/or sodium bicarbonate | |
| CN105037419B (en) | A kind of preparation method of chlorination diphenyl phosphate | |
| CN109912644B (en) | Post-treatment purification process for TCPP (trichloropropylphosphate) production crude product | |
| CN102532601A (en) | Novel halogen-free fire retardant ethanediamine diphenyl diphosphate and preparation method thereof | |
| CN105130781A (en) | Preparation method of 2-hydroxyacetophenone | |
| CN101270132A (en) | Method for preparing triphenylphosphine with diphenylbenzene phosphine oxide | |
| CN110451684A (en) | The processing method of Lauryl Alcohol ester production technology waste water | |
| CN110256488A (en) | A kind of preparation method of the aryl condensed phosphoric esters of micro content triphenyl phosphate | |
| EP3041816B1 (en) | Lactate production process | |
| CN103130721A (en) | Ornidazole green synthetic method | |
| CN213295217U (en) | Phosphorus reaction type flame retardant serialization apparatus for producing | |
| CN112608259B (en) | Synthetic method of 3-mercaptopropionic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |