CN101941989B - Tetra-(0,0-dialkyl phosphonyl) p-benzoquinone and preparation method thereof - Google Patents
Tetra-(0,0-dialkyl phosphonyl) p-benzoquinone and preparation method thereof Download PDFInfo
- Publication number
- CN101941989B CN101941989B CN2010102603556A CN201010260355A CN101941989B CN 101941989 B CN101941989 B CN 101941989B CN 2010102603556 A CN2010102603556 A CN 2010102603556A CN 201010260355 A CN201010260355 A CN 201010260355A CN 101941989 B CN101941989 B CN 101941989B
- Authority
- CN
- China
- Prior art keywords
- preparation
- phosphite
- sherwood oil
- benzoquinone
- para benzoquinone
- 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.)
- Expired - Fee Related
Links
- 0 *C(*=C(*1)Cl)C(Cl)=C1Cl Chemical compound *C(*=C(*1)Cl)C(Cl)=C1Cl 0.000 description 2
Landscapes
- Fireproofing Substances (AREA)
Abstract
The invention relates to tetra-(0,0-dialkyl phosphonyl) p-benzoquinone and a preparation method thereof. The structure of the compound is shown in the specification, wherein R is straight chain or branched chain alkyl containing 1-8 C atoms. The preparation method comprises the following steps: adding a certain molar ratio of chloranil and tris phosphite (P(OR)3) into an organic solvent under the heating condition for carrying out sustained reaction for a period of time, and then, purifying and drying the reactants to prepare the tetra-(0,0-dialkyl phosphonyl) p-benzoquinone. The tetra-(0,0-dialkyl phosphonyl) p-benzoquinone of the invention has high flame resistance, stable physical and chemical properties and good compatibility with high molecular materials, can be used as the flame retardant of polyester, polyamide, epoxy resin, glass reinforced plastic resin, paint and the like, is favorable for environment protection, has simple process, low equipment investment, low cost and high phosphorus content in products, and can realize scale production easily.
Description
Technical field
The present invention relates to a kind of organic phosphine compound and preparation method thereof, be specifically related to a kind of four (0,0-dialkyl phosphine acyl group) para benzoquinone and preparation method thereof, this compound can be used as the fire retardant of polyester, polymeric amide, epoxy resin, fiber glass resin, coating etc.
Background technology
At present, the whole world is very high to the non-halogen cry of fire retardant, because the organic phosphine fire retardant has low cigarette, low toxicity, the pollution-free favor that more receives people, the exploitation of environment-friendly type organic phosphine fire retardant has been become a research focus in the flame-retarded technology field.Though have novel organic phosphine fire retardant to succeed in developing at present,, hindered its large-scale production and application owing to reasons such as technology and price and processing characteristicies.The fire retardant kind that requires owing to the macromolecular material kind is more again to adapt is also more, and the organic phosphine fire retardant exists the property demanded urgently in market.This invention structural symmetry is good, belong to many phosphorus structure, and phosphorus content height, good stability, one-tenth charcoal property is good, volatility is low, and good, the good processability of intermiscibility of material, has very much novelty, and application development prospect is preferably arranged.
Summary of the invention
One of the object of the invention is to propose a kind of four (0,0-dialkyl phosphine acyl group) para benzoquinone compound, its synthesis technique is simple, physical and chemical performance stable, nontoxic, flame-retarded efficiency is high, with the macromolecular material consistency good, can overcome deficiency of the prior art.
For realizing the foregoing invention purpose, the present invention has adopted following technical scheme:
A kind of four (0,0-dialkyl phosphine acyl group) para benzoquinone is characterized in that the structure of this compound is shown below:
R is the straight or branched alkyl that contains 1～8 C atom.
Another object of the present invention is to propose the compound method of a kind of four (0,0-dialkyl phosphine acyl group) para benzoquinone, its technology is simple, be convenient to control, be easy to large-scale production, and low in raw material cost is easy to get, and facility investment is few, and is with low cost, and its technical scheme is following:
The preparation method of four (0,0-dialkyl phosphine acyl group) para benzoquinone as stated is characterized in that this method is:
Chloranil and tris phosphite (P (OR) with certain mol proportion
3), under heating condition, sustained reaction after for some time in organic solvent, to reactant purify, drying, process four (0,0-dialkyl phosphine acyl group) para benzoquinone.Wherein certain mol proportion is 1: 4～1: 8; Tris phosphite is a trimethyl phosphite, triethyl-phosphite, tricresyl phosphite propyl ester, tributyl phosphate, tricresyl phosphite pentyl ester, own ester of tricresyl phosphite or tricresyl phosphite monooctyl ester; Temperature of reaction is 60 ℃～130 ℃; Organic solvent can be a benzene, toluene, YLENE, chlorobenzene; Reaction times is 4～8h; Method of purification is for after steaming solvent (solvent recuperation utilization) with reactant; Cool off preliminary crystallization and go out portioned product; Add petroleum ether extraction again and go out the byproduct of reaction dialkyl alkylphosphonate, make product sufficient crystallising, filtration, dry four (0,0-dialkyl phosphine acyl group) para benzoquinone; Above-mentioned crystallization filtrated stock distillation is reclaimed sherwood oil and is obtained dialkyl alkylphosphonate.
The synthesis technique principle of this four (0,0-dialkyl phosphine acyl group) para benzoquinone is shown below:
Compared with prior art, beneficial effect of the present invention is:
1. because symmetry constitutional features, many phosphorus constitutional features of organic phosphine fire retardant four of the present invention (0,0-dialkyl phosphine acyl group) para benzoquinone, it is good with the macromolecular material intermiscibility, and can not change the mechanical property of material, the flame-retarded efficiency height;
2. four (0,0-dialkyl phosphine acyl group) of the present invention para benzoquinone is not halogen-containing, helps environmental protection, so good prospects for application is arranged;
The synthesis technique of four (0,0-dialkyl phosphine acyl group) 3. of the present invention para benzoquinone is single step reaction, and is simple and easy to control, and building-up process need not to add catalyzer, need not the special reaction condition, and equipment is simple, and is with low cost, is suitable for large-scale production.
The synthesis reaction solvent of four (0,0-dialkyl phosphine acyl group) 4. of the present invention para benzoquinone is directly recycled, and the distillation of purification solvent sherwood oil is reclaimed and used, and obtains by product organic phosphine fire retardant dialkyl alkylphosphonate simultaneously.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is further specified.
Embodiment 1 adds 0.2mol chloranil and 160ml benzene in the 500ml four-hole bottle of whisking appliance and TM is housed, stir and make its dissolving, is warmed up to 60 ℃; Drip the 1.0mol trimethyl phosphite in 3 hours, holding temperature reaction 7h, reaction finishes the back underpressure distillation and goes out benzene, is cooled to 25 ℃; Drip sherwood oil, slowly separate out white crystal, filter, filter cake is used petroleum ether; Filter cake gets white needle-like crystals four (0,0-dimethyl phosphine acyl group) para benzoquinone through vacuum-drying; Its productive rate is 60%, and fusing point is 97 ± 1 ℃, and decomposition temperature is 237 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the methyl-phosphorous acid dimethyl esters.
Embodiment 2 adds 0.2mol chloranil and 160ml toluene in the 500ml four-hole bottle of whisking appliance and TM is housed, stir and make its dissolving, is warmed up to 100 ℃; Drip the 0.8mol trimethyl phosphite in 3 hours, holding temperature reaction 6h, reaction finishes the back underpressure distillation and goes out toluene, is cooled to 25 ℃; Drip sherwood oil, slowly separate out white crystal, filter, filter cake is used petroleum ether; Filter cake gets white needle-like crystals four (0,0-dimethyl phosphine acyl group) para benzoquinone through vacuum-drying; Its productive rate is 73%, and fusing point is 97 ± 1 ℃, and decomposition temperature is 237 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the methyl-phosphorous acid dimethyl esters.
Embodiment 3 adds 0.2mol chloranil and 160ml toluene in the 500ml four-hole bottle of whisking appliance and TM is housed, stirring makes its dissolving, elevated temperature to 100 ℃; Drip the 1.6mol trimethyl phosphite in 3 hours, holding temperature reaction 6h, reaction finishes the back underpressure distillation and goes out toluene, is cooled to 25 ℃; Drip sherwood oil, slowly separate out white crystal, filter, filter cake is used petroleum ether; Filter cake gets white needle-like crystals four (0,0-dimethyl phosphine acyl group) para benzoquinone through vacuum-drying; Its productive rate is 88%, and fusing point is 97 ± 1 ℃, and decomposition temperature is 237 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the methyl-phosphorous acid dimethyl esters.
Embodiment 4 adds 0.2mol chloranil and 160ml toluene in the 500ml four-hole bottle of whisking appliance and TM is housed, stirring makes its dissolving, elevated temperature to 90 ℃; Drip the 1.2mol trimethyl phosphite in 3 hours, holding temperature reaction 6h, reaction finishes the back underpressure distillation and goes out toluene, is cooled to 25 ℃; Drip sherwood oil, slowly separate out white crystal, filter, filter cake is used petroleum ether; Filter cake gets white needle-like crystals four (0,0-dimethyl phosphine acyl group) para benzoquinone through vacuum-drying; Its productive rate is 90%, and fusing point is 97 ± 1 ℃, and decomposition temperature is 237 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the methyl-phosphorous acid dimethyl esters.
Embodiment 5 adds 0.2mol chloranil and 160ml chlorobenzene in the 500ml four-hole bottle of whisking appliance and TM is housed, stirring makes its dissolving, elevated temperature to 80 ℃; Drip the 1.4mol trimethyl phosphite in 3 hours, holding temperature reaction 4h, reaction finishes the back underpressure distillation and goes out chlorobenzene, is cooled to 25 ℃; Drip sherwood oil, slowly separate out white crystal, filter, filter cake is used petroleum ether; Filter cake gets white needle-like crystals four (0,0-dimethyl phosphine acyl group) para benzoquinone through vacuum-drying; Its productive rate is 70%, and fusing point is 97 ± 1 ℃, and decomposition temperature is 237 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the methyl-phosphorous acid dimethyl esters.
Embodiment 6 adds 0.2mol chloranil and 160ml YLENE in the 500ml four-hole bottle of whisking appliance and TM is housed, stirring makes its dissolving, elevated temperature to 80 ℃; Drip the 1.0mol trimethyl phosphite in 3 hours, holding temperature reaction 8h, reaction finishes the back underpressure distillation and goes out YLENE, is cooled to 25 ℃; Drip sherwood oil, slowly separate out white crystal, filter, filter cake is used petroleum ether; Filter cake gets white needle-like crystals four (0,0-dimethyl phosphine acyl group) para benzoquinone through vacuum-drying; Its productive rate is 83%, and fusing point is 97 ± 1 ℃, and decomposition temperature is 237 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the methyl-phosphorous acid dimethyl esters.
Embodiment 7 adds 0.2mol chloranil and 160ml YLENE in the 500ml four-hole bottle of whisking appliance and TM is housed, stirring makes its dissolving, elevated temperature to 90 ℃; Drip the 1.2mol trimethyl phosphite in 3 hours, holding temperature reaction 8h, reaction finishes the back underpressure distillation and goes out YLENE, is cooled to 25 ℃; Drip sherwood oil, slowly separate out white crystal, filter, filter cake is used petroleum ether; Filter cake gets white needle-like crystals four (0,0-dimethyl phosphine acyl group) para benzoquinone through vacuum-drying; Its productive rate is 86%, and fusing point is 97 ± 1 ℃, and decomposition temperature is 237 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the methyl-phosphorous acid dimethyl esters.
Embodiment 8 adds 0.2mol chloranil and 240ml benzene in the 1000ml four-hole bottle of whisking appliance and TM is housed, stirring makes its dissolving, elevated temperature to 80 ℃; Drip the 1.0mol triethyl-phosphite in 3 hours, holding temperature reaction 7h, reaction finishes the back underpressure distillation and goes out benzene, is cooled to 25 ℃; Drip sherwood oil, slowly separate out white crystal, filter, filter cake is used petroleum ether; Filter cake gets white needle-like crystals four (0, the 0-diethyl phosphonyl) para benzoquinone through vacuum-drying; Its productive rate is 62%, and fusing point is 179 ± 1 ℃, and decomposition temperature is 242 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the ethylphosphonic acid diethyl ester.
Embodiment 9 adds 0.2mol chloranil and 240ml chlorobenzene in the 1000ml four-hole bottle of whisking appliance and TM is housed, stirring makes its dissolving, elevated temperature to 130 ℃; Drip the 1.4mol triethyl-phosphite in 3 hours, holding temperature reaction 6h, reaction finishes the back underpressure distillation and goes out chlorobenzene, is cooled to 25 ℃; Drip sherwood oil, slowly separate out white crystal, filter, filter cake is used petroleum ether; Filter cake gets white needle-like crystals four (0, the 0-diethyl phosphonyl) para benzoquinone through vacuum-drying; Its productive rate is 75%, and fusing point is 179 ± 1 ℃, and decomposition temperature is 242 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the ethylphosphonic acid diethyl ester.
Embodiment 10 adds 0.2mol chloranil and 240ml toluene in the 1000ml four-hole bottle of whisking appliance and TM is housed, stirring makes its dissolving, elevated temperature to 100 ℃; Drip the 1.2mol triethyl-phosphite in 3 hours, holding temperature reaction 8h, reaction finishes the back underpressure distillation and goes out toluene, is cooled to 25 ℃; Drip sherwood oil, slowly separate out white crystal, filter, filter cake is used petroleum ether; Filter cake gets white needle-like crystals four (0, the 0-diethyl phosphonyl) para benzoquinone through vacuum-drying; Its productive rate is 80%, and fusing point is 179 ± 1 ℃, and decomposition temperature is 242 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the ethylphosphonic acid diethyl ester.
Embodiment 11 adds 0.2mol chloranil and 240ml toluene in the 1000ml four-hole bottle of whisking appliance and TM is housed, stirring makes its dissolving, elevated temperature to 110 ℃; Drip the 1.6mol triethyl-phosphite in 3 hours, holding temperature reaction 8h, reaction finishes the back underpressure distillation and goes out toluene, is cooled to 25 ℃; Drip sherwood oil, slowly separate out white crystal, filter, filter cake is used petroleum ether; Filter cake gets white needle-like crystals four (0, the 0-diethyl phosphonyl) para benzoquinone through vacuum-drying; Its productive rate is 86%, and fusing point is 179 ± 1 ℃, and decomposition temperature is 242 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the ethylphosphonic acid diethyl ester.
Embodiment 12 adds 0.2mol chloranil and 240ml YLENE in the 1000ml four-hole bottle of whisking appliance and TM is housed, stirring makes its dissolving, elevated temperature to 90 ℃; Drip the 1.0mol triethyl-phosphite in 3 hours, holding temperature reaction 6h, reaction finishes the back underpressure distillation and goes out YLENE, is cooled to 25 ℃; Drip sherwood oil, slowly separate out white crystal, filter, filter cake is used petroleum ether; Filter cake gets white needle-like crystals four (0, the 0-diethyl phosphonyl) para benzoquinone through vacuum-drying; Its productive rate is 78%, and fusing point is 179 ± 1 ℃, and decomposition temperature is 242 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the ethylphosphonic acid diethyl ester.
Embodiment 13 adds 0.2mol chloranil and 240ml YLENE in the 1000ml four-hole bottle of whisking appliance and TM is housed, stirring makes its dissolving, elevated temperature to 110 ℃; Drip the 1.2mol triethyl-phosphite in 3 hours, holding temperature reaction 6h, reaction finishes the back underpressure distillation and goes out YLENE, is cooled to 25 ℃; Drip sherwood oil, slowly separate out white crystal, filter, filter cake is used petroleum ether; Filter cake gets white needle-like crystals four (0, the 0-diethyl phosphonyl) para benzoquinone through vacuum-drying; Its productive rate is 90%, and fusing point is 179 ± 1 ℃, and decomposition temperature is 242 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the ethylphosphonic acid diethyl ester.
This case contriver is also with above-mentioned synthetic four (0; 0-dialkyl phosphine acyl group) para benzoquinone is applied in the fiber glass resin, after getting four (0,0-dialkyl phosphine acyl group) para benzoquinone and fiber glass resin and mixing red material that the back adds 4% white material and 2% and stir; Pour into and process the thick sheet material of 3mm in the mould that is placed with one deck glass wool cloth; Cut into the batten of wide 7mm, thick 3mm, long 150mm again, and its flame retardant properties is tested, test-results is as shown in the table:
This shows that above-mentioned four (0,0-dimethyl phosphine acyl group) para benzoquinone really has the excellent flame retardancy ability.
This shows that above-mentioned four (0, the 0-diethyl phosphonyl) para benzoquinone really has the excellent flame retardancy ability.
Claims (10)
1. a para benzoquinone compound is characterized in that, the structure of this compound is shown below:
R is the straight or branched alkyl that contains 1～8 C atom, and its prerequisite is that R is not the secondary alkyl group of 3 to 6 C atoms.
2. the preparation method of para benzoquinone compound according to claim 1 is characterized in that this method is:
With the chloranil of certain mol proportion and tris phosphite under heating condition, sustained reaction after for some time in organic solvent, to reactant purify, drying treatment, process the para benzoquinone compound.
3. preparation method according to claim 2 is characterized in that certain mol proportion is that the mol ratio of chloranil and tris phosphite is 1: 4～1: 8.
4. preparation method according to claim 2 is characterized in that tris phosphite is a trimethyl phosphite, triethyl-phosphite, tricresyl phosphite propyl ester, tributyl phosphate, tricresyl phosphite pentyl ester, the own ester of tricresyl phosphite, tricresyl phosphite monooctyl ester.
5. preparation method according to claim 2 is characterized in that heating condition is 60 ℃～130 ℃.
6. preparation method according to claim 2 is characterized in that organic solvent is benzene,toluene,xylene, chlorobenzene.
7. preparation method according to claim 2 is characterized in that the reaction times is 4～8h.
8. preparation method according to claim 2 is characterized in that method of purification is after reactant is steamed solvent, to cool off preliminary crystallization, drips the sherwood oil sufficient crystallising, filters oven dry.
9. preparation method according to claim 8 is characterized in that steaming solvent and directly reclaims use.
10. preparation method according to claim 8 is characterized in that dripping the sherwood oil sufficient crystallising, filters, and sherwood oil is reclaimed in its filtrated stock distillation, obtains by product organic phosphine fire retardant dialkyl alkylphosphonate simultaneously.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102603556A CN101941989B (en) | 2010-08-24 | 2010-08-24 | Tetra-(0,0-dialkyl phosphonyl) p-benzoquinone and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102603556A CN101941989B (en) | 2010-08-24 | 2010-08-24 | Tetra-(0,0-dialkyl phosphonyl) p-benzoquinone and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101941989A CN101941989A (en) | 2011-01-12 |
| CN101941989B true CN101941989B (en) | 2012-07-04 |
Family
ID=43434217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102603556A Expired - Fee Related CN101941989B (en) | 2010-08-24 | 2010-08-24 | Tetra-(0,0-dialkyl phosphonyl) p-benzoquinone and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101941989B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880624B (en) * | 2014-04-16 | 2015-07-29 | 苏州科技学院相城研究院 | Four allyloxy para benzoquinone compounds and preparation method thereof |
| CN108948087A (en) * | 2018-07-06 | 2018-12-07 | 苏州科技大学 | More silicon phosphine 1,4-benzoquinone compounds of coloured flame-retardant carbon forming agent and preparation method thereof |
| CN109021016A (en) * | 2018-07-06 | 2018-12-18 | 苏州科技大学 | Four PEPA oxygroup 1,4-benzoquinone compound of coloured flame-retardant carbon forming agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2935518A (en) * | 1958-09-12 | 1960-05-03 | Monsanto Chemicals | Reaction products of tetrahalogenated quinoid compounds and trisecondary alkyl phosphites and process of making same |
| US3159537A (en) * | 1960-12-20 | 1964-12-01 | American Cyanamid Co | Potentiation of tetracycline by phosphinic acid |
-
2010
- 2010-08-24 CN CN2010102603556A patent/CN101941989B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2935518A (en) * | 1958-09-12 | 1960-05-03 | Monsanto Chemicals | Reaction products of tetrahalogenated quinoid compounds and trisecondary alkyl phosphites and process of making same |
| US3159537A (en) * | 1960-12-20 | 1964-12-01 | American Cyanamid Co | Potentiation of tetracycline by phosphinic acid |
Non-Patent Citations (1)
| Title |
|---|
| Kazuya Kobiro et.al.p-Benzoquinone 2,3,5,6-Tetrakis(diisopropyl phosphonate): A Novel, Highly Bent p-Benzoquinone.《Chemistry Letters》.1999,(第7期),633-634. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101941989A (en) | 2011-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106243385B (en) | A kind of DOPO based flameproofings and preparation method thereof | |
| CN102146093B (en) | Cage-shaped organic silicon flame retardant charring agent and preparation method thereof | |
| CN102731549A (en) | Triazinetri-tri(chloropropyl) silicate compound and preparation method thereof | |
| CN101993456A (en) | Method for preparing phosphaphenanthrene and phosphazene halogen-free retardant agent | |
| CN101941989B (en) | Tetra-(0,0-dialkyl phosphonyl) p-benzoquinone and preparation method thereof | |
| CN102898450A (en) | Novel chlorine and bromine-containing bisilicate fire retardant compound and preparation method thereof | |
| WO2020019596A1 (en) | Phosphazene compound, composition comprising phosphazene compound, flame retardant comprising same, and use thereof | |
| CN102140115B (en) | Flame-retardant plasticizer of methyl silicate trichloroethyl ester compound and preparation method thereof | |
| CN102731825A (en) | Chloro- and bromo-containing silicate flame retardant compound and preparation method thereof | |
| CN102146092B (en) | Pentaerythritol methylsilicate and preparation method thereof | |
| CN105713042A (en) | Preparation method of bis(PEPA) phenylphosphonate compound | |
| CN105001265A (en) | Preparation method for flame retardant double-phosphorus-cage cyclic phosphate compound | |
| CN103275118A (en) | Phenyldipropylphosphinate compound and preparation method thereof | |
| CN104004024A (en) | Method for preparing caged tetracyclic phosphate siloxane flame-retardant charring agent | |
| CN104926875A (en) | Flame retardant hydroxymethyl phosphonyl heterocyclic phenylphosphonate compound and preparation method therefor | |
| CN102153780B (en) | Chlorine-containing methyl silicate flame retardant and preparation method thereof | |
| CN105503948A (en) | Di(tetrabromo bisphenol A) phenylphosphonothioate compound and preparation method thereof | |
| CN102174057B (en) | Organic silicon flame-retardant carbon-forming agent and preparation method thereof | |
| CN102731827A (en) | Novel tri(dichloropropyl) bisilicate flame retardant compound containing bromine and preparation method thereof | |
| CN103265574B (en) | Triazinyl triphenyl propyl phosphinate compound and preparation method thereof | |
| CN106478727B (en) | Fire retardant Phenylmethoxy silicic acid disulfide group phospha trioxa-l-phosphabicyclo octyl methyl compound and preparation method thereof | |
| CN103265578B (en) | Triazinyl triphenyl sec-butyl phosphinate compound and preparation method thereof | |
| CN103360625B (en) | Flame retardant tetra (O-methyl-phenyl phosphinic) glycoluril compound and preparation method therefor | |
| CN102140112A (en) | Halogenated organic silicate ester flame-retardant plasticizer compound and preparation method thereof | |
| CN106478726B (en) | Fire retardant diphenyl silicic acid disulfide group phospha trioxa-l-phosphabicyclo [2.2.2] octyl methyl compound and preparation method thereof |
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 | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| CB03 | Change of inventor or designer information |
Inventor after: Li Liuxin Inventor before: Wang Yanlin Inventor before: Yang Xing Inventor before: Ma Su Inventor before: Song Xiaohui |
|
| COR | Change of bibliographic data | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20161021 Address after: Xincai County of Henan province 463521 Lian Cun Zhen Tang Geng Cun Tang Geng two groups Patentee after: Li Liuxin Address before: 215011 Jiangsu high tech Zone Suzhou City Binhe Road, No. 1701 Patentee before: University of Science and Technology of Suzhou |
|
| DD01 | Delivery of document by public notice |
Addressee: Li Liuxin Document name: Notification of Passing Examination on Formalities |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120704 Termination date: 20180824 |