CN105001264A - Fire retardant, namely hydroxymethyl phosphine heterocyclic methylphosphonate compound, and preparation method therefor - Google Patents
Fire retardant, namely hydroxymethyl phosphine heterocyclic methylphosphonate compound, and preparation method therefor Download PDFInfo
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Abstract
The invention relates to a fire retardant, namely a hydroxymethyl phosphine heterocyclic methylphosphonate compound, and a preparation method therefor. The compound has a structure as shown in the specification. The preparation method is as follows: under the protection of nitrogen, equimolar hydroxymethyl phosphine and dimethyl methylphosphonate react at 110-160 DEG C for 4-10 hours in the presence of a catalyst; and purification treatment is performed to obtain a product, namely hydroxymethyl phosphine heterocyclic methylphosphonate. The compound is a high-phosphorus-content fire retardant and is excellent in flame retardant property and suitable for use as a fire retardant for unsaturated resin, polyvinyl alcohol, polyurethane, epoxy resin and the like. Moreover, the production process is simple, the equipment investment is low, and the industrialized production is easy to realize.
Description
Technical field
The present invention relates to a kind of organic phosphine fire retardant methylol phosphine heterocycle shape methyl-phosphorous acid ester cpds and preparation method thereof, be specifically related to a kind of 1-oxygen-1-methyl-4-methylol-2,6-dioxa-1,4-bis-phospha cyclohexane compound and preparation method thereof, this compound is suitable as the fire retardant of unsaturated polyester, polyvinyl alcohol, epoxy resin etc.; For urethane for adding reactive flame retardant; Also can be used as organic synthesis intermediate.
Background technology
According to the application of fire retardant, fire retardant can be divided into addition type and the large class of response type two.The former adds in by the course of processing of ignition resistant substrate, chemical reaction does not occur with other component in base material and base material, is be scattered in for physically in base material to give base material with flame retardant resistance, is used for thermal plasticity high polymer.The latter adds in by ignition resistant substrate manufacturing processed, or they are as the monomer of superpolymer, or participate in chemical reaction as linking agent, finally become the structural unit of superpolymer and give superpolymer with flame retardant resistance, being used for thermosetting high polymers.The complete processing of the fire-retardant superpolymer of additive flame retardant is simple, can meet the service requirements of most of material, but needs to solve the dispersiveness of fire retardant, consistency, the series of problems such as interface characteristics; The flame retardant resistance adopting reactive flame retardant to obtain then has relative permanent, and toxicity is lower, on also less by the impact of the physicals of flame-retardant polymer, but obtain the relative addition type of flame-retarded process and can arbitrarily not allocate.
The invention discloses a kind of reactive pattern machine phosphine fire retardant methylol phosphine heterocycle shape methyl-phosphorous acid ester cpds and preparation method thereof.Fire retardant of the present invention is ring texture, have that phosphorus content is high, good stability, flame-retarded efficiency are high, with the advantage such as material compatibility is good.Organic phosphine key (C-P key) in molecule can bring stability to compound, the stability of ring texture to compound also has contribution, simultaneously, also containing an activity hydroxy functional group in this structure, ingrain fireproofing material can be combined into as reactive flame retardant and macromolecular material in some aspects, have wide practical use.
Summary of the invention
An object of the present invention is to propose a kind of organic phosphine fire retardant methylol phosphine heterocycle shape methyl-phosphorous acid ester cpds, and its flame-retarded efficiency is high, is widely used, and can overcome deficiency of the prior art.
For achieving the above object, present invention employs following technical scheme:
A kind of organic phosphine fire retardant methylol phosphine heterocycle shape methyl-phosphorous acid ester cpds, it is characterized in that, the structure of this compound is shown below:
Another object of the present invention is to the preparation method proposing a kind of organic phosphine fire retardant methylol phosphine heterocycle shape methyl-phosphorous acid ester cpds, its technique is simple, facility investment is few, is easy to large-scale production, and the method is:
In the reactor that efficient fractionation plant is housed; under nitrogen protection; add equimolar tris(hydroxymethyl)phosphine and dimethyl methyl phosphonate, under stirring, then add a certain amount of catalyzer; be warming up to 110-160 DEG C of reaction 6-10h; control column top temperature not higher than 65 DEG C, the stopped reaction when the methyl alcohol fractionated out reaches theoretical amount, is cooled to less than 20 DEG C; purified process, obtains product methylol phosphine heterocycle shape methylphosphonate.
The method also can be:
In the reactor that efficient fractionation plant is housed; under nitrogen protection, organic solvent, equimolar tris(hydroxymethyl)phosphine and dimethyl methyl phosphonate is added, under stirring; add a certain amount of catalyzer again; be warming up to 110-160 DEG C of reaction 4-8h, control column top temperature not higher than 65 DEG C, the stopped reaction when the methyl alcohol fractionated out reaches theoretical amount; underpressure distillation removing organic solvent again; be cooled to less than 20 DEG C, purified process, obtain product methylol phosphine heterocycle shape methylphosphonate.
Organic solvent described above is methyl-phenoxide, toluene, ethylene glycol diethyl ether, dimethylbenzene or chlorobenzene, and its consumption volume milliliter number is 5-9 times of tris(hydroxymethyl)phosphine quality grams.
A certain amount of catalyzer described above is sodium methylate, triethylamine, pyridine or sodium hydroxide, and its consumption is the 1%-2% of tris(hydroxymethyl)phosphine quality.
Purification process described above is the frozen water adding product Theoretical Mass grams 2-3 times of volume milliliter number, and stir 20min, stratification, separates lower floor's feed liquid, water a small amount of in underpressure distillation removing material.
Organic phosphine fire retardant methylol phosphine heterocycle shape methylphosphonate of the present invention is colorless viscous liquid, and product yield is 80.3%-91.6%, refractive index: n
d 20=1.4575, density (25 DEG C): 1.602g/cm
3, decomposition temperature: 207 ± 5 DEG C.It is suitable as the fire retardant of unsaturated polyester, polyvinyl alcohol, epoxy resin etc., for urethane for adding reactive flame retardant, also can be used as organic synthesis intermediate, preparation technology's principle of this organic phosphine fire retardant methylol phosphine heterocycle shape methylphosphonate is shown below:
Compared with prior art, beneficial effect of the present invention is:
1. the phosphorus content of organic phosphine fire retardant methylol phosphine heterocycle shape methyl-phosphorous acid ester cpds of the present invention is up to 33.7%, flame-retarded efficiency is high, its ring texture symmetry is good, also containing an activity hydroxy functional group in this structure, ingrain fireproofing material can be combined into some macromolecular materials, product is stablized, and decomposition temperature is high, and good with the consistency of macromolecular material.
The methyl alcohol produced in the preparation of 2. organic phosphine fire retardant methylol phosphine heterocycle shape methyl-phosphorous acid ester cpds of the present invention and solvent used can all be recycled, and have good environmental benefit, have again good economic benefit.
3. the preparation technology of organic phosphine fire retardant methylol phosphine heterocycle shape methyl-phosphorous acid ester cpds of the present invention and equipment simple, convenient operation, with low cost, be easy to mass-producing and transform and produce.
Accompanying drawing explanation
In order to the stuctures and properties spy further illustrating product provides following accompanying drawing.
1, the infrared spectrogram of methylol phosphine heterocycle shape methylphosphonate, refers to Figure of description Fig. 1;
Fig. 1 shows, at 3451cm
-1place is the stretching vibration peak of hydroxyl O-H key; 2933cm
-1place is the stretching vibration peak of methylene radical c h bond, 1473cm
-1place is the flexural vibration peak of methylene radical c h bond; 2869cm
-1place is the stretching vibration peak of methyl c h bond, 1399cm
-1place is the flexural vibration peak of methyl c h bond; 1248cm
-1place is the stretching vibration peak of P=O double bond; 1136cm
-1and 1102cm
-1place is the stretching vibration peak of C-O key; 997cm
-1place is the stretching vibration peak of P-O key; 820cm
-1place is the stretching vibration peak of C-P key.
2, the nuclear magnetic spectrum figure of methylol phosphine heterocycle shape methylphosphonate, refers to Figure of description Fig. 2;
Fig. 2 shows, with deuterated water as solvent, δ 1.10-1.17 place is the H peak of methyl; δ 3.36-3.45 place is the H peak of hydroxyl; δ 3.82-3.90 place is the H peak of the methylene radical be connected with oxygen heteroatom; δ 3.90-3.96 place is the H peak of the methylene radical be connected with hydroxyl; δ 4.70 place is the H peak of deuterated water solvent.
Specific embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described further.
Embodiment 1, in the 100ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, is caught up with the air in most bottle with nitrogen, is added 12.40g (0.1mol) tris(hydroxymethyl)phosphine and 12.40g (0.1mol) dimethyl methyl phosphonate.Under stirring, add 0.14g Triethylamine catalyst, heat and continue to pass into nitrogen, be warming up to 110 DEG C of insulation reaction 10h, control column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol (reclaim and use) that reaction produces, the stopped reaction when methanol fraction reaches theoretical amount, is cooled to less than 20 DEG C, add 40ml frozen water, stir 20min, stratification, separates lower floor's feed liquid, water a small amount of in underpressure distillation removing material, obtain colorless viscous liquid methylol phosphine heterocycle shape methylphosphonate, productive rate is 80.3%, refractive index: n
d 20=1.4575, density (25 DEG C): 1.602g/cm
3, decomposition temperature: 207 ± 5 DEG C.
Embodiment 2, in the 100ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, is caught up with the air in most bottle with nitrogen, is added 12.40g (0.1mol) tris(hydroxymethyl)phosphine and 12.40g (0.1mol) dimethyl methyl phosphonate.Under stirring, add 0.18g sodium hydroxide catalyst, heat and continue to pass into nitrogen, be warming up to 160 DEG C of insulation reaction 6h, control column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol (reclaim and use) that reaction produces, the stopped reaction when methanol fraction reaches theoretical amount, is cooled to less than 20 DEG C, add 50ml frozen water, stir 20min, stratification, separates lower floor's feed liquid, water a small amount of in underpressure distillation removing material, obtain colorless viscous liquid methylol phosphine heterocycle shape methylphosphonate, productive rate is 82.5%, refractive index: n
d 20=1.4575, density (25 DEG C): 1.602g/cm
3, decomposition temperature: 207 ± 5 DEG C.
Embodiment 3 is in the 250ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, the air in most bottle is caught up with nitrogen, add 100ml methyl-phenoxide, 12.40g (0.1mol) tris(hydroxymethyl)phosphine and 12.40g (0.1mol) dimethyl methyl phosphonate.Under stirring, add 0.22g sodium methoxide catalyst, heat and continue to pass into nitrogen, be warming up to 150 DEG C of insulation reaction 4h, control column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol (reclaim and use) that reaction produces, the stopped reaction when methanol fraction reaches theoretical amount, underpressure distillation eliminates methyl-phenoxide, be cooled to less than 20 DEG C, add 45ml frozen water, stir 20min, stratification, separate lower floor's feed liquid, water a small amount of in underpressure distillation removing material, obtains colorless viscous liquid methylol phosphine heterocycle shape methylphosphonate, productive rate is 91.6%, refractive index: n
d 20=1.4575, density (25 DEG C): 1.602g/cm
3, decomposition temperature: 207 ± 5 DEG C.
Embodiment 4 is in the 250ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, the air in most bottle is caught up with nitrogen, add 105ml toluene, 12.40g (0.1mol) tris(hydroxymethyl)phosphine and 12.40g (0.1mol) dimethyl methyl phosphonate.Under stirring, add 0.20g Triethylamine catalyst, heat and continue to pass into nitrogen, be warming up to 110 DEG C of insulation reaction 8h, control column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol (reclaim and use) that reaction produces, the stopped reaction when methanol fraction reaches theoretical amount, underpressure distillation eliminates toluene, be cooled to less than 20 DEG C, add 40ml frozen water, stir 20min, stratification, separate lower floor's feed liquid, water a small amount of in underpressure distillation removing material, obtains colorless viscous liquid methylol phosphine heterocycle shape methylphosphonate, productive rate is 86.2%, refractive index: n
d 20=1.4575, density (25 DEG C): 1.602g/cm
3, decomposition temperature: 207 ± 5 DEG C.
Embodiment 5 is in the 250ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, the air in most bottle is caught up with nitrogen, add 90ml ethylene glycol diethyl ether, 12.40g (0.1mol) tris(hydroxymethyl)phosphine and 12.40g (0.1mol) dimethyl methyl phosphonate.Under stirring, add 0.18g pyridine catalyst, heat and continue to pass into nitrogen, be warming up to 120 DEG C of insulation reaction 7h, control column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol (reclaim and use) that reaction produces, the stopped reaction when methanol fraction reaches theoretical amount, underpressure distillation eliminates ethylene glycol diethyl ether, be cooled to less than 20 DEG C, add 50ml frozen water, stir 20min, stratification, separate lower floor's feed liquid, water a small amount of in underpressure distillation removing material, obtains colorless viscous liquid methylol phosphine heterocycle shape methylphosphonate, productive rate is 87.7%, refractive index: n
d 20=1.4575, density (25 DEG C): 1.602g/cm
3, decomposition temperature: 207 ± 5 DEG C.
Embodiment 6 is in the 250ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, the air in most bottle is caught up with nitrogen, add 80ml dimethylbenzene, 12.40g (0.1mol) tris(hydroxymethyl)phosphine and 12.40g (0.1mol) dimethyl methyl phosphonate.Under stirring, add 0.24g sodium methoxide catalyst, heat and continue to pass into nitrogen, be warming up to 140 DEG C of insulation reaction 5h, control column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol (reclaim and use) that reaction produces, the stopped reaction when methanol fraction reaches theoretical amount, underpressure distillation eliminates dimethylbenzene, be cooled to less than 20 DEG C, add 55ml frozen water, stir 20min, stratification, separate lower floor's feed liquid, water a small amount of in underpressure distillation removing material, obtains colorless viscous liquid methylol phosphine heterocycle shape methylphosphonate, productive rate is 89.4%, refractive index: n
d 20=1.4575, density (25 DEG C): 1.602g/cm
3, decomposition temperature: 207 ± 5 DEG C.
Embodiment 7 is in the 250ml four-hole boiling flask that agitator, thermometer, efficient fractionation plant are housed, the air in most bottle is caught up with nitrogen, add 70ml chlorobenzene, 12.40g (0.1mol) tris(hydroxymethyl)phosphine and 12.40g (0.1mol) dimethyl methyl phosphonate.Under stirring, add 0.16g sodium hydroxide catalyst, heat and continue to pass into nitrogen, be warming up to 130 DEG C of insulation reaction 6h, control column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol (reclaim and use) that reaction produces, the stopped reaction when methanol fraction reaches theoretical amount, underpressure distillation eliminates chlorobenzene, be cooled to less than 20 DEG C, add 50ml frozen water, stir 20min, stratification, separate lower floor's feed liquid, water a small amount of in underpressure distillation removing material, obtains colorless viscous liquid methylol phosphine heterocycle shape methylphosphonate, productive rate is 88.9%, refractive index: n
d 20=1.4575, density (25 DEG C): 1.602g/cm
3, decomposition temperature: 207 ± 5 DEG C.
Embodiment main technologic parameters prepared by table 1
The product methylol phosphine heterocycle shape methylphosphonate of above-mentioned preparation is also applied in unsaturated polyester by inventor.The limiting oxygen index(LOI) of reference: GB/T2406-2008 " Plastics Combustion method for testing performance-oxygen index method " test sample product.After being mixed in varing proportions with unsaturated polyester, cyclohexanone peroxide and cobalt naphthenate by product, pour in mould the batten making long 15cm, wide 0.7cm, thick 0.3cm into, test its flame retardant properties, the LOI result recorded is as shown in table 2:
The fire-retardant data of table 2 methylol phosphine heterocycle shape methylphosphonate in unsaturated polyester
As shown in Table 2, when not adding any fire retardant, the limiting oxygen index(LOI) of unsaturated polyester can only be 18%, belong to extremely incendive scope, when the addition of methylol phosphine heterocycle shape methylphosphonate accounts for 20% in unsaturated polyester material, its limiting oxygen index(LOI) has reached the difficulty combustion rank of 30%, illustrates that methylol phosphine heterocycle shape methylphosphonate prepared by the present invention has good flame retardant effect to unsaturated polyester.
Claims (6)
1. an organic phosphine fire retardant methylol phosphine heterocycle shape methyl-phosphorous acid ester cpds, it is characterized in that, the structure of this compound is shown below:
2. a preparation method for organic phosphine fire retardant methylol phosphine heterocycle shape methyl-phosphorous acid ester cpds, it is characterized in that, the method is:
In the reactor that efficient fractionation plant is housed; under nitrogen protection; add equimolar tris(hydroxymethyl)phosphine and dimethyl methyl phosphonate, under stirring, then add the catalyzer relative to tris(hydroxymethyl)phosphine quality 1%-2%; be warming up to 110-160 DEG C of reaction 6-10h; control column top temperature not higher than 65 DEG C, the stopped reaction when the methyl alcohol fractionated out reaches theoretical amount, is cooled to less than 20 DEG C; purified process, obtains product methylol phosphine heterocycle shape methylphosphonate.
3. a preparation method for organic phosphine fire retardant methylol phosphine heterocycle shape methyl-phosphorous acid ester cpds, it is characterized in that, the method is:
In the reactor that efficient fractionation plant is housed; under nitrogen protection; add organic solvent, equimolar tris(hydroxymethyl)phosphine and dimethyl methyl phosphonate; under stirring; add the catalyzer relative to tris(hydroxymethyl)phosphine quality 1%-2% again; be warming up to 110-160 DEG C of reaction 4-8h; control column top temperature not higher than 65 DEG C; the stopped reaction when the methyl alcohol fractionated out reaches theoretical amount; underpressure distillation removing organic solvent again; be cooled to less than 20 DEG C, purified process, obtain product methylol phosphine heterocycle shape methylphosphonate.
4. the preparation method of methylol phosphine heterocycle shape methyl-phosphorous acid ester cpds as claimed in claim 2, it is characterized in that: described organic solvent is methyl-phenoxide, toluene, ethylene glycol diethyl ether, dimethylbenzene or chlorobenzene, its consumption volume milliliter number is 5-9 times of tris(hydroxymethyl)phosphine quality grams.
5. the compounds process for production thereof of methylol phosphine heterocycle shape methylphosphonate as described in claim 2 and 3, is characterized in that: described catalyzer is sodium methylate, triethylamine, pyridine or sodium hydroxide.
6. the preparation method of methylol phosphine heterocycle shape methylphosphonate as described in claim 2 and 3, it is characterized in that: described purification process is the frozen water adding product Theoretical Mass grams 2-3 times of volume milliliter number, stir 20min, stratification, separate lower floor's feed liquid, water a small amount of in underpressure distillation removing material.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114292368A (en) * | 2022-01-26 | 2022-04-08 | 华北理工大学 | Organic silicon-phosphorus-containing acrylate core-shell toughening flame retardant and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4268459A (en) * | 1976-06-29 | 1981-05-19 | American Cyanamid Company | Cyclic diphosphonates |
| US4694094A (en) * | 1984-05-25 | 1987-09-15 | Societe Nationale Elf Aquitaine | Cyclic diphosphonites |
| EP0708109A1 (en) * | 1994-10-10 | 1996-04-24 | Hoechst Aktiengesellschaft | Process for the preparation of dicarbonic acids containing phosphorus |
| CN101230274A (en) * | 2007-12-27 | 2008-07-30 | 南京师范大学 | Method for preparing annular phosphonate or annular phosphate flame retardant |
-
2015
- 2015-07-07 CN CN201510404444.6A patent/CN105001264B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4268459A (en) * | 1976-06-29 | 1981-05-19 | American Cyanamid Company | Cyclic diphosphonates |
| US4694094A (en) * | 1984-05-25 | 1987-09-15 | Societe Nationale Elf Aquitaine | Cyclic diphosphonites |
| EP0708109A1 (en) * | 1994-10-10 | 1996-04-24 | Hoechst Aktiengesellschaft | Process for the preparation of dicarbonic acids containing phosphorus |
| CN101230274A (en) * | 2007-12-27 | 2008-07-30 | 南京师范大学 | Method for preparing annular phosphonate or annular phosphate flame retardant |
Non-Patent Citations (3)
| Title |
|---|
| A. TZSCHACH ET AL.: ""1, 3, 2, 5-Dioxadiphosphorinanes. Six-membered ring compounds containing two different phosphorus atoms"", 《JOURNAL OF CRYSTALLOGRAPHIC AND SPECTROSCOPIC RESEARCH》 * |
| 任荣翠等: ""笼状磷酸酯PEPA 的合成工艺改进"", 《塑料助剂》 * |
| 苏海晓等: "间苯二酚-双[二(季戊四醇)]磷酸酯的合成、表征和热稳定性", 《化工进展》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114292368A (en) * | 2022-01-26 | 2022-04-08 | 华北理工大学 | Organic silicon-phosphorus-containing acrylate core-shell toughening flame retardant and preparation method thereof |
| CN114292368B (en) * | 2022-01-26 | 2023-04-11 | 华北理工大学 | Organic silicon-phosphorus-containing acrylate core-shell toughening flame retardant and preparation method thereof |
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Effective date of registration: 20230427 Address after: 313018 No. 188, Liang Shan Road, Linghu Town, Nanxun District, Huzhou, Zhejiang. Patentee after: Zhejiang Rui hi tech materials Limited by Share Ltd. Address before: Suzhou science and Technology University Science and Technology Park, 1701 Binhe Road, Suzhou high tech Zone, Jiangsu Province, 215011 Patentee before: SUZHOU KINGMAN CHEMICAL TECHNOLOGY Co.,Ltd. |