CN104119380A - Halogen-free oligomerization phosphonate flame retardant and synthesis method thereof - Google Patents
Halogen-free oligomerization phosphonate flame retardant and synthesis method thereof Download PDFInfo
- Publication number
- CN104119380A CN104119380A CN201410150862.2A CN201410150862A CN104119380A CN 104119380 A CN104119380 A CN 104119380A CN 201410150862 A CN201410150862 A CN 201410150862A CN 104119380 A CN104119380 A CN 104119380A
- Authority
- CN
- China
- Prior art keywords
- fire retardant
- halogen
- flame retardant
- oligomeric phosphonate
- phosphonate
- 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.)
- Pending
Links
Landscapes
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a halogen-free oligomerization phosphonate flame retardant. The flame retardant is dipropylene glycol phosphonate oligomer. The invention also discloses a synthesis method and application of the flame retardant. The halogen-free oligomerization phosphonate flame retardant developed by the invention has the advantages of no halogen, low viscosity, a small possibility of gasification and precipitation and the like. A preparation method of novel halogen-free oligomerization phosphonate is green and environment-friendly, free of solvent, simple to operate, good in color and luster of a final product, low in acid value, low in viscosity and free of additional decoloring treatment. The synthesis method of the flame retardant is simple and convenient in post-treatment; the prepared flame retardant is excellent in flame retardant property and free of halogen, so that the flame retardant is environment-friendly.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of Halogen oligomeric phosphonate fire retardant and synthetic method thereof.
Background technology
Urethane foam is a kind of thermosetting resin, and it is cheap, is therefore widely used in various hot articles for use field.But urethane foam has a main drawback, it very easily burns, once after they light, there is uncontrollable burning.Therefore use in the field that urethane foam is feature at some, as automotive trim, flame retardant resistance is compulsory legally.
In order to make urethane foam there is flame retardant resistance, conventionally add the phosphoric acid ester that contains halogen as fire retardant.Usually add the haplotype phosphate flame retardant that contains halogen, as three (chloropropyl) phosphoric acid ester (TCPP), three (two chloropropyls) phosphoric acid ester (TDCP) etc., but this kind phosphate ester flame retardant molecule amount is low, easily gasification at normal temperatures, very easily separate out, and unstable.Once in the time that the urethane foam that comprises this based flame retardant is applied to urethane foam presence of fire will discharge poisonous, hydrogen halide excitatory.Therefore, in order to reduce vaporized flame retardant amount, overcome it and easily separate out, unsettled shortcoming, can be used the various polymer phosphoric acid esters that contain halogen as additive flame retardant.But the phosphoric acid ester of this height polymerization is because have high viscosity, bad dispersibility, so can become very poor by processed-type.
Along with the more and more attention of people to environmental protection, the fire retardant that this class contains halogen will be eliminated.At this moment, need to research and develop novel Halogen oligomeric phosphonate fire retardant and make up the deficiency that uses the micromolecular fire retardant of TCPP on urethane foam or use height polymer phosphoric acid ester combustion inhibitor to bring as additive flame retardant.
Summary of the invention
Goal of the invention: the object of the invention is for the deficiencies in the prior art, and a kind of Halogen oligomeric phosphonate fire retardant is provided.
Another object of the present invention is to provide the synthetic method of above-mentioned fire retardant.
The 3rd object of the present invention is the openly application of above-mentioned fire retardant.
Technical scheme: in order to reach foregoing invention object, the present invention specifically completes like this: a kind of Halogen oligomeric phosphonate fire retardant, this fire retardant is dipropylene glycol base phosphonate oligomers, molecular formula is suc as formula the compounds (I) Suo Shu:
R
1for-CH
3or-CH
2cH
3, R
2for-CH
3or-CH
2cH
3, R
3for-H or-CH
3, and 1≤n≤6, the constituent mass relative content that the constituent mass relative content of n=1 is 40～80%, n>=2 is 20～60%, mixes by above-mentioned mass percent.
Described Halogen oligomeric phosphonate fire retardant, its preparation method comprises the following steps: 4:3 gets phosphonic acid ester and dibasic alcohol in molar ratio, at 60～100 DEG C, add catalyst, and pass into protection of inert gas reaction and obtain the described compound of formula (I); Described phosphonic acid ester is at least one in dimethyl methyl phosphonate or diethyl ethylphosphate; Described dibasic alcohol is Diethylene Glycol or dipropylene glycol; Described rare gas element is nitrogen.
In the preparation method of this fire retardant, catalyzer is solid basic catalyst or liquid organic amine catalyzer, is preferably liquid organic amine catalyzer, and catalyst levels is 0.5%～4% of described dibasic alcohol quality, is preferably 1%～3%, further preferably 2%.
In the preparation method of this fire retardant, described solid basic catalyst is selected from NaOH, KOH, K
2cO
3, any one in sodium phenylate and sodium tetraphenylborate; Described liquid organic amine catalyzer is selected from any one in diethylamine, triethylamine, dimethylamine and Trimethylamine 99.
In the preparation method of this fire retardant, the reaction times of described reaction is 6h～12h, is preferably 8h.
The method of synthetic above-mentioned Halogen oligomeric phosphonate fire retardant, the steps include: that 4:3 gets phosphonic acid ester and dibasic alcohol in molar ratio, at 60～100 DEG C, adds catalyst, and passes into protection of inert gas reaction and obtain the described compound of formula (I); Described phosphonic acid ester is at least one in dimethyl methyl phosphonate or diethyl ethylphosphate; Described dibasic alcohol is Diethylene Glycol or dipropylene glycol; Described rare gas element is nitrogen.
Specifically synthesize Halogen oligomeric phosphonate as example taking dimethyl methyl phosphonate and dipropylene glycol, reaction equation is as follows:
The method of above-mentioned synthetic Halogen oligomeric phosphonate fire retardant, is characterized in that, described catalyzer is solid basic catalyst or liquid organic amine catalyzer, is preferably liquid organic amine catalyzer.
In above-mentioned building-up reactions, catalyst levels is 0.5%～4% of described dibasic alcohol quality, is preferably 1%～3%, further preferably 2%.
In above-mentioned building-up reactions, described solid basic catalyst is selected from NaOH, KOH, K
2cO
3, any one in sodium phenylate and sodium tetraphenylborate; Described liquid organic amine catalyzer is selected from any one in diethylamine, triethylamine, dimethylamine and Trimethylamine 99.
The reaction times of described building-up reactions is 6h～12h, is preferably 8h.
Fire retardant provided by the invention can be in the application of preparing in urethane foam.
Beneficial effect: the synthetic method of fire retardant of the present invention is simple, convenient post-treatment, the fire retardant of preparation not only has excellent flame retardant properties, also not halogen-containing, is a kind of environmentally friendly fire retardant.
The Halogen oligomeric phosphonate fire retardant of the present invention research and development has Halogen, low viscosity and is difficult for gasification and the advantage such as separates out.Preparation method's environmental protection of this New-type halide-free oligomeric phosphonate, does not need solvent, simple to operate.And the finished product color and luster is good, acid number is low, and viscosity is low, does not need decolouring in addition to process.
Embodiment
Embodiment 1
Is being furnished with agitator, dropping funnel, atmospheric distillation plant, thermometer, in four neck flasks of airway, add the dipropylene glycol of 134.2g, the dimethyl methyl phosphonate of 155g, the triethylamine of 2.6g, heating logical nitrogen, be slowly warming up to 60 DEG C, at this temperature, reacts 6h.The methyl alcohol of generation is steamed, and steam catalyst of triethylamine.Obtain a colourless transparent liquid 198g, yield 88%.
Its chemical structure be for:
1≤n≤6，
Embodiment 2
Is being furnished with agitator, dropping funnel, atmospheric distillation plant, thermometer, in four neck flasks of airway, add the dipropylene glycol of 134.2g, the dimethyl methyl phosphonate of 155g, the triethylamine of 2.8g, heating logical nitrogen, be slowly warming up to 60 DEG C, at this temperature, reacts 8h.The methyl alcohol of generation is steamed, and steam catalyst of triethylamine.Obtain a colourless transparent liquid 201g, yield 89.33%.
Embodiment 3
Is being furnished with agitator, dropping funnel, atmospheric distillation plant, thermometer, in four neck flasks of airway, add the dipropylene glycol of 134.2g, the dimethyl methyl phosphonate of 155g, the triethylamine of 2.8g, heating logical nitrogen, be slowly warming up to 60 DEG C, at this temperature, reacts 12h.The methyl alcohol of generation is steamed, and steam catalyst of triethylamine.Obtain a colourless transparent liquid 198.5g, yield 88.22%.
Embodiment 4
Is being furnished with agitator, dropping funnel, atmospheric distillation plant, thermometer, in four neck flasks of airway, add the dipropylene glycol of 134g, the dimethyl methyl phosphonate of 155g, the triethylamine of 2.8g, heating logical nitrogen, be slowly warming up to 80 DEG C, at this temperature, reacts 6h.The methyl alcohol of generation is steamed, and steam catalyst of triethylamine.Obtain a colourless transparent liquid 202g, yield 89.77%.
Embodiment 5
Is being furnished with agitator, dropping funnel, atmospheric distillation plant, thermometer, in four neck flasks of airway, add the dipropylene glycol of 134g, the dimethyl methyl phosphonate of 155g, the triethylamine of 2.8g, heating logical nitrogen, be slowly warming up to 80 DEG C, at this temperature, reacts 8h.The methyl alcohol of generation is steamed, and steam catalyst of triethylamine.Obtain a colourless transparent liquid 213g, yield 94.66%.
Embodiment 6
Is being furnished with agitator, dropping funnel, atmospheric distillation plant, thermometer, in four neck flasks of airway, add the dipropylene glycol of 134g, the dimethyl methyl phosphonate of 155g, the triethylamine of 2.8g, heating logical nitrogen, be slowly warming up to 80 DEG C, at this temperature, reacts 12h.The methyl alcohol of generation is steamed, and steam catalyst of triethylamine.Obtain a colourless transparent liquid 213.6g, yield 94.9%.
Embodiment 7
Be furnished with agitator, dropping funnel, atmospheric distillation plant, thermometer, in four neck flasks of airway, adds the dipropylene glycol of 134g, the dimethyl methyl phosphonate of 155g, the triethylamine of 2g, heating logical nitrogen, be slowly warming up to 100 DEG C, at this temperature, reacts 6h.The methyl alcohol of generation is steamed, and steam catalyst of triethylamine.Obtain a colourless transparent liquid 189.5g, yield 84.2%.
Embodiment 8
Is being furnished with agitator, dropping funnel, atmospheric distillation plant, thermometer, in four neck flasks of airway, add the dipropylene glycol of 134g, the dimethyl methyl phosphonate of 155g, the triethylamine of 2.5g, heating logical nitrogen, be slowly warming up to 100 DEG C, at this temperature, reacts 8h.The methyl alcohol of generation is steamed, and steam catalyst of triethylamine.Obtain a colourless transparent liquid 198.5g, yield 88.22%.
Embodiment 9
Is being furnished with agitator, dropping funnel, atmospheric distillation plant, thermometer, in four neck flasks of airway, add the dipropylene glycol of 134g, the dimethyl methyl phosphonate of 155g, the triethylamine of 2.5g, heating logical nitrogen, be slowly warming up to 100 DEG C, at this temperature, reacts 12h.The methyl alcohol of generation is steamed, and steam catalyst of triethylamine.Obtain a colourless transparent liquid 203.4g, yield 90.4%.
Embodiment 10
Is being furnished with agitator, dropping funnel, atmospheric distillation plant, thermometer, in four neck flasks of airway, add the Diethylene Glycol of 106g, the dimethyl methyl phosphonate of 150g, the triethylamine of 2.5g, heating logical nitrogen, be slowly warming up to 80 DEG C, at this temperature, reacts 8h.The methyl alcohol of generation is steamed, and steam catalyst of triethylamine.Obtain a colourless transparent liquid 179.5g, yield 93.5%.
Its chemical structural formula is:
1≤n≤6
Embodiment 11
Is being furnished with agitator, dropping funnel, atmospheric distillation plant, thermometer, in four neck flasks of airway, add the Diethylene Glycol of 106g, the dimethyl methyl phosphonate of 150g, the triethylamine of 2.5g, heating logical nitrogen, be slowly warming up to 100 DEG C, at this temperature, reacts 8h.The methyl alcohol of generation is steamed, and steam catalyst of triethylamine.Obtain a colourless transparent liquid 178.9g, yield 93.1%.
Embodiment 12 is basic identical with embodiment 1, but has following change:
Catalyst of triethylamine changes diethylamine into, and diethylamine consumption changes 2g into.
Embodiment 13 is basic identical with embodiment 1, but has following change:
Catalyst of triethylamine changes sodium tetraphenylborate into, and sodium tetraphenylborate consumption changes 2g into.
Embodiment 14 is basic identical with embodiment 10, but has following change:
Catalyst of triethylamine changes diethylamine into, and catalyst levels changes 3.5g into.
Embodiment 15 is basic identical with embodiment 11, but has following change:
Dimethyl methyl phosphonate changes diethyl ethylphosphate into.
Its chemical structural formula is:
1≤n≤6
In product different n value components through LC-MS (LC-MS) analytical results in table 1.
Other raw material one of the fire retardant of below being prepared by the inventive method and urethane foam is reinstated method below and is prepared flame-retardant polyurethane foam plastic.In table 2.
So the component except isocyanate component is mixed by predetermined proportion, and by stirring and evenly mix for 1 minute with 3000rpm in stirrer.Then, add isocyanate component, and mixture is continued under 3000rpm stir 5-7 second.Then fast gained mixture is injected to the cardboard boxes with square cross-section.Get started foaming, after several minutes, reach maximum volume.Then, in 80 DEG C of baking ovens, solidify foaming product 15 minutes.Obtain flame-retardant polyurethane foam plastic.
The fire retardant of preparing with the present invention and small molecules fire retardant TCPP are relatively not difficult to find out to this product has low atomization by the haze value of same formula foaming gained urethane foam product, are difficult for separating out, the advantage such as environmentally friendly.Comparative result is in table 3
Table 1
| Density (Kg/m 3) | 20 | 30 |
| Polyether glycol | 100 | 100 |
| Whipping agent water | 4.2 | 3.4 |
| Whipping agent methylene dichloride | 5.6 | ? |
| Catalyst A-33 | 0.13 | 0.19 |
| Catalyzer T-9 | 0.24 | 0.22 |
| Tensio-active agent L580 | 1.46 | 1.06 |
| Fire retardant | 18 | 14 |
| Isocyanic ester TDI | ? | ? |
| Index | 110 | 110 |
Table 2
Table 3
Claims (10)
1. a Halogen oligomeric phosphonate fire retardant, is characterized in that, this fire retardant is suc as formula the compounds (I) Suo Shu:
R
1for-CH
3or-CH
2cH
3, R
2for-CH
3or-CH
2cH
3, R
3for-H or-CH
3, and 1≤n≤6, the constituent mass relative content that the constituent mass relative content of n=1 is 40～80%, n>=2 is 20～60%.
2. Halogen oligomeric phosphonate fire retardant according to claim 1, it is characterized in that, the preparation method of this fire retardant is: 4:3 gets phosphonic acid ester and dibasic alcohol in molar ratio, at 60～100 DEG C, add catalyst, and pass into protection of inert gas reaction and obtain the described compound of formula (I); Described phosphonic acid ester is at least one in dimethyl methyl phosphonate or diethyl ethylphosphate; Described dibasic alcohol is Diethylene Glycol or dipropylene glycol; Described rare gas element is nitrogen.
3. Halogen oligomeric phosphonate fire retardant according to claim 2, it is characterized in that, catalyzer in the preparation method of this fire retardant is solid basic catalyst or liquid organic amine catalyzer, be preferably liquid organic amine catalyzer, catalyst levels is 0.5%～4% of described dibasic alcohol quality, be preferably 1%～3%, further preferably 2%.
4. Halogen oligomeric phosphonate fire retardant according to claim 2, is characterized in that, described in the preparation method of this fire retardant, solid basic catalyst is selected from NaOH, KOH, K
2cO
3, any one in sodium phenylate and sodium tetraphenylborate; Described liquid organic amine catalyzer is selected from any one in diethylamine, triethylamine, dimethylamine and Trimethylamine 99.
5. Halogen oligomeric phosphonate fire retardant according to claim 2, is characterized in that, the reaction times of reacting described in the preparation method of this fire retardant is 6h～12h, is preferably 8h.
6. the method for Halogen oligomeric phosphonate fire retardant described in synthetic claim 1, it is characterized in that, 4:3 gets phosphonic acid ester and dibasic alcohol in molar ratio, at 60～100 DEG C, add catalyst, and pass into protection of inert gas reaction and obtain the described compound of formula (I); Described phosphonic acid ester is at least one in dimethyl methyl phosphonate or diethyl ethylphosphate; Described dibasic alcohol is Diethylene Glycol or dipropylene glycol; Described rare gas element is nitrogen.
7. synthesize according to claim 6 the method for Halogen oligomeric phosphonate fire retardant, it is characterized in that, described catalyzer is solid basic catalyst or liquid organic amine catalyzer, be preferably liquid organic amine catalyzer, catalyst levels is 0.5%～4% of described dibasic alcohol quality, be preferably 1%～3%, further preferably 2%.
8. the method for synthesizing according to claim 6 Halogen oligomeric phosphonate fire retardant, is characterized in that, described solid basic catalyst is selected from NaOH, KOH, K
2cO
3, any one in sodium phenylate and sodium tetraphenylborate; Described liquid organic amine catalyzer is selected from any one in diethylamine, triethylamine, dimethylamine and Trimethylamine 99.
9. the method for synthesizing according to claim 6 Halogen oligomeric phosphonate fire retardant, is characterized in that, the reaction times of described reaction is 6h～12h, is preferably 8h.
10. a Halogen oligomeric phosphonate fire retardant, is characterized in that, is preparing the application in urethane foam at this fire retardant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410150862.2A CN104119380A (en) | 2014-04-15 | 2014-04-15 | Halogen-free oligomerization phosphonate flame retardant and synthesis method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410150862.2A CN104119380A (en) | 2014-04-15 | 2014-04-15 | Halogen-free oligomerization phosphonate flame retardant and synthesis method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104119380A true CN104119380A (en) | 2014-10-29 |
Family
ID=51765041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410150862.2A Pending CN104119380A (en) | 2014-04-15 | 2014-04-15 | Halogen-free oligomerization phosphonate flame retardant and synthesis method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104119380A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629087A (en) * | 2015-03-11 | 2015-05-20 | 中国科学院长春应用化学研究所 | Cyclic polyphosphoester oligmer, and preparation method and application thereof |
| CN108383973A (en) * | 2018-02-12 | 2018-08-10 | 吴艳飞 | A kind of full water foamed and sprayed soft flame retardant polyurethane thermal insulation material and preparation method thereof |
| CN109880058A (en) * | 2019-02-22 | 2019-06-14 | 四川大学 | A kind of preparation method of strand soft segment resistance combustion polyurethane foam |
| CN109988279A (en) * | 2019-02-22 | 2019-07-09 | 四川大学 | A kind of strand soft segment resistance combustion polyurethane foam |
| CN111363157A (en) * | 2020-02-26 | 2020-07-03 | 青岛长荣化工科技有限公司 | Preparation method of oligomeric phosphonate flame retardant |
| CN111393477A (en) * | 2020-04-22 | 2020-07-10 | 昆明理工大学 | Polyhydroxy phosphonate flame retardant and synthetic method thereof |
| CN114524843A (en) * | 2022-02-25 | 2022-05-24 | 青岛长荣化工科技有限公司 | Hydroxyl-terminated reactive flame retardant and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008073871A1 (en) * | 2006-12-11 | 2008-06-19 | Albemarle Corporation | Organophosphonate oligomers and mixtures thereof useful as flame retardants |
| RU2344141C2 (en) * | 2006-10-20 | 2009-01-20 | Альбина Петровна Рябкина | Fire retardant and method of production thereof |
| CN102071229A (en) * | 2009-11-20 | 2011-05-25 | 中国科学院大连化学物理研究所 | Method for epoxidizing cyclohexene by using enzymatic molecular oxygen |
-
2014
- 2014-04-15 CN CN201410150862.2A patent/CN104119380A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2344141C2 (en) * | 2006-10-20 | 2009-01-20 | Альбина Петровна Рябкина | Fire retardant and method of production thereof |
| WO2008073871A1 (en) * | 2006-12-11 | 2008-06-19 | Albemarle Corporation | Organophosphonate oligomers and mixtures thereof useful as flame retardants |
| CN102071229A (en) * | 2009-11-20 | 2011-05-25 | 中国科学院大连化学物理研究所 | Method for epoxidizing cyclohexene by using enzymatic molecular oxygen |
Non-Patent Citations (1)
| Title |
|---|
| 丁思月 等: "反应型低聚有机膦酸酯阻燃剂的合成与应用", 《聚氨酯工业》, vol. 27, no. 6, 28 December 2012 (2012-12-28) * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629087A (en) * | 2015-03-11 | 2015-05-20 | 中国科学院长春应用化学研究所 | Cyclic polyphosphoester oligmer, and preparation method and application thereof |
| CN108383973A (en) * | 2018-02-12 | 2018-08-10 | 吴艳飞 | A kind of full water foamed and sprayed soft flame retardant polyurethane thermal insulation material and preparation method thereof |
| CN108383973B (en) * | 2018-02-12 | 2020-12-22 | 吴艳飞 | Full-water foaming spraying soft flame-retardant polyurethane thermal insulation material and preparation method thereof |
| CN109880058A (en) * | 2019-02-22 | 2019-06-14 | 四川大学 | A kind of preparation method of strand soft segment resistance combustion polyurethane foam |
| CN109988279A (en) * | 2019-02-22 | 2019-07-09 | 四川大学 | A kind of strand soft segment resistance combustion polyurethane foam |
| CN109880058B (en) * | 2019-02-22 | 2021-05-25 | 四川大学 | Preparation method of molecular chain soft segment flame-retardant polyurethane foam |
| CN109988279B (en) * | 2019-02-22 | 2021-05-25 | 四川大学 | Molecular chain soft segment flame-retardant polyurethane foam |
| CN111363157A (en) * | 2020-02-26 | 2020-07-03 | 青岛长荣化工科技有限公司 | Preparation method of oligomeric phosphonate flame retardant |
| CN111393477A (en) * | 2020-04-22 | 2020-07-10 | 昆明理工大学 | Polyhydroxy phosphonate flame retardant and synthetic method thereof |
| CN111393477B (en) * | 2020-04-22 | 2024-02-20 | 昆明理工大学 | Polyhydroxy phosphonate flame retardant and synthetic method thereof |
| CN114524843A (en) * | 2022-02-25 | 2022-05-24 | 青岛长荣化工科技有限公司 | Hydroxyl-terminated reactive flame retardant and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104119380A (en) | Halogen-free oligomerization phosphonate flame retardant and synthesis method thereof | |
| Yuan et al. | Highly-efficient reinforcement and flame retardancy of rigid polyurethane foam with phosphorus-containing additive and nitrogen-containing compound | |
| Yang et al. | Synthesis, mechanical properties and fire behaviors of rigid polyurethane foam with a reactive flame retardant containing phosphazene and phosphate | |
| CN101899160B (en) | Preparation method of oligomerization phosphate polyalcohol | |
| CN104403128B (en) | Preparation method containing the biradical structure phosphonium flame retardants of phosphonitrile/DOPO | |
| Gao et al. | Effect of a novel phosphorous–nitrogen containing intumescent flame retardant on the fire retardancy and the thermal behaviour of poly (butylene terephthalate) | |
| CN106243385B (en) | A kind of DOPO based flameproofings and preparation method thereof | |
| ES2603730T3 (en) | Poly (alkylene phosphates) without halogen | |
| JP5641633B2 (en) | Mixtures of phosphorus-containing compounds, processes for their preparation and their use as flame retardants | |
| CN104004171A (en) | Preparation method of phosphorus-containing halogen-free environmentally-friendly flame-retardant polyester polyol | |
| Ma et al. | Effect of functional groups of magnolol-based cyclic phosphonate on structure and properties of flame retardant epoxy resin | |
| CN106565930A (en) | Phosphorus flame retardant and all water blown phosphorus containing flame retardant polyurethane foam based on same | |
| CN103992353A (en) | Flame retardant hexabutanol cyclotriphosphazene, and preparation method and application thereof | |
| CN102838778A (en) | Preparation method of nitrogen and phosphorus fire retardant, nitrogen and phosphorus fire retardant and application thereof | |
| CN104311876A (en) | Polymerization type phosphorus-containing flame retardant as well as preparation method and application thereof as epoxy resin flame retardant | |
| CN104479172B (en) | A kind of preparation method of the APP of Surface coating fluorine containing silicone oil | |
| CN102617645B (en) | 1-oxo-4-hydroxymethyl-1-phospholane-2, 6, 7-trioxabicyclo [2, 2, 2] octane derivative with flame retardation effect and preparation of derivative | |
| CN104558570A (en) | Synthesis of phosphorus containing polyester polyol and application of phosphorus containing polyester polyol in polyurethane | |
| CN102070869A (en) | Low-smoke density additive-type flame retardant resin and application thereof | |
| CN102634174A (en) | Preparation method of flame-retardant copolyester film of phosphorus, silicon and fluorine | |
| WO2019122923A1 (en) | Rigid foams | |
| KR20180024849A (en) | flame-retardant polyol, the manufacturing mothod thereof and polyurethan including the anti-flame property polyol | |
| CN105238418A (en) | Aqueous halogen-free fire retardant, and preparation method and application thereof | |
| CN102660009A (en) | Preparation method of flame-retardant linear copolyester resin | |
| JPS62241921A (en) | Reactive fireproof compound making hard polyurethane foam material fire-retardant and its production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141029 |