CN104292503A - Reactive phosphorous and nitrogen flame retardant and preparation method thereof - Google Patents
Reactive phosphorous and nitrogen flame retardant and preparation method thereof Download PDFInfo
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- CN104292503A CN104292503A CN201410556214.7A CN201410556214A CN104292503A CN 104292503 A CN104292503 A CN 104292503A CN 201410556214 A CN201410556214 A CN 201410556214A CN 104292503 A CN104292503 A CN 104292503A
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Abstract
The invention discloses a reactive phosphorous and nitrogen flame retardant and a preparation method thereof. The structural formula of the reactive phosphorous and nitrogen flame retardant is as shown in the specification, wherein R1 refers to alkyl, alkoxy, phenyl or phenoxy. The preparation method comprises the following steps: adding 2,2-bihydroxymethyl-3-nitro-1-propyl alcohol and an acid-binding agent into a reactor filled with solvents, dripping a phosphorus reagent, stirring to be uniform, controlling the temperature to be 0-60 DEG C, and reacting at the constant temperature for 4-12 hours; filtering after the reaction is ended, performing reduced-pressure vaporization on the filtrate to recover the solvent so as to obtain white solids, and performing vacuum drying, thereby obtaining the reactive phosphorous and nitrogen flame retardant. The preparation method of the reactive phosphorous and nitrogen flame retardant disclosed by the invention is simple in synthetic process and mild in conditions. According to the flame retardant, active hydroxyl functional groups in the molecules are chemically bonded to the high polymer materials or polymer raw materials, the intermiscibility with the high polymer materials can be improved, and the flame retardant can be applied to multiple high polymer materials.
Description
Technical field
The present invention relates to technical field of flame retardant, be specifically related to a kind of response type phosphor nitrogen combustion inhibitor and preparation method thereof.
Background technology
Major part macromolecular material is easy firing because its oxygen index is less, because macromolecular material burns fire one of the disaster becoming modern society caused, fire brings great threat to the life of the people, property safety, and the combustionproperty therefore how reducing macromolecular material has become current research focus.Traditional halogenated flame retardant causes its application to be constantly restricted due to the environmental safety potential problem existed in combustion, along with the enforcement of a series of laws and regulations, finds its suitable substitute extremely urgent.Phosphor nitrogen combustion inhibitor becomes the new lover of fire-retardant family due to few, the efficient and advantage such as nontoxic of its consumption, be considered to most potential halogen-free flame retardants.Phosphor nitrogen combustion inhibitor mainly contains addition type and the large class of response type two." addition type " fire retardant is applicable to most macromolecular material, but the fire-protection rating that this based flame retardant wants to meet material requires the addition that often needs are higher.This often causes Drawing abillity, mechanical property, electric property or mechanical property to be subject to larger destruction; this based flame retardant often can occur from material matrix internal migration out and in material surface frosting worse, thus affects work-ing life and the flame retardant properties thereof of material.And " response type " fire retardant can and macromolecular material between by firmly covalent linkage effect, effectively can solve the shortcoming of additive flame retardant, keep the various performances of material, prevent the migration of fire retardant to lose efficacy.Therefore, develop response type phosphor nitrogen combustion inhibitor to have great importance.
Summary of the invention
The object of the invention is to provide a kind of response type phosphor nitrogen combustion inhibitor and preparation method thereof for the environmental security of halogenated flame retardant and the shortcoming such as addition type phosphor nitrogen combustion inhibitor consumption is large.
For achieving the above object, the present invention is realized by following technical proposals:
A kind of response type phosphor nitrogen combustion inhibitor, its molecular structural formula is:
Wherein R
1for alkyl, alkoxyl group, phenyl or phenoxy group
The preparation method of above-mentioned reactive flame retardant, comprise the steps: in the reactor that solvent is housed, add 2,2-dihydroxymethyl-3-nitro-1-propyl alcohol and acid binding agent, instill phosphorus reagent subsequently, stir, temperature is controlled at 0 DEG C ~ 60 DEG C, isothermal reaction 4 ~ 12h, after completion of the reaction, filter, filtrate evaporated under reduced pressure recycling design, obtain white solid, obtain response type phosphor nitrogen combustion inhibitor through vacuum-drying.
By such scheme, every mole of 2,2-dihydroxymethyl-3-nitro-1-propyl alcohol need solvent to be 1000mL ~ 2000mL.
By such scheme, the mol ratio of described 2,2-dihydroxymethyl-3-nitro-1-propyl alcohol and acid binding agent is 1:2 ~ 3; Isothermal reaction 4 ~ 12h; Vacuum-drying temperature is 40 ~ 50 DEG C.
By such scheme, described solvent is the one in ether, methylene dichloride, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane or ethylene dichloride.
By such scheme, described acid binding agent is the one in triethylamine, pyridine, sodium hydroxide or sodium carbonate.
By such scheme, described phosphorus reagent is alkyl phosphinylidyne dichloro, alkylphosphonic acid carboxylic acid dimethyl ester, alkoxyl group phosphinylidyne dichloro, diphenylphosphoryl dichloro, phenyl phosphorus dimethyl phosphate or phenoxy group phosphinylidyne dichloro.
The present invention has following advantage compared with existing fire retardant technology: fire retardant of the present invention is not halogen-containing, good flame retardation effect, applied range, meet environmental requirement; Present invention process working condition is simple, productive rate is higher, last handling process is easy, is applicable to industrialization.
Embodiment
embodiment 1:
2 are added in the 500ml there-necked flask that thermometer, 100ml constant pressure funnel and device for absorbing tail gas be housed, 2-dihydroxymethyl-3-nitro-1-propyl alcohol (16.51g, 0.1mol), triethylamine (25.30g, 0.25mol) and 100ml methylene dichloride, open magnetic agitation, methyl phosphinylidyne dichloro (13.97g, 0.105mol) is dissolved in 50ml methylene dichloride, joins in constant pressure funnel, at 0 DEG C, be slowly added drop-wise in there-necked flask.After dropwising, continue reaction 10 hours, after reaction terminates, filter, filtrate evaporated under reduced pressure recycling design, obtain white solid, through 40 DEG C of vacuum-drying 6h, obtain white powder phosphor nitrogen combustion inhibitor solid 20.03 grams, yield 89%.
embodiment 2:
2 are added in the 500ml there-necked flask that thermometer, 100ml constant pressure funnel and device for absorbing tail gas be housed, 2-dihydroxymethyl-3-nitro-1-propyl alcohol (16.51g, 0.1mol), triethylamine (25.30g, 0.25mol) and 100ml methylene dichloride, open magnetic agitation, methoxyl group phosphinylidyne dichloro (15.63g, 0.105mol) is dissolved in 50ml methylene dichloride, joins in constant pressure funnel, at 60 DEG C, be slowly added drop-wise in there-necked flask.After dropwising, continue reaction 4 hours, after reaction terminates, filter, filtrate evaporated under reduced pressure recycling design, obtain white solid, through 50 DEG C of vacuum-drying 6h, obtain white powder phosphor nitrogen combustion inhibitor solid 21.25 grams, yield 89%.
embodiment 3:
2 are added in the 500ml there-necked flask that thermometer, 100ml constant pressure funnel and device for absorbing tail gas be housed, 2-dihydroxymethyl-3-nitro-1-propyl alcohol (16.51g, 0.1mol), triethylamine (25.30g, 0.25mol) and 100ml methylene dichloride, open magnetic agitation, diphenylphosphoryl dichloro (20.47g, 0.105mol) is dissolved in 50ml methylene dichloride, joins in constant pressure funnel, at 5 DEG C, be slowly added drop-wise in there-necked flask.After dropwising, continue reaction 12 hours, after reaction terminates, filter, filtrate evaporated under reduced pressure recycling design, obtain white solid, through 50 DEG C of vacuum-drying 6h, obtain white powder phosphor nitrogen combustion inhibitor solid 27.85 grams, yield 98%.
embodiment 4:
2 are added in the 500ml there-necked flask that thermometer, 100ml constant pressure funnel and device for absorbing tail gas be housed, 2-dihydroxymethyl-3-nitro-1-propyl alcohol (16.51g, 0.1mol), triethylamine (25.30g, 0.25mol) and 100ml methylene dichloride, open magnetic agitation, phenoxy group phosphinylidyne dichloro (22.22g, 0.105mol) is dissolved in 50ml methylene dichloride, joins in constant pressure funnel, below 5 DEG C, be slowly added drop-wise in there-necked flask.After dropwising, continue reaction 10 hours, after reaction terminates, filter, filtrate evaporated under reduced pressure recycling design, obtain white solid, through 40 DEG C of vacuum-drying 6h, obtain white powder phosphor nitrogen combustion inhibitor solid 29.15 grams, yield 94%.
embodiment 5:
2 are added in the 500ml there-necked flask that thermometer, 100ml constant pressure funnel and device for absorbing tail gas be housed, 2-dihydroxymethyl-3-nitro-1-propyl alcohol (16.51g, 0.1mol), triethylamine (25.30g, 0.25mol) and 100ml ether, open magnetic agitation, phenoxy group phosphinylidyne dichloro (22.22g, 0.105mol) is dissolved in 100ml ether, joins in constant pressure funnel, below 5 DEG C, be slowly added drop-wise in there-necked flask.After dropwising, continue reaction 10 hours, after reaction terminates, filter, filtrate evaporated under reduced pressure recycling design, obtain white solid, through 40 DEG C of vacuum-drying 6h, obtain white powder phosphor nitrogen combustion inhibitor solid 22.38 grams, yield 72%.
embodiment 6:
2 are added in the 500ml there-necked flask that thermometer, 100ml constant pressure funnel and device for absorbing tail gas be housed, 2-dihydroxymethyl-3-nitro-1-propyl alcohol (16.51g, 0.1mol), triethylamine (25.30g, 0.25mol) and 100ml tetrahydrofuran (THF), open magnetic agitation, phenoxy group phosphinylidyne dichloro (22.22g, 0.105mol) is dissolved in 50ml tetrahydrofuran (THF), joins in constant pressure funnel, below 5 DEG C, be slowly added drop-wise in there-necked flask.After dropwising, continue reaction 8 hours, after reaction terminates, filter, filtrate evaporated under reduced pressure recycling design, obtain white solid, through 50 DEG C of vacuum-drying 6h, obtain white powder phosphor nitrogen combustion inhibitor solid 29.57 grams, yield 94%.
Claims (5)
1. a response type phosphor nitrogen combustion inhibitor, is characterized in that this phosphor nitrogen combustion inhibitor molecular structure is:
Wherein R
1for alkyl, alkoxyl group, phenyl or phenoxy group.
2. the preparation method of a response type phosphor nitrogen combustion inhibitor as claimed in claim 1, it is characterized in that this preparation method comprises the steps: to add 2 in the reactor that solvent is housed, 2-dihydroxymethyl-3-nitro-1-propyl alcohol and acid binding agent, instill phosphorus reagent subsequently, stir, temperature is controlled at 0 DEG C ~ 60 DEG C, isothermal reaction 4 ~ 12h; After completion of the reaction, filter, filtrate evaporated under reduced pressure recycling design, obtain white solid, namely obtain response type phosphor nitrogen combustion inhibitor through vacuum-drying.
3. the preparation method of response type phosphor nitrogen combustion inhibitor according to claim 2, is characterized in that: described solvent is the one in ether, methylene dichloride, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane or ethylene dichloride; By every mole of 2,2-dihydroxymethyl-3-nitro-1-propyl alcohol meters, described solvent load is 1000mL ~ 2000mL.
4. the preparation method of response type phosphor nitrogen combustion inhibitor according to claim 2, is characterized in that: described acid binding agent is the one in triethylamine, pyridine, sodium hydroxide or sodium carbonate; The mol ratio of described 2,2-dihydroxymethyl-3-nitro-1-propyl alcohol and acid binding agent is 1:2 ~ 3; Isothermal reaction 4 ~ 12h; Vacuum-drying temperature is 40 ~ 50 DEG C.
5. the preparation method of response type phosphor nitrogen combustion inhibitor according to claim 2, is characterized in that: described phosphorus reagent is alkyl phosphinylidyne dichloro, alkylphosphonic acid carboxylic acid dimethyl ester, alkoxyl group phosphinylidyne dichloro, diphenylphosphoryl dichloro, phosphenylic acid dimethyl ester or phenoxy group phosphinylidyne dichloro.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017330A (en) * | 2015-07-07 | 2015-11-04 | 苏州凯马化学科技有限责任公司 | Hydroxymethyl thiophosphoryl heterocycle methylphosphonate compound and preparation method thereof |
| CN105037434A (en) * | 2015-07-07 | 2015-11-11 | 苏州凯马化学科技有限责任公司 | Hydroxymethyl thiophosphoryl heterocyclic phenylphosphonate compound and preparation method therefor |
| CN105037430A (en) * | 2015-07-07 | 2015-11-11 | 苏州凯马化学科技有限责任公司 | Hydroxymethyl phosphine heterocyclic phenylphosphonate compound and preparation method therefor |
| CN105037431A (en) * | 2015-07-07 | 2015-11-11 | 苏州凯马化学科技有限责任公司 | Preparation method for flame retardant trishydroxymethyl phosphine caged phosphorothioate compound |
| CN105037439A (en) * | 2015-07-07 | 2015-11-11 | 苏州凯马化学科技有限责任公司 | Hydroxymethyl phosphonyl heterocyclic phenylphosphonothioate compound and preparation method therefor |
| CN106397779A (en) * | 2016-09-19 | 2017-02-15 | 太原工业学院 | Phosphor-fluorine flame retardant and preparation method thereof |
| CN111393853A (en) * | 2020-04-29 | 2020-07-10 | 嘉兴学院 | Flame retardant containing flame-retardant synergistic composition and preparation method thereof |
| CN112442067A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-nitrogen-containing flame retardant with hydroxyl and preparation method and application thereof |
Citations (1)
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| KR20120087767A (en) * | 2011-01-28 | 2012-08-07 | 에이스앤이(주) | Product method of organic flame retardant phosphorus compound for complex flame retardant |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120087767A (en) * | 2011-01-28 | 2012-08-07 | 에이스앤이(주) | Product method of organic flame retardant phosphorus compound for complex flame retardant |
Non-Patent Citations (1)
| Title |
|---|
| XUEFENG YANG，ET AL.: "Synthesis of a novel ionic liquid containing phosphorus and its application in intumescent flame retardant polypropylene system", 《POLYM. ADV. TECHNOL.》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017330A (en) * | 2015-07-07 | 2015-11-04 | 苏州凯马化学科技有限责任公司 | Hydroxymethyl thiophosphoryl heterocycle methylphosphonate compound and preparation method thereof |
| CN105037434A (en) * | 2015-07-07 | 2015-11-11 | 苏州凯马化学科技有限责任公司 | Hydroxymethyl thiophosphoryl heterocyclic phenylphosphonate compound and preparation method therefor |
| CN105037430A (en) * | 2015-07-07 | 2015-11-11 | 苏州凯马化学科技有限责任公司 | Hydroxymethyl phosphine heterocyclic phenylphosphonate compound and preparation method therefor |
| CN105037431A (en) * | 2015-07-07 | 2015-11-11 | 苏州凯马化学科技有限责任公司 | Preparation method for flame retardant trishydroxymethyl phosphine caged phosphorothioate compound |
| CN105037439A (en) * | 2015-07-07 | 2015-11-11 | 苏州凯马化学科技有限责任公司 | Hydroxymethyl phosphonyl heterocyclic phenylphosphonothioate compound and preparation method therefor |
| CN106397779A (en) * | 2016-09-19 | 2017-02-15 | 太原工业学院 | Phosphor-fluorine flame retardant and preparation method thereof |
| CN106397779B (en) * | 2016-09-19 | 2019-12-06 | 太原工业学院 | phosphorus-fluorine flame retardant and preparation method thereof |
| CN112442067A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-nitrogen-containing flame retardant with hydroxyl and preparation method and application thereof |
| CN111393853A (en) * | 2020-04-29 | 2020-07-10 | 嘉兴学院 | Flame retardant containing flame-retardant synergistic composition and preparation method thereof |
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