CN101792530A - Polymer type halogen-free flame retardant (PDPTP) and preparation method thereof - Google Patents
Polymer type halogen-free flame retardant (PDPTP) and preparation method thereof Download PDFInfo
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- CN101792530A CN101792530A CN 201010127791 CN201010127791A CN101792530A CN 101792530 A CN101792530 A CN 101792530A CN 201010127791 CN201010127791 CN 201010127791 CN 201010127791 A CN201010127791 A CN 201010127791A CN 101792530 A CN101792530 A CN 101792530A
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Abstract
The invention discloses a polymer type halogen-free flame retardant (PDPTP) and a preparation method thereof. The method comprises the following steps of: weighing a raw material (I) and a raw material (II) in a reaction formula in a mol ratio of 1:0.9-1.1, and weighing a catalyst and the raw material (I) in a mol ratio of 0.001 to 0.1; adding the raw material (I), the raw material (II) and the catalyst into a reaction kettle provided with a stirrer and a thermometer; and performing reaction for 4 to 10 hours at the temperature of between 120 and 260 DEG C under the protection of nitrogen gas to obtain a white flame retardant. The method can also comprise the following steps of: adding the obtained white flame retardant into a solvent to completely dissolve the white flame retardant; then using a precipitant 4 to 8 times the volume of the solvent to perform precipitation; and performing filtration and vacuum drying to obtain a white crystal. The polymer type halogen-free flame retardant is the latest model flame retardant which is developed for solving the world problem of non-halogenated flame retardance of polymers such as polyester, epoxy resin, other engineering plastics and the like based on the newest requirements on non-halogenation of global flame retardant materials, has very good intermiscibility with resins, is easy to disperse, cannot be separated out and cannot reduce the mechanical strength of materials. Besides, the polymer type halogen-free flame retardant also has the advantages of low smoke, no toxicity and the like, is favorable for environmental pollution by containing no halogen, has a good development prospect, has a wide application range and a good flame-retardant effect. The provided preparation method is simple and easily controllable conditions.
Description
One, technical field
The invention belongs to polymer type halogen-free flame retardant agent technical field, be specifically related to a kind of polymer type halogen-free flame retardant agent and preparation method thereof.
Two, background technology
Because the latest requirement of the non-halogen environmental protection of global fire retardant material, fire-retardant to polymkeric substance such as polyester, Resins, epoxy and other engineering plastics suddenly treated the BACN that the demand property price ratio is high.Fire retardant is of a great variety, wherein phosphorus flame retardant particularly the organic phosphine fire retardant favored, be one of most important based flame retardant in each based flame retardant.Contain the C-P key in the organic phosphine fire retardant structure, brought stability to molecule, be adapted to high temperature process, aggretion type macromole fire retardant and resin have good intermiscibility, are easy to disperse, and do not separate out, and do not reduce the physical strength of material.Also have low cigarette, advantage such as nontoxic, not halogen-containing because of it again, have good development prospect.
Three, summary of the invention
The purpose of this invention is to provide a kind of new polymer type halogen-free flame retardant agent.
Another object of the present invention provides a kind of preparation method of polymer type halogen-free flame retardant agent of the present invention.
Polymer type halogen-free flame retardant agent provided by the invention is characterized in that this fire retardant is a base polymer that is obtained by following building-up reactions, promptly
Wherein n is that 1～100 integer X is chlorine atom or bromine atoms, and m is 0～3 integer, and R is any in phenyl, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl.And the outward appearance of this fire retardant is the white crystals thing, 235～250 ℃ of melt temperatures.
The present invention also provides a kind of method for preparing above-mentioned polymer type halogen-free flame retardant agent.This method is to be 1: 0.9～1.1 with the raw material in the above reaction formula (I) in molar ratio with raw material (II) earlier; catalyzer and raw material (I) mol ratio is the 0.001-0.1 weighing; add then and have agitator; in the reactor of thermometer; under nitrogen protection, promptly got white fire retardant in 4～10 hours in 120～260 ℃ of reactions of temperature.Also the white fire retardant that obtains can be added solvent again it is dissolved fully, precipitate with the precipitation agent of 4-8 times of quantity of solvent then and separate out, after filtration, obtain the white crystals thing after the vacuum-drying.
The catalyzer that is used for the inventive method is any of calcium chloride, aluminum chloride, zinc chloride, magnesium chloride, bariumchloride; Precipitation agent is any in anhydrous diethyl ether, anhydrous methanol, the dehydrated alcohol; Solvent is selected any in chloroform, phenylcarbinol, tetrachloroethane and 1: the 1 phenol-tetrachloroethane mixing solutions for use.
The present invention has following advantage:
1, polymer type halogen-free flame retardant agent provided by the invention is good as a kind of new flame-retardant additive and polymeric matrix consistency, is difficult for migration, has good weather resistance.
2, polymer type halogen-free flame retardant agent good flame retardation effect provided by the invention, and not halogen-containing, satisfy the up-to-date non-halogen requirement of fire retardant material fully.
3, preparation method provided by the invention is simple, and condition is easy to control.
4, polymer type halogen-free flame retardant agent applied range provided by the invention can be suitable for the fire-retardant of multiple polymers systems such as vibrin, polymeric amide, Resins, epoxy and unsaturated polyester simultaneously, and all can reach good flame-retardant effect.
Four, embodiment
Provide embodiment below so that the invention will be further described; but be pointed out that following examples can not be interpreted as limiting the scope of the invention, the person skilled in the art of this area foregoing according to the present invention still belongs to protection scope of the present invention to some nonessential improvement and the adjustment that the present invention makes.
Embodiment 1 is with 1 mole of phenyl phosphonothioic dichloride, 9, the 10-dihydro-9-oxy is assorted-1 mole of the assorted phenanthrene-Resorcinol (hereinafter to be referred as DOPO-HQ) of 10-phosphinylidyne, 0.01 mole in calcium chloride, adding has in the reactor of agitator, thermometer, feeds the nitrogen stirring and is warmed up to 160 ℃ of reactions 1 hour; Be warmed up to 240 ℃ of reactions 4 hours then; Cooling back adds the 200ml chloroform to be made it to dissolve fully, pour into then in the anhydrous diethyl ether of 5 times of volumes to precipitate, after filtration, after the vacuum-drying white crystals shape product.Productive rate is 99%, and melt temperature is 245 ℃.
Embodiment 2 is 1 mole of phenyl sulfo-phosphono dibromo, 1.1 moles of DOPO-HQ, and 0.02 mole of zinc chloride adds and has in the reactor of agitator, thermometer, feeds nitrogen and stirs and be warmed up to 160 ℃ of reactions 1 hour; Be warmed up to 250 ℃ of reactions 5 hours then; Cooling back adds the 150ml tetrachloroethane to be made it to dissolve fully, pour into then in the anhydrous diethyl ether of 7 times of volumes to precipitate, after filtration, after the vacuum-drying white crystals shape product.Productive rate is 95%, and melt temperature is 235 ℃.
Embodiment 3 is 1 mole of aminomethyl phenyl phosphonothioic dichloride, 0.95 mole of DOPO-HQ, and 0.05 mole in aluminum chloride adds and has in the reactor of agitator, thermometer, feeds nitrogen and stirs and be warmed up to 150 ℃ of reactions 2 hours; Be warmed up to 200 ℃ of reactions 3 hours then; Elevated temperature to 250 ℃ reaction is 1 hour again: the cooling back adds 1: 1 phenol-tetrachloroethane of 100ml to be made it to dissolve fully, pour into then in the anhydrous diethyl ether of 8 times of volumes to precipitate, after filtration, after the vacuum-drying white crystals shape product.Productive rate is 98%, and melt temperature is 235 ℃.
Embodiment 4 is 1 mole of phenyl phosphonothioic dichloride, 1.05 moles of DOPO-HQ, and 0.03 mole in calcium chloride adds and has in the reactor of agitator, thermometer, feeds nitrogen and stirs and be warmed up to 160 ℃ of reactions 3 hours; Be warmed up to 250 ℃ of reactions 3 hours then; Cooling back adds the 200ml chloroform to be made it to dissolve fully, pour into then in the anhydrous diethyl ether of 5 times of volumes to precipitate, after filtration, after the vacuum-drying white crystals shape product.Productive rate is 99%, and melt temperature is 240 ℃.
Embodiment 5 is 2,4,1 mole of 6-trimethylphenyl phosphonothioic dichloride, and 1 mole of ODOP-HQ, 0.015 mole in aluminum chloride adds and has in the reactor of agitator, thermometer, feeds nitrogen and stirs and be warmed up to 150 ℃ of reactions 2 hours; Be warmed up to 200 ℃ of reactions 6 hours then; Cooling back adds 1: 1 phenol one tetrachloroethane of 100ml to be made it to dissolve fully, pour into then in the dehydrated alcohol of 8 times of volumes to precipitate, after filtration, after the vacuum-drying white crystals shape product.Productive rate is 95%, and melt temperature is 250 ℃.
Embodiment 6 is 1 mole of 4-isopropyl phenyl phosphonothioic dichloride, 1.05 moles of DOPO-HQ, and 0.05 mole of zinc chloride adds and has in the reactor of agitator, thermometer, feeds nitrogen and stirs and be warmed up to 150 ℃ of reactions 1 hour; Be warmed up to 200 ℃ of reactions 4 hours then; Elevated temperature to 260 ℃ reaction is 2 hours again; Cooling back adds 1: 1 phenol one tetrachloroethane of 150ml to be made it to dissolve fully, pour into then in the dehydrated alcohol of 8 times of volumes to precipitate, after filtration, after the vacuum-drying white crystals shape product.Productive rate is 96%, and melt temperature is 235 ℃.
Embodiment 7 is 1 mole of ethylphenyl phosphonyl dichloride, 1 mole of DOPO-HQ, and 0.01 mole in calcium chloride adds and has in the reactor of agitator, thermometer, feeds nitrogen and stirs and be warmed up to 180 ℃ of reactions 2 hours; Be warmed up to 250 ℃ of reactions 4 hours then; Cooling back adds the 250ml phenylcarbinol to be made it to dissolve fully, pour into then in the anhydrous methanol of 8 times of volumes to precipitate, after filtration, after the vacuum-drying the white powder product.Productive rate is 98%, and melt temperature is 245 ℃.
Claims (7)
1. polymer type halogen-free flame retardant agent is characterized in that this fire retardant is a base polymer that is obtained by following building-up reactions, promptly
Wherein n is that 1～80 integer X is chlorine atom or bromine atoms, and R is the alkyl of alkyl or replacement, and the outward appearance of this fire retardant is the white crystals thing, 235～250 ℃ of melt temperatures.
2. polymer type halogen-free flame retardant agent according to claim 1 is characterized in that m is 0～3 integer; Alkyl is any in phenyl, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl.
3. according to the preparation method of the described polymer type halogen-free flame retardant agent of claim 1-2; it is characterized in that being 1: 0.9～1.1 with raw material (I) in molar ratio with raw material (II) earlier; catalyzer and raw material (I) mol ratio is 0.001～0.1 weighing; add then and have agitator; in the reactor of thermometer; under nitrogen protection, promptly got white fire retardant in 4-10 hour in 120～260 ℃ of reactions of temperature.
4. the preparation method of polymer type halogen-free flame retardant agent according to claim 3, it is characterized in that the white fire retardant that will obtain adds solvent again it is dissolved fully, precipitate with the precipitation agent of 4-8 times of quantity of solvent then and separate out, after filtration, obtain the white crystals thing after the vacuum-drying.
5. according to the preparation method of claim 3 or 4 described polymer type halogen-free flame retardant agent, it is characterized in that catalyzer is any in calcium chloride, aluminum chloride, zinc chloride, magnesium chloride, the bariumchloride.
6. according to the preparation method of claim 3 or 4 or 5 described polymer type halogen-free flame retardant agent, it is characterized in that precipitation agent is any in anhydrous diethyl ether, anhydrous methanol, the dehydrated alcohol.
7. according to claim 3 or 4 or the preparation method of 5 or 6 described polymer type halogen-free flame retardant agent, it is characterized in that solvent selects any in chloroform, phenylcarbinol, tetrachloroethane and 1: the 1 phenol-tetrachloroethane mixing solutions for use.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201010127791 CN101792530A (en) | 2010-03-19 | 2010-03-19 | Polymer type halogen-free flame retardant (PDPTP) and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585238A (en) * | 2012-03-12 | 2012-07-18 | 苏州萃智新技术开发有限公司 | Polymer type halogen-free fire retardant poly(9,10-dihydro-9-oxa-10-(2,5-dihyroxyphenyl) phosphaphenanthrene-10-oxide) thiophenylphosphonate (PDPTP) and preparation method thereof |
| CN103480412A (en) * | 2013-08-13 | 2014-01-01 | 滨海雅克化工有限公司 | Ionic liquid catalyst used in preparation of bisphenol A (phenyl polyphosphate) and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1563152A (en) * | 2004-03-19 | 2005-01-12 | 四川大学 | Polymer type phosphatic fire retardant, preparation method and usage |
| CN1835960A (en) * | 2003-06-18 | 2006-09-20 | 纺织和塑料研究协会图林根研究院 | Method for producing organic compounds contg poly-dopo, and use of the same |
| CN1910263A (en) * | 2003-12-26 | 2007-02-07 | 东洋纺织株式会社 | Process for producing phosphorus compound flame retardant, phosphorus compound flame retardant, and flame-retardant polyester |
| CN101613374A (en) * | 2009-07-22 | 2009-12-30 | 中国科学技术大学 | A kind of side group is polymeric phosphorus-containing flame retardant of DOPO and preparation method thereof |
-
2010
- 2010-03-19 CN CN 201010127791 patent/CN101792530A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1835960A (en) * | 2003-06-18 | 2006-09-20 | 纺织和塑料研究协会图林根研究院 | Method for producing organic compounds contg poly-dopo, and use of the same |
| CN1910263A (en) * | 2003-12-26 | 2007-02-07 | 东洋纺织株式会社 | Process for producing phosphorus compound flame retardant, phosphorus compound flame retardant, and flame-retardant polyester |
| CN1563152A (en) * | 2004-03-19 | 2005-01-12 | 四川大学 | Polymer type phosphatic fire retardant, preparation method and usage |
| CN101613374A (en) * | 2009-07-22 | 2009-12-30 | 中国科学技术大学 | A kind of side group is polymeric phosphorus-containing flame retardant of DOPO and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585238A (en) * | 2012-03-12 | 2012-07-18 | 苏州萃智新技术开发有限公司 | Polymer type halogen-free fire retardant poly(9,10-dihydro-9-oxa-10-(2,5-dihyroxyphenyl) phosphaphenanthrene-10-oxide) thiophenylphosphonate (PDPTP) and preparation method thereof |
| CN103480412A (en) * | 2013-08-13 | 2014-01-01 | 滨海雅克化工有限公司 | Ionic liquid catalyst used in preparation of bisphenol A (phenyl polyphosphate) and preparation method thereof |
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Open date: 20100804 |