CN105542159A - Branched chain type macromolecule phosphorus and nitrogen containing activity flame retardant and synthetic method thereof - Google Patents

Branched chain type macromolecule phosphorus and nitrogen containing activity flame retardant and synthetic method thereof Download PDF

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Publication number
CN105542159A
CN105542159A CN201610089996.7A CN201610089996A CN105542159A CN 105542159 A CN105542159 A CN 105542159A CN 201610089996 A CN201610089996 A CN 201610089996A CN 105542159 A CN105542159 A CN 105542159A
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flame retardant
phosphorus
branched chain
nitrogen containing
chain type
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CN105542159B (en
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戴李宗
邵志恒
陈国荣
李远源
林康彬
袁丛辉
许一婷
曾碧榕
罗伟昂
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Xiamen University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Fireproofing Substances (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention relates to a phosphorus and nitrogen containing flame retardant, in particular to a branched chain type macromolecule phosphorus and nitrogen containing activity flame retardant and a synthetic method thereof. The preparation method comprises the steps that under the nitrogen protection, paraformaldehyde, a solvent and polymine are sequentially added in a container provided with a stirring magneton and a condensation return device and then dissolved, DOPO is added, rotary evaporation and condensation are performed after the reaction is performed, and then reprecipitation, filtering and drying are performed to obtain the branched chain type macromolecule phosphorus and nitrogen containing activity flame retardant. The DOPO and the polymine not containing halogen and containing phosphorus and nitrogen are introduced into molecules, the flame retardant contains a plurality of active amido loci and can be used as a base material toughening agent, and the strength of the base material can be enhanced due to two rigid benzene rings on the phosphorus containing DOPO. The flame retardant performance of the material can be enhanced, and the mechanical performance is not affected. The branched chain type macromolecule phosphorus and nitrogen containing activity flame retardant can be used for polyester, epoxy resin, PBT and other flame-retardant modification materials. Due to poly-phosphorus and poly-nitrogen flame retardant synergism, the flame retardant efficiency is high, the addition quantity for the base material is small, the preparation method is easy and convenient to implement, raw materials are low in cost, and the yield is high.

Description

A kind of branched chain type macromole phosphorus-nitrogen containing reactive-type flame retardant and synthetic method thereof
Technical field
The present invention relates to a kind of phosphorus-nitrogen containing fire retardant, specifically relate to and can be used for the fire-retardant of polymer materials, improve the fire-retardant a kind of branched chain type macromole phosphorus-nitrogen containing reactive-type flame retardant with fire resistance of material and synthetic method thereof.
Background technology
Due to the combustibility of many polymkeric substance, once presence of fire after using these polymer materialss, just can threaten to life security, therefore flame retardance of polymer arouses the concern of relevant departments.When improving flame retardance of polymer performance and suppress its burning, release toxic smog gas becomes the necessary of polymkeric substance development.Flame retardance of polymer divides addition type and response type.Addition type easily runs off, and addition is large, also may affect the mechanical property of matrix.Reactive-type flame retardant can with some functional group reactions of matrix, form homogeneous material that can be compatible with body material, form intrinsically flame retarded macromolecular material.
In order to reach the fire-retardant object of intrinsic, amido or polyvalent alcohol can be introduced, being divided into halogen system and phosphorus system.But halogen system is fire-retardant can produce toxic gas, environmental pollution or injury human body therefore can be caused.Phosphorus-containing polyol or phosphorous amine compound are more satisfactory fire retardants.Chinese patent CN105218859A has synthesized a kind of response type Organophosphonate fire retardant, this compound contains hydroxyl reactive group, has better stability, can prepare Inherent Flame Retardant Polymers material as reactive flame retardant, use as additive flame retardant, can also plasticising.Chinese patent CN105061511A has synthesized bridged ring phosphonitrile reactive flame retardant, and this fire retardant has high rigidity, large space steric hindrance, many active sites, has fabulous thermostability, can be used as reactive flame retardant in epoxy resin.Chinese patent CN105061510A has prepared a kind of reactive type water-solubility fire retardant, and this fire retardant has the structure of Amino End Group and carboxyl, is applicable to obtain intrinsically flame retarded polymeric amide.
Therefore, the fire retardant researching and developing the inherent flame retardant halogen environmental protection with many reactive behavioies point is significant.
Summary of the invention
The present invention aims to provide simultaneously containing multiple reactive behavior site and nitrogen content is high, the fire-retardant group of DOPO phosphorous again, can be used in a kind of branched chain type macromole phosphorus-nitrogen containing reactive-type flame retardant and the synthetic method thereof of epoxy resin, polyester, PBT etc.
The chemical structural formula of described branched chain type macromole phosphorus-nitrogen containing reactive-type flame retardant (PEI-DOPO) is as follows:
Wherein, n is the polymerization degree, n=1 ~ 20.
The concrete steps of the preparation method of described branched chain type macromole phosphorus-nitrogen containing reactive-type flame retardant (PEI-DOPO) are as follows:
Under nitrogen protection, to be equipped with stir magneton and condensation reflux unit container in add paraformaldehyde, solvent and polymine successively, after to be dissolved; add DOPO, after reaction, concentrated by rotary evaporation; redeposition, filters, namely obtains branched chain type macromole phosphorus-nitrogen containing reactive-type flame retardant after drying.
The amido of described paraformaldehyde, polymine, the mol ratio of DOPO can be 1: 1: (0.8 ~ 4.2); The molecular weight of described polymine can be 600 ~ 10000; Described solvent can be DMF, and the consumption of solvent can be 2 ~ 20 times of each solid material total mass in mass ratio; The temperature of described reaction can be 50 ~ 80 DEG C, and the time of reaction can be 4 ~ 8h; The condition of described drying can be in vacuum drying oven dry; The solvent of described precipitation can be ethyl acetate, and described precipitation can repeated precipitation 2 ~ 4 times.
Compared with prior art, the present invention has following characteristics:
1) by not halogen-containing and the polymine of phosphorus-nitrogen containing and DOPO are incorporated in molecule, a kind of new branched type macromolecular structure fire retardant is obtained.
2) this fire retardant (PEI-DOPO) is containing multiple active amine site, can be used as body material toughner, and upper two the rigidity phenyl ring of phosphorous DOPO can increase body material intensity.Both can strongthener flame retardant properties, do not affect its mechanical property again.Can be used for the flame-retardant modified of polyester, epoxy resin, PBT etc.
3) upper many phosphorus many nitrogen cooperative flame retardants of this fire retardant (PEI-DOPO), flame retarding efficiency is high, few for body material addition, and preparation method is easy for this fire retardant, cheaper starting materials, and productive rate is higher, can carry out commercial industries.
Accompanying drawing explanation
Fig. 1 is embodiment 1 fire retardant PEI-DOPO's 1hNMR nuclear magnetic spectrogram.
Fig. 2 is embodiment 1 polymine PEI's 1hNMR nuclear magnetic spectrogram.
Fig. 3 is the infrared spectrum of embodiment 1 polymine PEI and fire retardant PEI-DOPO.
Embodiment
Below by drawings and Examples, the invention will be further described.
Embodiment 1:
Under nitrogen protection; to be equipped with stir magneton and condensation reflux unit 50ml there-necked flask in add 0.3g paraformaldehyde, 5mlN successively; dinethylformamide (DMF) and 1g polymine (molecular weight is 600) are dissolved in the solution of 1mlDMF; after to be dissolved; add 2.16gDOPO; then 70 DEG C are warmed up to gradually; reaction 4h; concentrated by rotary evaporation; by ethyl acetate precipitation twice, filtration drying obtains yellow solid powder and is required fire retardant (PEI-DOPO).
By Fig. 1's 1there is at 6.477 ~ 8.317ppm the ph-H proton peak that Fig. 2 polymine PEI does not have in HNMR nuclear magnetic spectrogram, and the P-H proton peak of the DOPO at pertinent literature report 8.885ppm place then disappears, and the successful synthesis of fire retardant PEI-DOPO is described as seen.
Contrasted by the infared spectrum of Fig. 2 polymine PEI and fire retardant PEI-DOPO, visible polymine is at 3279cm -1the N-H peak at place disappears, and at 1265cm -1and 1002cm -1near occurred respectively P=O peak and the P-O peak of DOPO also illustrate that the successful synthesis of fire retardant PEI-DOPO.
Embodiment 2:
Under nitrogen protection; to be equipped with stir magneton and condensation reflux unit 150ml there-necked flask in add 1.2g paraformaldehyde, 50mlN successively; dinethylformamide (DMF) and 6g polymine (molecular weight is 1800) are dissolved in the solution of 5mlDMF; after to be dissolved, add 8.64gDOPO, be then warmed up to 60 DEG C gradually; reaction 5h; concentrated by rotary evaporation, precipitates three times by ethyl acetate, and filtration drying obtains yellow solid powder and is PEI-DOPO.
Embodiment 3:
Under nitrogen protection; to be equipped with stir magneton and condensation reflux unit 50ml there-necked flask in add 0.6g paraformaldehyde, 8mlN successively; dinethylformamide (DMF) and 25g polymine (molecular weight is 10000) are dissolved in the solution of 2mlDMF; after to be dissolved, add 4.32gDOPO, be then warmed up to 55 DEG C gradually; reaction 6h; concentrated by rotary evaporation, precipitates three times by ethyl acetate, and filtration drying obtains yellow solid powder and is PEI-DOPO.
Embodiment 4:
Under nitrogen protection; to be equipped with stir magneton and condensation reflux unit 250ml there-necked flask in add 1.5g paraformaldehyde, 75mlN successively; dinethylformamide (DMF) and 7.5g polymine (molecular weight is 600) are dissolved in the solution of 25mlDMF; after to be dissolved, add 10.8gDOPO, be then warmed up to 80 DEG C gradually; reaction 6h; concentrated by rotary evaporation, by ethyl acetate precipitation twice, filtration drying obtains yellow solid powder and is PEI-DOPO.
The present invention mainly with polymine (PEI) and 9,10-dihydro-9 oxa--10-phospho hetero phenanthrene-10-oxide compound (DOPO) for raw material, synthesize phosphorus-nitrogen containing reactive-type flame retardant.Mainly first the paraformaldehyde and polymine (PEI) that are dissolved in solvent are added and be connected with nitrogen and the container of equipment condensation reflux unit and stirrer, then DOPO is added, temperature reaction, wash with solvent deposition, filtering vacuum is dry, finally obtains yellow solid powder and is described fire retardant (PEI-DOPO).The Large molecule active fire retardant of the present invention's synthesis, have preparation method simple, mild condition, cheaper starting materials, flame retardant properties is good, and good with matrix phase capacitive, also can be used for toughness reinforcing, and this fire retardant is not halogen-containing, is environment-friendlyflame-retardant flame-retardant material.

Claims (10)

1. a branched chain type macromole phosphorus-nitrogen containing reactive-type flame retardant, is characterized in that its chemical structural formula is as follows:
Wherein, n is the polymerization degree, n=1 ~ 20.
2. the preparation method of a kind of branched chain type macromole phosphorus-nitrogen containing reactive-type flame retardant as claimed in claim 1, is characterized in that its concrete steps are as follows:
Under nitrogen protection, to be equipped with stir magneton and condensation reflux unit container in add paraformaldehyde, solvent and polymine successively, after to be dissolved; add DOPO, after reaction, concentrated by rotary evaporation; redeposition, filters, namely obtains branched chain type macromole phosphorus-nitrogen containing reactive-type flame retardant after drying.
3. the preparation method of a kind of branched chain type macromole phosphorus-nitrogen containing reactive-type flame retardant as claimed in claim 1, is characterized in that the mol ratio of the amido of described paraformaldehyde, polymine, DOPO is 1: 1: (0.8 ~ 4.2).
4. the preparation method of a kind of branched chain type macromole phosphorus-nitrogen containing reactive-type flame retardant as claimed in claim 1, is characterized in that the molecular weight of described polymine is 600 ~ 10000.
5. the preparation method of a kind of branched chain type macromole phosphorus-nitrogen containing reactive-type flame retardant as claimed in claim 1, is characterized in that described solvent is DMF.
6. the preparation method of a kind of branched chain type macromole phosphorus-nitrogen containing reactive-type flame retardant as claimed in claim 1, is characterized in that the consumption of described solvent is 2 ~ 20 times of each solid material total mass in mass ratio.
7. the preparation method of a kind of branched chain type macromole phosphorus-nitrogen containing reactive-type flame retardant as claimed in claim 1, it is characterized in that the temperature of described reaction is 50 ~ 80 DEG C, the time of reaction is 4 ~ 8h.
8. the preparation method of a kind of branched chain type macromole phosphorus-nitrogen containing reactive-type flame retardant as claimed in claim 1, is characterized in that the condition of described drying is dry in vacuum drying oven.
9. the preparation method of a kind of branched chain type macromole phosphorus-nitrogen containing reactive-type flame retardant as claimed in claim 1, is characterized in that the solvent of described precipitation is ethyl acetate.
10. the preparation method of a kind of branched chain type macromole phosphorus-nitrogen containing reactive-type flame retardant as claimed in claim 1, is characterized in that described precipitation is repeated precipitation 2 ~ 4 times.
CN201610089996.7A 2016-02-18 2016-02-18 A kind of branched chain type macromolecular phosphorus-nitrogen containing reactive-type flame retardant and its synthetic method Active CN105542159B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107474247A (en) * 2017-07-28 2017-12-15 江南大学 A kind of preparation method of phosphorus nitrogen synergistic water soluble polymer fire retardant
CN107501492A (en) * 2017-08-10 2017-12-22 长春工业大学 Schiff bases formula phosphorus nitrogen expansion type combustion inhibitor and its production and use
CN110527100A (en) * 2019-09-12 2019-12-03 贵州省材料产业技术研究院 Poly- phosphamide fire retardant and its preparation method and application
CN114957655A (en) * 2022-05-18 2022-08-30 东莞市迪彩塑胶五金有限公司 Novel phosphorus-nitrogen high-molecular flame retardant and preparation method thereof

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Publication number Priority date Publication date Assignee Title
US20010003771A1 (en) * 1999-03-03 2001-06-14 Chun-Shan Wang Phosphorus-containing flame-retardant cured epoxy resins
CN104017210A (en) * 2014-06-06 2014-09-03 浙江大学宁波理工学院 Long-chain type metal coordination intumescent flame retardant and preparation method thereof
CN104262398A (en) * 2014-09-23 2015-01-07 厦门大学 Phosphorus-nitrogen type flame retardant containing active double bond as well as preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
US20010003771A1 (en) * 1999-03-03 2001-06-14 Chun-Shan Wang Phosphorus-containing flame-retardant cured epoxy resins
CN104017210A (en) * 2014-06-06 2014-09-03 浙江大学宁波理工学院 Long-chain type metal coordination intumescent flame retardant and preparation method thereof
CN104262398A (en) * 2014-09-23 2015-01-07 厦门大学 Phosphorus-nitrogen type flame retardant containing active double bond as well as preparation method and application thereof

Non-Patent Citations (1)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107474247A (en) * 2017-07-28 2017-12-15 江南大学 A kind of preparation method of phosphorus nitrogen synergistic water soluble polymer fire retardant
CN107501492A (en) * 2017-08-10 2017-12-22 长春工业大学 Schiff bases formula phosphorus nitrogen expansion type combustion inhibitor and its production and use
CN107501492B (en) * 2017-08-10 2019-06-07 长春工业大学 Schiff bases formula phosphorus nitrogen expansion type combustion inhibitor and its preparation method and application
CN110527100A (en) * 2019-09-12 2019-12-03 贵州省材料产业技术研究院 Poly- phosphamide fire retardant and its preparation method and application
CN114957655A (en) * 2022-05-18 2022-08-30 东莞市迪彩塑胶五金有限公司 Novel phosphorus-nitrogen high-molecular flame retardant and preparation method thereof
CN114957655B (en) * 2022-05-18 2023-11-28 东莞市迪彩塑胶五金有限公司 Phosphorus-nitrogen high-molecular flame retardant and preparation method thereof

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