CN104262553A - Flame-retardant block copolymer containing nitrogen and phosphorus and preparation method thereof - Google Patents
Flame-retardant block copolymer containing nitrogen and phosphorus and preparation method thereof Download PDFInfo
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- CN104262553A CN104262553A CN201410481714.9A CN201410481714A CN104262553A CN 104262553 A CN104262553 A CN 104262553A CN 201410481714 A CN201410481714 A CN 201410481714A CN 104262553 A CN104262553 A CN 104262553A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 75
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title abstract description 37
- 229910052698 phosphorus Inorganic materials 0.000 title abstract description 11
- 239000011574 phosphorus Substances 0.000 title abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000010257 thawing Methods 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000000693 micelle Substances 0.000 claims abstract description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract 6
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims abstract 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 43
- 229920001577 copolymer Polymers 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 238000001556 precipitation Methods 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 229920002246 poly[2-(dimethylamino)ethyl methacrylate] polymer Polymers 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 10
- POLZHVHESHDZRD-UHFFFAOYSA-N 2-hydroxyethyl 2-methylprop-2-enoate;phosphoric acid Chemical compound OP(O)(O)=O.CC(=C)C(=O)OCCO POLZHVHESHDZRD-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 7
- ZGRWZUDBZZBJQB-UHFFFAOYSA-N benzenecarbodithioic acid Chemical compound SC(=S)C1=CC=CC=C1 ZGRWZUDBZZBJQB-UHFFFAOYSA-N 0.000 claims description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000000502 dialysis Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims 2
- 238000007872 degassing Methods 0.000 abstract 2
- 230000001376 precipitating effect Effects 0.000 abstract 2
- 238000010791 quenching Methods 0.000 abstract 2
- 230000000171 quenching effect Effects 0.000 abstract 2
- WDFFWUVELIFAOP-UHFFFAOYSA-N 2,6-difluoro-4-nitroaniline Chemical compound NC1=C(F)C=C([N+]([O-])=O)C=C1F WDFFWUVELIFAOP-UHFFFAOYSA-N 0.000 abstract 1
- KOBJYYDWSKDEGY-UHFFFAOYSA-N 2-phenylpropan-2-yl benzenecarbodithioate Chemical compound C=1C=CC=CC=1C(C)(C)SC(=S)C1=CC=CC=C1 KOBJYYDWSKDEGY-UHFFFAOYSA-N 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- -1 carboxylic acid halides Chemical class 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a flame-retardant block copolymer containing nitrogen and phosphorus and a preparation method thereof and relates to a block copolymer. The flame-retardant block copolymer containing nitrogen and phosphorus is PMOEPm-b-PDMAEMAn. The preparation method comprises the steps of dissolving 2-hydroxyethyl methacrylate phosphate, cumyl dithiobenzoate and azobisisobutyronitrile in a solvent, carrying out freeze thawing and degassing until unfreezing is realized and no bubbles come out, carrying out polymerization reaction under the protection of inert gas, quenching with liquid nitrogen to stop the reaction, precipitating and drying to obtain a product which is a PMOEPm macromolecular chain transfer agent; dissolving the PMOEPm macromolecular chain transfer agent, dimethylaminoethyl methacrylate and azobisisobutyronitrile in the solvent, carrying out freeze thawing and degassing, carrying out polymerization reaction under the protection of inert gas, quenching with liquid nitrogen to stop the reaction and repeatedly precipitating with ethanol used as a precipitant to obtain the target product, namely, flame-retardant block copolymer containing nitrogen and phosphorus (PMOEPm-b-PDMAEMAn). The flame-retardant block copolymer containing nitrogen and phosphorus can be used in preparation of halogen-free flame retardant and self-assemble micelles.
Description
Technical field
The invention belongs to high molecular halogen-free flame retardant area, relate to a kind of segmented copolymer, especially relate to fire-retardant segmented copolymer of a kind of phosphorus-nitrogen containing with anti-flaming function and preparation method thereof.
Background technology
Tradition halogenated flame retardant especially brominated flame-retardant etc. has good flame retardant effect and was once widely used.But research finds, brominated flame-retardant can produce brominated diphenyl and the toxic substances such as Dioxins when burning, thus limits widely using of halogen containing flame-retardant.Therefore, new and effective, that Halogen, nontoxic flame-retardant system have become fire-retardant scientific research new direction is set up.
Traditional condensed phase halogen-free flame-retardant system is relevant to P, N, Si element, they effectively can promote the generation of stable intumescent char layer, suppress base material to continue thermal oxidative reaction occurs, improve the thermal degradation temperature of curing system, mass loss temperature and coke growing amount.Therefore, phosphorus nitrogen two kinds of elements have cooperative flame retardant effect.When phosphorus-nitrogen containing fire retardant uses, under high temperature, phosphoric promotes the formation of layer of charcoal, and nitrogen element easily releases the non-flammable gases such as ammonia, nitrogen, degree of depth oxynitride, water vapor, take away most of heat, greatly reduce the surface temperature of polymkeric substance, thus play phosphorus nitrogen cooperative flame retardant effect.Phosphorus nitrogen cooperative flame retardant system comprises the content of two aspects, is undertaken composite by phosphorus flame retardant and nitrogenated flame retardant on the one hand, by the interaction between fire retardant, produces cooperative flame retardant effect; Be that phosphorus nitrogen two kinds of elements are introduced in same molecular structure on the other hand, by the interaction between element, produce cooperative flame retardant effect.As disclosed a kind of phosphorus-nitrogen containing flame-retardant polymer and preparation method thereof in Chinese patent CN 102391403, this phosphorus-nitrogen containing flame-retardant polymer can be gathered monomer homopolymerization by a kind of phosphorus-nitrogen containing or can be gathered monomer copolymerization with other and forms, can use as a kind of flame-retardant additive, also can as a kind of Inherent Flame Retardant Polymers materials'use, with macromolecule matrix, there is better consistency, flame retardant properties is good, little to the mechanical impact of material matrix, and flame retardant properties is good.And for example disclose a kind of response type phosphorus-nitrogen containing flame retardant and its preparation method and application in Chinese patent CN 102225953.Reacted by the aminated compounds of phosphorous volution and carboxylic acid halides, or the aminated compounds of phosphorous volution and carboxylic acid reaction, obtain described response type phosphorus-nitrogen containing flame retardant.Recycle this response type phosphorus-nitrogen containing flame retardant and monomer to form multipolymer and carry out flame-retardant modified to macromolecular material, by the effect of fire retardant phosphorus nitrogen element cooperative flame retardant, improve the flame retardant effect to macromolecular material, decrease the usage quantity of fire retardant at macromolecular material, reduce the cost of fire retardant material.
Summary of the invention
The object of the present invention is to provide and the element phosphor nitrogen with flame retardant effect is bonded on polymer molecular chain simultaneously, thus reach cooperative flame retardant object, can be applicable in polymeric matrix, play and strengthen and the fire-retardant segmented copolymer of a kind of phosphorus-nitrogen containing acted on such as fire-retardant and preparation method thereof.
Fire-retardant segmented copolymer (the PMOEP of described phosphorus-nitrogen containing
m-b-PDMAEMA
n) chemical structural formula as follows:
Wherein n is the unit sum of methacrylic ester dimethylaminoethyl (DMAEMA) shared by polymer chain, 80≤n≤100;
M is the unit sum of methacrylic acid-2-hydroxyethyl ester phosphoric acid ester (MOEP) shared by polymer chain, 50≤m≤80;
The fire-retardant segmented copolymer of described phosphorus-nitrogen containing obtains by reversible addion-fragmentation chain transfer living polymerization RAFT method.
The concrete steps of the preparation method of the fire-retardant segmented copolymer of described phosphorus-nitrogen containing are as follows:
1) PMOEP
mthe synthesis of Macromolecular chain transfer agent
Methacrylic acid-2-hydroxyethyl ester phosphoric acid ester (MOEP), dithiobenzoic acid cumyl ester (CDB) and azo-bis-isobutyl cyanide (AIBN) are dissolved in solvent; through freeze thawing is degassed do not have bubble to emerge to thawing after under protection of inert gas, carry out polyreaction; again through the sudden cold stopped reaction of liquid nitrogen, be drying to obtain product P MOEP after precipitation agent precipitation with ethanol
mmacromolecular chain transfer agent;
2) PMOEP
m-b-PDMAEMA
nthe synthesis of di-block copolymer
By step 1) PMOEP that synthesizes
mmacromolecular chain transfer agent and methacrylic ester dimethylaminoethyl (DMAEMA) and azo-bis-isobutyl cyanide are dissolved in solvent; after freeze thawing is degassed under protection of inert gas polyreaction; again through the sudden cold stopped reaction of liquid nitrogen, be that namely precipitation agent repeated precipitation obtains the fire-retardant segmented copolymer (PMOEP of target product phosphorus-nitrogen containing with ethanol
m-b-PDMAEMA
n).
In step 1) in, the mol ratio of described methacrylic acid-2-hydroxyethyl ester phosphoric acid ester (MOEP), dithiobenzoic acid cumyl ester and azo-bis-isobutyl cyanide can be MOEP: CDB: AIBN=(50 ~ 80): 1: 0.2; Described solvent can be selected from methyl alcohol or dimethyl formamide (DMF) etc.; Describedly degassedly can be 3 ~ 5 times; The temperature of described polyreaction can be 60 ~ 70 DEG C, and polymerization reaction time can be 24 ~ 48h; The consumption of described solvent can be 3 ~ 5 times of methacrylic acid-2-hydroxyethyl ester phosphoric acid ester (MOEP), dithiobenzoic acid cumyl ester and azo-bis-isobutyl cyanide by volume; Described rare gas element can adopt argon gas etc.; The consumption of described precipitation agent can be 15 ~ 20 times of reaction solvent add-on by volume.
In step 2) in, described methacrylic ester dimethylaminoethyl (DMAEMA), PMOEP
mthe mol ratio of Macromolecular chain transfer agent, azo-bis-isobutyl cyanide can be DMAEMA: PMOEP
m: AIBN=(80 ~ 100): 1: 0.1; Described solvent can be methyl alcohol or dimethyl formamide (DMF) etc.; The consumption of described solvent can be methacrylic ester dimethylaminoethyl (DMAEMA), PMOEP by volume
mmacromolecular chain transfer agent, azo-bis-isobutyl cyanide 2 ~ 4 times; Describedly degassedly can be 3 ~ 5 times; The temperature of described polyreaction can be 60 ~ 70 DEG C, and the time of polyreaction can be 24 ~ 48h; Described rare gas element can adopt argon gas etc.; The consumption of described precipitation agent can be 15 ~ 20 times of repeated precipitation 2 ~ 3 times of reaction solvent add-on by volume, or adopts distill water dialysis purification postlyophilization.
The fire-retardant segmented copolymer of described phosphorus-nitrogen containing can be applied preparing in the field such as halogen-free flame retardants and self-assembled micelle.
Compared with prior art, the present invention has the following advantages:
1) adopt the fire-retardant segmented copolymer of RAFT polymerization synthesis target phosphorus-nitrogen containing, reaction conditions is gentle, by controlling the content of P, N in feed ratio telomerized polymer;
2) the phosphorus oh group and reactable tertiary amino group with excellent flame retardant performance are keyed in macromolecular chain by chemical bond simultaneously, significantly improve matrix resin consistency and flame retardant resistance.
3) the fire-retardant segmented copolymer of this phosphorus-nitrogen containing is simultaneously containing functional phosphorus hydroxyl and tertiary amino group, forms micella in biologically application etc. by intramolecule self-assembly.
Accompanying drawing explanation
Fig. 1 is the fire-retardant segmented copolymer PMOEP of phosphorus-nitrogen containing
m's
1h NMR nuclear magnetic spectrogram;
Fig. 2 is the fire-retardant segmented copolymer PMOEP of phosphorus-nitrogen containing
m's
31p NMR nuclear magnetic spectrogram;
Fig. 3 is the fire-retardant segmented copolymer PMOEP of phosphorus-nitrogen containing
m-b-PDMAEMA
n's
1h NMR nuclear magnetic spectrogram;
Fig. 4 is the fire-retardant segmented copolymer PMOEP of phosphorus-nitrogen containing
m-b-PDMAEMA
n's
31p NMR nuclear magnetic spectrogram.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described:
Embodiment 1:
(1) PMOEP
80the synthesis of Macromolecular chain transfer agent
By MOEP (0.9125g; 4mmol); CDB (13.62mg; 0.05mmol) and AIBN (1.64mg; 0.01mmol) be dissolved in 5ml anhydrous methanol; after degassed 3 ~ 5 times of continuous freeze thawing under argon shield in 65 DEG C of polymerizations, through the sudden cold stopped reaction of liquid nitrogen after reaction 24h, 15 times of volumes and 90ml ethanol are that namely precipitation agent repeated precipitation obtains product P MOEP 2 times
80.
(2) PMOEP
80-b-PDMAEMA
100the synthesis of two blocks
By PMOEP
80(0.3g; 0.03mmol); DMAEMA (0.6027ml; 3mmol); AIBN (1mg, 0.006mmol) is dissolved in 3ml anhydrous methanol, after degassed 3 ~ 5 times of continuous freeze thawing under argon shield in 65 DEG C of polymerizations; through the sudden cold stopped reaction of liquid nitrogen after reaction 24h, ethanol is that namely precipitation agent repeated precipitation obtains product P MOEP 2 times
80-b-PDMAEMA
100.
Embodiment 2:
(1) PMOEP
60the synthesis of Macromolecular chain transfer agent
By MOEP (0.6844g; 3mmol); CDB (13.62mg; 0.05mmol) and AIBN (1.64mg; 0.01mmol) be dissolved in 4.5ml anhydrous methanol; after degassed 3 ~ 5 times of continuous freeze thawing under argon shield in 65 DEG C of polymerizations, through the sudden cold stopped reaction of liquid nitrogen after reaction 24h, 15 times of volumes and 80ml ethanol are that namely precipitation agent repeated precipitation obtains product P MOEP 2 times
60.
(2) PMOEP
60-b-PDMAEMA
100the synthesis of two blocks
By PMOEP
60(0.225g; 0.0225mmol); DMAEMA (0.6027ml; 3mmol); AIBN (1mg, 0.006mmol) is dissolved in 3ml anhydrous methanol, after degassed 3 ~ 5 times of continuous freeze thawing under argon shield in 65 DEG C of polymerizations; through the sudden cold stopped reaction of liquid nitrogen after reaction 24h, ethanol is that namely precipitation agent repeated precipitation obtains product P MOEP 2 times
60-b-PDMAEMA
100.
Embodiment 3:
(1) PMOEP
80the synthesis of Macromolecular chain transfer agent
By MOEP (0.9125g; 4mmol); CDB (13.62mg; 0.05mmol) and AIBN (1.64mg; 0.01mmol) be dissolved in 4.5ml anhydrous methanol; after degassed 3 ~ 5 times of continuous freeze thawing under argon shield in 65 DEG C of polymerizations, through the sudden cold stopped reaction of liquid nitrogen after reaction 24h, 15 times of volumes and 80ml ethanol are that namely precipitation agent repeated precipitation obtains product P MOEP 2 times
80.
(2) PMOEP
80-b-PDMAEMA
80the synthesis of two blocks
By PMOEP
80(0.3g; 0.03mmol); DMAEMA (0.4822ml; 2.4mmol); AIBN (1mg, 0.006mmol) is dissolved in 3ml anhydrous methanol, after degassed 3 ~ 5 times of continuous freeze thawing under argon shield in 65 DEG C of polymerizations; through the sudden cold stopped reaction of liquid nitrogen after reaction 24h, ethanol is that namely precipitation agent repeated precipitation obtains product P MOEP 2 times
80-b-PDMAEMA
80.
The phosphorous homopolymer of target and the fire-retardant segmented copolymer of phosphorus nitrogen is obtained by polymerization in embodiment 1,
1in H NMR nuclear magnetic spectrogram (see Fig. 1), chemical shift δ=4.695 are the methene proton peak be connected with the oxygen of ester group, chemical shift δ=4.08 are the methene proton peak be connected with hydroxyethyl ester, and chemical shift δ=0.5 ~ 2.0 are the diagnostic protons peak after methacrylate-based monomer polymerization;
31unimodal chemical shift δ=1.889 unique in P NMR nuclear magnetic spectrogram (see Fig. 2) illustrate the successful synthesis of this homopolymer;
1the proton peak had more between chemical shift δ=3.6 ~ 4.2 in H NMR nuclear magnetic spectrogram (see Fig. 3) illustrates the existence of the methylene radical be connected with ester group oxygen in DMAEMA, and the proton peak near chemical shift δ=2.1 illustrates the existence of methylamino-;
31unimodal chemical shift δ=3.203 unique in P NMR nuclear magnetic spectrogram (see Fig. 4) illustrate that the P purity of this fire-retardant segmented copolymer is very high.Above
1h NMR and
31p NMR nuclear magnetic spectrum demonstrates the fire-retardant segmented copolymer PMOEP of phosphorus-nitrogen containing
80-b-PDMAEMA
100successful synthesis.
The invention provides fire-retardant segmented copolymer of a kind of phosphorus-nitrogen containing and preparation method thereof; (1) be the first block monomer with methacrylic acid-2-hydroxyethyl ester phosphoric acid ester (MOEP), be polymerized synthetic macromolecule chain-transfer agent by reversible addition-fragmentation chain transfer free radical (RAFT), after purification drying, carry out next step reaction; (2) with the polymerization system of the PMOEP living homopolymer of gained in step (1), monomers methyl methacrylate dimethylaminoethyl (DMAEMA), initiator composition, be dissolved in solvent, again carry out RAFT polymerization, finally obtain a kind of fire-retardant segmented copolymer of phosphorus-nitrogen containing.Methacrylic acid-2-hydroxyethyl ester the phosphoric acid ester with certain flame retardant effect is introduced in methyl methacrylate dimethylaminoethyl by the present invention, the high-molecular block copolymer of phosphorus-nitrogen containing while of obtaining a kind of, reach the object of cooperative flame retardant, this preparation process mild condition, simple to operate, the content of phosphorus nitrogen can be regulated by controlling feed ratio, after adulterating with matrix resin reactivity, in fields such as halogen-free flameproofs, there is good application prospect.
Claims (10)
1. the fire-retardant segmented copolymer of phosphorus-nitrogen containing, is characterized in that for PMOEP
m-b-PDMAEMA
n, its chemical structural formula is as follows:
Wherein n is the unit sum of methacrylic ester dimethylaminoethyl shared by polymer chain, 80≤n≤100;
M is the unit sum of methacrylic acid-2-hydroxyethyl ester phosphoric acid ester shared by polymer chain, 50≤m≤80.
2. the preparation method of the fire-retardant segmented copolymer of a kind of phosphorus-nitrogen containing as claimed in claim 1, is characterized in that its concrete steps are as follows:
1) PMOEP
mthe synthesis of Macromolecular chain transfer agent
Methacrylic acid-2-hydroxyethyl ester phosphoric acid ester, dithiobenzoic acid cumyl ester and azo-bis-isobutyl cyanide are dissolved in solvent; through freeze thawing is degassed do not have bubble to emerge to thawing after under protection of inert gas, carry out polyreaction; again through the sudden cold stopped reaction of liquid nitrogen, be drying to obtain product P MOEP after precipitation agent precipitation with ethanol
mmacromolecular chain transfer agent;
2) PMOEP
m-b-PDMAEMA
nthe synthesis of di-block copolymer
By step 1) PMOEP that synthesizes
mmacromolecular chain transfer agent and methacrylic ester dimethylaminoethyl and azo-bis-isobutyl cyanide are dissolved in solvent; after freeze thawing is degassed under protection of inert gas polyreaction; again through the sudden cold stopped reaction of liquid nitrogen, be that namely precipitation agent repeated precipitation obtains the fire-retardant segmented copolymer (PMOEP of target product phosphorus-nitrogen containing with ethanol
m-b-PDMAEMA
n).
3. the preparation method of the fire-retardant segmented copolymer of a kind of phosphorus-nitrogen containing as claimed in claim 2, it is characterized in that in step 1) in, the mol ratio of described methacrylic acid-2-hydroxyethyl ester phosphoric acid ester, dithiobenzoic acid cumyl ester and azo-bis-isobutyl cyanide is MOEP: CDB: AIBN=(50 ~ 80): 1: 0.2.
4. the preparation method of the fire-retardant segmented copolymer of a kind of phosphorus-nitrogen containing as claimed in claim 2, is characterized in that in step 1) in, described solvent selected from methanol or dimethyl formamide; Describedly degassedly can be 3 ~ 5 times.
5. the preparation method of the fire-retardant segmented copolymer of a kind of phosphorus-nitrogen containing as claimed in claim 2, is characterized in that in step 1) in, the temperature of described polyreaction is 60 ~ 70 DEG C, and polymerization reaction time is 24 ~ 48h.
6. the preparation method of the fire-retardant segmented copolymer of a kind of phosphorus-nitrogen containing as claimed in claim 2, it is characterized in that in step 1) in, the consumption of described solvent is 3 ~ 5 times of methacrylic acid-2-hydroxyethyl ester phosphoric acid ester, dithiobenzoic acid cumyl ester and azo-bis-isobutyl cyanide by volume; Described rare gas element can adopt argon gas; The consumption of described precipitation agent can be 15 ~ 20 times of reaction solvent add-on by volume.
7. the preparation method of the fire-retardant segmented copolymer of a kind of phosphorus-nitrogen containing as claimed in claim 2, is characterized in that in step 2) in, described methacrylic ester dimethylaminoethyl, PMOEP
mthe mol ratio of Macromolecular chain transfer agent, azo-bis-isobutyl cyanide is DMAEMA: PMOEP
m: AIBN=(80 ~ 100): 1: 0.1.
8. the preparation method of the fire-retardant segmented copolymer of a kind of phosphorus-nitrogen containing as claimed in claim 2, is characterized in that in step 2) in, described solvent is methyl alcohol or dimethyl formamide; The consumption of described solvent can be methacrylic ester dimethylaminoethyl, PMOEP by volume
mmacromolecular chain transfer agent, azo-bis-isobutyl cyanide 2 ~ 4 times; Describedly degassedly can be 3 ~ 5 times.
9. the preparation method of the fire-retardant segmented copolymer of a kind of phosphorus-nitrogen containing as claimed in claim 2, is characterized in that in step 2) in, the temperature of described polyreaction is 60 ~ 70 DEG C, and the time of polyreaction is 24 ~ 48h; Described rare gas element can adopt argon gas; The consumption of described precipitation agent can be 15 ~ 20 times of repeated precipitation 2 ~ 3 times of reaction solvent add-on by volume, or adopts distill water dialysis purification postlyophilization.
10. the fire-retardant segmented copolymer of a kind of phosphorus-nitrogen containing is preparing the application in halogen-free flame retardants and self-assembled micelle as claimed in claim 1.
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Cited By (14)
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| CN105732705A (en) * | 2016-01-27 | 2016-07-06 | 厦门大学 | Phosphorus-nitrogen-containing flame-retardant monomer and preparation method thereof |
| CN104829795B (en) * | 2015-06-05 | 2017-06-16 | 厦门大学 | A kind of reaction-type flame-retarding block copolymer and preparation method thereof |
| CN109486463A (en) * | 2018-12-04 | 2019-03-19 | 顺德职业技术学院 | Flame-retarded heat-conducting damp solidifying polyurethane hot melt adhesive and preparation method thereof |
| CN109609076A (en) * | 2018-12-04 | 2019-04-12 | 顺德职业技术学院 | Waterproof performance excellent flame polyurethane hot melt and preparation method thereof |
| CN109609078A (en) * | 2018-12-04 | 2019-04-12 | 顺德职业技术学院 | Organic-silicon-modified flame retardant polyurethane hot melt adhesive of wet-cured type and preparation method thereof |
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| CN109679560A (en) * | 2018-12-04 | 2019-04-26 | 顺德职业技术学院 | Thermally conductive organic-silicon-modified flame retardant polyurethane hot melt adhesive of moisture-curable and preparation method thereof |
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