CN104262553B - A kind of fire-retardant block copolymer of phosphorus-nitrogen containing and preparation method thereof - Google Patents
A kind of fire-retardant block copolymer of phosphorus-nitrogen containing and preparation method thereof Download PDFInfo
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Abstract
A kind of fire-retardant block copolymer of phosphorus-nitrogen containing and preparation method thereof, relates to a kind of block copolymer.The fire-retardant block copolymer of described phosphorus-nitrogen containing is PMOEPm‑b‑PDMAEMAn.Methacrylic acid 2 hydroxyethyl ester phosphate ester, dithiobenzoic acid cumyl ester and azo-bis-isobutyl cyanide are dissolved in solvent; through freeze thawing degassing to thaw do not have bubble to emerge after in inert gas shielding under carry out polyreaction; again through the sudden cold stopped reaction of liquid nitrogen, after precipitation, it is drying to obtain product PMOEPmMacromolecular chain transfer agent；By PMOEPmMacromolecular chain transfer agent and methacrylate dimethylaminoethyl and azo-bis-isobutyl cyanide are dissolved in solvent; through freeze thawing deaerate after in inert gas shielding under polyreaction; again through the sudden cold stopped reaction of liquid nitrogen, it is that precipitant repeated precipitation i.e. obtains target product phosphorus-nitrogen containing fire-retardant block copolymer (PMOEP with ethanolm‑b‑PDMAEMAn).Can apply in preparing halogen-free flame retardants and self-assembled micelle.
Description
Technical field
The invention belongs to high molecular halogen-free flame retardant area, relate to a kind of block copolymer, especially relate to anti-flaming function
Plant fire-retardant block copolymer of phosphorus-nitrogen containing 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
Finding, brominated flame-retardant can produce the noxious substance such as brominated diphenyl dioxin when burning, thus limits halogen containing flame-retardant
It is widely used.Therefore, new direction new and effective, that Halogen, nontoxic flame-retardant system have become fire-retardant scientific research is set up.
Traditional condensed phase halogen-free flame-retardant system is relevant to P, N, Si tri-elements, and they can effectively facilitate stable intumescent char layer
Generation, suppression base material continues thermal oxidative reaction, improves the thermal degradation temperature of curing system, mass loss temperature and coke
Growing amount.Therefore, two kinds of elements of phosphorus nitrogen have cooperative flame retardant effect.When phosphorus-nitrogen containing fire retardant uses, under high temperature, P elements promotees
Enter the formation of layer of charcoal, and nitrogen element easily releases the non-flammable gases such as ammonia, nitrogen, degree of depth nitrogen oxides, water vapour, take away big
Partial heat, greatly reduces the surface temperature of polymer, thus plays phosphorus nitrogen cooperative flame retardant effect.Phosphorus nitrogen cooperative flame retardant system
Including the content of two aspects, it is on the one hand that phosphorus flame retardant is compounded with nitrogenated flame retardant, by the phase between fire retardant
Interaction, produces cooperative flame retardant effect；On the other hand be that two kinds of elements of phosphorus nitrogen are introduced in same molecular structures, by element it
Between interaction, produce cooperative flame retardant effect.As Chinese patent CN 102391403 discloses a kind of fire-retardant polymerization of phosphorus-nitrogen containing
Thing and preparation method thereof, this phosphorus-nitrogen containing flame-retardant polymer can poly-monomer homopolymerization or can poly-monomer copolymerization with other by a kind of phosphorus-nitrogen containing
Form, can use as a kind of flame-retardant additive, it is also possible to as a kind of Inherent Flame Retardant Polymers materials'use, with macromolecule
Matrix has the more preferable compatibility, and fire resistance is good, little to the mechanical impact of material matrix, and fire resistance is good.In and for example
State's patent CN 102225953 discloses a kind of response type phosphorus-nitrogen containing flame retardant and its preparation method and application.By phosphorous volution
Aminated compounds react with carboxylic acid halides, or the aminated compounds of phosphorous volution and carboxylic acid reaction, obtain the resistance of described response type phosphorus nitrogen system
Combustion agent.Recycle this response type phosphorus-nitrogen containing flame retardant and macromolecular material is carried out flame-retardant modified, by resistance with monomer formation copolymer
Combustion agent phosphorus nitrogen element cooperative flame retardant effect, improves the flame retardant effect to macromolecular material, decreases fire retardant at macromolecular material
Usage amount, reduces the cost of fire proofing.
Summary of the invention
It is an object of the invention to provide and the element phosphor nitrogen with flame retardant effect is bonded on polymer molecular chain simultaneously, thus reach
To cooperative flame retardant purpose, can be applicable in polymeric matrix, play to strengthen and wait the fire-retardant block of a kind of phosphorus-nitrogen containing of effect altogether with fire-retardant
Polymers and preparation method thereof.
Described phosphorus-nitrogen containing fire-retardant block copolymer (PMOEPm-b-PDMAEMAn) chemical structural formula as follows:
Wherein n is the unit sum that methacrylate dimethylaminoethyl (DMAEMA) is shared in polymer chain, 80≤n≤
100；
M is the unit sum that methacrylic acid-2-hydroxyethyl ester phosphate ester (MOEP) is shared in polymer chain, 50≤m≤
80；
The fire-retardant block copolymer of described phosphorus-nitrogen containing can be prepared by reversible addion-fragmentation chain transfer living polymerization RAFT method.
Specifically comprising the following steps that of the preparation method of the fire-retardant block copolymer of described phosphorus-nitrogen containing
1)PMOEPmThe synthesis of Macromolecular chain transfer agent
By methacrylic acid-2-hydroxyethyl ester phosphate ester (MOEP), dithiobenzoic acid cumyl ester (CDB) and azo two isobutyl
Cyanogen (AIBN) is dissolved in solvent, through freeze thawing degassing to thaw do not have bubble to emerge after in inert gas shielding under carry out polyreaction,
Again through the sudden cold stopped reaction of liquid nitrogen, after precipitating with ethanol for precipitant, it is drying to obtain product PMOEPmMacromolecular chain transfer agent；
2)PMOEPm-b-PDMAEMAnThe synthesis of di-block copolymer
By step 1) PMOEP that synthesizesmMacromolecular chain transfer agent and methacrylate dimethylaminoethyl (DMAEMA) and azo two
Isobutyl cyanogen is dissolved in solvent, after freeze thawing deaerates in inert gas shielding under polyreaction, then through the sudden cold stopped reaction of liquid nitrogen, use
Ethanol is that precipitant repeated precipitation i.e. obtains target product phosphorus-nitrogen containing fire-retardant block copolymer (PMOEPm-b-PDMAEMAn)。
In step 1) in, described methacrylic acid-2-hydroxyethyl ester phosphate ester (MOEP), dithiobenzoic acid cumyl ester and idol
The mol ratio of nitrogen two isobutyl cyanogen can be MOEP: CDB: AIBN=(50～80): 1: 0.2；Described solvent is selected from methanol or two
Methylformamide (DMF) etc.；Described degassing can be 3～5 times；The temperature of described polyreaction can be 60～70 DEG C, polyreaction
Time can be 24～48h；The consumption of described solvent can be by volume methacrylic acid-2-hydroxyethyl ester phosphate ester (MOEP),
Dithiobenzoic acid cumyl ester and 3～5 times of azo-bis-isobutyl cyanide；Described noble gas can use argon etc.；Described precipitant
Consumption can be 15～20 times of reaction dissolvent addition by volume.
In step 2) in, described methacrylate dimethylaminoethyl (DMAEMA), PMOEPmMacromolecular chain transfer agent, idol
The mol ratio of nitrogen two isobutyl cyanogen can be DMAEMA: PMOEPm: AIBN=(80～100): 1: 0.1；Described solvent can be
Methanol or dimethylformamide (DMF) etc.；The consumption of described solvent can be methacrylate dimethylaminoethyl by volume
(DMAEMA)、PMOEPmMacromolecular chain transfer agent, 2～4 times of azo-bis-isobutyl cyanide；Described degassing can be 3～5 times；Described poly-
The temperature closing reaction can be 60～70 DEG C, and the time of polyreaction can be 24～48h；Described noble gas can use argon etc.；Institute
State 15～20 times of repeated precipitation 2～3 times that the consumption of precipitant can be reaction dissolvent addition by volume, or use distilled water saturating
Analysis purifies postlyophilization.
The fire-retardant block copolymer of described phosphorus-nitrogen containing can be applied in preparing the field such as halogen-free flame retardants and self-assembled micelle.
Compared with prior art, the invention have the advantages that
1) using the RAFT polymerization synthesis fire-retardant block copolymer of target phosphorus-nitrogen containing, reaction condition is gentle, can adjust by controlling rate of charge
The content of P, N in joint polymer；
2) the phosphorus oh group and reactable tertiary amino group with excellent flame retardant performance are keyed in big point by chemical bond simultaneously
In subchain, significantly improve the matrix resin compatibility and anti-flammability.
3) the fire-retardant block copolymer of this phosphorus-nitrogen containing contains functional phosphorus hydroxyl and tertiary amino group simultaneously, can be by intramolecule from group
Dress forms micelle in biologically application etc..
Accompanying drawing explanation
Fig. 1 is phosphorus-nitrogen containing fire-retardant block copolymer PMOEPm's1H NMR nuclear magnetic spectrogram；
Fig. 2 is phosphorus-nitrogen containing fire-retardant block copolymer PMOEPm's31P NMR nuclear magnetic spectrogram；
Fig. 3 is phosphorus-nitrogen containing fire-retardant block copolymer PMOEPm-b-PDMAEMAn's1H NMR nuclear magnetic spectrogram；
Fig. 4 is phosphorus-nitrogen containing fire-retardant block copolymer PMOEPm-b-PDMAEMAn's31P NMR nuclear magnetic spectrogram.
Detailed description of the invention
Below in conjunction with the accompanying drawings and embodiment the invention will be further described:
Embodiment 1:
(1)PMOEP80The synthesis of Macromolecular chain transfer agent
By molten to MOEP (0.9125g, 4mmol), CDB (13.62mg, 0.05mmol) and AIBN (1.64mg, 0.01mmol)
In 5ml absolute methanol, deaerate after 3～5 times under in argon shield in 65 DEG C of polymerizations through continuous freeze thawing, sudden through liquid nitrogen after reacting 24h
Cold stopped reaction, 15 times of volumes i.e. 90ml ethanol is that precipitant repeated precipitation i.e. obtains product PMOEP 2 times80。
(2)PMOEP80-b-PDMAEMA100The synthesis of two blocks
By PMOEP80(0.3g, 0.03mmol), DMAEMA (0.6027ml, 3mmol), AIBN (1mg, 0.006mmol) are dissolved in
In 3ml absolute methanol, deaerate after 3～5 times under in argon shield in 65 DEG C of polymerizations through continuous freeze thawing, sudden cold through liquid nitrogen after reacting 24h
Stopped reaction, ethanol is that precipitant repeated precipitation i.e. obtains product PMOEP 2 times80-b-PDMAEMA100。
Embodiment 2:
(1)PMOEP60The synthesis of Macromolecular chain transfer agent
By molten to MOEP (0.6844g, 3mmol), CDB (13.62mg, 0.05mmol) and AIBN (1.64mg, 0.01mmol)
In 4.5ml absolute methanol, deaerate after 3～5 times under in argon shield in 65 DEG C of polymerizations through continuous freeze thawing, react after 24h through liquid nitrogen
Sudden cold stopped reaction, 15 times of volumes i.e. 80ml ethanol is that precipitant repeated precipitation i.e. obtains product PMOEP 2 times60。
(2)PMOEP60-b-PDMAEMA100The synthesis of two blocks
By PMOEP60(0.225g, 0.0225mmol), DMAEMA (0.6027ml, 3mmol), AIBN (1mg, 0.006mmol)
It is dissolved in 3ml absolute methanol, deaerates after 3～5 times under in argon shield in 65 DEG C of polymerizations through continuous freeze thawing, react after 24h through liquid nitrogen
Sudden cold stopped reaction, ethanol is that precipitant repeated precipitation i.e. obtains product PMOEP 2 times60-b-PDMAEMA100。
Embodiment 3:
(1)PMOEP80The synthesis of Macromolecular chain transfer agent
By molten to MOEP (0.9125g, 4mmol), CDB (13.62mg, 0.05mmol) and AIBN (1.64mg, 0.01mmol)
In 4.5ml absolute methanol, deaerate after 3～5 times under in argon shield in 65 DEG C of polymerizations through continuous freeze thawing, react after 24h through liquid nitrogen
Sudden cold stopped reaction, 15 times of volumes i.e. 80ml ethanol is that precipitant repeated precipitation i.e. obtains product PMOEP 2 times80。
(2)PMOEP80-b-PDMAEMA80The synthesis of two blocks
By PMOEP80(0.3g, 0.03mmol), DMAEMA (0.4822ml, 2.4mmol), AIBN (1mg, 0.006mmol) is molten
In 3ml absolute methanol, deaerate after 3～5 times under in argon shield in 65 DEG C of polymerizations through continuous freeze thawing, sudden through liquid nitrogen after reacting 24h
Cold stopped reaction, ethanol is that precipitant repeated precipitation i.e. obtains product PMOEP 2 times80-b-PDMAEMA80。
The phosphorous homopolymer of target and the fire-retardant block copolymer of phosphorus nitrogen has been obtained by polymerization in embodiment 1,1H NMR nuclear magnetic spectrogram (see
In Fig. 1), chemical shift δ=4.695 are the methene proton peak that the oxygen with ester group is connected, and chemical shift δ=4.08 are and ethoxy
The methene proton peak that ester is connected, chemical shift δ=0.5～2.0 is the diagnostic protons peak after methacrylate-based monomer polymerization；31In P NMR nuclear magnetic spectrogram (see Fig. 2), unique unimodal chemical shift δ=1.889 illustrate the successful synthesis of this homopolymer；1H NMR
The Asia being connected with ester group oxygen in the proton peak explanation DMAEMA having more between chemical shift δ=3.6～4.2 in nuclear magnetic spectrogram (see Fig. 3)
The existence of methyl, the existence of the proton peak explanation methylamino near chemical shift δ=2.1；31In P NMR nuclear magnetic spectrogram (see Fig. 4)
Unique unimodal chemical shift δ=3.203 illustrate that the P purity of this fire-retardant block copolymer is the highest.Above1H NMR and31P NMR nuclear-magnetism
Collection of illustrative plates demonstrates phosphorus-nitrogen containing fire-retardant block copolymer PMOEP80-b-PDMAEMA100Successful synthesis.
The present invention provides a kind of fire-retardant block copolymer of phosphorus-nitrogen containing and preparation method thereof；(1) with methacrylic acid-2-hydroxyethyl ester
Phosphate ester (MOEP) is the first block monomer, is polymerized synthetic macromolecule by reversible addition-fragmentation chain transfer free radical (RAFT)
Chain-transferring agent, purifies and carries out next step reaction after drying；(2) with the PMOEP living homopolymer of gained, list in step (1)
The polymerization system of body methyl methacrylate dimethylaminoethyl (DMAEMA), initiator composition, is dissolved in solvent, again carries out
RAFT is polymerized, and finally gives the fire-retardant block copolymer of a kind of phosphorus-nitrogen containing.The present invention will have the metering system of certain flame retardant effect
Acid-2-hydroxyethyl ester phosphate ester introduces in methyl methacrylate dimethylaminoethyl, and the while of obtaining a kind of, the macromolecule of phosphorus-nitrogen containing is embedding
Section copolymer, reaches the purpose of cooperative flame retardant, and this preparation process mild condition is simple to operate, can adjust by controlling rate of charge
The content of joint phosphorus nitrogen, has good application prospect in fields such as halogen-free flameproofs after adulterating with matrix resin reactivity.
Claims (10)
1. the fire-retardant block copolymer of phosphorus-nitrogen containing, it is characterised in that for PMOEPm-b-PDMAEMAn, its chemical structural formula is as follows:
Wherein n is the unit sum that dimethylaminoethyl methacrylate is shared in polymer chain, 80≤n≤100；
M is the unit sum that methacrylic acid-2-hydroxyethyl ester phosphate ester is shared in polymer chain, 50≤m≤80.
The preparation method of the fire-retardant block copolymer of a kind of phosphorus-nitrogen containing the most as claimed in claim 1, it is characterised in that its concrete steps are such as
Under:
1)PMOEPmThe synthesis of Macromolecular chain transfer agent
Methacrylic acid-2-hydroxyethyl ester phosphate ester, dithiobenzoic acid cumyl ester and azodiisobutyronitrile are dissolved in solvent, warp
Freeze thawing degassing carries out polyreaction after there be not bubble to emerge to thawing under inert gas shielding, then through the sudden cold stopped reaction of liquid nitrogen, with
Ethanol is to be drying to obtain product PMOEP after precipitant precipitatesmMacromolecular chain transfer agent；
2)PMOEPm-b-PDMAEMAnThe synthesis of di-block copolymer
By step 1) PMOEP that synthesizesmMacromolecular chain transfer agent and dimethylaminoethyl methacrylate and azodiisobutyronitrile are dissolved in
In solvent, after freeze thawing deaerates in inert gas shielding under polyreaction, then through the sudden cold stopped reaction of liquid nitrogen, be precipitation with ethanol
Agent repeated precipitation i.e. obtains target product phosphorus-nitrogen containing fire-retardant block copolymer (PMOEPm-b-PDMAEMAn)。
The preparation method of the fire-retardant block copolymer of a kind of phosphorus-nitrogen containing the most as claimed in claim 2, it is characterised in that in step 1) in,
The mol ratio of described methacrylic acid-2-hydroxyethyl ester phosphate ester, dithiobenzoic acid cumyl ester and azodiisobutyronitrile is
MOEP: CDB: AIBN=(50～80): 1: 0.2.
The preparation method of the fire-retardant block copolymer of a kind of phosphorus-nitrogen containing the most as claimed in claim 2, it is characterised in that in step 1) in,
Described solvent selected from methanol or dimethylformamide；Described degassing can be 3～5 times.
The preparation method of the fire-retardant block copolymer of a kind of phosphorus-nitrogen containing the most as claimed in claim 2, it is characterised in that in step 1) in,
The temperature of described polyreaction is 60～70 DEG C, and polymerization reaction time is 24～48h.
The preparation method of the fire-retardant block copolymer of a kind of phosphorus-nitrogen containing the most as claimed in claim 2, it is characterised in that in step 1) in,
The consumption of described solvent is that methacrylic acid-2-hydroxyethyl ester phosphate ester, dithiobenzoic acid cumyl ester and azo two are different by volume
3～5 times of butyronitrile；Described noble gas can use argon；The consumption of described precipitant can be reaction dissolvent addition by volume
15～20 times.
The preparation method of the fire-retardant block copolymer of a kind of phosphorus-nitrogen containing the most as claimed in claim 2, it is characterised in that in step 2) in,
Described dimethylaminoethyl methacrylate, PMOEPmMacromolecular chain transfer agent, the mol ratio of azodiisobutyronitrile are
DMAEMA∶PMOEPm: AIBN=(80～100): 1: 0.1.
The preparation method of the fire-retardant block copolymer of a kind of phosphorus-nitrogen containing the most as claimed in claim 2, it is characterised in that in step 2) in,
Described solvent is methanol or dimethylformamide；The consumption of described solvent can be by volume dimethylaminoethyl methacrylate,
PMOEPmMacromolecular chain transfer agent, 2～4 times of azodiisobutyronitrile；Described degassing can be 3～5 times.
The preparation method of the fire-retardant block copolymer of a kind of phosphorus-nitrogen containing the most as claimed in claim 2, it is characterised 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 noble gas can use argon；Institute
State 15～20 times of repeated precipitation 2～3 times that the consumption of precipitant can be reaction dissolvent addition by volume, or use distilled water saturating
Analysis purifies postlyophilization.
The fire-retardant block copolymer of a kind of phosphorus-nitrogen containing the most as claimed in claim 1 answering in preparing halogen-free flame retardants and self-assembled micelle
With.
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| 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 |
| CN105732705B (en) * | 2016-01-27 | 2018-04-24 | 厦门大学 | A kind of phosphorus-nitrogen containing flame-retardant monomer 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 |
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| CN109651994A (en) * | 2018-12-04 | 2019-04-19 | 顺德职业技术学院 | Ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive and preparation method thereof |
| CN109666437A (en) * | 2018-12-04 | 2019-04-23 | 顺德职业技术学院 | Oil resistance excellent flame 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 |
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| CN109651992A (en) * | 2018-12-04 | 2019-04-19 | 顺德职业技术学院 | The excellent moisture-curable flame retardant polyurethane hot melt adhesive and preparation method thereof of weather resistance |
| 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 |
| CN109852320A (en) * | 2018-12-04 | 2019-06-07 | 顺德职业技术学院 | Graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive 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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