CN104211880A - Inflaming retarding segmented copolymer containing phosphorus and silicon and preparation method thereof - Google Patents
Inflaming retarding segmented copolymer containing phosphorus and silicon and preparation method thereof Download PDFInfo
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- CN104211880A CN104211880A CN201410490566.7A CN201410490566A CN104211880A CN 104211880 A CN104211880 A CN 104211880A CN 201410490566 A CN201410490566 A CN 201410490566A CN 104211880 A CN104211880 A CN 104211880A
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052698 phosphorus Inorganic materials 0.000 title abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title abstract description 7
- 239000011574 phosphorus Substances 0.000 title abstract description 7
- 229910052710 silicon Inorganic materials 0.000 title abstract description 6
- 239000010703 silicon Substances 0.000 title abstract description 4
- 230000000979 retarding effect Effects 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010257 thawing Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003063 flame retardant Substances 0.000 claims description 41
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 claims description 31
- 238000001556 precipitation Methods 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 11
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- ZGRWZUDBZZBJQB-UHFFFAOYSA-N benzenecarbodithioic acid Chemical compound SC(=S)C1=CC=CC=C1 ZGRWZUDBZZBJQB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 12
- 229920002521 macromolecule Polymers 0.000 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 abstract 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 2
- 238000007872 degassing Methods 0.000 abstract 2
- 238000004062 sedimentation Methods 0.000 abstract 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 abstract 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 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 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- -1 hydrogen halides Chemical class 0.000 description 9
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical class C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000013467 fragmentation Methods 0.000 description 3
- 238000006062 fragmentation reaction Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 0 C*CC(C)(*C(C)C(C)(CC(C)C)C(OCCOP1(Oc(cccc2)c2-c2c1cccc2)=O)=O)C(OCCC[S+](OC)(OC)OC)=O Chemical compound C*CC(C)(*C(C)C(C)(CC(C)C)C(OCCOP1(Oc(cccc2)c2-c2c1cccc2)=O)=O)C(OCCC[S+](OC)(OC)OC)=O 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
An inflaming retarding segmented copolymer containing phosphorus and silicon and a preparation method thereof relate to the segmented copolymer. The preparation method includes mixing 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide and carbon tetrachloride and adding the mixture into a solvent to obtain a mixture A; mixing methyl-hydroxyethyl acrylate and a triethylamine salt solution, adding the mixture into the mixture A, conducting filtering after reaction and conducting washing to obtain HEDOPO; dissolving the HEDOPO, dithio-benzoic acid-cumyl-ester and AIBN into the solvent, conducting freeze thawing degasification post polymerization reaction, stopping reaction through liquid nitrogen sudden cooling and conducting sedimentation to obtain a PHEDOPO macromolecule chain transfer agent; dissolving the PHEDOPO macromolecule chain transfer agent, 3-(isobutene-acyl-oxygen)-propyl-trimethoxy silane and the AIBN into tetrachloroethane, conducting continuous freeze thawing degasification post polymerization reaction, stopping the reaction through liquid nitrogen sudden cooling and conducting sedimentation through a precipitant to obtain the product the inflaming retarding segmented copolymer containing phosphorus and silicon.
Description
Technical field
The present invention relates to a kind of segmented copolymer, especially relate to fire-retardant segmented copolymer of a kind of containing phosphorus silicon having anti-flaming function and preparation method thereof.
Background technology
Halogen-containing flame retardant has good flame retardant effect Zeng Zuowei fire retardant material and is widely used, and Halogen fire retardant material can produce a large amount of smog and poisonous corrosive hydrogen halides gas in fire-retardant process, causes secondary harm.The World Health Organization (WHO) and many national environmental protection department have banned use of halogen containing flame-retardant, and novel halogen-free flame retardants becomes the product innovation that meets international standard development trend.Setting up New-type halide-free, nontoxic flame-retardant system has become the new direction of fire-retardant scientific research development.
Traditional condensed phase halogen-free flame-retardant system and P, Si, N element are relevant, they can effectively promote the generation of stable expansion coke layer, suppress base material and continue to occur thermal oxidative reaction, improve thermal degradation temperature, mass loss temperature and the coke growing amount of curing system.And the fire retardant of containing phosphorus silicon wherein, its synergistic mechanism is at high temperature, phosphoric promotes the formation of charcoal layer, stops the thermal oxidative reaction of charcoal layer and inflammable gas to discharge and element silicon forms silicon-dioxide and move to matrix surface, thus performance phosphorus silicon cooperative flame retardant effect.
In same molecular structure, introduce two kinds of elements of phosphorus silicon, by the synergy of two kinds of elements, improve matrix resin thermostability and flame retardant properties thereby play.As Chinese patent, CN200710178086.7 discloses a kind of organic silicon compound containing phosphorus and preparation method thereof, utilize phosphorus hydrogen bond active in 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivative to generate a kind of novel phosphorus-containing silicoorganic compound with the siloxanes generation addition reaction that contains two carbon-carbon double bonds; This compound contains two kinds of phosphorus and silicon simultaneously and has the element of flame retardant properties, can be used as fire-retardant for macromolecular material of additive flame retardant.Chinese patent CN201410041811.6 discloses a kind of containing phosphorus silicon segmented copolymer and preparation method thereof, taking methacryloxypropyl seven isobutyl-POSS, glycidyl methacrylate as monomer, pass through reversible addition-fragmentation chain transfer free radical polymerization, synthetic di-block copolymer, then by ring-opening reaction by 9, mix-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy is grafted on di-block copolymer, forms a kind of containing phosphorus silicon segmented copolymer.The DOPO that has polyhedron oligomeric silsesquioxanes and have excellent flame retardancy energy, with in chemical bond key entry macromolecular chain, is reached to the object of cooperative flame retardant, improved significantly matrix resin thermal characteristics and flame retardant resistance.
Summary of the invention
The object of the invention aims to provide and can be applicable to polymeric matrix, plays and strengthens fire-retardant fire-retardant segmented copolymer of a kind of containing phosphorus silicon that waits effect and preparation method thereof.
The chemical structural formula of the fire-retardant segmented copolymer of described containing phosphorus silicon is as follows:
Wherein the structural formula of HEDOPO monomer is:
N is HEDOPO shared unit sum in polymer chain, 50≤n≤100;
M is 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane shared unit sum in polymer chain, 10≤m≤30.
The preparation method of the fire-retardant segmented copolymer of described containing phosphorus silicon, comprises the following steps:
1) HEDOPO monomer is synthetic
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and tetracol phenixin are mixed, then join in solvent, obtain mixture A; By joining in mixture A after hydroxyethyl methylacrylate and the mixing of triethylamine salt solution, under condition of ice bath, react, after reaction, filter, wash filtrate, obtains HEDOPO monomer;
2) PHEDOPO macromolecular chain transfer agent is synthetic
HEDOPO monomer, dithiobenzoic acid cumyl ester (CDB) and azo-bis-isobutyl cyanide (AIBN) are dissolved in solvent, after freeze thawing is degassed, under protection of inert gas, carry out polyreaction, again through the sudden cold stopped reaction of liquid nitrogen, with obtaining pink product P HEDOPO macromolecular chain transfer agent after precipitation agent precipitation;
3) PHEDOPO-b-PKH570's is synthetic
Get step 2) synthetic PHEDOPO macromolecular chain transfer agent, 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane and azo-bis-isobutyl cyanide (AIBN) be dissolved in tetrachloroethane; after continuous freeze thawing is degassed under protection of inert gas polyreaction; again through the sudden cold stopped reaction of liquid nitrogen, precipitate and obtain the fire-retardant segmented copolymer of product containing phosphorus silicon (being PHEDOPO-b-PKH570 two blocks) with precipitation agent.
In step 1) in, the mol ratio of described 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), hydroxyethyl methylacrylate, triethylamine salt and tetracol phenixin can be 1: (1～1.5): (1～1.5): (1～1.5); Described will hydroxyethyl methylacrylate and triethylamine salt solution join in mixture A after mixing, can hydroxyethyl methylacrylate and triethylamine salt solution under condition of ice bath, join in mixture A after mixing; Described solvent can adopt methylene dichloride etc.; The time of described ice bath can be 1～2h; The time of described reaction can be 12～24h; Alkali liquid washing 3～4 times can be first used in described washing, then use distilled water wash 1～2 time.
In step 2) in, described solvent can adopt tetrachloroethane etc.; The mol ratio of described HEDOPO, dithiobenzoic acid cumyl ester (CDB), azo-bis-isobutyl cyanide (AIBN) can be (50～100): 1: 0.25; Described rare gas element can adopt argon gas etc.; The temperature of described polyreaction can be 60～80 DEG C, and the time of polyreaction can be 24～48h; Described precipitation agent can be selected from the one in methyl alcohol, ethanol, normal hexane etc.
In step 3) in, described 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane, PHEDOPO macromolecular chain transfer agent,
The mol ratio of azo-bis-isobutyl cyanide (AIBN) can be (5～15): 1: 0.1; Described rare gas element can adopt argon gas etc.; The temperature of described polyreaction can be 60～70 DEG C, and the time of polyreaction can be 24h～48h; Described precipitation agent can be selected from the one in methyl alcohol, ethanol, normal hexane etc.
Compared with prior art, the present invention has the following advantages:
1) adopt the synthetic containing phosphorus silicon segmented copolymer of RAFT polymerization, reaction conditions gentleness, can be by controlling the content of P, N in feed ratio telomerized polymer;
2) key in macromolecular chain by chemical bond thering is the phosphorous HEDOPO of excellent flame retardancy energy and the silane coupling agent with methoxyl group, reach phosphorus silicon cooperative flame retardant, can improve significantly and matrix resin consistency and flame retardant resistance;
3) this segmented copolymer contains functional methoxy group simultaneously, can be used for further modifying the inorganic nano-particles such as silicon-dioxide, is applied thereby can modify and improve inorganic nano-particle consistency field at inorganic nano-particle.
Brief description of the drawings
Fig. 1 is PHEDOPO macromolecular chain transfer agent
1h NMR nuclear magnetic spectrogram;
Fig. 2 is PHEDOPO macromolecular chain transfer agent
31p NMR nuclear magnetic spectrogram;
Fig. 3 is containing phosphorus silicon segmented copolymer PHEDOPO-b-PKH570's
1h NMR nuclear magnetic spectrogram;
Fig. 4 is containing phosphorus silicon segmented copolymer PHEDOPO-b-PKH570's
31p NMR nuclear magnetic spectrogram.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described:
Embodiment 1:
1) HEDOPO monomer is synthetic
First by DOPO (4.32g, 0.02mol) and tetracol phenixin (3.692g, 0.024mol) mix, joining magneton in 20ml dichloromethane solvent is uniformly mixed, by hydroxyethyl methylacrylate (3.1234g, 0.024mol) and triethylamine salt (2.4272g, 0.024mol) solution joins in the former after mixing, and ice bath, after for some time, under room temperature, react 24h again, filter, first use NaOH solution washing 3 times, use again deionized water wash 2 times, obtain HEDOPO monomer.
2) PHEDOPO
100synthesizing of macromolecular chain transfer agent
By HEDOPO (1.376g; 4mmol), CDB (0.0109g; 0.04mmol) and AIBN (0.00164g; 0.01mmol) be dissolved in 5mL tetrachloroethane; after degassed 5 times of continuous freeze thawing under argon shield in 65 DEG C of polymerizations; after reaction 24h, through the sudden cold stopped reaction of liquid nitrogen, be that 90mL ethanol is that precipitation agent repeated precipitation obtains product 2 times with 15 times of volumes.
3) PHEDOPO
100-b-PKH57010's is synthetic
By PHEDOPO
100(1.0568g; 0.1229mmol), 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane (0.3052; 0.01229mmol), AIBN (4mg; 0.0025mmol) be dissolved in 5mL tetrachloroethane; after degassed 4 times of continuous freeze thawing under argon shield in 65 DEG C of polymerizations; after reaction 24h, through the sudden cold stopped reaction of liquid nitrogen, taking ethanol as precipitation agent, precipitation obtains product P HEDOPO 2 times
100-b-PKH570
10two blocks.
Embodiment 2:
1) HEDOPO monomer is synthetic
First by DOPO (2.16g, 0.01mol) and tetracol phenixin (2.3076g, 0.015mol) mix, joining magneton in 10ml dichloromethane solvent is uniformly mixed, by hydroxyethyl methylacrylate (1.9521g, 0.015mol) and triethylamine salt (1.5179g, 0.015mol) solution joins in the former after mixing, ice bath, after for some time, under room temperature, react 24h again, filter, first use NaOH solution washing 3 times, use again deionized water wash 2 times, obtain HEDOPO monomer.
2) PHEDOPO
50synthesizing of macromolecular chain transfer agent
By HEDOPO (1.376g; 4mmol), CDB (0.0218g; 0.08mmol) and AIBN (0.00328g; 0.02mmol) be dissolved in 5mL tetrachloroethane; after degassed 5 times of continuous freeze thawing under argon shield in 65 DEG C of polymerizations; after reaction 24h, through the sudden cold stopped reaction of liquid nitrogen, be that 90mL ethanol is that precipitation agent repeated precipitation obtains product 2 times with 15 times of volumes.
3) PHEDOPO
50-b-PKH570
5synthetic
By PHEDOPO
50(1.032g; 0.06mmol), 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane (0.0451; 0.3mmol), AIBN (1mg; 0.006mmol) be dissolved in 5mL tetrachloroethane; after degassed 3 times of continuous freeze thawing under argon shield in 60 DEG C of polymerizations; after reaction 24h, through the sudden cold stopped reaction of liquid nitrogen, taking ethanol as precipitation agent, precipitation obtains product P HEDOPO 2 times
50-b-PKH570
5two blocks.
Embodiment 3:
1) HEDOPO monomer is synthetic
First by DOPO (2.16g, 0.01mol) and tetracol phenixin (1.3014g, 0.01mol) mix, joining magneton in 10ml dichloromethane solvent is uniformly mixed, by hydroxyethyl methylacrylate (1.5384g, 0.01mol) and triethylamine salt (1.0119g, 0.01mol) solution joins in the former after mixing, and ice bath, after for some time, under room temperature, react 24h, filter, first use NaOH solution washing 3 times, use again deionized water wash 2 times, obtain HEDOPO monomer.
2) PHEDOPO
80synthesizing of macromolecular chain transfer agent
By HEDOPO (2.752g; 8mmol), CDB (0.0272g; 0.1mmol) and AIBN (0.00328g; 0.02mmol) be dissolved in 5mL tetrachloroethane; after degassed 5 times of continuous freeze thawing under argon shield in 65 DEG C of polymerizations; after reaction 24h, through the sudden cold stopped reaction of liquid nitrogen, be that 90mL ethanol is that precipitation agent repeated precipitation obtains product 2 times with 15 times of volumes.
3) PHEDOPO
80-b-PKH570
15synthetic
By PHEDOPO
80(2.2025g; 0.08mmol), 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane (0.1987; 0.8mmol), AIBN (1mg; 0.006mmol) be dissolved in 5mL tetrachloroethane; after degassed 3 times of continuous freeze thawing under argon shield in 60 DEG C of polymerizations; after reaction 24h, through the sudden cold stopped reaction of liquid nitrogen, taking ethanol as precipitation agent, precipitation obtains product P HEDOPO 2 times
80-b-PKH570
15two blocks.
The phosphorous homopolymer of target and phosphorus silicon segmented copolymer are obtained by polymerization in embodiment 1, in 1H NMR nuclear magnetic spectrogram (seeing Fig. 1), chemical shift δ=7.1～7.8 are the proton peak on HEDOPO phenyl ring, δ=4.1 are the methene proton peak being connected with the oxygen of ester group, chemical shift δ=3.9 are the methene proton peak being connected with the sample of phosphorus oxygen base, and chemical shift δ=0.5-2.0 is the feature proton peak after methyl acrylic ester monomer polymerization;
31in P NMR nuclear magnetic spectrogram (seeing Fig. 2), the success of unique this homopolymer of unimodal chemical shift δ=12.7 explanation is synthetic;
1the existence of proton peak on methoxyl group in proton peak explanation 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane that in H NMR nuclear magnetic spectrogram (seeing Fig. 3), chemical shift δ=3.5 have more, although peak is sharper, this is because hydrolysis has occurred part methoxyl group, and the grafting number of design is smaller, so peak is relatively little, and there is no to find the peak of two keys, illustrate and in product, do not have monomer impurity, provable containing phosphorus silicon segmented copolymer PHEDOPO
100-b-PKH570
10synthetic;
31in P NMR nuclear magnetic spectrogram (seeing Fig. 4), the P purity of unique unimodal chemical shift δ=12.7 explanation segmented copolymer is very high.Above
1h NMR and
31p NMR nuclear magnetic spectrum has proved containing phosphorus silicon segmented copolymer PHEDOPO
100-b-PKH570
10synthetic.
The invention provides fire-retardant segmented copolymer of a kind of containing phosphorus silicon and preparation method thereof: (1) synthetic HEDOPO is the first block monomer, by reversible addition-fragmentation chain transfer free radical (RAFT) polymerization synthetic macromolecule chain-transfer agent; (2) taking the active homopolymer of above-mentioned gained PHEDOPO, 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane (silane coupling agent KH570), initiator as polymerization system, again, by reversible addition-fragmentation chain transfer free radical polymerization, synthesize the di-block copolymer of a kind of containing phosphorus silicon and methoxyl group.The present invention introduces the silane with methoxyl group in HEDOPO, reach the object of cooperative flame retardant, its reaction conditions gentleness, simple to operate, can regulate P, Si content by controlling feed ratio, can be used for further processing the inorganic nano-particles such as silicon-dioxide, improve the flame retardant properties of resin, there is good application prospect in fields such as halogen-free flameproofs.
Claims (10)
1. the fire-retardant segmented copolymer of containing phosphorus silicon, is characterized in that its chemical structural formula is as follows:
Wherein the structural formula of HEDOPO monomer is:
N is HEDOPO shared unit sum in polymer chain, 50≤n≤100;
M is 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane shared unit sum in polymer chain, 10≤m≤30.
2. the preparation method of the fire-retardant segmented copolymer of a kind of containing phosphorus silicon as claimed in claim 1, is characterized in that comprising the following steps:
1) HEDOPO monomer is synthetic
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and tetracol phenixin are mixed, then join in solvent, obtain mixture A; By joining in mixture A after hydroxyethyl methylacrylate and the mixing of triethylamine salt solution, under condition of ice bath, react, after reaction, filter, wash filtrate, obtains HEDOPO monomer;
2) PHEDOPO macromolecular chain transfer agent is synthetic
HEDOPO monomer, dithiobenzoic acid cumyl ester and azo-bis-isobutyl cyanide are dissolved in solvent, after freeze thawing is degassed, under protection of inert gas, carry out polyreaction, again through the sudden cold stopped reaction of liquid nitrogen, with obtaining pink product P HEDOPO macromolecular chain transfer agent after precipitation agent precipitation;
3) PHEDOPO-b-PKH570's is synthetic
Get step 2) synthetic PHEDOPO macromolecular chain transfer agent, 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane and azo-bis-isobutyl cyanide be dissolved in tetrachloroethane; after continuous freeze thawing is degassed under protection of inert gas polyreaction; again through the sudden cold stopped reaction of liquid nitrogen; precipitate and obtain the fire-retardant segmented copolymer of product containing phosphorus silicon, i.e. PHEDOPO-b-PKH570 two blocks with precipitation agent.
3. the preparation method of the fire-retardant segmented copolymer of a kind of containing phosphorus silicon as claimed in claim 2, it is characterized in that in step 1) in, the mol ratio of described 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, hydroxyethyl methylacrylate, triethylamine salt and tetracol phenixin is 1: (1～1.5): (1～1.5): (1～1.5).
4. the preparation method of the fire-retardant segmented copolymer of a kind of containing phosphorus silicon as claimed in claim 2, it is characterized in that in step 1) in, described will hydroxyethyl methylacrylate and triethylamine salt solution join in mixture A after mixing, be will hydroxyethyl methylacrylate and triethylamine salt solution under condition of ice bath, join in mixture A after mixing; Described solvent can adopt methylene dichloride; The time of described ice bath can be 1～2h; The time of described reaction can be 12～24h; Alkali liquid washing 3～4 times can be first used in described washing, then use distilled water wash 1～2 time.
5. the preparation method of the fire-retardant segmented copolymer of a kind of containing phosphorus silicon as claimed in claim 2, is characterized in that in step 2) in, described solvent adopts tetrachloroethane.
6. the preparation method of the fire-retardant segmented copolymer of a kind of containing phosphorus silicon as claimed in claim 2, it is characterized in that in step 2) in, the mol ratio of described HEDOPO, dithiobenzoic acid cumyl ester, azo-bis-isobutyl cyanide is (50～100): 1: 0.25; Described rare gas element can adopt argon gas.
7. the preparation method of the fire-retardant segmented copolymer of a kind of containing phosphorus silicon as claimed in claim 2, is characterized in that in step 2) in, the temperature of described polyreaction is 60～80 DEG C, the time of polyreaction is 24～48h; Described precipitation agent can be selected from the one in methyl alcohol, ethanol, normal hexane.
8. the preparation method of the fire-retardant segmented copolymer of a kind of containing phosphorus silicon as claimed in claim 2, it is characterized in that in step 3) in, the mol ratio of described 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane, PHEDOPO macromolecular chain transfer agent, azo-bis-isobutyl cyanide is (5～15): 1: 0.1; Described rare gas element can adopt argon gas.
9. the preparation method of the fire-retardant segmented copolymer of a kind of containing phosphorus silicon as claimed in claim 2, is characterized in that in step 3) in, the temperature of described polyreaction is 60～70 DEG C, the time of polyreaction is 24～48h.
10. the preparation method of the fire-retardant segmented copolymer of a kind of containing phosphorus silicon as claimed in claim 2, is characterized in that in step 3) in, described precipitation agent is selected from the one in methyl alcohol, ethanol, normal hexane.
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| CN103819634B (en) * | 2014-01-28 | 2016-06-01 | 厦门大学 | A kind of containing phosphorus silicon segmented copolymer and its preparation method |
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