CN106432332B - A kind of preparation method of phosphorus-nitrogen containing acrylate and its copolymer core-shell particles - Google Patents
A kind of preparation method of phosphorus-nitrogen containing acrylate and its copolymer core-shell particles Download PDFInfo
- Publication number
- CN106432332B CN106432332B CN201610814079.0A CN201610814079A CN106432332B CN 106432332 B CN106432332 B CN 106432332B CN 201610814079 A CN201610814079 A CN 201610814079A CN 106432332 B CN106432332 B CN 106432332B
- Authority
- CN
- China
- Prior art keywords
- phosphorus
- core
- nitrogen containing
- shell
- shell particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011258 core-shell material Substances 0.000 title claims abstract description 33
- 239000002245 particle Substances 0.000 title claims abstract description 28
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims abstract description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical group [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 24
- 229920001577 copolymer Chemical group 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000010792 warming Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000006210 lotion Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003995 emulsifying agent Substances 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims 1
- 238000007720 emulsion polymerization reaction Methods 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 18
- -1 diphenylphosphoryl dichloro, hydroxy-ethyl Chemical group 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 8
- 239000004609 Impact Modifier Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010556 emulsion polymerization method Methods 0.000 abstract description 3
- 238000004079 fireproofing Methods 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000003063 flame retardant Substances 0.000 description 12
- 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 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000000979 retarding effect Effects 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 1
- YCSMVPSDJIOXGN-UHFFFAOYSA-N CCCCCCCCCCCC[Na] Chemical compound CCCCCCCCCCCC[Na] YCSMVPSDJIOXGN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical compound Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- CKCQRGCWKDEOSO-UHFFFAOYSA-N n,n-diethylethanamine;prop-2-enoic acid Chemical compound OC(=O)C=C.CCN(CC)CC CKCQRGCWKDEOSO-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/44—Amides thereof
- C07F9/4403—Amides thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4419—Amides of aromatic acids (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/44—Amides thereof
- C07F9/4434—Amides thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4438—Ester with hydroxyalkyl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F275/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers containing phosphorus, selenium, tellurium or a metal as defined in group C08F30/00
Abstract
The invention discloses a kind of phosphorus-nitrogen containing acrylate and its copolymer core-shell particles preparation method.Using diphenylphosphoryl dichloro, hydroxy-ethyl acrylate and diethylamine as raw material in the present invention, triethylamine is acid binding agent, and phosphorus-nitrogen containing acrylate is obtained by the reaction at 0-5 DEG C in tetrahydrofuran, and synthetic method is simple, at low cost；The phosphorus-nitrogen containing acrylate can carry out radical copolymerization with other acrylic ester monomers.The present invention is prepared for the core-shell particles of phosphorus-nitrogen containing acrylate using core-shell emulsion polymerization method, have the advantages that structure, composition is adjustable, under the premise of not changing the structure of core-shell impact modifiers, particle itself has certain anti-flammability, is expected to be used for the toughening of fire proofing.
Description
Technical field
The present invention relates to the preparation methods of a kind of phosphorus-nitrogen containing acrylate and its copolymer core-shell particles, belong to producing high-molecular
The technical field of and polymer technology.
Background technology
In recent years, as environmental protection and the continuous improvement of security protection consciousness, halogen-free flame retardants have become opening for flame retardant area
Heat generating spot.However halogen-free flame retardants there are flame retarding efficiency it is low and it is fire-retardant after material mechanical performance it is bad the shortcomings of, solve " improve
Contradiction between anti-flammability and holding mechanical property " has become important topic.By " structurally-modified to be combined with function modified ", it is
Solve the problems, such as this new way.Acrylate copolymer particle with nucleocapsid is that the impact of many high molecular materials changes
Property agent, still, there is not yet reporting the flame retarding functionization of such core-shell impact modifiers particle.The invention mainly includes will
Ignition-proof element is combined with core-shell impact modifiers structure, prepares the impact modifying agent of novel flame-retardant functionalization.
Phosphoric acrylic ester can be used to prepare phosphorous resin, coating, the adhesive etc. of essence by radical copolymerization,
It can also be copolymerized with other flame-retardant monomers and prepare aggretion type fire retardant.Chinese patent 200910116317.0 discloses difunctional
Phosphoric acrylic ester（1）, and it is prepared for the flame retardant coating with dissaving structure with the amine compound of trifunctional, overspend
Change the toughness that structure is conducive to improve coating.Chinese patent 201510810594.7, which discloses, can be used for the novel of free radical polymerization
Phosphoric acrylic ester monomer（2）Preparation method, which, which can be used as reactive flame retardant and be added in polymer material, plays
Fire retardation.Chinese patent ZL201110128125.9 discloses a kind of phosphorus-nitrogen containing acrylate monomer（3）, which is used for
Polyacrylate dispersion is prepared, the usage amount of fire retardant is reduced.Chinese patent ZL201410096997.5 and
ZL201410096979.7 discloses phosphoric acrylic ester respectively（4,5）It is fire-retardant that aggretion type is prepared with copolymerization such as acrylate containing silicones
Agent can be used for the flame-retardant modified of the materials such as polystyrene.Temporarily have no the report for being used to prepare core-shell impact modifiers.Phosphorous third
There are mainly two types of methods for the preparation of olefin(e) acid ester：One is being obtained by acryloyl chloride and epoxy group or hydroxyl reaction, this method is closed
At of high cost, be not suitable for industrialization, such as United States Patent (USP) US5399733A and Chinese patent ZL201410096997.5 and
ZL201410096979.7；Another kind is monohydroxy acrylic acid matter and phosphorus（Phosphine）Acyl chloride reaction, due to phosphorus（Phosphine）Acyl chlorides price is low
It is honest and clean, it is easy to get extensively, is more suitable for industrializing, such as Chinese patent ZL200910116317.0.
It is characteristic of the invention that using phosphorus-nitrogen containing acrylate as comonomer, it is introduced into core-shell impact modifiers structure,
Flame retarding function is carried out to impact modifying agent.Phosphorus-nitrogen containing Synthetic method of acrylic ester in the present invention is simple, at low cost, is suitble to work
Industry produces, can be by free-radical polymerized with other acrylic ester monomers.Core-shell particles are prepared using core-shell emulsion polymerization method,
Have the advantages that structure, composition is adjustable；The core-shell particles of the present invention embody setting for " structurally-modified to be combined with function modified "
Thought is counted, under the premise of not changing the structure of core-shell impact modifiers, particle itself has certain anti-flammability, is expected to be used for
The toughening of fire proofing.
Invention content
It is an object of the present invention to provide the preparation methods of a kind of phosphorus-nitrogen containing acrylate and its copolymer core-shell particles.
Phosphorus-nitrogen containing acrylate in the present invention, structure feature such as formula（I）It is shown：
（I）.
Phosphorus-nitrogen containing acrylate in the present invention, preparation method are characterized in that：
By diphenylphosphoryl dichloro (PDCP) and triethylamine (TEA) in molar ratio 1:2.2 to 1:3 ratio and solvent tetrahydrochysene
Furans (THF) is added in the three-necked flask equipped with blender and is cooled to -5-0 DEG C, dropwise addition and diphenylphosphoryl dichloro (PDCP) etc.
Mole hydroxy-ethyl acrylate（HEA）, after being reacted 2-4 hours at 0-5 DEG C, it is added dropwise and diphenylphosphoryl dichloro (PDCP) equimolar
Diethylamine, after being reacted 2-4 hours at 0-5 DEG C, be warming up to room temperature reaction 2-6 hour, reaction mixture through filtering remove three
Ethylamine hydrochloride, obtained filtrate obtain pale yellow viscous liquid, as phosphorus-nitrogen containing after removing solvent and unreacted triethylamine
Acrylate monomer；Reaction equation such as formula（II）：
（II）.
The preparation method of the copolymer core-shell particles of phosphorus-nitrogen containing acrylate in the present invention, formula and process are as follows：
First by 80g distilled water, 0.4g sodium bicarbonates（NaHCO3）With emulsifier 2.5g lauryl sodium sulfate（SDS）,
1.5gOP-10 is added in the four-hole boiling flask of 250ml, and initiator potassium persulfate is added after its dissolving（KPS）0.1g, heating
To 60 DEG C, the interior nuclear monomer of 30%-50% is added（The mass ratio of phosphorus-nitrogen containing acrylate and butyl acrylate is 1:4 to 4:1 list
Body mixture）, remaining interior nuclear monomer is added dropwise after being warming up to 70-75 DEG C of initiation polymerization（Phosphorus-nitrogen containing acrylate and acrylic acid fourth
The mass ratio of ester is 1:4 to 4:1 monomer mixture）, after reacting 1-3 hours；0.1gKPS is added, shell monomers are added dropwise（Methyl
Methyl acrylate）, 75-80 DEG C of reaction temperature reacts 2-6 hours after being added dropwise, obtains polyalcohol nucleocapsid lotion；Wherein, interior
Nuclear monomer is 5 with shell monomers mass ratio:5 to 7:3；The mass ratio of total monomer and distilled water is 4:6 to 6:4.This lotion is through broken
It after breast, filters, washing, it is dry to get to copolymer core-shell particles.
Benefit of the invention is that：It is prepared for the core-shell particles of phosphorus-nitrogen containing acrylate using core-shell emulsion polymerization method, has
Have the advantages that structure, composition is adjustable, under the premise of not changing the structure of core-shell impact modifiers, particle itself has certain resistance
Combustion property, is expected to be used for the toughening of fire proofing.
Description of the drawings
The nucleus magnetic hydrogen spectrum of phosphorus-nitrogen containing acrylate in Fig. 1 embodiments 1.
The infrared spectrum of phosphorus-nitrogen containing acrylate in Fig. 2 embodiments 1.
Copolymer core-shell particles grading curve in Fig. 3 embodiments 2 and embodiment 3.
The burning heat release curve of copolymer core-shell particles in Fig. 4 embodiments 2 and embodiment 3.
Specific implementation mode
Present invention be described in more detail by the following examples phosphorus-nitrogen containing acrylate and its copolymer core-shell particles
The thermal decomposition of preparation method and the particle and burning latent heat releasing performance.
Embodiment 1
By diphenylphosphoryl dichloro (PDCP) 19.5g（0.1mol）With triethylamine (TEA) 25.3g（0.25mol）And solvent
Tetrahydrofuran (THF) 80mL is added in the three-necked flask equipped with blender and is cooled to -5-0 DEG C, dropwise addition hydroxy-ethyl acrylate
（HEA）After being reacted 3 hours at 0-5 DEG C, diethylamine (DEA) 7.3g (0.1mol) is added dropwise, at 0-5 DEG C in 11.6g (0.1mol)
After lower reaction 2 hours, it is warming up to room temperature reaction 4 hours, reaction mixture removes triethylamine hydrochloride, obtained filtrate through filtering
Crude product is obtained after removal solvent and unreacted triethylamine；Product is mobile phase with ethyl acetate, passes through neutral silica gel column layer
Analysis purifies, and it is phosphorus-nitrogen containing acrylate to obtain pale yellow viscous liquid after removal ethyl acetate.
Embodiment 2
First by 80ml distilled water be added to electric mixer, thermometer, reflux condensing tube 250ml four-hole boiling flask
In, later on agitating device, 0.4gNaHCO3,2.5gSDS and 1.5gOP-10, which is added, makes it be slowly stirred.After its dissolving
0.1gKPS is added to start to warm up, temperature rises to nuclear monomer in 60 DEG C or so rear addition 20g（Phosphorus-nitrogen containing acrylate 15g and third
The mixture of olefin(e) acid butyl ester 10g）, it is warming up to 70-75 DEG C, remaining interior nuclear monomer 36g is added dropwise after causing polymerization（Phosphorus-nitrogen containing third
The mixture of olefin(e) acid ester 10g and butyl acrylate 26g）, after reacting 2 hours, 0.1gKPS is added, shell monomers methyl-prop is added dropwise
E pioic acid methyl ester 21g, the reaction was continued 3 hours.Lotion after demulsification, obtain grain size 0.05 ~ 0.16 micron range copolymer core
Shell particles.
Embodiment 3
First by 80ml distilled water be added to electric mixer, thermometer, reflux condensing tube 250ml four-hole boiling flask
In, later on agitating device, 0.4gNaHCO3,2.5gSDS and 1.5gOP-10, which is added, makes it be slowly stirred.After its dissolving
0.1gKPS is added to start to warm up, temperature rises to nuclear monomer in 60 DEG C or so rear addition 20g（Phosphorus-nitrogen containing acrylate 16g and third
The mixture of olefin(e) acid butyl ester 4g）, it is warming up to 70-75 DEG C, remaining interior nuclear monomer 30g is added dropwise after causing polymerization（Phosphorus-nitrogen containing propylene
The mixture of acid esters 24g and butyl acrylate 6g）, after reacting 2 hours, 0.1gKPS is added, shell monomers methacrylic acid is added dropwise
Methyl esters 25g, the reaction was continued 3 hours.Lotion obtains 0.05 ~ 0.23 micron of copolymer core-shell particles of grain size after demulsification.
Claims (5)
1. copolymer core-shell particles, it is characterised in that：Using phosphorus-nitrogen containing acrylate and butyl acrylate shown in formula (I) as kernel
Monomer is reacted by core-shell emulsion polymerization and is prepared using methyl methacrylate as shell monomers；
2. the preparation method of copolymer core-shell particles according to claim 1, it is characterised in that be prepared as follows：
First by 80g distilled water, 0.4g sodium bicarbonates and emulsifier 2.5g lauryl sodium sulfate, 1.5gOP-10, it is added to
In the four-hole boiling flask of 250ml, initiator potassium persulfate 0.1g is added after its dissolving, is warming up to 60 DEG C, is added 30%-50%'s
Remaining interior nuclear monomer is added dropwise after being warming up to 70-75 DEG C of initiation polymerization, after reacting 1-3 hours in interior nuclear monomer；0.1gKPS is added,
Shell monomers are added dropwise, 75-80 DEG C of reaction temperature reacts 2-6 hours after being added dropwise, obtains polyalcohol nucleocapsid lotion；This lotion
It after demulsification, filters, washs, it is dry, obtain copolymer core-shell particles.
3. copolymer core-shell particles according to claim 1 or 2, it is characterised in that phosphorus-nitrogen containing third in the interior nuclear monomer
The mass ratio of olefin(e) acid ester and butyl acrylate is 1:4 to 4:1.
4. copolymer core-shell particles according to claim 1 or 2, it is characterised in that interior nuclear monomer and shell monomers mass ratio
It is 5:5 to 7:3.
5. the preparation method of copolymer core-shell particles according to claim 2, it is characterised in that total monomer and distilled water
Mass ratio is 4:6 to 6:4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610814079.0A CN106432332B (en) | 2016-09-12 | 2016-09-12 | A kind of preparation method of phosphorus-nitrogen containing acrylate and its copolymer core-shell particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610814079.0A CN106432332B (en) | 2016-09-12 | 2016-09-12 | A kind of preparation method of phosphorus-nitrogen containing acrylate and its copolymer core-shell particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106432332A CN106432332A (en) | 2017-02-22 |
| CN106432332B true CN106432332B (en) | 2018-10-26 |
Family
ID=58169098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610814079.0A Active CN106432332B (en) | 2016-09-12 | 2016-09-12 | A kind of preparation method of phosphorus-nitrogen containing acrylate and its copolymer core-shell particles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106432332B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112467120A (en) * | 2020-12-01 | 2021-03-09 | 桐乡市华璟科技有限公司 | Preparation method of nitrogen-phosphorus-doped porous carbon-coated manganese dioxide cathode material |
| KR102600082B1 (en) * | 2021-02-18 | 2023-11-07 | 경기대학교 산학협력단 | Composition for organic flame retardant compounds and method for manufacturing the same |
| CN114292368B (en) * | 2022-01-26 | 2023-04-11 | 华北理工大学 | Organic silicon-phosphorus-containing acrylate core-shell toughening flame retardant and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU10663A1 (en) * | 1928-04-23 | 1929-07-31 | Е.Г. Ефремов | Device for measuring small displacements of a parallel beam |
| SU1142487A1 (en) * | 1983-06-15 | 1985-02-28 | Волгоградский Ордена Трудового Красного Знамени Политехнический Институт | Ethylene-propylene-diene-base rubber mix |
| CN101497630A (en) * | 2009-03-09 | 2009-08-05 | 安徽恒远化工有限公司 | Phosphoric acrylic ester monomer, hyperbranched polymer flame retardant and preparation thereof |
-
2016
- 2016-09-12 CN CN201610814079.0A patent/CN106432332B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU10663A1 (en) * | 1928-04-23 | 1929-07-31 | Е.Г. Ефремов | Device for measuring small displacements of a parallel beam |
| SU1142487A1 (en) * | 1983-06-15 | 1985-02-28 | Волгоградский Ордена Трудового Красного Знамени Политехнический Институт | Ethylene-propylene-diene-base rubber mix |
| CN101497630A (en) * | 2009-03-09 | 2009-08-05 | 安徽恒远化工有限公司 | Phosphoric acrylic ester monomer, hyperbranched polymer flame retardant and preparation thereof |
Non-Patent Citations (3)
| Title |
|---|
| Grafting of Phosphonate Monomer onto Natural Rubber Latexes via Emulsion Polymerization;K. Kokklin et al;《Functionalized and Sensing Materials》;20101231;第93-94卷;第125-128页 * |
| Phosphonamidates as thermally latent anionic initiators of glycidyl phenyl ether: substituent effect on the initiator activity;Kim, Moonsuk et al;《Macromolecules》;20011231;第34卷;第409-414页 * |
| 核壳结构丙烯酸酯乳液的合成及性能研究;甘孟瑜等;《涂料工业》;20051231;第35卷;第5-8页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106432332A (en) | 2017-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106432332B (en) | A kind of preparation method of phosphorus-nitrogen containing acrylate and its copolymer core-shell particles | |
| CN107814860B (en) | A kind of polyacrylate fire retardant of phosphorus-nitrogen containing silicon and preparation method thereof | |
| CN104262553B (en) | A kind of fire-retardant block copolymer of phosphorus-nitrogen containing and preparation method thereof | |
| CN104910327B (en) | A kind of phosphorus nitrogen cooperative flame retardant epoxy polymer and preparation method thereof | |
| CN108795208A (en) | The preparation method of extinguishing waterborn hud typed acrylic resin coating and paint | |
| WO2014006464A1 (en) | Preparation method of polymeric phase-change material | |
| CN102099390B (en) | Method for preparing a polymer particle dispersion in an aqueous medium | |
| CN105085790B (en) | A kind of body flame acrylic acid ester emulsion and its preparation method and application | |
| CN104610515A (en) | Reactive group-contained comb-type graft copolymer, and preparation method and application thereof | |
| CN102408853A (en) | Water-based body flame-resistant acrylate adhesive and preparation method thereof | |
| CN106947031B (en) | A kind of flucride siloxane fire retardant and the preparation method and application thereof | |
| CN104592438B (en) | There is the three-layer nuclear shell structure interpenetrating networks emulsion and its synthetic method of high adhesion force to metal base | |
| CN104844745B (en) | A kind of response type phosphonium flame retardant and preparation method thereof | |
| CN102604622A (en) | Oil displacing agent containing imidazole ring quaternary ammonium salt polymer and preparation method | |
| Li et al. | Synthesis of starlike PtBA‐g‐PEO amphiphilic graft copolymer via highly efficient Cu‐catalyzed SET‐NRC reaction at ambient temperature | |
| CA3178772A1 (en) | Flameproof acrylate | |
| CN104804118B (en) | A kind of preparation method of high solids content and strong alkali resistance acrylic acid ester emulsion adhesive | |
| CN105085771A (en) | Waterborne acrylic resin and preparation method therefor | |
| CN106749833A (en) | Vinylidene chloride acrylate Organosiliconcopolymere latex and preparation method thereof | |
| CN105801875B (en) | The fluorosilicic block copolymer and preparation method and application of side chain ring containing benzoxazine | |
| CN107418125A (en) | A kind of method that multiphase polymer material is prepared using segmented copolymer latex | |
| CN104530309A (en) | Terminal double-bond free radical copolymerization fluorine-containing large-molecular monomer as well as preparation method and application thereof | |
| CN104086714A (en) | Quadripolymer dispersant and preparation method thereof | |
| CN104592439B (en) | A kind of interpenetrating networks emulsion and its synthetic method to metal base with high adhesion force | |
| CN103387631B (en) | A kind of preparation method of modification body flame-retardant polystyrene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20180911 Address after: 063009 Tangshan City Caofeidian District, Hebei Province, Tangshan Bay eco Town, Bohai Road, 21 Applicant after: NORTH CHINA University OF SCIENCE AND TECHNOLOGY Applicant after: CHANGSHU HUASHANG NEW MATERIAL TECHNOLOGY Co.,Ltd. Address before: 063009 Xinhua West Road, Tangshan City, Hebei Province, No. 46 Applicant before: NORTH CHINA University OF SCIENCE AND TECHNOLOGY |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231012 Address after: No.21 Bohai Avenue, Caofeidian new town, Tangshan City, Hebei Province 063200 Patentee after: NORTH CHINA University OF SCIENCE AND TECHNOLOGY Patentee after: GUANGDONG SHUNDE TONGCHENG NEW MATERIALS TECHNOLOGY CO.,LTD. Address before: 063009 Tangshan City Caofeidian District, Hebei Province, Tangshan Bay eco Town, Bohai Road, 21 Patentee before: NORTH CHINA University OF SCIENCE AND TECHNOLOGY Patentee before: CHANGSHU HUASHANG NEW MATERIAL TECHNOLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right |