CN116200018A - Flame-retardant polymer prepared based on modified bentonite and application thereof - Google Patents
Flame-retardant polymer prepared based on modified bentonite and application thereof Download PDFInfo
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- CN116200018A CN116200018A CN202211657780.8A CN202211657780A CN116200018A CN 116200018 A CN116200018 A CN 116200018A CN 202211657780 A CN202211657780 A CN 202211657780A CN 116200018 A CN116200018 A CN 116200018A
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- flame retardant
- flame
- bentonite
- polymer
- modified bentonite
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 148
- 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 claims abstract description 132
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical class O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229920000642 polymer Polymers 0.000 title claims abstract description 77
- -1 triazine compound Chemical class 0.000 claims abstract description 88
- 239000000440 bentonite Substances 0.000 claims abstract description 53
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 53
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- 238000005266 casting Methods 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims description 67
- 238000006243 chemical reaction Methods 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 31
- 238000002360 preparation method Methods 0.000 claims description 25
- TXFOLHZMICYNRM-UHFFFAOYSA-N dichlorophosphoryloxybenzene Chemical compound ClP(Cl)(=O)OC1=CC=CC=C1 TXFOLHZMICYNRM-UHFFFAOYSA-N 0.000 claims description 22
- 239000003513 alkali Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000004753 textile Substances 0.000 claims description 2
- 229920002521 macromolecule Polymers 0.000 claims 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims 1
- GJMMXPXHXFHBPK-UHFFFAOYSA-N [P].[Cl] Chemical compound [P].[Cl] GJMMXPXHXFHBPK-UHFFFAOYSA-N 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 144
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 69
- 239000002244 precipitate Substances 0.000 description 49
- 239000007864 aqueous solution Substances 0.000 description 48
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 45
- 239000008367 deionised water Substances 0.000 description 25
- 229910021641 deionized water Inorganic materials 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 238000000748 compression moulding Methods 0.000 description 12
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 10
- 229920000903 polyhydroxyalkanoate Polymers 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- NJRRDPVKZWHSMA-UHFFFAOYSA-N methyl 8-(2-methoxy-2-oxoethyl)-2,3,5,6,7,7a-hexahydro-1h-cyclopenta[b]pyrrolizine-8-carboxylate Chemical compound C1CCC2=C1C(CC(=O)OC)(C(=O)OC)C1CCCN12 NJRRDPVKZWHSMA-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 8
- 239000011229 interlayer Substances 0.000 description 8
- MCTRMTHCWARJFG-UHFFFAOYSA-N methyl 4-(2-methoxy-2-oxoethyl)-1,2,3,3a,5,6,7,8-octahydropyrrolo[1,2-a]indole-4-carboxylate Chemical compound C1CCCC2=C1C(CC(=O)OC)(C(=O)OC)C1CCCN12 MCTRMTHCWARJFG-UHFFFAOYSA-N 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229910052901 montmorillonite Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229920000954 Polyglycolide Polymers 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920000747 poly(lactic acid) Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000004633 polyglycolic acid Substances 0.000 description 3
- 239000004626 polylactic acid Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- JDRRUFKYXHZOAZ-UHFFFAOYSA-N ac1l7aaf Chemical compound C1CC2=CC=CC=C2C2=C1C(CC(=O)OC)(C(=O)OC)C1N2CCC1 JDRRUFKYXHZOAZ-UHFFFAOYSA-N 0.000 description 2
- ZPYCIFLOAZZZTO-UHFFFAOYSA-N ac1l7aai Chemical compound O=C1NNC(=O)CC11C(CCC=2C3=CC=CC=2)=C3N2CCCC21 ZPYCIFLOAZZZTO-UHFFFAOYSA-N 0.000 description 2
- VGYNDTWNLVWXNN-UHFFFAOYSA-N ac1l7aax Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(CC(=O)OC)(C(=O)OC)C1N2CCC1 VGYNDTWNLVWXNN-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- OANMFHPAAGDURI-UHFFFAOYSA-N methyl 8-(2-methoxy-2-oxoethyl)-2,3-diphenyl-5,6,7,7a-tetrahydrothieno[2,3-b]pyrrolizine-8-carboxylate Chemical compound COC(=O)CC1(C(=O)OC)C2CCCN2C2=C1SC(C=1C=CC=CC=1)=C2C1=CC=CC=C1 OANMFHPAAGDURI-UHFFFAOYSA-N 0.000 description 2
- UAXBMTOHMANBBV-UHFFFAOYSA-N methyl 8-(2-methoxy-2-oxoethyl)-2-(2-methoxyphenyl)-5,6,7,7a-tetrahydrothieno[2,3-b]pyrrolizine-8-carboxylate Chemical compound S1C=2C(CC(=O)OC)(C(=O)OC)C3CCCN3C=2C=C1C1=CC=CC=C1OC UAXBMTOHMANBBV-UHFFFAOYSA-N 0.000 description 2
- QIHWXBPPTRYXNO-UHFFFAOYSA-N methyl 8-(2-methoxy-2-oxoethyl)-2-propan-2-yl-5,6,7,7a-tetrahydrothieno[2,3-b]pyrrolizine-8-carboxylate Chemical compound C1=C(C(C)C)SC2=C1N1CCCC1C2(CC(=O)OC)C(=O)OC QIHWXBPPTRYXNO-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- MPFMDONSMLFXDQ-UHFFFAOYSA-N methyl 1-(2-methoxy-2-oxoethyl)-3-phenyl-2-phenylsulfanyl-5,6,7,8-tetrahydropyrrolizine-1-carboxylate Chemical compound COC(=O)CC1(C(=O)OC)C2CCCN2C(C=2C=CC=CC=2)=C1SC1=CC=CC=C1 MPFMDONSMLFXDQ-UHFFFAOYSA-N 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a flame-retardant polymer prepared based on modified bentonite and application thereof, and belongs to the field of materialics. The invention uses triazine compound and phosphorus-chlorine compound to generate polymerization reaction between bentonite layers to generate hyperbranched macromolecular flame retardant, and the hyperbranched macromolecular flame retardant is peeled off and modified on bentonite to obtain the flame retardant; and then the flame retardant polymer is prepared by melt blending or suspension casting with the polymer. The flame-retardant polymer obtained by the invention has good flame retardant property, thermal stability and high mechanical property.
Description
Technical Field
The invention relates to a flame-retardant polymer prepared based on modified bentonite and application thereof, belonging to the field of materialics.
Background
With the continuous development of modern society, polymer materials have been widely used in various fields, however, polymer materials are very easy to burn due to the influence of their own structures, and have serious influence on production safety, so that it is extremely important to improve the flame retardant property of polymer materials. The current optimal choice for improving the flame retardant property of the polymer is to add a flame retardant into a matrix, and the consumption of the flame retardant in the polymer auxiliary agent is high at the second place. However, with the development of flame retardant technology, there is a need for flame retardant polymer composites that, in addition to flame retardant properties, avoid significant damage to the mechanical properties of the substrate by the addition of flame retardants.
The addition of the inorganic filler is a simple and efficient method for improving the flame retardant property of the polymer material. Bentonite called "omnipotent earth" is a nonmetallic mineral based on montmorillonite, and montmorillonite is a three-dimensional lamellar structure composed of two layers of Si-O tetrahedra and one layer of Al-O octahedra. Bentonite has many excellent properties such as good thermal stability, high carbon residue, large reserves, low production cost, etc. At the same time, a large number of exchangeable cations (Na + 、K + 、Ca 2 + ) This provides a necessary condition for the multifunctional modification of bentonite. However, bentonite has a small lamellar spacing due to its own structure, and is easily agglomerated in the polymer matrix. In addition, bentonite has a general flame retardant effect, and cannot meet the requirements of fireproof materials.
In order to allow bentonite to perform better in the substrate, it is modified. The existing method for modifying montmorillonite by adopting a cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) prepares Organic Modified Montmorillonite (OMMT), and the interlayer spacing of the modified montmorillonite is increased from 1.11nm to 2.00nm, so that OMMT can be better dispersed when being added into a base material ABS, and the tensile strength and impact strength of the ABS are slightly improved. (ACS Omega 2020,5,19255-19267). The modified montmorillonite has expanded interlayer spacing, but has very little effect, and the layered structure of montmorillonite is still present, so that the montmorillonite can not be fully dispersed in the base material.
Therefore, it is important to develop a flame retardant polymer containing bentonite.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to prepare the flame-retardant polymer with good flame-retardant property, high thermal stability and excellent mechanical property. The bentonite used in the invention is peeled and modified by generating hyperbranched macromolecular flame retardant through the polymerization reaction between triazine compound and phosphorus-chlorine compound, wherein the theoretical content of the hyperbranched macromolecular flame retardant is 50-99%.
The invention provides a method for preparing a flame-retardant polymer, which is prepared by melt blending or suspension pouring of a polymer and modified bentonite;
the modified bentonite is prepared by the following steps:
(1) The method comprises the steps of (1) reacting trichloronitrile (CYC) with alcohol amine monomers in an alkaline environment to obtain a micromolecular flame retardant triazine compound (THT);
(2) Then dispersing the obtained micromolecular flame retardant triazine compound, bentonite and an alkali reagent in an organic solvent, uniformly mixing and reacting for a period of time; then dripping phenyl phosphoryl dichloride for continuous reaction, after the reaction is finished, separating solid from liquid, collecting solid, and washing to obtain the modified bentonite.
In one embodiment of the invention, 92-99 parts of polymer and 1-8 parts of modified bentonite are mixed according to parts by weight.
In one embodiment of the invention, the polymer is selected from any one or more of the following: polyhydroxyalkanoates, polylactic acid, polystyrene, polyglycolic acid, polyethylene, polypropylene, and polyethylene terephthalate.
In one embodiment of the present invention, the method for preparing a flame retardant polymer comprises:
method one, melt blending: taking 1-8 parts by weight of modified bentonite and 92-95 parts by weight of polymer, melt blending at a certain temperature through an extruder or a torque rheometer, and then obtaining a flame-retardant polymer through a molding process;
or, method two, suspension casting: 1-8 parts by weight of modified bentonite is added into methylene dichloride to obtain uniform suspension, 92-95 parts by weight of polymer is dissolved into the suspension, and then the suspension is poured into a film, and the flame-retardant polymer is obtained through a molding process.
In one embodiment of the present invention, the melt blending temperature is 160-260 DEG C
In one embodiment of the present invention, the structure of the alcohol amine monomer is as follows:
wherein R is 1 ＝-(CH 2 ) x CH 3 X is 0-1; r is R 2 ＝-(CH 2 ) y CH 3 Y is 0-3; r is R 3 ＝-(CH 2 ) z Z is 1 to 3.
In one embodiment of the invention, in the preparation process of the modified bentonite, the molar ratio of the trichloronitrile to the alcohol amine monomer in the step (1) is 1:3-5.
In one embodiment of the present invention, in the preparation process of the modified bentonite, the process in step (1) specifically includes: dissolving the trichloronitrile in dioxane to prepare a trichloronitrile solution; dispersing alcohol amine monomer and NaOH in the aqueous solution to obtain NaOH aqueous solution containing alcohol amine monomer; dropwise adding one third of NaOH aqueous solution containing an alcohol amine monomer into the trichloronitrile solution at the temperature of 1-5 ℃ for reacting for a period of time; then heating to 40-50 ℃, dropwise adding one third of NaOH aqueous solution containing alcohol amine monomers, and reacting for a period of time; and then heating to 80-90 ℃, continuously dropwise adding the rest one third of NaOH aqueous solution containing alcohol amine monomers for reaction, separating to obtain white precipitate after the reaction is finished, washing, and drying to obtain the micromolecular flame retardant triazine compound.
In one embodiment of the invention, the concentration of the trichloronitrile solution during the preparation of the modified bentonite is 0.1mol/300mL.
In one embodiment of the invention, in the preparation process of the modified bentonite, the concentration of the alcohol amine monomer in the NaOH aqueous solution containing the alcohol amine monomer is 0.1mol/50mL.
In one embodiment of the invention, the concentration of NaOH in the aqueous NaOH solution containing the alcohol amine monomer is 0.1mol/50mL in the preparation process of the modified bentonite.
In one embodiment of the invention, in the preparation process of the modified bentonite, one third of NaOH aqueous solution containing an alcohol amine monomer is dropwise added into the trichloronitrile solution at the temperature of 1-5 ℃ for reaction for 2-5h.
In one embodiment of the invention, in the preparation process of the modified bentonite, the temperature is raised to 40-50 ℃, one third of NaOH aqueous solution containing the alcohol amine monomer is dripped, and the reaction is carried out for 2-5 hours.
In one embodiment of the invention, in the preparation process of the modified bentonite, the temperature is raised to 80-90 ℃, and the rest one third of NaOH aqueous solution containing alcohol amine monomer is continuously added dropwise for reaction for 8-12h.
In one embodiment of the invention, in the preparation process of the modified bentonite, the mass ratio of the bentonite to the small molecular flame retardant triazine compound in the step (2) is 1: (1.9-7.6). Preferably 1: (0.8-12.5). Specific alternatives are 1:0.8, 1:1.2, 1:1.9, 1:3.6, 1:3.8, 1:5.7, 1:7.6, 1:12.3.
In one embodiment of the present invention, in the preparation process of the modified bentonite, the alkali reagent in the step (2) is: triethylamine, sodium bicarbonate, sodium hydroxide, sodium carbonate, and the like.
In one embodiment of the invention, in the preparation process of the modified bentonite, the molar ratio (2-8) of the small molecular flame retardant triazine compound to the phenylphosphoryl dichloride in the step (2): 3. preferably (2-4): 3.
in one embodiment of the present invention, in the preparation process of the modified bentonite, the mass ratio of bentonite to alkali agent in the step (2) is 1: (1.7-6.8). Preferably 1: (1.7-3.4).
In one embodiment of the invention, in the preparation process of the modified bentonite, the micromolecular flame retardant triazine compound obtained in the step (2), bentonite and an alkali reagent are dispersed in an organic solvent and are vigorously stirred for 15-30 hours at 30-60 ℃.
In one embodiment of the invention, in the preparation process of the modified bentonite, phenyl phosphoryl dichloride is dropwise added in the step (2) to continue to react for 8-12h.
In one embodiment of the invention, the structure of the small molecule flame retardant triazine compound is as follows:
wherein R is 1 ＝-(CH 2 ) x CH 3 X is 0-1; r is R 2 ＝-(CH 2 ) y CH 3 Y is 0-3; r is R 3 ＝-(CH 2 ) z Z is 1 to 3.
In one embodiment of the invention, in the preparation process of the modified bentonite, phenyl phosphoryl dichloride is dropwise added in the step (2) to continuously react, and a small molecular flame retardant triazine compound and a phosphorus-chlorine compound are subjected to polymerization reaction between bentonite layers to generate a hyperbranched macromolecular flame retardant so as to peel off the modified bentonite.
In one embodiment of the invention, the structural repeat units of the hyperbranched macromolecular flame retardant (HBM) are shown below:
wherein R is 1 ＝-(CH 2 ) x CH 3 X is 0-1; r is R 2 ＝-(CH 2 ) y CH 3 Y is 0-3; r is R 3 ＝-(CH 2 ) z Z is 1 to 3.
In one embodiment of the invention, the hyperbranched macromolecular flame retardant has a molecular weight ranging from 5000 to 50000.
In one embodiment of the present invention, the preparation method of the modified bentonite is as follows:
(1) Firstly, 1 mole part of trichloronitrile (CYC) is dissolved in a solvent A, and then, an aqueous solution containing 1 mole part of alcohol amine monomer and 1 mole part of PH agent 1 is dropwise added into the system at the temperature of 0-5 ℃; after 3 hours of reaction, the temperature of the system is raised to 45 ℃, and then an aqueous solution containing 1 mole part of the same alcohol amine monomer and 1 mole part of PH agent 1 is added into the system in a dropwise manner; after reacting for 3 hours, heating the system to 85 ℃, finally dripping aqueous solution containing 1 mole part of the same alcohol amine monomer and 1 mole part of PH agent 1 into the system, reacting for 10 hours, separating out white precipitate by deionized water, washing the precipitate for 3-5 times, and finally drying in a vacuum oven at 60 ℃ for 12 hours to obtain the micromolecular flame retardant THT.
(2) And (3) ultrasonically dispersing a certain amount of bentonite in a B solvent for 1 hour, then adding the bentonite into the B solvent containing THT and PH agent 2, then vigorously stirring a reaction system at a temperature of 40 ℃ for 24 hours, then dropwise adding Phenyl Phosphoryl Dichloride (PPDC) into the system, continuing to react for 11 hours after the dropwise adding is finished, filtering the precipitate after the reaction is finished, and washing the precipitate with deionized water and the A solvent for 3-5 times respectively to obtain the modified bentonite.
The invention provides a flame-retardant polymer based on the preparation method.
The invention also provides application of the flame-retardant polymer in the fields of medical equipment preparation, textile, construction, transportation and the like.
The invention has the beneficial effects that:
the invention provides a modified bentonite-based flame-retardant polymer and a preparation method thereof.
(1) The flame-retardant polymer provided by the invention has relatively excellent flame retardant property and good thermal stability. The small molecular flame retardant and the phenyl phosphoryl dichloride are introduced between the bentonite layers, and the small molecular flame retardant and the phenyl phosphoryl dichloride are polymerized to generate the hyperbranched macromolecular flame retardant, so that the hyperbranched macromolecular flame retardant has excellent flame retardant effect, and the bentonite has excellent thermal stability, so that the flame retardant polymer has good flame retardant property and thermal stability.
(2) The flame-retardant polymer has high mechanical property. This is because the modified bentonite has reached a exfoliated state, which allows for better dispersion in the substrate, resulting in a flame retardant polymer having superior mechanical properties.
Drawings
Fig. 1 is an XRD pattern before and after modification of bentonite in example 1.
FIG. 2 is a nuclear magnetic resonance spectrum of the macromolecular flame retardant obtained in comparative example 1.
Detailed Description
The polyhydroxyalkanoate of the present invention is derived from Ningbo Tianan biological materials, inc. and has a molecular weight of 590000. Polylactic acid is available from the company dadel Ke Bien and has a molecular weight of 130000. Polyethylene terephthalate: can be purchased from China petrochemical industry, chemical fiber Limited, and has a molecular weight of 36000.
Polystyrene: available from Shanghai macro Yue Ind Co., ltd, molecular weight is 260000. Polyglycolic acid: available from Shanghai Pu Jing chemical technologies Co., ltd, having a molecular weight of 150000.
Example 1
(1) Firstly, 0.1mol of trichloronitrile (CYC) is dissolved in 300mL of dioxane, and then 50mL of aqueous solution containing 0.1mol of alcohol amine monomer and 0.1mol of NaOH is dropwise added into the system at the temperature of 3 ℃; after 3 hours of reaction, the temperature of the system is raised to 45 ℃, and then 50mL of aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is added into the system dropwise; after reacting for 3 hours, the temperature of the system is raised to 85 ℃, finally, 50mL of aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is added into the system dropwise, white precipitate is separated out through deionized water after reacting for 10 hours, the precipitate is washed for 3 times, and finally, the small molecular flame retardant THT-1 is obtained after drying in a vacuum oven at 60 ℃ for 12 hours.
Wherein the structural formula of the alcohol amine monomer is
Wherein R is 1 ＝-CH 3 ，R 2 ＝-CH 3 ，R 3 ＝-CH 2 -。
(2) 3.57g of bentonite was ultrasonically dispersed in 50mL of acetonitrile solvent for 1 hour, then added to 100mL of acetonitrile solution containing 6.9g (0.02 mol) of THT-1 obtained in step (1) and 6.07g (0.06 mol) of triethylamine, then the reaction system was vigorously stirred at 40℃for 24 hours, then 6.0g (0.03 mol) of phenylphosphoryl dichloride (PPDC) was added dropwise to the system, the reaction was continued for 11 hours after the completion of the dropwise addition, the precipitate was filtered after the completion of the reaction, and then the precipitate was washed with deionized water and dioxane, respectively, 3 times to obtain flame-retardant modified bentonite-1.
(3) And (3) 5 parts by mass of the flame-retardant modified bentonite-1 obtained in the step (2) and 95 parts by mass of polyhydroxyalkanoate are subjected to melt blending at 160 ℃ through a torque rheometer, and then a flame-retardant polymer is obtained through a compression molding process.
Example 2
(1) Firstly, 0.1mol of trichloronitrile (CYC) is dissolved in 300mL of dioxane, and then 50mL of aqueous solution containing 0.1mol of alcohol amine monomer and 0.1mol of NaOH is dropwise added into the system at the temperature of 3 ℃; after 3 hours of reaction, the temperature of the system is raised to 45 ℃, and then 50mL of aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is added into the system dropwise; after reacting for 3 hours, the temperature of the system is raised to 85 ℃, finally, 50mL of aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is added into the system dropwise, white precipitate is separated out through deionized water after reacting for 10 hours, the precipitate is washed for 3 times, and finally, the small molecular flame retardant THT-2 is obtained after drying in a vacuum oven at 60 ℃ for 12 hours.
The structural formula of the alcohol amine monomer is
Wherein R is 1 ＝-CH 2 CH 3 ，R 2 ＝-CH 2 CH 3 ，R 3 ＝-CH 2 -。
(2) 5.77g of bentonite is dispersed in 50mL of acetonitrile solvent for 1h by ultrasonic, then added into 100mL of acetonitrile solution containing 6.9g (0.02 mol) of THT-2 obtained in the step (1) and 6.07g (0.06 mol) of triethylamine (the mass ratio of bentonite to THT-2 is 1:1.2), then the reaction system is vigorously stirred for 24h at the temperature of 40 ℃, then 6.0g (0.03 mol) of phenylphosphoryl dichloride (PPDC) is dropwise added into the system, the reaction is continued for 11h after the dropwise addition, the precipitate is filtered after the reaction is finished, and then the precipitate is washed with deionized water and dioxane for 3 times respectively to obtain the flame retardant modified bentonite-2.
(3) And (3) 5 parts by mass of the flame-retardant modified bentonite-2 obtained in the step (2) and 95 parts by mass of polyhydroxyalkanoate are subjected to melt blending at 160 ℃ through a torque rheometer, and then a flame-retardant polymer is obtained through a compression molding process.
Example 3
(1) Firstly, 0.1mol of trichloronitrile (CYC) is dissolved in 300mL of dioxane, and then 50mL of aqueous solution containing 0.1mol of alcohol amine monomer and 0.1mol of NaOH is dropwise added into the system at the temperature of 3 ℃; after 3 hours of reaction, the temperature of the system is raised to 45 ℃, and then 50mL of aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is added into the system dropwise; after reacting for 3 hours, the temperature of the system is raised to 85 ℃, finally, 50mL of aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is added into the system dropwise, white precipitate is separated out through deionized water after reacting for 10 hours, the precipitate is washed for 3 times, and finally, the small molecular flame retardant THT-3 is obtained after drying in a vacuum oven at 60 ℃ for 12 hours.
The structural formula of the alcohol amine monomer is
Wherein R is 1 ＝-CH 3 ，R 2 ＝-CH 2 CH 3 ，R 3 ＝-CH 2 -。
(2) 1.89g of bentonite is dispersed in 50mL of acetonitrile solvent for 1h by ultrasonic, then added into 100mL of acetonitrile solution containing 6.9g (0.02 mol) of THT-3 and 6.07g (0.06 mol) of triethylamine obtained in the step (1) (the mass ratio of bentonite to THT-2 is 1:3.6), then the reaction system is vigorously stirred for 24h at the temperature of 40 ℃, then 6.0g (0.03 mol) of phenylphosphoryl dichloride (PPDC) is dropwise added into the system, the reaction is continued for 11h after the dropwise addition, the precipitate is filtered after the reaction is finished, and then the precipitate is washed with deionized water and dioxane for 3 times respectively to obtain the flame retardant modified bentonite-3.
(3) And (3) melting and blending 5 parts by mass of the flame-retardant modified bentonite-3 obtained in the step (2) with 95 parts by mass of polyhydroxyalkanoate at 160 ℃ through a torque rheometer, and then obtaining the flame-retardant polymer composite material through a compression molding process.
Example 4
(1) Firstly, 0.1mol of trichloronitrile (CYC) is dissolved in 300mL of dioxane, and then 50mL of aqueous solution containing 0.1mol of alcohol amine monomer and 0.1mol of NaOH is dropwise added into the system at the temperature of 3 ℃; after 3 hours of reaction, the temperature of the system is raised to 45 ℃, and then 50mL of aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is added into the system dropwise; after reacting for 3 hours, the temperature of the system is raised to 85 ℃, finally, 50mL of aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is added into the system dropwise, white precipitate is separated out through deionized water after reacting for 10 hours, the precipitate is washed for 3 times, and finally, the small molecular flame retardant THT-4 is obtained after drying in a vacuum oven at 60 ℃ for 12 hours.
The structural formula of the alcohol amine monomer is
Wherein R is 1 ＝-CH 3 ，R 2 ＝-CH 2 CH 3 ，R 3 ＝-CH 2 CH 2 -。
(2) 0.56g of bentonite is dispersed in 50mL of acetonitrile solvent for 1h by ultrasonic, then added into 100mL of acetonitrile solution containing 6.9g (0.02 mol) of THT-4 and 6.07g (0.06 mol) of triethylamine (the mass ratio of bentonite to THT-2 is 1:12.3), then the reaction system is vigorously stirred for 24h at 40 ℃, then 6.0g (0.03 mol) of phenylphosphoryl dichloride (PPDC) is dropwise added into the system, the reaction is continued for 11h after the completion of the dropwise addition, the precipitate is filtered after the completion of the reaction, and then the precipitate is washed with deionized water and dioxane for 3 times respectively to obtain flame retardant modified bentonite-4.
(3) 5 parts by mass of flame-retardant modified bentonite-4 and 95 parts by mass of polyhydroxyalkanoate are melt blended at 160 ℃ through a torque rheometer, and then a flame-retardant polymer composite material is obtained through a compression molding process.
Example 5
(1) Firstly, 0.1mol of trichloronitrile (CYC) is dissolved in 300mL of dioxane, and then 50mL of aqueous solution containing 0.1mol of alcohol amine monomer and 0.1mol of NaOH is dropwise added into the system at the temperature of 3 ℃; after 3 hours of reaction, the temperature of the system is raised to 45 ℃, and then 50mL of aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is added into the system dropwise; after reacting for 3 hours, the temperature of the system is raised to 85 ℃, finally, 50mL of aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is added into the system dropwise, white precipitate is separated out through deionized water after reacting for 10 hours, the precipitate is washed for 3 times, and finally, the small molecular flame retardant THT-5 is obtained after drying in a vacuum oven at 60 ℃ for 12 hours.
The structural formula of the alcohol amine monomer is
Wherein R is 1 ＝-CH 2 CH 3 ，R 2 ＝-CH 2 CH 2 CH 3 ，R 3 ＝-CH 2 CH 2 CH 2 -。
(2) 8.76g of bentonite was ultrasonically dispersed in 50mL of acetonitrile solvent for 1 hour, then added to 100mL of acetonitrile solution containing 6.9g (0.02 mol) of THT-5 and 6.07g (0.06 mol) of triethylamine (the mass ratio of bentonite to THT-2 is 1:0.8), then the reaction system was vigorously stirred at 40℃for 24 hours, then 6.0g (0.03 mol) of phenylphosphoryl dichloride (PPDC) was dropwise added to the system, the reaction was continued for 11 hours after the completion of the dropwise addition, the precipitate was filtered after the completion of the reaction, and then the precipitate was washed with deionized water and dioxane, respectively, 3 times to obtain flame retardant modified bentonite-5.
(3) 5 parts by mass of flame-retardant modified bentonite-5 and 95 parts by mass of polyhydroxyalkanoate are melt blended at 160 ℃ through a torque rheometer, and then a flame-retardant polymer is obtained through a compression molding process.
Example 6
(1) Firstly, 0.1mol of trichloronitrile (CYC) is dissolved in 300mL of dioxane, and then 50mL of aqueous solution containing 0.1mol of alcohol amine monomer and 0.1mol of NaOH is dropwise added into the system at the temperature of 3 ℃; after 3 hours of reaction, the temperature of the system is raised to 45 ℃, and then 50mL of aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is added into the system dropwise; after reacting for 3 hours, the temperature of the system is raised to 85 ℃, finally, 50mL of aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is added into the system dropwise, white precipitate is separated out through deionized water after reacting for 10 hours, the precipitate is washed for 3 times, and finally, the small molecular flame retardant THT-6 is obtained after drying in a vacuum oven at 60 ℃ for 12 hours.
The structural formula of the alcohol amine monomer is
Wherein R is 1 ＝-CH 2 CH 3 ，R 2 ＝-CH 3 ，R 3 ＝-CH 2 -。
(2) 3.57g of bentonite was ultrasonically dispersed in 50mL of acetonitrile solvent for 1 hour, then added to 100mL of acetonitrile solution containing 6.9g (0.02 mol) of THT-6 and 6.07g (0.06 mol) of triethylamine, then the reaction system was vigorously stirred at 40℃for 24 hours, then 6.0g (0.03 mol) of phenylphosphoryl dichloride (PPDC) was dropwise added to the system, the reaction was continued for 11 hours after the completion of the dropwise addition, and after the completion of the reaction, the precipitate was filtered, and then washed with deionized water and dioxane, respectively, 3 times to obtain modified bentonite-6.
(3) 5 parts by mass of flame-retardant modified bentonite-6 and 95 parts by mass of polyethylene terephthalate are melt-blended at 260 ℃ through a torque rheometer, and then a flame-retardant polymer is obtained through a compression molding process.
Example 7
(1) Firstly, 0.1mol of trichloronitrile (CYC) is dissolved in 300mL dioxane, and then 50mL aqueous solution containing 0.1mol of alcohol amine monomer and 0.1mol of NaOH is dropwise added into the system at the temperature of 3 ℃; after 3 hours of reaction, the temperature of the system is raised to 45 ℃, and then 50mL aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is added into the system in a dropwise manner; after reacting for 3 hours, the temperature of the system is raised to 85 ℃, finally, 50mL aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is dripped into the system, white precipitate is separated out through deionized water after reacting for 10 hours, the precipitate is washed for 3 times, and finally, the small molecular flame retardant THT-7 is obtained after drying in a vacuum oven at 60 ℃ for 12 hours.
The structural formula of the alcohol amine monomer is
Wherein R is 1 ＝-CH 2 CH 3 ，R 2 ＝-CH 2 CH 2 CH 3 ，R 3 ＝-CH 2 -。
(2) 3.57g bentonite is dispersed in 50mL acetonitrile solvent for 1h by ultrasonic, then added into 100mL acetonitrile solution containing 6.9g (0.02 mol) THT-7 and 6.07g (0.06 mol) triethylamine, then the reaction system is vigorously stirred for 24h at 40 ℃, then 6.0g (0.03 mol) phenylphosphoryl dichloride (PPDC) is added dropwise into the system, the reaction is continued for 11h after the dropwise addition is completed, the precipitate is filtered after the reaction is completed, and then the precipitate is washed with deionized water and dioxane for 3 times respectively to obtain modified bentonite-7.
(3) 5 parts by mass of flame-retardant modified bentonite-7 and 95 parts by mass of polylactic acid are melt-blended at 185 ℃ through a torque rheometer, and then a flame-retardant polymer is obtained through a compression molding process.
Example 8
(1) Firstly, 0.1mol of trichloronitrile (CYC) is dissolved in 300mL dioxane, and then 50mL aqueous solution containing 0.1mol of alcohol amine monomer and 0.1mol of NaOH is dropwise added into the system at the temperature of 3 ℃; after 3 hours of reaction, the temperature of the system is raised to 45 ℃, and then 50mL aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is added into the system in a dropwise manner; after reacting for 3 hours, the temperature of the system is raised to 85 ℃, finally, 50mL aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is dripped into the system, white precipitate is separated out through deionized water after reacting for 10 hours, the precipitate is washed for 3 times, and finally, the small molecular flame retardant THT-8 is obtained after drying in a vacuum oven at 60 ℃ for 12 hours.
The structural formula of the alcohol amine monomer is
Wherein R is 1 ＝-CH 3 ，R 2 ＝-CH 3 ，R 3 ＝-CH 2 CH 2 CH 2 -。
(2) 5.77g bentonite is dispersed in 50mL acetonitrile solvent for 1h by ultrasonic, then added into 100mL acetonitrile solution containing 6.9g (0.02 mol) THT-8 and 6.07g (0.06 mol) triethylamine, then the reaction system is vigorously stirred for 24h at 40 ℃, then 6.0g (0.03 mol) phenylphosphoryl dichloride (PPDC) is added into the system in a dropwise manner, the reaction is continued for 11h after the dropwise addition, the precipitate is filtered after the reaction is finished, and then the precipitate is washed with deionized water and dioxane for 3 times respectively to obtain modified bentonite-8.
(3) 8 parts by mass of flame-retardant modified bentonite-8 and 92 parts by mass of polystyrene are melt-blended at 200 ℃ through a torque rheometer, and then a flame-retardant polymer is obtained through a compression molding process.
Example 9
(1) Firstly, 0.1mol of trichloronitrile (CYC) is dissolved in 300mL of dioxane, and then 50mL of aqueous solution containing 0.1mol of alcohol amine monomer and 0.1mol of NaOH is dropwise added into the system at the temperature of 3 ℃; after 3 hours of reaction, the temperature of the system is raised to 45 ℃, and then 50mL of aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is added into the system dropwise; after reacting for 3 hours, the temperature of the system is raised to 85 ℃, finally, 50mL of aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is added into the system dropwise, white precipitate is separated out through deionized water after reacting for 10 hours, the precipitate is washed for 3 times, and finally, the small molecular flame retardant THT-9 is obtained after drying in a vacuum oven at 60 ℃ for 12 hours.
The structural formula of the alcohol amine monomer is
Wherein R is 1 ＝-CH 3 ，R 2 ＝-CH 3 ，R 3 ＝CH 2 CH 2 -。
(2) 5.77g of bentonite was ultrasonically dispersed in 50mL of acetonitrile solvent for 1 hour, then added to 100mL of acetonitrile solution containing 6.9g (0.02 mol) of THT-2 and 6.07g (0.06 mol) of triethylamine, then the reaction system was vigorously stirred at 40℃for 24 hours, then 6.0g (0.03 mol) of phenylphosphoryl dichloride (PPDC) was dropwise added to the system, the reaction was continued for 11 hours after the completion of the dropwise addition, and after the completion of the reaction, the precipitate was filtered, and then washed with deionized water and dioxane, respectively, 3 times to obtain modified bentonite-9.
(3) 8 parts by mass of flame-retardant modified bentonite-9 and 92 parts by mass of polyglycolic acid are melt-blended at 230 ℃ through a torque rheometer, and then a flame-retardant polymer is obtained through a compression molding process.
The interlayer spacing of the modified bentonite obtained in the example was tested by X-ray diffraction (XRD) experiments under the conditions of a scan range from 2℃to 20℃at a scan rate of 2℃per minute, a voltage of 45kV and a current of 30mA. The test results are shown in Table 1.
TABLE 1
The interlayer spacing of the unmodified bentonite was 1.20nm. As can be seen from Table 1, the prepared modified bentonite has an interlayer spacing of 4.00nm or more and is in a completely peeled state. When the interlayer spacing of the modified bentonite reaches more than 4.00nm, the modified bentonite can be better dispersed in the matrix polymer.
The modified bentonite obtained in example 1 was characterized. Fig. 1 is an XRD pattern before and after bentonite modification. From fig. 1, it can be seen that bentonite exhibits a strong diffraction peak at 2θ=7.35°, which corresponds to the bottom reflection of the bentonite (001) crystal plane, and then the interlayer spacing d of bentonite is calculated to be 1.20nm according to the bragg equation (2dsin θ=nλ), whereas no diffraction peak is observed on the XRD spectrum of modified bentonite-1, and when 2θ=2.00°, the interlayer spacing of bentonite can be calculated to be 4.45nm according to the bragg equation, at which time it can be considered that bentonite is already in the exfoliated state, so that bentonite-1 has reached the exfoliated state after modification.
In order to examine the flame retardancy, heat resistance and mechanical properties of the flame retardant polymers prepared by the method of the present invention, the samples obtained in examples 1 to 9 were tested.
The specific measurement method is as follows:
the material was cut into 90 x 10 x 4mm bars for testing according to GBT 2406.2-2009. If the spline is extinguished within 3 minutes at a certain oxygen content (oxygen volume percent) and does not burn 5cm or less from the lower end of the spline ignition site, then the oxygen content should be increased until either of the above two conditions cannot be met, this critical value being the Limiting Oxygen Index (LOI) of the spline. When the oxygen index (LOI) is less than 22%, the material is considered flammable; when the oxygen index LOI is between 22% and 27%, the material is considered to be a combustible material; when the oxygen index LOI is greater than 27%, the material is considered to be a flame retardant material.
The materials were subjected to the vertical burn (UL-94) test according to ASTM D3801 standard. The sample size was 100X 12X 3mm 3 。
The flame retardant properties of the obtained flame retardant polymers were tested by Limiting Oxygen Index (LOI) experiments, and the results are shown in table 2.
TABLE 2
The mechanical properties of the resulting flame retardant polymers were tested using a universal tensile tester and with reference to standard GB/T1040-2006, with a tensile rate of 10mm/min, and each set of samples was tested 5 times for averaging. The results are shown in Table 3.
TABLE 3 Table 3
The resulting flame retardant polymer was tested for its thermal decomposition behaviour by means of a thermogravimetric analyzer (TGA/DSC/1100 SF). About 10mg of the sample was weighed and placed in a crucible, and the temperature was raised from 40℃to 800℃at a heating rate of 20℃per minute under a nitrogen atmosphere, with a nitrogen flow rate of 50mL/min. The results are shown in Table 4.
TABLE 4 Table 4
As can be seen from tables 1-3, the flame retardant polymer prepared has the following advantages: (1) the flame retardant property is excellent, the limiting oxygen index is more than 27%, and the flame retardant material standard is achieved; (2) the mechanical property is good, and the tensile strength is more than 20MPa; (3) high thermal stability, and high initial decomposition temperature (T 5wt％ ) The carbon residue amount is up to 3.8 at the temperature of more than 250 ℃ and 800 ℃. Thus, the first and second substrates are bonded together,the flame-retardant polymer obtained by the invention can be used in the fields of daily necessities, office supplies, traffic equipment, building industry, light industry and the like.
Example 10: condition optimization of modified bentonite
Referring to example 1, the conditions in step (2) were modified, and the corresponding flame retardant polymer was prepared with the other modifications.
The mass ratio of bentonite to THT-1 in the step (2) is only changed, the other materials are unchanged, and the corresponding obtained flame-retardant polymer is measured, wherein the performance result is as follows:
| mass ratio of bentonite to THT-1 | 1:0.19 | 1:1.9 | 1:3.8 | 1:5.7 | 1:7.6 | 1:19 |
| LOI(％) | 25.7 | 32.4 | 27.4 | 29.1 | 30.1 | 24.6 |
| Tensile Strength (MPa) | 18.9 | 23.8 | 21.5 | 20.1 | 22.8 | 20.3 |
| T 5wt％ (℃) | 262.1 | 286.4 | 285.7 | 276.5 | 281.4 | 259.8 |
| Carbon residue at 800 ℃ (%) | 3.1 | 4.0 | 3.8 | 3.4 | 3.0 | 3.0 |
(II) changing only the molar ratio of THT-1 to phenylphosphoryl dichloride in the step (2), and measuring the corresponding obtained flame-retardant polymer, wherein the performance results are shown as follows:
and (III) only changing the mass ratio of bentonite to triethylamine in the step (2), and measuring the corresponding obtained flame-retardant polymer without changing the other materials, wherein the performance results are shown as follows:
| mass ratio of bentonite to triethylamine | 1:0.17 | 1:1.7 | 1:3.4 | 1:5.1 | 1:6.8 | 1:17 |
| LOI(％) | 23.7 | 32.4 | 28.6 | 28.0 | 27.6 | 25.1 |
| Tensile Strength (MPa) | 19.9 | 23.8 | 21.6 | 21.9 | 22.0 | 17.5 |
| T 5wt％ (℃) | 264.8 | 286.4 | 295.5 | 289.1 | 282.5 | 262.1 |
| Carbon residue at 800 ℃ (%) | 3.1 | 4.0 | 3.5 | 3.1 | 3.3 | 3.0 |
Comparative example 1:
compared with the example 1, the addition forms (physical mixing) of the branched flame retardant, bentonite and the polymer are changed, the dosage of the polymer is unchanged, and the flame-retardant polymer is prepared as follows:
(1) Firstly, 0.1mol of trichloronitrile (CYC) is dissolved in 300mL of dioxane, and then 50mL of aqueous solution containing 0.1mol of alcohol amine monomer and 0.1mol of NaOH is dropwise added into the system at the temperature of 3 ℃; after 3 hours of reaction, the temperature of the system is raised to 45 ℃, and then 50mL of aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is added into the system dropwise; after reacting for 3 hours, the temperature of the system is raised to 85 ℃, finally, 50mL of aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is added into the system dropwise, white precipitate is separated out through deionized water after reacting for 10 hours, the precipitate is washed for 3 times, and finally, the small molecular flame retardant THT-1 is obtained after drying in a vacuum oven at 60 ℃ for 12 hours.
Wherein the structural formula of the alcohol amine monomer is
Wherein R is 1 ＝-CH 3 ，R 2 ＝-CH 3 ，R 3 ＝-CH 2 -。
(2) 6.9g (0.02 mol) of THT and 6.07g (0.06 mol) of Triethylamine (TEA) are added into 200mL of acetonitrile solution, 6.0g (0.03 mol) of phenylphosphoryl dichloride (PPDC) is added into the reaction system dropwise at the temperature of 3 ℃, after 2 hours of reaction, the reaction system is heated to 40 ℃ and then the reaction is continued for 11 hours, after the reaction is finished, the filtrate is filtered and collected, the precipitate is obtained by rotary evaporation, and then deionized water and dioxane are respectively used for washing the precipitate for 3 times to obtain the hyperbranched macromolecular flame retardant HBM.
Dispersing the obtained hyperbranched macromolecular flame retardant HBM in 100mL of acetonitrile solvent; then 50mL of acetonitrile dispersion containing 3.57g of bentonite was added, mixed well, stirred at 40 ℃ for 24 hours, and then the solid was collected by filtration and dried to obtain a mixed flame retardant.
(3) 5 parts by mass of the mixed flame retardant and 95 parts by mass of polyhydroxyalkanoate are melt-blended at 160 ℃ through a torque rheometer, and then a flame-retardant polymer is obtained through a compression molding process.
The macromolecular flame retardant obtained in the step (2) is subjected to 1 H NMR was characterized and the results are shown in fig. 2. In the figure, the chemical shift (. Delta.) occurs at-CH at 1.14-1.47 3 Delta appears-CH at 3.71-3.73 and 4.28-4.31 2 An absorption peak of-OH at 4.90-5.04, an absorption peak of phenyl at 7.23-7.52, an absorption peak of-NH-at 7.62-7.95, 1 the results of H NMR demonstrate the success of the synthesis of macromolecular flame retardants.
It was confirmed that the macromolecular flame retardant having the following repeating structural units was actually synthesized:
also illustrated is the bentonite modification of example 1, in which the macromolecular flame retardant is synthesized in situ between layers of bentonite to achieve intercalation stripping.
Comparative example 2:
compared with the example 1, the flame retardant polymer is prepared by changing the structure of the branched flame retardant and keeping the polymer dosage unchanged, and the specific steps are as follows:
(1) Firstly, 0.1mol of polychlorinated nitrile (CYC) is dissolved in 300mL of dioxane, and then 50mL of aqueous solution containing 0.1mol of alcohol amine monomer and 0.1mol of NaOH is dropwise added into the system at the temperature of 3 ℃; after 3 hours of reaction, the temperature of the system is raised to 45 ℃, and then 50mL of aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is added into the system dropwise; after 3 hours of reaction, the temperature of the system is raised to 85 ℃, finally 50mL of aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is added into the system dropwise, white precipitate is separated out through deionized water after 10 hours of reaction, the precipitate is washed for 3 times, and finally the small molecular flame retardant THT-10 is obtained after drying in a vacuum oven at 60 ℃ for 12 hours. The structural formula of the alcohol amine monomer is
Wherein R is 1 ＝-CH 2 CH 3 ，R 2 ＝-CH 2 CH 2 CH 2 CH 3 ，R 3 ＝-CH 2 CH 2 -。
(2) 3.57g of bentonite was ultrasonically dispersed in 50mL of acetonitrile solvent for 1 hour, then added to 100mL of acetonitrile solution containing 6.9g (0.02 mol) of THT-10 and 6.07g (0.06 mol) of triethylamine, then the reaction system was vigorously stirred at 40℃for 24 hours, then 6.0g (0.03 mol) of phenylphosphoryl dichloride (PPDC) was added dropwise to the system, the reaction was continued for 11 hours after the completion of the dropwise addition, the precipitate was filtered after the completion of the reaction, and then the precipitate was washed with deionized water and dioxane, respectively, 3 times to obtain modified bentonite-10.
(3) 5 parts by mass of modified bentonite-10 and 95 parts by mass of polyhydroxyalkanoate are melt blended at 160 ℃ through a torque rheometer, and then a flame-retardant polymer is obtained through a compression molding process.
Comparative example 3:
compared with the example 1, the branched flame retardant is changed into a small molecular flame retardant THT-1, the polymer dosage is unchanged, and the flame retardant polymer is prepared as follows:
(1) Firstly, 0.1mol of trichloronitrile (CYC) is dissolved in 300mL of dioxane, and then 50mL of aqueous solution containing 0.1mol of alcohol amine monomer and 0.1mol of NaOH is dropwise added into the system at the temperature of 3 ℃; after 3 hours of reaction, the temperature of the system is raised to 45 ℃, and then 50mL of aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is added into the system dropwise; after 3 hours of reaction, the temperature of the system is raised to 85 ℃, finally 50mL of aqueous solution containing 0.1mol of the same alcohol amine monomer and 0.1mol of NaOH is added into the system dropwise, white precipitate is separated out through deionized water after 10 hours of reaction, the precipitate is washed for 3 times, and finally the small molecular flame retardant THT-1 is obtained after drying in a vacuum oven at 60 ℃ for 12 hours.
The structural formula of the alcohol amine monomer is
Wherein R is 1 ＝-CH 3 ，R 2 ＝-CH 3 ，R 3 ＝-CH 2 -。
3.57g of bentonite was then mixed with 12.9g of the THT-1 obtained to give a flame-retardant mixture.
(2) 5 parts by mass of the flame retardant mixture and 95 parts by mass of polyhydroxyalkanoate are melt-blended at 160 ℃ by a torque rheometer, and then a flame retardant polymer is obtained by a compression molding process.
The flame retardant polymer in the comparative example was measured by the same method as mentioned in example 1. The results are shown in Table 5.
TABLE 5
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| LOI(％) | 26.8 | 25.4 | 26.1 |
| Tensile Strength (MPa) | 17.2 | 17.5 | 18.1 |
| T 5wt％ (℃) | 248.5 | 243.2 | 246.7 |
| Carbon residue at 800 ℃ (%) | 2.9 | 2.4 | 2.5 |
Those of ordinary skill in the art will appreciate that: the discussion of any of the embodiments above is merely exemplary and is not intended to suggest that the scope of the disclosure, including the claims, is limited to these examples; combinations of features of the above embodiments or in different embodiments are also possible within the idea of the invention, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity. Therefore, any omission, modification, equivalent replacement, improvement, etc. of the present invention should be included in the scope of the present invention.
Claims (10)
1. The preparation method of the flame-retardant polymer is characterized in that the flame-retardant polymer is prepared by melt blending or suspension pouring of the polymer and modified bentonite;
the modified bentonite is prepared by the following steps:
(1) The method comprises the steps of (1) reacting trichloronitrile (CYC) with alcohol amine monomers in an alkaline environment to obtain a micromolecular flame retardant triazine compound;
(2) Then dispersing the obtained micromolecular flame retardant triazine compound, bentonite and an alkali reagent in an organic solvent, uniformly mixing and reacting for a period of time; then dripping phenyl phosphoryl dichloride for continuous reaction, after the reaction is finished, separating solid from liquid, collecting solid, and washing to obtain the modified bentonite.
2. The flame retardant polymer of claim 1, wherein the method of preparing the flame retardant polymer comprises:
method one, melt blending: taking 1-8 parts by weight of modified bentonite and 92-95 parts by weight of polymer, melt blending at a certain temperature through an extruder or a torque rheometer, and then obtaining a flame-retardant polymer through a molding process;
or, method two, suspension casting: 1-8 parts by weight of modified bentonite is added into methylene dichloride to obtain uniform suspension, 92-95 parts by weight of polymer is dissolved into the suspension, and then the suspension is poured into a film, and the flame-retardant polymer is obtained through a molding process.
3. The flame retardant polymer of claim 1, wherein the structure of the alcohol amine monomer is as follows:
wherein R is 1 ＝-(CH 2 ) x CH 3 X is 0-1; r is R 2 ＝-(CH 2 ) y CH 3 Y is 0-3; r is R 3 ＝-(CH 2 ) z Z is 1 to 3.
4. The flame retardant polymer according to claim 1, wherein in the preparation of the modified bentonite, the mass ratio of bentonite to the small molecular flame retardant triazine compound in the step (2) is 1: (1.9-7.6).
5. The flame-retardant polymer according to claim 1, wherein in the preparation of the modified bentonite, the molar ratio of the small molecular flame retardant triazine compound to the phenylphosphoryl dichloride in the step (2) (2-8): 3.
6. the flame retardant polymer according to claim 1, wherein in the preparation process of the modified bentonite, the mass ratio of bentonite to alkali agent in the step (2) is 1: (1.7-6.8).
7. The flame retardant polymer of claim 1, wherein the small molecule flame retardant triazine compound has the structure shown below:
wherein R is 1 ＝-(CH 2 ) x CH 3 X is 0-1; r is R 2 ＝-(CH 2 ) y CH 3 Y is 0-3; r is R 3 ＝-(CH 2 ) z Z is 1 to 3.
8. The flame-retardant polymer according to claim 1, wherein in the preparation process of the modified bentonite, the phenyl phosphoryl dichloride is dropwise added in the step (2) to continue the reaction, and the micromolecular flame retardant triazine compound and the phosphorus chloride compound are subjected to polymerization reaction between bentonite layers to generate hyperbranched macromolecule flame retardant to peel off the modified bentonite;
the structural repeating units of the hyperbranched macromolecular flame retardant are shown as follows:
wherein R is 1 ＝-(CH 2 ) x CH 3 X is0-1；R 2 ＝-(CH 2 ) y CH 3 Y is 0-3; r is R 3 ＝-(CH 2 ) z Z is 1 to 3.
9. A flame retardant polymer prepared by the method of any one of claims 1-8.
10. Use of the flame retardant polymer according to claim 9 in the fields of medical device preparation, textiles, construction and transportation.
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