CN116178880B - Preparation method of intumescent flame retardant modified ABS resin - Google Patents
Preparation method of intumescent flame retardant modified ABS resin Download PDFInfo
- Publication number
- CN116178880B CN116178880B CN202310231049.7A CN202310231049A CN116178880B CN 116178880 B CN116178880 B CN 116178880B CN 202310231049 A CN202310231049 A CN 202310231049A CN 116178880 B CN116178880 B CN 116178880B
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- intumescent flame
- abs resin
- preparation
- aminophenylpiperazine
- 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
- 239000003063 flame retardant Substances 0.000 title claims abstract description 64
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 47
- 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 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 24
- YZTJYBJCZXZGCT-UHFFFAOYSA-N phenylpiperazine Chemical compound C1CNCCN1C1=CC=CC=C1 YZTJYBJCZXZGCT-UHFFFAOYSA-N 0.000 claims abstract description 21
- DAURIJZNKHAJSE-UHFFFAOYSA-N 4-phenylpiperazin-1-amine Chemical compound C1CN(N)CCN1C1=CC=CC=C1 DAURIJZNKHAJSE-UHFFFAOYSA-N 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- DPCIKFOUKGFQCM-UHFFFAOYSA-N 1-nitro-4-phenylpiperazine Chemical compound C1CN([N+](=O)[O-])CCN1C1=CC=CC=C1 DPCIKFOUKGFQCM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 238000010074 rubber mixing Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 abstract description 6
- 238000002485 combustion reaction Methods 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- QDCJIPFNVBDLRH-UHFFFAOYSA-N 5,5-dimethyl-1,3-dioxane Chemical compound CC1(C)COCOC1 QDCJIPFNVBDLRH-UHFFFAOYSA-N 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052794 bromium Inorganic materials 0.000 abstract description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003763 carbonization Methods 0.000 abstract 1
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- -1 flame retardant modified ABS Chemical class 0.000 description 17
- 239000000203 mixture Substances 0.000 description 8
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 6
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000012802 nanoclay Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
-
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention relates to the technical field of ABS resin, and discloses a preparation method of an intumescent flame retardant modified ABS resin, wherein piperazine reacts with p-chloronitrobenzene to obtain p-nitrophenylpiperazine, and palladium carbon is subjected to catalytic hydrogenation to obtain p-aminophenylpiperazine. The p-aminophenylpiperazine reacts with 5, 5-dimethyl-1, 3-dioxan endophosphoryl chloride to obtain a novel halogen-free biphosphoryl phenylpiperazine intumescent flame retardant, which does not contain halogen elements such as bromine and the like, and is environment-friendly; and then melt blending with ABS to obtain the ABS resin modified by the intumescent flame retardant. Phenyl is used as a carbon source, and dehydration and carbonization are carried out. Phosphorus element in the biphosphoryl phenylpiperazine intumescent flame retardant is used as an acid source, and metaphosphoric acid is formed during combustion. The nitrogen element is taken as an air source and does not react with air in a burning way, so that the carbon layer can be expanded, and the purpose of flame retardance is achieved.
Description
Technical Field
The invention relates to the technical field of ABS (Acrylonitrile butadiene styrene) resin, in particular to a preparation method of an intumescent flame retardant modified ABS resin.
Background
ABS is a graft copolymer of three monomers of acrylonitrile, 1, 3-butadiene and styrene, has the characteristics of high strength, good toughness, strong impact resistance, easy processing, good thermoplasticity and good wear resistance, and is often applied to the fields of automobiles, electronic and electric appliances, building materials and DIY manufacturing. However, the flame retardance of the ABS resin is poor, so how to improve the flame retardance of the ABS resin becomes a current hot spot, such as the modified flame-retardant acrylonitrile-butadiene-styrene copolymer compounded by the organized nano clay and the intumescent flame retardant disclosed in the document 'intumescent flame retardant/nano clay compound flame retardant ABS', and the nano clay can obviously reduce the heat release rate, the peak heat release rate and the total heat release amount of the ABS resin in a cone-shaped calorimetric test, thereby being beneficial to slowing down the fire spread.
The flame retardant can increase the heat resistance of the high polymer material, is mainly applied to flammable materials such as plastics, rubber, fibers and the like, and needs three main components of an acid source, a carbon source and an air source for generating expansion effect. The phosphorus-containing flame retardant forms metaphosphoric acid during combustion, and the metaphosphoric acid is polymerized into a stable multimerization state, so that oxygen can be isolated, and the metaphosphoric acid becomes a protective layer of the material. The carbon source is dehydrated and carbonized during combustion, heat transfer and oxygen diffusion are blocked, and development of a novel intumescent flame retardant is a research hotspot, and as in paper on design and synthesis of intumescent flame retardants of phosphate and cyanuric chloride and research on solid-liquid phase balance, phenol containing benzene rings is used as a carbon source, phosphorus oxychloride is used as an acid source, piperazine is used as a nitrogen source, and an N, N-piperazine diphenyl phosphate intumescent flame retardant is synthesized, so that the novel intumescent flame retardant has excellent flame retardant effect; the novel intumescent flame retardant biphosphoryl phenylpiperazine prepared by the invention is used for modifying ABS resin.
Disclosure of Invention
(One) solving the technical problems
Aiming at the defects of the prior art, the invention provides a preparation method of an intumescent flame retardant modified ABS resin, which solves the problem of flammability of the ABS resin.
(II) technical scheme
A preparation method of an intumescent flame retardant modified ABS resin, which comprises the following steps:
(1) Preparation of para-aminophenylpiperazine
Adding piperazine, p-chloronitrobenzene and potassium carbonate into a flask filled with N, N-dimethylformamide at 100-120 ℃, stirring and reacting for 18-24h, cooling to room temperature, adding water to separate out precipitate, filtering with water, washing with N-hexane, and obtaining p-nitrophenylpiperazine.
Placing p-nitrophenylpiperazine in a reaction kettle ventilated by nitrogen at 60-70 ℃, adding n-butanol and Pd/C, controlling the hydrogen pressure to be 0.5-1MPa, reacting for 5-10h, heating to 100-120 ℃, reacting for 2-4h, cooling to room temperature after reaction, crystallizing, washing by methanol, and drying to obtain p-aminophenylpiperazine.
(2) Preparation of biphosphoryl phenylpiperazine intumescent flame retardant
Adding p-aminophenylpiperazine, 5-dimethyl-1, 3-dioxan endophosphoryl chloride and triethylamine into a flask filled with a solvent, stirring at room temperature for reaction for 18-36h, distilling after the reaction, washing with water and recrystallizing to obtain the biphosphorylpiperazine intumescent flame retardant.
(3) Preparation of intumescent flame retardant modified ABS resin
And (3) blending the ABS resin and the biphosphoryl phenylpiperazine intumescent flame retardant in a mass ratio of 1:0.02-0.1 on an open rubber mixing mill at a roller temperature of 180-220 ℃ for 2-4min to obtain the intumescent flame retardant modified ABS resin.
Preferably, the mass ratio of piperazine, p-chloronitrobenzene and potassium carbonate in the step (1) is 1:3.5-4.2:2.5-3.5.
Preferably, the mass ratio of the p-nitrophenylpiperazine to the Pd/C catalyst in the step (1) is 1:0.2-0.3.
Preferably, the solvent of step (2) comprises acetonitrile, ethyl acetate, tetrahydrofuran, acetone or 1, 4-dioxane.
Preferably, in the step (2), the mass ratio of the p-aminophenylpiperazine to the 5, 5-dimethyl-1, 3-dioxaphosphorized chloride to the triethylamine is 1:1.4-1.8:1.5-2.2.
(III) beneficial technical effects
The piperazine reacts with p-chloronitrobenzene to obtain p-nitrophenylpiperazine, and palladium carbon catalytic hydrogenation is carried out to obtain p-aminophenylpiperazine. The p-aminophenylpiperazine reacts with 5, 5-dimethyl-1, 3-dioxan endophosphoryl chloride to obtain a novel halogen-free biphosphoryl phenylpiperazine intumescent flame retardant, which does not contain halogen elements such as bromine and the like, and is environment-friendly; and then melt blending with ABS to obtain the intumescent flame retardant modified ABS resin. Wherein the phenyl is used as a carbon source, dehydrated and carbonized, and is attached to the surface of the inflammable material to isolate air so as to achieve the aim of flame retardance. Phosphorus element in the biphosphoryl phenylpiperazine intumescent flame retardant is used as an acid source, metaphosphoric acid is formed during combustion, and the metaphosphoric acid is polymerized into stable polymer state to be attached to the surface of the inflammable material. The nitrogen element is used as an air source, the gas generated by decomposition does not react with air in a combustion way, the gas can expand the carbon layer, a fluffy and porous carbon layer is formed on the surface of the carbon layer, oxygen is isolated, and the flame-retardant polymer is combusted so as to achieve the aim of flame retardance.
Drawings
FIG. 1 is a route to the preparation of a biphosphoryl phenylpiperazine intumescent flame retardant.
Detailed Description
Example 1
(1) Preparation of para-aminophenylpiperazine
To a flask containing N, N-dimethylformamide at 120℃were added 2g of piperazine, 7.5g of p-chloronitrobenzene and 6g of potassium carbonate, and the mixture was stirred and reacted for 24 hours, cooled to room temperature, water was added to precipitate, and the precipitate was filtered with water, washed with N-hexane to obtain p-nitrophenylpiperazine.
Placing 3g of p-nitrophenylpiperazine into a reaction kettle ventilated by nitrogen at 65 ℃, adding n-butanol and 0.8g of Pd/C, controlling the hydrogen pressure to be 1MPa, reacting for 8 hours, heating to 120 ℃, reacting for 2 hours, cooling to room temperature after the reaction, crystallizing, washing by methanol, and drying to obtain the p-aminophenylpiperazine.
(2) Preparation of biphosphoryl phenylpiperazine intumescent flame retardant
2G of p-aminophenylpiperazine, 3g of 5, 5-dimethyl-1, 3-dioxaphosphorized chloride and 4g of triethylamine are added into a flask filled with tetrahydrofuran solvent, stirred at room temperature for reaction for 36 hours, distilled after reaction, washed with water and recrystallized to obtain the biphosphorylpiperazine intumescent flame retardant.
(3) Preparation of intumescent flame retardant modified ABS resin
At the roller temperature of 210 ℃, ABS resin with the mass of 200g and 4g of biphosphoryl phenylpiperazine intumescent flame retardant are mixed on an open rubber mixing mill, and the mixing time is 2min, so that the intumescent flame retardant modified ABS resin is obtained.
Example 2
(1) Preparation of para-aminophenylpiperazine
To a flask containing N, N-dimethylformamide at 100℃were added 2g of piperazine, 7g of p-chloronitrobenzene and 6g of potassium carbonate, and the mixture was stirred and reacted for 20 hours, cooled to room temperature, water was added to precipitate, and the precipitate was filtered with water, washed with N-hexane to obtain p-nitrophenylpiperazine.
Placing 3g of p-nitrophenylpiperazine into a reaction kettle ventilated by nitrogen at 65 ℃, adding n-butanol and 0.9g of Pd/C, controlling the hydrogen pressure to be 1MPa, reacting for 5 hours, heating to 110 ℃, reacting for 3 hours, cooling to room temperature after the reaction, crystallizing, washing by methanol, and drying to obtain the p-aminophenylpiperazine.
(2) Preparation of biphosphoryl phenylpiperazine intumescent flame retardant
2G of p-aminophenylpiperazine, 2.8g of 5, 5-dimethyl-1, 3-dioxaphosphorized chloride and 3g of triethylamine are added into a flask filled with acetonitrile solvent, stirred at room temperature for reaction for 24 hours, distilled after reaction, washed with water and recrystallized to obtain the biphosphorylpiperazine intumescent flame retardant.
(3) Preparation of intumescent flame retardant modified ABS resin
At the roller temperature of 220 ℃, ABS resin with the mass of 200g and 8g of biphosphoryl phenylpiperazine intumescent flame retardant are mixed on an open rubber mixing mill, and the mixing time is 4min, thus obtaining the intumescent flame retardant modified ABS resin.
Example 3
(1) Preparation of para-aminophenylpiperazine
To a flask containing N, N-dimethylformamide at 100℃were added 2g of piperazine, 7g of p-chloronitrobenzene and 5g of potassium carbonate, and the mixture was stirred and reacted for 18 hours, cooled to room temperature, water was added to precipitate, and the precipitate was filtered with water, washed with N-hexane to obtain p-nitrophenylpiperazine.
Placing 3g of p-nitrophenylpiperazine in a reaction kettle ventilated by nitrogen at 60 ℃, adding n-butanol and 0.6g of Pd/C, controlling the hydrogen pressure to be 0.5MPa, reacting for 5 hours, heating to 100 ℃, reacting for 2 hours, cooling to room temperature after the reaction, crystallizing, washing by methanol, and drying to obtain the p-aminophenylpiperazine.
(2) Preparation of biphosphoryl phenylpiperazine intumescent flame retardant
2G of p-aminophenylpiperazine, 3g of 5, 5-dimethyl-1, 3-dioxaphosphorized chloride and 4g of triethylamine are added into a flask filled with an ethyl acetate solvent, the mixture is stirred at room temperature for reaction for 18 hours, and after the reaction, the mixture is distilled, washed with water and recrystallized, so that the biphosphorylpiperazine intumescent flame retardant is obtained.
(3) Preparation of intumescent flame retardant modified ABS resin
At the roller temperature of 220 ℃, ABS resin with the mass of 200g and 10g of biphosphoryl phenylpiperazine intumescent flame retardant are mixed on an open rubber mixing mill, and the mixing time is 4min, thus obtaining the intumescent flame retardant modified ABS resin.
Example 4
(1) Preparation of para-aminophenylpiperazine
To a flask containing N, N-dimethylformamide at 120℃were added 2g of piperazine, 8.4g of p-chloronitrobenzene and 7g of potassium carbonate, and the mixture was stirred and reacted for 24 hours, cooled to room temperature, water was added to precipitate, and the precipitate was filtered with water, washed with N-hexane to obtain p-nitrophenylpiperazine.
3G of p-nitrophenylpiperazine is placed in a reaction kettle ventilated by nitrogen at 70 ℃, n-butanol and 0.9g of Pd/C are added, the reaction is carried out for 10 hours under the condition that the hydrogen pressure is controlled to be 1MPa, the temperature is raised to 120 ℃ for 4 hours, and the p-aminophenylpiperazine is obtained after cooling to room temperature, crystallizing, washing by methanol and drying after the reaction.
(2) Preparation of biphosphoryl phenylpiperazine intumescent flame retardant
2G of p-aminophenylpiperazine, 2.8g of 5, 5-dimethyl-1, 3-dioxaphosphorized chloride and 4.4g of triethylamine are added into a flask filled with an acetone solvent, and the mixture is stirred at room temperature for reaction for 18 hours, distilled after the reaction, washed with water and recrystallized to obtain the biphosphorylpiperazine intumescent flame retardant.
(3) Preparation of intumescent flame retardant modified ABS resin
At the roller temperature of 200 ℃, ABS resin with the mass of 200g and biphosphoryl phenylpiperazine intumescent flame retardant with the mass of 15g are mixed on an open rubber mixing mill, and the mixing time is 3min, thus obtaining the intumescent flame retardant modified ABS resin.
Example 5
(1) Preparation of para-aminophenylpiperazine
To a flask containing N, N-dimethylformamide at 110℃were added 2g of piperazine, 8g of p-chloronitrobenzene and 6g of potassium carbonate, and the mixture was stirred and reacted for 24 hours, cooled to room temperature, water was added to precipitate, and the precipitate was filtered with water, washed with N-hexane to obtain p-nitrophenylpiperazine.
Placing 3g of p-nitrophenylpiperazine in a reaction kettle ventilated by nitrogen at 60 ℃, adding n-butanol and 0.8g of Pd/C, controlling the hydrogen pressure to be 1MPa, reacting for 5 hours, heating to 100 ℃, reacting for 3 hours, cooling to room temperature after the reaction, crystallizing, washing by methanol, and drying to obtain the p-aminophenylpiperazine.
(2) Preparation of biphosphoryl phenylpiperazine intumescent flame retardant
2G of p-aminophenylpiperazine, 3.6g of 5, 5-dimethyl-1, 3-dioxan inner phosphoryl chloride and 3.8g of triethylamine are added into a flask filled with a1, 4-dioxane solvent, stirred and reacted for 24 hours at room temperature, distilled, washed with water and recrystallized to obtain the biphosphoryl phenylpiperazine intumescent flame retardant.
(3) Preparation of intumescent flame retardant modified ABS resin
At the roller temperature of 200 ℃, ABS resin with the mass of 200g and 20g of biphosphoryl phenylpiperazine intumescent flame retardant are mixed on an open rubber mixing mill, and the mixing time is 3min, thus obtaining the intumescent flame retardant modified ABS resin.
Tensile properties were measured according to GB/T1040.3-2006.
Flame retardancy was tested according to GB/T2406.1-2008.
The tensile strength of example 4 was the greatest, reaching 66.3MPa. The limiting oxygen index of example 5 was at a maximum of 33.5%.
Claims (5)
1. A preparation method of an intumescent flame retardant modified ABS resin is characterized in that: the preparation method comprises the following steps:
(1) Preparation of para-aminophenylpiperazine
Adding piperazine, p-chloronitrobenzene and potassium carbonate into a flask filled with N, N-dimethylformamide at 100-120 ℃, stirring and reacting for 18-24h, cooling to room temperature, adding water to separate out precipitate, filtering with water, washing with N-hexane, and obtaining p-nitrophenylpiperazine;
Placing p-nitrophenylpiperazine in a reaction kettle ventilated by nitrogen at 60-70 ℃, adding n-butanol and Pd/C, controlling the hydrogen pressure to be 0.5-1MPa, reacting for 5-10h, heating to 100-120 ℃, reacting for 2-4h, cooling to room temperature after reaction, crystallizing, washing by methanol, and drying to obtain p-aminophenylpiperazine;
(2) Preparation of biphosphoryl phenylpiperazine intumescent flame retardant
Adding p-aminophenylpiperazine, 5-dimethyl-1, 3-dioxan endophosphoryl chloride and triethylamine into a flask filled with a solvent, stirring at room temperature for reaction for 18-36h, distilling after reaction, washing with water, and recrystallizing to obtain a biphosphorylpiperazine intumescent flame retardant;
(3) Preparation of intumescent flame retardant modified ABS resin
And (3) blending the ABS resin and the biphosphoryl phenylpiperazine intumescent flame retardant in a mass ratio of 1:0.02-0.1 on an open rubber mixing mill at a roller temperature of 180-220 ℃ for 2-4min to obtain the intumescent flame retardant modified ABS resin.
2. The method for producing an intumescent flame retardant modified ABS resin according to claim 1, characterized in that: in the step (1), the mass ratio of piperazine to chloronitrobenzene to potassium carbonate is 1:3.5-4.2:2.5-3.5.
3. The method for producing an intumescent flame retardant modified ABS resin according to claim 1, characterized in that: the mass ratio of the p-nitrophenylpiperazine to the Pd/C catalyst in the step (1) is 1:0.2-0.3.
4. The method for producing an intumescent flame retardant modified ABS resin according to claim 1, characterized in that: the solvent in the step (2) comprises acetonitrile, ethyl acetate, tetrahydrofuran, acetone or 1, 4-dioxane.
5. The method for producing an intumescent flame retardant modified ABS resin according to claim 1, characterized in that: in the step (2), the mass ratio of the p-aminophenylpiperazine to the 5, 5-dimethyl-1, 3-dioxaphosphorized chloride to the triethylamine is 1:1.4-1.8:1.5-2.2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310231049.7A CN116178880B (en) | 2023-03-13 | 2023-03-13 | Preparation method of intumescent flame retardant modified ABS resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310231049.7A CN116178880B (en) | 2023-03-13 | 2023-03-13 | Preparation method of intumescent flame retardant modified ABS resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116178880A CN116178880A (en) | 2023-05-30 |
| CN116178880B true CN116178880B (en) | 2024-05-28 |
Family
ID=86442371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310231049.7A Active CN116178880B (en) | 2023-03-13 | 2023-03-13 | Preparation method of intumescent flame retardant modified ABS resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116178880B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117964984B (en) * | 2024-03-29 | 2024-05-31 | 广州豫顺新材料科技有限公司 | Preparation method of nano silicon dioxide composite flame retardant modified polystyrene |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004203846A (en) * | 2002-12-26 | 2004-07-22 | Polyplastics Co | Guanamine compound and its flame-retardant resin composition |
| CN103113409A (en) * | 2013-02-05 | 2013-05-22 | 东华大学 | Triazine ring structure containing caged organic phosphate and preparation method thereof |
| CN107286563A (en) * | 2017-07-06 | 2017-10-24 | 上海化工研究院有限公司 | A kind of expansion type flame retardant and its preparation and application for ABS electric switch outer covers |
| CN112457494A (en) * | 2020-12-14 | 2021-03-09 | 苏州苏克新型材料有限公司 | Method for manufacturing liquid crystal optical film |
| CN115584074A (en) * | 2022-11-14 | 2023-01-10 | 李小菊 | A kind of degradable flame-retardant modified polyethylene plastic and its preparation method |
-
2023
- 2023-03-13 CN CN202310231049.7A patent/CN116178880B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004203846A (en) * | 2002-12-26 | 2004-07-22 | Polyplastics Co | Guanamine compound and its flame-retardant resin composition |
| CN103113409A (en) * | 2013-02-05 | 2013-05-22 | 东华大学 | Triazine ring structure containing caged organic phosphate and preparation method thereof |
| CN107286563A (en) * | 2017-07-06 | 2017-10-24 | 上海化工研究院有限公司 | A kind of expansion type flame retardant and its preparation and application for ABS electric switch outer covers |
| CN112457494A (en) * | 2020-12-14 | 2021-03-09 | 苏州苏克新型材料有限公司 | Method for manufacturing liquid crystal optical film |
| CN115584074A (en) * | 2022-11-14 | 2023-01-10 | 李小菊 | A kind of degradable flame-retardant modified polyethylene plastic and its preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 1-(4-甲氧基苯基)-4-(4-氨基苯基)哌嗪的合成;童国通等;精细化工中间体;20031231;第33卷(第06期);第34-35, 45, 62页 * |
| 一种新型复配体系对ABS树脂的阻燃性能研究;刘伟等;新型工业化;20151231;第5卷(第02期);第1-6页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116178880A (en) | 2023-05-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106496729B (en) | Flame retardant polymer materials based on phosphorus-containing char-forming agent and hypophosphorous/phosphonate compound | |
| Peng et al. | A bio-based phosphaphenanthrene-containing derivative modified epoxy thermosets with good flame retardancy, high mechanical properties and transparency | |
| CN104371116B (en) | Preparation method and application of lignin-based intumescent flame retardant | |
| CN116178880B (en) | Preparation method of intumescent flame retardant modified ABS resin | |
| CN104725665B (en) | A kind of spiro-phosphate fire retardant containing s-triazine structure, preparation method and applications | |
| CN100463952C (en) | A kind of phosphorus-containing triazine ring flame retardant and preparation method thereof | |
| CN105175735B (en) | A kind of branched Phosphorus-nitrogen flame retardant and preparation method thereof | |
| CN110746646B (en) | Biomass-based flame retardant and preparation method thereof | |
| CN118108924B (en) | Halogen-free flame-retardant polyurethane elastomer and preparation process thereof | |
| CN115850641B (en) | Flame-retardant modified polyurethane material and synthesis method thereof | |
| CN113429628A (en) | Expandable phytate flame retardant, flame-retardant epoxy resin, and preparation method and application thereof | |
| CN105924645A (en) | Halogen-free expanding flame retardant containing polymeric macromolecule triazine rings and preparation method of halogen-free expanding flame retardant | |
| CN118047926B (en) | Preparation method of flame-retardant bio-based thermoplastic polyurethane elastomer | |
| CN106397778A (en) | Method for increasing yield and polymerization degree of polymeric phosphorus-nitrogen intumescent flame retardant | |
| CN113637160A (en) | Phosphorus-nitrogen star-shaped flame retardant containing triazine structure and preparation method and application thereof | |
| CN111606948B (en) | A kind of high-efficiency phosphine-nitrogen flame retardant and its preparation method and application | |
| CN115403709A (en) | Flame-retardant polypropylene foam plastic and preparation method thereof | |
| CN118006108B (en) | Polycarbonate material containing polymer halogen-free flame retardant and preparation process thereof | |
| CN110643066A (en) | Novel phosphorus-nitrogen flame retardant and preparation method thereof | |
| CN114350025A (en) | High-char-formation halogen-free composite intumescent flame retardant and flame-retardant polystyrene resin | |
| CN110922637B (en) | DOPO derivative flame-retardant photo-thermal stabilizer and preparation method and application thereof | |
| CN104262682A (en) | Oxaphosphaphenanthrene fire retardant containing cyclotriphosphazene and cup [4] aromatic ring structures as well as preparation method and application of oxaphosphaphenanthrene fire retardant | |
| CN117510993A (en) | Efficient flame retardant based on modified sepiolite and preparation method thereof | |
| CN113735905B (en) | Flame-retardant charring agent containing caged phosphonate amine organosilicon compound, and preparation method and application thereof | |
| CN116145415A (en) | A kind of flame retardant modifier, preparation and ultraviolet light initiation method for preparing flame retardant material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |