CN115232417B - Low-smoke flame-retardant plastic product semiconductive PVC sheath material - Google Patents
Low-smoke flame-retardant plastic product semiconductive PVC sheath material Download PDFInfo
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- 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 54
- 239000003063 flame retardant Substances 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 38
- 239000000779 smoke Substances 0.000 title claims abstract description 23
- 229920003023 plastic Polymers 0.000 title claims abstract description 21
- 239000004033 plastic Substances 0.000 title claims abstract description 21
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 46
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 79
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 32
- -1 benzotriazolyl benzene imino benzoic acid Chemical compound 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 19
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- CWQMIJNUOGCBRO-UHFFFAOYSA-N 2-(2H-benzotriazol-4-yl)benzaldehyde Chemical compound N1N=NC2=C1C=CC=C2C1=C(C=O)C=CC=C1 CWQMIJNUOGCBRO-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000012964 benzotriazole Substances 0.000 claims description 12
- PVIVWSKQVHYIEI-UHFFFAOYSA-N 2-(bromomethyl)benzaldehyde Chemical compound BrCC1=CC=CC=C1C=O PVIVWSKQVHYIEI-UHFFFAOYSA-N 0.000 claims description 11
- 239000004593 Epoxy Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 9
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 9
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 5
- 239000011230 binding agent Substances 0.000 claims 3
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 12
- 238000012986 modification Methods 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 6
- 238000002485 combustion reaction Methods 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 abstract description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 abstract description 2
- 230000004888 barrier function Effects 0.000 abstract description 2
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical class C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 238000009413 insulation Methods 0.000 abstract description 2
- 238000002955 isolation Methods 0.000 abstract description 2
- 239000005543 nano-size silicon particle Substances 0.000 abstract description 2
- 230000002265 prevention Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 150000003852 triazoles Chemical class 0.000 abstract description 2
- 230000003014 reinforcing effect Effects 0.000 abstract 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 42
- 239000000047 product Substances 0.000 description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000005406 washing Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000012043 crude product Substances 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 5
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 3
- IOHPVZBSOKLVMN-UHFFFAOYSA-N 2-(2-phenylethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CCC1=CC=CC=C1 IOHPVZBSOKLVMN-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- UMKARVFXJJITLN-UHFFFAOYSA-N lead;phosphorous acid Chemical compound [Pb].OP(O)O UMKARVFXJJITLN-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- RPKOEKXXKFUCFT-UHFFFAOYSA-N C(C1=CC=CC=C1)=O.N1N=NC2=C1C=CC=C2 Chemical compound C(C1=CC=CC=C1)=O.N1N=NC2=C1C=CC=C2 RPKOEKXXKFUCFT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of polyvinyl chloride, and discloses a low-smoke flame-retardant plastic product semiconductive PVC sheath material, wherein a POSS (polyhedral oligomeric silsesquioxane) -based flame retardant is used for blending, reinforcing and modifying polyvinyl chloride, and after organic modification, organic-inorganic hybrid POSS nano particles are better in interfacial compatibility with the polyvinyl chloride, can be more uniformly dispersed in a polyvinyl chloride matrix, and plays a better role in reinforcing and modifying; the POSS-based flame retardant generates nano silicon dioxide particles during combustion, and the modified triazole and phosphaphenanthrene form a nitrogen-phosphorus synergistic flame retardant system, and an expansion carbon layer formed on the surface of the silicon dioxide particles during combustion forms a silicon carbon barrier layer with stable structure with the silicon dioxide nano particles in a material matrix, so that the flame retardant effects of heat insulation, oxygen isolation, smoke escape inhibition and molten drop prevention are achieved.
Description
Technical Field
The invention relates to the technical field of polyvinyl chloride, in particular to a low-smoke flame-retardant plastic product semiconductive PVC sheath material and a synthesis method thereof.
Background
Polyvinyl chloride is widely applied to sealing materials, cable sheath materials, floor leather and the like, flame retardant modification is carried out on the polyvinyl chloride in recent years, development and application of the polyvinyl chloride in the cable sheath materials are expanded to be research trends, for example, patent CN110746646B discloses that a biomass-based flame retardant is synthesized from aminophenol, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and other raw materials, and the biomass-based flame retardant is applied to flame retardant modification of thermoplastic polymers such as the polyvinyl chloride.
POSS is a silicon-based organic-inorganic hybrid material, has good enhancement and modification effects on high polymer materials such as epoxy resin, polyvinyl chloride and the like, and can improve the flame retardant property of the high polymer materials such as epoxy resin, polyurethane and the like by reacting phosphorus-containing monomers with mercaptopropyl POSS and vinyl as disclosed in patent CN111072973B to obtain the phosphorus-containing POSS flame retardant with high thermal stability.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a low-smoke flame-retardant plastic product semiconductive PVC sheath material and a synthesis method thereof.
(II) technical scheme
In order to achieve the above purpose, the present invention provides the following technical solutions: a low smoke flame retardant plastic product semi-conductive PVC sheath material is synthesized by the following process:
(1) Adding benzotriazole, bromomethylbenzaldehyde and an acid coating agent into a solvent, reacting at a constant temperature of 20-35 ℃ for 3-8 h, concentrating under reduced pressure after the reaction, adding ethyl acetate and distilled water for extraction, combining organic phases, drying for removing water, dissolving the crude product into ethyl acetate, and recrystallizing to obtain the benzotriazolyl benzaldehyde.
(2) Adding 100 weight parts of benzotriazolyl benzaldehyde and 50-65 weight parts of 4-aminobenzoic acid into ethanol, heating to 65-80 ℃ to react for 4-10 h, adding ethanol after the reaction to recrystallize, and obtaining the benzotriazolyl benzene iminobenzoic acid.
(3) Adding 100 parts by weight of benzotriazol benzoiminobenzoic acid and 55-75 parts by weight of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into an ethanol solvent, heating to 55-70 ℃ to react for 6-18-h, concentrating under reduced pressure after the reaction, and washing the product with diethyl ether and acetone to obtain the triazole-phosphaphenanthrene-based benzoic acid derivative.
(4) Adding epoxy POSS and triazole-phosphaphenanthryl benzoic acid derivatives into toluene solvent, stirring and dissolving, then dropwise adding tetrabutylammonium bromide serving as a catalyst, heating and reacting, concentrating under reduced pressure, and washing products with acetone and ethanol to obtain the POSS-based flame retardant.
(5) 100 parts by weight of polyvinyl chloride resin, 1-6 parts by weight of POSS-based flame retardant, 1-2 parts by weight of lubricant, 40-50 parts by weight of plasticizer, 2-3 parts by weight of stabilizer and 7-10 parts by weight of conductive carbon black are added into a high-speed mixer to be uniformly mixed, and then the materials are added into a double-screw extruder to be melted and extruded to form a material, so that the low-smoke flame-retardant plastic product semiconductive PVC sheath material is prepared.
Preferably, the solvent in (1) comprises acetonitrile, acetone, tetrahydrofuran, toluene, N-dimethylformamide.
Preferably, the benzotriazole in the (1) is used in an amount of 100 parts by weight, 140-180 parts by weight of bromomethylbenzaldehyde and 130-220 parts by weight of acid coating agent.
Preferably, the acid applying agent in the step (1) comprises sodium hydroxide, potassium hydroxide and potassium carbonate.
Preferably, the epoxy POSS in the step (4) is used in an amount of 100 parts by weight, the triazole-phosphaphenanthryl benzoic acid derivative is 350-450 parts by weight, and the tetrabutylammonium bromide is 6-10 parts by weight.
Preferably, the reaction in (4) is carried out at a temperature of from 90 to 120℃for from 2 to 5 h.
(III) beneficial technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the low-smoke flame-retardant plastic product semiconductive PVC sheath material takes benzotriazole and bromomethyl benzaldehyde as reaction raw materials, the synthesized benzotriazole benzaldehyde sequentially reacts with 4-aminobenzoic acid and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to synthesize a novel triazole-phosphaphenanthrene flame-retardant micromolecule, then carboxyl and epoxy POSS of the novel triazole-phosphaphenanthrene flame-retardant micromolecule are utilized to carry out epoxy esterification reaction under the catalysis of tetrabutylammonium bromide to obtain a POSS-based flame retardant, the POSS is subjected to blending enhancement modification, and after organic modification, the organic-inorganic hybridization POSS nano particles are subjected to organic modification, the interface compatibility with the polyvinyl chloride is better, and the novel triazole-phosphaphenanthrene flame-retardant micromolecule can be more uniformly dispersed in a polyvinyl chloride matrix to play a better enhancement modification effect.
The POSS-based flame retardant generates nano silicon dioxide particles during combustion, and the modified triazole and phosphaphenanthrene form a nitrogen-phosphorus synergistic flame retardant system, and an expansion carbon layer formed on the surface of the silicon dioxide particles during combustion forms a silicon carbon barrier layer with stable structure with the silicon dioxide nano particles in a material matrix, so that the flame retardant effects of heat insulation, oxygen isolation, smoke escape inhibition and molten drop prevention are achieved, the flame retardance of polyvinyl chloride is obviously improved, and the development and application of the polyvinyl chloride in the fields of cable sheath materials and the like are expanded.
Drawings
FIG. 1 is a synthetic reaction diagram of a POSS-based flame retardant.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a low smoke flame retardant plastic product semi-conductive PVC sheath material is synthesized by the following process:
(1) Adding 100 parts by weight of benzotriazole, 140-180 parts by weight of bromomethylbenzaldehyde and 130-220 parts by weight of acid applying agent sodium hydroxide, potassium hydroxide or potassium carbonate into acetonitrile, acetone, tetrahydrofuran, toluene or N, N-dimethylformamide solvent, reacting at constant temperature of 20-35 ℃ for 3-8 h, concentrating under reduced pressure after the reaction, adding ethyl acetate and distilled water for extraction, merging organic phases, drying for removing water, dissolving the crude product into ethyl acetate, and recrystallizing to obtain the benzotriazolyl benzaldehyde.
(2) Adding 100 weight parts of benzotriazolyl benzaldehyde and 50-65 weight parts of 4-aminobenzoic acid into ethanol, heating to 65-80 ℃ to react for 4-10 h, adding ethanol after the reaction to recrystallize, and obtaining the benzotriazolyl benzene iminobenzoic acid. (3) Adding 100 parts by weight of benzotriazol benzoiminobenzoic acid and 55-75 parts by weight of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into an ethanol solvent, heating to 55-70 ℃ to react for 6-18-h, concentrating under reduced pressure after the reaction, and washing the product with diethyl ether and acetone to obtain the triazole-phosphaphenanthrene-based benzoic acid derivative.
(4) Adding 100 parts by weight of epoxy POSS and 350-450 parts by weight of triazole-phosphaphenanthryl benzoic acid derivative into a toluene solvent, stirring and dissolving, then dropwise adding 6-10 parts by weight of tetrabutylammonium bromide serving as a catalyst, heating to 90-120 ℃ for reaction at 2-5 h, concentrating under reduced pressure after the reaction, and washing a product with acetone and ethanol to obtain the POSS-based flame retardant.
(5) 100 parts by weight of polyvinyl chloride resin, 1-6 parts by weight of POSS-based flame retardant, 1-2 parts by weight of lubricant, 40-50 parts by weight of plasticizer, 2-3 parts by weight of stabilizer and 7-10 parts by weight of conductive carbon black are added into a high-speed mixer to be uniformly mixed, and then the materials are added into a double-screw extruder to be melted and extruded to form a material, so that the low-smoke flame-retardant plastic product semiconductive PVC sheath material is prepared.
Example 1
(1) Adding 5 g benzotriazole, 7 g bromomethylbenzaldehyde and 8.2 g acid agent potassium hydroxide into tetrahydrofuran solvent, reacting at constant temperature of 20 ℃ for 8 h, concentrating under reduced pressure after the reaction, adding ethyl acetate and distilled water for extraction, combining organic phases, drying for removing water, dissolving the crude product into ethyl acetate, and recrystallizing to obtain the benzotriazolyl benzaldehyde.
(2) Adding 10 g of benzotriazolyl benzaldehyde and 5.8 g of 4-aminobenzoic acid into ethanol, heating to 65 ℃ to react 10 h, adding ethanol after the reaction, and recrystallizing to obtain the benzotriazolyl benzene iminobenzoic acid.
(3) Adding 2 g of benzotriazol benzoiminobenzoic acid and 1.5 g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into an ethanol solvent, heating to 70 ℃ to react 6 h, concentrating under reduced pressure after the reaction, and washing the product with diethyl ether and acetone to obtain the triazole-phosphaphenanthrene benzoic acid derivative.
(4) Adding 2 g epoxy POSS and 7.5 g triazole-phosphaphenanthryl benzoic acid derivative into toluene solvent, stirring and dissolving, then dropwise adding 0.15 g catalyst tetrabutylammonium bromide, heating to 90 ℃ for reaction 4 h, concentrating under reduced pressure after the reaction, and washing the product with acetone and ethanol to obtain the POSS-based flame retardant.
(5) Adding 500 g polyvinyl chloride resin, 5 g POSS-based flame retardant, 10 g calcium stearate, 250 g dioctyl phthalate, 12 g tribasic lead sulfate and 40 g conductive carbon black into a high-speed mixer, uniformly mixing, and then adding the materials into a double-screw extruder for melting, extruding and making materials to prepare the low-smoke flame-retardant plastic product semiconductive PVC sheath material.
Example 2
(1) 5 g benzotriazole, 9 g bromomethylbenzaldehyde and 10.5 g potassium carbonate serving as an acid application agent are added into acetonitrile solvent, the mixture is reacted at a constant temperature of 35 ℃ for 3 h, the mixture is concentrated under reduced pressure after the reaction, ethyl acetate and distilled water are added for extraction, organic phases are combined, water is removed by drying, and the crude product is dissolved into ethyl acetate for recrystallization, so that the benzotriazolyl benzaldehyde is obtained.
(2) Adding 10 g of benzotriazolyl benzaldehyde and 6.5 g of 4-aminobenzoic acid into ethanol, heating to 65 ℃ to react 10 h, adding ethanol after the reaction, and recrystallizing to obtain the benzotriazolyl benzene iminobenzoic acid.
(3) Adding 2 g of benzotriazol benzoiminobenzoic acid and 1.2 g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into an ethanol solvent, heating to 70 ℃ to react 12 h, concentrating under reduced pressure after the reaction, and washing the product with diethyl ether and acetone to obtain the triazole-phosphaphenanthrene benzoic acid derivative.
(4) Adding 2 g epoxy POSS and 7.5 g triazole-phosphaphenanthryl benzoic acid derivative into toluene solvent, stirring and dissolving, then dropwise adding 0.2 g catalyst tetrabutylammonium bromide, heating to 90 ℃ for reaction 4 h, concentrating under reduced pressure after the reaction, and washing the product with acetone and ethanol to obtain the POSS-based flame retardant.
(5) Adding 500 g polyvinyl chloride resin, 20 g POSS-based flame retardant, 8 g calcium stearate, 200 g dioctyl phthalate, 10 g dibasic lead phosphite and 50 g conductive carbon black into a high-speed mixer, uniformly mixing, and then adding the materials into a double-screw extruder for melting, extruding and making materials, thus obtaining the low-smoke flame-retardant plastic product semiconductive PVC sheath material.
Example 3
(1) Adding 5 g benzotriazole, 7.8 g bromomethylbenzaldehyde and 7.5 g acid agent sodium hydroxide into an acetone solvent, reacting at a constant temperature of 35 ℃ for 8 h, concentrating under reduced pressure after the reaction, adding ethyl acetate and distilled water for extraction, merging organic phases, drying for removing water, dissolving the crude product into ethyl acetate, and recrystallizing to obtain the benzotriazolyl benzaldehyde.
(2) Adding 10 g of benzotriazolyl benzaldehyde and 6.5 g of 4-aminobenzoic acid into ethanol, heating to 65 ℃ to react 4 h, adding ethanol after the reaction, and recrystallizing to obtain the benzotriazolyl benzene iminobenzoic acid.
(3) Adding 2 g of benzotriazol benzoiminobenzoic acid and 1.4 g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into an ethanol solvent, heating to 55 ℃ to react for 18 h, concentrating under reduced pressure after the reaction, and washing the product with diethyl ether and acetone to obtain the triazole-phosphaphenanthrene benzoic acid derivative.
(4) Adding 2 g epoxy POSS and 7.4 g triazole-phosphaphenanthryl benzoic acid derivative into toluene solvent, stirring and dissolving, then dropwise adding 0.18 g catalyst tetrabutylammonium bromide, heating to 90 ℃ for reaction at 5 h, concentrating under reduced pressure after reaction, and washing the product with acetone and ethanol to obtain the POSS-based flame retardant.
(5) Adding 500 g polyvinyl chloride resin, 35 g POSS-based flame retardant, 10 g stearic acid, 220 g dioctyl phthalate, 10 g dibasic lead phosphite and 40 g conductive carbon black into a high-speed mixer, uniformly mixing, and then adding the materials into a double-screw extruder for melting and extruding to prepare the low-smoke flame-retardant plastic product semiconductive PVC sheath material.
Comparative example 1
(1) 5 g benzotriazole, 8.2 g bromomethylbenzaldehyde and 9.7 g acid agent sodium hydroxide are added into N, N-dimethylformamide solvent, the mixture is reacted at a constant temperature of 25 ℃ for 3 h, the mixture is concentrated under reduced pressure after the reaction, ethyl acetate and distilled water are added for extraction, the organic phases are combined and dried for water removal, and the crude product is dissolved into ethyl acetate for recrystallization, so that the benzotriazolyl benzaldehyde is obtained.
(2) Adding 10 g of benzotriazolyl benzaldehyde and 5.4 g of 4-aminobenzoic acid into ethanol, heating to 65 ℃ to react 10 h, adding ethanol after the reaction, and recrystallizing to obtain the benzotriazolyl benzene iminobenzoic acid.
(3) Adding 500 g polyvinyl chloride resin, 5 g benzotriazole benzene iminobenzoic acid, 8 g calcium stearate, 200 g dioctyl phthalate, 15 g tribasic lead sulfate and 40 g conductive carbon black into a high-speed mixer, uniformly mixing, and adding the materials into a double-screw extruder for melting, extruding and manufacturing to obtain the PVC sheath material.
Comparative example 2
(1) Adding 5 g benzotriazole, 9 g bromomethylbenzaldehyde and 7.8 g acid agent potassium carbonate into toluene solvent, reacting at constant temperature of 20 ℃ for 5 h, concentrating under reduced pressure after the reaction, adding ethyl acetate and distilled water for extraction, combining organic phases, drying for removing water, dissolving the crude product into ethyl acetate, and recrystallizing to obtain the benzotriazolyl benzaldehyde.
(2) Adding 10 g of benzotriazolyl benzaldehyde and 5.8 g of 4-aminobenzoic acid into ethanol, heating to 80 ℃ to react 4 h, adding ethanol after the reaction, and recrystallizing to obtain the benzotriazolyl benzene iminobenzoic acid.
(3) Adding 2 g of benzotriazol benzoiminobenzoic acid and 1.1 g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into an ethanol solvent, heating to 70 ℃ to react 12 h, concentrating under reduced pressure after the reaction, and washing the product with diethyl ether and acetone to obtain the triazole-phosphaphenanthrene benzoic acid derivative.
(4) Adding 500 g polyvinyl chloride resin, 30 g triazole-phosphaphenanthryl benzoic acid derivative, 10 g stearic acid, 250 g dioctyl phthalate, 12 g tribasic lead sulfate and 40 g conductive carbon black into a high-speed mixer, uniformly mixing, and adding the materials into a double-screw extruder for melting, extruding and manufacturing to obtain the PVC sheath material.
The method comprises the steps of (1) conducting flame-retardant performance test on a low-smoke flame-retardant plastic product semiconductive PVC sheath material through an oxygen index tester, and referring to GB/T2406-2008 standard; testing the fire grade by a UL94 method through a horizontal and vertical burning tester; the combustion performance was tested by cone calorimetric testing.
Through flame retardant performance tests, the addition of the POSS-based flame retardant obviously improves the limiting oxygen index of the polyvinyl chloride, the UL94 fire resistance and other flame retardance.
Claims (6)
1. A low-smoke flame-retardant plastic product semi-conductive PVC sheath material is characterized in that: the PVC sheath material is synthesized by the following process:
(1) Adding benzotriazole, bromomethylbenzaldehyde and an acid-binding agent into a solvent, and reacting at a constant temperature of 20-35 ℃ for 3-8 h to obtain benzotriazole-based benzaldehyde;
(2) Adding 100 weight parts of benzotriazolyl benzaldehyde and 50-65 weight parts of 4-aminobenzoic acid into ethanol, heating to 65-80 ℃ to react for 4-10 h, and obtaining benzotriazolyl benzene imino benzoic acid;
(3) Adding 100 parts by weight of benzotriazol benzoiminobenzoic acid and 55-75 parts by weight of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into an ethanol solvent, heating to 55-70 ℃ to react 6-18 h, and obtaining a triazole-phosphaphenanthreneylbenzoic acid derivative;
(4) Adding epoxy POSS and triazole-phosphaphenanthryl benzoic acid derivatives into toluene solvent, stirring and dissolving, and then dropwise adding tetrabutylammonium bromide serving as a catalyst to obtain a POSS-based flame retardant;
(5) 100 parts by weight of polyvinyl chloride resin, 1-6 parts by weight of POSS-based flame retardant, 1-2 parts by weight of lubricant, 40-50 parts by weight of plasticizer, 2-3 parts by weight of stabilizer and 7-10 parts by weight of conductive carbon black are added into a high-speed mixer to be uniformly mixed, and then the materials are added into a double-screw extruder to be melted and extruded to form a material, so that the low-smoke flame-retardant plastic product semiconductive PVC sheath material is prepared.
2. The low smoke, flame retardant plastic article semiconducting PVC sheathing compound of claim 1, wherein: the solvent in the step (1) comprises acetonitrile, acetone, tetrahydrofuran, toluene and N, N-dimethylformamide.
3. The low smoke, flame retardant plastic article semiconducting PVC sheathing compound of claim 1, wherein: the amount of the benzotriazole in the (1) is 100 parts by weight, the bromomethylbenzaldehyde is 140-180 parts by weight, and the acid binding agent is 130-220 parts by weight.
4. The low smoke, flame retardant plastic article semiconducting PVC sheathing compound of claim 1, wherein: the acid binding agent in the step (1) comprises sodium hydroxide, potassium hydroxide and potassium carbonate.
5. The low smoke, flame retardant plastic article semiconducting PVC sheathing compound of claim 1, wherein: the epoxy POSS in the step (4) is used in an amount of 100 parts by weight, the triazole-phosphaphenanthryl benzoic acid derivative is 350-450 parts by weight, and the tetrabutylammonium bromide is 6-10 parts by weight.
6. The low smoke, flame retardant plastic article semiconducting PVC sheathing compound of claim 1, wherein: the reaction in (4) is carried out at 90-120 ℃ for 2-5 h.
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| CN112194683A (en) * | 2020-10-12 | 2021-01-08 | 福建师范大学 | Preparation of phosphorus-containing polyhydroxy flame retardant and application of phosphorus-containing polyhydroxy flame retardant in flame-retardant polylactic acid |
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