CN117777615B - High-temperature-resistant flame-retardant PVC material and preparation method thereof - Google Patents
High-temperature-resistant flame-retardant PVC material and preparation method thereof Download PDFInfo
- Publication number
- CN117777615B CN117777615B CN202311670427.8A CN202311670427A CN117777615B CN 117777615 B CN117777615 B CN 117777615B CN 202311670427 A CN202311670427 A CN 202311670427A CN 117777615 B CN117777615 B CN 117777615B
- Authority
- CN
- China
- Prior art keywords
- parts
- flame retardant
- pvc material
- temperature
- resin
- 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 83
- 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 79
- 239000000463 material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 26
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 25
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920013822 aminosilicone Polymers 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 239000003921 oil Substances 0.000 claims abstract description 22
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000314 lubricant Substances 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 25
- 239000003607 modifier Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 238000002390 rotary evaporation Methods 0.000 claims description 12
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 claims description 11
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 abstract description 14
- 239000000779 smoke Substances 0.000 abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 7
- 230000004888 barrier function Effects 0.000 abstract description 4
- 230000009920 chelation Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 3
- 230000001629 suppression Effects 0.000 abstract description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 42
- 239000004800 polyvinyl chloride Substances 0.000 description 42
- 239000000203 mixture Substances 0.000 description 8
- 238000007792 addition Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012796 inorganic flame retardant Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical group [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000007112 amidation reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical group [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000002977 biomimetic material Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000006084 composite stabilizer Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000004209 oxidized polyethylene wax Substances 0.000 description 1
- 235000013873 oxidized polyethylene wax Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a high-temperature-resistant flame-retardant PVC material and a preparation method thereof, belonging to the technical field of halogen-free flame-retardant high polymer materials, and comprising the following components in parts by weight: 100 parts of PVC resin, 9-15 parts of AS resin, 5-8 parts of POE resin, 18-24 parts of composite flame retardant, 3.2-4 parts of heat stabilizer, 0.3-0.4 part of antioxidant and 0.9-1.2 parts of lubricant; the composite flame retardant takes zinc borate as a core, is prepared into an intermediate by click addition of thioglycollic acid and triallylamine, then reacts with small molecular amino silicone oil to form a silicon chain-containing block oligomer, and the two are combined through chelation, so that the composite flame retardant is not easy to migrate and segregate in a high-temperature environment, has good high-temperature stability, is easy to form a continuous and high-strength barrier layer during combustion, and has excellent flame retardant property and smoke suppression effect.
Description
Technical Field
The invention belongs to the technical field of halogen-free flame-retardant polymer materials, and particularly relates to a high-temperature-resistant flame-retardant PVC material and a preparation method thereof.
Background
PVC (polyvinyl chloride) is a polymer formed by polymerizing vinyl chloride monomers under the action of an initiator such as peroxide, azo compounds and the like or light and heat according to a free radical polymerization reaction mechanism; has been receiving a lot of attention since being found, and with the rapid development of polymer industry, has been applied to various industries of human society, such as aerospace, transportation, electronic and electric appliances, building materials and automobiles, and even in advanced fields of biomimetic materials and supermolecular materials, etc., the statue of polymer materials is known; PVC is a universal thermoplastic material, has the characteristics of low cost, wide sources, stable chemical properties and the like, is an important component of engineering materials, is widely applied to various aspects of electronic appliances, automobile parts, product packaging, articles for daily use and the like, and is second largest engineering plastic next to polyethylene; like other plastics, PVC materials have a certain flammability, greatly limiting their use in some fields.
In order to solve the problem of the flammability of PVC materials, the prior art generally combines flame retardant into PVC to improve the flame retardant property, and the mode has low cost and stronger operability, is easy to realize industrialization, and is a main direction of PVC flame retardant research; the traditional flame retardant mainly comprises halogen flame retardants, wherein halogen free radicals are separated at high temperature to capture and transfer the burning free radicals, so that the free radical depolymerization process of materials is stopped to achieve a flame retardant effect, and higher flame retardant efficiency can be achieved with a smaller addition amount, but the flame retardants are easy to decompose to generate a large amount of toxic gas in a high-temperature environment, so that environmental pollutants are caused, rescue hazard is caused when fire disaster occurs, and the flame retardants are gradually replaced; the phosphorus-nitrogen organic flame retardant is decomposed at a high temperature to generate flame-retardant gas, residual flame retardance is obtained to obtain a carbon layer, the existing P-N flame retardant has good low toxicity compared with halogen flame retardants, the existing P-N flame retardant is widely applied to various flame-retardant plastics, but the thermal stability of the flame retardant is easy to migrate and segregate in a high-heat environment or in a long-time service process, so that the flame retardant effect is uneven, the thermal stability of the flame retardant to a polymer is influenced, and the smoke amount in combustion is large; in addition, the flame retardant is an ideal flame retardant material, which is characterized in that the inorganic flame retardant is characterized in that moisture is released by utilizing high-temperature decomposition reaction, nonflammable inorganic oxide is generated by decomposition, the flame retardant achieves flame retardant effect, the flame retardant has extremely low toxicity and high-efficiency flame retardance, an expansion structure generated by decomposition has a certain heat insulation and smoke suppression effect, but the inorganic material has poor compatibility with a polymer matrix, the mechanical property of the matrix is greatly influenced, the surface of the inorganic flame retardant is uniformly dispersed into the matrix by modifying the surface of the inorganic flame retardant by compounding the coupling agent, and the compound coupling agent and the inorganic flame retardant are condensed in practical researches, so that the decomposition expansion of the inorganic flame retardant is influenced, the macroscopic appearance is slow in flame retardant response, and the combustion smoke quantity is increased.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention aims to provide a high-temperature-resistant flame-retardant PVC material and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
The high-temperature-resistant flame-retardant PVC material comprises the following raw materials in parts by weight:
100 parts of PVC resin, 9-15 parts of AS resin, 5-8 parts of POE resin, 18-24 parts of composite flame retardant, 3.2-4 parts of heat stabilizer, 0.3-0.4 part of antioxidant and 0.9-1.2 parts of lubricant;
the composite flame retardant is prepared by the following method:
Step A1: uniformly mixing triallylamine, dimethylphenylphosphine and ethanol, introducing nitrogen for protection, heating to 50-60 ℃, applying 120-180rpm mechanical stirring and 300-400W/m 2 ultraviolet irradiation, intermittently adding mercaptoacetic acid, controlling the total adding reaction time to be 2.5-3.5h, and removing ethanol by rotary evaporation under reduced pressure after the reaction is finished to obtain an intermediate;
Further, the ratio of the amount of triallylamine, thioglycollic acid, dimethylphenylphosphine and ethanol used was 0.3mol:0.102-0.105mol:15-20mg:45-60mL, under the initiation of dimethylphenylphosphine and ultraviolet radiation, thioglycollic acid and triallylamine are subjected to addition reaction to form a compound with a sulfur-nitrogen structure in the molecule and a branched carboxyl at the end.
Step A2: uniformly mixing an intermediate, thionyl chloride and dioxane, stirring at room temperature for 6 hours, then performing rotary evaporation until no chlorine is separated out, introducing nitrogen for protection, adding amino silicone oil, heating to 80-90 ℃, applying mechanical stirring at 60-80rpm, stirring at constant temperature for reacting for 5-7 hours, and performing rotary evaporation under reduced pressure after the reaction is finished to remove dioxane to obtain a film modifier;
Further, the ratio of the amino content of the intermediate, the amino silicone oil, the amount of thionyl chloride and dioxane was 0.1mol:0.38-0.45mol:25-32mL:220-350mL, wherein carboxyl in the intermediate structure is subjected to thionyl chloride, then amidation reaction is carried out on the carboxyl and active amino in the amino silicone oil, and a block oligomer of the intermediate and the amino silicone oil is formed through reasonable dosage regulation.
Further, the amino silicone oil is selected from small molecular amino silicone oil, the room temperature viscosity is not higher than 30mm 2/s, the small molecular amino silicone oil is easy to react and control the reaction, and is easy to decompose at high temperature to form a free organosilicon chain segment, so that an inorganic silicon flame-retardant layer is formed in combustion.
Step A3: uniformly mixing a coating modifier and dimethylacetamide, adding zinc borate micropowder, uniformly stirring, standing at room temperature for 24 hours, adding water for mixing, centrifuging to remove water phase, and vacuum drying to obtain a composite flame retardant;
Further, the dosage ratio of the zinc borate micropowder, the coating modifier and the dimethylacetamide is 50g:4.5-6.5g:65-80mL, the sulfur-nitrogen structure introduced by the intermediate into the film modifier is easy to form a stable six-membered chelate ring with zinc borate, and the film modifier is loaded on the surface of zinc borate micro powder through chelation.
Further, the fineness of the zinc borate micropowder is 2-5 mu m, and the particle size is favorable for the high-efficiency load of the coating modifier.
The preparation method of the high-temperature-resistant flame-retardant PVC material comprises the following specific operations: mixing the raw materials uniformly by a high-speed mixer, loading into a torque rheometer, banburying at 155-170 ℃ and a rotating speed of 40rpm until the torque is stable, discharging and granulating to obtain the high-temperature-resistant flame-retardant PVC material.
The invention has the beneficial effects that:
According to the invention, the PVC resin is used as a main material, and a composite flame retardant is compounded to endow the PVC material with excellent high-temperature resistance and flame retardance; the composite flame retardant is prepared by preparing an intermediate from thioglycollic acid and triallylamine through click addition, performing thionyl chloride treatment, performing amidation reaction with amino silicone oil to form a silicon chain-containing block oligomer, preparing a film modifier, and then loading the film modifier onto the surface of zinc borate micro powder by utilizing the chelating property of a sulfur-nitrogen structure in the structure of the film modifier to prepare the flame retardant with an organic-inorganic composite structure; compared with the existing flame retardant, the surface-loaded block oligomer has good thermal stability, is not easy to decompose and migrate under the conventional heating condition, and shows good high temperature resistance; in a high heat or combustion environment, the chelation of a film modifier on the surface of zinc borate micro powder is weakened, the film modifier is separated from a load, zinc borate can be effectively heated to decompose and expand, expansion pores are formed in PVC materials, meanwhile, a sulfur-carbon structure with low bond energy in the separated film modifier structure is preferentially broken to form a large number of easily-dissociated silicon-containing short chains, sulfur free radicals exposed by the broken bonds are further promoted to decompose the silicon-containing short chains into inorganic silicon, the inorganic silicon is attached between the expansion pores and a carbonization network of organic matters, a continuous and high-strength barrier layer is easy to form, on one hand, the deep combustion is prevented, the high-strength and stable micro-pore barrier layer has a strong flame retardant effect, on the other hand, the high-strength and stable micro-pore barrier layer can effectively adsorb and prevent smoke release generated by combustion, and excellent low smoke performance is shown in an actual combustion test.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1, a high temperature resistant flame retardant PVC material was prepared as follows:
1) Preparation of composite flame retardant
Step A1: mixing triallylamine, dimethylphenylphosphine and ethanol, introducing nitrogen for protection, controlling the temperature at 60 ℃, applying 180rpm mechanical stirring, applying 400W/m 2 ultraviolet irradiation by using a UVA ultraviolet light source, taking the equivalent of mercaptoacetic acid to be divided into four parts, adding intermittently for 10min, continuing constant-temperature stirring irradiation reaction after complete addition, controlling the total adding reaction time of the mercaptoacetic acid to be 2.5h, and controlling the dosage ratio of triallylamine, mercaptoacetic acid, dimethylphenylphosphine and ethanol to be 0.3mol in the reaction: 0.105mol:20mg:60mL, the reaction is finished, the ethanol is removed rapidly by decompression rotary evaporation, the esterification of solvent ethanol is avoided, and the intermediate is prepared.
Step A2: taking an intermediate, thionyl chloride and dioxane, mixing uniformly, stirring at 80rpm for 6 hours at room temperature, then steaming thionyl chloride in a rotary mode until no chlorine is separated out, introducing nitrogen for protection, adding amino silicone oil (in the embodiment, the S-KF-8010 type small molecular amino silicone oil is adopted, the room temperature viscosity is 12mm 2/s, provided by Suzhou Jian dao electronic Co., ltd.), heating to 80 ℃, stirring at 80rpm for reaction for 5 hours, wherein the amino content of the intermediate and the amino silicone oil, the dosage ratio of the thionyl chloride and the dioxane is 0.1mol:0.45mol:32mL:220mL, and removing dioxane after the reaction is finished by reduced pressure rotary evaporation, thus obtaining the coating modifier.
Step A3: mixing the coating modifier and dimethylacetamide, adding zinc borate micropowder (commercial zinc borate micropowder with average particle diameter of 2-3 μm provided by Jinan Jin Ying Tay chemical Co., ltd.) into the mixture, rapidly stirring the mixture at 600rpm, and standing the mixture at room temperature for 24 hours, wherein the dosage ratio of the zinc borate micropowder, the coating modifier and dimethylacetamide is 50g:4.5g:65mL, adding water prepared by 1.2 times of the projection substrate, mixing, centrifuging to remove the water phase, taking the bottom sediment, and drying in vacuum to obtain the composite flame retardant.
2) Preparation of high-temperature-resistant flame-retardant PVC material
The weight is as follows:
100 parts of PVC resin, namely SG-3 type PVC resin in the embodiment, which is provided by the chemical industry Co., ltd. Of Wuhan Ji Ye L;
15 parts of AS resin, wherein PN-127H type AS resin is adopted in the embodiment, and is provided by Qimei industry Co., ltd;
5 parts of POE resin, wherein in the examples, resin of the type U.S. Dow 8150 is adopted, which is provided by Shanghai Yixin Di New Material Co., ltd;
18 parts of a composite flame retardant prepared in this example;
3.2 parts of heat stabilizer, wherein in the embodiment, a CT05P calcium zinc composite stabilizer is adopted and provided by Shanghai Kunrui chemical industry Co., ltd;
0.4 part of antioxidant, wherein in the embodiment, an antioxidant 1010 and an antioxidant 168 are mixed according to a mass ratio of 1:1;
0.9 part of lubricant, in each example, H-3325 type oxidized polyethylene wax was used as the lubricant, which was supplied by Minhong (Shanghai) investment control Co., ltd.
And (3) adding the raw materials into a high-speed mixer, mixing at a high speed of 1200rpm for 10min, loading the mixture into a torque rheometer, banburying at 155 ℃ and a rotating speed of 40rpm until the torque is stable, discharging and granulating to obtain the high-temperature-resistant flame-retardant PVC material.
Example 2, a high temperature resistant flame retardant PVC material was prepared, specifically as follows:
1) Preparation of composite flame retardant
Step A1: mixing triallylamine, dimethylphenylphosphine and ethanol, introducing nitrogen for protection, controlling the temperature at 50 ℃, applying 120rpm mechanical stirring, applying 300W/m 2 ultraviolet irradiation by using a UVA ultraviolet light source, dividing the mercaptoacetic acid into four parts, adding intermittently for 15min, continuing constant-temperature stirring irradiation reaction after complete addition, controlling the total adding reaction time of the mercaptoacetic acid to be 3.5h, and controlling the dosage ratio of triallylamine, mercaptoacetic acid, dimethylphenylphosphine and ethanol to be 0.3mol in the reaction: 0.102mol:15mg:45mL, the reaction is finished, the ethanol is removed rapidly by decompression rotary evaporation, the esterification of solvent ethanol is avoided, and the intermediate is prepared.
Step A2: taking an intermediate, thionyl chloride and dioxane, mixing uniformly, stirring at 80rpm for 6 hours at room temperature, then steaming thionyl chloride in a rotary way until no chlorine is separated out, introducing nitrogen for protection, adding amino silicone oil (in the embodiment, the S-KF-8010 type small molecular amino silicone oil is adopted, the room temperature viscosity is 12mm 2/s, provided by Suzhou Jian dao electronic Co., ltd.), heating to 85 ℃, stirring at 70rpm for reaction for 6 hours, wherein the amino content of the intermediate and the amino silicone oil, the dosage ratio of the thionyl chloride and the dioxane is 0.1mol:0.42mol:28mL:260mL, and removing dioxane after the reaction is finished by reduced pressure rotary evaporation, thus obtaining the coating modifier.
Step A3: mixing the coating modifier and dimethylacetamide, adding zinc borate micropowder (commercial zinc borate micropowder with average particle diameter of 3-5 μm provided by Jinan Jin Ying Tay chemical Co., ltd.) into the mixture, rapidly stirring at 600rpm, standing at room temperature for 24h, wherein the dosage ratio of the zinc borate micropowder, the coating modifier and dimethylacetamide is 50g:5.5g:70mL, adding water prepared by 1.2 times of the projection substrate, mixing, centrifuging to remove the water phase, taking the bottom sediment, and drying in vacuum to obtain the composite flame retardant.
2) Preparation of high-temperature-resistant flame-retardant PVC material
The weight is as follows: 100 parts of PVC resin, 9 parts of AS resin, 8 parts of POE resin, 24 parts of composite flame retardant, 3.8 parts of heat stabilizer, 0.3 part of antioxidant and 1 part of lubricant;
And (3) adding the raw materials into a high-speed mixer, mixing at a high speed of 1200rpm for 10min, loading the mixture into a torque rheometer, banburying at 165 ℃ and a rotating speed of 40rpm until the torque is stable, discharging and granulating to obtain the high-temperature-resistant flame-retardant PVC material.
Example 3, a high temperature resistant flame retardant PVC material was prepared as follows:
1) Preparation of composite flame retardant
Step A1: mixing triallylamine, dimethylphenylphosphine and ethanol, introducing nitrogen for protection, controlling the temperature to 55 ℃, applying 180rpm mechanical stirring, applying 360W/m 2 ultraviolet irradiation by using a UVA ultraviolet light source, dividing the mercaptoacetic acid into four parts, intermittently adding for 10min, continuing constant-temperature stirring irradiation reaction after complete addition, controlling the total adding reaction time of the mercaptoacetic acid to be 3h, and controlling the dosage ratio of triallylamine, mercaptoacetic acid, dimethylphenylphosphine and ethanol to be 0.3mol in the reaction: 0.104mol:18mg:55mL, the reaction is finished, the ethanol is removed rapidly by reduced pressure rotary evaporation, the esterification of solvent ethanol is avoided, and the intermediate is prepared.
Step A2: taking an intermediate, thionyl chloride and dioxane, mixing uniformly, stirring at 80rpm for 6 hours at room temperature, then steaming thionyl chloride in a rotary mode until no chlorine is separated out, introducing nitrogen for protection, adding amino silicone oil (DY-N323 type small molecular amino silicone oil is adopted in the embodiment, the room temperature viscosity is 25mm 2/s and is provided by Shandong Dayi chemical industry Co., ltd.), heating to 90 ℃, stirring at 80rpm for reaction for 7 hours, wherein the amino content of the intermediate and the amino silicone oil, the dosage ratio of the thionyl chloride and the dioxane is 0.1mol:0.38mol:25mL:350mL, and removing dioxane after the reaction is finished by reduced pressure rotary evaporation to prepare the coating modifier.
Step A3: mixing the coating modifier and dimethylacetamide, adding zinc borate micropowder (commercial zinc borate micropowder with average particle diameter of 3-5 μm provided by Jinan Jin Ying Tay chemical Co., ltd.) into the mixture, rapidly stirring at 600rpm, standing at room temperature for 24h, wherein the dosage ratio of the zinc borate micropowder, the coating modifier and dimethylacetamide is 50g:6.5g:80mL, adding water prepared by 1.2 times of the projection substrate, mixing, centrifuging to remove the water phase, taking the bottom sediment, and drying in vacuum to obtain the composite flame retardant.
2) Preparation of high-temperature-resistant flame-retardant PVC material
The weight is as follows: 100 parts of PVC resin, 12 parts of AS resin, 6 parts of POE resin, 22 parts of composite flame retardant, 4 parts of heat stabilizer, 0.3 part of antioxidant and 1.2 parts of lubricant;
And (3) adding the raw materials into a high-speed mixer, mixing at a high speed of 1200rpm for 10min, loading the mixture into a torque rheometer, banburying at 170 ℃ and a rotating speed of 40rpm until the torque is stable, discharging and granulating to obtain the high-temperature-resistant flame-retardant PVC material.
Comparative example, a flame-retardant PVC material is prepared by adopting zinc borate and a special flame retardant for commercial PVC to synergistically modify PVC, and the specific steps are as follows:
The specific formula comprises the following components: 100 parts of PVC resin, 12 parts of AS resin, 7 parts of POE resin, 20 parts of zinc borate micropowder (the same AS in example 3), 4.5 parts of special PVC flame retardant (model TF-1V, provided by Jiangxi Ten New Material technology Co., ltd.), 0.7 part of composite coupling agent (model LD-121, provided by Yangzhou City Dada resin Co., ltd.), 4 parts of heat stabilizer, 0.3 part of antioxidant and 1.6 parts of lubricant; the specific implementation method is the same as that of the embodiment 3.
Placing the prepared PVC material into a vulcanizing press, controlling the temperature to be 200+/-5 ℃, the pressure to be 1.5MPa, the holding pressure and hot pressing time to be 5min, pressing the PVC material into a sheet-shaped blank, sampling the sheet-shaped blank, performing a tensile test according to GB/T1040.1-2018 standard, preparing a sample with the thickness of 2mm, performing a combustion test according to UL94 combustion tester, performing a smoke density test according to GB/T8323.2-2018 standard, and specific test data are shown in table 1:
TABLE 1
| Example 1 | Example 2 | Example 3 | Comparative example | |
| Tensile Strength/MPa | 31.5 | 38.2 | 35.7 | 26.4 |
| Combustion grade | V-0 | V-0 | V-0 | V-1 |
| Smoke density mg/g | 54 | 92 | 68 | 161 |
As shown in the data of Table 1, the tensile strength of the PVC material prepared by the invention reaches 31.5-38.2MPa, the PVC material has higher mechanical strength compared with the comparative example, the combustion grade reaches V-0 grade, the smoke density is lower than 100mg/g, and the PVC material has excellent flame retardant and low smoke performance.
To verify the high temperature resistant and flame retardant properties of the prepared PVC material, the sheet blank is placed in a nitrogen atmosphere furnace, heated to 100+/-2 ℃, heat-preserved and baked for 2 hours, then cooled to room temperature along with the furnace, kept stand for 2 hours, reciprocally circulated for 100 weeks, and the sample is intercepted again for tensile and combustion test, wherein specific test data are shown in Table 2:
TABLE 2
| Example 1 | Example 2 | Example 3 | Comparative example | |
| Tensile Strength/MPa | 29.6 | 35.1 | 34.3 | 21.5 |
| Combustion grade | V-0 | V-0 | V-0 | V-2 |
As can be seen from the data in Table 2, the PVC material prepared by the invention has small reduction in mechanical properties after cyclic baking, has no obvious change in flame retardant property, still maintains V-0 level, and has obviously deteriorated flame retardant property in comparative examples.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (7)
1. The high-temperature-resistant flame-retardant PVC material is characterized by comprising the following components in parts by weight:
100 parts of PVC resin, 9-15 parts of AS resin, 5-8 parts of POE resin, 18-24 parts of composite flame retardant, 3.2-4 parts of heat stabilizer, 0.3-0.4 part of antioxidant and 0.9-1.2 parts of lubricant;
the composite flame retardant is prepared by the following method:
Step A1: uniformly mixing triallylamine, dimethylphenylphosphine and ethanol, introducing nitrogen for protection, heating to 50-60 ℃, stirring, assisting in ultraviolet irradiation of 300-400W/m 2, intermittently adding thioglycollic acid, controlling the total adding reaction time to be 2.5-3.5h, and removing ethanol by reduced pressure rotary evaporation after the reaction is finished to obtain an intermediate;
Step A2: uniformly mixing an intermediate, thionyl chloride and dioxane, stirring at room temperature for 6 hours, then performing rotary evaporation until no chlorine is separated out, introducing nitrogen for protection, adding amino silicone oil, heating to 80-90 ℃, stirring at constant temperature for reacting for 5-7 hours, and performing rotary evaporation under reduced pressure after the reaction is finished to remove the dioxane to obtain a film modifier;
Step A3: mixing the film modifier and dimethylacetamide uniformly, adding zinc borate micropowder, stirring uniformly, standing at room temperature for 24 hours, adding water for mixing, centrifuging to remove water phase, and vacuum drying to obtain the composite flame retardant.
2. The high temperature resistant and flame retardant PVC material according to claim 1, wherein the ratio of triallylamine, thioglycollic acid, dimethylphenylphosphine and ethanol is 0.3mol:0.102-0.105mol:15-20mg:45-60mL.
3. The high temperature resistant and flame retardant PVC material according to claim 2, wherein the ratio of the amino content of the intermediate and the amino silicone oil to the dosage of thionyl chloride and dioxane is 0.1mol:0.38-0.45mol:25-32mL:220-350mL.
4. A high temperature resistant flame retardant PVC material according to claim 3, wherein the amino silicone oil is a small molecular amino silicone oil having a room temperature viscosity of not more than 30mm 2/s.
5. The high temperature resistant and flame retardant PVC material according to claim 4, wherein the dosage ratio of the zinc borate micro powder, the coating modifier and the dimethylacetamide is 50g:4.5-6.5g:65-80mL.
6. The high temperature resistant and flame retardant PVC material according to claim 5, wherein the fineness of the zinc borate micropowder is 2-5 μm.
7. The method for preparing the high-temperature-resistant flame-retardant PVC material according to claim 1, which is characterized by comprising the following specific operations: mixing the raw materials uniformly, banburying at 155-170 ℃ until the torque is stable, discharging and granulating to obtain the high-temperature-resistant flame-retardant PVC material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311670427.8A CN117777615B (en) | 2023-12-07 | 2023-12-07 | High-temperature-resistant flame-retardant PVC material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311670427.8A CN117777615B (en) | 2023-12-07 | 2023-12-07 | High-temperature-resistant flame-retardant PVC material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117777615A CN117777615A (en) | 2024-03-29 |
| CN117777615B true CN117777615B (en) | 2024-06-07 |
Family
ID=90389845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311670427.8A Active CN117777615B (en) | 2023-12-07 | 2023-12-07 | High-temperature-resistant flame-retardant PVC material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117777615B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111548581A (en) * | 2020-06-11 | 2020-08-18 | 安徽奥凯材料股份有限公司 | Flame-retardant smoke suppressant and preparation method of flame-retardant smoke suppressant for PVC (polyvinyl chloride) sheet |
| WO2020233028A1 (en) * | 2019-05-22 | 2020-11-26 | 宁波先锋新材料股份有限公司 | Flame-retardant and smoke-suppressing soft polyvinyl chloride composite material having good mechanical performance and preparation method therefor |
| CN115260673A (en) * | 2022-08-26 | 2022-11-01 | 中广核三角洲（江苏）塑化有限公司 | Flexible high-strength flame-retardant PVC cable material for drag chain cable and preparation method thereof |
| CN116814021A (en) * | 2023-08-29 | 2023-09-29 | 金弘盛线缆有限公司 | High-strength wear-resistant cable |
| CN116855010A (en) * | 2023-07-06 | 2023-10-10 | 康命源（贵州）科技发展有限公司 | Polyolefin pipeline material based on anhydrous calcium sulfate produced by phosphogypsum |
| CN116891605A (en) * | 2023-08-30 | 2023-10-17 | 天津市佰盟科技发展有限公司 | Aging-resistant composite material for automobiles and preparation method thereof |
| CN117004234A (en) * | 2023-10-07 | 2023-11-07 | 广州市瑞合新材料科技有限公司 | Flame-retardant wire and cable silicone rubber and preparation method thereof |
-
2023
- 2023-12-07 CN CN202311670427.8A patent/CN117777615B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020233028A1 (en) * | 2019-05-22 | 2020-11-26 | 宁波先锋新材料股份有限公司 | Flame-retardant and smoke-suppressing soft polyvinyl chloride composite material having good mechanical performance and preparation method therefor |
| CN111548581A (en) * | 2020-06-11 | 2020-08-18 | 安徽奥凯材料股份有限公司 | Flame-retardant smoke suppressant and preparation method of flame-retardant smoke suppressant for PVC (polyvinyl chloride) sheet |
| CN115260673A (en) * | 2022-08-26 | 2022-11-01 | 中广核三角洲（江苏）塑化有限公司 | Flexible high-strength flame-retardant PVC cable material for drag chain cable and preparation method thereof |
| CN116855010A (en) * | 2023-07-06 | 2023-10-10 | 康命源（贵州）科技发展有限公司 | Polyolefin pipeline material based on anhydrous calcium sulfate produced by phosphogypsum |
| CN116814021A (en) * | 2023-08-29 | 2023-09-29 | 金弘盛线缆有限公司 | High-strength wear-resistant cable |
| CN116891605A (en) * | 2023-08-30 | 2023-10-17 | 天津市佰盟科技发展有限公司 | Aging-resistant composite material for automobiles and preparation method thereof |
| CN117004234A (en) * | 2023-10-07 | 2023-11-07 | 广州市瑞合新材料科技有限公司 | Flame-retardant wire and cable silicone rubber and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 硼酸锌/氢氧化铝对聚氯乙烯纺织结构材料阻燃及稳定性的影响;赵程波;张斌;韩建;;纺织学报;20170115(01);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117777615A (en) | 2024-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110698600B (en) | Preparation method and application of bulk flame-retardant polypropylene graft | |
| CN107674328B (en) | Halogen-free flame-retardant irradiation crosslinking cable material and preparation method thereof | |
| WO2021129219A1 (en) | Photovoltaic cable insulating material and preparation method therefor | |
| CN108503895B (en) | Preparation method of lanthanum-loaded organic phosphorus-modified nitrogen-doped graphene and flame-retardant modified ABS thereof | |
| CN112662184A (en) | Flame-retardant silicone rubber material and preparation method thereof | |
| Huang et al. | Flame retardant polypropylene with a single molecule intumescent flame retardant based on chitosan | |
| CN108623844A (en) | DOPO-LDH composite fire retardants and preparation method thereof and halogen-free flame retardant ethylene propylene diene monomer (EPDM) material and its application | |
| CN115011078A (en) | Flame-retardant environment-friendly PET plastic and preparation method thereof | |
| CN117777615B (en) | High-temperature-resistant flame-retardant PVC material and preparation method thereof | |
| CN106832508B (en) | A kind of preparation method of High-temperature-resandant andant flame-retardant cable material | |
| CN112898666A (en) | Modified semi-siloxane synergistic intumescent flame-retardant low-density polyethylene and preparation method thereof | |
| CN112094502A (en) | High-temperature-resistant mixed silicone rubber and preparation method thereof | |
| CN117004127A (en) | Chitosan-based high-flame-retardance MPP pipe and preparation method thereof | |
| CN110054809B (en) | Composite flame retardant, preparation method thereof and application thereof in polypropylene | |
| CN109988411B (en) | Flame-retardant smoke-suppression thermoplastic polyurethane antistatic composite material and preparation method thereof | |
| CN116376179A (en) | Flame-retardant rubber material, preparation method thereof and sealing strip | |
| CN113637256B (en) | Preparation method of EVA nano flame-retardant compound based on magnesium/zinc/boron/nitrogen synergy | |
| CN111040249B (en) | Rubber-plastic flame-retardant additive and rubber-plastic material containing same | |
| CN109897357B (en) | High-stability halogen-free environment-friendly flame retardant for plastics and preparation method thereof | |
| CN113667070A (en) | Low-smoke halogen-free flame-retardant cable compatilizer, maleic anhydride grafted modified polyolefin and preparation method thereof | |
| CN113150489A (en) | ABS composite material and preparation method thereof | |
| CN111073298A (en) | Flame-retardant plugging agent for substation and preparation method and use method thereof | |
| CN114773707B (en) | Beta-cyclodextrin microcapsule ammonium polyphosphate intumescent flame-retardant low-density polyethylene and preparation method thereof | |
| CN111875968A (en) | Flame-retardant silicone rubber for low-pressure sealing and preparation method thereof | |
| CN117777335B (en) | Expandable polystyrene containing graphite carbon black composite particles and preparation method thereof |
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 |