CN117126498A - Fireproof PVC material and preparation method thereof - Google Patents
Fireproof PVC material and preparation method thereof Download PDFInfo
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- CN117126498A CN117126498A CN202311025645.6A CN202311025645A CN117126498A CN 117126498 A CN117126498 A CN 117126498A CN 202311025645 A CN202311025645 A CN 202311025645A CN 117126498 A CN117126498 A CN 117126498A
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- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 30
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 12
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 claims abstract description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000002390 rotary evaporation Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 239000003480 eluent Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 17
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 16
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- LWNLXVXSCCLRRZ-UHFFFAOYSA-N dichlorophosphane Chemical compound ClPCl LWNLXVXSCCLRRZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000004440 column chromatography Methods 0.000 claims description 12
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- IBZKBSXREAQDTO-UHFFFAOYSA-N 2-methoxy-n-(2-methoxyethyl)ethanamine Chemical compound COCCNCCOC IBZKBSXREAQDTO-UHFFFAOYSA-N 0.000 claims description 8
- FFFHZYDWPBMWHY-UHFFFAOYSA-N HOMOCYSTEINE Chemical compound OC(=O)C(N)CCS FFFHZYDWPBMWHY-UHFFFAOYSA-N 0.000 claims description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- CKJXMHLOGAUSSD-UHFFFAOYSA-N triphenyl-[(E)-prop-1-enyl]stannane Chemical compound C(=CC)[Sn](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 CKJXMHLOGAUSSD-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 2
- 230000009970 fire resistant effect Effects 0.000 claims 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 239000004014 plasticizer Substances 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 45
- 229920000915 polyvinyl chloride Polymers 0.000 description 44
- 239000004800 polyvinyl chloride Substances 0.000 description 44
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000012046 mixed solvent Substances 0.000 description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 2
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004110 Zinc silicate Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 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 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/44—Amides thereof
- C07F9/4461—Amides thereof the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4465—Amides thereof the amide moiety containing a substituent or a structure which is considered as characteristic of aliphatic amines
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- 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
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
- C08K5/58—Organo-tin compounds containing sulfur
-
- 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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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)
Abstract
The invention discloses a fireproof PVC material and a preparation method thereof, and belongs to the technical field of PVC materials. The PVC material is prepared by melt blending PVC slices, an auxiliary agent and di-n-octyl phthalate, wherein the mass ratio of the PVC slices to the auxiliary agent to the di-n-octyl phthalate is 100:10-20:10, the di-n-octyl phthalate is taken as a plasticizer, the impact resistance of the PVC material can be increased, brittle fracture is not easy to occur when the PVC material is impacted, the auxiliary agent is added into the PVC material, various functional groups are introduced into the auxiliary agent, the PVC material is endowed with high-efficiency fireproof performance, the high rigidity can achieve a relatively strong toughening effect, the mechanical property of the PVC material is ensured, the thermal stability and the heat resistance of the PVC material can be improved to a certain extent, and the PVC material has important application significance.
Description
Technical Field
The invention belongs to the technical field of PVC materials, and particularly relates to a fireproof PVC material and a preparation method thereof.
Background
PVC is also called polyvinyl chloride, has been the general plastic with the largest output in the world, has wide application in the wire and cable industry because of low cost, good insulativity and high cost performance, wherein communication cables develop heat for several years, and is mainly used for transmitting data, the structural size of the products is usually smaller and uniform, the manufacturing precision requirement is high, and the PVC is a cable product which is mainly researched in the industry. The defects of the PVC material are also exposed in wide use, the PVC material has certain flame retardance, but the traditional polyvinyl chloride material cannot meet the requirements of the PVC material in the flame-retardant field, and the PVC material is poor in self thermal stability, so that the application field of the PVC material is limited.
In this regard, the chinese patent application publication No. CN105400101a discloses a PVC flame retardant, which comprises the following components in parts by weight: 10-25 parts of antimony dioxide; 15-25 parts of dioctyl phthalate; 10-15 parts of zinc borate; 5-15 parts of calcium stearate; 1-5 parts of magnesium hydroxide; 1-5 parts of zinc silicate, which takes antimony dioxide, magnesium hydroxide and other components as inorganic flame retardants, is easy to agglomerate and uneven in dispersion in PVC materials, and can improve the flame retardant property of PVC to a certain extent, but has limited improvement effect, but can reduce the mechanical property of PVC, and cannot provide heat resistance, thus having the defects.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a fireproof PVC material and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the fireproof PVC material comprises the following steps:
placing the PVC slices in a vacuum oven, drying at 60 ℃ for 5 hours, adding the fully dried PVC slices, an auxiliary agent and di-n-octyl phthalate (plasticizer) into a banburying chamber of a Hark torque rheometer, rapidly extruding a material rod, and preparing the fireproof PVC material after the melt blending material is completely and uniformly mixed and fully plasticized; plasticizing condition of the Hark torque rheometer: the rotor speed was 30r/min, the temperature was 200℃and the time was set at 8min.
Further, the mass ratio of the PVC slice to the auxiliary agent to the di-n-octyl phthalate is 100:10-20:10.
Further, the auxiliary agent is prepared by the following steps:
s1, mixing propenyl triphenyltin, AIBN (azobisisobutyronitrile), pyridine and 2-amino-4-mercaptobutyric acid, keeping constant stirring, maintaining the temperature of a system at 70 ℃, reacting for 4 hours, removing part of solvent by rotary evaporation, purifying by column chromatography (eluent adopts a mixed solvent of benzene/methanol with the volume ratio of 2:1), and removing the eluent by rotary evaporation to obtain an intermediate 1; the ratio of the dosage of the propenyl triphenyltin, the pyridine, the 2-amino-4-mercaptobutyric acid and the AIBN is 38.4g to 100mL to 13.5g to 0.5g;
under the action of AIBN, the unsaturated carbon-carbon double bond on the propenyl triphenyltin molecule and-SH on 2-amino-4-mercaptobutyric acid undergo a click reaction of mercapto-alkene to obtain an intermediate 1, and the reaction process is as follows:
s2, adding dichlorophosphine, bis (2-methoxyethyl) amine and carbon tetrachloride into a three-neck flask with a stirring and reflux device under the protection of room temperature and nitrogen, uniformly stirring, slowly heating to 80 ℃, stopping heating after reflux reaction for 6 hours, and evaporating unreacted dichlorophosphine and solvent under reduced pressure after the temperature in the reaction flask is reduced to 30 ℃ to obtain an intermediate 2; the dosage ratio of the dichlorophosphine to the bis (2-methoxyethyl) amine to the carbon tetrachloride is 13.1g to 13.3g to 100mL;
acylating the dichlorophosphine and the bis (2-methoxyethyl) amine, and controlling the molar ratio of the dichlorophosphine to the bis (2-methoxyethyl) amine to be close to 1:1 and slightly excessive dichlorophosphine to ensure that only one-Cl on the dichlorophosphine participates in the reaction to obtain an intermediate 2; the specific reaction process is as follows:
s3, dissolving the intermediate 1 and n-octanol in pyridine, slowly adding concentrated sulfuric acid (a catalyst and a dehydrating agent) into the solution while stirring, heating to 80 ℃ for reaction for 2 hours, removing most of the solvent by rotary evaporation after the reaction is finished, purifying by column chromatography (eluent adopts a mixed solvent of benzene and diethyl ether, the volume ratio of the benzene to the diethyl ether is 2:1), and removing the eluent by rotary evaporation to obtain an intermediate 3; the dosage ratio of the intermediate 1 to the n-octanol to the pyridine to the concentrated sulfuric acid is 52.6g to 13.1g to 150mL to 10mL;
under the catalysis of concentrated sulfuric acid, the carboxyl on the intermediate 1 and the hydroxyl on n-octanol are subjected to esterification reaction to obtain an intermediate 3; the specific reaction process is as follows:
s4, under the protection of room temperature and nitrogen, adding the intermediate 2, the intermediate 3 and pyridine into a three-neck flask provided with a stirring and refluxing device, uniformly mixing and stirring, heating to 120 ℃, refluxing for 6 hours, stopping heating, removing most of the solvent by rotary evaporation after the temperature in the reaction flask is reduced to 30 ℃, purifying by column chromatography (eluent adopts a mixed solvent of benzene/ethyl acetate, the volume ratio of the benzene to the ethyl acetate is 2:1), and removing the eluent by rotary evaporation to obtain an auxiliary agent; the dosage ratio of the intermediate 2 to the intermediate 3 to the pyridine is 63.2g:22.9g:200mL;
the intermediate 2 and the intermediate 3 undergo an acylation reaction to obtain an auxiliary agent; the specific reaction process is as follows:
the organic tin is introduced into the molecule, and the organic tin is used as a heat stabilizer, so that the PVC material can be endowed with certain heat stability and heat resistance, and three benzene rings are connected with the tin, so that the molecule has certain rigidity, the reinforced and toughened composite effect is generated, and the processing formability and the heat deformation temperature of the material can be improved; in addition, the auxiliary agent molecules contain long carbon chains which can be inserted between PVC macromolecular chains, so that the toughening effect is further improved; the auxiliary agent can play the role of nitrogen flame retardant, and can be decomposed when heated, and the main product is NH 3 、N 2 、H 2 0、NO、NO 2 The non-combustible gas has the functions of heat absorption, temperature reduction anddiluting and the like, so that the auxiliary agent has fireproof performance; in addition, the phosphorus and nitrogen in the auxiliary agent generate P-N synergistic flame retardant effect, so that the fireproof performance of the auxiliary agent is further enhanced.
The invention has the beneficial effects that:
the fireproof PVC material is prepared by melt blending PVC slices, an auxiliary agent and di-n-octyl phthalate, and the di-n-octyl phthalate is taken as a plasticizer, so that the impact resistance of the PVC material can be increased, and the PVC material is not easy to crack when impacted; the PVC material is added with the auxiliary agent, various functional groups are introduced into the auxiliary agent, so that the high-efficiency fireproof performance of the PVC material is endowed, the high rigidity can play a strong role in toughening, the mechanical properties of the PVC material are ensured, the thermal stability and the heat resistance of the PVC material can be improved to a certain extent, and the PVC material has important application significance.
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
Preparing an auxiliary agent:
s1, mixing 38.4g of propenyl triphenyltin, 0.5g of AIBN (azodiisobutyronitrile), 100mL of pyridine and 13.5g of 2-amino-4-mercaptobutyric acid, keeping constant stirring, maintaining the temperature of the system at 70 ℃, reacting for 4 hours, removing part of solvent by rotary evaporation after the reaction is finished, purifying by column chromatography (eluent adopts a mixed solvent of benzene/methanol with the volume ratio of 2:1), and removing the eluent by rotary evaporation to obtain an intermediate 1;
s2, adding 13.1g of dichlorophosphine, 13.3g of bis (2-methoxyethyl) amine and 100mL of carbon tetrachloride into a three-neck flask with a stirring and reflux device under the protection of room temperature and nitrogen, uniformly stirring, slowly heating to 80 ℃, stopping heating after reflux reaction for 6 hours, and evaporating unreacted dichlorophosphine and solvent under reduced pressure after the temperature in the reaction flask is reduced to 30 ℃ to obtain an intermediate 2;
s3, dissolving 52.6g of the intermediate 1 and 13.1g of n-octanol in 150mL of pyridine, slowly adding 10mL of concentrated sulfuric acid into the solution while stirring, heating to 80 ℃ for reaction for 2 hours, removing most of the solvent by rotary evaporation after the reaction is finished, purifying by column chromatography (eluent adopts a mixed solvent of benzene/diethyl ether, the volume ratio of the benzene/diethyl ether is 2:1), and removing the eluent by rotary evaporation to obtain an intermediate 3;
s4, under the protection of room temperature and nitrogen, adding 63.2g of intermediate 2, 22.9g of intermediate 3 and 200mL of pyridine into a three-neck flask with a stirring and reflux device, uniformly mixing and stirring, heating to 120 ℃, refluxing for 6 hours, stopping heating, removing most of the solvent by rotary evaporation after the temperature in a reaction bottle is reduced to 30 ℃, purifying by column chromatography (eluent adopts a mixed solvent of benzene/ethyl acetate, the volume ratio of the benzene to the ethyl acetate is 2:1), and removing the eluent by rotary evaporation to obtain the auxiliary agent.
Example 2
Preparing an auxiliary agent:
s1, mixing 76.8g of propenyl triphenyltin, 1g of AIBN (azodiisobutyronitrile), 150mL of pyridine and 27g of 2-amino-4-mercaptobutyric acid, keeping constant stirring, maintaining the temperature of the system at 70 ℃, reacting for 4 hours, removing part of solvent by rotary evaporation after the reaction is finished, purifying by column chromatography (eluent adopts a mixed solvent of benzene/methanol with the volume ratio of 2:1), and removing the eluent by rotary evaporation to obtain an intermediate 1;
s2, adding 26.2g of dichlorophosphine, 26.6g of bis (2-methoxyethyl) amine and 100mL of carbon tetrachloride into a three-neck flask with a stirring and reflux device under the protection of room temperature and nitrogen, uniformly stirring, slowly heating to 80 ℃, stopping heating after reflux reaction for 6 hours, and evaporating unreacted dichlorophosphine and solvent under reduced pressure after the temperature in the reaction flask is reduced to 30 ℃ to obtain an intermediate 2;
s3, dissolving 105.2g of the intermediate 1 and 26.2g of n-octanol in 300mL of pyridine, slowly adding 20mL of concentrated sulfuric acid into the solution while stirring, heating to 80 ℃ for reaction for 2 hours, removing most of the solvent by rotary evaporation after the reaction is finished, purifying by column chromatography (eluent adopts a mixed solvent of benzene/diethyl ether, the volume ratio of the benzene/diethyl ether is 2:1), and removing the eluent by rotary evaporation to obtain an intermediate 3;
s4, under the protection of room temperature and nitrogen, adding 126.4g of intermediate 2, 45.8g of intermediate 3 and 300mL of pyridine into a three-neck flask with a stirring and reflux device, uniformly mixing and stirring, heating to 120 ℃, refluxing for 6 hours, stopping heating, removing most of the solvent by rotary evaporation after the temperature in a reaction bottle is reduced to 30 ℃, purifying by column chromatography (eluent adopts a mixed solvent of benzene/ethyl acetate, the volume ratio of the benzene to the ethyl acetate is 2:1), and removing the eluent by rotary evaporation to obtain the auxiliary agent.
Example 3
The PVC chips were placed in a vacuum oven and dried at 60℃for 5 hours, 100g of the fully dried PVC chips, 10g of the auxiliary agent prepared in example 1 and 10g of di-n-octyl phthalate (plasticizer) were added into a banburying chamber of a Hark torque rheometer, a rod was rapidly extruded, and after the melt blend materials were completely mixed uniformly and fully plasticized, a fireproof PVC material was prepared.
Example 4
The PVC chips were placed in a vacuum oven and dried at 60℃for 5 hours, 100g of the fully dried PVC chips, 15g of the auxiliary agent prepared in example 1 and 10g of di-n-octyl phthalate (plasticizer) were added into a banburying chamber of a Hark torque rheometer, a rod was rapidly extruded, and the flame-retardant PVC material was prepared after the melt-blended material was completely and uniformly mixed and fully plasticized.
Example 5
The PVC chips were placed in a vacuum oven and dried at 60℃for 5 hours, 100g of the fully dried PVC chips, 20g of the auxiliary agent prepared in example 2 and 10g of di-n-octyl phthalate (plasticizer) were added into a banburying chamber of a Hark torque rheometer, a rod was rapidly extruded, and after the melt blending material was completely and uniformly mixed and fully plasticized, a fireproof PVC material was prepared.
Comparative example 1
The same mass of Maleimide (MI) copolymer was added as a heat-resistant polymer modifier without addition of an auxiliary agent, and the remaining steps were the same as those of example 4.
Comparative example 2
The procedure of example 4 was followed except that no auxiliary was added and an equivalent mass of P-N synergistic flame retardant (Nanjing medium-molecular new materials Co., ltd.) was added.
Comparative example 3
The procedure was the same as in example 4, except that no auxiliary agent was added.
Examples 3-5, comparative examples 1-3, were prepared into corresponding shapes to be tested according to different criteria, and the following performance tests were performed:
the limiting oxygen index is measured by adopting national standard GB/T2406-2008 'test method for Plastic Combustion Performance';
the tensile strength and the elongation at break are measured by adopting the national standard GB/T1040-92 plastic tensile property test method;
the thermal stability test is carried out at 200 ℃ by adopting a Congo red method specified by the national standard GB/T2917.1-2002, and the time for changing the Congo red from red to blue is recorded;
the notch impact strength is tested by adopting national standard GB/T1043.1-2008 'determination of impact Property of Plastic simply supported Beam';
the test results are shown in the following table:
from the table, the modified PVC material has high-efficiency fireproof performance, high rigidity and strong toughening effect, ensures the mechanical property of the PVC material, has certain thermal stability and heat resistance, and has important application significance.
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 (8)
1. The preparation method of the fireproof PVC material is characterized by comprising the following steps of:
and (3) placing the PVC slices in a vacuum oven, drying at 60 ℃ for 5 hours, adding the fully dried PVC slices, the auxiliary agent and the di-n-octyl phthalate into a banburying chamber of a Hark torque rheometer, rapidly extruding a material rod, and preparing the fireproof PVC material after the melted and blended materials are completely and uniformly mixed and fully plasticized.
2. The method for preparing the fireproof PVC material according to claim 1, wherein the mass ratio of PVC slices, auxiliary agents and di-n-octyl phthalate is 100:10-20:10.
3. The method for preparing a fireproof PVC material according to claim 1, wherein the auxiliary agent is prepared by the steps of:
s1, mixing propenyl triphenyltin, AIBN, pyridine and 2-amino-4-mercaptobutyric acid, stirring, reacting for 4 hours at 70 ℃, removing part of solvent by rotary evaporation after the reaction is finished, purifying by column chromatography, and removing eluent by rotary evaporation to obtain an intermediate 1;
s2, adding dichlorophosphine, bis (2-methoxyethyl) amine and carbon tetrachloride into a three-neck flask with a stirring and reflux device under the protection of room temperature and nitrogen, uniformly stirring, heating to 80 ℃, carrying out reflux reaction for 6 hours, stopping heating, and carrying out reduced pressure distillation to remove unreacted dichlorophosphine and solvent after the temperature in the reaction flask is reduced to 30 ℃ to obtain an intermediate 2;
s3, dissolving the intermediate 1 and n-octanol in pyridine, slowly adding concentrated sulfuric acid into the solution while stirring, heating to 80 ℃ for reaction for 2 hours, removing most of the solvent by rotary evaporation after the reaction is finished, purifying by column chromatography, and removing eluent by rotary evaporation to obtain an intermediate 3;
s4, under the protection of room temperature and nitrogen, adding the intermediate 2, the intermediate 3 and pyridine into a three-neck flask with a stirring and reflux device, uniformly mixing and stirring, heating to 120 ℃, carrying out reflux reaction for 6 hours, stopping heating, carrying out rotary evaporation firstly after the temperature is reduced to 30 ℃, purifying through column chromatography, and removing eluent through rotary evaporation to obtain the auxiliary agent.
4. The method for preparing a fireproof PVC material according to claim 3, wherein the ratio of the amounts of propenyl triphenyltin, pyridine, 2-amino-4-mercaptobutyric acid and AIBN in step S1 is 38.4g to 100mL to 13.5g to 0.5g.
5. A method for preparing a fire-resistant PVC material according to claim 3, wherein the ratio of the amounts of dichlorophosphine, bis (2-methoxyethyl) amine, and carbon tetrachloride used in step S2 is 13.1g to 13.3g to 100ml.
6. The method for preparing a fireproof PVC material according to claim 3, wherein the ratio of the amounts of the intermediate 1, n-octanol, pyridine and concentrated sulfuric acid in the step S3 is 52.6g:13.1g:150mL:10mL.
7. A method for preparing a fire-resistant PVC material according to claim 3, wherein the ratio of the amounts of intermediate 2, intermediate 3 and pyridine in step S4 is 63.2g:22.9g:200ml.
8. A fire resistant PVC material prepared according to the method of any one of claims 1 to 7.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2832751A (en) * | 1951-06-21 | 1958-04-29 | Metal & Thermit Corp | Polyvinyl chloride stabilized with butyl tin s, s', s" tris |
| CN112442082A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Reactive flame retardant and preparation method and application thereof |
| CN116462923A (en) * | 2023-06-19 | 2023-07-21 | 广东裕泰实业集团有限公司 | Flame-retardant modified PVC film |
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2023
- 2023-08-15 CN CN202311025645.6A patent/CN117126498A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2832751A (en) * | 1951-06-21 | 1958-04-29 | Metal & Thermit Corp | Polyvinyl chloride stabilized with butyl tin s, s', s" tris |
| CN112442082A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Reactive flame retardant and preparation method and application thereof |
| CN116462923A (en) * | 2023-06-19 | 2023-07-21 | 广东裕泰实业集团有限公司 | Flame-retardant modified PVC film |
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