CN116947928A - Phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer and preparation method and application thereof - Google Patents
Phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer and preparation method and application thereof Download PDFInfo
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- CN116947928A CN116947928A CN202310918379.3A CN202310918379A CN116947928A CN 116947928 A CN116947928 A CN 116947928A CN 202310918379 A CN202310918379 A CN 202310918379A CN 116947928 A CN116947928 A CN 116947928A
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- castor oil
- phosphorus
- carboxyl
- nitrogen
- terminated
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- 239000004359 castor oil Substances 0.000 title claims abstract description 171
- 235000019438 castor oil Nutrition 0.000 title claims abstract description 171
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 title claims abstract description 171
- 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 85
- 239000003063 flame retardant Substances 0.000 title claims abstract description 84
- 239000004014 plasticizer Substances 0.000 title claims abstract description 75
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 238000002156 mixing Methods 0.000 claims abstract description 44
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 44
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 43
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 42
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 31
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 30
- 239000011574 phosphorus Substances 0.000 claims abstract description 30
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 29
- 239000004593 Epoxy Substances 0.000 claims abstract description 26
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 25
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 24
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 229960000583 acetic acid Drugs 0.000 claims abstract description 16
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 16
- -1 amine compound Chemical class 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract 4
- 238000004821 distillation Methods 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 7
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 claims description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 3
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 3
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 3
- OAXARSVKYJPDPA-UHFFFAOYSA-N tert-butyl 4-prop-2-ynylpiperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(CC#C)CC1 OAXARSVKYJPDPA-UHFFFAOYSA-N 0.000 claims description 3
- QQYNRBAAQFZCLF-FBXFSONDSA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-epoxyisobenzofuran-1,3-dione Chemical compound O1[C@@H]2[C@@H]3C(=O)OC(=O)[C@@H]3[C@H]1C=C2 QQYNRBAAQFZCLF-FBXFSONDSA-N 0.000 claims description 2
- LWMIDUUVMLBKQF-UHFFFAOYSA-N 4-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound CC1CC=CC2C(=O)OC(=O)C12 LWMIDUUVMLBKQF-UHFFFAOYSA-N 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 6
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 21
- 239000000463 material Substances 0.000 description 16
- 238000001816 cooling Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- 238000004321 preservation Methods 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 229960001701 chloroform Drugs 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical compound CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000006084 composite stabilizer Substances 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- 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 description 1
- IIGNZLVHOZEOPV-UHFFFAOYSA-N 3-Methoxybenzyl alcohol Chemical compound COC1=CC=CC(CO)=C1 IIGNZLVHOZEOPV-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- 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
- 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
- C08L2201/14—Gas barrier composition
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- 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)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The application relates to a preparation method of a phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer, which comprises the following steps: s1, mixing castor oil, double bond-containing dianhydride and an amine catalyst for reaction to obtain carboxyl-terminated vinyl castor oil; s2, mixing and reacting the carboxyl-terminated vinyl castor oil with glacial acetic acid, hydrogen peroxide and phosphoric acid to obtain epoxy carboxyl-terminated castor oil; s3, mixing and reacting the epoxy carboxyl terminated castor oil with DOPO and an acidic catalyst to obtain phosphorus carboxyl terminated castor oil; s4, mixing and reacting the phosphorus-containing terminal carboxyl castor oil and the amine compound to obtain the phosphorus-containing nitrogen castor oil-based flame-retardant plasticizer. The application also relates to the phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer prepared by the preparation method. The application also relates to application of the phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer in preparation of polyvinyl chloride rubber.
Description
Technical Field
The application relates to the technical field of chemical industry, in particular to a preparation method and application of a phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer based plasticizer with excellent flame retardant property.
Background
This section provides background information related to the present application, which does not necessarily constitute prior art.
Transparent polyvinyl chloride (PVC) resins are one of the important products among PVC-derived products, and have been widely demanded in various fields such as construction, automobiles, electricity, agriculture, and packaging. In the electrical field, the transparent PVC resin needs to have certain flame retardance as insulation and a sheath, so that the flame retardant is required to be added, but the transparency of the transparent PVC resin is not influenced by the added flame retardant, namely, the flame retardant needs to have good compatibility with the PVC resin or similar refractive index, so that the PVC resin containing the flame retardant is ensured to have good transparency, and the problem of flame retardant migration is not easy to occur. The plasticizer is an important additive added into plastics, resins or elastomers to change the processability, plasticity, flexibility and tensile properties of the plasticizer, and a flame-retardant structure is introduced into the structure of the plasticizer, so that the plasticizer has flame retardance and the problem of compatibility of the existing flame retardant and PVC resin can be solved. The existing flame-retardant plasticizer is generally prepared from fossil fuel, but the preparation of fossil fuel belongs to non-renewable resources.
Castor oil has been widely used in paint, foam, flame retardant, plasticizer, etc. because of its advantages of reproducibility, low cost, little environmental pollution, biodegradability, etc. Castor oil is a light yellow viscous non-drying oil, and mainly comprises fatty glyceride, wherein the molecular structure of the castor oil contains three active reaction groups such as hydroxyl, ester group and double bond, and the three active reaction groups can perform chemical reactions such as esterification, hydrolysis, double bond addition, epoxidation ring opening and the like. The castor oil based products with different performances can be obtained by modifying the chemical structure of the castor oil based products according to the structural characteristics of the molecules by utilizing the principles of addition, polycondensation, esterification and the like.
Disclosure of Invention
The application aims to provide a phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer and a preparation method thereof, which are used for improving the flame retardance and transparency of a transparent PVC cable.
In order to achieve the above purpose, the application adopts the following technical scheme: a preparation method of a phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer comprises the following steps:
s1, mixing castor oil, double bond-containing dianhydride and an amine catalyst for reaction to obtain carboxyl-terminated vinyl castor oil;
s2, mixing and reacting the carboxyl-terminated vinyl castor oil with glacial acetic acid, hydrogen peroxide and phosphoric acid to obtain epoxy carboxyl-terminated castor oil;
s3, mixing and reacting the epoxy carboxyl terminated castor oil with DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and an acid catalyst to obtain phosphorus carboxyl terminated castor oil;
s4, mixing and reacting the phosphorus-containing terminal carboxyl castor oil and the amine compound to obtain the phosphorus-containing nitrogen castor oil-based flame-retardant plasticizer.
In the step S1, the double bond-containing dianhydride is at least one of maleic anhydride, norbornene dianhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, methyl tetrahydrophthalic anhydride, 3-methyl tetrahydrophthalic anhydride and external-3, 6-epoxy-1, 2,3, 6-tetrahydrophthalic anhydride.
Wherein the amine catalyst is at least one of N, N-dimethyl cyclohexylamine, triethylamine and N, N-dimethyl benzylamine.
Preferably, the molar ratio of the castor oil to the double bond-containing dianhydride is 1: (3-4) the addition amount of the amine catalyst is 1% -1.5% of the total mass of the castor oil and the double bond-containing dianhydride. The reaction temperature of the mixed reaction of castor oil, double bond-containing dianhydride and amine catalyst is 115-125 ℃ and the reaction time is 3-5h.
In the step S2, the hydrogen peroxide is derived from 30% by mass of hydrogen peroxide. The carboxyl-terminated vinyl castor oil comprises, by mass, 83-151 parts of carboxyl-terminated vinyl castor oil, 14-18 parts of glacial acetic acid, 72-96 parts of 30% hydrogen peroxide and 0.09-0.12 part of phosphoric acid. The reaction temperature of the mixed reaction of the carboxyl-terminated vinyl castor oil, glacial acetic acid, 30% of hydrogen peroxide and phosphoric acid is 55-65 ℃, the reaction time is 3-6h, and the temperature is reduced to 50-55 ℃ after the reaction is completed, and then the vacuum pumping and the water removal are carried out.
In the step S3, the reaction temperature of the mixed reaction of the epoxy carboxyl terminated castor oil and DOPO and the acid catalyst is 130-170 ℃ and the reaction time is 3-6h.
Preferably, the ratio of the amounts of the substances of epoxy-terminated castor oil, DOPO, acid catalyst is 1: (2-3): (2-3).
Preferably, the acidic catalyst is a phosphoric acid solution of 85% mass fraction.
In step S4, the amine compound is at least one of propylamine, ethylenediamine, aniline, and N, N-dimethyl-p-phenylenediamine. The ratio of the amounts of the substances of the phosphorus-terminated castor oil and the amine compound is 1: (3-4), the reaction temperature of the mixing reaction is 50-70 ℃ and the reaction time is 4-7h, after the reaction is completed, the temperature is increased to 90-100 ℃ and reduced pressure distillation is carried out for not less than 2h, and the phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer is obtained.
In one or more embodiments, a method of preparing a phosphorus nitrogen containing castor oil based flame retardant plasticizer includes the steps of:
s1, uniformly mixing castor oil and double bond-containing dianhydride in a solvent (any one of tetrahydrofuran, dichloromethane, chloroform and acetone), adding an amine catalyst, wherein the reaction temperature is 25-60 ℃ and nitrogen is protected, and the molar ratio of the castor oil to the double bond-containing dianhydride is 1: (3-4) azo diisobutyronitrile is used as a catalyst, the catalyst content is 1-1.5% of the mass of the ricinoleic acid ethyl ester methacrylate, the reaction time is 3-5h, and the carboxyl-terminated vinyl castor oil is obtained after the reaction is finished and purified;
s2, uniformly mixing 83-151 parts by mass of carboxyl-terminated vinyl castor oil obtained in the step S1, 14-18 parts by mass of glacial acetic acid, 72-96 parts by mass of hydrogen peroxide with the mass fraction concentration of 30% and 0.09-0.12 part by mass of phosphoric acid, reacting at 55-65 ℃ for 3-6 hours, cooling to 50-55 ℃ after the reaction is completed, and vacuumizing to remove water to obtain epoxy carboxyl-terminated castor oil;
s3, uniformly mixing the epoxy carboxyl terminated castor oil obtained in the step S2 and DOPO in a solvent (any one of tetrahydrofuran, dichloromethane, chloroform and acetone), and then adding a phosphoric acid solution with the mass fraction of 85%, wherein the reaction temperature is 130-170 ℃, the reaction time is 3-6h, and nitrogen protection is carried out, wherein the mass ratio of the epoxy carboxyl terminated castor oil, DOPO and the phosphoric acid solution is 1: (2-3): (2-3) purifying after the reaction is finished to obtain phosphorus-containing carboxyl terminated castor oil;
s4, uniformly mixing phosphorus-containing carboxyl-terminated castor oil and amine compounds in a solvent (any one of tetrahydrofuran, dichloromethane, trichloromethane and acetone), wherein the reaction temperature is 50-70 ℃, and nitrogen protection is carried out, wherein the molar ratio of the phosphorus-containing carboxyl-terminated castor oil to the amine compounds is 1 (3-4), the reaction time is 4-7h, and after the reaction is completed, the temperature is increased to 90-100 ℃ and reduced pressure distillation is carried out for not less than 2h, so as to obtain the phosphorus-containing nitrogen castor oil-based flame retardant plasticizer.
On the other hand, the application also provides the phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer prepared by the preparation method.
On the other hand, the application also provides application of the phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer in preparation of polyvinyl chloride rubber.
In one or more embodiments, the phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer provided by the application is blended with PVC and the like to prepare a PVC material, and the mechanical property, the flame retardant property and the like of the PVC material are tested, so that the PVC material using the phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer can be unexpectedly found to improve the flame retardance and the transparency at the same time.
The beneficial effects are that: the application prepares the phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer with excellent flame retardant property by improving the structure of the castor oil-based plasticizer, more specifically, DOPO containing flame retardant element P (phosphorus) and amine compound containing N (nitrogen) element are introduced into the structure of the castor oil-based plasticizer. The phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer provided by the application has excellent flame retardant property and thermal stability, can be used for preparing polyvinyl chloride rubber, and can enable the polyvinyl chloride rubber to meet the VW-1 combustion grade and the temperature resistant grade of minus 20-80 ℃.
Detailed Description
It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
The application provides a phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer, which has an excellent flame-retardant effect due to at least the following factors:
1. when the phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer burns at high temperature, phosphoric acid or polyphosphoric acid which is not easy to volatilize is generated, a high-viscosity molten vitreous and compact carbonized layer can be formed on the surface, and the carbonized layer can isolate a matrix from heat and oxygen;
2. the phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer can be decomposed to generate free radicals such as PO, HPO, and the like in the combustion process, and can capture active H free radicals or OH free radicals in a gas phase state;
3. the phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer can generate non-combustible gas in the combustion process, so that the carbon layer is expanded, and heat transfer is better isolated.
The application also provides a preparation method of the phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer, which comprises the following steps:
s1, mixing castor oil, double bond-containing dianhydride and an amine catalyst for reaction to obtain carboxyl-terminated vinyl castor oil;
s2, mixing and reacting the carboxyl-terminated vinyl castor oil with glacial acetic acid, hydrogen peroxide and phosphoric acid to obtain epoxy carboxyl-terminated castor oil, wherein the castor oil has more double bonds compared with soybean oil through reaction with double bond-containing dianhydride, and the double bonds on the same carbon chain are farther away, so that when epoxy groups are generated by oxidation, the distance between the epoxy groups is further away, and the reaction inhibition caused by steric effect is reduced;
s3, mixing and reacting the epoxy carboxyl terminated castor oil with DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and an acid catalyst to obtain phosphorus carboxyl terminated castor oil;
s4, mixing and reacting the phosphorus-containing terminal carboxyl castor oil and the amine compound to obtain the phosphorus-containing nitrogen castor oil-based flame-retardant plasticizer, wherein the P element of DOPO and the N element of the amine compound are introduced into the molecular structure of the castor oil-based plasticizer to obtain an excellent flame-retardant effect, and the P element and the N element have a synergistic flame-retardant effect, so that the flame-retardant efficiency can be remarkably improved.
Example 1
The embodiment provides a phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer, and the preparation method comprises the following steps:
s1, taking 400g of castor oil, carrying out reduced pressure distillation and dehydration for 30min at 110 ℃, cooling to 50 ℃, adding 195g of tetrahydrophthalic anhydride and 6g of triethylamine, uniformly mixing, stirring, heating to 120 ℃, and carrying out heat preservation reaction for 4h to obtain carboxyl-terminated vinyl castor oil;
s2, uniformly mixing 100 parts by mass of the product obtained in the step S1, 15 parts by mass of glacial acetic acid, 80 parts by mass of 30% hydrogen peroxide and 0.09 part by mass of phosphoric acid, reacting at 55 ℃ for 4 hours, and vacuumizing at 50 ℃ for removing water to obtain epoxy terminal carboxyl castor oil;
s3, mixing 292g of the product obtained in the step S2, 87g of DOPO and 0.3g of phosphoric acid, reacting at 130 ℃ for 4 hours, and cooling to 40 ℃ to obtain phosphorus-containing carboxyl terminated castor oil;
and S4, adding 29g of propylamine into the product obtained in the step S3, carrying out heat preservation at 40 ℃ for reaction, and then heating to 90 ℃ and carrying out reduced pressure distillation for 2 hours to obtain the phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer.
Example 2
The embodiment provides a phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer, and the preparation method comprises the following steps:
s1, taking 400g of castor oil, carrying out reduced pressure distillation and dehydration for 30min at 110 ℃, cooling to 50 ℃, adding 211g of norbornene dianhydride and 6g of N, N-dimethylcyclohexylamine, uniformly mixing, stirring, heating to 120 ℃, and carrying out heat preservation reaction for 4h to obtain carboxyl-terminated vinyl castor oil;
s2, uniformly mixing 110 parts by mass of the product obtained in the step S1, 14 parts by mass of glacial acetic acid, 90 parts by mass of 30% hydrogen peroxide and 0.1 part by mass of phosphoric acid, reacting at 55 ℃ for 4 hours, and vacuumizing at 50 ℃ for removing water to obtain epoxy terminal carboxyl castor oil;
s3, mixing 300g of the product obtained in the step S2, 87g of DOPO and 0.3g of phosphoric acid, reacting at 140 ℃ for 4 hours, and cooling to 50 ℃ to obtain phosphorus-containing carboxyl terminated castor oil;
s4, adding 30g of ethylenediamine into the product obtained in the step S3, carrying out reaction at the temperature of 50 ℃, and then heating to 95 ℃ and carrying out reduced pressure distillation for 2 hours to obtain the phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer.
Example 3
The embodiment provides a phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer, and the preparation method comprises the following steps:
s1, taking 400g of castor oil, carrying out reduced pressure distillation and dehydration for 30min at 110 ℃, cooling to 50 ℃, adding 213g of exo-3, 6-epoxy-1, 2,3, 6-tetrahydrophthalic anhydride and 6g of N, N-dimethylcyclohexylamine, uniformly mixing, stirring and heating to 120 ℃, and then carrying out heat preservation reaction for 4h to obtain carboxyl-terminated vinyl castor oil;
s2, uniformly mixing 115 parts by mass of the product obtained in the step S1, 16 parts by mass of glacial acetic acid, 85 parts by mass of 30% hydrogen peroxide and 0.11 part by mass of phosphoric acid, reacting for 4 hours at 55 ℃, and vacuumizing and removing water at 50 ℃ to obtain epoxy terminal carboxyl castor oil;
s3, mixing 301g of the product obtained in the step S2, 87g of DOPO and 0.3g of phosphoric acid, reacting at 140 ℃ for 4 hours, and cooling to 60 ℃ to obtain phosphorus-containing carboxyl terminated castor oil;
and S4, adding 47g of aniline into the product of the step S3, carrying out heat preservation at 60 ℃ for reaction, and then heating to 100 ℃ and carrying out reduced pressure distillation for 2 hours to obtain the phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer.
Example 4
The embodiment provides a phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer, and the preparation method comprises the following steps:
s1, taking 400g of castor oil, carrying out reduced pressure distillation and dehydration for 30min at 110 ℃, cooling to 50 ℃, adding 213g of methyltetrahydrophthalic anhydride and 6g of N, N-dimethylcyclohexylamine, uniformly mixing, stirring, heating to 120 ℃, and then carrying out heat preservation reaction for 4h to obtain carboxyl-terminated vinyl castor oil;
s2, uniformly mixing 120 parts by mass of the product obtained in the step S1, 14 parts by mass of glacial acetic acid, 90 parts by mass of 30% hydrogen peroxide and 0.1 part by mass of phosphoric acid, reacting at 55 ℃ for 4 hours, and vacuumizing at 50 ℃ for removing water to obtain epoxy terminal carboxyl castor oil;
s3, mixing 301g of the product obtained in the step S2, 87g of DOPO and 0.3g of phosphoric acid, reacting at 140 ℃ for 4 hours, and cooling to 55 ℃ to obtain phosphorus-containing carboxyl terminated castor oil;
and S4, adding 30g of ethylenediamine into the product obtained in the step S3, preserving heat at 55 ℃ for reaction, and then heating to 90 ℃ and distilling for 2 hours under reduced pressure to obtain the phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer.
Example 5
The embodiment provides a phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer, and the preparation method comprises the following steps:
s1, taking 400g of castor oil, carrying out reduced pressure distillation and dehydration for 30min at 110 ℃, cooling to 50 ℃, adding 319g of bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride and 7g of N, N-dimethylcyclohexylamine, uniformly mixing, stirring, heating to 120 ℃, and then carrying out heat preservation reaction for 4h to obtain carboxyl-terminated vinyl castor oil;
s2, uniformly mixing 140 parts by mass of the product obtained in the step S1, 18 parts by mass of glacial acetic acid, 90 parts by mass of 30% hydrogen peroxide and 0.12 part by mass of phosphoric acid, reacting for 5 hours at 55 ℃, and vacuumizing and removing water at 50 ℃ to obtain epoxy terminal carboxyl castor oil;
s3, mixing 350g of the product obtained in the step S2, 87g of DOPO and 0.3g of phosphoric acid, reacting at 160 ℃ for 6 hours, and cooling to 70 ℃ to obtain phosphorus-containing carboxyl terminated castor oil;
and S4, adding 47g of aniline into the product of the step S3, carrying out heat preservation at 70 ℃ for reaction, and then heating to 100 ℃ and carrying out reduced pressure distillation for 2 hours to obtain the phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer.
Example 6
The embodiment provides a phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer, and the preparation method comprises the following steps:
s1, taking 400g of castor oil, carrying out reduced pressure distillation and dehydration for 30min at 110 ℃, cooling to 50 ℃, adding 229g of methylnadic anhydride and 6g of N, N-dimethylcyclohexylamine, uniformly mixing, stirring, heating to 120 ℃, and then carrying out heat preservation reaction for 4h to obtain carboxyl-terminated vinyl castor oil;
s2, uniformly mixing 130 parts by mass of the product obtained in the step S1, 17 parts by mass of glacial acetic acid, 85 parts by mass of 30% hydrogen peroxide and 0.09 part by mass of phosphoric acid, reacting at 55 ℃ for 4 hours, and vacuumizing at 50 ℃ for removing water to obtain epoxy terminal carboxyl castor oil;
s3, mixing 308g of the product obtained in the step S2, 87g of DOPO and 0.3g of phosphoric acid, reacting at 150 ℃ for 5 hours, and cooling to 65 ℃ to obtain phosphorus-containing carboxyl terminated castor oil;
and S4, adding 68g of N, N-dimethyl p-phenylenediamine into the product obtained in the step S3, preserving the heat at 65 ℃ for reaction, and then heating to 95 ℃ for reduced pressure distillation for 2 hours to obtain the phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer.
Examples 7 to 12
Examples 7-12 each provide a polyvinyl chloride sheath provided with flame resistance and high transparency, which can be applied to HDMI wires, and which is prepared by the following method:
the phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer, polyvinyl chloride, chloroprene rubber and calcium/zinc composite stabilizer are taken as raw materials, blended at 120+/-10 ℃ to obtain a mixture according to the formula of a sizing material for preparing a polyvinyl chloride sheath shown in table 1 (the unit is parts by mass), and the mixture is subjected to thermoplastic in an internal mixer at 165 ℃ for 5min. And then extruding and granulating at 180 ℃ by using an extruder.
The polyvinyl chloride sheath provided in example 7 used the phosphorus-nitrogen containing castor oil based flame retardant plasticizer provided in example 1; the polyvinyl chloride sheath provided in example 8 uses the phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer provided in example 2; example 9 provides a polyvinyl chloride jacket using the phosphorus-nitrogen containing castor oil based flame retardant plasticizer provided in example 3; the polyvinyl chloride sheath provided in example 10 used the phosphorus-nitrogen containing castor oil-based flame retardant plasticizer provided in example 4; the polyvinyl chloride sheath provided in example 11 used the phosphorus-nitrogen containing castor oil based flame retardant plasticizer provided in example 5; the polyvinyl chloride sheath provided in example 12 used the phosphorus-nitrogen containing castor oil based flame retardant plasticizer provided in example 6.
The transmittance test of the polyvinyl chloride sheath was tested according to the GB/T12010.8-2010 standard.
TABLE 1
| Examples | 7 | 8 | 9 | 10 | 11 | 12 |
| Polyvinyl chloride | 100 | 100 | 100 | 100 | 100 | 100 |
| Phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer | 25 | 25 | 25 | 25 | 25 | 25 |
| Neoprene rubber | 15 | 15 | 15 | 15 | 15 | 15 |
| Calcium/zinc composite stabilizer | 3 | 3 | 3 | 3 | 3 | 3 |
The results of the test for the properties of polyvinyl chloride sheaths made according to the compound formulation in table 1 are shown in table 2 below.
It can be found from the data that the flame resistant high clarity polyvinyl chloride jackets prepared using the phosphorus nitrogen containing castor oil based flame retardant plasticizers provided in examples 1-6, respectively, substantially meet the criteria except that the polyvinyl chloride jackets provided in examples 7-9 failed to cold bend at-40 ℃. According to the test results of Table 2, the polyvinyl chloride sheath rubber material obtained by adopting the phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer provided by the application has the characteristics of high transparency, has a VW-1 combustion grade and a temperature resistance grade of minus 20-80 ℃, and can also resist a low temperature of minus 40 ℃.
TABLE 2
Example 13
The embodiment provides a phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer, which is blended with PVC and the like to prepare a PVC material, and the performance of the PVC material is tested.
The phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer is prepared by the following steps:
s1, taking 400g of castor oil, carrying out reduced pressure distillation and dehydration for 30min at 110 ℃, cooling to 50 ℃, adding 128g of maleic anhydride and 6g of triethylamine, uniformly mixing, stirring, heating to 120 ℃, and carrying out heat preservation reaction for 4h to obtain carboxyl-terminated vinyl castor oil;
s2, uniformly mixing 100 parts by mass of the product obtained in the step S1, 15 parts by mass of glacial acetic acid, 80 parts by mass of 30% hydrogen peroxide and 0.09 part by mass of phosphoric acid, reacting at 55 ℃ for 4 hours, and vacuumizing at 50 ℃ for removing water to obtain epoxy terminal carboxyl castor oil;
s3, mixing 292g of the product obtained in the step S2, 87g of DOPO and 0.3g of phosphoric acid, reacting at 130 ℃ for 4 hours, and cooling to 40 ℃ to obtain the phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer;
and S4, adding 47g of aniline into the product of the step S3, carrying out heat preservation at 40 ℃ for reaction, and then heating to 90 ℃ and carrying out reduced pressure distillation for 2 hours to obtain the phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer.
In step S1, the castor oil corresponds to the molecular structural formula:
in the step S1, castor oil, maleic anhydride and triethylamine are mixed to react to generate carboxyl terminated vinyl castor oil, and the step can carry out one-arm and two-arm formation on three arms of the castor oil, so that the steric hindrance effect of the subsequent epoxy carboxyl terminated castor oil and flame retardant DOPO reaction is reduced, and the reaction efficiency of the epoxy carboxyl terminated castor oil and the flame retardant DOPO is improved. The molecular structural formula corresponding to the carboxyl-terminated vinyl castor oil is as follows:
in the step S2, the carboxyl-terminated vinyl castor oil is subjected to epoxidation under the action of mixed acid and hydrogen peroxide, and epoxy carboxyl-terminated castor oil is correspondingly generated, wherein the molecular structural formula corresponding to the epoxy carboxyl-terminated castor oil is as follows:
in the step S3, epoxy carboxyl terminated castor oil reacts with flame retardant DOPO and phosphoric acid, epoxy carboxyl terminated castor oil and flame retardant DOPO are grafted by utilizing epoxy groups, and the phosphorus carboxyl terminated castor oil is obtained, wherein the molecular structural formula corresponding to the phosphorus carboxyl terminated castor oil is as follows:
in the step S4, the reaction of the phosphorus-containing carboxyl-terminated castor oil and the aniline utilizes the epoxy group to graft the phosphorus-containing carboxyl-terminated castor oil and the aniline to generate the phosphorus-containing nitrogen castor oil-based flame-retardant plasticizer, and the molecular structural formula corresponding to the phosphorus-containing nitrogen castor oil-based flame-retardant plasticizer is as follows:
the phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer provided by the embodiment takes castor oil as a base material, belongs to a vegetable oil-based plasticizer, is harmless to human bodies, has a relative molecular mass which is larger than that of a phthalic plasticizer, has small migration, is grafted with phosphorus and nitrogen, and can be added into a PVC cable base material, so that the plasticity and toughness of the PVC base material can be improved, and the high temperature resistance of the PVC cable material can be improved.
The preparation method of the PVC material provided by the embodiment comprises the following steps:
s1, heating PVC resin to 115 ℃ in a vacuum state, adding phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer for mixing, and finally stirring at 1600r/min for 25min at constant temperature to obtain a mixture;
s2, placing the mixture into a double-screw extruder for extrusion granulation to obtain the PVC material, wherein the extrusion conditions are as follows: the rotating speed of the screw is 600r/min, and the discharging temperature of the machine head is 170-185 ℃.
When 20wt% of the phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer is added to the PVC material, the limiting oxygen index is 28.4+/-1.0%, the tensile strength is 27+/-0.5 MPa, the elongation at break is 220+/-5%, and the initial thermal decomposition temperature is 240 ℃.
When 40wt% of the phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer is added into a PVC material, the limiting oxygen index is 31.3+/-0.8%, the tensile strength is 18+/-0.6 MPa, the elongation at break is 318+/-7%, and the initial thermal decomposition temperature is 298 ℃.
When 60wt% of the phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer is added to the PVC material, the limiting oxygen index is 29.1+/-1.1%, the tensile strength is 11+/-0.2 MPa, the elongation at break is 446+/-11%, and the initial thermal decomposition temperature is 277 ℃.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the application, which are described in detail and are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.
Claims (10)
1. The preparation method of the phosphorus-nitrogen-containing castor oil-based flame-retardant plasticizer is characterized by comprising the following steps of:
s1, mixing castor oil, double bond-containing dianhydride and an amine catalyst for reaction to obtain carboxyl-terminated vinyl castor oil;
s2, mixing and reacting the carboxyl-terminated vinyl castor oil with glacial acetic acid, hydrogen peroxide and phosphoric acid to obtain epoxy carboxyl-terminated castor oil;
s3, mixing and reacting the epoxy carboxyl terminated castor oil with DOPO and an acidic catalyst to obtain phosphorus carboxyl terminated castor oil;
s4, mixing and reacting the phosphorus-containing terminal carboxyl castor oil and the amine compound to obtain the phosphorus-containing nitrogen castor oil-based flame-retardant plasticizer.
2. The method according to claim 1, wherein,
the double bond-containing dianhydride is at least one of maleic anhydride, norbornene dianhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, methyl tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride and exo-3, 6-epoxy-1, 2,3, 6-tetrahydrophthalic anhydride;
the amine catalyst is at least one of N, N-dimethyl cyclohexylamine, triethylamine and N, N-dimethyl benzylamine.
3. The method according to claim 2, wherein,
in the step S1, the molar ratio of the castor oil to the double bond-containing dianhydride is 1: (3-4) the addition amount of the amine catalyst is 1% -1.5% of the total mass of the castor oil and the double bond-containing dianhydride;
the reaction temperature of the mixed reaction of castor oil, double bond-containing dianhydride and amine catalyst is 115-125 ℃ and the reaction time is 3-5h.
4. The method according to claim 1, wherein the hydrogen peroxide is derived from 30% by mass of hydrogen peroxide.
5. The method according to claim 4, wherein,
in the step S2, the addition amount of the carboxyl-terminated vinyl castor oil is 83-151 parts by mass, the addition amount of the glacial acetic acid is 14-18 parts by mass, the addition amount of the 30% hydrogen peroxide is 72-96 parts by mass, and the addition amount of the phosphoric acid is 0.09-0.12 part by mass;
the reaction temperature of the mixed reaction of the carboxyl-terminated vinyl castor oil, glacial acetic acid, 30% of hydrogen peroxide and phosphoric acid is 55-65 ℃, the reaction time is 3-6h, and the temperature is reduced to 50-55 ℃ after the reaction is completed, and then the vacuum pumping and the water removal are carried out.
6. The method according to claim 1, wherein in the step S3, the ratio of the amounts of the substances of the epoxy-terminated castor oil, the DOPO and the acidic catalyst is 1: (2-3):
(2-3)；
the reaction temperature of the mixed reaction of the epoxy carboxyl terminated castor oil and DOPO and the acid catalyst is 130-170 ℃ and the reaction time is 3-6h.
7. The method according to claim 6, wherein the acidic catalyst is a phosphoric acid solution of 85% by mass.
8. The method according to claim 1, wherein in the step S4, the amine compound is at least one of propylamine, ethylenediamine, aniline, N-dimethyl-p-phenylenediamine;
the ratio of the amounts of the substances of the phosphorus-terminated castor oil and the amine compound is 1: (3-4), the reaction temperature of the mixing reaction is 50-70 ℃, the reaction time is 4-7h, the temperature is increased to 90-100 ℃ after the reaction is completed, and reduced pressure distillation is carried out for not less than 2h, so that the phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer is obtained.
9. A phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer prepared by the method of any one of claims 1 to 8.
10. Use of the phosphorus-nitrogen-containing castor oil-based flame retardant plasticizer according to claim 9 for the preparation of polyvinyl chloride compounds.
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| CN118344686B (en) * | 2024-06-17 | 2024-09-10 | 山东振曦新材料科技有限公司 | PVC material containing flame-retardant plasticizer and preparation method thereof |
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