CN112210131A - 一种阻燃橡胶及其制备方法 - Google Patents
一种阻燃橡胶及其制备方法 Download PDFInfo
- Publication number
- CN112210131A CN112210131A CN202011111331.4A CN202011111331A CN112210131A CN 112210131 A CN112210131 A CN 112210131A CN 202011111331 A CN202011111331 A CN 202011111331A CN 112210131 A CN112210131 A CN 112210131A
- Authority
- CN
- China
- Prior art keywords
- parts
- flame retardant
- rubber
- natural rubber
- polymer type
- 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.)
- Withdrawn
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 61
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229920001971 elastomer Polymers 0.000 title claims abstract description 26
- 239000005060 rubber Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 29
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 29
- 229920001194 natural rubber Polymers 0.000 claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000006229 carbon black Substances 0.000 claims abstract description 8
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 8
- 239000010439 graphite Substances 0.000 claims abstract description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012188 paraffin wax Substances 0.000 claims abstract description 8
- 239000008117 stearic acid Substances 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 239000011593 sulfur Substances 0.000 claims abstract description 8
- 239000011787 zinc oxide Substances 0.000 claims abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- URGNHDJCYWEAKG-UHFFFAOYSA-N 1-bromo-4-[(4-bromophenyl)-phenylphosphoryl]benzene Chemical compound C1=CC(Br)=CC=C1P(=O)(C=1C=CC(Br)=CC=1)C1=CC=CC=C1 URGNHDJCYWEAKG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005859 coupling reaction Methods 0.000 claims abstract description 5
- YERHJBPPDGHCRJ-UHFFFAOYSA-N 1-[4-(1-oxoprop-2-enyl)-1-piperazinyl]-2-propen-1-one Chemical group C=CC(=O)N1CCN(C(=O)C=C)CC1 YERHJBPPDGHCRJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- IRQWEODKXLDORP-UHFFFAOYSA-N 4-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=C)C=C1 IRQWEODKXLDORP-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 229910052763 palladium Inorganic materials 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000013067 intermediate product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- MBJBQKGVONGEEM-UHFFFAOYSA-N CC1=CC=CC=C1.C(C=C)(=O)N1CCN(CC1)C(C=C)=O Chemical compound CC1=CC=CC=C1.C(C=C)(=O)N1CCN(CC1)C(C=C)=O MBJBQKGVONGEEM-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical group [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VMPZJKXDACAVKM-UHFFFAOYSA-N CC1=CC=CC=C1.C(=C)C1=CC=C(C(=O)O)C=C1 Chemical compound CC1=CC=CC=C1.C(=C)C1=CC=C(C(=O)O)C=C1 VMPZJKXDACAVKM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- 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
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6509—Six-membered rings
- C07F9/650952—Six-membered rings having the nitrogen atoms in the positions 1 and 4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/148—Side-chains having aromatic units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/22—Molecular weight
- C08G2261/228—Polymers, i.e. more than 10 repeat units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/316—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain bridged by heteroatoms, e.g. N, P, Si or B
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/334—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
- C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/35—Macromonomers, i.e. comprising more than 10 repeat units
- C08G2261/354—Macromonomers, i.e. comprising more than 10 repeat units containing hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/413—Heck reactions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/70—Post-treatment
- C08G2261/72—Derivatisation
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
- C08L2201/22—Halogen free composition
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
本发明公开了一种阻燃橡胶及其制备方法，该橡胶组成原料各组份的质量份数为：天然橡胶100份、氧化锌3～6份、硬脂酸1～2份、防老剂4010NA 1～2份、石蜡3～6份、硫磺1～3份、促进剂CZ 0.5～1份、促进剂DM 0.5～3份、炭黑(N330)20份、可膨胀石墨1～10份、聚合物型阻燃剂0～40份；聚合物型阻燃剂是以四三苯基磷钯[Pd(PPh3)4]为催化剂，1,4‑二丙烯酰基哌嗪与双(4‑溴苯基)苯基氧化膦经Heck偶联聚合，再以4‑乙烯基苯甲酸封端制备得到，聚合度x＝1～12；采用本方法制备的天然橡胶具有优异的阻燃性能、机械性能，并且改善了阻燃剂添加到橡胶基体中引起的机械性能下降问题。适用于轮胎、天然橡胶板材、管材，电线电缆，汽车用橡胶零件等。
Description
技术领域
本发明属于橡胶工艺技术技术领域，具体涉及一种阻燃橡胶及其制备方法。
背景技术
天然橡胶因具有优良的回弹性、绝缘性、隔水性和可塑性，已广泛应用于汽车轮胎、飞机轮胎、防水材料、密封材料、减隔震材料、胶管及电器配件中。天然橡胶极易燃烧，且会产生大量黑烟，给火场中人们的逃生造成极大威胁，有必要对天然橡胶进行阻燃改性。橡胶中添加阻燃剂能有效提高橡胶制品的阻燃性能，目前广泛应用的阻燃剂大都是卤系阻燃剂，虽然阻燃效果较好，但是易产生卤化氢等有害气体，造成环境污染等问题，使其应用受到限制。膨胀型阻燃剂因其低毒、环保等优点，在聚乙烯、聚丙烯、环氧树脂等高分子材料中获得广泛应用。以聚磷酸铵(APP)和季戊四醇(PER)复配组成的阻燃剂是典型的膨胀阻燃体系，在多种高分子材料中表现出优异的阻燃效果。但膨胀型阻燃剂多为添加型的阻燃剂，其的强极性使其与天然橡胶材料基体难以很好的相容，使得阻燃剂在聚合物基体内容易发生迁移，在基体内易团聚分散不均，从而导致橡胶材料的阻燃性能、力学性能大幅度下降。
发明内容
本发明的目的是针对添加型膨胀阻燃体系阻燃剂与天然橡胶基体相容性差的问题，提供一种通过化学方法链接磷氮类阻燃剂的天然橡胶，该阻燃天然橡胶具有良好的阻燃性，并且仍能保持优异的机械性能。
一种阻燃橡胶，其组分包括：
按重量份数计算，天然橡胶100份、氧化锌3～6份、硬脂酸1～2份、防老剂4010NA 1～2份、石蜡3～6份、硫磺1～3份、促进剂CZ 0.5～1份、促进剂DM 0.5～3份、炭黑(N330)20份、可膨胀石墨1～10份、聚合物型阻燃剂0～40份。
所述聚合物型阻燃剂具有式(I)分子结构：
其中，x取值为1～12。
一种阻燃橡胶及其制备方法，所述制备方法包括以下步骤：
(1)将天然橡胶生胶在开炼机上塑炼10-15min；
(2)按各组分质量配比依次添加到天然橡胶中混炼；胶料混炼加料顺序如下：硬脂酸，氧化锌，促进剂CZ，促进剂DM，防老剂4010NA，炭黑，可膨胀石墨，石蜡，聚合物型阻燃剂，硫磺；
(3)将上述混炼胶在开炼机上进行打三角包、下片，混炼胶放置24h后使用平板硫化机硫化，硫化温度为130-160℃。
所述的聚合物型阻燃剂，制备方法如下：
(1)以四三苯基磷钯[Pd(PPh3)4]为催化剂，三乙胺为缚酸剂，甲苯为反应溶剂，1,4-二丙烯酰基哌嗪滴入含双(4-溴苯基)苯基氧化膦的反应体系中，经Heck偶联反应，制备苯基溴封端的中间体A。
(2)以四三苯基磷钯[Pd(PPh3)4]为催化剂，三乙胺为缚酸剂，甲苯为反应溶剂，4-乙烯基苯甲酸滴入含中间体A的反应体系中，经Heck偶联反应，制备聚合物型阻燃剂。
本发明的优点与效果是：
(1)本发明阻燃橡胶采用的聚合物型阻燃剂，可以通过化学键合很好的接枝到天然橡胶上，与天然橡胶有良好的相容性，实现阻燃剂在天然橡胶基体中均匀分散，能够防止迁移。
(2)本发明所述的聚合物型阻燃剂不含卤素、有效减少了高分子燃烧时有毒有害气体的排放，减少了对环境的污染和对人体的伤害。
(3)本发明公开的阻燃橡胶具有优异的阻燃性能以及良好的机械性能。
附图说明
图1为聚合物型阻燃剂的1H-NMR。
具体实施方式
为使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解，下面结合具体实施方式，进一步阐述本发明本发明测试：
实施例1
制备聚合物型阻燃剂A。
第一步：称取9.14g(0.09mol)三乙胺、8.69g(0.03mol)三(邻甲基苯基)磷、20.03g(0.05mol)双(4-溴苯基)苯基氧化膦和50mL无水甲苯中放入反应釜中，通入N2，并抽换气3次，加入1.6g(0.01mol)乙酸钯，加热至45℃搅拌反应2h后继续升温至90℃，将15mL浓度为1mol/L的1,4-二丙烯酰基哌嗪的甲苯溶液于0.5h内滴加至上述反应体系中，滴完后保温搅拌反应7h后，冷却至40℃，趁热过滤，取滤液减压蒸馏得到粗产物；经硅胶柱层析纯化[洗脱剂：m(二氯甲烷)/(石油醚)＝10:1]，得到中间产物A。
1H-NMR计算得到聚合度x≈1，参阅附图1，产率为88.3％。
第二步：称取11.57g中间产物A重新溶解于30mL甲苯中，并加入3.88g(0.04mol)三乙胺和1.25g(0.004mol)三(邻甲基苯基)磷，开启氮气保护，充分搅拌溶解后加入0.23g(0.001mol)乙酸钯，加热至45℃搅拌反应2h后继续升温至90℃，开始滴加30mL浓度为1mol/L的4-乙烯基苯甲酸甲苯溶液于0.5h内滴完后，保温搅拌反应8h结束反应，冷却至40℃，趁热过滤，取滤液减压蒸馏得到粗产物，以二氯甲烷溶解粗产物，加入水/甲醇(V/V＝3:1)混合溶液进行萃取，重复3次后，减压蒸馏得到聚合物型阻燃剂，记为A。
聚合物型含磷氮阻燃剂的1H-NMR谱图采用BrukerAV-400核磁共振仪测定，溶剂为CDCl3(TMS内标)，结果参阅附图1。
实施例1
制备聚合物型阻燃剂B。
第一步：称取12.75g(0.13mol)三乙胺、13.11g(0.04mol)三(邻甲基苯基)磷、30.21g(0.07mol)双(4-溴苯基)苯基氧化膦和70mL无水甲苯中放入反应釜中，加入2.42g(0.01mol)乙酸钯，加热至45℃搅拌反应2h后继续升温至80℃，将80mL浓度为0.4mol/L的1,4-二丙烯酰基哌嗪甲苯溶液于0.5h内滴加至上述反应体系中，滴完后保温搅拌反应12h；剩余步骤与实施例1相同。
1H-NMR计算得到聚合度x≈12，产率为76.3％。
第二步：称取33.02g中间产物A重新溶解于60mL甲苯中，并加入1.65g(0.02mol)三乙胺和3.58g(0.012mol)三(邻甲基苯基)磷，开启氮气保护，充分搅拌溶解后加入0.66g(0.003mol)乙酸钯，加热至45℃搅拌反应2h后继续升温至90℃，开始滴加12mL浓度为1mol/L的4-乙烯基苯甲酸甲苯溶液于0.5h内滴完；剩余步骤与实施例1相同，得到聚合物型阻燃剂B。
实施例3
天然橡胶的配方，按重量份数计算：天然橡胶100份、氧化锌6份、硬脂酸2份、防老剂4010NA 1份、石蜡3份、硫磺3份、促进剂CZ0.5份、促进剂DM 1份、炭黑(N330)20份、可膨胀石墨10份、聚合物型阻燃剂A40份。
将天然橡胶生胶在开炼机上塑炼15min。按照质量配依次加入各组分，将上述混炼胶在开炼机上进行打三角包、下片，混炼胶放置24h后使用平板硫化机硫化，硫化温度为160℃。
实施例4
天然橡胶的配方，按重量份数计算：天然橡胶100份、氧化锌4份、硬脂酸2份、防老剂4010NA 2份、石蜡4份、硫磺3份、促进剂CZ 1份、促进剂DM 1份、炭黑(N330)20份、可膨胀石墨5份、聚合物型阻燃剂A20份。
硫化温度为145℃，其余与实施例3相同。
实施例5
与实施例3的不同之处在于，配方组分中聚合物型阻燃剂A替换成聚合物型阻燃剂B。
实施例6
与实施例4的不同之处在于，配方组分中聚合物型阻燃剂A替换成聚合物型阻燃剂B。
对比例1
无阻燃天然橡胶配方：按重量份数计算，天然橡胶100份、氧化锌6份、硬脂酸2份、防老剂4010NA 0.5份、石蜡3份、硫磺3份、促进剂CZ 0.5份、促进剂DM 0.8份、炭黑(N330)20份，可膨胀石墨10份。
硫化温度为130℃，其余与实施例3相同。
实施例3～6和对比例1制备的橡胶的极限氧指数(LOI)按照GB/T 2406.2-2009进行测试；垂直燃烧测试按GB/T 2408-2008进行测试；拉伸强度和断裂伸长率参照GB/T 528-2009进行。测试结果参见表1所示。
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (3)
1.一种阻燃天然橡胶，其特征在于，按重量份数计算，包括如下组分：
天然橡胶100份、氧化锌3～6份、硬脂酸1～2份、防老剂4010NA 1～2份、石蜡3～6份、硫磺1～3份、促进剂CZ 0.5～1份、促进剂DM 0.5～3份、炭黑(N330)20份、可膨胀石墨1～10份、聚合物型阻燃剂0～40份；
所述聚合物型阻燃剂具有式(I)结构：
其中，x取值为1～12。
2.一种阻燃天然橡胶的制备方法，其特征在于，包括以下步骤：
(1)将天然橡胶生胶在开炼机上塑炼10-15min；
(2)按各组分质量配比依次添加到天然橡胶中混炼；胶料混炼加料顺序如下：硬脂酸，氧化锌，促进剂CZ，促进剂DM，防老剂4010NA，炭黑，可膨胀石墨，石蜡，聚合物型阻燃剂，硫磺；
(3)将上述混炼胶在开炼机上进行打三角包、下片，混炼胶放置24h后使用平板硫化机硫化，硫化温度为130-160℃。
3.根据权利要求1或2所述的一种阻燃天然橡胶及其制备方法，其特征在于，所述的聚合物型阻燃剂制备方法包括：
(1)以四三苯基磷钯[Pd(PPh3)4]为催化剂，三乙胺为缚酸剂，甲苯为反应溶剂，1,4-二丙烯酰基哌嗪滴入含双(4-溴苯基)苯基氧化膦的反应体系中，经Heck偶联反应，制备苯基溴封端的中间体A。
(2)以四三苯基磷钯[Pd(PPh3)4]为催化剂，三乙胺为缚酸剂，甲苯为反应溶剂，4-乙烯基苯甲酸滴入含中间体A的反应体系中，经Heck偶联反应，制备聚合物型阻燃剂。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011111331.4A CN112210131A (zh) | 2020-10-16 | 2020-10-16 | 一种阻燃橡胶及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011111331.4A CN112210131A (zh) | 2020-10-16 | 2020-10-16 | 一种阻燃橡胶及其制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112210131A true CN112210131A (zh) | 2021-01-12 |
Family
ID=74055502
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011111331.4A Withdrawn CN112210131A (zh) | 2020-10-16 | 2020-10-16 | 一种阻燃橡胶及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112210131A (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114334262A (zh) * | 2022-01-24 | 2022-04-12 | 安徽鸿海电缆有限公司 | 一种氟塑料绝缘硅橡胶护套耐高温控制电缆 |
| CN115028891A (zh) * | 2022-06-10 | 2022-09-09 | 安徽建筑大学 | 一种阻燃导热剂、其制备方法及其在橡胶复合材料中的应用 |
-
2020
- 2020-10-16 CN CN202011111331.4A patent/CN112210131A/zh not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114334262A (zh) * | 2022-01-24 | 2022-04-12 | 安徽鸿海电缆有限公司 | 一种氟塑料绝缘硅橡胶护套耐高温控制电缆 |
| CN114334262B (zh) * | 2022-01-24 | 2023-06-27 | 安徽鸿海电缆有限公司 | 一种氟塑料绝缘硅橡胶护套耐高温控制电缆 |
| CN115028891A (zh) * | 2022-06-10 | 2022-09-09 | 安徽建筑大学 | 一种阻燃导热剂、其制备方法及其在橡胶复合材料中的应用 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113956572B (zh) | 一种阻燃聚烯烃组合物及其制备方法 | |
| CN112210131A (zh) | 一种阻燃橡胶及其制备方法 | |
| CN102838778A (zh) | 一种氮磷阻燃剂及其制备方法与应用 | |
| CN110746646B (zh) | 生物质基阻燃剂及其制备方法 | |
| CN105086925B (zh) | 一种环保阻燃硅酮密封胶及其制备方法 | |
| CN112321955A (zh) | 一种环保型阻燃绝缘橡胶复合材料及其制备方法 | |
| CN110591382A (zh) | 低密度无卤阻燃石墨烯导热硅胶及其制备方法 | |
| CN114349968A (zh) | 一种poss改性磷腈阻燃剂及其制备方法、一种聚碳酸酯阻燃复合材料及其制备方法 | |
| CN1974648A (zh) | 一种聚烯烃用含硅阻燃剂及其制备方法与应用 | |
| CN110684358A (zh) | 新能源动力电池的填充发泡灌封硅胶、制备方法及应用 | |
| CN109206663B (zh) | 一种新型含氮有机锑阻燃剂及其制备方法 | |
| CN105601845B (zh) | 一种高分子量含腈基聚硅氧烷的合成及过氧化物型热硫化腈硅橡胶的制备方法 | |
| CN116478357A (zh) | 含端异氰酸酯基团的dopo基反应型阻燃剂及其制备方法和应用 | |
| CN107501526B (zh) | 一种dopo型环氧树脂固化剂及其制备方法 | |
| CN114230978B (zh) | 一种基于含磷硅酸镍晶须的阻燃环氧树脂及制备方法 | |
| CN115716936A (zh) | 一种磷杂菲硅氧烷生物基阻燃支化大分子及其制备方法和应用 | |
| CN112094297A (zh) | 一种含恶二唑环反应型阻燃剂及其制备方法 | |
| CN103936971A (zh) | 一种有机高分子含磷阻燃剂 | |
| CN109575324A (zh) | 一种化学改性的透明阻燃pet母粒及其制造方法和用途 | |
| CN111117209B (zh) | 一种聚氨酯阻燃抗静电复合材料的制备方法 | |
| CN114350025A (zh) | 高成炭无卤复合膨胀阻燃剂以及阻燃型聚苯乙烯树脂 | |
| CN102911418A (zh) | 超浓乳液制备聚丙烯酸酯-有机p阻燃剂的方法 | |
| CN112250915A (zh) | 一种阻燃橡胶及其制备方法 | |
| CN114685937A (zh) | 阻燃环氧树脂复合材料及其制备方法 | |
| CN108299783B (zh) | 一种高强度阻燃电缆料及其制备方法 |
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 | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20210112 |
|
| WW01 | Invention patent application withdrawn after publication |