CN112876676A - Organic phosphorus flame-retardant copolymerized nylon and preparation method thereof - Google Patents
Organic phosphorus flame-retardant copolymerized nylon and preparation method thereof Download PDFInfo
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- CN112876676A CN112876676A CN202110275486.XA CN202110275486A CN112876676A CN 112876676 A CN112876676 A CN 112876676A CN 202110275486 A CN202110275486 A CN 202110275486A CN 112876676 A CN112876676 A CN 112876676A
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- monomer
- lactam
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 128
- 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 121
- 229920001778 nylon Polymers 0.000 title claims abstract description 60
- 239000004677 Nylon Substances 0.000 title claims abstract description 59
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 36
- 239000011574 phosphorus Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 22
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 22
- 150000004985 diamines Chemical class 0.000 claims abstract description 22
- -1 tire cords Substances 0.000 claims abstract description 17
- DVPHDWQFZRBFND-DMHDVGBCSA-N 1-o-[2-[(3ar,5r,6s,6ar)-2,2-dimethyl-6-prop-2-enoyloxy-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]-2-[4-[(2s,3r)-1-butan-2-ylsulfanyl-2-(2-chlorophenyl)-4-oxoazetidin-3-yl]oxy-4-oxobutanoyl]oxyethyl] 4-o-[(2s,3r)-1-butan-2-ylsulfanyl-2-(2-chloropheny Chemical group C1([C@H]2[C@H](C(N2SC(C)CC)=O)OC(=O)CCC(=O)OC(COC(=O)CCC(=O)O[C@@H]2[C@@H](N(C2=O)SC(C)CC)C=2C(=CC=CC=2)Cl)[C@@H]2[C@@H]([C@H]3OC(C)(C)O[C@H]3O2)OC(=O)C=C)=CC=CC=C1Cl DVPHDWQFZRBFND-DMHDVGBCSA-N 0.000 claims abstract description 15
- 230000001105 regulatory effect Effects 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 45
- 239000000463 material Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 150000003951 lactams Chemical class 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 239000012467 final product Substances 0.000 claims description 21
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 20
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical group NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 16
- 238000011049 filling Methods 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 12
- 125000004185 ester group Chemical group 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 8
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 8
- 239000005711 Benzoic acid Substances 0.000 claims description 8
- 235000010233 benzoic acid Nutrition 0.000 claims description 8
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 8
- 238000012693 lactam polymerization Methods 0.000 claims description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 7
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- IRFSXVIRXMYULF-UHFFFAOYSA-N 1,2-dihydroquinoline Chemical compound C1=CC=C2C=CCNC2=C1 IRFSXVIRXMYULF-UHFFFAOYSA-N 0.000 claims description 5
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 5
- 235000011054 acetic acid Nutrition 0.000 claims description 5
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 5
- DQSYGNJXYMAPMV-UHFFFAOYSA-N 2,6-ditert-butyl-4-(3,5-ditert-butyl-4-hydroxyphenyl)sulfanylphenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(SC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 DQSYGNJXYMAPMV-UHFFFAOYSA-N 0.000 claims description 4
- QFNNDGVVMCZKEY-UHFFFAOYSA-N azacyclododecan-2-one Chemical compound O=C1CCCCCCCCCCN1 QFNNDGVVMCZKEY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- DDLUSQPEQUJVOY-UHFFFAOYSA-N nonane-1,1-diamine Chemical compound CCCCCCCCC(N)N DDLUSQPEQUJVOY-UHFFFAOYSA-N 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
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 150000004984 aromatic diamines Chemical class 0.000 claims description 3
- XJIAZXYLMDIWLU-UHFFFAOYSA-N undecane-1,1-diamine Chemical compound CCCCCCCCCCC(N)N XJIAZXYLMDIWLU-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims 18
- 238000004519 manufacturing process Methods 0.000 claims 3
- YDLSUFFXJYEVHW-UHFFFAOYSA-N azonan-2-one Chemical compound O=C1CCCCCCCN1 YDLSUFFXJYEVHW-UHFFFAOYSA-N 0.000 claims 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 239000004753 textile Substances 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 239000011810 insulating material Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 9
- 239000004952 Polyamide Substances 0.000 description 8
- 229920002647 polyamide Polymers 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000009775 high-speed stirring Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229920002292 Nylon 6 Polymers 0.000 description 4
- JYVWZHOGCZHONC-UHFFFAOYSA-N aminomethyl(phenyl)phosphinic acid Chemical compound NCP(O)(=O)C1=CC=CC=C1 JYVWZHOGCZHONC-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- LIUSEHJHXZRLBI-UHFFFAOYSA-N chloromethyl(phenyl)phosphinic acid Chemical compound ClCP(=O)(O)C1=CC=CC=C1 LIUSEHJHXZRLBI-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical class C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 2
- JMLPVHXESHXUSV-UHFFFAOYSA-N dodecane-1,1-diamine Chemical compound CCCCCCCCCCCC(N)N JMLPVHXESHXUSV-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000004260 weight control Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011777 magnesium Chemical group 0.000 description 1
- 229910052749 magnesium Chemical group 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000011591 potassium Chemical group 0.000 description 1
- 229910052700 potassium Chemical group 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011734 sodium Chemical group 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid 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
- 239000002341 toxic gas Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
Abstract
The invention discloses an organic phosphorus flame-retardant copolymerized nylon and a preparation method thereof. The preparation method comprises the following steps: (1) reacting an organic phosphorus flame-retardant monomer with a diamine monomer to form salt; (2) and (2) adding the lactam monomer, the salt or the solution thereof in the step (1), the antioxidant, the catalyst and the molecular weight regulator into a reaction kettle, and polymerizing under an inert atmosphere by regulating and controlling the reaction temperature and pressure to obtain the required organophosphorus flame-retardant copolymerized nylon. The organic phosphorus flame-retardant nylon prepared by the invention needs less reaction flame retardant, has controllable viscosity and excellent flame-retardant property in the preparation process, and can be used in various fields of textiles, insulating materials, tire cords, films and the like.
Description
The present case is application number: 201610932391.X, the name of the invention is: an organic phosphorus flame-retardant copolymerized nylon and a divisional application of a preparation method thereof.
Technical Field
The invention relates to an organic phosphorus flame-retardant copolymerized nylon and a preparation method thereof, belongs to the field of high-molecular flame-retardant materials, and particularly relates to flame-retardant copolymerized nylon for textile, packaging materials, automobile parts, motor parts, engineering plastics and the like and a preparation method thereof.
Background
Nylon is widely used in the fields of building, chemical engineering, traffic, military and the like due to the excellent performances of high strength, heat resistance, wear resistance, solvent resistance and the like. But the amido bond and the water molecule can form hydrogen bond, so that the product has poor dimensional stability and electrical property reduction due to larger water absorption, and simultaneously, the product has the defects of low impact strength in a dry state or at low temperature, opacity, poor solubility and the like, thereby limiting the wider application of the product. In addition, the non-flame retardancy of nylon itself limits its applications. Therefore, the modification of nylon with good flame retardant property has been studied by the industry personnel.
There are generally two ways in which the flame retardant nylon material can be modified: one is adding reactive flame retardant, introducing functional group with flame retardant activity in the nylon copolymerization process; the other is to blend an additive flame retardant and a related synergistic flame retardant into nylon. The latter is susceptible to factors such as dispersibility, compatibility, interfacial properties, etc.; to achieve a certain flame retardancy, the use of a larger amount of additive flame retardant can cause great damage to mechanical properties and electrical properties, thereby limiting the application thereof. The reactive flame retardant can well solve the problems, the molecular structure of the reactive flame retardant is copolymerized into the main chain of the nylon molecule, the problems of volatilization, migration, seepage and the like do not exist, and the reactive flame retardant can provide reliable flame retardant performance within the service life of the material.
At present, the commonly used flame retardants mainly include halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants, inorganic filler type flame retardants, and the like. Halogen-containing flame retardants have been widely used as flame retardant materials for high polymers due to their high flame retardancy, but they are harmful to the environment and human body because of the generation of toxic gases and fumes during combustion, and have been restricted by the European Union. Therefore, the development of a novel flame retardant which is efficient, durable and environmentally friendly has been the subject of intense research in this field. The phosphorus flame retardant, especially the organic phosphorus flame retardant has a prospect of replacing halogen-containing flame retardants. The phosphorus flame retardant can simultaneously act in a condensed phase and a gas phase, and the flame retardant mechanism is that the flame retardant generates products such as phosphoric acid, polyphosphoric acid and the like in the combustion process, so that the dehydration and carbonization of a polymer are promoted, a glassy protective layer is formed, and the heat and substance transfer between the condensed phase and the gas phase is prevented. The combustion process of the phosphorus-containing flame retardant does not generate toxic and harmful gas, has less smoke generation amount and has better flame retardant effect.
The prepared organic phosphorus flame-retardant copolymerized nylon has great academic research and industrial market value. The copolymerization modification can change the main chain, branched chain and molecular chain structure of the polymer, improve the heat resistance, crystallinity, transparency, flexibility, solubility and the like of the nylon polymer, and hopefully obtain a nylon product with low cost and excellent comprehensive performance.
The patent with publication number CN104744690A discloses a preparation method of flame-retardant nylon 6, which comprises the following steps: (1) heating aminomethyl phenyl phosphinic acid, thionyl chloride and ether according to a certain molar ratio in a reaction kettle for reaction to prepare chloromethyl phenyl phosphinic acid; (2) introducing ammonia gas into the chloromethyl phenyl phosphinic acid in a sodium hydroxide solution to carry out ammoniation reaction to prepare aminomethyl phenyl phosphinic acid; (3) the flame-retardant nylon 6 is prepared by polymerizing nylon polymerization monomer caprolactam, aminomethyl phenyl phosphinic acid and a catalyst. The flame retardant disclosed in the patent has no negative influence on the mechanical properties of nylon 6, and can also enable nylon 6 to have good flame retardant effect under the condition of small addition amount of the flame retardant.
Patent publication No. CN103694468A discloses a preparation method of nylon resin: mixing a polymerization monomer, a catalyst, a reactive flame retardant (DOPO derivative) and a char forming agent, and carrying out high-temperature polycondensation to prepare the nylon resin. Wherein the polymerized monomer is one or more of a compound containing carboxyl of amino and lactam; or a diacid and a diamine. The flame retardant is one or more of five DOPO derivatives. The phosphorus-containing flame retardants described in this patent are stable within the polymer and are not easily lost after copolymerization with the monomer. The finally prepared flame-retardant nylon has excellent mechanical properties and can pass a UL-94V-0 test.
The patent publication No. JPH09328543 relates to a polyamide copolymer containing phosphorus in the main chain and a method for preparing the same. The preparation method comprises the steps of (1) pre-reacting phosphorus-containing dicarboxylate with diamine to form salt; (2) the salt is condensed with other comonomers (diacid and diamine, or caprolactam) to produce polyamide copolymers. In this patent, the dicarboxylate is
Wherein R is1Is straight chain or branched chain alkyl with 1 to 8 carbon atoms; r2Is H or methyl. When the phosphorus content in the prepared polyamide copolymer is 6.48-6.58ppm, the limit oxygen index can reach 28.9-29.9%, and the polyamide copolymer has better flame retardant property. But the relative viscosity of the prepared polyamide material is only 0.78-0.82, and the mechanical property and other properties of the material sample have larger promotion space.
The patent with the publication number of CN1042621619A relates to phosphorus-containing flame-retardant polyamide and a preparation method and application thereof. The preparation method comprises the following steps: (1) carrying out pre-polycondensation reaction on hypophosphite used for flame retardance and diamine to generate an oligomer; (2) carrying out pre-polycondensation reaction on the oligomer and dicarboxylic acid salt in a nitrogen atmosphere to obtain a prepolymer; (3) after two times of pre-polycondensation reaction, raising the temperature and reducing the air pressure to normal pressure; (4) raising the temperature and pumping air to trueAnd discharging to obtain the flame-retardant polyamide material. The flame retardant used in this patent is
Wherein R is1And R2Is straight-chain, branched or cyclic C1-C15Alkylene radical, C6-C15Arylene or aralkylene; m is a metal element, and when a is 1, M is lithium, sodium or potassium; when a is 2, M is calcium or magnesium. In the invention, when the phosphorus content reaches more than 0.48 percent, the flame-retardant polyamide can pass the UL-94V-0 grade, and the LOI value is also obviously improved.
As described above, although the prior art has proposed a lot of nylon materials with good flame retardant properties, there is still a strong need in the art for flame retardant nylon with good mechanical properties and flame retardant properties.
Disclosure of Invention
The invention aims to prepare a novel organic phosphorus flame-retardant copolymerized nylon material aiming at the scene that the flame-retardant nylon in the market mainly takes blending as a main part. The novel organic phosphorus flame-retardant nylon is characterized in that the novel organic phosphorus flame-retardant nylon is prepared by pre-polycondensing a flame-retardant monomer with diamine by utilizing the characteristic that the flame-retardant monomer has two carboxylic acid groups, and then polycondensing the flame-retardant monomer with a lactam monomer and copolymerizing the flame-retardant monomer and the diamine. In the process, the addition amount of the flame retardant is small, no synergistic flame retardant is needed, and the obtained nylon material has excellent mechanical property and flame retardant property.
The technical scheme of the invention is as follows:
a flame-retardant nylon, which has a general formula shown as the following formula (1):
wherein R is selected from H, C1-C5Alkyl radical, C6-C10Aryl radical, C3-C10A heteroaryl group; r is preferably H, C1-C3Alkyl radical, C6-C8Aryl radical, C3-C6A heteroaryl group;
R1、R2each independently selected from straight chain and branched chainOr cyclic C1-C10Alkylene radical, C6-C15Arylene or aralkylene, C3-C10An ester group; r1、R2Each independently of the others is preferably straight-chain, branched or cyclic C1-C5Alkylene radical, C6-C10Arylene or aralkylene, C3-C8An ester group;
R3is selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10A heteroaryl group; r3Preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
R4is selected from C3-C12Linear or branched alkylene; r4Preferably C3-C8Linear or branched alkylene;
x represents 1 to 50, y represents 1 to 50, and n represents 1 to 100; x is preferably from 2 to 30, y is preferably from 2 to 30, and n is preferably from 2 to 80, more preferably from 5 to 50.
The preparation method of the flame-retardant nylon comprises the following steps:
(A) reacting an organic phosphorus flame-retardant monomer or a derivative thereof shown in a formula (2) with a diamine monomer shown in a formula (3);
wherein R is selected from H, C1-C5Alkyl radical, C6-C10Aryl radical, C3-C10A heteroaryl group; r is preferably H, C1-C3Alkyl radical, C6-C8Aryl radical, C3-C6A heteroaryl group;
R1、R2each independently selected from linear, branched or cyclic C1-C10Alkylene radical, C6-C15Arylene or aralkylene, C3-C10An ester group; r1、R2Each independently of the otherPreferably is straight-chain, branched or cyclic C1-C5Alkylene radical, C6-C10Arylene or aralkylene, C3-C8An ester group;
R3is selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10A heteroaryl group; r3Preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
obtaining a compound of the following formula (4):
wherein R is4Is selected from C3-C12Linear or branched alkylene; preferably C3-C8Linear or branched alkylene;
(B) reacting a compound of formula (4) with a lactam of formula (5) to obtain a nylon of formula (1):
wherein, R, R1、R2、R3、R4X, y, n are as defined above;
preferably, the flame retardant monomer of formula (2) is reacted with the diamine monomer of formula (3) in a molar ratio of 1:0.1 to 20, preferably 1:0.5 to 10, more preferably 1:1 to 2.
In step (A), the reaction is preferably carried out in the presence of a solvent such as water or an organic solvent such as an alcoholic solvent, preferably with a slight excess (for example, a molar excess of 0.1 to 10%, preferably 0.5 to 5%) of the diamine-based monomer, so that the salt solution is prepared at a pH of 7 to 9. The reaction temperature is increased from room temperature to 40-70 ℃ within 5-20 min.
Preferably, the diamine monomer in step (A) is selected from the group consisting of hexamethylenediamine, decamethylenediamine, nonanediamine, undecanediamine, dodecanediamine, and fatsGroup C6-C20One or more of imino diamine, aromatic diamine and alicyclic diamine.
In the step (B), preferably, the lactam monomer, the reaction product of the step (A), the antioxidant, the catalyst, the molecular weight regulator and a proper amount of water are added into a reaction kettle, and the reaction temperature and the pressure are regulated and controlled under the nitrogen atmosphere to prepare the required organophosphorus flame-retardant copolymerized nylon.
In step (B), further, the lactam monomers are caprolactam, decanolactam, undecanolactam, dodecanolactam, and various lactam monomers having lactam characteristics.
Further, the antioxidant is one or more of compounds such as p-phenylenediamine and dihydroquinoline and derivatives thereof, 2, 6-di-tert-butyl-4-methylphenol, bis (3, 5-di-tert-butyl-4-hydroxyphenyl) sulfide, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and the like.
Furthermore, the catalyst is one or more of sodium hypophosphite, methyl benzene sulfonic acid, a new ferrocene chiral nylon ligand and the like.
Further, the molecular weight regulator is one or more of benzoic acid, adipic acid, acetic acid and the like.
Further, the step (B) specifically includes the following steps:
a. adding a lactam monomer, the salt obtained in the step (A), a catalyst, an antioxidant, a molecular weight regulator and a proper amount of water into a reaction kettle, vacuumizing, and filling nitrogen for several times to ensure that the pressure in the kettle is 0.1-0.5MPa at the initial stage of reaction;
b. heating the reaction kettle to 200 ℃ and 250 ℃, and maintaining the reaction condition for 30-180min when the pressure is 1.6-2.1 MPa;
c. slowly releasing the pressure to normal pressure at the temperature of 230 ℃ and 280 ℃, then vacuumizing to-0.01 to-0.1 MPa, and copolymerizing for 10-180 min;
d. and finally, filling nitrogen, discharging materials, cooling, granulating, extracting and drying to obtain a final product.
Further, in the step a, the total amount of the lactam monomer added is 8-100 times, preferably 10-40 times, more preferably 12-30 times of the mass of the flame retardant; the catalyst and the antioxidant are 0.01 to 1.0 percent of the mass of the lactam polymerization monomer or the lactam polymer, preferably 0.05 to 0.5 percent of the mass of the lactam polymerization monomer or the lactam polymer, more preferably 0.08 to 0.2 percent of the mass of the lactam polymerization monomer or the lactam polymer, and more preferably about 1/1000.
To be provided with
And hexamethylenediamine and caprolactam, the mechanism of the reaction is: the flame-retardant monomer reacts with hexamethylene diamine to form salt, and then the salt and caprolactam are copolymerized to form the flame-retardant nylon. The reaction equation is:
the invention has the beneficial effects that:
as long as the flame-retardant nylon accounts for 6 percent of the total mass of the polymer, the flame-retardant nylon can basically reach UL-94V-0 level, the limit oxygen index range is 27 to 32 percent, the flame-retardant nylon has low smoke, low toxicity, high efficiency, stability and controllable viscosity, and solves the problem that a plurality of phosphorus-containing monomers disclosed in the prior art cannot realize higher polymerization degree when the phosphorus content is increased.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The molecular structure of the organophosphorus flame-retardant nylon is shown as the following formula 1:
wherein R is selected from H, C1-C5Alkyl radical, C6-C10Aryl radical, C3-C10A heteroaryl group; r is preferably H, C1-C3Alkyl radical, C6-C8Aryl radical, C3-C6A heteroaryl group;
R1、R2each independently selected from linear, branched or cyclic C1-C10Alkylene radical, C6-C15Arylene or aralkylene, C3-C10An ester group; r1、R2Each independently of the others is preferably straight-chain, branched or cyclic C1-C5Alkylene radical, C6-C10Arylene or aralkylene, C3-C8An ester group;
R3is selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10A heteroaryl group; r3Preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
R4is selected from C3-C12Linear or branched alkylene; r4Preferably C3-C8Linear or branched alkylene;
x represents 1 to 50, y represents 1 to 50, and n represents 1 to 100; x is preferably from 2 to 30, y is preferably from 2 to 30, and n is preferably from 2 to 80, more preferably from 5 to 50.
The preparation method of the flame-retardant nylon comprises the following steps:
(A) reacting an organic phosphorus flame-retardant monomer or a derivative thereof with a diamine monomer to enable an excessive amino group to prepare salt;
(B) and (b) reacting the reaction product obtained in the step (A) with lactam to generate the flame-retardant nylon.
In step (A), preferably, the flame retardant is reacted with the diamine-based monomer in a molar ratio of 1:0.1 to 20, preferably 1:0.5 to 10, more preferably 1:1 to 2.
In step (A), the reaction may be carried out in a solvent such as water or an organic solvent such as an alcohol solvent, preferably, the diamine-based monomer is used in a slight excess so that a salt solution having a pH of 7 to 9 is prepared. The reaction temperature is increased from room temperature to 40-70 ℃ within 5-20 min.
Preferably, the diamine monomer in step (A) is hexamethylenediamine, decamethylenediamine, nonanediamine, undecanediamine, dodecanediamine, aliphatic C6-C20One or more of imino diamine, aromatic diamine and alicyclic diamine.
In the step (B), preferably, the lactam monomer, the reaction product of the step (a), the antioxidant, the molecular weight regulator, the catalyst, and a suitable amount of water (e.g., 1 to 10 wt.% of the reaction system, and further 3 to 5 wt.% of water) are added into a reaction kettle, and the reaction temperature and pressure are regulated and controlled under a nitrogen atmosphere to obtain the desired organophosphorus flame retardant copolymerized nylon.
In step (B), the lactam monomers are caprolactam, decanolactam, undecanolactam, dodecanolactam and various lactam monomers with lactam characteristics.
Further, the antioxidant is one or more of compounds such as p-phenylenediamine and dihydroquinoline and derivatives thereof, 2, 6-di-tert-butyl-4-methylphenol, bis (3, 5-di-tert-butyl-4-hydroxyphenyl) sulfide, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and the like.
Furthermore, the catalyst is one or more of sodium hypophosphite, methyl benzene sulfonic acid, a new ferrocene chiral nylon ligand and the like.
Further, the molecular weight regulator is one or more of benzoic acid, adipic acid, acetic acid and the like.
Further, the step (B) specifically includes the steps of:
a. adding a lactam monomer, the salt obtained in the step (A), a catalyst, a molecular weight regulator, an antioxidant and a proper amount of water into a reaction kettle, vacuumizing, and filling nitrogen for several times to ensure that the pressure in the kettle is 0.1-0.5MPa at the initial stage of reaction;
b. heating the reaction kettle to 200 ℃ and 250 ℃, and maintaining the reaction condition for 30-180min when the pressure is 1.6-2.1 MPa;
c. slowly releasing the pressure to normal pressure at the temperature of 230 ℃ and 280 ℃, then vacuumizing to-0.01 to-0.1 MPa, and copolymerizing for 10-180 min;
d. and finally, filling nitrogen, discharging materials, cooling, granulating, extracting and drying to obtain a final product.
Further, in the step a, the total amount of the lactam monomer added is 8-100 times, preferably 10-40 times and more preferably about 12-30 times of the mass of the flame retardant; the catalyst and the antioxidant are 0.01 to 1.0 percent of the mass of the lactam polymerization monomer or the lactam polymer, preferably 0.05 to 0.5 percent of the mass of the lactam polymerization monomer or the lactam polymer, more preferably 0.08 to 0.2 percent of the mass of the lactam polymerization monomer or the lactam polymer, and more preferably about 1/1000.
The examples of the invention are as follows:
the methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like described in the following examples are commercially available unless otherwise specified.
Example 1:
at 50 ℃, a flame-retardant monomer and hexamethylene diamine are mixed in a small amount of water according to a molar ratio of 1: 1.3 stirring to react for 0.5h, adjusting the pH value of the solution to 7.5, and drying to form salt. Adding caprolactam monomer, the salt (accounting for 6 percent of the total mass of the monomer), 1 per thousand of catalyst sodium hypophosphite, antioxidant p-phenylenediamine, molecular weight regulator benzoic acid and 3 percent of deionized water into a reaction kettle, vacuumizing, filling nitrogen for three times, and finally keeping the pressure in the reaction kettle at 0.25 MPa. Heating the reaction kettle, keeping high-speed stirring, and keeping constant temperature and pressure for 2h when the temperature of the reaction kettle reaches 225 ℃ and the pressure is 1.75 MPa. Then the temperature is raised to 260 ℃ and the pressure is released to the normal pressure within 1.5 h. Vacuumizing to-0.05 MPa, charging nitrogen to 0.2MPa after the stirring speed is reduced for a certain value and is stable, discharging the materials, cooling, granulating, extracting and drying to obtain a final product, wherein the relative viscosity of the final product is 2.3, the limited oxygen index is 27.5%, and the flame retardant grade reaches UL-94V-0. Wherein the organic phosphorus flame-retardant monomer is as follows:
example 2:
at 50 ℃, a flame-retardant monomer and hexamethylene diamine are mixed in a small amount of water according to a molar ratio of 1: 1.1 stirring and reacting for 40min, adjusting the pH value of the solution to 7.3, and drying to form salt. Adding a decanolactam monomer, the salt (accounting for 7 percent of the total mass of the monomer), 1 per thousand of catalyst methyl benzenesulfonic acid, antioxidant 2, 6-di-tert-butyl-4-methylphenol, molecular weight regulator adipic acid and 5 percent of deionized water into a reaction kettle, vacuumizing, filling nitrogen for three times, and finally keeping the pressure in the reaction kettle at 0.2 MPa. Heating the reaction kettle, keeping high-speed stirring, and keeping constant temperature and pressure for 2h when the temperature of the reaction kettle reaches 220 ℃ and the pressure is 1.9 MPa. Then the temperature is increased to 270 ℃, and the pressure is released to the normal pressure within 2 hours. Vacuumizing to-0.08 MPa, charging nitrogen to 0.3MPa after the stirring speed is reduced for a certain value and is stable, discharging the materials, cooling, granulating, extracting and drying to obtain a final product, wherein the relative viscosity of the final product is 2.05, the limited oxygen index of the final product is 28.5%, and the flame retardant grade reaches UL-94V-0. Wherein the organic phosphorus flame-retardant monomer is as follows:
example 3:
and (2) at the temperature of 40 ℃, mixing the flame-retardant monomer and decamethylene diamine in a small amount of water according to the molar ratio of 1: 1.1 stirring and reacting for 1h, adjusting the pH value of the solution to 7.8, and drying to form salt. Preparing caprolactam monomer and laurolactam monomer according to the mass ratio of 7:3, adding the salt (accounting for 6.5 percent of the total mass of the monomers), 1 per thousand of catalyst sodium hypophosphite, antioxidant dihydroquinoline, molecular weight control agent benzoic acid and 3.8 percent of deionized water into a reaction kettle, vacuumizing, filling nitrogen for three times, finally keeping the pressure in the reaction kettle at 0.3MPa, heating the reaction kettle, keeping high-speed stirring, and keeping constant temperature and pressure for 1.7 hours when the temperature of the reaction kettle reaches 240 ℃ and the pressure is 1.8 MPa. Then the temperature is raised to 260 ℃ and the pressure is released to the normal pressure within 1.5 h. Vacuumizing to-0.06 MPa, charging nitrogen to 0.3MPa after the stirring speed is reduced for a certain value and is stable, discharging the materials, cooling, granulating, extracting and drying to obtain a final product, wherein the relative viscosity of the final product is 2.1, the limited oxygen index is 30.2%, and the flame retardant grade reaches UL-94V-0. Wherein the organic phosphorus flame-retardant monomer is as follows:
example 4:
flame-retardant monomer and nonane diamine are mixed in a small amount of water at a molar ratio of 1: 1.3 stirring and reacting for 1h, adjusting the pH value of the solution to 7.3, and drying to form salt. Adding an undecanolactam monomer, the salt (accounting for 7.5 percent of the total mass of the monomers), a catalyst sodium hypophosphite accounting for 1 per thousand of the total mass of the monomers, an antioxidant 2, 6-di-tert-butyl-4-methylphenol, a molecular weight controller acetic acid and deionized water accounting for 5.5 percent of the total mass of the monomers into a reaction kettle, vacuumizing, filling nitrogen for three times, and finally keeping the pressure in the reaction kettle at 0.2 MPa. The reaction kettle is heated and kept stirring at a high speed. When the temperature of the reaction kettle reaches 235 ℃ and the pressure is 1.7MPa, the temperature and the pressure are constant for 2 hours. Then the temperature is increased to 265 ℃, and the pressure is released to the normal pressure within 2 hours. Vacuumizing to-0.09 MPa, introducing nitrogen to 0.3MPa after the stirring speed is reduced for a certain value and is stable, discharging the materials, cooling, granulating, extracting and drying to obtain a final product, wherein the relative viscosity of the final product is 2.3, the limited oxygen index of the final product is 28.8, and the flame retardant grade reaches UL-94V-0. Wherein the organic phosphorus flame-retardant monomer is as follows:
example 5:
flame-retardant monomer and hexamethylene diamine are mixed in a small amount of water at the temperature of 42 ℃ according to the molar ratio of 1: 1.2 stirring to react for 30min, adjusting the pH value of the solution to 7.4, and drying to form salt. Adding caprolactam monomer, the above-mentioned salt (8% of total monomer mass), catalyst methyl benzenesulfonic acid, antioxidant p-phenylenediamine, molecular weight regulator adipic acid whose content is 1 ‰, and deionized water whose content is 6% into reaction still, vacuum-pumping, filling nitrogen gas three times, finally keeping pressure in the reaction still at 0.35 MPa. The reaction kettle is heated and kept stirring at a high speed. When the temperature of the reaction kettle reaches 230 ℃ and the pressure is 1.8MPa, the temperature and the pressure are constant for 2 hours. Then the temperature is raised to 260 ℃, and the pressure is released to the normal pressure within 1 hour. Vacuumizing to-0.05 MP, introducing nitrogen to 0.3MPa after the stirring speed is reduced for a certain value and is stable, discharging the materials, cooling, granulating, extracting and drying to obtain a final product, wherein the relative viscosity of the final product is 2.13, the limited oxygen index of the final product is 29.2 percent, and the flame retardant grade of the final product reaches UL-94V-0. Wherein the organophosphorus flame-retardant monomer:
example 6:
and (2) at the temperature of 55 ℃, mixing a flame retardant monomer and decamethylene diamine in an aqueous solution according to a molar ratio of 1: the reaction is stirred for 1 hour at 1.35, the pH of the solution is adjusted to 7.7, and the solution is dried to form salt. Adding a decanolactam monomer, the above salt (accounting for 9 percent of the total mass of the monomer), 1 per thousand of catalyst methyl benzene sulfonic acid, antioxidant p-phenylenediamine, molecular weight control agent benzoic acid and 5 percent of deionized water into a reaction kettle, vacuumizing, filling nitrogen for three times, and finally keeping the pressure in the reaction kettle at 0.25 MPa. Heating the reaction kettle, keeping high-speed stirring, and keeping constant temperature and pressure for 2h when the temperature of the reaction kettle reaches 235 ℃ and the pressure is 1.8 MPa. Then the temperature is increased to 270 ℃, and the pressure is released to the normal pressure within 2 hours. Vacuumizing to-0.1 MPa, charging nitrogen to 0.3MPa after the stirring speed is reduced for a certain value and is stable, discharging the materials, cooling, granulating, extracting and drying to obtain a final product, wherein the relative viscosity of the final product is 2.15, the limited oxygen index is 30.6, and the flame retardant grade reaches UL-94V-0. Wherein the organic phosphorus flame-retardant monomer is as follows:
example 7:
and (2) at the temperature of 55 ℃, mixing the flame-retardant monomer and hexamethylene diamine in a small amount of water according to the molar ratio of 1: 1.3 stirring to react for 0.5h, adjusting the pH value of the solution to 7.5, and drying to form salt. Adding caprolactam monomer, the salt (accounting for 10 percent of the total mass of the monomer), 1 per thousand of catalyst sodium hypophosphite, antioxidant p-phenylenediamine, molecular weight regulator benzoic acid and 3 percent of deionized water into a reaction kettle, vacuumizing, filling nitrogen for three times, and finally keeping the pressure in the reaction kettle at 0.25 MPa. Heating the reaction kettle, keeping high-speed stirring, and keeping constant temperature and pressure for 2h when the temperature of the reaction kettle reaches 225 ℃ and the pressure is 1.75 MPa. Then the temperature is raised to 260 ℃ and the pressure is released to the normal pressure within 1.5 h. Vacuumizing to-0.05 MPa, after the stirring speed is reduced for a certain value and is stable, filling nitrogen to 0.2MPa, discharging the materials, cooling, granulating, extracting and drying to obtain a final product, wherein the P content is 8.2-8.5%, the relative viscosity is 2.3, the limited oxygen index is 31.5%, and the flame retardant grade reaches UL-94V-0. Wherein the organic phosphorus flame-retardant monomer is as follows:
test samples made of nylon materials to which no flame retardant was added were referred to as "PA", and test samples made of the organophosphorus flame retardant nylon materials obtained in the above examples 1 to 7 were referred to as "FR-A" - "FR-G" in this order.
The test specimen preparation procedure for all the above-mentioned specimens is referred to GB/T9532-.
1. Limiting Oxygen Index (LOI) test
The limit oxygen index test refers to the standard GB/T2406.2-2009 combustion behavior determination by oxygen index method for plastics, and the limit oxygen index is determined by a type limit oxygen index determinator at room temperature. Spline specification: 80mm 10mm 4 mm.
UL-94 testing
The vertical combustion test refers to the standard of GB/T2408-2008 horizontal method and vertical method for testing the combustion performance of plastics, and is carried out at room temperature by adopting a CFZ-5 type vertical combustion tester. Spline specification: 125mm 13.2mm 3.2 mm. The sample strip is vertically fixed on the sample clamp, the part clamped at the upper end is 6mm, the distance between the lower end of the sample strip and absorbent cotton (4mm thick) is 300mm, flame is applied at the position 10mm from the bottom end of the sample strip, and the test data of the sample strip is recorded. After the specimen extinguishes, it is reignited according to the criteria in Table 1 below and the test data recorded.
TABLE 1 comparative standards for assay grade
3. Conclusion of the test
The flame retardant property test result of the embodiment shows that the existence of the organophosphorus flame retardant structure improves the flame retardant property of the nylon. When the content of the flame-retardant monomer reaches more than 6 percent, the flame-retardant grade of the copolymerized nylon is UL-94V-0 grade, and the LOI value is also improved. The invention can prove that the method is feasible and efficient for modifying the flame retardance of the nylon by utilizing the reactive organophosphorus flame retardant monomer. The organophosphorus flame-retardant copolymerized nylon obtained by the scheme provided by the invention has higher LOI and higher relative viscosity value. Due to the presence of end groups, conventional solid tackifying processes can be used to obtain a variety of desired viscosity values when higher viscosity materials are to be obtained.
The above description is only a preferred embodiment of the present invention, and does not limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims (9)
1. An organic phosphorus flame-retardant copolymerized nylon, which has the general formula shown as the following formula (1):
wherein R is selected from H, C1-C5Alkyl radical, C6-C10Aryl radical, C3-C10A heteroaryl group; r is preferably H, C1-C3Alkyl radical, C6-C8Aryl radical, C3-C6A heteroaryl group;
R1、R2each independently selected from linear, branched or cyclic C1-C10Alkylene radical, C6-C15Arylene or aralkylene, C3-C10An ester group; r1、R2Each independently of the others is preferably straight-chain, branched or cyclic C1-C5Alkylene radical, C6-C10Arylene or aralkylene, C3-C8An ester group;
R3is selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10A heteroaryl group; r3Preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
R4is selected from C3-C12Linear or branched alkylene; r4Preferably C3-C8Linear or branched alkylene;
x is 2-50, y is 2-50; x is preferably from 2 to 30 and y is preferably from 2 to 50; n is 5 to 100, preferably 50 to 80.
2. The organophosphorus flame retardant copolymerized nylon of claim 1, wherein x is 2 to 30, y is 2 to 30; n is 5 to 100, preferably 50 to 80.
3. The organophosphorus flame retardant copolymerized nylon according to claim 1 or 2, which is prepared by a method for preparing a flame retardant nylon comprising the steps of:
(A) reacting an organic phosphorus flame-retardant monomer or a derivative thereof shown in a formula (2) with a diamine monomer shown in a formula (3);
wherein R is selected from H, C1-C5Alkyl radical, C6-C10Aryl radical, C3-C10A heteroaryl group; r is preferably H, C1-C3Alkyl radical, C6-C8Aryl radical, C3-C6A heteroaryl group;
R1、R2each independently selected from linear, branched or cyclic C1-C10Alkylene radical, C6-C15Arylene or aralkylene, C3-C10An ester group; r1、R2Each independently preferably being a straight-chain, branched or cyclic C1-C5Alkylene radical, C6-C10Arylene or aralkylene, C3-C8An ester group;
R3is selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10A heteroaryl group; r3Preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
obtaining a compound of the following formula (4):
wherein R is4Is selected from C3-C12Linear or branched alkylene; preferably C3-C8Linear or branched alkylene;
(B) reacting a compound of formula (4) with a lactam of formula (5) to obtain a nylon of formula (1):
wherein, R, R1、R2、R3、R4X, y, n are as defined above;
the method is characterized in that:
in step (A), the flame retardant monomer of formula (2) is reacted with the diamine monomer of formula (3) in a molar ratio of 1:1-2, and the diamine monomer is in slight excess (for example, 0.1-10%, preferably 0.5-5% molar excess) to prepare a salt solution having a pH of 7-9;
wherein, the step (B) comprises the following steps:
a. adding a lactam monomer, the salt obtained in the step (A), a catalyst, a molecular weight regulator, an antioxidant and a proper amount of water into a reaction kettle, vacuumizing, and filling nitrogen for several times to ensure that the pressure in the kettle is 0.1-0.5MPa at the initial stage of reaction;
b. heating the reaction kettle to 200 ℃ and 250 ℃, and maintaining the reaction condition for 30-180min when the pressure is 1.6-2.1 MPa;
c. slowly releasing the pressure to normal pressure at the temperature of 230 ℃ and 280 ℃, then vacuumizing to-0.01 to-0.1 MPa, and copolymerizing for 10-180 min;
d. finally, filling nitrogen, discharging materials, cooling, granulating, extracting and drying to obtain a final product;
wherein, in the step a, the total amount of the lactam monomer is 8-30 times, preferably 8-12 times, and more preferably 10-12 times of the mass of the flame retardant monomer.
4. The organophosphorus flame retardant copolymerized nylon of claim 3, wherein:
in step (B), the lactam monomer is one or more of caprolactam, capryllactam, undecanolactam, dodecanolactam and various lactam monomers with lactam characteristics; and/or
The antioxidant is one or more of compounds such as p-phenylenediamine, dihydroquinoline and the like and derivatives thereof, 2, 6-di-tert-butyl-4-methylphenol, bis (3, 5-di-tert-butyl-4-hydroxyphenyl) thioether, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and the like; and/or
The catalyst is one or more of sodium hypophosphite, methyl benzenesulfonic acid, a new ferrocene chiral nylon ligand and the like; and/or
The molecular weight regulator is one or more of benzoic acid, adipic acid and acetic acid.
5. A process for preparing a flame retardant nylon according to any one of claims 1 to 4, which comprises the steps of:
(A) reacting an organic phosphorus flame-retardant monomer or a derivative thereof shown in a formula (2) with a diamine monomer shown in a formula (3);
wherein R is selected from H, C1-C5Alkyl radical, C6-C10Aryl radical, C3-C10A heteroaryl group; r is preferably H, C1-C3Alkyl radical, C6-C8Aryl radical, C3-C6A heteroaryl group;
R1、R2each independently selected from linear, branched or cyclic C1-C10Alkylene radical, C6-C15Arylene or aralkylene, C3-C10An ester group; r1、R2Each independently preferably being a straight-chain, branched or cyclic C1-C5Alkylene radical, C6-C10Arylene or aralkylene, C3-C8An ester group;
R3is selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10A heteroaryl group; r3Preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
obtaining a compound of the following formula (4):
wherein R is4Is selected from C3-C12Linear or branched alkylene; preferably C3-C8Linear or branched alkylene;
(B) reacting a compound of formula (4) with a lactam of formula (5) to obtain a nylon of formula (1):
wherein, R, R1、R2、R3、R4X, y, n are as defined above;
wherein, the flame-retardant monomer of the formula (2) and the diamine monomer of the formula (3) are reacted according to a molar ratio of 1:1-10, preferably 1: 1-2;
wherein, in step (A), the diamine-based monomer is slightly in excess (e.g., 0.1 to 10%, preferably 0.5 to 5% molar excess) so that the pH of the prepared salt solution is 7 to 9.
6. The production method according to claim 5, wherein:
in the step (A), the diamine monomer is hexamethylene diamine, decamethylene diamine, nonane diamine, undecane diamine, dodecane diamine, aliphatic C6-C20One or more of imino diamine, aromatic diamine and alicyclic diamine; and/or
In the step (B), the lactam monomer, the reaction product of the step (A), the antioxidant, the molecular weight regulator and the catalyst are added into a reaction kettle, and the reaction temperature and the pressure are regulated and controlled under the nitrogen atmosphere to prepare the required organic phosphorus flame-retardant copolymerized nylon material.
7. The production method according to claim 5 or 6, wherein, in the step (B), the lactam monomer is one or more of caprolactam, caprylolactam, undecyl lactam, lauryl lactam, and various lactam monomers having lactam characteristics; and/or
The antioxidant is one or more of compounds such as p-phenylenediamine, dihydroquinoline and the like and derivatives thereof, 2, 6-di-tert-butyl-4-methylphenol, bis (3, 5-di-tert-butyl-4-hydroxyphenyl) thioether, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and the like; and/or
The catalyst is one or more of sodium hypophosphite, methyl benzenesulfonic acid, a new ferrocene chiral nylon ligand and the like; and/or
The molecular weight regulator is one or more of benzoic acid, adipic acid and acetic acid.
8. The preparation method according to any one of claims 5 to 7, wherein the step (B) specifically comprises the steps of:
a. adding a lactam monomer, the salt obtained in the step (A), a catalyst, a molecular weight regulator, an antioxidant and a proper amount of water into a reaction kettle, vacuumizing, and filling nitrogen for several times to ensure that the pressure in the kettle is 0.1-0.5MPa at the initial stage of reaction;
b. heating the reaction kettle to 200 ℃ and 250 ℃, and maintaining the reaction condition for 30-180min when the pressure is 1.6-2.1 MPa;
c. slowly releasing the pressure to normal pressure at the temperature of 230 ℃ and 280 ℃, then vacuumizing to-0.01 to-0.1 MPa, and copolymerizing for 10-180 min;
d. and finally, filling nitrogen, discharging materials, cooling, granulating, extracting and drying to obtain a final product.
9. The preparation method according to claim 8, wherein in step a, the total amount of the lactam monomer added is 8 to 30 times, preferably 8 to 12 times, more preferably 10 to 12 times the mass of the flame retardant monomer; the catalyst and the antioxidant are 0.01 to 1.0 percent of the mass of the lactam polymerization monomer or the lactam polymer, preferably 0.05 to 0.5 percent, more preferably 0.08 to 0.2 percent, and more preferably about 1/1000 for example.
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| CN104311877A (en) * | 2014-08-29 | 2015-01-28 | 成都拓利化工实业有限公司 | Reaction type nylon flame retardant and preparation method |
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| CN114591623A (en) * | 2022-04-26 | 2022-06-07 | 华润化学材料科技股份有限公司 | High-impact-toughness flame-retardant nylon elastomer material and preparation method thereof |
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| CN114989419A (en) * | 2022-06-21 | 2022-09-02 | 浙江理工大学 | Polyamide for industrial yarn, preparation method thereof and fiber |
| CN114989420A (en) * | 2022-06-21 | 2022-09-02 | 浙江理工大学 | Modified polyamide, preparation method thereof and fiber |
| CN114989421A (en) * | 2022-06-21 | 2022-09-02 | 浙江理工大学 | Modified polyamide material, preparation method thereof and fiber |
| CN115160562A (en) * | 2022-07-22 | 2022-10-11 | 四川轻化工大学 | Phosphorus-containing flame-retardant high-temperature-resistant copolymerized nylon and preparation method thereof |
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