CN113527669A - Organic phosphorus copolymerized flame-retardant polyamide and preparation method thereof - Google Patents
Organic phosphorus copolymerized flame-retardant polyamide and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 116
- 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 110
- 239000004952 Polyamide Substances 0.000 title claims abstract description 59
- 229920002647 polyamide Polymers 0.000 title claims abstract description 59
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 40
- 239000011574 phosphorus Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- -1 diamine salt Chemical class 0.000 claims abstract description 65
- 239000000178 monomer Substances 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 150000004985 diamines Chemical class 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 20
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 4
- 230000001276 controlling effect Effects 0.000 claims abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical group NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 239000012467 final product Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000004185 ester group Chemical group 0.000 claims description 12
- 238000011049 filling Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 11
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 10
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 8
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-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 7
- 150000004984 aromatic diamines Chemical class 0.000 claims description 7
- JMLPVHXESHXUSV-UHFFFAOYSA-N dodecane-1,1-diamine Chemical compound CCCCCCCCCCCC(N)N JMLPVHXESHXUSV-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- DDLUSQPEQUJVOY-UHFFFAOYSA-N nonane-1,1-diamine Chemical compound CCCCCCCCC(N)N DDLUSQPEQUJVOY-UHFFFAOYSA-N 0.000 claims description 7
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 7
- XJIAZXYLMDIWLU-UHFFFAOYSA-N undecane-1,1-diamine Chemical compound CCCCCCCCCCC(N)N XJIAZXYLMDIWLU-UHFFFAOYSA-N 0.000 claims description 7
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 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 6
- 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 5
- 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 5
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 5
- IRFSXVIRXMYULF-UHFFFAOYSA-N 1,2-dihydroquinoline Chemical compound C1=CC=C2C=CCNC2=C1 IRFSXVIRXMYULF-UHFFFAOYSA-N 0.000 claims description 4
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 claims description 4
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001470 diamides Chemical class 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
- 230000008569 process Effects 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- MXAOILAHPVJWBS-UHFFFAOYSA-N 10-(azepan-1-yl)-10-oxodecanamide Chemical compound NC(=O)CCCCCCCCC(=O)N1CCCCCC1 MXAOILAHPVJWBS-UHFFFAOYSA-N 0.000 claims description 3
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 3
- DJZKNOVUNYPPEE-UHFFFAOYSA-N tetradecane-1,4,11,14-tetracarboxamide Chemical compound NC(=O)CCCC(C(N)=O)CCCCCCC(C(N)=O)CCCC(N)=O DJZKNOVUNYPPEE-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000004642 Polyimide Substances 0.000 claims 1
- 229920001721 polyimide Polymers 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 24
- 238000007334 copolymerization reaction Methods 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000011810 insulating material Substances 0.000 abstract 1
- 239000004753 textile Substances 0.000 abstract 1
- 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
- 238000003756 stirring Methods 0.000 description 12
- 238000002485 combustion reaction Methods 0.000 description 7
- 229920002302 Nylon 6,6 Polymers 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000009775 high-speed stirring Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 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 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-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
- 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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- JXASPPWQHFOWPL-UHFFFAOYSA-N Tamarixin Natural products C1=C(O)C(OC)=CC=C1C1=C(OC2C(C(O)C(O)C(CO)O2)O)C(=O)C2=C(O)C=C(O)C=C2O1 JXASPPWQHFOWPL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 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
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 125000000524 functional group Chemical group 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
- 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
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- FJXWKBZRTWEWBJ-UHFFFAOYSA-N nonanediamide Chemical compound NC(=O)CCCCCCCC(N)=O FJXWKBZRTWEWBJ-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 238000002464 physical blending Methods 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
- 238000005086 pumping Methods 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
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an organic phosphorus copolymerized flame-retardant polyamide and a preparation method thereof. The preparation method specifically comprises the following steps: (A) reacting an organic phosphorus flame-retardant monomer with a diamine monomer to form salt; (B) and (2) adding diacid, diamine or diamine salt or solution thereof, the salt or solution thereof obtained in the step (A), an antioxidant, a catalyst and deionized water into a reaction kettle, and preparing the required organic phosphorus copolymerization flame-retardant polyamide material by regulating and controlling the reaction temperature and pressure under the nitrogen atmosphere. The organic phosphorus polyamide material prepared by the invention has the advantages of small addition amount of the reaction flame retardant, no need of adding a synergistic flame retardant, controllable viscosity in the preparation process, excellent mechanical property of the obtained product, excellent flame retardant property, and suitability for various fields such as textiles, insulating materials, tire cords, films and the like.
Description
The present case is application number: 201610951282.2, title of the invention: an organic phosphorus copolymerized flame-retardant polyamide and a divisional application of a patent application of a preparation method thereof.
Technical Field
The invention belongs to the technical field of synthesis of flame-retardant polymers, relates to a preparation method of copolymerized flame-retardant polyamide, and particularly relates to a phosphorus-containing reactive flame retardant copolymerized polymer material embedded in a polyamide molecular chain and a preparation method thereof.
Background
The polyamide has excellent performances such as high strength, heat resistance, wear resistance, solvent resistance and the like, and is widely applied to the fields of buildings, chemical engineering, traffic, military and the like. However, polyamides are not inherently flame retardant and may cause or exacerbate fire hazards. Therefore, the modification of polyamide to obtain polyamide with good flame-retardant properties has been studied by the industry.
There are generally two ways in which the flame retardant polyamide material can be modified: one is adding reactive flame retardant, introducing functional group with flame retardant activity in the nylon copolymerization process; and the other is that after the polyamide is polymerized, an additive flame retardant and a related synergistic flame retardant are added and blended. The latter physical blending mode is influenced by the factors of dispersibility, compatibility, interfacial property and the like, while the former does not have the problems because of chemical reaction. In addition, to achieve a certain flame retardance, the use amount of the additive flame retardant is large, so that the mechanical property and the electrical property are greatly damaged, and the application of the additive flame retardant is limited. 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 polyamide molecule, the problems of volatilization, migration, exudation 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. The former can be used as reactive flame retardant. Halogen-containing flame retardants have been widely used as flame retardant materials for high polymers due to their high flame retardancy, but they are gradually limited in use because they generate toxic gases and fumes during combustion, which are harmful to the environment and human body. The phosphorus flame retardant, especially the organic phosphorus flame retardant has a prospect of replacing halogen-containing flame retardants. The phosphorus flame retardant can act in a condensed phase and a gas phase at the same time, and the flame retardant mechanism is that the flame retardant can generate 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. Particularly, the reactive phosphorus flame retardant can enter the molecular main chain of a high polymer material needing flame retardance in a polymerization mode, does not migrate and exude, and is effective for a long time.
The patent with publication number CN104231262A discloses a preparation method of organophosphorus copolymerized flame-retardant polyamide, which comprises the following steps: (1) reacting a flame-retardant monomer with a diamine monomer in advance to prepare a prepolymer; (2) and adding a polymerization monomer, a catalyst and the prepolymer into the reaction kettle in a certain sequence. The flame retardant in this patent is
Or a derivative of a substrate thereof; wherein said R1And R2Alkylene groups each having 1 to 10 carbon atoms; or R1And R2Any of which is H; x1、X2Is H or 1 to 4 halogens which can substitute H on the benzene ring. Copolymerization obtained in the present inventionThe flame retardant grade of the product can reach UL94V-0 grade, the limit oxygen index is greatly improved, the lowest value can reach 32, and the highest value can reach 45.
The patent with the publication number of CN104262619A 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) and raising the temperature, pumping air to vacuum, and discharging to obtain the flame-retardant polyamide material. The flame retardant in this patent is
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
As described above, although the prior art has proposed many phosphorus-containing polyamides with good flame retardant properties, there is still a strong need in the art for flame retardant polyamides with good mechanical properties and flame retardant properties.
Disclosure of Invention
The invention aims to prepare a novel organic phosphorus copolymerization flame-retardant polyamide material aiming at the situation that the existing market of flame-retardant polyamide mainly adopts blending. The method is characterized in that the novel organic phosphorus copolymerized flame-retardant polyamide is prepared by salifying a flame-retardant monomer with diamine by utilizing the characteristic that the flame-retardant monomer has two carboxylic acid groups and then carrying out polycondensation with diamine salt of dicarboxylic acid. In the process, the addition amount of the flame retardant is small, no synergistic flame retardant is needed, and the obtained polyamide material has excellent mechanical and electrical properties.
The technical scheme of the invention is as follows:
a flame-retardant polyamide represented by the following general 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, or 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;
R3、R4、R5each independently selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10A heteroaryl group; r3、R4、R5Each independently is preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
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 polyamide 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 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):
(B) reacting a compound of formula (4) with a diacid of formula (5) and a diamine of formula (6), or with a diamide salt of formula (7) or a solution thereof,
wherein R is4And R5Is selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10A heteroaryl group; r4And R5Preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
obtaining a polyamide of formula (1):
wherein, R, R1、R2、R3、R4、R5X, 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 generally 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 diamine-based monomer, so that the resulting salt solution has 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 hexamethylenediamine, decamethylenediamine, nonanediamine, undecanediamine, dodecanediamine, aliphatic C6-C20One or more of imino diamine, aromatic diamine and alicyclic diamineAnd (4) seed preparation.
In the step (B), the molar ratio of the diacid of the formula (5) to the diamine of the formula (6) is not particularly limited, and for example, the molar ratio of the diacid of the formula (5) to the diamine of the formula (6) may be 1:1.01 to 10, preferably 1:1.1 to 2, more preferably about 1: 1.5.
In the step (B), preferably, diacid, diamine or diamine salt or solution thereof, the reaction product (salt or salt solution) of the step (A), an antioxidant, a catalyst and deionized water are added into a reaction kettle, and the reaction temperature and pressure are regulated and controlled under the nitrogen atmosphere to prepare the required organophosphorus copolymerized flame-retardant polyamide.
In step (B), further, the polymerized monomeric diacid is, for example, one or more of adipic acid, sebacic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, phthalic acid or their derivatives, and other aliphatic and aromatic dicarboxylic acids; diamines are, for example, hexamethylenediamine, nonamethylenediamine, decamethylenediamine, undecanediamine, dodecanediamine, and aliphatic C6-C20One or more of an imino diamine, an aromatic diamine, or an alicyclic diamine; and the diamine salt is one or more of hexamethylene adipamide, pentamethylene adipamide, hexamethylene azelainate, hexamethylene sebacamide, octanedioyl octanediamine, octanedioyl hexamethylene diamine, and octanedioyl octanediamine.
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.
Further, the catalyst is one or more of sodium hypophosphite, methyl benzene sulfonic acid, a new ferrocene chiral polyamide ligand and the like.
Further preferably, the step (B) specifically includes the following steps:
a. adding polymerized monomer diacid and diamine or diamine salt or solution thereof, the reaction product obtained in the step (A), a catalyst, an antioxidant and deionized 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 the 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 addition amount of the polymerized monomer diacid and the diamine or the diamine salt or the solution thereof is 8 to 100 times, preferably 12 to 30 times of the mass of the flame retardant; the catalyst and the antioxidant are respectively 0.01-1.0 percent of the mass of the polymerized monomer, preferably 0.05-0.5 percent of the mass of the polymerized monomer, more preferably 0.08-0.2 percent of the mass of the polymerized monomer, and more preferably about 1/1000 percent of the mass of the polymerized monomer; the amount of water added to the system (including water added separately, water entrained with the product of step (A), and water entrained with the dibasic amide salt) is 10 to 60%, preferably 30 to 50%, of the total mass of the reactants.
In the present invention, the flame retardant and the diamine-based monomer are preferably mixed in advance in a ratio of, for example, 1: (1-2) salifying, adding the obtained salt into a polymerization monomer, and participating in polymerization reaction under the action of a catalyst. The flame retardant property of the obtained polyamide material meets the requirement of flame retardant grade UL-94V-0.
To be provided with
Hexamethylenediamine, PA66 salt, for example, the mechanism of the reaction is: the flame-retardant monomer reacts with hexamethylene diamine to form salt, and then the salt and nylon 66 salt are copolymerized to form the flame-retardant polyamide. The reaction process can be written as:
the invention has the beneficial effects that:
as long as the flame-retardant polyamide containing phosphorus flame-retardant monomers accounting for about 6 percent of the total mass of reactants is included, the grade of UL-94V-0 can be basically achieved, the limit oxygen index range is 27-32 percent, the smoke is low, the toxicity is low, the efficiency is stable, the viscosity is controllable, and the problem that a plurality of phosphorus-containing monomers disclosed in the prior art cannot achieve high polymerization degree when the phosphorus content is increased is solved.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The molecular structure of the organophosphorus flame-retardant polyamide 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;
R3、R4、R5each independently selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10A heteroaryl group; r3、R4、R5Each independently is preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
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 organic phosphorus copolymerized flame-retardant polyamide specifically comprises the following steps:
(A) reacting an organic phosphorus flame-retardant monomer with diamine, preferably, leading amino to be excessive to generate a salt solution;
(B) reacting the reaction product of step (A) with diacid and diamine or diamine salt or solution thereof to prepare the organophosphorus copolymerized flame retardant polyamide.
In step (A), the diamine-based monomer is preferably used in a slight excess so that the salt solution has 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 hexamethylenediamine, decamethylenediamine, nonanediamine, undecanediamine, dodecanediamine, aliphatic C6-C20One or more of imino diamine, aromatic diamine and alicyclic diamine.
In the step (B), preferably, the polymerization monomer, the reaction product of the step (A), the antioxidant, the catalyst and the deionized water are added into a reaction kettle, and the reaction temperature and the reaction pressure are regulated and controlled under the nitrogen atmosphere to prepare the required organic phosphorus copolymerization flame-retardant polyamide material.
In step (B), further, the polymeric monomeric dibasic acid is one or more of, for example, adipic acid, sebacic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, phthalic acid or derivatives thereof, and other aliphatic and aromatic dicarboxylic acids; the diamine compound is, for example, hexamethylenediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, and aliphatic C6-C20One or more of an imino diamine, an aromatic diamine, or an alicyclic diamine; the diamine salt-type compound is, for example, one or more of polyhexamethylene adipamide, polypentylene adipamide, polyhexamethylene azelamide, polyhexamethylene sebacamide, polyhexamethylene suberoyl, polyhexamethylene dodecanoamide, and polyhexamethylene suberoyl.
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.
Further, the catalyst is one or more of sodium hypophosphite, methyl benzene sulfonic acid, a new ferrocene chiral polyamide ligand and the like.
Further preferably, the step (B) specifically includes the following steps:
a. adding polymerized monomer diacid and diamine or diamine salt or solution thereof, the reaction product obtained in the step (A), a catalyst, an antioxidant and deionized 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 the 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 addition amount of the polymerization monomer is 8-100 times, preferably 10-40 times, and more preferably 12-30 times of the mass of the flame retardant; the catalyst and the antioxidant are respectively 0.01 to 1.0 percent of the mass of the polymerization monomer (or the binary amide salt), preferably 0.05 to 0.5 percent of the mass of the polymerization monomer (or the binary amide salt), more preferably 0.08 to 0.2 percent of the mass of the polymerization monomer (or the binary amide salt), and more preferably about 1/1000; the amount of water added in the system is 10-60%, preferably 30-50% of the total mass of the reactants.
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. "%" is by mass fraction unless otherwise specified.
Example 1:
and (2) at 40 ℃, mixing the flame-retardant monomer and hexamethylene diamine in an aqueous solution according to a molar ratio of 1:1.2 stirring and reacting for 0.5h, adjusting the pH value of the solution to 7.2, and drying to form salt. Adding 50% nylon 66 salt (hexamethylene adipamide salt) solution, the obtained salt accounting for 6.0% of the salt mass, 1 per mill of catalyst sodium hypophosphite and antioxidant p-phenylenediamine into a reaction kettle, vacuumizing, filling nitrogen for 5 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 1.5h when the temperature of the reaction kettle reaches 220 ℃ and the pressure is 1.8 MPa. Then the temperature is raised to 250 ℃, and the pressure is released to the normal pressure within 1 hour. 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 the UL94V-0 grade. Wherein the organic phosphorus flame-retardant monomer is as follows:
example 2:
at 50 ℃, the flame-retardant monomer and hexamethylene diamine are mixed in an aqueous solution according to a molar ratio of 1: 1.3 stirring and reacting for 1h, adjusting the pH value of the solution to 7.8, and drying to form salt.
Mixing adipic acid and hexamethylenediamine according to a molar ratio of 1:1.2, adding 7% of the salt, 1 per thousand of catalyst methyl benzenesulfonic acid, 2, 6-di-tert-butyl-4-methylphenol as an antioxidant and 35% of deionized water into a reaction kettle, vacuumizing, filling nitrogen for 3 times, and finally keeping the pressure in the reaction kettle at 0.3 MPa. Heating the reaction kettle, keeping high-speed stirring, and keeping constant temperature and pressure for 1.6h when the temperature of the reaction kettle reaches 215 ℃ and the pressure is 1.7 MPa. Then the temperature is raised to 240 ℃, 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 the final product, wherein the relative viscosity of the final product is 2.1, the limited oxygen index is 29 percent, and the flame retardant grade reaches the UL94V-0 grade. Wherein the organic phosphorus flame-retardant monomer is as follows:
example 3:
and (2) mixing the flame-retardant monomer and nonane diamine in an aqueous solution at the temperature of 60 ℃ according to the molar ratio of 1:1.5 stirring and reacting for 1h, adjusting the pH value of the solution to 7.6, and drying to form salt. Adding 1:1.1 molar ratio of undecane diacid and hexamethylene diamine, 8% of the salt, 1 per thousand of catalyst sodium hypophosphite, antioxidant bis (3, 5-di-tert-butyl-4-hydroxyphenyl) thioether and 40% of deionized water into a reaction kettle, vacuumizing, charging nitrogen for 4 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 245 ℃ and the pressure is 1.7MPa, the temperature and the pressure are constant for 2 hours. Then the temperature is raised to 255 ℃, 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 2.0, the limited oxygen index is 32.2%, and the flame retardant grade reaches UL 94V-0. Wherein the organic phosphorus flame-retardant monomer is as follows:
example 4:
mixing a flame retardant and hexamethylene diamine in a molar ratio of 1:1.2 stirring and reacting for 50min, adjusting the pH value of the solution to 7.4, and drying to form salt. Adding undecanedioic acid and octanediamine with the molar ratio of 1:1.15, 8 percent of the salt, 1 per thousand of the catalyst of methyl benzenesulfonic acid, antioxidant of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 40 percent of deionized water into a reaction kettle, vacuumizing, filling nitrogen for 3 times, and finally keeping the pressure in the reaction kettle 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 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 2.05, the limited oxygen index of the final product is 31.5%, and the flame retardant grade of the final product reaches UL 94V-0. Wherein the organic phosphorus flame-retardant monomer is as follows:
example 5
At 65 ℃, the flame-retardant monomer and hexamethylene diamine are mixed in an aqueous solution according to a molar ratio of 1:1.2 stirring and reacting for 0.5h, adjusting the pH value of the solution to 7.3, and drying to form salt. Adding 50% nylon 66 salt (hexamethylene adipamide salt) solution, 10.0% salt, 1 ‰ sodium hypophosphite as catalyst, and p-phenylenediamine as antioxidant into a reaction kettle, vacuumizing, introducing nitrogen for 3 times, and maintaining 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 1.5h when the temperature of the reaction kettle reaches 240 ℃ and the pressure is 1.95 MPa. Then the temperature is raised to 260 ℃, and the pressure is released to the normal pressure within 1 hour. Vacuumizing to-0.05 MPa, after the stirring speed is reduced for a certain value and is stable, filling nitrogen to 0.4MPa, discharging the materials, cooling, granulating, extracting and drying to obtain a final product, wherein the P content is 0.82-0.86 wt%, the relative viscosity is 2.25, the limited oxygen index is 34.0%, and the flame retardant grade reaches the UL94V-0 grade. Wherein the organic phosphorus flame-retardant monomer is as follows:
1. preparation of the samples
Test specimens made of polyamide materials to which no flame retardant was added were referred to as "PA", and test specimens made of the organophosphorus flame retardant polyamide materials obtained in the above examples 1 to 5 were referred to as "FR-A" - "FR-E" in this order.
The test specimen preparation procedure for all the above-mentioned specimens is referred to GB/T9532-.
2. 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
4. 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 polyamide. When the content of the flame-retardant monomer reaches more than 6 percent, the flame-retardant polyamide can pass the V-0 test of UL-94, and the LOI value is improved along with the flame-retardant polyamide. Therefore, the invention proves that the method is feasible and efficient for modifying the polyamide flame retardance by utilizing the reactive organic phosphorus flame retardant. The organic phosphorus copolymerization flame-retardant polyamide material obtained by the scheme provided by the invention has higher limited oxygen index 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 copolymerized flame-retardant polyamide, 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 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;
R3、R4、R5each independently selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10A heteroaryl group; r3、R4、R5Each independently is preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
x represents 2 to 50, y represents 2 to 50, and n represents 5 to 100.
2. The organophosphorus copolymerized flame retardant polyamide according to claim 1, wherein x is 2 to 30, y is 2 to 30, and n is 5 to 100, preferably 50 to 80.
3. The organophosphorus copolymerized flame retardant polyamide according to claim 1 or 2, which is produced by a production method 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):
(B) reacting a compound of formula (4) with a diacid of formula (5) and a diamine of formula (6), or with a diamide salt of formula (7) or a solution thereof,
wherein R is4And R5Is selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10A heteroaryl group; r4And R5Preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
obtaining a polyamide of formula (1):
wherein, R, R1、R2、R3、R4、R5X, y, n are as defined above;
in the step (A), the flame-retardant monomer shown in the formula (2) and the diamine monomer shown in the formula (3) react according to a molar ratio of 1:1-2, and the diamine monomer is slightly excessive, so that the pH value of the prepared salt solution is 7-9; (ii) a
The step (B) specifically comprises the following steps:
a. adding a polymerization monomer, namely diacid and diamine or diamine salt or solution thereof, a reaction product obtained in the step (A), a catalyst, an antioxidant and deionized 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 the 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 addition amount of the polymerized monomer diacid and the diamine or the diamine salt or the solution thereof is 8 to 30 times, preferably 8 to 12 times, and more preferably 10 to 12 times of the mass of the flame-retardant monomer.
4. The organophosphorus copolymerized flame-retardant polyimide according to claim 3Amine, wherein, in step (B), the polymerized monomeric diacid is one or more of adipic acid, sebacic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, phthalic acid or their derivatives, and other aliphatic and aromatic dicarboxylic acids; the diamine is selected from hexamethylenediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, and aliphatic C6-C20One or more of an imino diamine, an aromatic diamine, or an alicyclic diamine; and the binary amide salt is one or more of hexamethylene adipamide, pentamethylene adipamide, hexamethylene azelainate, hexamethylene sebacamide, octanedioyl diamine, and octanedioyl diamine;
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 and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester;
the catalyst is one or more of sodium hypophosphite, methyl benzene sulfonic acid and a new ferrocene chiral polyamide ligand.
5. Process for the preparation of a flame retardant polyamide according to any of claims 1 to 4, 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):
(B) reacting a compound of formula (4) with a diacid of formula (5) and a diamine of formula (6), or with a diamide salt of formula (7) or a solution thereof,
wherein R is4And R5Is selected from C3-C12Linear, branched or cyclic alkylene, C6-C10Arylene radical, C3-C10A heteroaryl group; r4And R5Preferably C3-C8Linear, branched or cyclic alkylene, C6-C8Arylene radical, C3-C8A heteroaryl group;
obtaining a polyamide of formula (1):
wherein, R, R1、R2、R3、R4、R5X, y, n are as defined above;
wherein, in the step (A), the flame-retardant monomer of the formula (2) and the diamine monomer of the formula (3) are reacted according to a molar ratio of 1:0.5-10, preferably 1: 1-2; the diamine monomer is present in slight excess to give a salt solution having a pH of 7 to 9.
6. The preparation method according to claim 5, wherein, in the step (A), the reaction temperature is raised from room temperature to 40-70 ℃ within 5-20 min; and/or
In the step (A), the diamine monomer is hexamethylenediamine, decamethylenediamine, nonanediamine, undecanediamine, dodecanediamine, aliphatic C6-C20One or more of imino diamine, aromatic diamine and alicyclic diamine; and/or
In the step (B), adding diacid, diamine or diamine salt or solution thereof, the reaction product of the step (A), namely the compound of the formula (4), an antioxidant, a catalyst and deionized water into a reaction kettle, and regulating and controlling the reaction temperature and pressure under the nitrogen atmosphere to prepare the required organic phosphorus copolymerized flame-retardant polyamide material.
7. The production method according to claim 5 or 6, wherein in the step (B), the polymerized monomer diacid is one or more of adipic acid, sebacic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, phthalic acid or their derivatives and other aliphatic and aromatic dicarboxylic acids; the diamine is selected from hexamethylenediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, and aliphatic C6-C20One or more of an imino diamine, an aromatic diamine, or an alicyclic diamine; and the diamine salt is one or more of hexamethylene adipamide, pentamethylene adipamide, hexamethylene azelainate, hexamethylene sebacamide, octanedioyl octanediamine, octanedioyl hexamethylene diamine, and octanedioyl octanediamine.
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 and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester; and/or
The catalyst is one or more of sodium hypophosphite, methyl benzene sulfonic acid and a new ferrocene chiral polyamide ligand.
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 polymerization monomer, namely diacid and diamine or diamine salt or solution thereof, a reaction product obtained in the step (A), a catalyst, an antioxidant and deionized 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 the 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 addition amount of the polymeric monomer diacid and diamine or diamide salt or solution thereof is 8-30 times, preferably 8-12 times, more preferably 10-12 times the mass of the flame retardant monomer; the catalyst and the antioxidant are respectively 0.01 to 1.0 percent of the mass of the diacid and the diamine or the diamine salt or the solution of the diacid and the diamine salt or the diamine salt, preferably 0.05 to 0.5 percent of the mass of the solution of the diamine or the diamine salt, more preferably 0.08 to 0.2 percent of the mass of the solution of the diamine or the diamine salt, and more preferably about 1/1000; the amount of water added in the system is 10-60%, preferably 30-50% of the total mass of the reactants.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09328543A (en) * | 1996-06-12 | 1997-12-22 | Nippon Chem Ind Co Ltd | Phosphorus-containing copolyamide and flame-retardant copolyamide |
| CN103694468A (en) * | 2014-01-14 | 2014-04-02 | 株洲时代新材料科技股份有限公司 | Nylon resin and preparation method thereof |
| CN104231262A (en) * | 2014-09-23 | 2014-12-24 | 江苏瑞美福实业有限公司 | Preparation method for organic phosphorus copolymerized antiflaming polyamide material |
| 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 |
| CN104744690A (en) * | 2015-04-09 | 2015-07-01 | 泰索新材料科技（杭州）有限公司 | Flame-retardant nylon 6 and preparation method thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665515B (en) * | 2009-10-20 | 2013-05-08 | 苏州科技学院 | P-N collaborative type flame-retardant compound and preparation method thereof |
| WO2014148519A1 (en) * | 2013-03-21 | 2014-09-25 | ユニチカ株式会社 | Semiaromatic polyamide resin composition and molded body formed by molding same |
| CA2908191A1 (en) * | 2013-03-28 | 2014-10-02 | Deutsche Institute Fur Textil -Und Faserforschung Denkendorf | Flame-resistant polyamide, method for the production of said flame-resistant polyamide, and use of said flame-resistant polyamide |
| CN104211954B (en) * | 2013-05-30 | 2016-10-05 | 辽宁银珠化纺集团有限公司 | A kind of preparation method of halogen-free flame-proof nylon 66 having polymer |
| CN104211955A (en) * | 2013-05-31 | 2014-12-17 | 骏马化纤股份有限公司 | Halogen-free flame-retardation nylon 6 montmorillonite nanocomposite and preparation method thereof |
| CN104650349A (en) * | 2013-11-20 | 2015-05-27 | 东丽纤维研究所（中国）有限公司 | Halogen-free phosphorus-nitrogen flame retardant, preparation method thereof, flame-retarding polyester therewith and application of the flame-retarding polyester |
| CN103819666B (en) * | 2014-02-20 | 2017-01-25 | 株洲时代新材料科技股份有限公司 | High flame retardant nylon resin and its preparation method |
| CN104262619B (en) * | 2014-09-15 | 2016-07-13 | 浙江理工大学 | A kind of phosphor-containing flame-proof polyamide and preparation method thereof and application |
| CN105254873A (en) * | 2015-09-25 | 2016-01-20 | 四川东材科技集团股份有限公司 | Flame retardant nylon resin and preparation method thereof |
-
2016
- 2016-10-25 CN CN201610951282.2A patent/CN106496551A/en active Pending
- 2016-10-25 CN CN202110930545.2A patent/CN113527669A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09328543A (en) * | 1996-06-12 | 1997-12-22 | Nippon Chem Ind Co Ltd | Phosphorus-containing copolyamide and flame-retardant copolyamide |
| CN103694468A (en) * | 2014-01-14 | 2014-04-02 | 株洲时代新材料科技股份有限公司 | Nylon resin and preparation method thereof |
| 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 |
| CN104231262A (en) * | 2014-09-23 | 2014-12-24 | 江苏瑞美福实业有限公司 | Preparation method for organic phosphorus copolymerized antiflaming polyamide material |
| CN104744690A (en) * | 2015-04-09 | 2015-07-01 | 泰索新材料科技（杭州）有限公司 | Flame-retardant nylon 6 and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114989422A (en) * | 2022-06-21 | 2022-09-02 | 浙江理工大学 | Polyamide material for industrial yarn, 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 |
| CN115160562B (en) * | 2022-07-22 | 2024-05-21 | 濮阳市盛通聚源新材料有限公司 | Phosphorus-containing flame-retardant high-temperature-resistant copolymerized nylon and preparation method thereof |
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| CN116217921B (en) * | 2023-01-18 | 2023-09-12 | 烟台锦合晟新材料科技有限公司 | Phosphorus-containing in-situ flame-retardant polyamide |
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