CN101200542B - Method for preparing high temperature nylon - Google Patents
Method for preparing high temperature nylon Download PDFInfo
- Publication number
- CN101200542B CN101200542B CN200610147385XA CN200610147385A CN101200542B CN 101200542 B CN101200542 B CN 101200542B CN 200610147385X A CN200610147385X A CN 200610147385XA CN 200610147385 A CN200610147385 A CN 200610147385A CN 101200542 B CN101200542 B CN 101200542B
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- CN
- China
- Prior art keywords
- salt
- temperature
- nylon
- acid
- polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004677 Nylon Substances 0.000 title claims abstract description 62
- 229920001778 nylon Polymers 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 68
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 59
- 238000009826 distribution Methods 0.000 claims abstract description 19
- 150000004985 diamines Chemical class 0.000 claims abstract description 17
- 239000007790 solid phase Substances 0.000 claims abstract description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 8
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 19
- 238000007334 copolymerization reaction Methods 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000006068 polycondensation reaction Methods 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001802 infusion Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000003750 conditioning effect Effects 0.000 claims description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 4
- 150000003016 phosphoric acids Chemical class 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical group [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 3
- 239000002683 reaction inhibitor Substances 0.000 claims description 3
- -1 diamine salt Chemical class 0.000 abstract description 22
- 238000002360 preparation method Methods 0.000 abstract description 12
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 239000004952 Polyamide Substances 0.000 abstract description 7
- 238000001879 gelation Methods 0.000 abstract description 7
- 229920002647 polyamide Polymers 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000009833 condensation Methods 0.000 abstract description 5
- 230000005494 condensation Effects 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 5
- 150000001412 amines Chemical group 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 150000001408 amides Chemical class 0.000 description 49
- 239000000203 mixture Substances 0.000 description 24
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 18
- 239000002245 particle Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 230000006378 damage Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 6
- 238000009434 installation Methods 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- ZRSKSQHEOZFGLJ-UHFFFAOYSA-N ammonium adipate Chemical class [NH4+].[NH4+].[O-]C(=O)CCCCC([O-])=O ZRSKSQHEOZFGLJ-UHFFFAOYSA-N 0.000 description 4
- 235000019293 ammonium adipate Nutrition 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 description 4
- 150000004692 metal hydroxides Chemical class 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 229920003656 Daiamid® Polymers 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- JMHSCWJIDIKGNZ-UHFFFAOYSA-N 4-carbamoylbenzoic acid Chemical group NC(=O)C1=CC=C(C(O)=O)C=C1 JMHSCWJIDIKGNZ-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- ALBYIUDWACNRRB-UHFFFAOYSA-N hexanamide Chemical compound CCCCCC(N)=O ALBYIUDWACNRRB-UHFFFAOYSA-N 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 229940005605 valeric acid Drugs 0.000 description 2
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
- PGGROMGHWHXWJL-UHFFFAOYSA-N 4-(azepane-1-carbonyl)benzamide Chemical group C1=CC(C(=O)N)=CC=C1C(=O)N1CCCCCC1 PGGROMGHWHXWJL-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- MPLPRHAEROXQEU-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCCCCCC(=O)O)(=O)O.[C] Chemical class C(CCCCCCCCCCCCCCCCCCCCC(=O)O)(=O)O.[C] MPLPRHAEROXQEU-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- XTBMQKZEIICCCS-UHFFFAOYSA-N hexane-1,5-diamine Chemical compound CC(N)CCCCN XTBMQKZEIICCCS-UHFFFAOYSA-N 0.000 description 1
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 1
- FCTUFEMNZZTICP-UHFFFAOYSA-N icosan-3-yl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCC(CC)OP(O)(O)=O FCTUFEMNZZTICP-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 229910000400 magnesium phosphate tribasic Inorganic materials 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- NFIYTPYOYDDLGO-UHFFFAOYSA-N phosphoric acid;sodium Chemical compound [Na].OP(O)(O)=O NFIYTPYOYDDLGO-UHFFFAOYSA-N 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 229940093916 potassium phosphate Drugs 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- BPSKTAWBYDTMAN-UHFFFAOYSA-N tridecane-1,13-diamine Chemical compound NCCCCCCCCCCCCCN BPSKTAWBYDTMAN-UHFFFAOYSA-N 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Polyamides (AREA)
Abstract
The present invention provides a preparation method of high-temperature nylon, including the following steps: (a) dicarboxylic acid and diamine are used to prepare 6T salt or 6I salt under the temperature of 80 to 110 DEG C and the carbon atomicity n of the obtained paraphthaloyl acidhexamethylene diamine salt or m-phthalic acryl acidhexamethylene diamine salt is 4 to 16; (b) 6T salt or 6I salt obtained in step (a) and 66 salt or hexanolactam are polymerized to obtain primary condensation compound and the characteristic viscosity of the primary condensation compound in dense sulfuric acid is 0.09 to 0.25dl/g under the temperature of 30 DEG C; (c) the primary condensation compound obtained in step (b) is under solid phase condensation and polymerization to obtain the high-temperature nylon under the temperature of not more than 250 DEG C. The method provided by the present invention can increase the polyamide size stability, mechanic performance and heat resistance, reduce the molecular weight distribution of the high-temperature nylon, and prevent the occurrence of amine exchange, thermal degradation, gelation and other side reactions.
Description
Technical field
The present invention relates to a kind of preparation method of macromolecular material, relate to a kind of method for preparing high-temperature nylon particularly.
Background technology
Owing to have excellent performance and fusion moldability, with nylon 6, nylon 66 and nylon 1212 is the crystal type polymeric amide widespread use in garment fabric and Industrial materials of representative, and can be widely used in automobile, field such as electric as general engineering plastic.But because described general polymeric amide exists thermotolerance not enough, suction causes inferior positions such as size instability.Particularly in recent years, the polymeric amide as fields such as electric element, trolley parts required to have high performance.For example, along with the development of the surface mounting technique (SMT) in electric element field, polymeric amide need have high heat resistance, for example reflow soldering thermotolerance; Comprise the engine chamber field of components at trolley part, used polymeric amide need have the thermotolerance higher than traditional polymeric amide etc.Yet conventional polyamide material has been difficult to satisfy the requirement on electric and the automobile as nylon 6, nylon 66 and nylon 1212.Therefore, press for dimensional stability, temperature tolerance and the mechanical property that improves polymeric amide.
In order to satisfy this requirement, Japanese Patent JP 02251352, JP 034317, JP 03161507, JP 859825, in the patents such as JP 8198963, disclosed the dicarboxylic acid component that forms by terephthalic acid and m-phthalic acid or hexanodioic acid and mainly by 1,6-hexane diamines etc. are formed the method that diamine components is produced partially aromatic polyamide.Weak point wherein is that its preparation process need remain under the hot environment for a long time, such two amine components highly volatile in high temperature polymerization process, and polymerization time is long, causes side reactions such as thermal destruction and gelation easily, has had a strong impact on the quality of partially aromatic polyamide.Also have a deficiency to be that the viscosity ratio of the partially aromatic polyamide that aggregates into is bigger, be difficult for discharge, cause the yield of polymeric amide low.
U.S. Pat 4722997, US 4131712, and US 4433146, and US 4438257 grades have disclosed 1, and the method for 4-butane diamines and hexanodioic acid production polymeric amide is all open, and some of them are industrialization.But it has weak point equally.For example, raw material with diamine in US 4131712 methods directly is added in the reactive polyblend, a difficulty that is wherein run into is exactly, under temperature of reaction, the final step diamine can volatilize significantly, therefore just need some means and prevent the escape of diamine and it is stayed in the reaction mixture, to avoid loss of yield and to keep stoichiometric balance.
In order to produce polymeric amide, in pressurized reactor, will be in the dicarboxylic acid under the melting state and the discontinuous method of diamine components direct polymerization, be widely used so far.Yet, the polymeric amide of being produced must keep for a long time in one step of reaction being not less than under the high temperature of fusing point so that obtain the high-molecular weight polymeric amide in the back in the method, but because the fusing point of polymeric amide is near their decomposition temperature, thermal destruction usually takes place in polymeric amide as a result, damages its quality.So under prior art, be difficult in the molecular weight that polymeric amide does not take place to improve under the pyrolytic situation polymeric amide.
By melt polymerization process high-molecular weight polymeric amide, polymerization that need be under molten state for a long time.Because the reaction times prolongs thermal history is increased, might cause the polymeric amide degraded.In addition, need special polymerization unit, this is that the molten state polymeric amide keeps enough power uniformly in the polymeric kettle because normally used whipping device can not obtain making, and causes synthetic nylon resin molecular weight distribution inhomogeneous.And, compare with shifting low-viscosity polyamides, with in the fused/operational difficulty that high-viscosity polyamide is shifted out from the polymeric kettle transfer many, the amount of remaining polymeric amide that is attached to the polymeric kettle inwall is also bigger.
In sum, this area lacks a kind of dimensional stability, high-temperature nylon that mechanical property and high thermal resistance improve and preparation method thereof, this preparation method can dwindle the molecular weight distribution of high-temperature nylon, stop the generation of side reactions such as acid amides exchange, thermal destruction and gelation simultaneously.
Summary of the invention
The objective of the invention is to obtain a kind of preparation method of high-temperature nylon, it can dwindle the molecular weight distribution of high-temperature nylon, stop the generation of side reactions such as acid amides exchange, thermal destruction and gelation simultaneously.
Another object of the present invention is to obtain a kind of dimensional stability, the high-temperature nylon that mechanical property and high thermal resistance improve.
Another object of the present invention is to obtain a kind of purposes of high-temperature nylon of the present invention.
In a first aspect of the present invention, a kind of method for preparing high-temperature nylon is provided, may further comprise the steps: (a) dicarboxylic acids and diamines make 6T salt or 6I salt under 80～110 ℃, carbonatoms n=4～16 of gained 6T salt or 6I salt; (b) 6T that obtains of step (a) or 6I salt and 66 salt or hexanolactam polycondensation make elementary condenses, and described elementary condenses intrinsic viscosity in 30 ℃, the vitriol oil is 0.09～0.25dl/g; (c) solid phase polycondensation makes high-temperature nylon to the elementary condenses that obtains of step (b) under 250 ℃ the temperature not being higher than.
Preferably, described diamines is selected from the aliphatic diamine of 4～16 carbon.
In a preferred embodiment of the present invention, may further comprise the steps in the step (a): the dispersion of aromatic acid in the water of 2～5 times of its weight (i) is provided, the dispersion of diamine in the water of 1～3 times of its weight (ii) is provided, (iii) the dispersion that step (i) and step are (ii) obtained according to etc. molar ratio reaction, obtain the solution of 6T salt or 6I salt; The 6T salt that (iv) step is (iii) obtained or the solution of 6I salt carry out crystallization, obtain described 6T salt or 6I salt.
In a preferred embodiment of the present invention, the temperature of step (i) is 60～130 ℃, preferred 80～100 ℃; And/or step temperature (ii) is 60～120 ℃, preferred 80～100 ℃; And/or step (iii) temperature be controlled at 60～105 ℃, preferred 80～100 ℃, the pH value of reaction end is 6.5～8.0, preferred 7.0～7.5; And/or step (iii) in dispersion go in the hybrid reactor with the metering infusion, make its molar ratio reaction such as grade; And/or the solution of the 6T salt that (iii) obtains of step or 6I salt injects crystallizer, through the refrigerated water cooling, makes the salts solution crystallization, and the mixture with crystal/water moves in the whizzer then, can obtain the nylon salt finished product of white powder after the separation.
In a preferred embodiment of the present invention, the preparation of 6T salt or 6I salt comprises the steps:
(1) aromatic acid of content 〉=99% is dissolved in 2～5 times the deionized water, is heated to 60～130 ℃ while stirring, preferred 80～100 ℃;
(2) diamine is dissolved in 1～3 times the deionized water, is heated to 60～120 ℃ while stirring, preferred 80～100 ℃;
(3) with two kinds of raw materials according to etc. mol ratio go into the metering infusion and react in the hybrid reactor, temperature of reaction is controlled at 60～105 ℃, preferred 80～100 ℃, the pH value of reaction end is 6.5～8.0, preferred 7.0～7.5;
(4) salts solution is injected crystallizer, through the refrigerated water cooling, make the salts solution crystallization, the mixture with crystal/water moves in the whizzer then, can obtain the nylon salt finished product of white powder after the separation.
In a preferred embodiment of the present invention, the copolymerization weight ratio of 6T in the step (b) or 6I salt and 66 salt or hexanolactam is in 35/65～70/30, and preferably, the copolymerization weight ratio is in 40/60～60/40 scope; And/or the polymerization temperature in the described step (b) is 230～260 ℃, and pressure is 2.1～2.6MPa.
In a preferred embodiment of the present invention, the polymerization temperature in the step (c) is 200～240 ℃.
In a preferred embodiment of the present invention, add phosphorus-containing catalyst in step (a) or step (b) or the step (c), described phosphorus-containing catalyst is selected from hypophosphite, phosphoric acid salt, ortho phosphorous acid, phosphoric acid, phosphoric acid ester or its combination.
Preferably, the consumption of phosphorus-containing catalyst is 0.001～5wt% with respect to the total content of di-carboxylic acid and diamine.
In a preferred embodiment of the present invention, in step (a) or step (b) or step (c), add polymerization degree conditioning agent, permutoid reaction inhibitor, nucleator or its combination.
The high-temperature nylon that the present invention provides a kind of method of the present invention to make on the other hand, molecular weight distribution are 1.6～2.2.
In a preferred embodiment of the present invention, its crystallization enthalpy surpasses 60J/g, and heat-drawn wire is 154～157 ℃.
The present invention has an aspect that the application of a kind of high-temperature nylon of the present invention at electronics, electric, auto parts machinery is provided again.
Embodiment
The inventor is through extensive and deep research, by improving preparation technology, monomer is made the required salt of polymerizing polyamide reaction, be condensed into elementary condenses by monomer salt then, elementary condenses further aggregates into again has the required high-temperature nylon of high-molecular weight (HPN).By three step polyreaction methods, the molecular weight distribution of having dwindled high-temperature nylon has stoped the generation of side reactions such as acid amides exchange, thermal destruction and gelation simultaneously, and has improved the crystallization degree of high-temperature nylon, the high-temperature nylon of obtained performance excellence.
6T salt of the present invention for example is hexamethylene terephthalamide salt, and 6I salt for example is 6I hexamethylene isoterephalamide salt.
The implication of " polymeric amide " of the present invention is identical with nylon.
The present invention's " composition " is meant the raw material combination thing of preparation high-temperature nylon.
High-temperature nylon
High-temperature nylon of the present invention (HPN) is the high-temperature nylon that contains the amido linkage that aliphatic diamine and dicarboxylic acid (for example terephthalic acid) by 4～16 carbon form, and the fusing point of high-temperature nylon of the present invention, preferred 260～320 ℃, and more preferably 280～320 ℃.The reason of preferred this scope is: when fusing point hangs down, can not make the heat-resisting nylon resin that meets the object of the invention; And fusing point needs high temperature to produce the problem that foams because of pyrolysis owing to nylon resin adds when too high man-hour.
Aliphatic diamine specific examples as having 4～16 carbon has 1,4-diaminobutane, 1,5-diamino pentane, 1,1,5-diamino-2-methylpentane, 1,7-diamino heptane, 1,8-diamino octane, 1,9-diamino nonane, 1, the 10-diamino decane, 2,11-diamino hendecane, 1,12-diamino 12 carbon alkane, 1,1 3-diamino n-tridecane and 1, aliphatic Alkylenediamines such as 14-diamino n-tetradecane.In these aliphatic diamines, many long chain aliphatic diamine of carbonatoms especially are owing to can make the water-absorbent of the polymeric amide that is obtained reduce and preferred the use.These aliphatic diamines can use separately or two or more and usefulness separately.As above-mentioned carbon number is 4～16 aliphatic diamine composition, because carbon number is 6, and promptly 2,6-diamino hexane and 1, overall target is good especially can preferably use for the thermotolerance of 5-diamino-copolyamide that the 2-methylpentane generated and crystallinity etc.
In high-temperature nylon of the present invention (HPN), the raw material of using as the part amide structure unit that forms outside the above-mentioned terephthalic acid amide structure unit, for example ε-Ji Neixianan, ζ-oenantholactam are arranged, lactams such as η-spicy inner formyl amine, omega-lauric lactam
Dicarboxylic acid of the present invention is not particularly limited, only otherwise goal of the invention of the present invention (for example fusing point) is produced restriction to get final product.As diacid, also have oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, hendecane diacid, 12 carbon docosandioic acids, brassylic acid, n-tetradecane diacid, aliphatic dicarboxylic acids such as pentadecane diacid, aromatic dicarboxylic acids such as m-phthalic acid or the like.In the amide structure unit that is derived by these materials, hexanamide, hexamethylene adipamide and hexa-methylene isophthaloyl amine are particularly suited for using separately or combination and usefulness in the present invention.
Use 1, the 6-diamino hexane is during as the unitary aliphatic diamine composition of terephthalic acid amide structure, the preferred copolyamide that contains 6T that uses wherein has the repeating unit of being made up of at least a structural unit of selecting in structural unit (I) and the structural unit (II)～(IV):
(the hexylidene terephthalamide units below is designated as 6T)
(hexylidene adipamide units, below note does 66)
(hexylidene isophthaloyl amine unit below is designated as 6I)
(hexanamide unit, below note does 6)
In containing the above-mentioned high-temperature nylon of 6T, for example in the multipolymer of two compositions, it consists of, and copolymerization is 35/65～85/15 than in feed stage by weight under the situation of 6T/6I, and is preferred 50/50～75/25, more preferably in 60/40～70/30 scope.In addition, consist of in copolymerization under the situation of 6T/66, copolymerization is 20/80～80/20 than in feed stage by weight, and is preferred 30/70～70/30, more preferably is in 35/65～60/40 scope.And copolymerization consists of under the situation of 6T/6, and the copolymerization ratio of feed stage is 40/60～90/10 by weight, and is preferred 55/45～85/15, more preferably is in 60/40～80/20 scope.These contain the copolymerization ratio of the copolyamide of 6T, the copolymerization ratio when preferably selecting to obtain melting point polymer and being in crystallinity copolyamide in 270～330 ℃ of scopes.
In these copolyamides, angle from the crystallization characteristic, 6T/66 is desirable especially, and the ratio of copolymerization by weight is in 35/65～70/30, and the copolyamide that especially is in 40/60～60/40 scope can realize that it has excellent characteristic.
Containing in the polymeric amide of 6T in the present invention, can also be three compositions or more multicomponent multipolymer; Form as preferred copolymerization in this case, can enumerate the composition of the 6T/6I/66 that contains 6T/66 and 6T/66/6 and so on.Wherein, the 6T/66 composition in these copolyamides, with more than the 50wt% for well, preferably more than the 60wt%, more preferably more than the 70wt%.
Phosphorus-containing catalyst
In order to add the degraded of fast response and the polymeric amide that prevents to generate, preferably when the preparation polymeric amide, use phosphorus-containing catalyst, preferred hypophosphite, phosphoric acid salt, ortho phosphorous acid, phosphoric acid, phosphoric acid ester etc.The specific examples of ortho phosphorous acid salt, preferred inferior sodium phosphate, ortho phosphorous acid potassium, Lime Hypophosphate, ortho phosphorous acid magnesium, ortho phosphorous acid aluminium, ortho phosphorous acid barium, ortho phosphorous acid zinc, ammonium hypophosphite etc.The specific examples of phosphoric acid salt, preferably phosphoric acid sodium, potassiumphosphate, potassium primary phosphate, calcium phosphate, trimagnesium phosphate, barium phosphate, ammonium phosphate etc.The specific examples of phosphoric acid ester, preferred ethyl octadecyl phosphoric acid ester etc.
The amount of phosphorus-containing catalyst is with respect to the total content of di-carboxylic acid and diamine, preferably between 0.001～5wt%, more preferably between 0.01～2wt%, more preferably at 0.05～1wt%.Though in addition its interpolation time before high-polymerization degreeization is finished whenever all can, preferably raw material add the elementary condenses polymerization in back before finishing during in interpolation, and can add repeatedly.Also can make the adding that combines of different Phosphorus catalyst in addition.
Polymerization degree conditioning agent
In addition, polyreaction of the present invention can add polymerization degree conditioning agent, i.e. end-capping reagent for the ease of the polymerization degree of adjusting polymeric amide and the polymerization degree of high-polymerization degreeization.End-capping reagent can be the simple function group compound, has the reactivity of or end carboxyl amino with the polymeric amide middle-end.Because their hyperergy and polymeric amide end group are stable with their end-blockings, preferred end-capping reagent is monocarboxylic acid compound or monoamine compound.Owing to be convenient to handle, more preferably monocarboxylic acid.In addition, acid anhydrides, monoesters, monohydroxy-alcohol also can be used as end-capping reagent.
The amount of end-capping reagent is with respect to the total content of di-carboxylic acid and diamine, preferably between 0.1～15mol%.
Described monocarboxylic acid comprises, for example, and aliphatics monocarboxylic acid such as acetate, propionic acid, butyric acid, valeric acid, caproic acid, sad, lauric acid and isopropylformic acid; Aromatic series monocarboxylic acid such as phenylformic acid, toluic acid and toluylic acid; And above-mentioned any two kinds mixture.Consider the stability of reactivity, cost and end-blocking end group, wherein preferred acetate, propionic acid, butyric acid, valeric acid, caproic acid, sad, lauric acid and phenylformic acid.
The permutoid reaction inhibitor
In daiamid composition of the present invention, add metal hydroxides and/or metal oxide and can suppress the permutoid reaction of acid amides between the polymeric amide, thereby improve the thermotolerance of gained daiamid composition.When polymeric amide comprises an acidic catalyst or acid additives, add metal hydroxides and/or metal oxide and reduce effective especially the fusing point that suppresses to cause owing to the acid amides permutoid reaction.The preferred add-on of described metal hydroxides and/or metal oxide is 0.1～20 weight %, is more preferably 1～10 weight %, calculates with composition total weight.
Metal hydroxides comprises magnesium hydroxide, aluminium hydroxide, calcium hydroxide and hydrated barta.Also can use the mixture of above-claimed cpd.Wherein magnesium hydroxide and aluminium hydroxide are preferred, and they can effectively suppress the permutoid reaction of acid amides between the polymeric amide, and make the gained polymeric amide that thermotolerance and flame retardant resistance be arranged.
Metal oxide comprises magnesium oxide, aluminum oxide, calcium oxide and barium oxide.Also can use the mixture of above-claimed cpd.Wherein magnesium oxide and/or aluminum oxide are preferred, and they can effectively suppress the permutoid reaction of acid amides between the polymeric amide, and make the gained polymeric amide that thermotolerance and flame retardant resistance be arranged.
Nucleator
Daiamid composition of the present invention can use and comprise the nucleator that is generally used for polymeric amide.The example of described nucleator comprises talcum powder, silicon-dioxide, magnesium oxide, aluminum oxide, calcium stearate, barium stearate, Zinic stearas and above-mentioned any several mixture.Talcum powder preferably wherein is because it can improve the crystallization rate of polymeric amide effectively.In order to improve the consistency of they and polymeric amide, nucleator can carry out surface treatment with silane coupling agent, titanium coupling agent etc.
The content of nucleator is preferably 0.01～10wt%, and more preferably 0.1～1wt% calculates with composition total weight.Nucleator can add in the polymerization process of polymeric amide, or adds by doing to mix or pass through the forcing machine fusion.
Below each step of preparation method of the present invention is described in detail:
Three step polymerizations
High-temperature nylon of the present invention (HPN) prepares by the following method.
Prepare nylon salt at first at low temperatures, make elementary condenses then under given conditions, again by later stage solid phase polycondensation step, thereby realize high-polymerization degreeization, this is a kind of three step polymerizations.
For example be:
(a) aromatic acid of content 〉=99% is dissolved in 2～5 times the deionized water, is heated to 60～130 ℃ while stirring, preferred 80～100 ℃;
(b) diamine is dissolved in 1～3 times the deionized water, is heated to 60～120 ℃ while stirring, preferred 80～100 ℃;
(c) with two kinds of raw materials according to etc. mol ratio go into the metering infusion and react in the hybrid reactor, temperature of reaction is controlled at 60～105 ℃, preferred 80～100 ℃, the pH value of reaction end is 6.5～8.0, preferred 7.0～7.5;
(d) salts solution is injected crystallizer, through the refrigerated water cooling, make the salts solution crystallization, the mixture with crystal/water moves in the whizzer then, can obtain the nylon salt finished product of white powder after the separation.
The preparation nylon salt
Prepare 6T and/or 6I salt at first at low temperatures.The aromatic acid of content 〉=99% is added in the dissolution kettle, the deionized water that adds 2～5 times again, be heated to 60～130 ℃ of preferred temperature while stirring, more preferably 80～100 ℃, in another dissolution kettle, diamine is dissolved in simultaneously in 1～3 times the deionized water, and be heated to preferred temperature at 60～120 ℃, more preferably 80～100 ℃.With two kinds of raw materials according to etc. mol ratio go into the metering infusion and react in the hybrid reactor, temperature of reaction is controlled at 60～105 ℃, more preferably 80～100 ℃, the pH value of reaction end is preferably 6.5～8.0, and more preferably 7.0～7.5, after salts solution is injected crystallizer, through the refrigerated water cooling, make the salts solution crystallization, the mixture with crystal/water moves in the whizzer then, can obtain the nylon salt finished product of white powder after the separation, the molecular formula of nylon salt is
-OOC (C
6H
4) COO
-+H
3N (CH
2)
nNH
3 +, n=4～16 wherein.
The raw material of production nylon salt of the present invention preferably contains by the aliphatic diamine of 4～16 carbon and terephthalic acid or m-phthalic acid.
Elementary condensation
The nylon salt that above-mentioned steps is made places polymermaking autoclave, uses water as solvent and is made into solution, under agitation carries out polyreaction.Preferably, the adding concentration of raw material more than the preferred 20wt%, and is in below the 80wt% more than 10wt% in the solution, below the preferred 60wt%.
Under agitation condition, carry out the formation operation of elementary condenses in the mode of increasing temperature and pressure.After reinforced, polymerization temperature is improved and be controlled in 230～330 ℃ of temperature ranges preferred 230～260 ℃.Carrying out polymeric simultaneously, polymerization pressure is controlled in 0.5～3MPa pressure range.When top temperature and top pressure needn't last till the polymerization termination, but till also can lasting till when polymerization stops.
When the polymerization of above-mentioned elementary condenses, though the highest polymerization temperature is higher than 230 ℃ and be lower than 330 ℃, but be under 280～320 ℃ the situation for the fusing point of polymeric amide, be up to Da Wendu and can be located at and be lower than about 50 ℃ of copolyamide fusing point, preferably be lower than about 20 ℃ of this fusing point; And be higher than 20 ℃ of this fusing points, preferably be higher than in the scope of 5 ℃ of this fusing points.When being up to Da Wendu and being lower than 240 ℃, not only can not fully improve the polymerization degree of elementary condenses, and owing to have difference between all compositions of the copolymerization reactivity separately, thereby form chain and distribute and go up the high elementary condenses of block, so even block arranged by making it still residual in the polymkeric substance that high-polymerization degreeization obtains.In addition, if the highest polymerization temperature surpasses 330 ℃, then copolyamide be subjected to that thermal process is long to reduce every performance, so be undesirable.
Though top pressure can be higher than 0.5MPa and be lower than in the 3MPa scope when elementary condenses formed, preferably be higher than 2MPa and be lower than 2.6MPa.When being higher than 3MPa,, the polymerization degree occurring and increase the not high problem of reactivity of slowing down and generating elementary condenses because water-content increases in the reaction system.In addition, if top pressure is lower than 0.5MPa, then the danger that elementary condenses is separated out can appear in polymeric kettle.
The water ratio of elementary condenses is less than 10wt%, preferably less than 5wt%.When water ratio is higher than 10wt%, be difficult to high-polymerization degreeization.In addition, elementary condenses preferably was ground into it suitable granularity before high-polymerization degreeization.
The prepolymer that above-mentioned steps makes intrinsic viscosity in 30 ℃, the vitriol oil is 0.1～0.25dl/g.With the prepolymer solid state polymerization.The intrinsic viscosity of prepolymer is 0.1～0.25dl/g, and the polymerization of prepolymer keeps good carboxyl and amino balance, seldom reduces rate of polymerization, obtains narrow molecular weight distribution, the polymeric amide of excellent properties and excellent molding processability is arranged.When solid state polymerization is adopted in the polymerization of prepolymer, preferably in reducing pressure or inert gas, carry out.In addition, when temperature was 200～240 ℃, polymeric rate of polymerization height, productivity was high and painted or gelation reduces.
Solid phase polycondensation
The polymerization degree that improves oligopolymer by solid phase polycondensation is the normal at present method that adopts.Concerning high-temperature nylon, at first by the melt polymerization process low-viscosity polyamides, then in solid-state thermal treatment down.Because the polymerization degree can increase when temperature was lower than fusing point,, avoided because the variable color that thermal destruction produces so solid state polymerization is better than melt polymerization.
The equipment that the present invention carries out solid phase drying or solid state polymerization has no particular limits, and can use a kind of intermittent apparatus or a kind of continuous equipment with regard to it is designed to heating installation.If use the intermittent type heating installation, when charging into rare gas element such as nitrogen or during to equipment pump drainage gas, heating realizes by the heat passage heat of equipment surface.The example of intermittent type heating installation comprises the rotary drum heating installation, promptly common alleged rotary drum dryer, and taper moisture eliminator and rotatory drier and internal configuration have the taper heating installation of rotating paddle.As the successive type heating installation, available is vertical gas flow moisture eliminator, and promptly common alleged hopper dryer wherein heats by the dry nitrogen air-flow that heated and realizes; Level heat transfer moisture eliminator promptly is commonly referred to pedal-type dryer, and wherein when charging into nitrogen, the heat of the heating surface of equipment is realized heating.
During solid phase polycondensation, earlier temperature of charge is risen to 100～140 ℃, vacuumize heating, earlier the aqueous vapor of high-temperature nylon was evaporated 0.5～4 hour, more preferably 1～2 hour,, prevent the material variable color so that aqueous vapor is evaporated fully.Charge into shielding gas then, preferred nitrogen, helium etc. are warming up to the stable solid phase polycondensation that carries out high-temperature nylon of setting with material, and temperature preferably is lower than 100～20 ℃ of its fusing points, more preferably less than 80～50 ℃ of its fusing points.Preferred 0.5～12 hour of solid phase polycondensation time, more preferably 2～6 hours.
Positively effect of the present invention is:
The inventive method with the major advantage that polymeric polyamide method is in the past compared is, the amine volatilization that the inventive method has effectively avoided high-temperature nylon to take place in polymerization process, the possibility of resin thermal destruction or gelation, make things convenient for the transfer of material simultaneously, reduce high-temperature nylon attached to the possibility on the reactor wall, improved production efficiency.The melt polymerization of the general superpolyamide fluidized polymer of its needed output investment ratio and solid-state polymerization processing are much lower, have avoided need transforming the investment that causes to long steps such as reactor, drying machine and distiller of the residence time.The advantage of this method for solid phase polymerization is to optimize arranging of molecular chain, improves the polymerization degree, shortens the residence time simultaneously, not agglomeration of solid granulates etc.
Further advantage of the present invention is oxidation and the degraded that it can avoid polymkeric substance, this be because all compositions all be in sealing with prevent with coverage condition that air contacts under.
Below in conjunction with specific embodiment, further illustrate the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, for example is " condition in the smooth organic chemistry handbook of Bel Si (Chemical Industry Press, 1996), or the condition of advising according to manufacturer.Ratio and per-cent are based on weight, unless stated otherwise.
All characteristics are all measured by the following method in embodiment and reference examples.
1, limiting viscosity [η]
The sample dissolution of the high-temperature nylon that will test is 0.05,0.1,0.2 or the solution of 0.4g/dl to obtain concentration in the vitriol oil, the bent 30 ℃ of dense logarithm viscosity number of ratio η that measure each sample solution down
RlhAs follows
η
rln＝[ln(t/t
0)]/C (dl/g)；
T wherein
0The flushing time (second) of expression solvent, t represents the flushing time (second) of sample solution, C represents the concentration of sample in the sample solution.
With η
RlnData to be extrapolated to concentration be 0 scope, with the limiting viscosity [η] that obtains sample.
2、GPC
Measure the molecular weight distribution of sample with Waters-991 type gel chromatograph.Nylon 6 is standard specimen, and meta-cresol is a solvent.
3、DSC
The DSC test is carried out on Perkin-Elmer Diamond type differential scanning calorimeter.Demarcate with pure indium (In) and pure zinc (Zn), the temperature measuring tolerance range is main 0.01 ℃.The experiment of all DSC is all carried out in identical nitrogen gas stream, example weight 5～6mg.Sample at first is heated to 350 ℃ with the temperature rise rate of 10 ℃/min, and constant temperature 5min is cooled to normal temperature with same speed after eliminating thermal history again.Note the crystallization enthalpy of sample temperature-fall period.
4、HDT
Heat-drawn wire (HDT) according to ASTM D648 standard test sample under 1.82MPa.
Embodiment 1
The 166.13Kg terephthalic acid is added in the dissolution kettle, add 2 times deionized water again, be heated to 100 ℃ while stirring.The 116.21Kg hexanediamine is joined in 1 times of deionized water simultaneously, under 80 ℃ of temperature condition, dissolve.Simultaneously two kinds of solution are sent into mixing tank with volume pump respectively, after enter neutralizing well, 90 ℃ of neutral temperatures of control, PH 7.1～7.2.Reactant enters crystallizer and cools off by refrigerated water, makes temperature reduce to 25 ℃, and forms crystallization.Material is put into whizzer, obtain wet nylon 6T salt 266.25Kg after the separation, yield 94.3%, water content 13.6%.284.9 ℃ of the fusing points of nylon salt, free acid content 0.15%, unhindered amina content 0.21%.
Oneself two ammonium adipates (66 salt) of the salt that 3150g terephthalic acid and hexanediamine are formed, 2100g, 20g phenylformic acid, 5g sodium hypophosphite monohydrate and 2.5 liters of distilled water add the 20L polymeric kettles, logical then nitrogen three times, air displacement in the still is come out, with in 2 hours, the raise temperature to 240 ℃ of this mixture of gained mixture.Meanwhile, the internal pressure of autoclave is 2MPa.Be reflected under the constant voltage of 240 ℃ constant temperature and 2MPa and continued into 2 hours, keep-up pressure constant by removing formed water.After this, made the internal pressure of autoclave be reduced to 1MPa in 30 minutes, reaction mixture continues to stir 1 hour under the pressure of 240 ℃ and 1MPa, thereby acquired character viscosity [η] is 0.19dl/g, and molecular weight distribution is 5.4 prepolymer.Prepolymer is 100 ℃ of following drying under reduced pressure 12 hours, and is crushed into the particle that particle diameter is not more than 2mm.Make this particle 230 ℃ and-carried out solid state polymerization 4 hours under the pressure of 0.1MPa, thereby obtain white high-temperature nylon (HPN), its limiting viscosity [η] is 1.04dl/g, molecular weight distribution is 2.1, crystallization enthalpy is 65.28J/g, heat-drawn wire is 155 ℃.
The comparative example
With the 1600g terephthalic acid, 1100g hexanediamine, 2490g66 salt, 5g sodium hypophosphite are as catalyzer, and the 30g phenylformic acid adds in the 20L polymeric kettle as terminator and 6L water.Concrete converging operation obtains the elementary condenses of high-temperature nylon with embodiment 1, then it is carried out solid phase polycondensation with embodiment 1, obtain white high-temperature nylon (HPN), its limiting viscosity [η] is 0.84dl/g, and molecular weight distribution is 6.1, crystallization enthalpy is 37.52J/g, and heat-drawn wire is 142 ℃.
Embodiment 2
Oneself two ammonium adipates (66 salt) of the salt that 3250g terephthalic acid and hexanediamine are formed, 2100g, 40g acetate, 5g sodium hypophosphite monohydrate and 2.5 liters of distilled water add the 20L polymeric kettles, carry out warming temperature according to embodiment 1 then, making intrinsic viscosity is 0.14dl/g, and molecular weight distribution is 5.3 prepolymer.Prepolymer is 100 ℃ of following drying under reduced pressure 12 hours, and is crushed into the particle that particle diameter is not more than 2mm.Make this particle 230 ℃ and-carried out solid state polymerization 4 hours under the pressure of 0.1MPa, thereby obtain white high-temperature nylon (HPN), its limiting viscosity [η] is 1.14dl/g, molecular weight distribution is 1.9, crystallization enthalpy is 62.24J/g, heat-drawn wire is 157 ℃.
Embodiment 3
Oneself two ammonium adipates (66 salt) of the salt that 3250g terephthalic acid and hexanediamine are formed, 1100g, 1000g ε-Ji Neixianan, 30g acetate, 5g sodium hypophosphite monohydrate and 2.5 liters of distilled water add the 20L polymeric kettles, carry out warming temperature according to embodiment 1 then, making intrinsic viscosity is 0.09dl/g, and molecular weight distribution is 5.8 prepolymer.Prepolymer is 100 ℃ of following drying under reduced pressure 12 hours, and is crushed into the particle that particle diameter is not more than 2mm.Make this particle 230 ℃ and-carried out solid state polymerization 3 hours under the pressure of 0.1MPa, thereby obtain white high-temperature nylon (HPN), its limiting viscosity [η] is 1.12dl/g, molecular weight distribution is 2.1, crystallization enthalpy is 59.75J/g, heat-drawn wire is 154 ℃.
Embodiment 4
Oneself two ammonium adipates (66 salt) of the salt that 3250g terephthalic acid and hexanediamine are formed, 2100g, 40g phenylformic acid, 10g sodium hypophosphite monohydrate and 2.5 liters of distilled water add the 20L polymeric kettles, carry out warming temperature according to embodiment 1 then, making intrinsic viscosity is 0.09dl/g, and molecular weight distribution is 5.6 prepolymer.Prepolymer is 100 ℃ of following drying under reduced pressure 12 hours, and is crushed into the particle that particle diameter is not more than 2mm.Make this particle 230 ℃ and-carried out solid state polymerization 2 hours under the pressure of 0.1MPa, thereby obtain white high-temperature nylon (HPN), its limiting viscosity [η] is 1.06dl/g, molecular weight distribution is 2.0, crystallization enthalpy is 61.55J/g, heat-drawn wire is 153 ℃.
Embodiment 5
Under need not the condition of Phosphorus catalyst, press the method operation of embodiment 1, carry out the polymerization of elementary condenses; And use mode similarly to Example 1 to carry out the high-polymerization degree operation.Thereby obtain white high-temperature nylon (HPN), its limiting viscosity [η] is 1.06dl/g, and molecular weight distribution is 2.1, and crystallization enthalpy is 61.76J/g, and heat-drawn wire is 151 ℃.
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (10)
1. a method for preparing high-temperature nylon is characterized in that, may further comprise the steps:
(a) dicarboxylic acid and diamines make 6T salt or 6I salt under 80～100 ℃; May further comprise the steps in the described step (a):
(i) provide the dispersion of dicarboxylic acid in the water of 2～5 times of its weight, the temperature of step (i) is 80～100 ℃,
The dispersion of diamine in the water of 1～3 times of its weight (ii) is provided, and step temperature (ii) is 80～100 ℃,
(iii) the dispersion that step (i) and step are (ii) obtained according to etc. molar ratio reaction, obtain the solution of 6T salt or 6I salt; Step (iii) temperature is controlled at 80～100 ℃, and the pH value of reaction end is 6.5～8.0,
Wherein, step (iii) in dispersion go in the hybrid reactor with the metering infusion, make its molar ratio reaction such as grade;
The 6T salt that (iv) step is (iii) obtained or the solution of 6I salt carry out crystallization, obtain described 6T salt or 6I salt;
(b) 6T that obtains of step (a) or 6I salt and 66 salt or hexanolactam polycondensation make elementary condenses, and described elementary condenses intrinsic viscosity in 30 ℃, the vitriol oil is 0.09～0.25dl/g;
(c) solid phase polycondensation makes high-temperature nylon to the elementary condenses that obtains of step (b) under 250 ℃ the temperature not being higher than.
2. the method for claim 1 is characterized in that,
The step (iii) pH value of reaction end is 7.0～7.5.
3. the method for claim 1 is characterized in that,
The copolymerization weight ratio of 6T in the step (b) or 6I salt and 66 salt or hexanolactam is in 35/65～70/30, and/or
Polymerization temperature in the described step (b) is 230～260 ℃, and pressure is 2～2.6MPa.
4. method as claimed in claim 3 is characterized in that the copolymerization weight ratio is in 40/60～60/40 scope.
5. the method for claim 1 is characterized in that, the polymerization temperature in the step (c) is 200～240 ℃.
6. the method for claim 1 is characterized in that, adds phosphorus-containing catalyst in step (a) or step (b) or the step (c), and described phosphorus-containing catalyst is selected from hypophosphite, phosphoric acid salt, ortho phosphorous acid, phosphoric acid, phosphoric acid ester or its combination.
7. the method for claim 1 is characterized in that, adds polymerization degree conditioning agent, permutoid reaction inhibitor, nucleator or its combination in step (a) or step (b) or step (c).
8. a high-temperature nylon that makes as each described method of claim 1～7 is characterized in that molecular weight distribution is 1.6～2.2.
9. high-temperature nylon as claimed in claim 8 is characterized in that, its crystallization enthalpy surpasses 60J/g, and heat-drawn wire is 154～157 ℃.
10. a high-temperature nylon as claimed in claim 8 is in the application of electronics, electric, auto parts machinery.
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| CN103102486B (en) * | 2011-11-15 | 2016-07-13 | 上海杰事杰新材料(集团)股份有限公司 | A kind of nylon and preparation method thereof |
| CN103159951B (en) * | 2011-12-13 | 2017-04-12 | 上海杰事杰新材料(集团)股份有限公司 | Method and apparatus for preparing high temperature nylon |
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| CN106928451A (en) * | 2015-12-31 | 2017-07-07 | 上海杰事杰新材料(集团)股份有限公司 | High temperature resistant PA6T copolymers and preparation method thereof |
| CN107652429B (en) * | 2017-10-20 | 2018-10-16 | 广州市万佳成塑料有限公司 | A kind of production method of low molecular weight nylon 6T powder synthesis high molecular weight nylon 6T resins |
| CN108796829A (en) * | 2018-05-24 | 2018-11-13 | 江阴市华思诚无纺布有限公司 | A kind of antistatic polyester non-woven cloth and preparation method thereof |
| CN109824887B (en) * | 2019-01-31 | 2021-04-20 | 珠海派锐尔新材料有限公司 | Preparation method of nylon microsphere powder |
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