CN105017525A - Branched modifier and corresponding flame retardant nylon resin - Google Patents
Branched modifier and corresponding flame retardant nylon resin Download PDFInfo
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- CN105017525A CN105017525A CN201510418725.7A CN201510418725A CN105017525A CN 105017525 A CN105017525 A CN 105017525A CN 201510418725 A CN201510418725 A CN 201510418725A CN 105017525 A CN105017525 A CN 105017525A
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- phosphonitrile
- ring
- flame retardant
- tri
- nylon resin
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 68
- 239000004677 Nylon Substances 0.000 title claims abstract description 50
- 229920001778 nylon Polymers 0.000 title claims abstract description 50
- 239000011347 resin Substances 0.000 title claims abstract description 37
- 229920005989 resin Polymers 0.000 title claims abstract description 37
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000003607 modifier Substances 0.000 title abstract 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 15
- 150000004985 diamines Chemical class 0.000 claims abstract description 9
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract 7
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims description 37
- 238000012986 modification Methods 0.000 claims description 36
- 230000004048 modification Effects 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000004215 Carbon black (E152) Substances 0.000 claims description 14
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- -1 4-carboxyphenoxy) ring Chemical group 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 8
- 150000001413 amino acids Chemical class 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical group [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 4
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- CJYXCQLOZNIMFP-UHFFFAOYSA-N azocan-2-one Chemical compound O=C1CCCCCCN1 CJYXCQLOZNIMFP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 2
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 125000001142 dicarboxylic acid group Chemical group 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012434 nucleophilic reagent Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001012 protector Effects 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical group [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Landscapes
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a branched modifier having the structure shown in the formula (VII), wherein R2-R7 are the same or different and are independently hydrocarbonyl or substituted hydrocarbonyl containing 1-20 carbon atoms, the substituted hydrocarbonyl is hydrocarbonyl containing terminated carboxyl or terminated amino, and at least one of R2-R7 is substituted hydrocarbonyl containing terminated carboxyl or terminated amino. The invention also provides a flame retardant nylon resin, a reactive flame retardant and diamine or dicarboxylic acid form a salt with equal mole ratio, the obtained salt solution is mixed with a nylon polymeric monomer and the branched modifier, and then a polycondensation reaction is carried out to obtain the flame retardant nylon resin. The flame retardant nylon resin has the characteristics of no halogen, environmental protection, no dripping during combustion, high flame retardant efficiency, high flame retardant grade, permanent flame retardancy and no migration.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of branched modification agent, and use the nylon resin of described branched modification agent.
Background technology
Nylon, because having good mechanical property, heat-resisting weathering resistance and electrical insulation capability, is widely used in the fields such as automobile, electronic apparatus, mechanical means and defence and military.But, because the oxygen index of nylon material is low, combustionvelocity is fast, heat release is high, produce a large amount of dense smoke and molten drop especially in combustion, very easily propagating flame, threat to life property safety, greatly limit its range of application.Therefore, the flame retardant resistance improving nylon material is extremely urgent.
In order to improve the flame retardant properties of nylon, the industrial method mainly through physical blending realizes.It is by fire retardant and nylon resin by screw rod blended come.Because the addition of fire retardant is large, in the course of processing, fire retardant is easily reunited formation stress concentration, causes the mechanical properties decrease of nylon material.In addition, due to additional fire retardant and nylon resin poor compatibility, fire retardant easily to material surface migration, causes Flame Retardancy not lasting.
In order to overcome the above problems, the synthesis report of reactive pattern fire-retardant nylon resin.As adopted CEPPA as reactive flame retardant in Chinese patent CN1266445A, prepare reaction-type flame-retarding Nylon 66, this resin has halogen-free flameproof, fire retardant and the feature such as not to separate out, but can drip during this fire-retardant nylon resin burning, resistance to elevated temperatures is poor simultaneously, easily decompose under high temperature, affect range of application.
Summary of the invention
The object of the present invention is to provide a kind of branched modification agent, for improving the flame retardant properties of nylon.
Another object of the present invention is to provide the fire-retardant nylon resin using described branched modification agent, and not only comprehensive mechanical property is good for it, and flame retardant rating is high, has permanent fire retardant, and fluidity of molten is high, can meet various processed and applied demand preferably.
In order to solve the problem, the present invention by the following technical solutions:
Branched modification agent of the present invention is with ring three phosphonitrile for kernel, and it has structure shown in formula (VII):
Wherein, R
2-R
7identical or different, be the alkyl containing 1-20 carbon atom or substituted hydrocarbon radical independently of one another, described substituted hydrocarbon radical is the alkyl containing end carboxyl or Amino End Group, and R
2-R
7in have one at least for the substituted hydrocarbon radical containing end carboxyl or Amino End Group.
Further, R
2-R
7independently of one another for containing the aliphatic alkyl of 1-20 carbon atom or aliphatics substituted hydrocarbon radical, alicyclic alkyl or alicyclic substituted hydrocarbon radical containing 3-20 carbon atom or be the aromatic hydrocarbyl or the aromatic series substituted hydrocarbon radical that contain 6-20 carbon atom; Described substituted hydrocarbon radical is the alkyl containing end carboxyl or Amino End Group, preferred R
2-R
7in altogether containing 3-18 end carboxyl or hold amido.
In a particular embodiment of the present invention, described branched modification agent is selected from 1, 3, 5-triple phenoxyl-1, 3, 5-tri-(4-carboxyphenoxy) ring three phosphonitrile, 1, 3, 5-triple phenoxyl-1, 3, 5-tri-(4-amino-benzene oxygen) ring three phosphonitrile, 1, 3, 5-tri-neopentyl oxygen-1, 3, 5-tri-(4-amino-benzene oxygen) ring three phosphonitrile, six (4-carboxyphenoxy) ring three phosphonitrile, six (4-amino-benzene oxygen) ring three phosphonitrile, 1, 3, 5-tri-(4-amino-benzene oxygen)-1, 3, 5-tri-(2, 4-diamino phenoxy) ring three phosphonitrile, six (3, 5-di carboxyl phenyloxy) ring three phosphonitrile, six (2, 4-diamino phenoxy) ring three phosphonitrile, 1, 3, 5-tri-(3, 5-di carboxyl phenyloxy)-1, 3, 5-tri-(2, 3, 5-tri-carboxyphenoxy) ring three phosphonitrile, six (2, 4, 6-tri-carboxyl benzyloxy) ring three phosphonitrile and six (2, 4, 6-triamino phenoxy group) at least one in ring three phosphonitrile.
According to the present invention; the preparation method of the branched modification agent containing end carboxyl comprises: be dissolved in organic solvent by hexachlorocyclotriphosphazene, p-Hydroxybenzaldehyde and catalyzer; obtain intermediate product after back flow reaction 20-30h at protection of inert gas 60-65 DEG C, then add alkali, oxygenant and acid-respons and obtain.
According to the present invention; the preparation method of the branched modification agent containing Amino End Group comprises: be dissolved in organic solvent by hexachlorocyclotriphosphazene, p-NP and catalyzer; obtain intermediate product after back flow reaction 20-30h at protection of inert gas 60-65 DEG C, then add reductive agent and acid-respons obtains.
In a particular embodiment of the present invention, described catalyzer is Anhydrous potassium carbonate and/or anhydrous sodium carbonate; Described organic solvent is tetrahydrofuran (THF); Described alkali is sodium hydroxide and/or potassium hydroxide; Described oxygenant is potassium permanganate; Described reductive agent is tin protochloride; Described acid is hydrochloric acid.
N in described branched modification agent, P element content are high, and have good flame retardant effect, its multiple end carboxyl contained or Amino End Group can react with reaction monomers and prepare branched Nylon resin in addition, make the melt flowability of gained resin excellent.
Fire-retardant nylon resin of the present invention, comprises and branched modification agent of the present invention and nylon polymerization monomer reaction being obtained.
Further, described fire-retardant nylon resin adopts following methods to prepare:
By reactive flame retardant and diamine or di-carboxylic acid salify in water, carry out polycondensation after being mixed with nylon polymerization monomer and branched modification agent of the present invention by gained salts solution, obtain described fire-retardant nylon resin.
Further, described reactive flame retardant contains two end carboxyl or two Amino End Group, preferably from having formula (I) at least one in the compound of structure formula (IV) Suo Shi:
Further, described diamine is selected from least one in Ursol D, hexanediamine, decamethylene diamine and dodecamethylene diamine, preferred hexanediamine.
Further, described di-carboxylic acid is selected from least one in terephthalic acid, hexanodioic acid, sebacic acid and dodecanedioic acid, preferred hexanodioic acid and/or sebacic acid.
Further, described nylon polymerization monomer is for having at least one in the lactan of structure shown in the amino acid of structure shown in formula (V) and formula (VI):
Wherein R
1and R
1 'for the alkyl containing 1-20 carbon atom, be preferably the straight chain saturated alkyl containing 1-20 carbon atom.In a particular embodiment of the present invention, amino acid shown in described formula (V) is preferably 11-aminoundecanoic acid and/or 12－aminolauric acid, and the lactan shown in described formula (VI) is preferably hexanolactam, oenantholactam, 11 lactan or laurolactam.
In a particular embodiment of the present invention, the diamine of described reactive flame retardant and mole number such as grade or di-carboxylic acid salify in water, the consumption of amino acid and/or lactan is determined according to required product characteristics.
In a particular embodiment of the present invention, the consumption of described reactive flame retardant is the 0.5%-15% of reaction monomers weight, and the consumption of described branched modification agent is the 0.5%-10% of reaction monomers weight.Described reaction monomers is diamine, di-carboxylic acid in the present invention, and amino acid and/or lactan, the component namely except reactive flame retardant and branched modification agent.
Further, in described preparation method, catalyzer fast reaction speed can be used, described catalyzer be selected from water, phosphoric acid, phosphoric acid ester, phosphorous acid ester or amino acid any one.Catalyzer can be added to the water before the reaction together with polymerization single polymerization monomer, also can be to add separately in the reaction later stage.
Further, described polycondensation is carried out in an inert atmosphere, and reaction conditions is: temperature of reaction 180-280 DEG C, reaction pressure 0.2-2.0MPa, reaction times 2-4h.
In a particular embodiment of the present invention, described fire-retardant nylon resin adopts following methods to prepare: by reactive flame retardant and the diamine or the di-carboxylic acid salify in water that wait mole number, again gained salts solution is mixed with nylon polymerization monomer and branched modification agent, the material prepared is dropped in reactor, by atmosphere in inert gas replacement still, described reactor is heated to 180-260 DEG C, after still internal pressure reaches 0.2-2.0MPa, reaction 2-4h; Then make still internal pressure slowly unload to normal pressure, vacuumize reaction 1-4h, in still, vacuum degree control is between-0.03 to-0.1Mpa; Discharging after normal pressure is risen to until still internal pressure.
The flame retardant rating of described branching fire-retardant nylon resin reaches UL94V0 level, has permanent fire retardant.
Compared with prior art, the present invention has obvious advantage:
1, the polymerizing condition in the present invention is gentleer, and speed of reaction is fast, and production efficiency is high, and cost is lower.
2, the fire-retardant nylon resin in the present invention has halogen-free environmental, and burning is not dripped, and flame retarding efficiency is high, and flame retardant rating is high, and permanent fire retardant such as not to move at the feature.This is because using the ring three phosphonitrile end carboxyl that is kernel or the agent of Amino End Group branched modification and the DOPO radical reaction type fire retardant containing reactive behavior end group as paradigmatic structure unit, polyreaction is carried out with nylon monomer, described branched modification agent and reactive flame retardant contain multiple amido or carboxyl, such functional group can dewater with the carboxyl in nylon polymerization monomer or amido generation polycondensation, thus realizing the growth of molecule segment, the structural unit therefore in branched modification agent and reactive flame retardant is all stably present in polymer molecule segment.Meanwhile, the base branched modification agent of ring three phosphonitrile and DOPO radical reaction type fire retardant can interact, and serve combustion and to char synergistic effect, thus the characteristic making the fire-retardant nylon resin prepared possess burning not drip.
3, the fire-retardant nylon resin in the present invention is due to the existence of branched structure, and the fluidity of molten of resin is high, can meet various processed and applied demand preferably.
Embodiment
Below in conjunction with concrete embodiment and comparison example, the present invention is further illustrated, but the present invention is not limited to these embodiments.
Preparation example 1
The preparation method of end carboxyl ring three phosphonitrile base branched modification agent
For six (4-carboxyphenoxy) ring three phosphonitrile, its synthesis step is as follows:
Magneton, thermometer, constant pressure funnel, condensing reflux pipe and N are being housed
2in the 1L there-necked flask of protector, add 125g p-Hydroxybenzaldehyde, 140g Anhydrous potassium carbonate and 500ml tetrahydrofuran (THF) successively, stirred at ambient temperature makes it dissolve; Taking 50g hexachlorocyclotriphosphazene is dissolved in 100ml tetrahydrofuran (THF), it is slowly added drop-wise in above-mentioned reaction system, dropwises rear 65 DEG C of backflow 24h.Filter, concentrated filtrate, is poured in deionized water and produces white precipitate, by the throw out deionized water wash twice obtained, recrystallization in ethyl acetate, the dry 24h of room temperature in vacuo, namely arrive intermediate product six (4-aldehyde radical phenoxy group) ring three phosphonitrile, productive rate is 92.5%.
In 1L beaker, add 50g six (4-aldehyde radical phenoxy group) ring three phosphonitrile, 16g NaOH, 300mL water and 300mLTHF, under stirring, slowly add 120g KMnO in batches
4do not disappear to solution red-purple.Suction filtration, filtrate is first revolved and is steamed removing THF, then to be acidified to pH with HCl be 3-4, and separate out a large amount of white precipitate, suction filtration, 50 DEG C of vacuum-drying 24h, obtain white powder, and be product six (4-carboxyphenoxy) ring three phosphonitrile, productive rate is 97.1%.
Preparation method and the aforesaid method of other end carboxyl ring three phosphonitrile base branched modification agent are similar, only need adjust the consumption of corresponding nucleophilic reagent.
Preparation example 2
The preparation method of Amino End Group ring three phosphonitrile base branched modification agent
For six (4-amino-benzene oxygen) ring three phosphonitrile, its synthesis step is as follows:
Magneton, thermometer, constant pressure funnel, condensing reflux pipe and N are being housed
2in the 500ml there-necked flask of protector, add 20g hexachlorocyclotriphosphazene successively, 58g p-NP, 58g salt of wormwood and 250ml tetrahydrofuran (THF); At N
2the lower heated and stirred of protection, 65 DEG C of backflow 24h.By reacted mixture filtered while hot, by filter residue successively with the cleaning of frozen water, acetone, methyl alcohol and ether, finally solid is put into vacuum drying oven drying at room temperature 24h, obtaining white powder is intermediate product six (4-oil of mirbane oxygen) ring three phosphonitrile, and productive rate is 84.7%.
Take 10g six (4-oil of mirbane oxygen) ring three phosphonitrile, 60g tin protochloride, 50ml concentrated hydrochloric acid and 200ml ethanol in 500ml there-necked flask, stir and be heated to 80 DEG C of reaction 4h.Suction filtration, gained solid distilled water repetitive scrubbing twice, by filter residue vacuum-drying 24h, obtains pale yellow powder, is product six (4-amino-benzene oxygen) ring three phosphonitrile, productive rate 86.3%.
Preparation method and the aforesaid method of other Amino End Group ring three phosphonitrile base branched modification agent are similar, only need adjust the consumption of corresponding nucleophilic reagent.
Embodiment
Embodiment 1-6 and comparative example 1-4 all prepares nylon resin by raw material shown in table 1 and consumption, and wherein comparative example 1 and 2 does not use reactive flame retardant and branched modification agent, and comparative example 3 does not use branched modification agent, and comparative example 4 does not use reactive flame retardant.Concrete preparation method is as follows:
(1) in ratio shown in table 1, first by reactive flame retardant and diamine or di-carboxylic acid salify in water, then by gained salts solution and nylon polymerization monomer and branched modification agent mixture even.
(2) material prepared is dropped in autoclave, fasten feeding cover, connect water of condensation; Being filled with high pure nitrogen to still internal pressure is 0.2-0.5MPa, slowly opens vent valve and vacuumizes, and makes still internal pressure be down to-0.03 to-0.05MPa, repeatable operation like this 3 times, and being finally filled with high pure nitrogen to still internal pressure is normal pressure, then fastens vent valve;
(3) described reactor is heated, reach 180-260 DEG C at temperature in the kettle, after still internal pressure reaches 0.2-2.0MPa, reaction 2-4h;
(4) open vent valve, still internal pressure is slowly unloaded to normal pressure, then vacuumize reaction 1-4h, in still, vacuum degree control is between-0.03 to-0.1Mpa;
(5) being finally filled with high pure nitrogen to still internal pressure is malleation, after leaving standstill balance for some time, opens bleeder valve at the bottom of still, allow material by cooling trough, wire drawing pelletizing, poach 12-24h at 90-100 DEG C, vacuum-drying 10-20h at 80-150 DEG C, obtains branching fire-retardant nylon resin.
Material formula table (the unit: g) of table 1 embodiment and comparative example
Gained nylon resin is tested, the results are shown in table 2.Wherein flame retardant rating presses UL94 standard test; Limiting oxygen index(LOI) presses GB/T2406-1993 standard test; Melting index measures according to ASTM standard D1238, and test condition is 235 DEG C, 0.375kg; Tensile strength is undertaken by GB/T 1040-2006 " mensuration of plastic tensile performance "; Flexural strength is undertaken by GB/T 9341-2008 " mensuration of plastics bending property "; Notched Izod impact strength is undertaken by GB/T 1043-2008 " mensuration of plastics Charpy Impact performance ".
Resin property test result prepared by table 2 embodiment and comparative example
Consolidated statement 1 and table 2 visible, compared with comparative example 1-4, in the present invention, the fluidity of molten of the fire-retardant nylon resin that embodiment 1-6 obtains is high, and comprehensive mechanical property difference is little, and oxygen index is high, and flame retardant rating reaches UL94V0 level.
The preparation of conventional flame retardant nylon resin is owing to adding the three components such as fire retardant, and its comprehensive mechanical property declines obviously.And the present invention is owing to have employed branched modification agent and reactive flame retardant, synergistic effect between the two improves the mobility of product, and flame retardant properties is improved significantly simultaneously, good mechanical performance.
Above to branched modification agent provided by the invention; and use the nylon resin of described branched modification agent to be described in detail; apply specific examples herein to set forth principle of the present invention and embodiment; the explanation of above embodiment just understands method of the present invention and core concept thereof for helping; should be understood that; to those skilled in the art; under the premise without departing from the principles of the invention; can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (10)
1. a branched modification agent, it has structure shown in formula (VII):
Wherein, R
2-R
7identical or different, be the alkyl containing 1-20 carbon atom or substituted hydrocarbon radical independently of one another, described substituted hydrocarbon radical is the alkyl containing end carboxyl or Amino End Group, and R
2-R
7in have one at least for the substituted hydrocarbon radical containing end carboxyl or Amino End Group.
2. branched modification agent according to claim 1, is characterized in that, described R
2-R
7independently of one another for containing the aliphatic alkyl of 1-20 carbon atom or aliphatics substituted hydrocarbon radical, alicyclic alkyl or alicyclic substituted hydrocarbon radical containing 3-20 carbon atom or be the aromatic hydrocarbyl or the aromatic series substituted hydrocarbon radical that contain 6-20 carbon atom; Described substituted hydrocarbon radical is the alkyl containing end carboxyl or Amino End Group, preferred R
2-R
7in altogether containing 3-18 end carboxyl or hold amido.
3. branched modification agent according to claim 1 and 2, it is characterized in that, described branched modification agent is selected from 1, 3, 5-triple phenoxyl-1, 3, 5-tri-(4-carboxyphenoxy) ring three phosphonitrile, 1, 3, 5-triple phenoxyl-1, 3, 5-tri-(4-amino-benzene oxygen) ring three phosphonitrile, 1, 3, 5-tri-neopentyl oxygen-1, 3, 5-tri-(4-amino-benzene oxygen) ring three phosphonitrile, six (4-carboxyphenoxy) ring three phosphonitrile, six (4-amino-benzene oxygen) ring three phosphonitrile, 1, 3, 5-tri-(4-amino-benzene oxygen)-1, 3, 5-tri-(2, 4-diamino phenoxy) ring three phosphonitrile, six (3, 5-di carboxyl phenyloxy) ring three phosphonitrile, six (2, 4-diamino phenoxy) ring three phosphonitrile, 1, 3, 5-tri-(3, 5-di carboxyl phenyloxy)-1, 3, 5-tri-(2, 3, 5-tri-carboxyphenoxy) ring three phosphonitrile, six (2, 4, 6-tri-carboxyl benzyloxy) ring three phosphonitrile and six (2, 4, 6-triamino phenoxy group) at least one in ring three phosphonitrile.
4. a fire-retardant nylon resin, comprises and the branched modification agent according to any one of claims 1 to 3 and nylon polymerization monomer reaction being obtained.
5. a fire-retardant nylon resin, by by reactive flame retardant and diamine or di-carboxylic acid salify in water, carry out polycondensation after being mixed with the branched modification agent according to any one of nylon polymerization monomer and claims 1 to 3 by gained salts solution and prepare.
6. fire-retardant nylon resin according to claim 5, it is characterized in that, described reactive flame retardant contains two end carboxyl or two Amino End Group, is preferably selected from and has formula (I) at least one in the compound of structure formula (IV) Suo Shi:
7. fire-retardant nylon resin according to claim 5, is characterized in that, described diamine is selected from least one in Ursol D, hexanediamine, decamethylene diamine and dodecamethylene diamine, preferred hexanediamine; And/or
Described di-carboxylic acid is selected from least one in terephthalic acid, hexanodioic acid, sebacic acid and dodecanedioic acid, preferred hexanodioic acid and/or sebacic acid.
8. fire-retardant nylon resin according to claim 5, is characterized in that, described nylon polymerization monomer is for having at least one in the lactan of structure shown in the amino acid of structure shown in formula (V) and formula (VI):
H
2N-R
1-COOH (v)
Wherein R
1and R
1' be the alkyl containing 1-20 carbon atom, be preferably the straight chain saturated alkyl containing 1-20 carbon atom; Amino acid shown in described formula (V) is preferably 11-aminoundecanoic acid and/or 12－aminolauric acid, and the lactan shown in described formula (VI) is preferably hexanolactam, oenantholactam, 11 lactan or laurolactam.
9. fire-retardant nylon resin according to claim 5, is characterized in that, described polycondensation is carried out in an inert atmosphere, and reaction conditions is: temperature of reaction 180-280 DEG C, reaction pressure 0.2-2.0MPa, reaction times 2-4h.
10. the fire-retardant nylon resin according to any one of claim 5 to 9, its flame retardant rating reaches UL94 V0 level, has permanent fire retardant.
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| CN112480398B (en) * | 2019-09-11 | 2023-11-07 | 广东广山新材料股份有限公司 | Flame-retardant polyamide resin and preparation method and application thereof |
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| WO2025132641A1 (en) * | 2023-12-22 | 2025-06-26 | Arkema France | Inherently flame-retardant polyamide and polyether block amide |
| FR3157395A1 (en) * | 2023-12-22 | 2025-06-27 | Arkema France | Self-flame retardant polyamide and polyether block amide |
| CN119144150A (en) * | 2024-11-21 | 2024-12-17 | 江苏旭信机械制造有限公司 | Wear-resistant nylon product with heat conduction function and preparation method thereof |
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