CN103642036A - Polyamide resin and polyamide composition composed of same - Google Patents
Polyamide resin and polyamide composition composed of same Download PDFInfo
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- CN103642036A CN103642036A CN201310559505.7A CN201310559505A CN103642036A CN 103642036 A CN103642036 A CN 103642036A CN 201310559505 A CN201310559505 A CN 201310559505A CN 103642036 A CN103642036 A CN 103642036A
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- polyamide resin
- acid
- diamines
- diamine
- diacid
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- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 87
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 239000004952 Polyamide Substances 0.000 title abstract 3
- 229920002647 polyamide Polymers 0.000 title abstract 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 11
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 8
- 239000012764 mineral filler Substances 0.000 claims abstract description 6
- 150000004985 diamines Chemical class 0.000 claims description 64
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 229920003656 Daiamid® Polymers 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 13
- 125000002723 alicyclic group Chemical group 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 8
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 8
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 8
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 8
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 8
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- -1 salicylate compound Chemical class 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 5
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 claims description 4
- GAGWMWLBYJPFDD-UHFFFAOYSA-N 2-methyloctane-1,8-diamine Chemical compound NCC(C)CCCCCCN GAGWMWLBYJPFDD-UHFFFAOYSA-N 0.000 claims description 4
- KIBVFIDMXQZCBS-UHFFFAOYSA-N 2-methyloctanedioic acid Chemical compound OC(=O)C(C)CCCCCC(O)=O KIBVFIDMXQZCBS-UHFFFAOYSA-N 0.000 claims description 4
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 4
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical class CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 4
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims description 4
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 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
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 3
- 150000008301 phosphite esters Chemical class 0.000 claims description 3
- YKIBJOMJPMLJTB-UHFFFAOYSA-M sodium;octacosanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O YKIBJOMJPMLJTB-UHFFFAOYSA-M 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 229920000587 hyperbranched polymer Polymers 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012763 reinforcing filler Substances 0.000 claims description 2
- 229960001860 salicylate Drugs 0.000 claims description 2
- 229920006012 semi-aromatic polyamide Polymers 0.000 abstract description 3
- 230000004927 fusion Effects 0.000 abstract description 2
- 238000001746 injection moulding Methods 0.000 abstract description 2
- 239000005711 Benzoic acid Substances 0.000 abstract 1
- 239000000654 additive Substances 0.000 abstract 1
- 235000010233 benzoic acid Nutrition 0.000 abstract 1
- 230000003252 repetitive effect Effects 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 150000001408 amides Chemical class 0.000 description 8
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 235000021050 feed intake Nutrition 0.000 description 3
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 3
- 229920006119 nylon 10T Polymers 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 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 1
- JKNIZYPLBHSGAC-UHFFFAOYSA-N CC(C)(C)C1=CC(=C(C(=C1)C(C)(C)C)O)CCC(=O)NCCCCCCNC(=O)CCC2=C(C(=CC(=C2)C(C)(C)C)C(C)(C)C)O Chemical compound CC(C)(C)C1=CC(=C(C(=C1)C(C)(C)C)O)CCC(=O)NCCCCCCNC(=O)CCC2=C(C(=CC(=C2)C(C)(C)C)C(C)(C)C)O JKNIZYPLBHSGAC-UHFFFAOYSA-N 0.000 description 1
- 206010010904 Convulsion Diseases 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CLOSGAJTMIWYSO-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C=1C=C(C=C(C1)C(C)(C)C)C(O)C(CO)(CO)CO Chemical class OP(O)OP(O)O.C(C)(C)(C)C=1C=C(C=C(C1)C(C)(C)C)C(O)C(CO)(CO)CO CLOSGAJTMIWYSO-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 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 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a polyamide resin A which has a relative viscosity of 1.2-1.8 in 98% concentrated sulfuric acid at 25 DEG C; the polyamide resin A has an amino end group value of 20-60 mol/t, and a carboxyl end group value of 70-130 mol/t; in the polyamide resin A, the proportion of benzoic acid in repetitive units is 2-6 mol%; the polyamide resin A is polymerized by adding polyfunctional compounds during the polymerization process; the adding amount of the polyfunctional compounds is 0.1-1 mol%. The polyamide composition comprises the following components: 31-99 wt% of polyamide resin A; 0-68 wt% of polyamide resin B; 0.8-40 wt% of mineral fillers; and 0.2-1 wt% of other additives. The polyamide resin A of the invention has low apparent viscosity under fusion conditions, has high fluidity; when a certain ratio of polyamide resin A is added into semi-aromatic polyamide, the prepared polyamide composition has high fluidity and comparable mechanical properties, and is applicable to conditions with high injection molding product dimension requirements.
Description
Technical field
The present invention relates to polymeric material field, particularly a kind of polyamide resin and consisting of daiamid composition.
Background technology
Polymeric amide is because having good over-all properties, comprise mechanical property, thermotolerance, wearability, chemical proofing and self lubricity, and frictional coefficient is low, there is certain flame retardant resistance, be easy to processing etc., it is extensively suitable for, by glass fibre and other filler filling enhancing modified, improves performance and broadened application scope.In recent years semiaromatic polyamide composition due to its resistance toheat and mechanical property more excellent and by focus development.
The polyamide resin being polymerized by decamethylene diamine and terephthalic acid, water-intake rate is low, and fusing point is high, and development is at present rapidly.Yet with respect to PA6T polyamide resin, the melt viscosity of polyamide resin is higher.In the time of large of needs injection moulding or the part with complicated structure, high melt viscosity is very disadvantageous, need to improve mould temperature or back pressure and realize.Aforesaid operations means are inevitably brought the problem of resin degraded, have limited the application of polyamide resin in a lot of fields.Therefore, industry need badly a kind of high workability polyamide resin and consisting of daiamid composition.
Summary of the invention
In order to overcome the shortcoming and deficiency of prior art, primary and foremost purpose of the present invention is to provide a kind of polyamide resin with high workability.
The present invention is achieved by the following technical solutions;
A polyamide resin A, 25
oc, the relative viscosity in 98% vitriol oil is 1.1-1.8; The amino value of end of described polyamide resin A is 20-60mol/t, and end carboxyl value is 70-130mol/t; In described polyamide resin A, the ratio that phenylformic acid accounts for repeating unit is 2-6mol%.
Preferably, described polyamide resin A is 25
oc, the relative viscosity in 98% vitriol oil is 1.2-1.7; The amino value of end of described polyamide resin A is 30-50mol/t, and end carboxyl value is 80-110mol/t; In described polyamide resin A, the ratio that phenylformic acid accounts for repeating unit is 3-5mol%.
Described polyamide resin A, described polyamide resin A, by mole% meter, is comprised of the repeating unit that contains following monomer:
Other dicarboxylic acid of the terephthalic acid of dicarboxylic acid: 80-100mol% and 0 ~ 20mol%;
The aliphatie diamine with 8-20 carbon atom of aliphatie diamine: 80-100mol% and other aliphatie diamines of 0 ~ 20mol%;
Wherein, described other dicarboxylic acid are selected from one or more of aliphatic dicarboxylic acid, m-phthalic acid, alicyclic dicarboxylic acid;
Described other aliphatie diamines are selected from one or more of aliphatie diamine with 2-7 carbon atom.
Described aliphatic dicarboxylic acid is selected from one or more of oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, 2-methyl suberic acid, nonane diacid, sebacic acid, undecandioic acid, 12 diacid, 13 diacid, 14 diacid.
Described alicyclic dicarboxylic acid is selected from the alicyclic diacid of the alicyclic structure with 3-10 carbon atom; Be preferably Isosorbide-5-Nitrae-cyclohexane diacid, 1,3-cyclohexane diacid, 1, one or more of 3-pentamethylene diacid.
The aliphatie diamine of the described 8-20 of a having carbon atom is selected from one or more of octamethylenediamine, nonamethylene diamine, 2-methyl octamethylenediamine, decamethylene diamine, 11 diamines, 12 diamines, 13 diamines, 14 diamines, 15 diamines, 16 diamines, 17 diamines, 18 diamines, 19 diamines, two amino dodecanes.
The aliphatie diamine of the described 2-7 of a having carbon atom is selected from one or more of quadrol, propylene diamine, butanediamine, pentamethylene diamine, 2 methyl pentamethylenediamine, hexanediamine, heptamethylene diamine.
Described polyamide resin A is polymerized by add polyfunctional compound in polymerization process, and the addition of described polyfunctional compound is 0.1 ~ 1mol%, is preferably 0.1 ~ 0.5mol%.
Described polymerization process has no particular limits concerning polyamide resin A of the present invention; It can be to be polymerized by ordinary melt polymerization process, for example, by being polymerized in single stage method autoclave; Also can be to be polymerized in comprising the technique of preparing prepolymer, this prepolymer can pass through solid state polymerization, or melt polymerization in forcing machine, or melting vacuum polymerization in another one reactor, to improve the molecular weight of polyamide resin A; For example by prepolymer solid state polymerization processes, obtain polyamide resin A: in the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, by proportioning, add each reaction raw materials, then add sodium hypophosphite and deionized water; Sodium hypophosphite weight is 0.1% of outer other weight that feed intake of deionizing water, and deionized water weight is 30% of the weight that always feeds intake; Vacuumize and be filled with high pure nitrogen as protection gas, under agitation 2 hours, be warmed up to 220
oc, by reaction mixture 220
oc stirs 1 hour, then under agitation makes the temperature of reactant be elevated to 230
oc; Reaction is 230
ounder the constant temperature of C and the constant voltage of 2.2Mpa, proceed 2 hours, by removing formed water, keep constant pressure, reacted rear discharging, prepolymer is in 80
ounder C, vacuum-drying is 24 hours, obtains prepolymer product, and described prepolymer product is 250
ounder C, 50Pa vacuum condition, solid-phase tack producing is 10 hours, obtains polyamide resin A.
Described polyfunctional compound is selected from
The described addition that adds polyfunctional compound in polymerization process is 0.1 ~ 1mol%, is preferably 0.1 ~ 0.5mol%.
The principle of polyamide resin A of the present invention is to utilize the polyfunctional compound adding in polymerization process, thereby in polymer formation process, obtain forming the polyamide resin A of star or branched structure, the polyamide resin A of the star-like or branched structure obtaining can significantly improve its mobility.If the addition of the polyfunctional compound adding in polymerization process is lower than 0.1mol%, the star-like or branched structure of polyamide resin A is less, does not have the effect that mobility is improved; If the addition of the polyfunctional compound adding in polymerization process is higher than 1mol%, the star-like or branched structure of polyamide resin A is too much, and the polyamide resin A being polymerized easily occurs crosslinked, also there is no use value
A daiamid composition that comprises described polyamide resin A, percentage ratio meter by weight, comprises following component:
Polyamide resin A 31 ~ 99%;
Polyamide resin B 0 ~ 68%;
Mineral filler 0.8 ~ 40%;
Other auxiliary agents 0.2 ~ 1%;
Wherein, described polyamide resin B is 25
oc, the relative viscosity in 98% vitriol oil is 2.0-2.4; The amino value of end of described polyamide resin B is 20-60mol/t, and end carboxyl value is 70-130mol/t; In described polyamide resin B, the ratio that phenylformic acid accounts for repeating unit is 0.5-4mol%.
Preferably, described polyamide resin B is 25
oc, the relative viscosity in 98% vitriol oil is 2.1-2.3; The amino value of end of described polyamide resin B is 30-50mol/t, and end carboxyl value is 80-110mol/t; In described polyamide resin B, the ratio that phenylformic acid accounts for repeating unit is 1-3.5mol%.
Described polyamide resin B, by mole% meter, is comprised of the repeating unit that contains following monomer:
Other dicarboxylic acid of the terephthalic acid of dicarboxylic acid: 80-100mol% and 0 ~ 20mol%;
The aliphatie diamine with 8-20 carbon atom of aliphatie diamine: 80-100mol% and other aliphatie diamines of 0 ~ 20mol%;
Wherein, described other dicarboxylic acid are selected from one or more of aliphatic dicarboxylic acid, m-phthalic acid, alicyclic dicarboxylic acid;
Described other aliphatie diamines are selected from one or more of aliphatie diamine with 2-7 carbon atom.
Described aliphatic dicarboxylic acid is selected from one or more of oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, 2-methyl suberic acid, nonane diacid, sebacic acid, undecandioic acid, 12 diacid, 13 diacid, 14 diacid.
Described alicyclic dicarboxylic acid is selected from the alicyclic diacid of the alicyclic structure with 3-10 carbon atom; Be preferably Isosorbide-5-Nitrae-cyclohexane diacid, 1,3-cyclohexane diacid, 1, one or more of 3-pentamethylene diacid.
The aliphatie diamine of the described 8-20 of a having carbon atom is selected from one or more of octamethylenediamine, nonamethylene diamine, 2-methyl octamethylenediamine, decamethylene diamine, 11 diamines, 12 diamines, 13 diamines, 14 diamines, 15 diamines, 16 diamines, 17 diamines, 18 diamines, 19 diamines, two amino dodecanes.
The aliphatie diamine of the described 2-7 of a having carbon atom is selected from one or more of quadrol, propylene diamine, butanediamine, pentamethylene diamine, 2 methyl pentamethylenediamine, hexanediamine, heptamethylene diamine.
Described mineral filler is selected from titanium dioxide, nano zine oxide, talcous one or more mixtures.
The particle diameter of described titanium dioxide is selected from 0.2-0.3um; Purity >=98% of described nano zine oxide, particle diameter is selected from 20-80 nm; Described talcous particle diameter is selected from 500-2000 order.
Described other auxiliary agent is selected from one or more mixtures of antioxidant, photostabilizer, flow ability modifying agent;
Described antioxidant is selected from Hinered phenols antioxidant and/or phosphite ester kind antioxidant;
Preferably, described Hinered phenols antioxidant is selected from 1, 3-benzene diamide-N, N '-bis-(2, 2, 6, 6-tetramethyl--4-piperidyl), β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester, β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl alcohol ester, N, N '-bis-[β-(3, 5-di-tert-butyl-hydroxy phenyl) propionyl]-1, 6-hexanediamine, 1, 3, 5-tri-(3, 5-di-t-butyl-4-convulsion base Bian Ji) 2, 4, 6-Three methyl Benzene, 1, 3, 5-tri-(the 4-tertiary butyl-3-hydroxyl-2, 6-dimethyl Bian Ji) 1, 3, 5-triazine-2, 4, 6-(1H, 3H, 5H) one or more mixtures of triketone, described phosphite ester kind antioxidant is selected from one or more mixtures of three (2,4-DTBP) phosphorous acid ester, two (3,5-di-tert-butyl-phenyl) pentaerythritol diphosphites.
Described photostabilizer is selected from one or more mixtures of benzophenone cpd, salicylate compound, azimidobenzene compound; Described flow ability modifying agent is selected from one or more mixtures of E wax, EBS, montanic acid sodium salt, hyperbranched polymer.
The present invention compared with prior art, has following beneficial effect:
Polyamide resin A of the present invention, apparent viscosity under melting condition is lower, there is higher mobility, when add a certain proportion of polyamide resin A in semiaromatic polyamide composition, the daiamid composition of preparing gained has high mobility and substantially suitable mechanical property, can be used for the occasion higher to injection-molded item dimensional requirement.
Embodiment
Now embodiment and comparative example starting material used are done to following explanation, but are not limited to these materials:
PA6T/66 resin used derives from the HTN502 type product of E.I.Du Pont Company;
Titanium dioxide used is the rutile titanium dioxide R103 of the particle diameter 0.2-0.3 μ m of E.I.Du Pont Company;
The efficient resistance to xanthochromia agent oxidation inhibitor 1098 of amine nylon of oxidation inhibitor Shi Shuan key used chemical company;
Flow ability modifying agent used is the montanic acid sodium salt Licowax OP that the part of Clariant company replaces.
The performance test of embodiment and comparative example is undertaken by following standard or method:
The testing method of the fusing point of gained polymeric amide: with reference to ASTM D3418-2003, Standard Test Method for Transition Temperatures of Polymers By Differential Scanning Calorimetry; Concrete testing method is: the fusing point that adopts Perkin Elmer Dimond dsc analysis instrument test sample; Nitrogen atmosphere, flow velocity is 40mL/min; First with 10 during test
oc/min is warming up to 340
oc, 340
oc keeps 2min, then with 10
oc/min is cooled to 50
oc, then with 10
oc/min is warming up to 340
oc, is made as fusing point by endotherm peak temperature now
t m;
The testing method of gained polymeric amide relative viscosity: with reference to GB12006.1-89, polymeric amide viscosity number measuring method; Concrete testing method is: 25 ± 0.01
oin 98% the vitriol oil of C, measure the relative viscosity that concentration is the polymeric amide of 0.25g/dl
η r;
The testing method of gained polymeric amide terminal amino group content: with autopotentiometric titrator titration sample terminal amino group content; Get 0.5g polymkeric substance, add phenol 45mL and anhydrous methanol 3mL, reflux, after observation sample dissolves completely, is chilled to room temperature, with the hydrochloric acid standard solution titration terminal amino group content of having demarcated;
The testing method of gained polymeric amide content of carboxyl end group: with autopotentiometric titrator titration sample content of carboxyl end group; Get 0.5g polymkeric substance, add ortho-cresol 50mL, reflux and dissolve, let cool the rear 400 μ L formaldehyde solutions that add rapidly, with the KOH-ethanolic soln titration content of carboxyl end group of having demarcated;
The testing method of gained polymeric amide apparent viscosity: carry out with the LCR-7000 of Dynisco company type capillary rheometer, adopt CZ394-20 type mouth mould, shearing rate is 1000s
-1, probe temperature is 330
oc, the fusion time is 5min.
Tensile strength: measure according to ISO 527-2, test condition is 23
oc and 10mm/min;
Elongation at break: measure according to ISO 527-2, test condition is 23
oc and 10mm/min;
Flexural strength and modulus in flexure: according to ISO 178, measure, test condition is 23
oc and 2mm/min;
Notched Izod impact strength: measure according to ISO 180/1A, test condition is 23
oc, breach type is A type.
Unnotched impact strength: measure according to ISO 180/1A, test condition is 23
oc.
Helicoidal flow line length: adopt self-control Archimedean screw line of flow mould, the groove width 5mm that flows, high 2.5mm.
Below by embodiment, further illustrate the present invention, following examples are preferably embodiment of the present invention, but embodiments of the present invention are not subject to the restriction of following embodiment.
the preparation of embodiment A 1 ~ A15(polyamide resin A) and comparative example 1 ~ 4:
In the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, in the ratio in table 1, add reaction raw materials, then add sodium hypophosphite and deionized water; Sodium hypophosphite weight is 0.1% of outer other weight that feed intake of deionizing water, and deionized water weight is 30% of the weight that always feeds intake; Vacuumize and be filled with high pure nitrogen as protection gas, under agitation 2 hours, be warmed up to 220
oc, by reaction mixture 220
oc stirs 1 hour, then under agitation makes the temperature of reactant be elevated to 230
oc; Reaction is 230
ounder the constant temperature of C and the constant voltage of 2.2Mpa, proceed 2 hours, by removing formed water, keep constant pressure, reacted rear discharging, prepolymer is in 80
ounder C, vacuum-drying is 24 hours, obtains prepolymer product, and described prepolymer product is 250
ounder C, 50Pa vacuum condition, solid-phase tack producing is 10 hours, obtains polyamide resin A.Performance test is in Table 1.
Table 1
Continued 1
embodiment B 1 ~ B10: the preparation of polyamide resin B
In the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, in the ratio in table 2, add reaction raw materials, then add sodium hypophosphite and deionized water; Sodium hypophosphite weight is 0.1% of outer other weight that feed intake of deionizing water, and deionized water weight is 30% of the weight that always feeds intake; Vacuumize and be filled with high pure nitrogen as protection gas, under agitation 2 hours, be warmed up to 220
oc, by reaction mixture 220
oc stirs 1 hour, then under agitation makes the temperature of reactant be elevated to 230
oc.Reaction is 230
ounder the constant temperature of C and the constant voltage of 2.2Mpa, proceed 2 hours, by removing formed water, keep constant pressure, reacted rear discharging, prepolymer is in 80
ounder C, vacuum-drying is 24 hours, obtains prepolymer product, and described prepolymer product is 250
ounder C, 50Pa vacuum condition, solid-phase tack producing is 10 hours, obtains polyamide resin B; Performance test is in Table 2.
Table 2
embodiment C 1 ~ C9 and comparative example 5 ~ 10: the preparation of daiamid composition
The formula of pressing table 3 by polyamide resin A, polyamide resin B, titanium dioxide, talcum powder, other auxiliary agent high-speed mixer and mixing evenly after, by main spout, add in twin screw extruder, reinforcing filler is fed by side feeding scale side, extrude, cross water cooling, granulation obtains described daiamid composition after being also dried; Wherein, extrusion temperature is 330
oc.
Table 3
Continued 3
By embodiment A 1 ~ A15, comparative example 1 ~ 4 and Embodiment B 1 ~ B10, can find out, along with the increase of the addition of polyfunctional compound, the relative viscosity of gained polyamide resin A first reduces rear increase; When the addition of polyfunctional compound is 0, obtain the PA10T polyamide resin that relative viscosity is higher (comparative example 3); When the addition of polyfunctional compound surpasses 1mol%, obtain the PA10T polyamide resin that relative viscosity is higher (comparative example 1), this derives from the cross-linked effect that the addition of polyfunctional compound produces when too much.The addition that is polyfunctional compound must be controlled at certain limit, just can obtain the polyamide resin A that mobility is higher; Meanwhile, by regulating the benzoic content of end-capping reagent, also can realize the object (comparative example 2) of the mobility that improves PA10T polyamide resin.
By Embodiment C 1 ~ C9 and comparative example 5 ~ 10, relatively can find out, use the polyamide resin A of embodiment A 1 ~ A15 to carry out modification as matrix resin, with take PA6T/66 and compare as matrix resin resulting composition (comparative example 7), can obtain the daiamid composition that mobility is higher.Comparative example 5 is because matrix resin viscosity is higher, therefore the mobility of daiamid composition is very poor; Although comparative example 6 mobility are also fine, because the molecular weight of its matrix resin itself is lower, cause the mechanical property of daiamid composition very poor, there is no practical value; The content of each polyamide resin content range under claim not in comparative example 8, its mobility and mechanical property are all not as good as Embodiment C 1 ~ C9.
Claims (17)
1. a polyamide resin A, is characterized in that: described polyamide resin A is 25
oc, the relative viscosity in 98% vitriol oil is 1.1-1.8; The amino value of end of described polyamide resin A is 20-60mol/t, and end carboxyl value is 70-130mol/t; In described polyamide resin A, the ratio that phenylformic acid accounts for repeating unit is 2-6mol%.
2. polyamide resin A according to claim 1, is characterized in that, described polyamide resin A is 25
oc, the relative viscosity in 98% vitriol oil is 1.2-1.7; The amino value of end of described polyamide resin A is 30-50mol/t, and end carboxyl value is 80-110mol/t; In described polyamide resin A, the ratio that phenylformic acid accounts for repeating unit is 3-5mol%.
3. polyamide resin A according to claim 1, it is characterized in that, described polyamide resin A is polymerized by add polyfunctional compound in polymerization process, and the addition of described polyfunctional compound is 0.1 ~ 1mol%, is preferably 0.1 ~ 0.5mol%.
4. polyamide resin A according to claim 3, is characterized in that, described polyfunctional compound is selected from
5. according to the polyamide resin A described in claim 1 ~ 4 any one, it is characterized in that described polyamide resin A, by mole% meter, is comprised of the repeating unit that contains following monomer:
Other dicarboxylic acid of the terephthalic acid of dicarboxylic acid: 80-100mol% and 0 ~ 20mol%;
The aliphatie diamine with 8-20 carbon atom of aliphatie diamine: 80-100mol% and other aliphatie diamines of 0 ~ 20mol%;
Wherein, described other dicarboxylic acid are selected from one or more of aliphatic dicarboxylic acid, m-phthalic acid, alicyclic dicarboxylic acid;
Described other aliphatie diamines are selected from one or more of aliphatie diamine with 2-7 carbon atom.
6. polyamide resin A according to claim 5, it is characterized in that, described aliphatic dicarboxylic acid is selected from one or more of oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, 2-methyl suberic acid, nonane diacid, sebacic acid, undecandioic acid, 12 diacid, 13 diacid, 14 diacid.
7. polyamide resin A according to claim 5, is characterized in that, described alicyclic dicarboxylic acid is selected from the alicyclic diacid of the alicyclic structure with 3-10 carbon atom; Be preferably Isosorbide-5-Nitrae-cyclohexane diacid, 1,3-cyclohexane diacid, 1, one or more of 3-pentamethylene diacid.
8. polyamide resin A according to claim 5, it is characterized in that, described in there is 8-20 carbon atom aliphatie diamine be selected from one or more of octamethylenediamine, nonamethylene diamine, 2-methyl octamethylenediamine, decamethylene diamine, 11 diamines, 12 diamines, 13 diamines, 14 diamines, 15 diamines, 16 diamines, 17 diamines, 18 diamines, 19 diamines, two amino dodecanes.
9. polyamide resin A according to claim 5, is characterized in that, described in there is 2-7 carbon atom aliphatie diamine be selected from one or more of quadrol, propylene diamine, butanediamine, pentamethylene diamine, 2 methyl pentamethylenediamine, hexanediamine, heptamethylene diamine.
10. a daiamid composition that comprises the polyamide resin A described in claim 1 ~ 4 any one, percentage ratio meter by weight, comprises following component:
Polyamide resin A 31 ~ 99%;
Polyamide resin B 0 ~ 68%;
Mineral filler 0.8 ~ 40%;
Other auxiliary agent 0.2 ~ 1%;
Wherein, described polyamide resin B is 25
oc, the relative viscosity in 98% vitriol oil is 2.0-2.4; The amino value of end of described polyamide resin B is 20-60mol/t, and end carboxyl value is 70-130mol/t; In described polyamide resin B, the ratio that phenylformic acid accounts for repeating unit is 0.5-5mol%.
11. daiamid compositions according to claim 10, is characterized in that, described polyamide resin B, by mole% meter, is comprised of the repeating unit that contains following monomer:
Other dicarboxylic acid of the terephthalic acid of dicarboxylic acid: 80-100mol% and 0 ~ 20mol%;
The aliphatie diamine with 8-20 carbon atom of aliphatie diamine: 80-100mol% and other aliphatie diamines of 0 ~ 20mol%;
Wherein, described other dicarboxylic acid are selected from one or more of aliphatic dicarboxylic acid, m-phthalic acid, alicyclic dicarboxylic acid;
Described other aliphatie diamines are selected from one or more of aliphatie diamine with 2-7 carbon atom.
12. daiamid compositions according to claim 11, it is characterized in that, described aliphatic dicarboxylic acid is selected from one or more of oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, 2-methyl suberic acid, nonane diacid, sebacic acid, undecandioic acid, 12 diacid, 13 diacid, 14 diacid.
13. daiamid compositions according to claim 11, it is characterized in that, described in there is 8-20 carbon atom aliphatie diamine be selected from one or more of octamethylenediamine, nonamethylene diamine, 2-methyl octamethylenediamine, decamethylene diamine, 11 diamines, 12 diamines, 13 diamines, 14 diamines, 15 diamines, 16 diamines, 17 diamines, 18 diamines, 19 diamines, two amino dodecanes.
14. daiamid compositions according to claim 11, is characterized in that, described in there is 2-7 carbon atom aliphatie diamine be selected from one or more of quadrol, propylene diamine, butanediamine, pentamethylene diamine, 2 methyl pentamethylenediamine, hexanediamine, heptamethylene diamine.
15. daiamid compositions according to claim 10, is characterized in that, described mineral filler be selected from titanium dioxide, nano zine oxide, talcous one or more; The particle diameter of described titanium dioxide is selected from 0.2-0.3um; Purity >=98% of described nano zine oxide, particle diameter is selected from 20-80 nm; Described talcous particle diameter is selected from 500-2000 order.
16. daiamid compositions according to claim 10, is characterized in that, described other auxiliary agent is selected from one or more of antioxidant, photostabilizer, flow ability modifying agent; Described antioxidant is selected from Hinered phenols antioxidant and/or phosphite ester kind antioxidant; Described photostabilizer is selected from one or more of benzophenone cpd, salicylate compound, azimidobenzene compound; Described flow ability modifying agent is selected from one or more of E wax, EBS, montanic acid sodium salt, hyperbranched polymer.
The preparation method of 17. 1 kinds of daiamid compositions as claimed in claim 10, it is characterized in that, comprise the steps: by polyamide resin A, polyamide resin B, mineral filler and other auxiliary agent be placed in high-speed mixer and mixing evenly after, by main spout, add in twin screw extruder, reinforcing filler is fed by side feeding scale side, 310
oc ~ 330
ounder C, extrude, cross water cooling, granulation obtains product after being also dried.
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| CN105348514A (en) * | 2015-11-30 | 2016-02-24 | 广东优巨先进材料研究有限公司 | Polyamide composite material capable of being used for 3D printing and preparation method thereof |
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| CN106866980A (en) * | 2017-03-22 | 2017-06-20 | 中国科学院理化技术研究所 | Semi-aromatic polyamide resin and preparation method thereof |
| CN109627435A (en) * | 2018-12-13 | 2019-04-16 | 沧州旭阳科技有限公司 | A kind of method preparing permanent anti-static branched polyamide elastomer, by elastomer of this method preparation and application thereof |
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| CN116253872B (en) * | 2021-12-10 | 2024-10-29 | 上海凯赛生物技术股份有限公司 | High-temperature-resistant polyamide resin and preparation method thereof |
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Application publication date: 20140319 |