CN117777435A - Semi-aromatic copolyamide, semi-aromatic polyamide composition, and preparation method and application thereof - Google Patents
Semi-aromatic copolyamide, semi-aromatic polyamide composition, and preparation method and application thereof Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 229920006012 semi-aromatic polyamide Polymers 0.000 title claims abstract description 57
- 229920006024 semi-aromatic copolyamide Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000007062 hydrolysis Effects 0.000 claims abstract description 22
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 12
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 12
- 229920005565 cyclic polymer Polymers 0.000 claims abstract description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 239000003381 stabilizer Substances 0.000 claims description 16
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 125000004122 cyclic group Chemical group 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000314 lubricant Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- -1 calcium carboxylate Chemical class 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 claims description 10
- 230000009477 glass transition Effects 0.000 claims description 10
- 150000001718 carbodiimides Chemical class 0.000 claims description 9
- 239000002826 coolant Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 8
- 239000012760 heat stabilizer Substances 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 8
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 150000001879 copper Chemical class 0.000 claims description 5
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012779 reinforcing material Substances 0.000 claims description 5
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 4
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 4
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000007599 discharging Methods 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
- 239000002245 particle Substances 0.000 claims description 4
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- 239000013638 trimer Substances 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
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- 239000002216 antistatic agent Substances 0.000 claims description 3
- 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 claims description 3
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 239000012763 reinforcing filler Substances 0.000 claims description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
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- 230000006872 improvement Effects 0.000 claims description 2
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- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
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- 239000003112 inhibitor Substances 0.000 claims 4
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims 2
- 238000005755 formation reaction Methods 0.000 claims 1
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- 229940037312 stearamide Drugs 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 47
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- 229920001577 copolymer Polymers 0.000 description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 8
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000539 dimer Substances 0.000 description 5
- 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 4
- 239000005711 Benzoic acid Substances 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
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- 239000002131 composite material Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
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- 150000004985 diamines Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229920006119 nylon 10T Polymers 0.000 description 3
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HERSSAVMHCMYSQ-UHFFFAOYSA-N 1,8-diazacyclotetradecane-2,9-dione Chemical compound O=C1CCCCCNC(=O)CCCCCN1 HERSSAVMHCMYSQ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
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- 230000003179 granulation Effects 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- ZRXYYPBERCJDHZ-UHFFFAOYSA-N 1,1-bis[2,4-bis(2-phenylpropan-2-yl)phenyl]-2,2-bis(hydroxymethyl)propane-1,3-diol phosphorous acid Chemical compound P(O)(O)O.P(O)(O)O.C(C)(C)(C1=CC=CC=C1)C1=C(C=CC(=C1)C(C)(C)C1=CC=CC=C1)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C1=CC=CC=C1)C(C)(C)C1=CC=CC=C1 ZRXYYPBERCJDHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 239000012620 biological material Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
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- 230000003750 conditioning effect Effects 0.000 description 1
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- 238000007334 copolymerization reaction Methods 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
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- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical group [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of polymer material preparation, in particular to semi-aromatic copolyamide, a semi-aromatic polyamide composition, and a preparation method and application thereof. The semi-aromatic copolyamide comprises the following raw materials in parts by mass: (a1) 30 to 65 parts by mass of 6T units (a 2) 30 to 60 parts by mass of 4T units, 5T units or M5T units; (a3) 0 to 15 parts by mass of a 9T unit, a10T unit, or a 12T unit; (a 4) 0 to 3 parts by mass of a cyclic polymer unit; wherein the sum of the components (a 1) to (a 4) constitutes 100 parts by mass of the semiaromatic copolyamide. Further, after the semi-aromatic copolyamide and the heat-stable hydrolysis-resistant alcoholysis-resistant master batch are subjected to melt extrusion, the semi-aromatic polyamide composition which is resistant to high temperature, ethylene glycol solution, long-term thermal oxidative aging and better in processability is prepared, and the prepared product can be contacted with ethylene glycol for a long time at high temperature to keep high strength, especially in the field of automobiles.
Description
Technical Field
The invention relates to the field of polymer material preparation, in particular to semi-aromatic copolyamide, a semi-aromatic polyamide composition, and a preparation method and application thereof.
Background
Semi-aromatic nylons are widely used in the automotive, LED and electronic and electrical fields for their excellent high temperature resistance and mechanical properties. Wherein, the water pipe joint in the automobile part requires the part to have high strength and hot water resistance; the semi-aromatic nylon is used for the air inlet manifold, the ejector and the throttle module of the air inlet module because of the excellent heat resistance and chemical resistance; the water chamber, the fastener of the inlet (outlet) and the control valve of the cooling system pay more attention to the heat resistance, the hot water resistance and the cooling liquid resistance of the material, wherein the cooling liquid mainly comprises glycol and water, and the improved semi-aromatic nylon can be used for a plurality of application scenes in direct contact with the glycol.
CN111117230a discloses the case of PA56 compositions for car coolant resistance, even after compounding PA513 or PA514, the tensile strength is only 71-91MPa after 48h of ethylene glycol soaking. Meanwhile, the composition mainly comprising PA56 has no high-temperature resistance. CN111117233a is an unsaturated anhydride-olefin copolymer based on PA56, the retention rate of tensile strength after the composition is soaked in ethylene glycol can only reach 40%, and based on PA56 itself, the water absorption is high, and even if the olefin polymer is subjected to composite modification and graft modification of long-chain nylon, good ethylene glycol resistance is difficult to reach.
The resin used in the CN103732653a example is based on PA5T/6T composition and does not relate to the use case of hydrolysis and cooling fluid resistance. CN114920926a discloses PA5T/XT (X < =6) for automotive cooling system tubing, with a retention of tensile strength after hydrolysis at 80 ℃ of only 60-70%. CN119928665 discloses PA5T/512, which does not involve the introduction of other monomers to improve its higher water absorption and the reduction of temperature resistance after the introduction of aliphatic copolymers, in particular in terms of glass transition temperature. The glass transition temperature is reported by EP3222649 (CN 107325548A) as a key indicator of coolant-resistant materials.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention aims to provide a solvent-resistant and thermo-oxidative aging-resistant semi-aromatic copolyamide, a semi-aromatic polyamide composition, a preparation method and an application thereof, wherein the semi-aromatic polyamide composition or an article prepared by the index method can be applied to the automotive field, especially a cooling system for direct/indirect contact of an ethylene glycol-water mixture (1:1), and is used for solving the problems in the prior art.
To achieve the above and other related objects, the present invention is achieved by the following technical means.
The invention provides a semi-aromatic copolyamide, which comprises the following raw materials in parts by mass:
(a1) 30 to 65 parts by mass of 6T units; (a2) 30 to 60 parts by mass of a 4T unit, a5T unit or an M5T unit;
(a3) 0 to 15 parts by mass of a 9T unit, a10T unit, or a 12T unit; (a 4) 0 to 3 parts by mass of a cyclic polymer unit; wherein the sum of components (a 1) to (a 4) constitutes 100 parts by mass of the semiaromatic copolyamide;
the invention provides a semi-aromatic polyamide composition, which comprises the following raw materials in parts by mass:
component A:40 to 65 parts by mass of a semiaromatic copolyamide according to the first aspect of the invention;
component B:3-15 parts by mass of heat-stable hydrolysis-resistant alcoholysis-resistant master batch;
component C:30-60 parts by mass of reinforcing material and/or filler;
component D:0-2 parts by mass of a heat stabilizer;
component E:0-5 parts by mass of auxiliary agents and/or additives;
the sum of the components A to E constitutes 100 parts by mass.
In a third aspect, the present invention provides a process for preparing the semiaromatic polyamide composition according to the second aspect of the invention, comprising the steps of:
s1: mixing the components (a 1) - (a 4), and obtaining a component A through a salt forming, prepolymerization and post-polymerization process;
s2: and (3) after the component A and the component E are fully mixed, extruding and granulating.
According to a fourth aspect of the present invention, there is provided a semiaromatic polyamide composition prepared by the process for preparing a semiaromatic polyamide composition according to the third aspect of the present invention.
In a fifth aspect the present invention provides the use of a semiaromatic polyamide composition according to the second aspect of the invention for the preparation of a part in direct or indirect contact with an ethylene glycol-water coolant.
Compared with the prior art, the invention has the beneficial effects that:
the high-temperature-resistant semi-aromatic copolyamide is prepared by polycondensing composite short-chain diamine and terephthalic acid, simultaneously optionally introducing long-chain diamine and terephthalic acid for copolymerization, further optionally adding a cyclic polymer unit (such as a cyclic dimer, trimer or tetramer unit and the like) for polymerization, and further, after melt extrusion of the semi-aromatic copolyamide and the heat-stable hydrolysis-resistant alcoholysis-resistant master batch, preparing the semi-aromatic polyamide composition (namely the semi-aromatic copolymerized high-temperature-resistant nylon) with high temperature resistance, glycol solution resistance, long-term thermal oxidative aging resistance and better processability through the synergistic effect of the components. The glass transition temperature is controllable, the fluidity of the processed melt is good, and the method has obvious advantages in preparing high-filling composite materials or manufacturing complex parts. The invention has the advantages of mild polymerization conditions, simple equipment, excellent product performance, simplicity and easy implementation and wide application field.
The material has good thermal oxidative aging resistance, and the tensile elongation at break is higher than 1.3% after 500 hours of thermal oxidative aging at 170 ℃. Meanwhile, the material has good glycol water solution resistance, after being soaked in glycol-water mixture for 1008h at 130 ℃, the elongation at break is more than or equal to 1.8%, and the tensile strength reaches more than 140 MPa.
Detailed Description
Experiments of the applicant of the invention show that the main body is copolymerized by compounding short-chain diamine (such as 1, 4-butanediamine, 1, 5-pentanediamine, 2-methylpentanediamine and 1, 6-hexanediamine according to a proportion) and terephthalic acid, and simultaneously long-chain diamine (such as 1, 9-nonanediamine, 1, 10-decanediamine, 1, 12-dodecanediamine and the like) and cyclic dimer are introduced, so that the flexibility of chain segments can be adjusted, the processability is improved, the high rigidity and high heat resistance of the product are realized, the high crystallinity of semi-aromatic nylon is maintained, and further the mechanical property and chemical resistance of the composite reinforced material are carried out with more reinforcing materials, and the thermal-stability hydrolysis-resistant and alcoholysis-resistant master batch is blended, melted and extruded. Through the synergistic effect of the components, after the composition is soaked in an ethylene glycol-water mixture (1:1) at 130 ℃ for 1008 hours, the tensile strength can still be kept very good, the retention rate of the tensile strength is more than 50%, the water resistance and the ethylene glycol water solution resistance of the material are improved, and finally the semi-aromatic copolymerized high-temperature nylon composition with high filling, thermal oxidative aging resistance, excellent ethylene glycol water solution resistance and better processability is prepared, and the prepared product can be contacted with ethylene glycol for a long time at high temperature to keep high strength, especially in the field of automobiles. And on the basis of this, the present invention has been completed.
Half-partAromatic copolyamide
The first aspect of the present invention provides a semiaromatic copolyamide comprising, in parts by mass: (a 1) 30 to 65 parts by mass of a6T unit; (a2) 30 to 60 parts by mass of a 4T unit, a5T unit or an M5T unit; (a3) 0 to 15 parts by mass of a 9T unit, a10T unit or a 12T unit; (a 4) 0 to 3 parts by mass of a cyclic polymer unit; wherein the sum of the components (a 1) to (a 4) constitutes 100 parts by mass of the semiaromatic copolyamide.
In the semi-aromatic copolyamide provided by the invention, a6T unit, a 4T unit, a5T unit, an M5T unit, a 9T unit, a10T unit, an 11T unit and a 12T unit are shown as follows:
in the semi-aromatic copolyamide provided by the invention, the component (a 1) can be selected from 30-40 parts by mass, 40-50 parts by mass, 50-65 parts by mass or the like based on the mass of the semi-aromatic copolyamide. The 6T unit is formed from 1, 6-hexamethylenediamine and terephthalic acid.
In the semi-aromatic copolyamide provided by the invention, the component (a 2) can be selected from 30-40 parts by mass, 40-50 parts by mass, 50-60 parts by mass or the like based on the mass of the semi-aromatic copolyamide. The 4T unit is formed from 1, 4-butanediamine and terephthalic acid. The 5T unit is formed from 1, 5-pentanediamine and terephthalic acid. The M5T unit is formed from 2-methyl-pentanediamine and terephthalic acid.
In the semi-aromatic copolyamide provided by the invention, the component (a 3) can be selected from 0-5 parts by mass, 0-1 parts by mass, 1-5 parts by mass, 5-10 parts by mass, 10-15 parts by mass or the like based on the mass of the semi-aromatic copolyamide. The 9T unit is formed from 1, 9-nonanediamine and terephthalic acid; the 10T unit is formed from 1, 10-decanediamine and terephthalic acid; the 12T unit is formed from 1, 12-dodecanediamine and terephthalic acid.
In the semiaromatic copolyamide provided by the invention, the component (a 4) can be selected from 0-1 parts by mass, 1-2 parts by mass, 2-3 parts by mass or the like based on the parts by mass of the semiaromatic copolyamide.
In the semi-aromatic copolyamide provided by the invention, the cyclic polymer unit is selected from one or a combination of more of a cyclic dimer unit (1), a cyclic trimer unit (2) or a cyclic tetramer unit (3); preferably, the cyclic polymer unit is one or more of the following structures:
semi-aromatic polyamide composition
The invention provides a semi-aromatic polyamide composition, which comprises the following raw materials in parts by mass:
component A:40 to 65 parts by mass of a semiaromatic copolyamide according to the first aspect of the invention;
component B:3-15 parts by mass of heat-stable hydrolysis-resistant alcoholysis-resistant master batch;
component C:30-60 parts by mass of reinforcing material and/or filler;
component D:0-2 parts by mass of a heat stabilizer;
component E:0-5 parts by mass of auxiliary agents and/or additives;
preferably, when the raw materials of the composition include the component a-component E, the sum of the component a-component E constitutes 100 parts by mass.
In the semi-aromatic polyamide composition provided by the invention, the component A can be selected from 40-50 parts by mass, 50-65 parts by mass, 40-45 parts by mass, 45-50 parts by mass, 50-55 parts by mass, 55-60 parts by mass, 60-65 parts by mass or the like based on the mass of the semi-aromatic polyamide composition.
In the semi-aromatic polyamide composition provided by the invention, in the component B, the heat-stable hydrolysis-resistant and alcoholysis-resistant masterbatch is selected from the group consisting of polyamide, an anti-hydrolysis agent, a copper salt heat stabilizer and a lubricant, wherein the polyamide is selected from the group consisting of semi-aromatic copolyamide PA6T/66. The hydrolysis resistance agent is selected from one or more of monomer carbodiimide hydrolysis resistance agent, polymeric carbodiimide hydrolysis resistance agent and liquid carbodiimide hydrolysis resistance agent, preferably high polymeric carbodiimide; . The copper salt stabilizer is selected from any one of copper chloride, copper bromide, copper iodide and copper phosphate, preferably copper iodide. The lubricant is selected from one of calcium carboxylate with long carbon chain as main component, ethylene bis stearamide EBS, TAF, silicone powder, pentaerythritol stearate, preferably calcium carboxylate with long carbon chain as main component, and has the trade name of CAV102.
The mass ratio of the polyamide to the anti-hydrolysis agent to the copper salt heat stabilizer to the lubricant is 85-90:5-10:2-6:0.2-1.0.
In the semi-aromatic polyamide composition provided by the invention, the component (B) can be selected from 3-8 parts by mass, 3-5 parts by mass, 5-10 parts by mass, 10-15 parts by mass and the like based on the mass of the semi-aromatic polyamide composition.
In the semi-aromatic polyamide composition provided by the invention, the component C is one or a combination of more of glass fiber, carbon fiber, talcum powder and mica flakes.
In the semi-aromatic polyamide composition provided by the invention, the component C can be selected from 30-40 parts by mass, 40-50 parts by mass, 50-60 parts by mass or the like based on the mass of the semi-aromatic polyamide composition.
In the semi-aromatic polyamide composition provided by the invention, in the component D, the heat stabilizer is selected from one or more of hindered phenol stabilizers, phosphite stabilizers, hindered amine stabilizers, triazine stabilizers, sulfur-containing stabilizers and inorganic phosphorus-containing stabilizers. The stabilizer can be used alone or in combination.
In the semiaromatic polyamide composition provided by the invention, the component D can be selected from 0-0.005 parts by mass, 0.005-2 parts by mass, 0.005-1 parts by mass, 1-2 parts by mass and the like based on the mass of the semiaromatic polyamide composition.
In the semi-aromatic polyamide composition provided by the invention, the component E comprises one or a combination of a plurality of lubricants, nucleating agents, antistatic agents, release agents, flow improvement aids and the like. The lubricant is, for example, one or more selected from calcium carboxylate (trade name is CAV 102), ethylene bis stearamide EBS, TAF, silicone powder, pentaerythritol stearate, etc. which mainly contain a long carbon chain. The nucleating agent is selected from one or more of P22, P32, LH-501, HK-145, etc. The antistatic agent is selected from one or more of conductive carbon black, graphene and carbon nanotubes. The release agent is selected from zinc stearate, stearic acid, paraffin, silicone oil, etc. The flow improving auxiliary agent is selected from one or a combination of more of stearic acid, nano silicon dioxide, talcum powder, glass microsphere powder and the like.
In the semi-aromatic polyamide composition provided by the invention, the component E can be selected from 0-2 parts by mass, 0-1 parts by mass, 1-2 parts by mass, 2-5 parts by mass or the like based on the mass of the semi-aromatic polyamide composition. Preferably 0 to 2 parts by mass.
In the semi-aromatic polyamide composition provided by the invention, the semi-aromatic polyamide composition has good long-term heat resistance, and polyamide particles are tested by using a Differential Scanning Calorimetry (DSC), and the glass transition temperature is in the range of 120-170 ℃, preferably 130-170 ℃, and especially 135-170 ℃ at the heating rate of 10 ℃/min.
The semi-aromatic polyamide composition has good thermo-oxidative aging resistance, and the tensile strength retention rate is more than or equal to 70%, preferably more than or equal to 75% after aging for 500 hours at 170 ℃; more preferably 75% or more and less than 100%.
In addition, the material has good ethylene glycol-water mixture (1:1) resistance, and after the ethylene glycol-water mixture is soaked for 1008h at 130 ℃, the elongation at break is more than or equal to 1.5%, preferably more than or equal to 1.8%, and more preferably 1.8% -3.4%.
Process for preparing semiaromatic polyamide composition
In a third aspect, the present invention provides a process for preparing the semiaromatic polyamide composition according to the second aspect of the invention, comprising the steps of:
s1: the components (a 1) - (a 4) are subjected to salt forming, prepolymerization and post polymerization to obtain a component A;
s2: and (3) after the component A and the component E are fully mixed, extruding and granulating.
In the step S1, (a 1) to (a 4) salification and prepolymerization are carried out in the same pressure reaction vessel.
In the step S1, the monomers in the steps (a 1) - (a 4) and a proper amount of water are subjected to salt forming reaction in a first temperature section, and a second temperature section is subjected to prepolymerization reaction; wherein the amount of salt forming and pre-polymerization added is 0-30wt.%, preferably 1-20wt.%; the first temperature section for salification is 150-190 ℃, preferably 170-180 ℃; the polymerization second temperature section is 200-280 ℃, preferably 220-270 ℃; the pressure reaction vessel is a conventional vertical reaction kettle, a horizontal reaction kettle, a rotary drum and other pressure polymerization equipment; the stirring equipment is an anchor type, frame type and spiral belt type stirrer.
Specifically, in the component (a 1), the raw materials of the 6T unit include 1, 6-hexamethylenediamine and terephthalic acid; in the component (a 2), the raw materials of the 4T unit comprise 1, 4-butanediamine and terephthalic acid; in the component (a 2), the raw materials of the 5T unit comprise 1, 5-pentanediamine and terephthalic acid; in the component (a 2), the raw materials of the M5T unit comprise 2-methyl-pentanediamine and terephthalic acid; in the component (a 3), the raw materials of the 9T unit comprise 1, 9-nonanediamine and terephthalic acid; the raw materials of the 10T unit comprise 1, 10-decanediamine and terephthalic acid; the raw materials of the 12T unit comprise 1, 12-dodecadiamine and terephthalic acid. In component (a 4), the cyclic multimeric unit is selected from one or more of a cyclic dimer unit (1), a cyclic trimer unit (2) or a cyclic tetramer unit (3); preferably, the cyclic polymer unit is one or more of the following structures:
in the step S1, discharging and crushing are carried out after the polymerization is completed, and the size of crushed particles is less than or equal to 3mm. The crushed material is solid-phase polymerized (specifically, for example, transferred to a solid-phase polymerization kettle for post-polymerization), and the post-polymerization temperature is 220-280 ℃, preferably 230-260 ℃. The post-polymerization pressure is less than 400Pa, preferably less than or equal to 50Pa, and the copolymer component A is obtained after tackifying.
In step S2, component a-component E is fully mixed by high-speed dispersion (e.g., in a high-speed disperser), and then extruded and granulated at a higher processing temperature. Optionally, the component A and the component B are primarily mixed by a high-speed mixer, then the mixture is blended with the component D and the component E in the high-speed mixer, the component C is added by a side feeding port, extrusion and granulation are carried out at a high processing temperature after full mixing, the temperature of the extruder is 100-350 rpm (the rotating speed can be 150-350 rpm, 100-150 rpm, 150-250 rpm, 250-350 rpm and the like, for example), the temperature of each section of the extruder is 210-230 ℃, 270-290 ℃, 300-310 ℃, 310-330 ℃, 320-340 ℃, 330-350 ℃, 320-340 ℃, 310-330 ℃ (preferably 220 ℃,280 ℃,320 ℃,340 ℃,330 ℃,320 ℃) and the semi-aromatic composition is obtained through melt plasticization, extrusion and granulation.
The semiaromatic polyamide composition according to the third aspect of the invention may further be obtained by a process for the preparation of semiaromatic polyamide compositions.
Application of
In a fourth aspect the present invention provides the use of a semiaromatic polyamide composition according to the second aspect of the invention for the preparation of a part in direct or indirect contact with an aqueous ethylene glycol solution.
In particular, the method comprises the steps of,
the surface of the component is formed into a component in direct contact with ethylene glycol-water solution or a component in indirect contact with ethylene glycol through injection molding, extrusion or blow molding, and a chemical-resistant coating is arranged on the surface of the component. In particular in the form of coolant manifolds, coolant fluid lines, water inlets and outlets, thermostats, coolers, coolant tanks, pumps, valves and connectors in the coolant circuit or assemblies of these components for motor vehicles, or in the form of fuel lines, hydraulic lines, brake lines, clutch lines, urea lines or brake tanks or fuel tanks.
Further advantages and effects of the present invention will become apparent to those skilled in the art from the disclosure of the present invention, which is described by the following specific examples.
Before the embodiments of the invention are explained in further detail, it is to be understood that the invention is not limited in its scope to the particular embodiments described below; it is also to be understood that the terminology used in the examples of the invention is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the invention. The test methods in the following examples, in which specific conditions are not noted, are generally conducted under conventional conditions or under conditions recommended by the respective manufacturers.
Where numerical ranges are provided in the examples, it is understood that unless otherwise stated herein, both endpoints of each numerical range and any number between the two endpoints are significant both in the numerical range. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, materials used in the embodiments, any methods, devices, and materials of the prior art similar or equivalent to those described in the embodiments of the present invention may be used to practice the present invention according to the knowledge of one skilled in the art and the description of the present invention.
1. Test standard
(1) Tensile and flexural performance test conditions: the tensile strength and elongation at break were measured by placing a tensile bar in a constant temperature and humidity cabinet (25 ℃, rh=50%) for 24 hours, testing with a testing machine at a tensile speed of 5mm/min with a test standard of ISO 527-1/-2:2019. The bending strength is tested by placing the bending sample bar in a constant temperature and humidity box for 24 hours, and using a testing machine, wherein the testing standard is ISO178:2019.
(2) Water absorption test conditions: the test specimens were dried in a 100deg.C oven, cooled with the oven, and the tensile bars were immersed in 95℃water for 336 hours. After the surface moisture was wiped off with cotton cloth, the weight gain relative to the initial weight was determined. Test standard ISO 62:2008.
(3) Relative viscosity: the test sample was dissolved using 98% concentrated sulfuric acid at a concentration of 0.01g/mL at a test temperature of 25℃and test standard ISO 307:2019.
(4) Melting point and glass transition temperature test conditions: weighing 5-8 mg of polymer particles, heating the sample to 350 ℃ for melting for 3min under the protection of nitrogen, cooling to 50 ℃, heating to 350 ℃, and heating to 10 ℃/min. Test Standard ISO 11357-3:2018.
(5) Hydrolytic stability test for coolant: ethylene glycol resistance stability was determined according to GM standard GMW16360 (2016). The tensile bars were treated in a pressure vessel containing a 130℃glycol-water mixture (1:1) for either 504 hours or 1008 hours. After the treatment, the sample was cooled to 23℃in a cooling liquid, taken out of the cooling liquid, rinsed with water, dried sufficiently, and subjected to a tensile test after conditioning.
2. Raw materials
(1) Aliphatic diamines:
1, 6-hexanediamine: injeweidanylon chemical Co., ltd
1, 5-pentanediamine: kaiser biological materials Co Ltd
1, 10-decanediamine: shandong Chiyue chemical Co., ltd
(2) Aromatic diacid:
terephthalic acid: petrochemical Co.Ltd
(3) Dimer:
caprolactam cyclic dimer: shanghai Michel Biochemical technologies Co., ltd
(4) Preparation method of heat-stable hydrolysis-resistant alcoholysis-resistant master batch
The material is prepared by mixing, melting and extruding the following raw materials in percentage by mass: 85% -90% of polyamide PA6T/66, 5% -10% of high-polymerization carbodiimide (STABILIZER 4000 of PUZHAN), 2% -6% of cuprous iodide and 0.2% -0.5% of lubricant Licom CaV102.
(5) Fibrous reinforcing material
Glass fiber: chongqing glass fiber, trade mark ECS301HP-3-H, chongqing International composite material Co., ltd., average fiber diameter 10 μm, average fiber length 3 μm, excellent cold liquid resistance, excellent high temperature resistance.
(6) Heat stabilizer: antioxidant
AO-1：1098 and->608, and the mass ratio of the antioxidant is 2:3.
1098: n, N' - (hexane-1, 6-diyl) bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide]Basf.
608: bis (2, 4-dicumylphenyl) pentaerythritol-bisphosphite, qitides Corp
(7) Lubricant
Licom CaV102: calcium carboxylate salt with long carbon chain as main component, and Clariant.
PETS: pentaerythritol stearate, the water-soluble organic solvent and the water-soluble organic solvent,p, longsha (Lonza)
Other raw materials used in the present invention are all commercially available products.
Example 1
Synthesis of PA 6T/5T/10T/dimer copolymer: 4113g of hexamethylenediamine, 3806g of pentamethylenediamine, 1908g of decaenediamine, 13922g of terephthalic acid, 484g of caprolactam cyclic dimer, 154g of benzoic acid, 3.1g of sodium hypophosphite and 1346g of water were charged into a pressure reactor equipped with a magnetic coupling and stirred. The high-pressure reaction kettle is subjected to nitrogen replacement, high-purity nitrogen is filled as protective gas, and the high-pressure reaction kettle is heated to 180 ℃ for salification reaction under stirring for 1 hour. After 1 hour of reaction, the reaction mixture was heated to 250℃and reacted at a constant temperature of 250℃and a constant pressure of 2.5MPa for 2 hours, and the pressure in the autoclave was kept constant by discharging water through pressure relief. Discharging after the reaction is finished, and vacuum drying the prepolymer at 80 ℃ for 24 hours to obtain the prepolymer. The prepolymer was broken and subjected to solid-phase adhesion in a vacuum drum at 260℃under 50Pa to obtain a PA 6T/5T/10T/dimer copolymer. The copolymer had a melting point of 305℃and a glass transition temperature of 141℃and a relative viscosity of 2.45.
Preparation of ethylene glycol high temperature resistant polyamide mixture: 23.75kg of PA6T/5T/10T/dimer copolymer, 5.48kg of heat-stable hydrolysis-resistant alcoholysis-resistant master batch and other auxiliary agents of lubricant are mixed at high speed under the rotation speed of 150rpm, extrusion processing is carried out by a double screw, and glass fiber is added from a side feeding port. The semi-aromatic polyamide composition PA-1 is obtained by melt plasticizing, extruding and granulating at the temperature of 220 ℃,280 ℃,310 ℃,320 ℃,330 ℃,340 ℃,340 ℃,330 ℃ and 320 ℃ of each section of the extruder.
Examples 2 to 8 were prepared similarly to example 1, except that they are shown in Table 1.
Comparative example 1:
synthesis of PA 6T/5T: 5142g of hexamethylenediamine, 4757g of pentylene diamine, 15101g of terephthalic acid, 162g of benzoic acid, 3.1g of sodium hypophosphite and 1346g of water were charged into a pressure reactor equipped with a magnetic coupling and stirred. PA6T/5T copolymer was prepared by the same preparation method as in example 1. The copolymer had a melting point of 309℃and a glass transition temperature of 138℃and a relative viscosity of 2.45. A semi-aromatic polyamide composition based on PA6T/5T was obtained according to the same modification process as a test comparison of comparative example 1.
Comparative example 2:
synthesis of PA10T homopolymer: 12722g of decanediamine, 12278g of terephthalic acid, 162g of benzoic acid, 3.1g of sodium hypophosphite and 1346g of water were charged into a pressure reactor equipped with a magnetic coupling and stirred. The same preparation as in example 1 was carried out to obtain a PA10T homopolymer. The melting point of the product was 318℃and the glass transition temperature 125℃and the relative viscosity was 2.10. A semi-aromatic polyamide composition based on PA10T was obtained following the same modification procedure as a test comparison for comparative example 2.
Comparative example 3:
synthesis of PA6T/6I copolymer: 10280g of hexamethylenediamine, 10301g of terephthalic acid, 4415g of isophthalic acid, 162g of benzoic acid, 3.1g of sodium hypophosphite and 1346g of water were charged into a pressure reactor equipped with a magnetic coupling and stirred. A PA6T/6I copolymer was prepared in the same manner as in example 1. The copolymer had a melting point of 325℃and a glass transition temperature of 125℃and a relative viscosity of 2.18. A semi-aromatic polyamide composition based on PA6T/6I was obtained following the same modification procedure as a test comparison for comparative example 3.
Table 1 data on the properties of the semi-aromatic copolyamide obtained in each example
Table 2 data on the properties of semi-aromatic high temperature resistant nylons obtained in examples
As can be seen from the comparison of examples 1-8 and comparative examples 1-3, the material compounded by the long-chain and short-chain semi-aromatic copolyamides and the dimer, and the hydrolysis-resistant alcoholysis master batch shows obvious ethylene glycol resistance, the tensile strength of examples 1-8 is about 140MPa after being soaked in an ethylene glycol aqueous solution for 1008 hours at 130 ℃, and the strength of the comparative example is only 120MPa after being soaked in the ethylene glycol aqueous solution. In addition, both elongation at break and flexural strength show the same trend.
Also, examples 1 to 8 exhibited good long-term heat resistance after 500 hours of thermo-oxidative aging with a tensile strength retention of 75% or more.
While the present invention has been described in terms of preferred embodiments, it will be apparent to those skilled in the art that the present invention can be practiced with modification and alteration and combination of the process described herein without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (10)
1. The semi-aromatic copolyamide comprises the following raw materials in parts by mass:
(a1) 30 to 65 parts by mass of 6T units; (a2) 30 to 60 parts by mass of a 4T unit, a5T unit or an M5T unit; (a3) 0 to 15 parts by mass of a 9T unit, a10T unit, or a 12T unit; (a 4) 0 to 3 parts by mass of a cyclic polymer unit; wherein the sum of components (a 1) to (a 4) constitutes 100 parts by mass of the semiaromatic copolyamide;
6T segments：
4T segments：
5T segments：
M5T segments：
9T segments：
10T segments：
12T segments：
2. the semiaromatic copolyamide according to claim 1, wherein in component (a 1), the 6T units are formed from 1, 6-hexamethylenediamine and terephthalic acid;
and/or, in component (a 2), the 4T unit is formed from 1, 4-butanediamine and terephthalic acid;
and/or, in component (a 2), the 5T unit is formed from 1, 5-pentanediamine and terephthalic acid;
and/or, in component (a 2), the M5T unit is formed from 2-methyl-pentanediamine and terephthalic acid;
and/or, in component (a 3), the 9T unit is formed from 1, 9-nonanediamine and terephthalic acid;
and/or, in component (a 3), the 10T unit is formed from 1, 10-decanediamine and terephthalic acid;
and/or, in component (a 3), the 12T unit is formed from 1, 12-dodecanediamine and terephthalic acid;
and/or, in component (a 4), the cyclic multimeric units are selected from the group consisting of one or more of cyclic dimer units (1), cyclic trimer units (2) or cyclic tetramer units (3); preferably, the cyclic polymer unit is one or more of the following structures:
3. the semiaromatic polyamide composition is characterized by comprising the following raw materials in parts by mass: component A:40-65 parts by mass of the semiaromatic copolyamide as defined in any of claims 1 to 3;
component B:3-15 parts by mass of heat-stable hydrolysis-resistant alcoholysis-resistant master batch;
component C:30-60 parts by mass of reinforcing material and/or filler;
component D:0-2 parts by mass of a heat stabilizer;
component E:0-5 parts by mass of auxiliary agents and/or additives;
the sum of the components A to E constitutes 100 parts by mass.
4. The semiaromatic polyamide composition of claim 3, wherein the heat-stable hydrolysis-resistant and alcoholysis-resistant master batch of component B consists of polyamide, an anti-hydrolysis agent, a copper salt heat stabilizer and a lubricant;
and/or the component C is selected from one or a combination of more of glass fiber, carbon fiber, talcum powder and mica flake;
and/or the component D is selected from one or a combination of more of hindered phenol stabilizers, phosphite stabilizers, hindered amine stabilizers, triazine stabilizers, sulfur-containing stabilizers and inorganic phosphorus-containing stabilizers;
and/or the component E is selected from one or a combination of a plurality of lubricants, antistatic agents, release agents and flow improvement aids;
and/or, the mass part of the component E is 0-2 mass parts.
5. The semiaromatic polyamide composition of claim 4, wherein the polyamide in the heat stable hydrolysis-resistant and alcoholysis-resistant masterbatch of component B is selected from the group consisting of semiaromatic copolyamides PA6T/66;
and/or the hydrolysis inhibitor is selected from one or more of a monomeric carbodiimide hydrolysis inhibitor, a polymeric carbodiimide hydrolysis inhibitor and a liquid carbodiimide hydrolysis inhibitor, preferably a highly polymeric carbodiimide;
and/or the copper salt stabilizer is selected from any one of copper chloride, copper bromide, copper iodide and copper phosphate, preferably copper iodide; and/or the lubricant is selected from any one of calcium carboxylate with long carbon chain as main component, vinyl bis stearamide EBS, TAF, silicone powder and pentaerythritol stearate, preferably the calcium carboxylate with long carbon chain as main component.
6. The semiaromatic polyamide composition according to any of claims 3-5, characterized in that it has a glass transition temperature of 120 ℃ to 170 ℃, preferably 130 ℃ to 170 ℃, more preferably 135 ℃ to 170 ℃ at a rate of rise of 10 ℃/min;
and/or, the semiaromatic polyamide composition is aged for 500 hours at 170 ℃, with a tensile strength retention of 70% or more, preferably 75% or more;
and/or, after the semi-aromatic polyamide composition is soaked in an ethylene glycol-water mixture for 1008h at 130 ℃, the elongation at break is more than or equal to 1.5%, and preferably more than or equal to 1.8%.
7. A process for the preparation of a semiaromatic polyamide composition as claimed in any of claims 3 to 6, characterized by comprising the steps of:
s1: mixing the components (a 1) - (a 4), and obtaining a component A through a salt forming, prepolymerization and post-polymerization process;
s2: and (3) after the component A and the component E are fully mixed, extruding and granulating.
8. The process for preparing a semiaromatic polyamide composition as claimed in claim 7, characterized in that,
in step S1, the salification and prepolymerization of components (a 1) - (a 4) are accomplished in the same pressure reaction vessel;
and/or, in the step S1, the monomers and water of the components (a 1) - (a 4) undergo a salt formation reaction in a first temperature section, and undergo a prepolymerization reaction in a second temperature section; wherein the amount of salt forming and pre-polymerization added is 0-30wt.%, preferably 1-20wt.%; the first temperature section for salification is 150-190 ℃, preferably 170-180 ℃; the second temperature stage of the prepolymerization is 200-280 ℃, preferably 220-270 ℃;
and/or, in the step S1, discharging and crushing are carried out after the prepolymerization is finished, wherein the size of crushed particles is less than or equal to 3mm; solid-phase polymerizing the crushed materials, wherein the post-polymerization temperature is 220-280 ℃, and preferably 230-260 ℃; the post polymerization pressure is less than 400Pa, preferably less than or equal to 50Pa, and the semi-aromatic copolyamide is obtained after tackifying;
and/or, in the step S2, the semi-aromatic polyamide composition is obtained by carrying out high-speed dispersion and mixing on the component A-component E, extruding and granulating at a high processing temperature, wherein the rotating speed of the extruder is 100-350 rpm, the temperature of each section of the extruder is 210-230 ℃, 270-290 ℃, 300-310 ℃, 310-330 ℃, 320-340 ℃, 330-350 ℃, 320-340 ℃, 310-330 ℃, and extruding and granulating.
9. A semiaromatic polyamide composition prepared by the process for preparing a semiaromatic polyamide composition according to any of claims 7-8.
10. Use of a semiaromatic polyamide composition as claimed in any of claims 3-6 for the preparation of parts in direct or indirect contact with ethylene glycol-water coolant.
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| WO2023029374A1 (en) * | 2021-08-30 | 2023-03-09 | 上海凯赛生物技术股份有限公司 | High-temperature-resistant semi-aromatic polyamide and preparation method therefor, composition, and molded article |
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| US20170298225A1 (en) * | 2014-10-03 | 2017-10-19 | Dsm Ip Assets B.V. | Chemically resistant thermoplastic compositions |
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