CN106565953A - Preparation method of PA6 system polyamide thermoplastic elastomer - Google Patents
Preparation method of PA6 system polyamide thermoplastic elastomer Download PDFInfo
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- CN106565953A CN106565953A CN201610969716.1A CN201610969716A CN106565953A CN 106565953 A CN106565953 A CN 106565953A CN 201610969716 A CN201610969716 A CN 201610969716A CN 106565953 A CN106565953 A CN 106565953A
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- 229920006345 thermoplastic polyamide Polymers 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 105
- 238000003756 stirring Methods 0.000 claims abstract description 79
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- 229920000151 polyglycol Polymers 0.000 claims abstract description 11
- 239000010695 polyglycol Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 230000032050 esterification Effects 0.000 claims abstract description 8
- 238000005886 esterification reaction Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 5
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 5
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 14
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 14
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 14
- JJMDCOVWQOJGCB-UHFFFAOYSA-N 5-aminopentanoic acid Chemical compound [NH3+]CCCCC([O-])=O JJMDCOVWQOJGCB-UHFFFAOYSA-N 0.000 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 11
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 8
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 8
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 7
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 6
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- 229960002684 aminocaproic acid Drugs 0.000 claims description 6
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 6
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 5
- 229940035437 1,3-propanediol Drugs 0.000 claims description 5
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 5
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 5
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 claims description 5
- XDOLZJYETYVRKV-UHFFFAOYSA-N 7-Aminoheptanoic acid Chemical compound NCCCCCCC(O)=O XDOLZJYETYVRKV-UHFFFAOYSA-N 0.000 claims description 5
- UQXNEWQGGVUVQA-UHFFFAOYSA-N 8-aminooctanoic acid Chemical compound NCCCCCCCC(O)=O UQXNEWQGGVUVQA-UHFFFAOYSA-N 0.000 claims description 5
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 5
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 5
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 5
- 150000002148 esters Chemical group 0.000 claims description 5
- 229940071125 manganese acetate Drugs 0.000 claims description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 5
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 5
- 229940077386 sodium benzenesulfonate Drugs 0.000 claims description 5
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 4
- 229960003692 gamma aminobutyric acid Drugs 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 4
- 239000011654 magnesium acetate Substances 0.000 claims description 4
- 229940069446 magnesium acetate Drugs 0.000 claims description 4
- 235000011285 magnesium acetate Nutrition 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 239000002981 blocking agent Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 21
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 9
- 229920000570 polyether Polymers 0.000 description 9
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000003301 hydrolyzing effect Effects 0.000 description 6
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 238000012661 block copolymerization Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000012653 anionic ring-opening polymerization Methods 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
The invention provides a preparation method of a PA6 system polyamide thermoplastic elastomer. The preparation method is characterized by comprising the following steps that 100 parts of caprolactam, 1-10 parts of deionized water, 0-10 parts of auxiliary ring opening agent, 1-60 parts of an end-capping reagent and 0-3 parts of a heat stabilizer are added into a reaction vessel, nitrogen is led in to substitute air in the reaction vessel, reaction is made for 2 h to 4 h, depressurization is carried out to achieve the pressure ranging from 100 Pa to 2000 Pa, and reaction is continuously made for 1 h to 2 h; the pressure is adjusted to be ordinary pressure, 1-80 parts of dihydric alcohol and 0-10 parts of an esterification catalyst are added, the temperature is adjusted to range from 220 DEG C to 260 DEG C, and reacting is carried out for 1 h to 3 h; and depressurization is carried out until the ordinary pressure is obtained, 20-400 parts of polyglycol and 0.1-10 parts of a transesterification catalyst are added, reaction is made for 0.5 h to 2 h at the temperature ranging from 200 DEG C to 220 DEG C at the stirring speed being 50 r/min to 500 r/min, depressurization is gradually carried out until the pressure ranges from 0 to 200 Pa, the temperature rises to 220 DEG C to 280 DEG C, reaction is continuously made for 1 h to 3 h, and a polymer is obtained. The preparation method of the PA6 system polyamide thermoplastic elastomer is high in caprolactam conversion rate, high in polymerization rate, high in inherent viscosity, good in chain segment regularity, excellent in elasticity and adjustable in shore hardness, and overcomes the shortcomings in the prior art.
Description
Technical Field
The invention relates to a preparation method of a PA6 series polyamide thermoplastic elastomer. In particular to a method for preparing PA6 polyamide thermoplastic elastomer by preparing a carboxyl-terminated PA6 prepolymer by a hydrolytic ring-opening polymerization method, then adding dihydric alcohol for esterification, and finally adding polyglycol for ester exchange reaction.
Background
The polyamide thermoplastic elastomer is a thermoplastic elastomer which is easy to process and has excellent performance. Is a block copolymer composed of polyamide hard blocks and polyether soft blocks.
The PA6 series polyamide thermoplastic elastomer is a semi-crystalline block copolymer with PA6 as a hard block and polyether as a soft block. The synthesis methods can be generally divided into two main categories: one is hydrolytic ring-opening polymerization; another class is anionic ring-opening polymerization processes. The anion ring-opening polymerization method has high requirements on the purity of raw materials, and most of the method needs to use an activating agent phosgene. Phosgene is extremely toxic, huge potential safety hazards exist in the production process, and the product performance is poor, so that the application requirements of some fields are difficult to meet.
In patent CN101747510A, a hydrolytic ring-opening polymerization method is adopted to prepare PA6 and a diisocyanate hard segment, then a polyether soft segment is added, and the PA6 type polyamide thermoplastic elastomer is prepared after esterification and polycondensation. The method requires the addition of diisocyanate at high temperature, which is harmful to human body.
French patent 2273021 uses dicarboxyl polyamide with average molecular weight of 3000-15000 and polyether diol with average molecular weight of 200-6000 to prepare polyamide thermoplastic elastomer through melt polycondensation.
The patent J63-182343 utilizes the melt polycondensation of amino-terminated polyamide and carboxyl-terminated polyether to prepare the polyether amide thermoplastic elastomer.
In patent CN103772643A, a hydrolysis ring-opening polymerization method is used to prepare a PA6 prepolymer, and then a heat-resistant modified polyurethane is used as a soft segment to prepare a PA6 polyamide thermoplastic elastomer.
The patent CN105199099A firstly utilizes a hydrolytic ring-opening polymerization method to prepare a PA6 hard segment, and then adds a polyether amine soft segment to prepare a PA6 type block copolymerization thermoplastic elastomer.
The above methods are all methods for preparing the polyamide thermoplastic elastomer by adopting a hydrolytic ring-opening polymerization method to prepare a PA6 hard segment, and then directly copolymerizing the PA6 hard segment with a polyether or polyurethane soft segment. The caprolactam conversion is low and the extraction process consumes a large amount of water. The reaction is heterogeneous, and the reaction rate is low. And the molar ratio of the PA6 hard segment to the polyether or polyurethane soft segment needs to be accurately controlled during feeding, the molecular weight of the product is not high, and the performance is poor.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of PA6 polyamide thermoplastic elastomer. In particular to a method for achieving the purposes of high caprolactam conversion rate, high reaction rate and easy reaction control (the molar ratio of soft and hard chain segments does not need to be strictly controlled during feeding) by adopting a 'difference complement ester exchange' principle. The PA6 series polyamide thermoplastic elastomer with high intrinsic viscosity, good segment regularity and excellent product performance is prepared.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of PA6 series polyamide thermoplastic elastomer is characterized by comprising the following steps:
the first step is as follows: adding 100 parts of caprolactam, 1-10 parts of deionized water, 0-10 parts of ring opening aid, 1-60 parts of blocking agent and 0-3 parts of heat stabilizer into a reaction container, introducing nitrogen to replace air in the reactor, pressurizing to 1-10 bar, heating to 240-280 ℃ at a stirring speed of 50-500 r/min, reacting for 1-4 hours, reducing the pressure to 100-2000 Pa, and continuing to react for 1-2 hours;
the second step is that: after the first-step reaction is finished, adjusting the pressure to normal pressure, adding 1-80 parts of dihydric alcohol and 0-10 parts of esterification catalyst, and reacting for 1-3 hours under the conditions that the temperature is 220-260 ℃, the pressure is 0-8 bar, and the stirring speed is 50-500 r/min;
the third step: and after the second-step reaction is finished, reducing the pressure to normal pressure, adding 20-400 parts of polyglycol and 0.1-10 parts of ester exchange catalyst, reacting at 200-220 ℃ and at a stirring speed of 50-500 r/min for 0.5-2 hours, gradually reducing the pressure to 0-200 Pa, heating to 220-280 ℃, continuing to react for 1-3 hours to obtain a polymer, and drying the polymer to obtain the PA6 polyamide thermoplastic elastomer.
Preferably, the ring-opening aid is one of 4-aminobutyric acid, 5-aminopentanoic acid, 6-aminocaproic acid, 7-aminoheptanoic acid and 8-aminocaprylic acid.
Preferably, the end-capping agent is one of terephthalic acid, isophthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid.
Preferably, the heat stabilizer is one of triphenyl phosphate, triphenyl phosphite, Irganox1010, Irganox168 and Irganox 245.
Preferably, the diol is one of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol.
Preferably, the esterification catalyst is one of toluene-4-sulfonic acid, sodium benzenesulfonate, phenol-4-sulfonic acid, tetrabutyl titanate and isopropyl titanate.
Preferably, the transesterification catalyst is one of tetrabutyl titanate, isopropyl titanate, zinc acetate, manganese acetate, antimony acetate, magnesium acetate and antimony trioxide.
Preferably, the polyglycol is one of polyethylene glycol, polypropylene glycol and polytetrahydrofuran ether glycol, and the molecular weight range is 500-10000.
The invention relates to a preparation method of a PA6 series polyamide thermoplastic elastomer, which comprises the steps of preparing a carboxyl-terminated PA6 prepolymer by a hydrolytic ring-opening polymerization method, then adding dihydric alcohol for esterification, finally adding polyglycol, and preparing a block copolymerization thermoplastic elastomer by an ester exchange reaction. The general structural formula is as follows:
wherein: m is more than or equal to 4; n is more than or equal to 1.
Wherein,is a diacid. The diacid is selected from terephthalic acid, isophthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid or adipic acid. Preference is given to terephthalic acid, isophthalic acid and adipic acid
Is diol or polyglycol, and the probability of the two is related to the ratio of diacid to polyglycol. The diol is ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol or 1, 6-hexanediol. Ethylene glycol and 1, 4-butanediol are preferred.
The hard segment is a carboxyl-terminated PA6 prepolymer, the molecular weight of the prepolymer is 500-10000, preferably 1000-6000, and the molecular weight accounts for 10-90% of the total weight of the elastomer.
The soft segment is polyglycol with a molecular weight of 500-10000, preferably 1000-6000, and accounts for 10-90% of the total weight of the elastomer.
The invention has the advantages that the caprolactam conversion rate is high, and the product can be directly used without extraction; the PA6 prepolymer and the polyglycol are in homogeneous reaction during polymerization, the polymerization rate is high, and the product has high intrinsic viscosity; the molar ratio of reactants does not need to be accurately controlled during feeding, and the process is simple; the product has good segment regularity, excellent elasticity and adjustable Shore hardness. Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Unless otherwise specified, the parts referred to in the present invention are all numerical values in the case of an equivalent unit mass, i.e., 1g per part, and if 1g per part, 100 parts per part, or 100 g.
The molecular weight of the polyalkylene glycol in the present invention means the number average molecular weight in (g/mol).
The soft segment content in the examples of the invention is determined by NMR hydrogenSpectrum (A)1H-NMR) chart and the sum of the characteristic peak areas corresponding to the polyamide and the polyether.
The intrinsic viscosity test procedure in the examples of the present invention was as follows:
a0.25. + -. 0.005g sample was dissolved in 96.00. + -. 0.2% concentrated sulfuric acid, and the viscosity was measured at 25 ℃ by means of an Ubbelohde viscometer. The specific test principle and method are shown in GBT 12006.1-2009. The intrinsic viscosity is calculated according to the following formula:
wherein, [ η ]]Is an intrinsic viscosity of ηspTo increase the specific viscosity, ηrRelative viscosity, C is sample concentration in g/dl.
Example 1
A preparation method of PA6 series polyamide thermoplastic elastomer comprises the following steps:
the first step is as follows: a500 mL polymerization vessel was charged with 120g of caprolactam, 5g of deionized water, 1.2g of 4-aminobutyric acid, 22.5g of terephthalic acid, and 0.1g of triphenyl phosphite. Introducing nitrogen into the kettle, replacing the air in the kettle, and pressurizing to 10 bar. The temperature was raised to 270 ℃ at a stirring speed of 200 r/min. After 1.5 hours of reaction, the pressure was reduced to 1000Pa, and the reaction was continued for 1 hour.
The second step is that: after the first step reaction is finished, the pressure is adjusted to normal pressure. 25.2g of ethylene glycol and 0.3g of tetrabutyl titanate are added and reacted for 2 hours at a temperature of 240 ℃, a pressure of 8bar and a stirring speed of 200 r/min.
The third step: after the second step reaction is finished, reducing the pressure to normal pressure. 122g of polyethylene glycol having a molecular weight of 1000 and 0.3g of tetrabutyl titanate were added and reacted at 220 ℃ and a stirring speed of 200r/min for 1 hour. Then gradually reducing the pressure to 50Pa, raising the temperature to 250 ℃, and continuing to react for 2 hours at the stirring speed of 200r/min to obtain the polymer. Drying to obtain the PA6 series polyamide thermoplastic elastomer. The intrinsic viscosity is 0.589dl/g, the soft segment content is 50%, the tensile strength is 29MPa, the elongation at break is 300%, and the Shore hardness is 57D.
Example 2:
a preparation method of PA6 series polyamide thermoplastic elastomer comprises the following steps:
the first step is as follows: a500 mL polymerization vessel was charged with 120g of caprolactam, 10.2g of isophthalic acid, 5g of deionized water, 1.2g of 4-aminobutyric acid, and 0.1g of triphenyl phosphite. Introducing nitrogen into the kettle, replacing the air in the kettle, and pressurizing to 10 bar. The temperature was raised to 270 ℃ at a stirring speed of 200 r/min. After 1.5 hours of reaction, the pressure was reduced to 1000Pa, and the reaction was continued for 1 hour.
The second step is that: after the first reaction step was completed, the pressure was adjusted to normal pressure. 14g of 1, 3-propanediol and 0.3g of tetrabutyl titanate are added and reacted for 2 hours at a temperature of 245 ℃, a pressure of 7bar and a stirring speed of 200 r/min.
The third step: after the second step reaction is completed, the pressure is reduced to normal pressure. 111g of polypropylene glycol having a molecular weight of 2000 and 0.3g of zinc acetate were added thereto, and the mixture was reacted at 220 ℃ and a stirring speed of 200r/min for 1 hour. Then gradually reducing the pressure to 50Pa, raising the temperature to 250 ℃, and continuing to react for 2 hours at the stirring speed of 200r/min to obtain the polymer. Drying to obtain the PA6 series polyamide thermoplastic elastomer. The intrinsic viscosity is 0.575dl/g, the soft segment content is 66%, the tensile strength is 28MPa, the elongation at break is 320%, and the Shore hardness is 55D.
Example 3:
a preparation method of PA6 series polyamide thermoplastic elastomer comprises the following steps:
the first step is as follows: a500 mL polymerization vessel was charged with 120g of caprolactam, 3.5g of oxalic acid, 5g of deionized water, and 0.1g of Irganox 1010. Introducing nitrogen into the kettle, replacing the air in the kettle, and pressurizing to 10 bar. The temperature was raised to 270 ℃ at a stirring speed of 200 r/min. After 4 hours of reaction, the pressure was reduced to 1000Pa, and the reaction was continued for 1 hour.
The second step is that: after the first reaction step was completed, the pressure was adjusted to normal pressure. 10.5g of 1, 4-butanediol and 0.3g of tetrabutyl titanate are added, the pressure is increased to 6bar, and the reaction is carried out for 2 hours under the conditions of the temperature of 250 ℃, the pressure of 6bar and the stirring speed of 200 r/min.
The third step: after the second step reaction is completed, the pressure is reduced to normal pressure. 105g of polytetrahydrofuran ether glycol with the molecular weight of 3000 and 0.3g of antimony acetate are added and reacted for 1 hour at 220 ℃ and the stirring speed of 200 r/min. Then gradually reducing the pressure to 50Pa, raising the temperature to 250 ℃, and continuing to react for 2 hours at the stirring speed of 200r/min to obtain the polymer. Drying to obtain the PA6 series polyamide thermoplastic elastomer. The intrinsic viscosity is 0.561dl/g, the soft segment content is 33%, the tensile strength is 26MPa, the elongation at break is 350%, and the Shore hardness is 50D.
Example 4:
a preparation method of PA6 series polyamide thermoplastic elastomer comprises the following steps:
the first step is as follows: a500 mL polymerization vessel was charged with 120g of caprolactam, 3g of malonic acid, 5g of deionized water, and 0.1g of Irganox 168. Introducing nitrogen into the kettle, replacing the air in the kettle, and pressurizing to 10 bar. The temperature was raised to 270 ℃ at a stirring speed of 200 r/min. After 4 hours of reaction, the pressure was reduced to 1000Pa, and the reaction was continued for 1 hour.
The second step is that: after the first reaction step was completed, the pressure was adjusted to normal pressure. Adding 1g, 5-pentanediol and 0.3g tetrabutyl titanate, pressurizing to 5bar, and reacting for 2 hours at 255 ℃, 5bar and 200r/min of stirring speed;
the third step: after the water yield of the second step reaction reaches more than 3.5g, the pressure is reduced to normal pressure. 105g of polyethylene glycol with the molecular weight of 4000 and 0.3g of magnesium acetate are added to react for 1 hour at 220 ℃ and at the stirring speed of 200 r/min. Then gradually reducing the pressure to 50Pa, raising the temperature to 250 ℃, and continuing to react for 2 hours at the stirring speed of 200r/min to obtain the polymer. Drying to obtain the PA6 series polyamide thermoplastic elastomer. The intrinsic viscosity is 0.665dl/g, the soft segment content is 50%, the tensile strength is 32MPa, the elongation at break is 290%, and the Shore hardness is 59D.
Example 5:
a preparation method of PA6 series polyamide thermoplastic elastomer comprises the following steps:
the first step is as follows: into a 500mL polymerization vessel were added 120g of caprolactam, 2.7g of succinic acid, 5g of deionized water, and 1.2g of 5-aminovaleric acid. Introducing nitrogen into the kettle, replacing the air in the kettle, and pressurizing to 10 bar. The temperature was raised to 270 ℃ at a stirring speed of 200 r/min. After 2 hours of reaction, the pressure was reduced to 1000Pa, and the reaction was continued for 1 hour.
The second step is that: after the first reaction step was completed, the pressure was adjusted to normal pressure. 8.2g of 1, 6-hexanediol and 0.3g of tetrabutyl titanate are added, the pressure is increased to 4bar, and the reaction is carried out at 260 ℃ and 4bar for 2 hours at a stirring speed of 200 r/min.
The third step: after the water yield of the second step reaction reaches more than 3.5g, the pressure is reduced to normal pressure. 105g of polytetrahydrofuran ether glycol having a molecular weight of 5000 and 0.3g of tetrabutyl titanate were added and reacted at 220 ℃ under a stirring speed of 200r/min for 1 hour. Then gradually reducing the pressure to 50Pa, raising the temperature to 250 ℃, and continuing to react for 2 hours at the stirring speed of 200r/min to obtain the polymer. Drying to obtain the PA6 series polyamide thermoplastic elastomer. The intrinsic viscosity is 0.685dl/g, the soft segment content is 66%, the tensile strength is 36MPa, the elongation at break is 270%, and the Shore hardness is 63D.
Example 6:
a preparation method of PA6 series polyamide thermoplastic elastomer comprises the following steps:
the first step is as follows: a500 mL polymerization vessel was charged with 120g of caprolactam, 2.5g of glutaric acid, 5g of deionized water, 1.2g of 5-aminovaleric acid, and 0.1g of Irganox 1010. Introducing nitrogen into the kettle, replacing the air in the kettle, and pressurizing to 10 bar. The temperature was raised to 270 ℃ at a stirring speed of 120 r/min. After 2 hours of reaction, the pressure was reduced to 1000Pa, and the reaction was continued for 1 hour.
The second step is that: after the first reaction step was completed, the pressure was adjusted to normal pressure. 3.6 g of ethylene glycol and 0.3g of isopropyl titanate are added, the pressure is increased to 8bar, and the mixture is reacted for 2 hours under the conditions that the temperature is 240 ℃, the pressure is 8bar and the stirring speed is 120 r/min.
The third step: after the water yield of the second step reaction reaches more than 1.6g, the pressure is reduced to normal pressure. 105g of polypropylene glycol having a molecular weight of 6000 and 0.3g of isopropyl titanate were added thereto, and the mixture was reacted at 220 ℃ and a stirring speed of 120r/min for 1 hour. Then gradually reducing the pressure to 50Pa, raising the temperature to 250 ℃, and continuing to react for 2 hours at the stirring speed of 200r/min to obtain the polymer. Drying to obtain the PA6 series polyamide thermoplastic elastomer. The intrinsic viscosity is 0.672dl/g, the soft segment content is 33%, the tensile strength is 35MPa, the elongation at break is 280%, and the Shore hardness is 60D.
Example 7:
a preparation method of PA6 series polyamide thermoplastic elastomer comprises the following steps:
the first step is as follows: a500 mL polymerization vessel was charged with 120g of caprolactam, 2.4g of adipic acid, 5g of deionized water, and 1.2g of 5-aminopentanoic acid. Introducing nitrogen into the kettle, replacing the air in the kettle, and pressurizing to 10 bar. The temperature was raised to 260 ℃ at a stirring speed of 120 r/min. After 2 hours of reaction, the pressure was reduced to 1000Pa, and the reaction was continued for 1 hour.
The second step is that: after the first reaction step was completed, the pressure was adjusted to normal pressure. 3.8g of 1, 3-propanediol and 0.3g of isopropyl titanate are added, the pressure is increased to 7bar, and the reaction is carried out for 2 hours at the temperature of 245 ℃, the pressure of 7bar and the stirring speed of 120 r/min.
The third step: after the water yield of the second step reaction reaches more than 3.5g, the pressure is reduced to normal pressure. 105g of polypropylene glycol having a molecular weight of 7000 and 0.3g of isopropyl titanate were added thereto, and the mixture was reacted at 220 ℃ and a stirring speed of 120r/min for 1 hour. Then gradually reducing the pressure to 50Pa, raising the temperature to 250 ℃, and continuing to react for 2 hours at the stirring speed of 200r/min to obtain the polymer. Drying to obtain the PA6 series polyamide thermoplastic elastomer. The intrinsic viscosity is 0.719dl/g, the soft segment content is 50%, the tensile strength is 43MPa, the elongation at break is 230%, and the Shore hardness is 68D.
Example 8:
a preparation method of PA6 series polyamide thermoplastic elastomer comprises the following steps:
the first step is as follows: a500 mL polymerization vessel was charged with 120g of caprolactam, 2.4g of terephthalic acid, 5g of deionized water, 1.2g of 5-aminopentanoic acid, and 0.1g of triphenyl phosphite. Introducing nitrogen into the kettle, replacing the air in the kettle, and pressurizing to 10 bar. The temperature was raised to 260 ℃ at a stirring speed of 120 r/min. After 2 hours of reaction, the pressure was reduced to 1000Pa, and the reaction was continued for 1 hour.
The second step is that: after the first reaction step was completed, the pressure was adjusted to normal pressure. 3.9g of 1, 4-butanediol were added, the pressure was increased to 6bar, and the reaction was carried out at 250 ℃ and 6bar under a stirring speed of 120r/min for 3 hours.
The third step: after the water yield of the second step reaction reaches more than 3.5g, the pressure is reduced to normal pressure. 105g of polytetrahydrofuran ether glycol with molecular weight of 8000 and 0.3g of zinc acetate are added to react for 1 hour at 220 ℃ and at a stirring speed of 120 r/min. Then gradually reducing the pressure to 50Pa, raising the temperature to 250 ℃, and continuing to react for 2 hours at the stirring speed of 200r/min to obtain the polymer. Drying to obtain the PA6 series polyamide thermoplastic elastomer. The intrinsic viscosity is 0.679dl/g, the soft segment content is 66%, the tensile strength is 40MPa, the elongation at break is 300%, and the Shore hardness is 60D.
Example 9:
a preparation method of PA6 series polyamide thermoplastic elastomer comprises the following steps:
the first step is as follows: a500 mL polymerization vessel was charged with 120g of caprolactam, 2.1g of isophthalic acid, 5g of deionized water, 1.2g of 6-aminocaproic acid, and 0.1g of triphenyl phosphite. Introducing nitrogen into the kettle, replacing the air in the kettle, and pressurizing to 10 bar. The temperature was raised to 260 ℃ at a stirring speed of 120 r/min. After 2 hours of reaction, the pressure was reduced to 1000Pa, and the reaction was continued for 1 hour.
The second step is that: after the first reaction step was completed, the pressure was adjusted to normal pressure. 4g of 1, 5-pentanediol was added, the pressure was increased to 5bar, and the reaction was carried out at 255 ℃ and 5bar with a stirring speed of 120r/min for 3 hours.
The third step: after the water yield of the second step reaction reaches more than 1.6g, the pressure is reduced to normal pressure. 105g of polyethylene glycol having a molecular weight of 9000 and 0.3g of antimony acetate were added thereto, and the mixture was reacted at 220 ℃ for 1 hour with a stirring speed of 120 r/min. Then gradually reducing the pressure to 50Pa, raising the temperature to 250 ℃, and continuing to react for 2 hours at the stirring speed of 200r/min to obtain the polymer. Drying to obtain the PA6 series polyamide thermoplastic elastomer. The intrinsic viscosity is 0.699dl/g, the soft segment content is 33%, the tensile strength is 38MPa, the elongation at break is 260%, and the Shore hardness is 64D.
Example 10
A preparation method of PA6 series polyamide thermoplastic elastomer comprises the following steps:
the first step is as follows: a500 mL polymerization vessel was charged with 120g of caprolactam, 1.0g of oxalic acid, 5g of deionized water, 1.2g of 6-aminocaproic acid, and 0.1g of Irganox 245. Introducing nitrogen into the kettle, replacing the air in the kettle, and pressurizing to 10 bar. The temperature was raised to 260 ℃ at a stirring speed of 120 r/min. After 2 hours of reaction, the pressure was reduced to 1000Pa, and the reaction was continued for 1 hour.
The second step is that: after the first reaction step was completed, the pressure was adjusted to normal pressure. 4g of 1, 6-hexanediol and 0.3g of isopropyl titanate are added, the pressure is increased to 4bar, and the reaction is carried out at 260 ℃ and 4bar under a stirring speed of 120r/min for 2 hours.
The third step: after the water yield of the second step reaction reaches more than 3.5g, the pressure is reduced to normal pressure. 105g of polypropylene glycol having a molecular weight of 10000 and 0.3g of magnesium acetate were added thereto, and the mixture was reacted at 220 ℃ and a stirring speed of 120r/min for 1 hour. Then gradually reducing the pressure to 50Pa, raising the temperature to 250 ℃, and continuing to react for 2 hours at the stirring speed of 200r/min to obtain the polymer. Drying to obtain the PA6 series polyamide thermoplastic elastomer. The intrinsic viscosity is 0.738dl/g, the soft segment content is 50%, the tensile strength is 45MPa, the elongation at break is 200%, and the Shore hardness is 70D.
Example 11:
a preparation method of PA6 series polyamide thermoplastic elastomer comprises the following steps:
the first step is as follows: a500 mL polymerization vessel was charged with 120g of caprolactam, 13.1g of malonic acid, 5g of deionized water, 1.2g of 6-aminocaproic acid, and 0.1g of Irganox 245. Introducing nitrogen into the kettle, replacing the air in the kettle, and pressurizing to 10 bar. The temperature was raised to 260 ℃ at a stirring speed of 120 r/min. After 2 hours of reaction, the pressure was reduced to 1000Pa, and the reaction was continued for 1 hour.
The second step is that: after the first reaction step was completed, the pressure was adjusted to normal pressure. Adding 23.5g of ethylene glycol and 0.4g of sodium benzenesulfonate, pressurizing to 8bar, and reacting for 2 hours at the temperature of 240 ℃, the pressure of 8bar and the stirring speed of 120 r/min.
The third step: after the water yield of the second step reaction reaches more than 3.5g, the pressure is reduced to normal pressure. 227g of polyethylene glycol with molecular weight of 2000 and 0.2g of antimony trioxide are added to react for 1 hour at 220 ℃ and at a stirring speed of 120 r/min. Then gradually reducing the pressure to 50Pa, raising the temperature to 250 ℃, and continuing to react for 2 hours at the stirring speed of 200r/min to obtain the polymer. Drying to obtain the PA6 series polyamide thermoplastic elastomer. The intrinsic viscosity is 0.503dl/g, the soft segment content is 66%, the tensile strength is 20MPa, the elongation at break is 400%, and the Shore hardness is 40D.
Example 12:
a preparation method of PA6 series polyamide thermoplastic elastomer comprises the following steps:
the first step is as follows: a500 mL polymerization vessel was charged with 120g of caprolactam, 7.1g of succinic acid, 5g of deionized water, 1.2g of 6-aminocaproic acid, and 0.1g of triphenyl phosphate. Introducing nitrogen into the kettle, replacing the air in the kettle, and pressurizing to 10 bar. The temperature was raised to 260 ℃ at a stirring speed of 120 r/min. After 2 hours of reaction, the pressure was reduced to 1000Pa, and the reaction was continued for 1 hour.
The second step is that: after the first reaction step was completed, the pressure was adjusted to normal pressure. Adding 1.7 g, 3-propylene glycol and 0.4g sodium benzenesulfonate, pressurizing to 7bar, and reacting at 245 deg.C under 7bar and stirring speed of 120r/min for 2 hr.
The third step: after the water yield of the second step reaction reaches more than 1.6g, the pressure is reduced to normal pressure. 216g of polytetrahydrofuran ether glycol with the molecular weight of 4000 and 0.2g of antimony trioxide are added to react for 1 hour at 220 ℃ and at the stirring speed of 120 r/min. Then gradually reducing the pressure to 50Pa, raising the temperature to 250 ℃, and continuing to react for 2 hours at the stirring speed of 200r/min to obtain the polymer. Drying to obtain the PA6 series polyamide thermoplastic elastomer. The intrinsic viscosity is 0.546dl/g, the soft segment content is 33%, the tensile strength is 21MPa, the elongation at break is 380%, and the Shore hardness is 47D.
Example 13:
a preparation method of PA6 series polyamide thermoplastic elastomer comprises the following steps:
the first step is as follows: a500 mL polymerization vessel was charged with 120g of caprolactam, 5.2g of glutaric acid, 5g of deionized water, 1.2g of 7-aminoheptanoic acid, and 0.1g of Irganox 1010. Introducing nitrogen into the kettle, replacing the air in the kettle, and pressurizing to 10 bar. The temperature was raised to 250 ℃ at a stirring speed of 120 r/min. After 2.5 hours of reaction, the pressure was reduced to 1000Pa, and the reaction was continued for 1 hour.
The second step is that: after the first reaction step was completed, the pressure was adjusted to normal pressure. Adding 1.6g, 4-butanediol and 0.4g sodium benzenesulfonate, pressurizing to 6bar, and reacting at 250 deg.C under 6bar and stirring speed of 120r/min for 2 hr.
The third step: after the water yield of the second step reaction reaches more than 3.5g, the pressure is reduced to normal pressure. Adding 213g of polytetrahydrofuran ether glycol with the molecular weight of 6000 and 0.2g of antimony trioxide, and reacting at 220 ℃ and the stirring speed of 120r/min for 1 hour. Then gradually reducing the pressure to 50Pa, raising the temperature to 250 ℃, and continuing to react for 2 hours at the stirring speed of 200r/min to obtain the polymer. Drying to obtain the PA6 series polyamide thermoplastic elastomer. The intrinsic viscosity is 0.561dl/g, the soft segment content is 50%, the tensile strength is 24MPa, the elongation at break is 350%, and the Shore hardness is 53D.
Example 14:
a preparation method of PA6 series polyamide thermoplastic elastomer comprises the following steps:
the first step is as follows: a500 mL polymerization vessel was charged with 120g of caprolactam, 4.3g of adipic acid, 5g of deionized water, 1.2g of 7-aminoheptanoic acid, and 0.1g of Irganox 1010. Introducing nitrogen into the kettle, replacing the air in the kettle, and pressurizing to 10 bar. The temperature was raised to 250 ℃ at a stirring speed of 120 r/min. After 2.5 hours of reaction, the pressure was reduced to 1000Pa, and the reaction was continued for 1 hour.
The second step is that: after the first reaction step was completed, the pressure was adjusted to normal pressure. 9.1g of 1, 5-pentanediol and 0.4g of toluene-4-sulfonic acid were added, the pressure was increased to 5bar, and the reaction was carried out at 255 ℃ and 5bar under a stirring speed of 120r/min for 2 hours.
The third step: after the water yield of the second step reaction reaches more than 3.5g, the pressure is reduced to normal pressure. 211g of polyethylene glycol with molecular weight of 8000 and 0.2g of antimony trioxide are added to react for 1 hour at 220 ℃ and at a stirring speed of 120 r/min. Then gradually reducing the pressure to 50Pa, raising the temperature to 250 ℃, and continuing to react for 2 hours at the stirring speed of 200r/min to obtain the polymer. Drying to obtain the PA6 series polyamide thermoplastic elastomer. The intrinsic viscosity is 0.568dl/g, the soft segment content is 66%, the tensile strength is 28MPa, the elongation at break is 320%, and the Shore hardness is 55D.
Example 15:
a preparation method of PA6 series polyamide thermoplastic elastomer comprises the following steps:
the first step is as follows: a500 mL polymerization vessel was charged with 120g of caprolactam, 3.9g of terephthalic acid, 5g of deionized water, 1.2g of 7-aminoheptanoic acid, and 0.1g of triphenyl phosphate. Introducing nitrogen into the kettle, replacing the air in the kettle, and pressurizing to 10 bar. The temperature was raised to 250 ℃ at a stirring speed of 120 r/min. After 2.5 hours of reaction, the pressure was reduced to 1000Pa, and the reaction was continued for 1 hour.
The second step is that: after the first reaction step was completed, the pressure was adjusted to normal pressure. 8.3g of 1, 6-hexanediol and 0.4g of toluene-4-sulfonic acid were added, the mixture was pressurized to 4bar, and the reaction was carried out at 260 ℃ and 4bar under a stirring speed of 120r/min for 2 hours.
The third step: after the water yield of the second step reaction reaches more than 1.6g, the pressure is reduced to normal pressure. 126g of polypropylene glycol with the molecular weight of 6000 and 0.2g of antimony trioxide are added to react for 1 hour at 220 ℃ and at the stirring speed of 120 r/min. Then gradually reducing the pressure to 50Pa, raising the temperature to 250 ℃, and continuing to react for 2 hours at the stirring speed of 200r/min to obtain the polymer. Drying to obtain the PA6 series polyamide thermoplastic elastomer. The intrinsic viscosity is 0.546dl/g, the soft segment content is 33%, the tensile strength is 26MPa, the elongation at break is 330%, and the Shore hardness is 52D.
Example 16:
a preparation method of PA6 series polyamide thermoplastic elastomer comprises the following steps:
the first step is as follows: a500 mL polymerization vessel was charged with 120g of caprolactam, 3.2g of isophthalic acid, 5g of deionized water, 1.2g of 8-aminocaprylic acid, and 0.1g of triphenyl phosphate. Introducing nitrogen into the kettle, replacing the air in the kettle, and pressurizing to 10 bar. The temperature was raised to 250 ℃ at a stirring speed of 120 r/min. After 2.5 hours of reaction, the pressure was reduced to 1000Pa, and the reaction was continued for 1 hour.
The second step is that: after the first reaction step was completed, the pressure was adjusted to normal pressure. Adding 3.6 g of ethylene glycol and 0.4g of toluene-4-sulfonic acid, pressurizing to 8bar, and reacting for 2 hours at the temperature of 240 ℃, the pressure of 8bar and the stirring speed of 120 r/min.
The third step: after the water yield of the second step reaction reaches more than 3.5g, the pressure is reduced to normal pressure. 70g of polytetrahydrofuran ether glycol with the molecular weight of 4000 and 0.4g of manganese acetate are added to react for 1 hour at 220 ℃ and at the stirring speed of 120 r/min. Then gradually reducing the pressure to 50Pa, raising the temperature to 250 ℃, and continuing to react for 2 hours at the stirring speed of 200r/min to obtain the polymer. Drying to obtain the PA6 series polyamide thermoplastic elastomer. The intrinsic viscosity is 0.665dl/g, the soft segment content is 50%, the tensile strength is 30MPa, the elongation at break is 300%, and the Shore hardness is 58D.
Example 17:
a preparation method of PA6 series polyamide thermoplastic elastomer comprises the following steps:
the first step is as follows: a500 mL polymerization vessel was charged with 120g of caprolactam, 1.5g of oxalic acid, 5g of deionized water, 1.2g of 8-aminocaprylic acid, and 0.1g of Irganox 245. Introducing nitrogen into the kettle, replacing the air in the kettle, and pressurizing to 10 bar. The temperature was raised to 250 ℃ at a stirring speed of 120 r/min. After 2.5 hours of reaction, the pressure was reduced to 1000Pa, and the reaction was continued for 1 hour.
The second step is that: after the first reaction step was completed, the pressure was adjusted to normal pressure. 3.7g of 1, 3-propanediol and 0.5g of phenol-4-sulfonic acid are added, the pressure is increased to 7bar, and the reaction is carried out for 2 hours under the conditions that the temperature is 245 ℃, the pressure is 7bar and the stirring speed is 120 r/min.
The third step: after the water yield of the second step reaction reaches more than 3.5g, the pressure is reduced to normal pressure. Adding 29g of polypropylene glycol with molecular weight of 2000 and 0.4g of manganese acetate, and reacting at 220 ℃ and a stirring speed of 120r/min for 1 hour. Then gradually reducing the pressure to 50Pa, raising the temperature to 250 ℃, and continuing to react for 2 hours at the stirring speed of 200r/min to obtain the polymer. Drying to obtain the PA6 series polyamide thermoplastic elastomer. The intrinsic viscosity is 0.705dl/g, the soft segment content is 66%, the tensile strength is 35MPa, the elongation at break is 200%, and the Shore hardness is 65D.
Example 18:
a preparation method of PA6 series polyamide thermoplastic elastomer comprises the following steps:
the first step is as follows: a500 mL polymerization vessel was charged with 120g of caprolactam, 1.5g of malonic acid, 5g of deionized water, 1.2g of 8-aminocaprylic acid, and 0.1g of triphenyl phosphate. Introducing nitrogen into the kettle, replacing the air in the kettle, and pressurizing to 10 bar. The temperature was raised to 250 ℃ at a stirring speed of 120 r/min. After 2.5 hours of reaction, the pressure was reduced to 1000Pa, and the reaction was continued for 1 hour.
The second step is that: after the first reaction step was completed, the pressure was adjusted to normal pressure. 3..9g of 1, 4-butanediol and 0.5g of phenol-4-sulfonic acid are added, the pressure is increased to 6bar, and the reaction is carried out for 2 hours under the conditions that the temperature is 250 ℃, the pressure is 6bar and the stirring speed is 120 r/min.
The third step: after the water yield of the second step reaction reaches more than 1.6g, the pressure is reduced to normal pressure. Adding 13g of polyethylene glycol with the molecular weight of 1000 and 0.4g of manganese acetate, and reacting for 1 hour at 220 ℃ and at the stirring speed of 120 r/min. Then gradually reducing the pressure to 50Pa, raising the temperature to 250 ℃, and continuing to react for 2 hours at the stirring speed of 200r/min to obtain the polymer. Drying to obtain the PA6 series polyamide thermoplastic elastomer. The intrinsic viscosity is 0.738dl/g, the soft segment content is 33 percent, the tensile strength is 42MPa, the elongation at break is 150 percent, and the Shore hardness is 70D.
Claims (8)
1. A preparation method of PA6 series polyamide thermoplastic elastomer is characterized by comprising the following steps:
the first step is as follows: adding 100 parts of caprolactam, 1-10 parts of deionized water, 0-10 parts of ring opening aid, 1-60 parts of blocking agent and 0-3 parts of heat stabilizer into a reaction container, introducing nitrogen to replace air in the reactor, pressurizing to 1-10 bar, heating to 240-280 ℃ at a stirring speed of 50-500 r/min, reacting for 1-4 hours, reducing the pressure to 100-2000 Pa, and continuing to react for 1-2 hours;
the second step is that: after the first-step reaction is finished, adjusting the pressure to normal pressure, adding 1-80 parts of dihydric alcohol and 0-10 parts of esterification catalyst, and reacting for 1-3 hours at the temperature of 220-260 ℃, the pressure of 0-8 bar and the stirring speed of 50-500 r/min;
the third step: and after the second-step reaction is finished, reducing the pressure to normal pressure, adding 20-400 parts of polyglycol and 0.1-10 parts of ester exchange catalyst, reacting at 200-220 ℃ and at a stirring speed of 50-500 r/min for 0.5-2 hours, gradually reducing the pressure to 0-200 Pa, heating to 220-280 ℃, continuing to react for 1-3 hours to obtain a polymer, and drying the polymer to obtain the PA6 polyamide thermoplastic elastomer.
2. The process for preparing a polyamide thermoplastic elastomer of PA6 series according to claim 1, wherein the ring-opening aid is one of 4-aminobutyric acid, 5-aminopentanoic acid, 6-aminocaproic acid, 7-aminoheptanoic acid and 8-aminocaprylic acid.
3. The method for preparing a thermoplastic elastomer of PA6 series polyamide as claimed in claim 1, wherein the end-capping reagent is one of terephthalic acid, isophthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid.
4. The process for preparing PA6 series polyamide thermoplastic elastomer as claimed in claim 1, wherein the heat stabilizer is one of triphenyl phosphate, triphenyl phosphite, Irganox1010, Irganox168 and Irganox 245.
5. The method for preparing a polyamide thermoplastic elastomer of PA6 series as claimed in claim 1, wherein the diol is one of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol.
6. The process for preparing a polyamide thermoplastic elastomer of PA6 series according to claim 1, wherein the esterification catalyst is one of toluene-4-sulfonic acid, sodium benzenesulfonate, phenol-4-sulfonic acid, tetrabutyl titanate and isopropyl titanate.
7. The method of claim 1, wherein the transesterification catalyst is one of tetrabutyl titanate, isopropyl titanate, zinc acetate, manganese acetate, antimony acetate, magnesium acetate, and antimony trioxide.
8. The method for preparing a thermoplastic elastomer of PA6 series polyamide as claimed in claim 1, wherein the polyglycol is one of polyethylene glycol, polypropylene glycol and polytetrahydrofuran ether glycol, and the molecular weight is 500-10000.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106935317A (en) * | 2017-05-04 | 2017-07-07 | 川叶电子科技（上海）股份有限公司 | A kind of compound insulation wire and preparation method thereof |
| CN107698771A (en) * | 2017-09-19 | 2018-02-16 | 东华大学 | A kind of high resilience PA6 based thermoplastic elastomers and preparation method thereof |
| CN108129668A (en) * | 2017-12-25 | 2018-06-08 | 徐州工程学院 | A kind of thermoplastic elastomer (TPE) PA66-b-PEG compounds and its synthetic method and application |
| CN109208113A (en) * | 2018-09-06 | 2019-01-15 | 北京旭阳科技有限公司 | A kind of polyamide 6 elastomer and preparation method thereof |
| WO2019033485A1 (en) * | 2017-08-18 | 2019-02-21 | 浙江心源科技有限公司 | Method for preparing extruded nylon elastomer in twin-screw reactor |
| CN109705338A (en) * | 2018-11-26 | 2019-05-03 | 东华大学 | A kind of low melting-point PA6 elastomer and preparation method thereof |
| CN110886029A (en) * | 2018-09-10 | 2020-03-17 | 北京旭阳科技有限公司 | Antistatic polyamide 6 fiber and preparation method thereof |
| CN113215679A (en) * | 2021-04-30 | 2021-08-06 | 东华大学 | Preparation method of light-absorbing and heating polyamide-based elastic fiber |
| CN113402713A (en) * | 2021-06-22 | 2021-09-17 | 湖北三宁碳磷基新材料产业技术研究院有限公司 | Preparation method of polyamide elastomer |
| CN114249889A (en) * | 2020-09-25 | 2022-03-29 | 华润化学材料科技股份有限公司 | Polyamide elastomer and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106935317B (en) * | 2017-05-04 | 2018-06-08 | 川叶电子科技（上海）股份有限公司 | A kind of compound insulation wire and preparation method thereof |
| CN106935317A (en) * | 2017-05-04 | 2017-07-07 | 川叶电子科技（上海）股份有限公司 | A kind of compound insulation wire and preparation method thereof |
| WO2019033485A1 (en) * | 2017-08-18 | 2019-02-21 | 浙江心源科技有限公司 | Method for preparing extruded nylon elastomer in twin-screw reactor |
| CN107698771A (en) * | 2017-09-19 | 2018-02-16 | 东华大学 | A kind of high resilience PA6 based thermoplastic elastomers and preparation method thereof |
| CN108129668A (en) * | 2017-12-25 | 2018-06-08 | 徐州工程学院 | A kind of thermoplastic elastomer (TPE) PA66-b-PEG compounds and its synthetic method and application |
| CN109208113A (en) * | 2018-09-06 | 2019-01-15 | 北京旭阳科技有限公司 | A kind of polyamide 6 elastomer and preparation method thereof |
| CN110886029B (en) * | 2018-09-10 | 2022-04-22 | 北京旭阳科技有限公司 | Antistatic polyamide 6 fiber and preparation method thereof |
| CN110886029A (en) * | 2018-09-10 | 2020-03-17 | 北京旭阳科技有限公司 | Antistatic polyamide 6 fiber and preparation method thereof |
| CN109705338A (en) * | 2018-11-26 | 2019-05-03 | 东华大学 | A kind of low melting-point PA6 elastomer and preparation method thereof |
| CN114249889A (en) * | 2020-09-25 | 2022-03-29 | 华润化学材料科技股份有限公司 | Polyamide elastomer and preparation method and application thereof |
| CN114249889B (en) * | 2020-09-25 | 2023-07-25 | 华润化学材料科技股份有限公司 | Polyamide elastomer and preparation method and application thereof |
| CN113215679A (en) * | 2021-04-30 | 2021-08-06 | 东华大学 | Preparation method of light-absorbing and heating polyamide-based elastic fiber |
| CN113215679B (en) * | 2021-04-30 | 2022-06-17 | 东华大学 | Preparation method of light-absorbing and heating polyamide-based elastic fiber |
| CN113402713A (en) * | 2021-06-22 | 2021-09-17 | 湖北三宁碳磷基新材料产业技术研究院有限公司 | Preparation method of polyamide elastomer |
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