CN115044034B - Preparation method of polyamide with high viscosity - Google Patents
Preparation method of polyamide with high viscosity Download PDFInfo
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- CN115044034B CN115044034B CN202210647245.8A CN202210647245A CN115044034B CN 115044034 B CN115044034 B CN 115044034B CN 202210647245 A CN202210647245 A CN 202210647245A CN 115044034 B CN115044034 B CN 115044034B
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- polyamide
- melt
- crystallinity
- tackifying
- phase polycondensation
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 132
- 229920002647 polyamide Polymers 0.000 title claims abstract description 132
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 55
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 47
- 239000007790 solid phase Substances 0.000 claims abstract description 35
- 239000000155 melt Substances 0.000 claims description 39
- 238000001125 extrusion Methods 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000002667 nucleating agent Substances 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000009987 spinning Methods 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 6
- 238000012544 monitoring process Methods 0.000 abstract description 3
- 238000002844 melting Methods 0.000 description 18
- 230000008018 melting Effects 0.000 description 18
- 230000001276 controlling effect Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229920006122 polyamide resin Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- -1 aliphatic diamine Chemical class 0.000 description 5
- 238000000113 differential scanning calorimetry Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- JJMDCOVWQOJGCB-UHFFFAOYSA-N 5-aminopentanoic acid Chemical compound [NH3+]CCCCC([O-])=O JJMDCOVWQOJGCB-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XAUQWYHSQICPAZ-UHFFFAOYSA-N 10-amino-decanoic acid Chemical compound NCCCCCCCCCC(O)=O XAUQWYHSQICPAZ-UHFFFAOYSA-N 0.000 description 1
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- VWPQCOZMXULHDM-UHFFFAOYSA-N 9-aminononanoic acid Chemical compound NCCCCCCCCC(O)=O VWPQCOZMXULHDM-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- 102100021202 Desmocollin-1 Human genes 0.000 description 1
- 101000968043 Homo sapiens Desmocollin-1 Proteins 0.000 description 1
- 101000880960 Homo sapiens Desmocollin-3 Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical group 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002023 wood Substances 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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
-
- 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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- 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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- 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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
- C08G69/30—Solid state polycondensation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Polyamides (AREA)
Abstract
The invention belongs to the technical field of polyamide, and particularly relates to a preparation method of high-viscosity polyamide. The preparation method of the polyamide comprises the following steps: solid-phase polycondensation tackifying or melt polycondensation tackifying of the polyamide prepolymer to obtain first polyamide, wherein the enthalpy value of the first polyamide is A1; and (3) improving the crystallinity of the first polyamide, wherein in the process of improving the crystallinity of the first polyamide, the enthalpy value of the first polyamide is monitored to be A2, and when A2: a1 When 1, stopping increasing the crystallinity of the first polyamide to prepare second polyamide; and (3) carrying out solid-phase polycondensation and tackifying on the second polyamide to obtain the polyamide. The polyamide of the invention is prepared into polyamide with high viscosity through distribution tackifying; the increase of the crystallinity is controlled by monitoring and controlling the increase of the enthalpy value of the first polyamide, so that the viscosity of the second polyamide is obviously improved in the solid phase polycondensation process, and the prepared polyamide melt is free of floc.
Description
Technical Field
The invention belongs to the technical field of polyamide, and particularly relates to a preparation method of high-viscosity polyamide.
Background
Polyamides are a high molecular polymer material, which exhibits better mechanical properties, chemical resistance and aging resistance, and in particular better viscosity, at higher molecular weights, which is generally desirable in applications. However, when the molecular weight reaches a certain level, the molecular weight is not uniformly distributed, and when the molecular weight exceeds a certain amount, the melt fluidity of the ultrahigh molecular weight polyamide is remarkably deteriorated, and the high viscosity polyamide is obtained, but there are many infusible gel materials after heating and melting, and the melting and the processing are impossible. The problem of uneven molecular weight distribution limits the simultaneous improvement of the viscosity and the high melt flowability of the polyamide.
Therefore, it is necessary to provide a process for producing a polyamide with high viscosity, which can maintain good melt fluidity of the product and can greatly increase the viscosity of the polyamide while melting gel-free.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. To this end, the invention proposes a process for the preparation of polyamides with high viscosity; the method can lead the molecular weight distribution of the product to be uniform, keep good melt fluidity and melt gel-free substances, and simultaneously can greatly improve the viscosity of the polyamide.
In the present invention, the crystallinity mentioned is specifically the crystallinity measured by Differential Scanning Calorimetry (DSC).
The invention is characterized in that: the polymerization (solid-phase polycondensation tackifying or melt polycondensation tackifying) of polyamide is followed by controlling the enthalpy value and further controlling the crystallinity and further solid-phase polycondensation tackifying, and the step-by-step tackifying method of the pre-polymerization-polycondensation (solid-phase polycondensation tackifying or melt polycondensation tackifying) -crystallinity-solid-phase polycondensation (solid-phase polycondensation tackifying) of controlling the enthalpy value can lead the molecular weight distribution in the product to be uniform, and can also keep good melt fluidity and melting gel-free substances of the product under the condition of greatly improving the viscosity of the polyamide.
In a first aspect the present invention provides a process for the preparation of a polyamide.
Specifically, a preparation method of polyamide comprises the following steps:
(1) Solid-phase polycondensation tackifying or melt polycondensation tackifying of the polyamide prepolymer is carried out to obtain first polyamide, and the enthalpy value of the first polyamide is A1;
(2) And (3) improving the crystallinity of the first polyamide, wherein in the process of improving the crystallinity of the first polyamide, the enthalpy value of the first polyamide is monitored to be A2, and when A2: a1 When 1, stopping increasing the crystallinity of the first polyamide to prepare a second polyamide; the method for improving the crystallinity of the first polyamide comprises at least one of an extrusion stretching method, a melt fiber spinning method or a melt blowing method;
(3) And (3) carrying out solid-phase polycondensation tackifying on the second polyamide to obtain the polyamide.
Compared with the prior art, the preparation method of the polyamide provided by the first aspect of the invention has the following beneficial effects: the polyamide of the present invention is prepared into a polyamide (1.5-3.0 dl/g) having a high viscosity by "prepolymerization-polycondensation (solid phase polycondensation tackifying or melt polycondensation tackifying) -improving crystallinity-solid phase polycondensation (solid phase polycondensation tackifying)"; when the crystallinity of the first polyamide is improved, the invention controls the increment of the crystallinity of the first polyamide by monitoring and controlling the increment of the enthalpy value of the first polyamide, so that the viscosity of the second polyamide is obviously improved in the solid phase polycondensation process, the viscosity of the second polyamide can be improved from 0.6-1.0dl/g to 1.5-3.0dl/g, and the prepared polyamide melt is free of floccules.
Preferably, in step (1), the type of the polyamide prepolymer includes a semiaromatic polyamide prepolymer.
Preferably, the raw material of the semi-aromatic polyamide prepolymer comprises at least one of dibasic acid, diamine, caprolactam or amino acid; further preferably, the raw material of the semiaromatic polyamide prepolymer further comprises an auxiliary agent.
Preferably, the dibasic acid comprises at least one of an aromatic dibasic acid or an aliphatic dibasic acid; preferably, the aromatic dibasic acid includes at least one of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid and isophthalic acid; the aliphatic dibasic acid includes at least one of C4-C15 aliphatic dibasic acids.
Preferably, the diamine comprises at least one of a C4-C15 aliphatic diamine; further preferably, the diamine comprises 1, 6-hexamethylenediamine.
Preferably, the amino acid comprises at least one of 5-aminopentanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
Preferably, the auxiliary agent comprises a catalyst and a blocking agent; the catalyst is at least one of phosphoric acid, phosphorous acid, hypophosphorous acid or salts or esters thereof; the end-capping agent is a monocarboxylic acid.
Preferably, the polymerization process of the polyamide prepolymer is as follows: the preparation method comprises the steps of adopting water as a solvent, carrying out salt forming reaction at 60-80 ℃, regulating pH to 7-8 after the reaction is finished, concentrating the generated salt to 65-75wt%, adding an auxiliary agent, carrying out prepolymerization reaction on the concentrated salt by using a high-temperature high-pressure melting method, wherein the reaction temperature is 200-340 ℃, the pressure is 2.5-4MPa, preserving heat for 1-3h when the temperature is raised to above 200 ℃, then opening an exhaust valve, carrying out forward reaction of water vapor propelling polymerization by discharging, and discharging after the prepolymerization reaction is finished to obtain the first polyamide.
Preferably, the reaction temperature of the solid phase polycondensation tackifying is 180-250 ℃, the reaction time is 3-15h, and the reaction is carried out under the atmosphere of protective gas or under the vacuum condition; further preferably, the protective gas atmosphere is a nitrogen atmosphere.
Preferably, in step (1), the a1=20 to 60mJ/mg.
Preferably, in step (2), the a2=60 to 120mJ/mg.
Preferably, in step (2), the A2: a1 = (1.1-2.25): 1; further preferably, the A2: a1 = (1.8-2.25): 1.
Preferably, in step (2), the method for improving the crystallinity of the first polyamide includes at least one of an extrusion stretching method, a melt fiber spinning method, and a melt blowing method.
Preferably, the extrusion stretching includes a melt extrusion method.
Preferably, the apparatus used in the melt extrusion method comprises a single screw extruder or a twin screw extruder.
Preferably, the melt extrusion process has a die draw ratio (ratio of extruder material extrusion speed to die draw speed) of greater than 2 and less than 10; more preferably, the melt extrusion process has a die draw ratio of greater than 5 and less than 10.
Preferably, the cooling rate of the melt extrusion process material is less than 30 ℃/s; more preferably the melt extrusion process has a cooling rate of less than 15 ℃/s.
Preferably, the step of melt extrusion method may further comprise adding a nucleating agent, wherein the nucleating agent comprises at least one of an inorganic nucleating agent and an organic nucleating agent.
Preferably, the inorganic nucleating agent is at least one of talcum powder, calcium carbonate, silicon dioxide, alum, titanium dioxide, calcium oxide, magnesium oxide, carbon black, mica, rare earth metal and alkali metal halide.
Preferably, the organic nucleating agent is at least one of aliphatic carboxylic acid metal compound, sorbitol benzylidene derivative, aromatic carboxylic acid metal compound, organic phosphate, wood acid and derivatives thereof, sodium benzoate and bis (p-tert-butylbenzoic acid) carboxyaluminum.
Preferably, in step (2), the intrinsic viscosity of the second polyamide is between 0.5 and 1.2dl/g; further preferably, the intrinsic viscosity of the second polyamide is 0.6 to 1.0dl/g.
Preferably, the reaction temperature of the solid phase polycondensation tackifying is 180-250 ℃, the reaction time is 3-15h, and the reaction is carried out under the condition of protective gas atmosphere or vacuum; further preferably, the protective gas atmosphere includes a nitrogen atmosphere.
In a second aspect the invention provides a polyamide having an intrinsic viscosity of 1.5 to 3.0dl/g and a melt index of 50 to 600g/10min, the polyamide having a melt free of flocs; further preferably, the polyamide has an intrinsic viscosity of 1.8 to 2.4dl/g.
Compared with the prior art, the invention has the following beneficial effects:
(1) The polyamide of the present invention is prepared into a polyamide (1.5-3.0 dl/g) having a high viscosity by "prepolymerization-polycondensation (solid phase polycondensation tackifying or melt polycondensation tackifying) -improving crystallinity-solid phase polycondensation (solid phase polycondensation tackifying)"; when the crystallinity of the first polyamide is improved, the invention controls the increment of the crystallinity of the first polyamide by monitoring and controlling the increment of the enthalpy value of the first polyamide, so that the viscosity of the second polyamide is obviously improved in the solid phase polycondensation process, the viscosity of the second polyamide can be improved from 0.6-1.0dl/g to 1.5-3.0dl/g, and the prepared polyamide melt is free of floccules.
In addition, by the step-by-step tackifying method of controlling the enthalpy value of polyamide after polymerization (solid-phase polycondensation tackifying or melt polycondensation tackifying) and further controlling the crystallinity of the polyamide and further controlling the solid-phase polycondensation tackifying, and controlling the enthalpy value of the polyamide, namely the step-by-step tackifying method of prepolymerization-polycondensation (solid-phase polycondensation tackifying or melt polycondensation tackifying) -improving the crystallinity-solid-phase polycondensation (solid-phase polycondensation tackifying), the molecular weight distribution in the product can be uniform, and the good melt fluidity and melting gel-free substance of the product can be maintained under the condition of greatly improving the viscosity of the polyamide.
(2) According to the invention, the degree of improvement of the crystallinity of the first polyamide can be controlled more accurately by further controlling the grain cutting draft ratio and the cooling speed of the material in the process of the melt extrusion method.
(3) The addition of a nucleating agent during the step of the melt extrusion process can enhance the crystallization rate and crystallinity of the first polyamide.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
Melting point and enthalpy values were measured using the following methods:
testing DSC melting point of sample with a Metrele DSC1 STARe System analyzer under nitrogen atmosphere, heating to 340 deg.C at 10deg.C/min, maintaining at 340 deg.C for 3min, cooling to 25 deg.C at 10deg.C/min, heating to 340 deg.C at 10deg.C/min, and setting the endothermic peak temperature as melting point T m . The heat of fusion is calculated from the cumulative value of the endothermic peaks caused by melting at the first temperature rise.
The melt index was measured using the following method:
the melt index was measured at a temperature 20℃above the melting point of the polyamide resin, a pore diameter of 2mm, and a weight of 1.2 Kg.
The intrinsic viscosity was measured using the following method:
polyamide logarithmic viscosity eta at concentrations of 0.25, 0.50, 0.75 and 1g/dl measured in concentrated sulfuric acid at 25 DEG C inh . Wherein eta inh Represents logarithmic reduced viscosity in dl/g, t 0 Indicating the time of solvent flow (sec),t 1 the flow-through time (sec) of the sample solution is represented, and C represents the concentration (g/dl) of the sample solution. Will eta inh Extrapolated to a concentration of 0g/dl, plotted to give an intrinsic viscosity eta.
η inh ＝[ln(t 1 /t 0 )]/C
Example 1
A polyamide with high viscosity and a preparation method thereof, wherein the preparation process and related characterization data are as follows:
(1) The autoclave has a specification of 20L and is provided with magnetic coupling stirring, a condenser tube, an exhaust port and a pressure explosion-proof port. 3320g of terephthalic acid, 2320g of 1, 6-hexamethylenediamine and 2260g of caprolactam are added into an autoclave, 4kg of deionized water is added, salt forming reaction is carried out at 60 ℃, the solution is clarified after the reaction, pH=7.5-7.8 is regulated, the solution is stabilized for 1h to prepare a polyamide salt solution, and the polyamide salt solution is heated and concentrated to 70wt% of the original solution. And (3) continuously adding 25g of benzoic acid and 16g of sodium hypophosphite for mixing after concentration, purging with nitrogen, heating to 220 ℃, simultaneously raising the pressure to 3.2MPa for prepolymerization, maintaining the temperature and the pressure for reaction for 1.5h, opening an exhaust valve after the reaction, and performing forward reaction of polymerization by discharging water vapor to prepare the polyamide prepolymer.
(2) The polyamide prepolymer was dried using a vacuum oven for 10 hours, and then subjected to vacuum evacuation at 200℃and solid-phase polycondensation to tackify for 8 hours to obtain a first polyamide having a measured enthalpy value A1 of 35mJ/mg and an intrinsic viscosity of 0.8dl/g.
(step (1) and step (2) are the prior polyamide prepolymerization technology and solid phase polycondensation tackifying technology of the applicant)
(3) And processing the first polyamide by a double-screw extruder through a melt extrusion method, and improving the crystallinity of the first polyamide. The melt extrusion process had a die cut draft ratio of 5, a material cooling rate of 20 ℃/s, 6g of nucleating agent potassium iodide added during the process (0.1% by mass of the first polyamide resin), and the enthalpy value of the first polyamide was monitored as A2 during the melt extrusion process, and when A2 was 70mJ/mg, the increase of the crystallinity of the first polyamide was stopped to obtain a second polyamide, and the intrinsic viscosity was measured to be 0.95dl/g.
(4) And (3) carrying out solid-phase polycondensation and tackifying on the second polyamide for 10 hours in a nitrogen atmosphere at 200 ℃ to obtain a finished polyamide product, wherein the intrinsic viscosity is 1.8dl/g, and the DSC melting point is 290 ℃.
The larger the molecular weight of the polyamide, the longer the molecular chain, the larger the intermolecular force, the more difficult the flow, and the higher the viscosity; the polyamide of the present invention has a higher molecular weight and a longer molecular chain, as can be indirectly shown by the fact that the viscosity of the polyamide can be significantly increased by the process of "thickening-crystallinity-solid phase polycondensation and thickening". Moreover, the polyamide resin of example 1 of the present invention was examined to maintain good melt fluidity at 20 ℃ (290 ℃ +20 ℃ =310℃) above the DSC melting point, the melt index was 280g/10min, and the melt was free of floc, thus showing uniform molecular weight distribution in the product.
The existing crystallinity test method cannot obtain absolute value of crystallinity, only can obtain relative value, and the tested result of each method has certain deviation. The crystallinity of the polyamide can be compared by comparing the enthalpy value at the time of melting. Since the enthalpy value at 100% crystallization is a constant value for the same material, the crystallinity can be found by the following formula:
C m is crystallinity; deltaH m1 Is the enthalpy value of the material when in hot melting; deltaH m0 Is the enthalpy value of the hot melt at 100% crystallization of the material.
The production process of polyamide is the polymerization process of polymer, and the polymer cannot control and produce high molecular chains with the same molecular structure, so that the properties of different batches of products often have differences even in the same process. By controlling the enthalpy values (namely A1 and A2) of the polyamide in the process of distributed tackifying, the crystallinity of the polyamide in the process of fractional tackifying can be accurately monitored, so that the required specific high-viscosity product can be accurately and repeatedly prepared. Moreover, the polyamides produced by controlled stepwise tackifying have high viscosity and melt floc-free.
Example 2
A polyamide with high viscosity and a preparation method thereof, wherein the preparation process and related characterization data are as follows:
(1) The autoclave has a specification of 20L and is provided with magnetic coupling stirring, a condenser tube, an exhaust port and a pressure explosion-proof port. 2490g of terephthalic acid, 2190g of 1, 6-adipic acid and 3480g of 1, 6-hexamethylenediamine are added into an autoclave, 4kg of deionized water is added, salt forming reaction is carried out at 60 ℃, the solution is clarified after the reaction, the pH value is regulated to be 7.5-7.8, the solution is stabilized for 1h, and the polyamide salt solution is prepared, and the polyamide salt solution is heated and concentrated to 70wt% of the original solution. And (3) continuously adding 18g of benzoic acid and 20g of sodium hypophosphite for mixing after concentration, purging with nitrogen, heating to 220 ℃, simultaneously raising the pressure to 3.2MPa for prepolymerization, maintaining the temperature and the pressure for reaction for 1.5h, opening an exhaust valve after the reaction, and performing forward reaction of polymerization by discharging water vapor to prepare the polyamide prepolymer.
(2) The polyamide prepolymer was dried using a vacuum oven for 10 hours, and then subjected to vacuum pumping at 220℃and solid phase polycondensation to tackify for 6 hours to obtain a first polyamide having a measured enthalpy value A1 of 40mJ/mg and an intrinsic viscosity of 0.9dl/g.
(3) And processing the first polyamide by a double-screw extruder through a melt extrusion method, and improving the crystallinity of the first polyamide. The melt extrusion method has a pelletization draft ratio of 3, a material cooling rate of 25 ℃/s, a nucleating agent talc powder added in the process of 6g accounting for 0.1 percent of the mass fraction of the first polyamide resin, and the enthalpy value of the first polyamide is monitored to be A2 in the melt extrusion process, when A2 is 90mJ/mg, the crystallization degree of the first polyamide is stopped to be raised, the second polyamide is prepared, and the intrinsic viscosity is measured to be 0.95dl/g, and the DSC melting point is 300 ℃.
(4) The second polyamide was solid phase polycondensed at 220℃under nitrogen for 8 hours to give a polyamide final product, the intrinsic viscosity of which was found to be 2.4dl/g.
The polyamide resin of example 2 of the present invention was tested to maintain good melt flow above the melting point of 20 ℃ (300 ℃ +20 ℃ =320℃), a melt index of 150g/10min, and no floc in the melt.
Comparative example 1
A polyamide and a method for producing the same, comparative example 1 differs from example 1 in that comparative example 1 does not have step (3), and the second polyamide is directly subjected to the second solid-phase polycondensation tackifying without increasing the crystallinity by the melt extrusion method.
The intrinsic viscosity of comparative example 1 was measured to be 1.75dl/g, the melt flowability of the polyamide resin at 20℃above the melting point was generally (worse than in examples 1, 2), the melt index was 45g/10min, and the melt had floc.
Claims (8)
1. A process for the preparation of a polyamide comprising the steps of:
(1) Solid-phase polycondensation tackifying or melt polycondensation tackifying of the polyamide prepolymer is carried out to obtain first polyamide, and the enthalpy value of the first polyamide is A1;
(2) And (3) improving the crystallinity of the first polyamide, wherein in the process of improving the crystallinity of the first polyamide, the enthalpy value of the first polyamide is monitored to be A2, and when A2: a1 When 1, stopping increasing the crystallinity of the first polyamide to prepare a second polyamide; the method for improving the crystallinity of the first polyamide comprises at least one of an extrusion stretching method, a melt fiber spinning method or a melt blowing method;
(3) Performing solid-phase polycondensation tackifying on the second polyamide to obtain the polyamide;
in the step (1), the type of the polyamide prepolymer is a semi-aromatic polyamide prepolymer, and the raw materials of the semi-aromatic polyamide prepolymer are terephthalic acid, 1, 6-hexamethylenediamine, caprolactam or terephthalic acid, 1, 6-adipic acid and 1, 6-hexamethylenediamine;
a1=20-60 mJ/mg and a2=60-120 mJ/mg.
2. The method of claim 1, wherein in step (2), the extrusion stretching method comprises a melt extrusion method.
3. The method of claim 2, wherein the melt extrusion process has a die draw ratio of greater than 2 and less than 10.
4. The method of claim 2, wherein the melt extrusion material is cooled at a rate of less than 30 ℃/s.
5. The method according to claim 2, wherein a nucleating agent including at least one of an inorganic nucleating agent and an organic nucleating agent is further added to the melt extrusion method.
6. The process according to claim 1, wherein in step (2), the intrinsic viscosity of the second polyamide is 0.5 to 1.2dl/g.
7. The method according to claim 1, wherein in the step (3), the reaction temperature of the solid phase polycondensation and adhesion is 180 to 250 ℃ and the reaction time is 3 to 15 hours, and the reaction is carried out under a protective gas atmosphere or under vacuum conditions.
8. A polyamide produced by the production process according to any one of claims 1 to 7, wherein the polyamide has an intrinsic viscosity of 1.5 to 3.0dl/g and a melt index of 50 to 600g/10min, and the melt of the polyamide is free of flocs.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4945152A (en) * | 1986-11-20 | 1990-07-31 | Stamicarbon B.V. | Molded nylon 4.6 article having first and second enthalpy |
| CN110294842A (en) * | 2019-05-24 | 2019-10-01 | 金发科技股份有限公司 | A kind of semiaromatic polyamide composition and its synthetic method and the polyamide moulding composition being made from it |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4945152A (en) * | 1986-11-20 | 1990-07-31 | Stamicarbon B.V. | Molded nylon 4.6 article having first and second enthalpy |
| CN110294842A (en) * | 2019-05-24 | 2019-10-01 | 金发科技股份有限公司 | A kind of semiaromatic polyamide composition and its synthetic method and the polyamide moulding composition being made from it |
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