CN103911002A - Novel nanometer polyamide 66 resin - Google Patents
Novel nanometer polyamide 66 resin Download PDFInfo
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- CN103911002A CN103911002A CN201410092830.1A CN201410092830A CN103911002A CN 103911002 A CN103911002 A CN 103911002A CN 201410092830 A CN201410092830 A CN 201410092830A CN 103911002 A CN103911002 A CN 103911002A
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- China
- Prior art keywords
- resin
- traction
- polymerization
- rotating speed
- tractor
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- 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
-
- 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
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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 discloses novel nanometer polyamide 66 resin. The novel nanometer polyamide 66 resin is obtained by subjecting monomers hexanedioic acid and hexylenediamine to polymerization, and subjecting the materials obtained by polymerization to a strip casting step and a granule cutting step to obtain slices. A traction step is arranged between the strip casting step and the granule cutting step, namely, the materials are prepared into strips by the strip casting step and the strips are cooled in a water bath and are subjected to traction through traction engines to a granulator. The traction is multistage. The rotating speed of the traction engine at a later stage is faster than the rotating speed of the traction engine at an earlier stage. By the multistage traction, the degree of crystallization of the resin material is increased, the degree of structural order in the amorphous region is increased, the water content of the slices finally obtained is reduced and the water absorption of the resin is reduced, thus omitting the need of drying before processing.
Description
Technical field
The invention belongs to Material Field, relate in particular to a kind of novel nano polyamide 66 resin.
Background technology
Polyamide 66 is called again nylon 66, is a kind of engineering speed of a large amount of uses, is widely used in the fields such as machinery, automobile, electrical equipment, weaving, chemical industry, aviation.This material has good mechanical property, and physical strength is high, heat-resisting good weatherability.But existing polyamide 66 resin water-absorbent is high, poor dimensional stability is easily adsorbed polar solvent, needs drying treatment before processing, has therefore limited the application of this material.
Summary of the invention
The present invention has developed a kind of novel nano polyamide 66 resin, by suitable processing, makes the fiber of obtained resin finer and close, and water-absorbent declines, and section water content declines, and has reduced the needs to processing front drying treatment.
Specifically, the present invention has adopted following technical scheme:
A kind of novel nano polyamide 66 resin; it is by making hexanodioic acid and hexanediamine monomer carry out polyreaction; the material that polymerization obtains becomes section by Cast Strip step and pelletizing step again and obtains; it is characterized in that; between Cast Strip and pelletizing step, also comprise distraction step; be that material becomes band by Cast Strip step; after band is cooling in water-bath, is drawn to and reaches dicing machine through tractor; wherein said traction is multistage traction, and the rotating speed of every rear one-level tractor is all fast than the rotating speed of previous stage tractor.
Preferably, the progression of described multistage traction is two-stage at least.In one embodiment, the progression of described multistage traction is three grades.
More preferably, after every, the rotating speed of one-level tractor is all 2 times of rotating speed of its previous stage tractor.
Preferably, the polymerization of hexanodioic acid and hexanediamine monomer comprises prepolymerization and post polymerization, and prepolymerization is to carry out in pre-polymerization reactor, reaction pressure 17.5 bar, 200 ℃ to 255 ℃ of temperature of reaction, post polymerization is to carry out in post-polymerization device, reaction pressure is normal pressure, 238 ℃ of temperature of reaction.
More preferably, between prepolymerization and post polymerization step, also comprise flash distillation step, flash distillation is to carry out in flasher, and in flasher, pressure is reduced to normal pressure by 17.5 bar, and temperature of charge is 228 ℃ to 235 ℃.
Beneficial effect: the present invention, by multistage stretching is carried out in polymer material Cast Strip, improves the degree of order of material degree of crystallinity and noncrystalline domain, reduces the potential of water content and water suction, thus water-intake rate reduced.The polyamide 66 resin section obtaining by such processing reduces processing front dry needing, and the shelf lives of section extends, and therefore following process is more convenient, and still less, the quality guaranteed period extends in energy demand, is conducive to improve the quality product of finished product.
Embodiment
Describe the present invention in detail below in conjunction with specific embodiment.
The object of this invention is to provide a kind of novel nanometer polyamide 66 resins, the resin-phase ratio of this resin and prior art, has better crystal type, and the degree of order of noncrystalline domain is higher.Because the water suction of resin is all from noncrystalline domain, therefore resin of the present invention makes the embedding of water molecules become difficulty, thereby has reduced water-intake rate.The raising of degree of crystallinity and the raising of the degree of order of noncrystalline domain make resin fibre finer and close, thereby can obtain the mechanical property of raising.
Polyamide 66 resin section is the high polymers of the acid amides linear structure that made by nylon salt polymerization, and its main production process can be divided into the allotment of nylon salt liquid, polymerization, pelletizing, dry, packing.
Auxiliary facility has power system, steam system, hot enzyme boiler systems, de-salted water preparation system, water coolant preparation system, instrument wind preparation system, N2 gas securing system, TiO2 mixing system, acetic acid mixing system.
1, nylon salt liquid allotment
1.1, dry nylon salt dissolves
The de-salted water of the 80-90 getting ready ℃ is imported to 8M
3in dissolving vessel, drop into dry nylon salt in 50% ratio, then drive agitator and stir 30 minutes, (solution is as clear as crystal) sample examination concentration after 66 salt fully dissolve.
1.2, nylon salt liquid allotment
Result by chemical examination adds various additives again, and it is 50 ± 0.1% qualified solution that 66 saline solutions are deployed into concentration, then with transferpump paper filter importing 16M after blue web filter and pump before pump
3in hold-up vessel, supplying with Polymerization Production Line uses continuously.
2, the formation of polyamide 66
2.1, precondensation
16M
366 saline solutions in hold-up vessel circulate with impeller pump, on circulation line, enter vaporizer by automatically controlled valve, make the concentration of saline solution be concentrated into 65% from 50%.
After concentrated, 65% saline solution is transported to tubular type preheater through syringe pump, saline solution is heated to 200 ℃ of initial reaction temperatures in preheater, and residence time of material is 5-6 minute, and constant pressure is at 17.5 bar.Preheater adopts heat-conducting oil heating, 225 ℃ of heat conductive oil inlet temperature, and 216 ℃ of temperature outs, can suitably adjust according to the condition of production.
Pre-polymerization reactor is the main container of polycondensation, and structure is chuck cartridge type, and material is walked tube side, and thermal oil is walked shell side, and it is divided into three sections; R1, R2, R3, polycondensation is mainly carried out in R3, and dissolved water and the water of separating out pass through outside exhaust steam tube discharge chamber.
Reaction formula: nH2N (CH2) 6NH2+nHOOC (CH2) 4COOH ← → { HN (CH2) 6NHCO (CH2) 4CO } n+2nH2O ↑
n｛H2N(CH2)6NH2·HOOC(CH2)4COOH｝←→｛HN(CH2)6NHOC(CH2)4CO｝n+2nH2O↑
205 ℃ of R1 entrance temperature of charge, 208 ℃ of R2 entrance temperature of charge, 220 ℃ of R3 entrance temperature of charge, 255 ℃ of R3 outlet material temperature; Front liquid level 65%, rear liquid level 58%, rear liquid level is reconciled automatically by syringe pump stroke.Whole reaction process constant pressure is at 17.5 bar, and pressure has the automatically controlled valve on exhaust steam tube to reconcile.Reactor adopts heat-conducting oil heating, 222 ℃ of R1 heat conductive oil inlet temperature, and 224 ℃ of temperature outs, 232 ℃ of R2 heat conductive oil inlet temperature, 243 ℃ of temperature outs, 246 ℃ of R3 heat conductive oil inlet temperature, 240 ℃ of temperature outs, can suitably adjust according to the condition of production.
2.2, post polymerization
Material has completed first one-step polycondensation in reactor, no longer includes free hexanediamine and hexanodioic acid in system, now for polycondensation is proceeded down, must deduct pressure and be beneficial to separating out of low molecular water.
To flasher, pass through the step-down of reducing coil pipe by flash distillation pump delivery from reactor material out, import is 17.5 bar, exports as normal pressure.228 ℃ of inlet feed temperature, 235 ℃ of outlet material temperature.Flasher is to adopt thermal oil to invade the heating of bubble formula, 264 ℃ of heat conductive oil inlet temperature, 260 ℃ of temperature outs.Can suitably adjust according to the condition of production residence time of material 2-3 second.
Produce when semi-dulling chips, can on the material pipeline between flash distillation pump and flasher, inject 11% TiO2 suspension, make TiO2 content in polymkeric substance 0.3%, this section of pipeline is jacket pipe common name T1, adopts heat-conducting oil heating, 249 ℃ of inlet temperatures, 230 ℃ of temperature outs, 238 ℃ of temperature of charge.Can suitably adjust parameter according to the condition of production.
Post polymerization device is the reactor that material completes final polymerization process, will discharge whole polycondensation moisture content here, water is by the spiral propeller rotation in device, makes material on sea whelk, form the film that 3mm is thick, and moisture content is evaporated under normal pressure from face, outside exhaust steam tube discharge chamber.Polymerizer adopts thermal oil insulation, and 253 ℃ of imports, export 251 ℃.Front liquid level 65%, rear liquid level 55%, controls automatically by spiral propeller, residence time of material 45-60 minute.
3, Cast Strip, section
From post polymerization device material out, be transported to end of extruded band through two topping-up pumps, end of extruded band φ 6 × 15 holes have two, the using and the reserved.Through cooling trough, water eliminator, tractor, dicing machine section, tractor, dicing machine throughput are 1.2 tons/hour two covers, the using and the reserved.Every suit tractor is divided into prime traction and rear class traction, also has in some cases middle rank traction.The rotating speed of every one-level tractor should be adjusted according to needed throughput, but the criterion that should follow is, the rotating speed of each rear class tractor should be 2 times of rotating speed of its previous stage tractor.Section sample examination, by product standard optimized production process.
4, dry, packing
Through 60-80 ℃ of dicing machine section temperature out and still contain moisture, can also be with the N that fills of higher standard
2drying plant dehumidifies.Section after dehumidifying is packed, and general employing of packing packs to reduce steam contact.But advantage of the present invention is, the water absorption decreased that the resin slicer obtaining absorbs water again, therefore the in the situation that of short term stored, can be in bulk, and can directly supply with next stage processing and without need to being dried again in next stage first being processed, therefore reduce the priming cost such as packing, dry power consumption, also reduced in addition operation steps and time, improved production efficiency.In seal-packed situation, can also standing storage.
5, experiment
Resin slicer to resin slicer of the present invention and employing produced in conventional processes has carried out water suction experiment.The lucky board PA66 resin that conventional P A66 resin adopts PORT OF YIXING Xin Nilong factory to produce.
For two kinds of resins, at 85 ℃, toast 24 hours simultaneously, thoroughly to remove contained moisture, then the resin of baking is respectively got to 1 kilogram of soak at room temperature 24 hours in water, separately respectively get 1 kilogram of soak at room temperature 48 hours in water, drying is weighed, and calculates water-intake rate.
Water-intake rate=(sample kilogram number-1 after soaking) * 100%
In water, soak after 24 hours, the water-intake rate of conventional resins is approximately 1.9%, and resin of the present invention is approximately 0.3%.And in water, soak after 48 hours, the water-intake rate of conventional resins is approximately 2.3%, resin of the present invention is approximately 1.0%.
In conjunction with specific embodiments embodiments of the present invention are described in detail above, but the invention is not restricted to above-mentioned embodiment, in the ken possessing at affiliated technical field those of ordinary skill, can also under the prerequisite that does not depart from aim of the present invention, make a variety of changes.
Claims (6)
1. a novel nano polyamide 66 resin; it is by making hexanodioic acid and hexanediamine monomer carry out polyreaction; the material that polymerization obtains becomes section by Cast Strip step and pelletizing step again and obtains; it is characterized in that; between Cast Strip and pelletizing step, also comprise distraction step; be that material becomes band by Cast Strip step; after band is cooling in water-bath, is drawn to and reaches dicing machine through tractor; wherein said traction is multistage traction, and the rotating speed of every rear one-level tractor is all fast than the rotating speed of previous stage tractor.
2. novel nano polyamide 66 resin as claimed in claim 1, is characterized in that, the progression of described multistage traction is two-stage at least.
3. novel nano polyamide 66 resin as claimed in claim 2, is characterized in that, the progression of described multistage traction is three grades.
4. novel nano polyamide 66 resin as claimed any one in claims 1 to 3, is characterized in that, every after the rotating speed of one-level tractor be all 2 times of rotating speed of its previous stage tractor.
5. novel nano polyamide 66 resin as claimed any one in claims 1 to 3, it is characterized in that, the polymerization of hexanodioic acid and hexanediamine monomer comprises prepolymerization and post polymerization, prepolymerization is to carry out in pre-polymerization reactor, reaction pressure 17.5 bar, 200 ℃ to 255 ℃ of temperature of reaction, post polymerization is to carry out in post-polymerization device, reaction pressure is normal pressure, 238 ℃ of temperature of reaction.
6. novel nano polyamide 66 resin as claimed in claim 5, is characterized in that, between prepolymerization and post polymerization step, also comprises flash distillation step, flash distillation is to carry out in flasher, in flasher, pressure is reduced to normal pressure by 17.5 bar, and temperature of charge is 228 ℃ to 235 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410092830.1A CN103911002A (en) | 2014-03-14 | 2014-03-14 | Novel nanometer polyamide 66 resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410092830.1A CN103911002A (en) | 2014-03-14 | 2014-03-14 | Novel nanometer polyamide 66 resin |
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| CN103911002A true CN103911002A (en) | 2014-07-09 |
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| CN201410092830.1A Pending CN103911002A (en) | 2014-03-14 | 2014-03-14 | Novel nanometer polyamide 66 resin |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401021A (en) * | 2000-02-10 | 2003-03-05 | 吴羽化学工业株式会社 | High strength polyester amide fiber and process for producing the same |
| US20080200640A1 (en) * | 2005-07-06 | 2008-08-21 | Han In-Sik | Aromatic Polyamide Filament And Method Of Manufacturing The Same |
| CN101914818A (en) * | 2010-08-09 | 2010-12-15 | 陈晓美 | Method for manufacturing wear-resistant high-strength polyester fibers |
-
2014
- 2014-03-14 CN CN201410092830.1A patent/CN103911002A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401021A (en) * | 2000-02-10 | 2003-03-05 | 吴羽化学工业株式会社 | High strength polyester amide fiber and process for producing the same |
| US20080200640A1 (en) * | 2005-07-06 | 2008-08-21 | Han In-Sik | Aromatic Polyamide Filament And Method Of Manufacturing The Same |
| CN101914818A (en) * | 2010-08-09 | 2010-12-15 | 陈晓美 | Method for manufacturing wear-resistant high-strength polyester fibers |
Non-Patent Citations (3)
| Title |
|---|
| 刘长明等: "《航空航天纺织材料学》", 30 June 1989, 航空工业出版社 * |
| 宁冲冲 等: "降低尼龙制品吸水率的研究进展", 《塑料科技》 * |
| ***，陈开来等: "《工程塑料手册 材料卷》", 31 October 2004, 机械工业出版社 * |
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Application publication date: 20140709 |