CN1408745A - Intermittent polymerization and continuous production method of ultra-high viscosity nylon 6 engineering plastic - Google Patents
Intermittent polymerization and continuous production method of ultra-high viscosity nylon 6 engineering plastic Download PDFInfo
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- CN1408745A CN1408745A CN 01128620 CN01128620A CN1408745A CN 1408745 A CN1408745 A CN 1408745A CN 01128620 CN01128620 CN 01128620 CN 01128620 A CN01128620 A CN 01128620A CN 1408745 A CN1408745 A CN 1408745A
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- China
- Prior art keywords
- still
- polymerization
- hexanolactam
- engineering plastic
- raw material
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 14
- 229920002292 Nylon 6 Polymers 0.000 title claims abstract description 11
- 229920006351 engineering plastic Polymers 0.000 title claims abstract description 11
- 238000010924 continuous production Methods 0.000 title claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 34
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 238000007599 discharging Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 238000006073 displacement reaction Methods 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims 1
- 238000003825 pressing Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000003513 alkali Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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- Polyamides (AREA)
Abstract
The invention relates to a discontinuous polymerization and continuous production method of ultra-high viscosity nylon 6 engineering plastic, which is characterized by comprising the following steps: firstly, preparing an auxiliary agent, feeding and replacing, heating to melt, hydrolyzing and opening a ring, wherein the kettle pressure is 0.8-1.0 MPa, the material temperature is 250-290 ℃, the pressure in the kettle (to 0MPa) is removed, the polymerization is maintained for 60-180 minutes under vacuum, then, the material is pressed into a balance tank, the pressure in the tank is 0.3-0.5 MPa, and the quantitative and continuous discharging is carried out from the bottom at the material temperature of 265-275 ℃ to obtain the nylon 6 engineering plastic with the relative viscosity of more than 5.0. The method is suitable for producing the ultra-high viscosity nylon 6 engineering plastic by using caprolactam and the low polymer thereof.
Description
Technical field:
The present invention relates to a kind of batch polymerization, continuous production method of high viscosity nylon 6 engineering plastic.
Background technology:
In batch polymerization, the interruption production method of application number for high viscosity nylon 6 engineering plastic has been described in detail in detail in the application for a patent for invention of " 01106918X ", though this method can be brought up to the relative viscosity of polymkeric substance more than 5.0, but its defective is also fairly obvious, mainly shows following two aspects:
1, owing to being interrupted, polymerization production carries out, so product relative viscosity heterogeneity, unstable product quality that every still is produced.
2, owing to always have a little waste material to discharge during each discharging, so yield is lower, cost is operated cumbersome than higher.
Summary of the invention:
The batch polymerization, the continuous production method that the purpose of this invention is to provide a kind of high viscosity nylon 6 engineering plastic.
The present invention realizes by following steps:
1, prescription:
(1) by raw material: distilled water: 85% phosphoric acid: sodium hydroxide=100: 3～5: 0.15～0.25: 0.08～0.13 (weight ratio) and every still charging capacity accurately take by weighing various auxiliary agents.
(2) add distilled water, the sodium hydroxide that takes by weighing in the container successively, add 85% the phosphoric acid that takes by weighing after the cooling again.
(3), and contain alkali (content of alkali must not be greater than 1.5%, otherwise quality product is bad) if raw material is a hexanolactam oligomer, then need be with acid (hydrochloric acid, sulfuric acid, preferably phosphoric acid) with the alkali PH=7 that neutralizes, at this moment prescription is calculated as follows:
Raw material: distilled water: 85% phosphoric acid=100: 3～5: 0.03～0.06 (the used acid of neutralization bases is not being calculated within the prescription).
2, the displacement that feeds intake:
At first ready raw material is all dropped in the molten-bath, pour the auxiliary agent for preparing by the prescription requirement into, fasten feeding cover, with purity 99.9% nitrogen pressurising 0.2Mpa, open vent valve and make the still pressure drop, fasten vent valve, the beginning heat temperature raising to 0Mpa (repeating again to do once).Then
3, intensification fusing
When material all melts the back (is 60 ℃～80 ℃ when raw material is hexanolactam, be disconnected ℃ of 140 ℃～product when raw material is hexanolactam oligomer) start and stir, when temperature of charge rises to 170 ℃～180 ℃, suspend and stir, allow static 10～15 minutes of material, open vent valve earlier the still internal pressure is reduced to 0Mpa, fasten vent valve, open blow-off valve at the bottom of the still again, the mechanical impurity that is deposited at the bottom of the still is emitted, fasten blow-off valve, (if raw material be not hexanolactam oligomer then need not discharge impurities), open still then at the bottom of by-pass valve material is entered in the polymeric kettle of insulation (250 ℃～280 ℃).Then
4, hydrolysis:
After material enters in the polymeric kettle, under agitation continue heat temperature raising, when temperature of charge rises to 260 ℃～280 ℃ (by vent valve the still internal pressure being controlled between 0.6～1.0Mpa) in temperature-rise period, stop extraneous heating, open vent valve the still internal pressure is unloaded to 0Mpa.Then
5, vacuum polymerization:
After still is pressed and is unsnatched, under agitation begin to vacuumize, under the situation that the material of guaranteeing to float is not rushed to summit, vacuum tightness big as much as possible (requirement reaches-0.07～-0.09Mpa), material liquid surface high as much as possible (from about the about 400mm～450mm in still top), the vacuum polymerization time generally was controlled at 2～3 hours, and in vacuum, the material core temperature requires to be no more than 280 ℃.Then
6, balance cooling discharge:
After the material polymerization is good, with purity is that 99.9% nitrogen is pressurized to 0.5～0.8Mpa, material is pressed into surge tank through bleeder valve, and (this moment, the temperature of surge tank was 265 ℃～275 ℃, pressure is 0.3～0.5Mpa, jar interior half jar of material jar continuous discharging in the end in addition this moment) in, mix, at this moment carry out the adjusting of molecular weight between sized molecules with former material, it is progressively reached unanimity, under new state, set up a new running balance.Two vacuum polymerization stills replace independent operation separately, the material that polymerization is good is all squeezed in the surge tank, and material residence time in surge tank is controlled by discharging speed, is 2～3 hours, the tank bottoms material is extruded casting through bleeder valve, high sticking pump or screw extrusion press, carries out pelletizing after going into the tank cooling and shaping.
7, used starting material of the present invention and specification are as follows:
(1) raw material
Be applicable to that hexanolactam, hexanolactam oligomer or both are by the mixture of different ratios (if contain alkali in the hexanolactam oligomer, requiring total content＜1.5% of alkali in the material that every still drops into).
(2) auxiliary agent
Water: distilled water
85% phosphoric acid: analytical pure
Sodium hydroxide: analytical pure
Neutralization is with sour: available hydrochloric acid (analytical pure), sulfuric acid (analytical pure), the most handy phosphoric acid (analytical pure).
Positively effect of the present invention is:
(1) on the basis of former batch polymerization, increase a surge tank, equilibrium process is separated from polymerization system, reach the quantity-produced purpose.
(2) compare with former interruption method, increased yield, reduced cost, improved output.
(3) relative viscosity of polymkeric substance can reach more than 5.0 equally, and the relative viscosity homogeneous of product, steady quality.
(4) available hexanolactam oligomer is produced, and has reduced the pollution to environment, so this achievement belongs to environmental protection project.
(5) because the relative viscosity of polymkeric substance is very high, every good physical and chemical properties of product, therefore purposes is very extensive, it not only plays crucial effect in departments such as machinery, electronics, electrical equipment, weavings, especially be indispensable at extraordinary industrial sectors such as middle and high shelves automobile, shipbuilding, rail transportation system, military project, aerospace, even play irreplaceable effect.
Embodiment:
Embodiment 1, adds the 123kg hexanolactam in the molten-bath of 200 liters, adopts following prescription as calculated:
Distilled water: 5kg
85%H
3PO
4: 0.23kg (analytical pure)
NaoH:0.12kg (analytical pure)
At first add 5kg distilled water, add 0.12kg sodium hydroxide again, after the cooling, add 0.23kg phosphoric acid at last, nitrogen replacement post-heating with 99.9% heats up, when temperature of charge rises to 80 ℃, start and stir, when temperature of charge rises to 180 ℃, stopped to stir material 15 minutes, this moment still internal pressure 0.25Mpa, open by-pass valve at the bottom of the still, material is pressed in the polymeric kettle of insulation (250 ℃), fasten by-pass valve (molten-bath is reformulated reinforced again), continue to be warming up to 260 ℃, in temperature-rise period by vent valve the hydrolysis pressure-controlling between 0.8-0.9Mpa, under this pressure, when temperature of charge rose to 270 ℃, hydrolysis was complete, stop heating, the beginning release, pressure unloads to 0Mpa after 30 minutes, opens vacuum pump immediately and vacuumizes 2.5 hours, vacuum tightness reaches-0.09Mpa, temperature of charge rises to 283 ℃, stop to vacuumize, material is pressed in the surge tank of insulation (265 ℃), also have half jar of material just with the continuous discharging of the speed of per minute 1kg in this moment jar with the nitrogen of purity 99.9%, extrude casting through sticking pump of height or screw extrusion press, go into pelletizing behind the tank cooling and shaping.Through sampling analysis, the relative viscosity of polymkeric substance is 5.316, is 5.60 after the extraction.
Embodiment 2:
Add hexanolactam oligomer 123Kg in the molten-bath of 200 liters, through the on-site sampling analysis, the hexanolactam low-grade polymer contains alkali 0.42%, adopts following prescription as calculated:
Distilled water: 5kg
85% phosphoric acid: 0.58kg (comprising that neutralization is with sour)
At first ready material auxiliary agent is dropped in the molten-bath, fasten charge cavity purity and be 99.9% nitrogen replacement 2 times, be warming up to 160 ℃ then, begin to stir, when temperature of charge rises to 180 ℃, stopped to stir 10 minutes, open the discharge of still bottom valve earlier and be deposited on the low foreign material of still, fasten blow-off valve, open still at the bottom of by-pass valve material is pressed in the polymeric kettle, operating and control with embodiment 1 later on is 4.72 through the relative viscosity of sampling analysis polymkeric substance.
Claims (3)
1, the batch polymerization of high viscosity nylon 6 engineering plastic, continuous production method is characterized in that comprising following process:
(1) formulation aid:
By raw material: distilled water: 85% phosphoric acid: sodium hydroxide=100: 3～5: 0.15～0.25: 0.06～0.13 (weight ratio) and every still charging capacity accurately take by weighing the amount of various auxiliary agents,
In a container, add distilled water, the sodium hydroxide take by weighing successively, wait to be chilled to and add 85% the phosphoric acid that takes by weighing after the room temperature again, then
(2) displacement that feeds intake:
Add in the molten-bath with raw material with by the ready auxiliary agent of proportioning, with purity is that 99.9% nitrogen replacement post-heating heats up, and treats that material all melts (hexanolactam is 60 ℃～80 ℃, and hexanolactam oligomer is 140 ℃～170 ℃), after enter in the polymeric kettle of insulation, then
(3) intensification fusing
When material all melts the back (is 60 ℃～80 ℃ when raw material is hexanolactam, be 140 ℃～170 ℃ when raw material is hexanolactam oligomer) start and stir, when temperature of charge rises to 170 ℃～180 ℃, suspend and stir, allow static 10～15 minutes of material, open vent valve earlier the still internal pressure is reduced to 0Mpa, fasten vent valve, open blow-off valve at the bottom of the still again, the mechanical impurity that is deposited at the bottom of the still is emitted, fasten blow-off valve, (if raw material be not hexanolactam oligomer then need not discharge impurities), by-pass valve enters material in the polymeric kettle of insulation (250 ℃～280 ℃), then at the bottom of opening still then
(4) hydrolysis:
Under agitation continue heat temperature raising, controlled polymerization symbol internal pressure is 0.8～1.0Mpa, when temperature of charge rises to 250 ℃～290 ℃, stops heating, slowly lays down still internal pressure (to 0Mpa), then
(5) vacuum polymerization:
Still begins to vacuumize after pressing and unsnatching, and vacuum tightness is-0.05～-0.09Mpa, temperature of charge remains on 250 ℃～290 ℃, and the vacuum polymerization time is 60～180 minutes, then
(6) balance cooling discharge:
Stop after the material polymerization is good stirring, it with purity 99.9% nitrogen pressurising, eliminate vacuum, and be pressurized to 0.5～0.8Mpa, opening the still bottom valve is pressed into material in the surge tank of insulation (265 ℃～275 ℃), (a jar internal pressure is 0.3～0.5Mpa), and controlling the residence time of material in jar with the discharging speed of tank bottoms material is 2～3 hours, keeps half jar of material to realize serialization production in jar at least.
2, method according to claim 1 is characterized in that being applicable to that with hexanolactam, hexanolactam oligomer and the two mixture by different ratios be the raw material production high viscosity nylon 6 engineering plastic.
3, method according to claim 1 is characterized in that adding certain proportion sodium hydroxide in batching, is applicable to interruption method and continuous processing production high viscosity nylon 6 engineering plastic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011286202A CN1155644C (en) | 2001-09-26 | 2001-09-26 | Intermittent polymerization and continuous production method of ultra-high viscosity nylon 6 engineering plastic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011286202A CN1155644C (en) | 2001-09-26 | 2001-09-26 | Intermittent polymerization and continuous production method of ultra-high viscosity nylon 6 engineering plastic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1408745A true CN1408745A (en) | 2003-04-09 |
| CN1155644C CN1155644C (en) | 2004-06-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011286202A Expired - Fee Related CN1155644C (en) | 2001-09-26 | 2001-09-26 | Intermittent polymerization and continuous production method of ultra-high viscosity nylon 6 engineering plastic |
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| Country | Link |
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| CN (1) | CN1155644C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460445C (en) * | 2003-04-18 | 2009-02-11 | 上海杰事杰新材料股份有限公司 | Touthness nylon, its preparation method and use |
| CN102775600A (en) * | 2012-08-01 | 2012-11-14 | 武汉森大科技研究发展中心 | Polymerization manufacturing technique and device for polyamide |
-
2001
- 2001-09-26 CN CNB011286202A patent/CN1155644C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460445C (en) * | 2003-04-18 | 2009-02-11 | 上海杰事杰新材料股份有限公司 | Touthness nylon, its preparation method and use |
| CN102775600A (en) * | 2012-08-01 | 2012-11-14 | 武汉森大科技研究发展中心 | Polymerization manufacturing technique and device for polyamide |
| CN102775600B (en) * | 2012-08-01 | 2014-02-26 | 武汉森大科技研究发展中心 | Polymerization manufacturing technique and device for polyamide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1155644C (en) | 2004-06-30 |
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