CN102532526B - Continuous polymerization production process of high-viscosity polyamide 6 - Google Patents
Continuous polymerization production process of high-viscosity polyamide 6 Download PDFInfo
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Abstract
The invention relates to a continuous polymerization process of high-viscosity polyamide 6, comprising the following steps of: preparing caprolactam with de-ionized water; pre-heating the mixed caprolactam to a temperature in a range of 220+/-30 DEG C by a pre-heater and conveying the mixed caprolactam into a pre-polymerizer by a feeding pump to carry out hydrolyzed ring opening and pre-polymerization on the caprolactam, wherein the pressure of the ring opening and the pre-polymerization is 2.50+/-0.50 bar, the temperature is in a range of 270+/-15 DEG C and the flow of the caprolactam is 2200+/-500 kg/h; then, discharging materials into a post-polymerizer to carry out post-polymerization to obtain a polymer melt, wherein the pressure of the post-polymerization is 0.35+/-0.25 bar and the temperature is 250+/-30 DEG C; treating the polymer melt by a polymer filter, a casting strip head, an underwater granulator and a vibrating screen to obtain slices; adding the slices into a pre-extracting water pot to carry out pre-extraction with hot water at the temperature in a range of 115+/-10 DEG C; then, conveying the treated slices into an extracting tower and extracting with the hot water at the temperature in a range of 100+/-20 DEG C; conveying the extracted slices into a drying tower and carrying out counter-current drying by nitrogen gas; drying at the temperature in a range of 120+/-30 DEG C and discharging the dried slices into a slice cooling bin; and conveying the cooled slices into a slice storage bin and a slice packaging bin by the nitrogen gas and packaging to obtain the high-viscosity polyamide 6 slices with the relative viscosity of 3.4-4.0.
Description
Technical field
What the present invention relates to is a kind of full-bodied polyamide 6 continuous polymerization production process; Particularly a kind of large scale continuous prod relative viscosity is the technique of 3.4～4.0 high-viscosity polyamide, 6 sections.
Background technology
For the same polymkeric substance, high melt viscosity is the reflection of high molecular weight, and high molecular weight means higher physical and mechanical properties.Therefore, high-viscosity polyamide 6 is being extruded and blowing prepares the aspects such as tubing, bottle, thin slice, film, engineering plastics and high-performance fiber and all has application advantage.In above-mentioned application, high melt viscosity all has favorable influence to the performance of processing characteristics and products obtained therefrom.
The method of producing polyamide 6 belongs to known content already.For example be disclosed in " plastics industry handbook-polymeric amide ", Chemical Industry Press, Beijing, 2001, P54-55.According to these methods, ε-caprolactam generates epsilon-amino caproic acid under the effect of initiator (being generally water), carry out subsequently polycondensation between epsilon-amino caproic acid or carry out addition polymerization with ε-caprolactam and obtain the polymeric amide of high molecular, in the simultaneous acid amides permutoid reaction of polycondensation and addition polymerization:
(1) hydrolysis:
(2) condensation polymerization:
(3) addition polymerization:
(4) acid amides exchange:
In above-mentioned reaction, it is the first step of polymerization process that the ε-caprolactam hydrolysis generates epsilon-amino caproic acid, is also a slowest step of speed of reaction, normally carries out under higher temperature and pressure, in order to improve hydrolysis rate.But in operation subsequently, need decompression and water that the water that adds before with polymerization and polycondensation generate is removed under rare gas element (for example nitrogen) effect, so that the proceeding and the more generation of superpolyamide of polycondensation.By this concept and technique, the viscosity of final polyamide melt depends on the water content of melt.
The feature of ε-caprolactam polymerization is the formation of molecular balance.For example, under the temperature of reaction of 270 ℃, also there are approximately caprolactam monomer and the cyclic oligomer of 10% residual content in polymerisate except polymkeric substance.The existence of these low-molecular weight compounds is unfavorable to the downstream application of polyamide 6, therefore need to its with the water hot extraction stripping or vacuum take off lactamize and remove.
The industrial-scale production of polyamide 6 is normally carried out in the VK pipe, and the technique of international mature mainly contains the Processes and apparatus of the exploitations such as Ji Ma, Yi Wenda-Ka Feixie, noy, A Jiafei.These techniques generally include and the master operations such as hexanolactam melting, hexanolactam charging, pre-polymerization, post polymerization, pelletizing, extraction, drying and packing conveying, and polyreaction was carried out at the temperature of 240～270 ℃ 15～30 hours.China is mainly also to introduce above-mentioned technique for the polymerization technique of polyamide 6 section at present.In general, usually in 2.6～3.0 scopes, the gained polyamide 6 section is mainly used in spinning and low side injection moulding, extrudes etc. with the relative viscosity (m-cresol solution with 1wt% is measured under 25 ℃) of the polyamide 6 section of above-mentioned explained hereafter.
For the needed high viscosity chips of some Application Areas, traditional method is to adopt process for solid state polycondensation, anionic polymerization, chainextender method etc.
Process for solid state polycondensation is at the temperature of 30～80 ℃ below melting point polymer, carry out under the condition of vacuum or rare gas element adverse current.For example, the polyamide 6 section take relative viscosity as 2.8 can bring up to 3.8 in the relative viscosity of carrying out under 185 ℃ cutting into slices after the solid phase aftercondensated in 24 hours as raw material.
The chain extension method is that chainextender is reacted by forcing machine the method that obtains high viscosity chips of extruding together with polyamide 6 section.For example number of patent application is that 99109659.2 employings contain 3 of 2 benzoxazine rings, and it is that chainextender makes high-viscosity polyamide 6 that 4-dihydro-3-replaces benzoxazine.Number of patent application: 200580026598.0 also disclose a kind of method for preparing superpolyamide, it is characterized in that making polymeric amide A) and compd B) react at the temperature of 150～350 ℃, wherein said compd B) discharge isocyanic acid under this temperature of reaction, polymeric amide A used) in amino end group concentration more than or equal to carboxyl end group concentration.Number of patent application: 03127422.6 has reported the two lactan of carbonyl has been joined in the mixture of the polymeric amide of lower molecular weight and polyester, and melting mixing prepares high molecular weight polyesters-amide block copolymers.
Number of patent application: 97107315.5 provide a kind of production technique of technogy of linear high-viscosity nylon 6.This technique adds hexanolactam and anionic catalyst in melting kettle in proportion in the lump, in 130～180 ℃ of temperature, dewater under vacuum, get water content less than the monomer of 300ppm, add again promotor and composite catalyst, then send into continuously and quantitatively prepolymerization reactor, carry out the open loop pre-polymerization, again prepolymer is sent into continuously and quantitatively multi-functional high vacuum four spiro rod reaction machines, carry out successive polymerization, deviate from simultaneously unconverted monomer, polymkeric substance carries out cooling, pelletizing by head continuous Cast Strip, makes technogy of linear high-viscosity nylon 6.
The report of prior art is usually the growth of molecular chain when adding polymerizing catalyst to be beneficial to polycondensation and shortens reaction time in the production of high-viscosity polyamide 6.Catalyzer commonly used in polymerization technology for polyamide 6 can be phosphoric acid ester catalyzer, organosilane ester catalyzer, amino acids catalyzer and hexanolactam saline catalyst.The phosphoric acid ester catalyzer is as phosphoric acid, xylenylphosphate, Tritolyl Phosphate, di(2-ethylhexyl)phosphate propyl benzene ester, phosphorous acid diformazan phenyl ester, tricresyl phosphite etc.; The organosilane ester catalyzer is as propyl hexanoate, utyl hexanoate, butyl propionate, n-octyl propionate, propyl valerate, propyl butyrate etc.; The amino acids catalyzer is as hexosamine, Padil, alanine, aminobutyric acid, aminocaprylic acid, aminoundecanoic acid etc.; The hexanolactam saline catalyst is as hexanolactam sodium salt, hexanolactam sylvite etc.Above-mentioned catalyzer can use separately, can similar mixing use, and also can inhomogeneity mix use, as long as its total consumption is that 0.1%～2% of monomeric charge amount just can reach the technological effect of expection.
Number of patent application: 00113446.9 has reported a kind of production method of high viscosity nylon 6 engineering plastic.It is characterized in that at first 100 parts of raw materials, 3～4 parts of distilled water and 0.1～0.2 part of phosphorylated ligand being made, then displacement feeds intake, hydrolysis, it is 0.8～1.0MPa that still is pressed, temperature of charge is 250 ℃～290 ℃, again-0.5～-kept polymerization 60～180 minutes under 0.9MPa vacuum tightness, last static balance 60～120 minutes makes relative viscosity greater than 5.0 nylon 6 engineering plastic.
The method of above-mentioned employing chainextender and catalyzer is all to carry out in polymeric kettle, polycondensation vessel or screw extrusion press, and it is to be interrupted to carry out that its polymerization is produced, the product relative viscosity heterogeneity that every still is produced, unstable product quality.And during batch production, each discharging always has a little waste material to discharge, and need to clean equipment such as polymeric kettles, and operation is trouble, causes yield to reduce.Chainextender and catalyzer add also that cost further improves.
Number of patent application: 01128620.2 has just carried out some improves, and a kind of batch polymerization, continuous production method of high viscosity nylon 6 engineering plastic is provided.It increases a surge tank on the basis of CN1116339C, equilibrium process is separated from polymerization system, reaches the quantity-produced purpose.Number of patent application: done on this basis further improvement for 01114571.4.It is that 100 parts of raw materials, 3～4 parts of distilled water and 0.1～0.2 part of phosphorylated ligand are made equally, then displacement feeds intake, hydrolysis, hydrolyzer pressure is 0.8～1.0MPa, and temperature of charge is 250 ℃～280 ℃, after release, material is quantitatively squeezed in U-shaped polymerizing pipe by toothed gear pump, again-0.03～-0.09MPa vacuum tightness under the successive polymerization time be 2～3 hours, at last material is inputted in surge tank, static balance 2～3 hours makes relative viscosity and is 4.5～5.5 nylon 6 engineering plastic.But can recognize the still unrealized real continous way production of this technique from the embodiment of this patent, be still and belong to step production, and reaction process also needs with addition of catalyzer; The i.e. reaction raw materials that adds by in batches; after catalyzer carries out preliminary hydrolysis reaction; open again the bleeder valve at the bottom of tank after the hydrolyzer release; squeeze in U-shaped polymerizing pipe repolymerization after reaction for some time by toothed gear pump; stopped in surge tank 2-3 hour, and then opened bleeder valve at the bottom of tank, get with the high volume pump that glues; extrude casting by the casting plate, the empty tank of crossing enters the dicing machine pelletizing.Above-mentionedly unload press operation, add the enforcements descriptions such as surge tank and stops therein and remain the operating method that belongs to intermittence type polymerization.Contrast its number of patent application: 01114571.4 and number of patent application: 00113446.9, number of patent application: the character narrate of 01128620.2 embodiment, also can find out between them similarly, only the description when polymerization is slightly different.
By above industrial analysis as can be known, the production method of at present high-viscosity polyamide 6 sections is that the production technique that to add all with conventional relative viscosity be 2.6～3.0 polyamide 6 section of technical process or additive has more different, therefore its enforcement is difficult to carry out in the plant-scale VK pipe of routine, perhaps, need during enforcement existing conventional equipment is done larger change.The more important thing is, above-mentioned technique all rests on imagination and industrializing implementation stage not yet at present, and none is estimated the inner quality of gained high-viscosity polyamide 6 sections, this will directly have influence on the application in downstream undoubtedly, especially in the application of high-end field, therefore, the industrial applications effect of above technique is also unknown.
Summary of the invention
Deficiency for the 6 section production technologies of high-viscosity polyamide in the past, the object of the invention is to, it is the technique of 3.4～4.0 high-viscosity polyamide, 6 sections that a kind of large scale continuous prod relative viscosity is provided, can realize carrying out in existing 30,000 ton/years of successive polymerization production units, the products obtained therefrom steady quality is reliable.
Technical scheme of the present invention is: comprise following processing step:
(1) preparation of raw material: the solid hexanolactam after melting in the melting tank or directly, future, liquid hexanolactam was squeezed into the hexanolactam tundish together with the deionized water that accounts for caprolactam quality 1～4%, is mixed in tundish and stores;
(2) hydrolysis and front poly-: the hexanolactam that mixes is transported to after preheater is preheating to 220 ± 30 ℃ in pre-polymerization device VK pipe, carry out hexanolactam hydrolysis and pre-polymerization, open loop and front poly-pressure are 2.50 ± 0.50bar, and temperature is 270 ± 15 ℃; The hexanolactam flow is 2200 ± 500kg/h;
(3) poly-after: as to be delivered in post polymerization device VK pipe by the lasting discharge of pre-polymerization device VK pipe and to carry out post polymerization; Pressure 0.35 ± the 0.25bar of post polymerization, temperature is 250 ± 30 ℃;
(4) Cast Strip pelletizing: cut into slices after the polymer melt of (3) step gained passes through polymer filter, end of extruded band, underwater pelletizer, vibratory screening apparatus;
(5) extraction: the pre-extraction of the input of cutting into slices water pot extracts in advance with 115 ± 10 ℃ of hot water, then through the section water slush pump, section is transported in extraction tower, extracts with the hot water of 100 ± 20 ℃;
(6) section that obtains through the extraction of (5) step is transported to drying tower, uses the nitrogen counter current drying, and is dry under 120 ± 30 ℃, and get final product.
For making quality product of the present invention more stable, the present invention particularly preferably is caprolactam flow 1900～2500kg/h in described (1) step.
In described (6) step, the drying temperature on drying tower top is controlled at 125～150 ℃; The drying temperature of bottom is controlled at 125～140 ℃; The flow control of nitrogen is at 11000～11500m
3/ h.
Technique of the present invention has been completed the test of the large-scale industrial production that reaches month on 30,000 ton/years of production lines, can realize that fully in VK pipe large scale continuous prod relative viscosity is 3.4～4.0 high-viscosity polyamide 6 sections, and stable and reliable product quality (the concrete excellent results of implementing can referring to the result of implementation of embodiment 1-3).Advantage of the present invention is, by the adjustment to processing condition, particularly is for the tight control on temperature in caprolactam flow, post polymerization pressure and drying tower and nitrogen flow link; Thereby realize that little change is not done or done to existing 30,000 ton/years of successive polymerization production units just can reach production requirement of the present invention.
Embodiment
Following examples are in order to set forth the present invention; Rather than limitation of the invention further.
Embodiment 1: the solid hexanolactam after melting in the melting tank or directly will squeezed into the hexanolactam tundish from the liquid hexanolactam of hexanolactam producer together with 1～4% deionized water, mix in tundish and store, with fresh feed pump, the hexanolactam that mixes after being preheating to 200 ℃, preheater is transported in pre-polymerization device (VK pipe), carry out hexanolactam hydrolysis and pre-polymerization, open loop and front poly-pressure are 2.50bar, temperature is 275 ℃, the hexanolactam flow is 2000kg/h, with by front poly-discharging pump polymerizer discharge backward; Rear poly-pressure is 0.2bar, and temperature is 245～270 ℃, with using the discharging toothed gear pump with the outside discharge of polymer melt; Cut into slices after polymer melt process polymer filter, end of extruded band, underwater pelletizer, vibratory screening apparatus; The pre-extraction of the input of cutting into slices water pot extracts in advance with 115 ℃ of hot water, then through the section water slush pump, section is transported in extraction tower, hot water with 90 ℃ extracts, section through extraction is transported to drying tower with the section water slush pump again, use the nitrogen counter current drying, dry under 128～142 ℃, nitrogen flow is 11000m
3/ h,, the section of subsequent drying is discharged into the cooling feed bin of section, then is transported to section with nitrogen and stores feed bin and slice packaging feed bin, packs, and namely obtains relative viscosity and be 3.61 high-viscosity polyamide 6 sections.
High-viscosity polyamide 6 section polymerization production units, partly be comprised of hexanolactam fusing system (standby), titanium dioxide compounding system (standby), phenylformic acid compounding system (standby), hexanolactam feed system, pre-polymerization device, post polymerization device, pelletizing system, extraction tower, drying tower and conveying and packaging, whole system adopts the DCS automatization to control.
The polymerization of high-viscosity polyamide 6 from the hexanolactam charging, through pre-polymerization, post polymerization, pelletizing, extraction, drying, is carried out under Full-closed system and nitrogen protection.
According to the specific application area of high-viscosity polyamide 6, can be before polymerization in hexanolactam or adding specific other auxiliary agent or processing material during in the pelletizing of melt Cast Strip after polymerization, required amount changes with additive or auxiliary agent.
These specific other auxiliary agents or processing material are known in those skilled in the art, such as the mixture that comprises molecular weight regulator, antioxidant, anti-light aging agent, lubricant or releasing agent, nucleator, static inhibitor, fire retardant, organic or inorganic tinting material, filler, toughener etc. and above-mentioned additive.
Based on intelligible reason, for satisfying the requirement of implementing process, need the device of producing conventional section is carried out a little change.
Change can comprise the type of heating of polymerizing pipe, changes boiler into by the electrically heated of conventional equipment and heats to obtain rate of heating and more uniform heats faster.
Produce high-viscosity polyamide 6 sections higher to the seal request of polymerizing pipe and system, therefore equipment such as the fondant filter of the higher voltage withstand class of selection and pumps.
Condition and the result of different embodiment are as follows:
The implementation condition of each embodiment of table 1
Table 2 result of implementation
Claims (2)
1. polyamide 6 continuous polymerization production process comprises following processing step:
(1) preparation of raw material: with after the melting of solid hexanolactam or directly, liquid hexanolactam being squeezed into the hexanolactam tundish together with the deionized water that accounts for caprolactam quality 1～4%, mix in tundish and store;
(2) hydrolysis and front poly-: the hexanolactam that mixes is transported to after preheater is preheating to 220 ± 30 ℃ in pre-polymerization device VK pipe, carry out hexanolactam hydrolysis and pre-polymerization, open loop and front poly-pressure are 2.50 ± 0.50bar, and temperature is 270 ± 15 ℃; The hexanolactam flow is 2200 ± 500kg/h;
(3) poly-after: as to be delivered in post polymerization device VK pipe by the lasting discharge of pre-polymerization device VK pipe and to carry out post polymerization; Pressure 0.35 ± the 0.25bar of post polymerization, temperature is 250 ± 30 ℃;
(4) Cast Strip pelletizing: cut into slices after the polymer melt of (3) step gained passes through polymer filter, end of extruded band, underwater pelletizer, vibratory screening apparatus;
(5) extraction: the pre-extraction of the input of cutting into slices water pot extracts in advance with 115 ± 10 ℃ of hot water, then through the section water slush pump, section is transported in extraction tower, extracts with the hot water of 100 ± 20 ℃;
(6) section that obtains through the extraction of (5) step is transported to drying tower, uses the nitrogen counter current drying, and is dry under 120 ± 30 ℃, and get final product;
In described (6) step, the drying temperature on drying tower top is controlled at 125～150 ℃; The drying temperature of bottom is controlled at 125～140 ℃; The flow control of nitrogen is at 11000～11500m
3/ h.
2. production technique according to claim 1, caprolactam flow 1900～2500kg/h in described (1) step.
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| CN103360597B (en) * | 2012-04-10 | 2016-11-16 | 江阴市强力化纤有限公司 | The production method of high uniformity colourity section |
| EP2964690A1 (en) * | 2013-03-07 | 2016-01-13 | Basf Se | Preparation of polyamides by hydrolytic polymerization, postpolymerization and subsequent extraction |
| EP2964691A1 (en) * | 2013-03-07 | 2016-01-13 | Basf Se | Production of polyamides by hydrolytic polymerization and multiple extraction |
| KR101568908B1 (en) * | 2013-12-02 | 2015-11-12 | 지에스칼텍스 주식회사 | Apparatus and method for manufacturing particulate polyamide resin |
| CN104356639B (en) * | 2014-10-17 | 2017-09-05 | 衡水金轮塑业科技股份有限公司 | A kind of nylon 6 resin, its preparation method and its application for packaging material for food |
| CN105504267A (en) * | 2016-02-23 | 2016-04-20 | 江苏弘盛新材料股份有限公司 | Three-phase hydrolytic polymerization process for nylon 6 |
| CN107674198A (en) * | 2016-08-01 | 2018-02-09 | 江苏瑞美福实业有限公司 | A kind of preparation method of high-viscosity polyamide 6 |
| CN110437441A (en) * | 2018-05-04 | 2019-11-12 | 江苏瑞美福实业有限公司 | The preparation method of graphene oxide modified polyamide -6 |
| CN110437440A (en) * | 2018-05-04 | 2019-11-12 | 江苏瑞美福实业有限公司 | The manufacturing method of high heat resistance high mechanical strength polyamide 6 |
| CN108822290A (en) * | 2018-07-30 | 2018-11-16 | 江苏百利达股份有限公司 | A kind of preparation system and method for high viscosity nylon 6 slice |
| CN111100287B (en) * | 2018-10-26 | 2023-01-20 | 中国石油化工股份有限公司 | Method for producing high-viscosity polyamide |
| CN109852046B (en) * | 2018-12-25 | 2021-02-19 | 中国纺织科学研究院有限公司 | Continuous preparation system of functional master batch, functional polyamide production system comprising same and functional polyamide production method |
| CN113336937A (en) * | 2021-07-02 | 2021-09-03 | 中国纺织科学研究院有限公司 | Preparation method of polyamide 6 and polyamide 6 |
| CN114057621B (en) * | 2021-11-29 | 2023-04-21 | 东华大学 | Method for efficiently depolymerizing waste polyamide 6 and application thereof |
| CN117225333B (en) * | 2023-11-10 | 2024-03-15 | 海阳科技股份有限公司 | Production device and process for extraction-free drying-free nylon slices |
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| DE2918828A1 (en) * | 1979-05-10 | 1980-11-20 | Basf Ag | METHOD FOR THE CONTINUOUS PRODUCTION OF POLYCAPROLACTAM AND A DEVICE FOR CARRYING OUT THE METHOD |
| CN1106029A (en) * | 1994-01-24 | 1995-08-02 | 威海市锦纶综丝厂 | Nylon-6 resin for island fibre and its preparation technology |
| NL1010161C2 (en) * | 1998-09-23 | 2000-03-24 | Dsm Nv | Process for the production of polyamide-6 starting èpsilon caprolactam. |
| CN1124302C (en) * | 2000-09-29 | 2003-10-15 | 中国石化集团巴陵石油化工有限责任公司 | Method for producing polyamide 6 section |
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