CN105694093A - Loop opening agent system for caprolactam polymerization extraction concentrate cyclic polymer and preparation method and application thereof - Google Patents
Loop opening agent system for caprolactam polymerization extraction concentrate cyclic polymer and preparation method and application thereof Download PDFInfo
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- CN105694093A CN105694093A CN201610048447.5A CN201610048447A CN105694093A CN 105694093 A CN105694093 A CN 105694093A CN 201610048447 A CN201610048447 A CN 201610048447A CN 105694093 A CN105694093 A CN 105694093A
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000605 extraction Methods 0.000 title claims abstract description 13
- 239000012141 concentrate Substances 0.000 title abstract 4
- 229920005565 cyclic polymer Polymers 0.000 title abstract 2
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 49
- 239000000243 solution Substances 0.000 claims abstract description 39
- 239000000654 additive Substances 0.000 claims abstract description 36
- 230000000996 additive effect Effects 0.000 claims abstract description 36
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims abstract description 18
- 239000007853 buffer solution Substances 0.000 claims abstract description 16
- ALSPKRWQCLSJLV-UHFFFAOYSA-N azanium;acetic acid;acetate Chemical group [NH4+].CC(O)=O.CC([O-])=O ALSPKRWQCLSJLV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000007142 ring opening reaction Methods 0.000 claims description 44
- 239000000284 extract Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 238000005453 pelletization Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 7
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005695 Ammonium acetate Substances 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 229940043376 ammonium acetate Drugs 0.000 claims description 4
- 235000019257 ammonium acetate Nutrition 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 230000006641 stabilisation Effects 0.000 claims description 4
- 238000011105 stabilization Methods 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims description 4
- 239000000872 buffer Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 abstract description 21
- 238000005516 engineering process Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 230000002411 adverse Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 abstract 3
- 235000019801 trisodium phosphate Nutrition 0.000 abstract 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 238000005520 cutting process Methods 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 239000003607 modifier Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 229910000162 sodium phosphate Inorganic materials 0.000 abstract 1
- 239000001488 sodium phosphate Substances 0.000 abstract 1
- 235000011008 sodium phosphates Nutrition 0.000 abstract 1
- 238000000034 method Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 5
- 230000026676 system process Effects 0.000 description 5
- 239000000178 monomer Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 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
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
-
- 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
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
-
- 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
- C08G69/46—Post-polymerisation treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Polyamides (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a loop opening agent system for a caprolactam polymerization extraction concentrate cyclic polymer and a preparation method and an application thereof. The loop opening agent system comprises an additive A and an additive B, wherein the additive A is a Na3PO4 (sodium phosphate) solution, the additive B is an acetic acid - ammonium acetate buffer solution, the mass concentration of the Na3PO4 solution is 6% to 10%, and the pH (potential of hydrogen) value of the acetic acid-ammonium acetate buffer solution is 4 to 7; mixing caprolactam polymerization extraction concentrate, the additive A and the additive B, performing loop opening reaction, and mixing the reacted solution and fresh caprolactam to form the polymerizing raw material; preheating the raw material, mixing with a modifier and a flatting agent, putting into a pre-polymerizing tower to perform pre-polymerizing loop opening reaction, finally polymerizing, cutting grains, centrifuging and flinging, so as to obtain a wet slice. The loop opening agent system has the advantages that the adverse effect on product quality and equipment due to the higher content of cyclic oligomer in the existing direct recycling technology of caprolactam polymerization extraction concentrate is reduced, the product quality is improved, and the production cost is reduced.
Description
[technical field]
The present invention relates to a kind of caprolactam polymerization and extract concentration pendular ring aggressiveness ring opening agent system and its preparation method and application。
[background technology]
When caprolactam polymerization reaction terminates, about containing the monomer of about 10% and oligomer in reactant system, wherein caprolactam about 70%, cyclic oligomer about 25%, wire oligomer about 5%。Through extracting, these monomers and oligomer are dispersed in extraction water。
In these monomers and oligomer, general monomer and linear oligomer have higher reactivity, and cyclic oligomer then reactivity is relatively low, especially cyclic dimer, along with the carrying out of reaction, accumulate gradually, have a strong impact on the quality of section；And cyclic dimer bulk melting point is up to more than 340 DEG C, it is easy to blocking pipeline, cause damage of facilities。
Current extraction water recovery process has catalysis polymerization technology, oligomer cracking repolymerization technology, concentrated solution direct reuse technology, cyclic dimer biodegradation technique etc.。Catalysis polymerization technology is with second BASF AG for representative, extraction concentrated solution and fresh caprolactam are mixed to form solution by them, heating, pressurization, in fixing bed, prepolymerization process is carried out for catalyst with metal-oxide, then through flash distillation, decompression polymerization, in the section obtained, extractable significantly reduces；Concentrated solution cracking repolymerization technology need to through high temperature phosphorous acid depolymerization, dewater in advance, process, cost of equipment and the cost of technology such as rectification higher；And in concentrated solution direct reuse technology, directly participate in being polymerized with the mixing of fresh caprolactam if concentrated solution is unprocessed, owing to product quality and equipment can be adversely affected by the accumulation of cyclic oligomer levels, raw material availability is not high yet simultaneously。
Therefore, finding one and can make cyclic oligomer open loop again at preheating temperature, and reduce material or compound system that cyclic oligomer generates in pre-polymerization process, to improving product quality, to reduce cost significant。
[summary of the invention]
One of the technical problem to be solved in the present invention, it is in that to provide a kind of caprolactam polymerization to extract concentration pendular ring aggressiveness ring opening agent system, current caprolactam polymerization can be reduced and extract the higher adverse effect that product quality and equipment are caused of cyclic oligomer content in concentrated solution direct reuse technique, improve product quality, reduce production cost。
The present invention is realized in one of above-mentioned technical problem:
A kind of caprolactam polymerization extracts concentration pendular ring aggressiveness ring opening agent system, and described ring opening agent system includes additive A and additive B, described additive A be mainly composed of Na3PO4Solution, described additive B be mainly composed of acetic acid-ammonium acetate buffer。
Further, described Na3PO4Concentration of polymer solution is 6%～10%。
Further, described acetic acid-ammonium acetate buffer solution pH is 4～7。
The two of the technical problem to be solved in the present invention, it is in that the preparation method providing a kind of caprolactam polymerization to extract concentration pendular ring aggressiveness ring opening agent system, current caprolactam polymerization can be reduced and extract the higher adverse effect that product quality and equipment are caused of cyclic oligomer content in concentrated solution direct reuse technique, improve product quality, reduce production cost。
The present invention is realized in the twos' of above-mentioned technical problem:
The preparation method that a kind of caprolactam polymerization extracts concentration pendular ring aggressiveness ring opening agent system, the preparation method of described ring opening agent system is as follows:
Step one, in additive A surge-tank add desalted water, and heat to 90 DEG C, weigh the desired amount of Na3PO4Crystal, blanking is to surge-tank, and mechanical agitation is uniform, then with in transport pump to daily groove and be incubated 90 DEG C stand-by；
Step 2, in additive B surge-tank, add desalted water, and heat to 80 DEG C, add ammonium acetate crystal, stirring, and be slowly added to a certain amount of glacial acetic acid, reconcile buffer solution to required pH, be delivered in daily groove after stirring to be incubated 80 DEG C stand-by。
The three of the technical problem to be solved in the present invention, it is in that the application providing a kind of caprolactam polymerization to extract concentration pendular ring aggressiveness ring opening agent system, current caprolactam polymerization can be reduced and extract the higher adverse effect that product quality and equipment are caused of cyclic oligomer content in concentrated solution direct reuse technique, improve product quality, reduce production cost。
The present invention is realized in the threes' of above-mentioned technical problem:
A kind of caprolactam polymerization extracts the application of concentration pendular ring aggressiveness ring opening agent system, and the application of described ring opening agent system is as follows:
By ring opening agent system good for above-mentioned configuration, extract concentrated solution according to caprolactam polymerization, additive A, additive B mass fraction are respectively as follows: the amount of 2%～4%, 2%～4.5%, 91.5%～96% and are delivered to reactor and carry out ring-opening reaction, described reactor center temperature controls at 150 DEG C, and reacted solution is directly polymerized needed raw material with the mixing conduct of fresh caprolactam；Mix in static mixer with modifying agent and the delustering agent of caprolactam polymerization after polymerization needed raw material is preheated to 140 DEG C, subsequently into prepolymerization tower carries out prepolymerization ring-opening reaction, then obtain wet section then through after eventually poly-, pelletizing, centrifuge dripping；
Further, described prepolymerization Open loop temperature is stable at 243 DEG C～250 DEG C, and final polymerization temperature stabilization is at 250 DEG C～255 DEG C, and pelletizing coolant-temperature gage maintains and is about 14 DEG C。
Further, described Na3PO4Concentration of polymer solution is 6%～10%。
Further, described acetic acid-ammonium acetate buffer solution pH is 4～7。
Present invention have the advantage that
Problem to be solved by this invention is to reduce the higher adverse effect that product quality and equipment are caused of cyclic oligomer content in current concentrated solution direct reuse technique。Use open loop system prepared by the present invention that the content of cyclic oligomer can be made to reduce about 52%, obtain extractable in wet section simultaneously after making centrifuge dripping and reduce about 19%, bigger economic benefit can be produced。
Owing to present invention employs buffer solution and Na3PO4For the open loop system of main component, adapt to the change of recovered liquid fluctuation, promote ring aggressiveness open loop, and have the effect of the formation reducing polymerization process medium ring polymers, to improving raw material availability and product quality has positive role, and production cost can be substantially reduced。
[accompanying drawing explanation]
The present invention is further illustrated in conjunction with the embodiments with reference to the accompanying drawings。
Fig. 1 is the technique for applying schematic flow sheet of the inventive method。
[detailed description of the invention]
Refer to shown in Fig. 1, embodiments of the invention are described in detail。
As it is shown in figure 1, a kind of caprolactam polymerization involved in the present invention extracts concentration pendular ring aggressiveness ring opening agent system, it is characterised in that: described ring opening agent system includes additive A and additive B, described additive A be mainly composed of Na3PO4Solution, described additive B be mainly composed of acetic acid-ammonium acetate buffer。Described Na3PO4Concentration of polymer solution is 6%～10%。Described acetic acid-ammonium acetate buffer solution pH is 4～7。
The invention still further relates to the preparation method that above-mentioned a kind of caprolactam polymerization extracts concentration pendular ring aggressiveness ring opening agent system, the preparation method of described ring opening agent system is as follows:
Step one, in additive A surge-tank add desalted water, and heat to 90 DEG C, weigh the desired amount of Na3PO4Crystal, blanking is to surge-tank, and mechanical agitation is uniform, then with in transport pump to daily groove and be incubated 90 DEG C stand-by；
Step 2, in additive B surge-tank, add desalted water, and heat to 80 DEG C, add ammonium acetate crystal, stirring, and be slowly added to a certain amount of glacial acetic acid, reconcile buffer solution to required pH, be delivered in daily groove after stirring to be incubated 80 DEG C stand-by。
The present invention further relates to above-mentioned a kind of caprolactam polymerization and extracts the application of concentration pendular ring aggressiveness ring opening agent system, and the application of described ring opening agent system is as follows:
By ring opening agent system good for above-mentioned configuration, it is delivered to reactor according to the mass ratio of caprolactam polymerization extraction concentrated solution/additive A/additive B=100/2.5/2.5 and carries out ring-opening reaction, described reactor center temperature controls at 150 DEG C, and reacted solution is directly polymerized needed raw material with the mixing conduct of fresh caprolactam；Mix in static mixer with modifying agent and the delustering agent of caprolactam polymerization after polymerization needed raw material is preheated to 140 DEG C, subsequently into prepolymerization tower carries out prepolymerization ring-opening reaction, then obtain wet section then through after eventually poly-, pelletizing, centrifuge dripping。
Described prepolymerization Open loop temperature is stable at 243 DEG C～250 DEG C, and final polymerization temperature stabilization is at 250 DEG C～255 DEG C, and pelletizing coolant-temperature gage maintains and is about 14 DEG C。
Described ring opening agent system is applied to caprolactam and returns the extraction concentrated solution of the recovered liquid after polyreaction, is extracted by caprolactam polymerization after concentrated solution carries out open loop, rejoins fresh caprolactam carrying out new one and takes turns polyreaction。
The present invention is further elaborated by the examples below。
Embodiment 1
Additive A surge-tank adds a certain amount of desalted water, and heats to 90 DEG C, weigh the Na of desalted water quality 7%3PO4Crystal, blanking to surge-tank, mechanical agitation 1h, then with transport pump in daily groove and be incubated 90 DEG C stand-by。
Additive B surge-tank adds a certain amount of desalted water, and heats to 80 DEG C, add a certain amount of ammonium acetate crystal, open stirring, and be slowly added to glacial acetic acid, reconcile buffer solution to pH=7, be delivered in daily groove after stirring to be incubated 80 DEG C stand-by。
By ring opening agent system good for above-mentioned configuration, it is delivered to tubular reactor according to the mass ratio of caprolactam polymerization extraction concentrated solution/additive A/additive B=100/2.5/2.5 and carries out ring-opening reaction, tubular reactor central temperature controls at 150 DEG C, solution after ring-opening reaction is directly polymerized needed raw material with the mixing conduct of fresh caprolactam, modifying agent and delustering agent with caprolactam polymerization after this raw material preheating to 140 DEG C is mixed in static mixer, react subsequently in prepolymerization tower, then obtain wet section then through after eventually poly-, pelletizing, centrifuge dripping。Prepolymerization Open loop temperature is stable at 243 DEG C～250 DEG C, and pressure stability is at about 1500mbar；Final polymerization VK pipe temperature stabilization is at 250 DEG C～255 DEG C, and pressure stability is at 1296mbara, and pelletizing water enters coolant-temperature gage maintenance and is about 14 DEG C。Idiographic flow is shown in Fig. 1.
After testing, in the concentrated solution after this open loop system processes, caprolactam about 71.05%, cyclic oligomer about 13.25%, wire oligomer about 15.70%。
Embodiment 2
Preparation method and polymerization technique according to embodiment 1 are operated, and institute is the difference is that Na3PO4Mass concentration be 8.5%, the pH of acetic acid-ammonium acetate buffer solution is 6.5。
After testing, in the concentrated solution after this compound open loop system processes, caprolactam about 71.10%, cyclic oligomer about 12.75%, wire oligomer about 16.15%。
Embodiment 3
Preparation method and polymerization technique according to embodiment 1 are operated, and institute is the difference is that Na3PO4Mass concentration be 8.5%, the pH of acetic acid-ammonium acetate buffer solution is 5.5。
After testing, in the concentrated solution after this compound open loop system processes, caprolactam about 71.15%, cyclic oligomer about 12.25%, wire oligomer about 16.60%。
Embodiment 4
Preparation method and polymerization technique according to embodiment 1 are operated, and institute is the difference is that Na3PO4Mass concentration be 7.5%, the pH of acetic acid-ammonium acetate buffer solution is 5.5。
After testing, in the concentrated solution after this compound open loop system processes, caprolactam about 71.17%, cyclic oligomer about 12.75%, wire oligomer about 16.83%。
Embodiment 5
Preparation method and polymerization technique according to embodiment 1 are operated, and institute is respectively as follows: 3%, 2%, 95% the difference is that caprolactam polymerization extraction concentrated solution, additive A, additive B mass fraction。
After testing, in the concentrated solution after this compound system processes, caprolactam about 71.23%, cyclic oligomer about 13.15%, wire oligomer about 15.62%。
Problem to be solved by this invention is to reduce the higher adverse effect that product quality and equipment are caused of cyclic oligomer content in current concentrated solution direct reuse technique。Use open loop system prepared by the present invention that the content of cyclic oligomer can be made to reduce about 52%, obtain extractable in wet section simultaneously after making centrifuge dripping and reduce about 19%, bigger economic benefit can be produced。
Owing to present invention employs buffer solution and Na3PO4For the open loop system of main component, adapt to the change of recovered liquid fluctuation, promote ring aggressiveness open loop, and have the effect of the formation reducing polymerization process medium ring polymers, to improving raw material availability and product quality has positive role, and production cost can be substantially reduced。
Although the foregoing describing the specific embodiment of the present invention; but those familiar with the art is to be understood that; we are merely exemplary described specific embodiment; rather than for the restriction to the scope of the present invention; those of ordinary skill in the art, in the equivalent modification made according to the spirit of the present invention and change, should be encompassed in the scope of the claimed protection of the present invention。
Claims (9)
1. a caprolactam polymerization extracts concentration pendular ring aggressiveness ring opening agent system, it is characterised in that: described ring opening agent system includes additive A and additive B, described additive A be mainly composed of Na3PO4Solution, described additive B be mainly composed of acetic acid-ammonium acetate buffer。
2. a kind of caprolactam polymerization according to claim 1 extracts concentration pendular ring aggressiveness ring opening agent system, it is characterised in that: described Na3PO4Concentration of polymer solution is 6%～10%。
3. a kind of caprolactam polymerization according to claim 1 extracts concentration pendular ring aggressiveness ring opening agent system, it is characterised in that: described acetic acid-ammonium acetate buffer solution pH is 4～7。
4. the preparation method that a kind of caprolactam polymerization according to any one of claims 1 to 3 extracts concentration pendular ring aggressiveness ring opening agent system, it is characterised in that: the preparation method of described ring opening agent system is as follows:
Step one, in additive A surge-tank add desalted water, and heat to 90 DEG C, weigh the desired amount of Na3PO4Crystal, blanking is to surge-tank, and mechanical agitation is uniform, then with in transport pump to daily groove and be incubated 90 DEG C stand-by；
Step 2, in additive B surge-tank, add desalted water, and heat to 80 DEG C, add ammonium acetate crystal, stirring, and be slowly added to a certain amount of glacial acetic acid, reconcile buffer solution to required pH, be delivered in daily groove after stirring to be incubated 80 DEG C stand-by。
5. a caprolactam polymerization extracts the application concentrating pendular ring aggressiveness ring opening agent system, it is characterized in that: described ring opening agent system is that a kind of caprolactam polymerization described in claim 1 extracts concentration pendular ring aggressiveness ring opening agent system, and the application of described ring opening agent system is as follows:
By ring opening agent system good for above-mentioned configuration, it is delivered to reactor according to certain mass than after mixing with caprolactam extraction concentrated solution and carries out ring-opening reaction, described reactor center temperature controls at 150 DEG C, and reacted solution is directly polymerized needed raw material with the mixing conduct of fresh caprolactam；Mix in static mixer with modifying agent and the delustering agent of caprolactam polymerization after polymerization needed raw material is preheated to 140 DEG C, subsequently into prepolymerization tower carries out prepolymerization ring-opening reaction, then obtain wet section then through after eventually poly-, pelletizing, centrifuge dripping。
6. a kind of caprolactam polymerization according to claim 5 extracts the application of concentration pendular ring aggressiveness ring opening agent system, it is characterised in that: caprolactam polymerization extraction concentrated solution, additive A, additive B mass fraction are respectively as follows: 2%～4%, 2%～4.5%, 91.5%～96%。
7. a kind of caprolactam polymerization according to claim 5 extracts the application of concentration pendular ring aggressiveness ring opening agent system, it is characterized in that: described prepolymerization Open loop temperature is stable at 243 DEG C～250 DEG C, final polymerization temperature stabilization is at 250 DEG C～255 DEG C, and pelletizing coolant-temperature gage maintains and is about 14 DEG C。
8. a kind of caprolactam polymerization according to claim 5 extracts the application of concentration pendular ring aggressiveness ring opening agent system, it is characterised in that: described Na3PO4Concentration of polymer solution is 6%～10%。
9. a kind of caprolactam polymerization according to claim 5 extracts the application of concentration pendular ring aggressiveness ring opening agent system, it is characterised in that: described acetic acid-ammonium acetate buffer solution pH is 4～7。
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| CN114426769A (en) * | 2020-09-22 | 2022-05-03 | 中国石油化工股份有限公司 | Application of caprolactam recovered in process of preparing nylon 6 by hydrolyzing, ring-opening and polymerizing caprolactam and cyclic oligomer mixture thereof |
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| CN1345889A (en) * | 2000-09-29 | 2002-04-24 | 巴陵石化岳阳石油化工总厂 | Method for producing polyamide 6 section |
| CN103159951A (en) * | 2011-12-13 | 2013-06-19 | 上海杰事杰新材料(集团)股份有限公司 | Method and apparatus for preparing high temperature nylon |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114426769A (en) * | 2020-09-22 | 2022-05-03 | 中国石油化工股份有限公司 | Application of caprolactam recovered in process of preparing nylon 6 by hydrolyzing, ring-opening and polymerizing caprolactam and cyclic oligomer mixture thereof |
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