CN1153232A - Method for producing nylon 6 by using caprolactam oligomer residue - Google Patents
Method for producing nylon 6 by using caprolactam oligomer residue Download PDFInfo
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- CN1153232A CN1153232A CN 96118401 CN96118401A CN1153232A CN 1153232 A CN1153232 A CN 1153232A CN 96118401 CN96118401 CN 96118401 CN 96118401 A CN96118401 A CN 96118401A CN 1153232 A CN1153232 A CN 1153232A
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- nylon
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229920002292 Nylon 6 Polymers 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 9
- -1 sodium (potassium) caprolactam salts Chemical class 0.000 claims abstract description 7
- 150000003014 phosphoric acid esters Chemical class 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- MOMGDEWWZBKDDR-UHFFFAOYSA-M sodium;3,4,5,6-tetrahydro-2h-azepin-7-olate Chemical compound [Na+].O=C1CCCCC[N-]1 MOMGDEWWZBKDDR-UHFFFAOYSA-M 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000005453 pelletization Methods 0.000 claims description 2
- 239000002685 polymerization catalyst Substances 0.000 claims description 2
- 150000003109 potassium Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 6
- 229920006351 engineering plastic Polymers 0.000 abstract description 4
- 150000001413 amino acids Chemical class 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 150000002895 organic esters Chemical class 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 6
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 5
- 239000004677 Nylon Substances 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 5
- 235000004279 alanine Nutrition 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- 239000001103 potassium chloride Substances 0.000 description 5
- 235000011164 potassium chloride Nutrition 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 2
- HASUJDLTAYUWCO-UHFFFAOYSA-N 2-aminoundecanoic acid Chemical compound CCCCCCCCCC(N)C(O)=O HASUJDLTAYUWCO-UHFFFAOYSA-N 0.000 description 2
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 2
- RPRPDTXKGSIXMD-UHFFFAOYSA-N Caproic acid n-butyl ester Natural products CCCCCC(=O)OCCCC RPRPDTXKGSIXMD-UHFFFAOYSA-N 0.000 description 2
- CEQGYPPMTKWBIU-UHFFFAOYSA-N Octyl propanoate Chemical compound CCCCCCCCOC(=O)CC CEQGYPPMTKWBIU-UHFFFAOYSA-N 0.000 description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 2
- ROJKPKOYARNFNB-UHFFFAOYSA-N Propyl pentanoate Chemical compound CCCCC(=O)OCCC ROJKPKOYARNFNB-UHFFFAOYSA-N 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 229940124277 aminobutyric acid Drugs 0.000 description 2
- 229960002684 aminocaproic acid Drugs 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AKVBCGQVQXPRLD-UHFFFAOYSA-N 2-aminooctanoic acid Chemical compound CCCCCCC(N)C(O)=O AKVBCGQVQXPRLD-UHFFFAOYSA-N 0.000 description 1
- HWXRWNDOEKHFTL-UHFFFAOYSA-M 2-propylhexanoate Chemical compound CCCCC(C([O-])=O)CCC HWXRWNDOEKHFTL-UHFFFAOYSA-M 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 description 1
- VCAFTIGPOYBOIC-UHFFFAOYSA-N phenyl dihydrogen phosphite Chemical class OP(O)OC1=CC=CC=C1 VCAFTIGPOYBOIC-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- HTUIWRWYYVBCFT-UHFFFAOYSA-N propyl hexanoate Chemical compound CCCCCC(=O)OCCC HTUIWRWYYVBCFT-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Polyamides (AREA)
Abstract
The invention discloses a method for preparing nylon 6 by using caprolactam residues, which comprises the steps of adopting one or more compounds of phosphate esters, organic esters, amino acids and sodium (potassium) caprolactam salts as a catalyst, carrying out ring-opening polymerization at the temperature of 220-250 ℃, and carrying out vacuum polymerization at the temperature of 260-285 ℃ and under the pressure of-0.10 MPa of residual pressure to obtain a nylon 6 product with the relative viscosity of 2.5-3.0. The invention is suitable for producing high viscosity nylon 6 products by polymerization of different alkali contents, especially high alkali residues, the product performance meets the requirements of engineering plastics, and the invention can be used for preparing various engineering plastic products.
Description
The present invention relates to utilize hexanolactam oligomer residue to make the method for nylon 6, especially in the process with caprolactam Joint Production nylon 6, the oligomer residue that extraction process reclaims, or in the caprolactam production process, the high-boiling components residue of refining 2 sections discharges adopts catalyst polymerization to produce the method for nylon 6 engineering plastic.
As everyone knows, produce in the nylon 6 slice process at the caprolactam hydrolytic polymerization, the nylon 6 that comes out from polymerization pipe contains monomer and oligomer about 10%, must it be separated through extraction.Extraction water can be used as polymer raw through distillation recovery section monomer, and the high-boiling components at the bottom of the tower is the 2%-3% that the oligomer residue amount accounts for nylon output, and its composition is roughly as follows:
Table 1 oligomer residue is formed
| Form | Caprolactam | Dimer | Tripolymer | The tetramer | Pentamer | Other |
| Content (%) | ????53.4 | ??16.0 | ??8.6 | ??12.0 | ???7.8 | ??2.2 |
In the prior art, oligomer residue is not fully utilized, and environment is caused very big pollution.The disclosed technology of CN1085918A is to be main raw material with nylon 6 oligomer, produces terpolymer by catalytic polymerization and makes modification of nylon, and its oligomer rate of recovery is on the low side, and prepared modification of nylon physical and chemical performance is also undesirable.In addition, also have the people that caprolactam is reclaimed in the oligomer cracking, the rate of recovery is about 60%, and this method is that oligomer at high temperature is degraded into caprolactam, and the rate of recovery is low, and about 40% waste residue can't utilize, and its energy consumption is high and reclaim poor product quality.According to investigations, the someone adopts Hydrolyze method that oligomer is directly used in polymerization and produces nylon 6 slice recently, content of monomer is more than 60% in this method requirement oligomer residue, and polymerization time reaches 25～32 hours, polymerization temperature is up to 290 ℃, the product relative viscosity is but below 2.5, and this method is not suitable for handling high-alkali residue especially.
The objective of the invention is to: provide a kind of reaction time short, polymerization temperature is lower, and is applicable to the oligomer of different alkalescence, especially high-alkali oligomer residue is made the method for relative viscosity at the high molecular weight nylon more than 2.5 6.
In order to reach purpose of the present invention, adopted following technical scheme: adopt catalyst polymerization, polymerization catalyst is respectively with general formula
Phosphoric acid ester (R
1, R
2, R
3Can distinguish or simultaneously for H C
6H
5, C
6H
4H
3, (CH
2)
nCH
3, the positive integer of n=1～6),
Organosilane ester (positive integer of m=1～4, another positive integer of n=2～6), NH
2(CH
2)
nOne or more or its mixture of COOH amino acids (positive integers of n=1～10) and sodium caprolactam (or potassium) salt, course of reaction mainly comprises: (1), 100 parts of (weight) oligomer residues and 0.1～2 part of (weight) catalyst are added in the still, behind the heating and melting, ring-opening polymerization is 2～4 hours under 220～250 ℃ temperature; (2), under 260～285 ℃ the temperature, overbottom pressure is under the pressure of-0.10～0.10MPa, vacuum polymerization reaction 2.5～4 hours obtains relative viscosity and is 2.5～3.0 nylon 6 products.
Catalyst of the present invention can be monobasic, binary or ternary.The phosphoric acid ester catalyst is as phenyl-phosphite, triphenyl phosphate, phosphorous acid diphenyl ester, xylenylphosphate, di(2-ethylhexyl)phosphate propyl ester and phosphoric acid etc.; The organosilane ester catalyst is as: propyl hexanoate, butyl propionate, propyl valerate, octyl propionate, propyl butyrate, and butyl hexanoate etc.; The amino acids catalyst is as alanine, aminobutyric acid, aminoundecanoic acid, aminocaproic acid, amion acetic acid and aminocaprylic acid etc.; The caprolactam salt catalyst can be used hexanolactam sylvite (or sodium salt).Above-mentioned catalyst can use separately, can similar mixing use, and also can inhomogeneity mix use, as long as its total consumption within aforesaid scope, all can reach the technological effect of expection.
In implementing process of the present invention, the difference in the ring-opening polymerization stage because of the residue moisture, generally between 0.5～1.5MPa, pressure can not be too high, otherwise equipment breakdown may occur for the pressure in the polymeric kettle.After ring-opening polymerization is finished, begin to drive and press and vacuumize, steam in the still and the unreacted monomer of part are extracted, to promote increasing of polymerization later stage strand, this stage polymerization temperature should be controlled at 260～285 ℃, promptly be higher than the viscosity of the temperature of ring-opening polymerization, thereby help the extracting of lower-molecular substance, promote the growth of strand with the reduction system.The overbottom pressure of vacuum polymerization can be controlled in-0.10～0.10MPa, the reaction time in this stage was generally 2.5～4 hours, there are a lot of methods can be in order to judge reaction end, as reaching 19A when stir current when above, can stop to stir, but leave standstill just discharging after 0.5～1 hour, the relative viscosity of product can reach more than 2.5.
The present invention's technical scheme preferably is: catalytic polymerization adopts binary or three-way catalyst, promptly adopts aforesaid certain catalyst in two classes or three classes simultaneously, helps vacuum polymerization stage strand and increases, and shortens reaction time.
The present invention's technical scheme preferably can also be: the oligomer residue of per 100 parts (weight) need be used 0.5～1.5 part of catalyst (gross weight), in this catalyst amount scope, in the aforesaid different time of temperature range internal reaction, the reaction end of controlling well all can get a desired effect.The optimum range of catalyst amount is: the oligomer residue of per 100 parts of weight is with 0.5～1.5 part (weight), and technology controlling and process is stable in this amount ranges, and the strand rate of rise is moderate, so product quality is also comparatively stable.
The present invention has following tangible advantage:
1, adopt the composite catalyzing polymerization, be suitable for the residue of Different Alkali content, particularly can make high-alkali residue aggregate into the high visocity nylon 6 product, this is that the hydrolytic polymerization method can't realize;
2, the employing catalytic polymerization is with short production cycle, and the product relative viscosity can reach more than 2.5 in 8 hours, and properties of product reach the requirement (properties of product see Table 3) of nylon engineering plastic;
3, relative viscosity easy and simple to handle, as can to regulate product as required.
Below the present invention is described in further detail by specific embodiment:
Embodiment 1:
In the stainless steel polymeric kettle, add pH value and be 100 parts of 8.7 hexanolactam oligomer residues, 1.5 parts of phenyl-phosphites (being parts by weight), be heated to 170 ℃ of fusions, treat to open stirring after the complete fusion of material, and continue to heat up, under 220～250 ℃ temperature, carry out ring-opening polymerization, reacted 3 hours, when the still internal pressure reaches 1.5MPa, beginning drive to press and vacuumize, to 260C, be to react 3.5 hours under the pressure of-0.10～0.10MPa the still temperature rise in overbottom pressure, when stir current reaches 19A, stop to stir, discharging pelletizing after 1 hour is left standstill in insulation, and section extracted 3 hours under 95 ℃ of left and right sides temperature, vacuumize is 8 hours under the overbottom pressure of-0.04MPa, the products obtained therefrom relative viscosity is 2.71, and content of monomer 2% gets product and weighs 84.9 parts.
Example 2～15:
With pH value is 100 parts of 6.5～9.0 oligomer residues, and the catalyst and the consumption thereof of adding see Table 2, and method of operating, reaction temperature and vacuum are with example 1, and the reaction time sees Table 2, and product quality sees Table 3, and product yield is 83～88 parts (weight).
Table 2 technology controlling and process table
| Embodiment | Catalyst | Reaction time (hour) | ||
| Title | Addition (part) | Ring-opening polymerization | Vacuum polymerization | |
| ???1 | Phenyl-phosphite | ????1.5 | ????3.0 | ????3.5 |
| ???2 | Propyl hexanoate | ????0.5 | ????3.8 | ????4.0 |
| ???3 | Alanine | ????0.1 | ????3.5 | ????4.0 |
| ???4 | The caprolactam sodium salt | ????0.3 | ????3.7 | ????4.0 |
| ???5 | A, triphenyl phosphite B, hexanolactam sylvite | ???A、0.1 ???B、0.3 | ????3.6 | ????3.9 |
| ???6 | A, butyl propionate B, aminobutyric acid | ???A、0.2 ???B、0.5 | ????2.2 | ????4.0 |
| ???7 | A, phosphoric acid B, aminoundecanoic acid | ???A、1.5 ???B、0.5 | ????3.2 | ????3.3 |
| ???8 | A, diphenyl phosphate B, caprolactam sodium salt | ???A、0.2 ???B、0.4 | ????3.3 | ????3.7 |
| ???9 | A, propyl valerate B, alanine | ???A、0.2 ???B、0.5 | ????4.0 | ????2.5 |
| ???10 | A, alanine B, hexanolactam sylvite | ???A、0.3 ???B、0.2 | ????3.5 | ????3.5 |
| ???11 | A, xylenylphosphate B, amion acetic acid | ???A、0.2 ???B、0.4 | ????2.1 | ????3.9 |
| ???12 | A, octyl propionate B, hexanolactam sylvite | ???A、0.4 ???B、0.4 | ????3.2 | ????3.8 |
| ???13 | A, phosphoric acid B, propyl butyrate C, alanine | ???A、0.5 ???B、0.1 ???C、0.4 | ????2.0 | ????4.0 |
| ???14 | A, triphenyl phosphite B, aminocaproic acid C, hexanolactam sylvite | ???A、0.5 ???B、0.1 ???C、0.6 | ????3.3 | ????2.7 |
| ???15 | A, di(2-ethylhexyl)phosphate propyl ester B, amion acetic acid C, butyl hexanoate | ???A、1.2 ???B、0.3 ???C、0.5 | ????2.8 | ????3.2 |
Table 3 product quality and physical and mechanical properties table
| Embodiment | Relative viscosity | Content of monomer (%) | Water content (%) | TENSILE STRENGTH (MPa) | Bending strength (MPa) | Notched Izod impact strength (kg/m 2) | Extension at break (%) |
| ???1 | ??2.71 | ????1.9 | ??0.8 | ???58.8 | ??88.3 | ????5.4 | ????27.0 |
| ???2 | ??2.60 | ????1.9 | ??0.7 | ???59.2 | ??88.5 | ????5.3 | ????27.3 |
| ???3 | ??2.50 | ????2.0 | ??0.9 | ???60.3 | ??88.0 | ????5.2 | ????27.7 |
| ???4 | ??2.51 | ????2.0 | ??1.0 | ???62.5 | ??88.1 | ????5.4 | ????27.9 |
| ???5 | ??2.68 | ????1.9 | ??0.7 | ???63.3 | ??88.9 | ????5.6 | ????27.2 |
| ???6 | ??2.72 | ????2.0 | ??0.8 | ???59.9 | ??89.0 | ????5.8 | ????27.4 |
| ???7 | ??2.90 | ????1.6 | ??0.5 | ???63.8 | ??89.8 | ????6.5 | ????28.0 |
| ???8 | ??2.88 | ????1.7 | ??0.6 | ???64.0 | ??89.7 | ????6.3 | ????27.6 |
| ???9 | ??2.75 | ????1.7 | ??0.6 | ???61.2 | ??89.5 | ????6.0 | ????27.1 |
| ???10 | ??2.73 | ????1.8 | ??0.7 | ???60.9 | ??89.4 | ????6.0 | ????27.9 |
| ???11 | ??2.87 | ????1.7 | ??0.8 | ???61.9 | ??89.5 | ????6.4 | ????27.8 |
| ???12 | ??2.74 | ????1.9 | ??1.0 | ???62.4 | ??89.0 | ????5.7 | ????27.5 |
| ???13 | ??2.98 | ????1.5 | ??0.5 | ???64.0 | ??90.0 | ????6.5 | ????27.9 |
| ???14 | ??2.97 | ????1.6 | ??0.5 | ???63.1 | ??90.0 | ????6.4 | ????27.7 |
| ???15 | ??2.79 | ????1.9 | ??0.4 | ???61.1 | ??89.0 | ????5.9 | ????27.3 |
Annotate: physical and mechanical properties standard: GB528-82.
Claims (3)
1, a kind of method of utilizing hexanolactam oligomer residue to make nylon 6 comprises processes such as heating and melting, ring-opening polymerization, vacuum polymerization, Cast Strip pelletizing and drying, the invention is characterized in: polymerization catalyst adopts general formula to be respectively
Phosphoric acid ester (R
1, R
2, R
3Can distinguish or simultaneously for H C
6H
5, C
6H
4H
3, (CH
2)
nCH
3, the positive integer of n=1～6),
Organosilane ester (positive integer of m=1～4, another positive integer of n=2～6), NH
2(CH
2)
nOne or more or its mixture of COOH amino acids (positive integers of n=1～10) and sodium caprolactam (or potassium) salt, course of reaction mainly comprises:
(1), 100 parts of (weight) oligomer residues and 0.1～2 part of (weight) catalyst are added in the still, behind the heating and melting, ring-opening polymerization is 2～4 hours under 220～250 ℃ temperature;
(2), under 260～285 ℃ the temperature, overbottom pressure is under the pressure of-0.10～0.10MPa, vacuum polymerization reaction 2.5～4 hours obtains relative viscosity and is 2.5～3.0 nylon 6 products.
2, the method for manufacturing nylon 6 according to claim 1 is characterized in that: adopt binary or three-way catalyst.
3, the method for manufacturing nylon 6 according to claim 1 and 2 is characterized in that: oligomer residue 100 parts (weight) uses 0.5～1.5 part of catalyst (total amount, weight).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96118401A CN1049703C (en) | 1996-11-04 | 1996-11-04 | Method for producing nylon 6 by using caprolactam oligomer residue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96118401A CN1049703C (en) | 1996-11-04 | 1996-11-04 | Method for producing nylon 6 by using caprolactam oligomer residue |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1153232A true CN1153232A (en) | 1997-07-02 |
| CN1049703C CN1049703C (en) | 2000-02-23 |
Family
ID=5125062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96118401A Expired - Fee Related CN1049703C (en) | 1996-11-04 | 1996-11-04 | Method for producing nylon 6 by using caprolactam oligomer residue |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1049703C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964589A (en) * | 2012-12-07 | 2013-03-13 | 株洲时代新材料科技股份有限公司 | Preparation method of branched nylon resin |
| CN104356639A (en) * | 2014-10-17 | 2015-02-18 | 衡水金轮塑业有限公司 | Nylon 6 resin for food packaging materials as well as preparation method and application thereof |
| 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3534817A1 (en) * | 1985-09-30 | 1987-04-02 | Davy Mckee Ag | Process for the preparation of polyamide |
| CN1058026A (en) * | 1991-06-19 | 1992-01-22 | 杨思会 | Method with useless nylon polymerization monomer moulding casting nylon |
| CN1085918A (en) * | 1992-10-08 | 1994-04-27 | 李盈念 | A kind of preparation method of modification of nylon |
-
1996
- 1996-11-04 CN CN96118401A patent/CN1049703C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964589A (en) * | 2012-12-07 | 2013-03-13 | 株洲时代新材料科技股份有限公司 | Preparation method of branched nylon resin |
| CN104356639A (en) * | 2014-10-17 | 2015-02-18 | 衡水金轮塑业有限公司 | Nylon 6 resin for food packaging materials as well as preparation method and application thereof |
| 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1049703C (en) | 2000-02-23 |
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