AU722606B2 - Liquid multi-component system for executing the anionic lactam polymerization - Google Patents
Liquid multi-component system for executing the anionic lactam polymerization Download PDFInfo
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- AU722606B2 AU722606B2 AU12314/97A AU1231497A AU722606B2 AU 722606 B2 AU722606 B2 AU 722606B2 AU 12314/97 A AU12314/97 A AU 12314/97A AU 1231497 A AU1231497 A AU 1231497A AU 722606 B2 AU722606 B2 AU 722606B2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
- C08G69/18—Anionic polymerisation
- C08G69/20—Anionic polymerisation characterised by the catalysts used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
- C08G69/18—Anionic polymerisation
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Description
AUSTRALIA
Patents Act COMPLETE SPECIFICATION
(ORIGINAL)
Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority Related Art: .o Name of Applicant: Ems-Inventa AG Actual Inventor(s): Eduard Schmid Roman Eder Address for Service: PHILLIPS ORMONDE FITZPATRICK :i Patent and Trade Mark Attorneys 367 Collins Street Melbourne 3000 AUSTRALIA Invention Title: LIQUID MULTI-COMPONENT SYSTEM FOR EXECUTING THE ANIONIC LACTAM POLYMERIZATION Our Ref 479122 POF Code: 260767/226745 The following statement is a full description of this invention, including the best method of performing it known to applicant(s): 1
KAM
(al?%S LIQUID MULTI-COMPONENT SYSTEM FOR EXECUTING AN ANIONIC LACTAM
POLYMERIZATION
FIELD OF THE INVENTION :The instant invention relates to a liquid multi-component system for executing the anionic lactam polymerization, the use of the multi-component system for producing shaped bodies made of polylactam, and to the shaped bodies so produced.
In accordance with the relevant prior art, polyamides are mainly produced by the hydrolytic polymerization process from molten lactams at temperatures of approximately 200 to 320 0 C, wherein often a pressure phase with the addition of water for opening the ring of the lactam is interposed ahead. This reaction proceeds slowly. The reaction product, preferably a granular material, is converted to useful articles in a subsequent step, for example by means of an injection molding or extrusion process.
13.01.97 hkl 2.- Strong bases which, for example, can lead to the formation of metal lactamate, can also cause the conversion of lactam to polyamide. The corresponding polymerization reaction proceeds slowly and was replaced by the activated anionic lactam polymerization, wherein the reaction is greatly accelerated, and the polymerization temperature can be lowered below the melting point of the polymer. In this method the catalyst and activator are separately added to the molten lactam.
In this case the catalyst usually is present as a solid, for example in the form of an alkali- or alkaline earth-lactamate. Also, many of the activators (or co-catalysts), such as carbodiimides and blocked isocyanates are solids. The disadvantage of the free isocyanates, many of which are liquids, is their high toxicity.
The anionic lactam polymerization and the activated anionic lactam polymerization, as well as all aspects of polyamide synthesis and the corresponding applications are described, for example, in the Plastics Manual, Volume VI, Polyamides, C. Hanser, publishers, Minchen.
The activated anionic lactam polymerization is generally performed to produce so-called cast parts or semi-finished goods of large dimensions, such a profiles, preferably in accordance with the so-called 2-tank method.
Here lactam melts of the same volume and containing the catalyst respectively the cocatalyst are produced, combined and intensely mixed. Thereby the polymerization is started by this and the melt can be processed immediately thereafter into finished parts, for example by means of the so-called monomer casting process.
In this process it is necessary to observe as much as possible that the lactam melts are free of water and oxygen, the mixing and processing steps take place in an inert gas, and S 25 the melts, in particular catalyst-containing melts, are quickly processed, since it has only a limited processing time.
So-called liquid catalyst systems were developed to ease the rapid and homogeneous distribution of the catalyst, for example magnesium or sodium lactamate, in the lactam melt.
Reference is made in German Patent Publication DE-22 30 732 C3 to the difficulties 30 caused by the addition of catalysts in solid form, for example metallic lactamate, to the activator- containing lactam melt. An inhomogeneous polymer is created unless rapid dissolving and even distribution are assured.
To solve the problem, a solution of alkali lactamate in lactam, which is liquid and can be stored at 90°C and which additionally contains 0.3 to 5.0 weight-% of a low-volatile amine, is proposed by German Patent Publication DE-A-14 95 132.
A catalyst solution of metal lactamate in an N-disubstituted urea, in particular in Nmethylpyrrolidone, is described in US Patent 3,575,938. The improved addition and distribution of this catalyst solution in an activated lactam melt also permits the production of mineral-filled products.
In accordance with the teachings of German Patent Publication DE 22 30 732 C3, it is necessary to prevent the crust formation, quickly exhibited by catalyst solutions made of alkali lactamate in 2-pyrrolidone and which interferes with the process, by the addition of higher alcohols.
Catalyst solutions with a high degree of stability when stored even at low temperatures are described in European Patent Publication EP 0 438 762 B1, which allow a rapid reaction and lead to polyamide with a relatively low amount of extractable content. They consist of lactam, for example 2-pyrrolidone, special glycols, hydrocarbons and selectively contain amine.
In the cited prior art it is still necessary for performing the activated anionic lactam polymerization to use the activator and catalyst solutions separately.
Thereby it is a preferred procedure that first a homogeneous solution of the S" activator and, if required, further additives, in an anhydrous lactam melt is produced, and in a further process step the catalyst solution is added and homogenously distributed in the melt and thereby starting the reaction.
The essential disadvantages of the process in accordance with the prior art are therefore in the necessity of the separate addition of activator and of catalyst solution to the lactam melt in discontinuous process, or the use of two storage containers, namely one container each for respectively the activated and for the catalyst-containing lactam melt, both of which have only a limited shelf life.
OBJECT AND SUMMARY OF THE INVENTION It would therefore be desirable to overcome the disadvantages of the prior art by means of a suitable catalyst/activator system and to simplify in this way the lactam polymerization.
This can be achieved by means of the liquid multi-component system for RALgprorming the anionic lactam polymerization of the invention, the use -4of this system as described herein and the shaped bodies produced in this manner.
In one aspect the present invention provides a liquid multi-component system for performing the anionic lactam polymerization from at least a basic composition of a) 30 to 80 parts by weight of a liquid solvating component containing at least one liquid solvating compound, wherein the solvating component is able to solvate the catalyst and partly the activator, b) 5 to 40 parts by weight of a catalytic component containing at least one catalyst, c) 5 to 40 parts by weight of an activator component containing at least one activator compound.
which add up to 100 parts, and additionally of 0 to 50 parts by weight of production and/or use-related o* o S 15 additives, wherein the solvating compounds of component a) contain aliphatic, cycloaliphatic or aromatic hetero atoms or hetero groups, which are sufficiently alkylated or sterically hindered and which are not capable of undergoing a condensation reaction, and wherein said compounds are 20 selected from the group consisting of acid amides, lactams, alkylated lactams, N, N'-dialkylated ureas, which can also be cyclic, carboxylic acid esters, polyether esters with molecular weight (Mn) between 250 and 2000 and ethylene oxide, propylene oxide and butylene oxide segments, or the corresponding copolymers or block-copolymers, sterically hindered phenols, ester of phosphorus, N-alkylated amines or polyamines, N-dialkylated carbamic acid esters, dimethyl sulfoxide and alkyl oxazolines.
In a further aspect the present invention provides use of the liquid multicomponent system in accordance with the invention for producing shaped bodies of polylactam in accordance with the process of activated anionic lactam polymerisation.
In an even further aspect the present invention provides a shaped body produced by using the liquid multi-component system in accordance with the ~invention in a process of the activated anionic lactam polymerisation.
X:\fIol.,\Spies\l12314.doc 4a It is attained in particular by means of a liquid multi-component system stable when stored and containing both the activator and catalyst thereby making unnecessary the separate use of activator and catalyst and so opening to the system improvements in the use and the formulations and the process variants.
In the multi-component system in accordance with the invention, aliphatic, cycloaliphatic or aromatic solvating compounds with hetero atoms or hetero groups, which are not capable of condensation reactions are suitable as structural elements that possess a solvating power for the catalyst and partly the activator, which is also called co-catalyst.
1o Such hetero atoms or hetero groups are, for example -CONR-, R'R"N-CO- OR, RR'NCONR"R'", phenolic -OH, SO 2 -NRR', P(-OR) 3 CO- and -COOR, where R, and are the same or different radicals with at least one C-atom or with H, whereby the hetero atom has to be sufficiently alkylated or sterically hindered, that it can not enter into a condensation reaction.
9 15 N, S, P and O are preferred hetero atoms.
The solvating compounds a) preferably contains several of these structural elements with a solvating power.
Particularly preferred are solvating compounds in which two radicals R", bonded to the hetero atoms or hetero groups are connected with each other, by forming a ring.
The multi-component systems in accordance with the invention have an unexpectedly good stability against oxygen and against aging. The reasons for this are not clear. For example, it can be assumed that the aging resistance is due to the formation of an addition compound of the catalyst and activator, while hydrophobic radicals in the activator or the basic component a) could also be responsible for the protection against oxygen and moisture.
Members of solvating component a) have been selected from the group of lactams, alkylated lactams, wherein the radical can be linear or cyclic and in particular contains 1 to 8 C-atoms, N-linear and N-cyclic alkylated ureas, carboxylic acid esters, polyetheresters with molecular weights (Mn) between 250 and 2000 and ethylene.
oxide, butylene oxide and propylene oxide structural elements, sterically hindered phenols, esters of phosphorus, N-alkylated amines and alkyl oxazoline and composites of similar ring structure, containing hetero groups.
Preferred composites of the component a) are those with adjacent, carboxylic acid ester groups, sterically hindered phenols, phenol esters and sterically hindered phenol esters.
Further composites are longer-chain triesters of phosphorus, such as, for example, trisnonylphenyl phosphite, or the lactams of the group of butyro-, valero-, capro, enantho- and laurinlactam and their N-alkylated derivatives, in particular Nalkylated C5 and C6 lactams, such as N-methyl caprolactam, and in particular N-alkyl pyrrolidons, such as N-methyl and N-octyl pyrrolidon and in special mixture of cyclic carbonamide.
Further composites are N,N'-dialkylated ureas, for example, tetramethyl and tetrabutyl urea, and the cyclic ureas N,N'-dimethylethylene and N,N'dimethylpropylene urea.
Furthermore, esters of phthalic acid, oxalic acid, adipinic acid, malonic acid, succinic acid, maleic acid with C1 to C18 alcohols, wherein alcohols with 1 to 8 Catoms are preferred and the alcohols selectively contain double bonds, side chains or hetero atoms, as well as of the completely esterified and acylated hydroxy acids, for example of citric acid, wherein the radical coming from the alcohol, can also be the 2ethylhexyl radical. Carboxylic acid esters with short-chain alcohols with 1 to 8 Catoms, and polyols, for example ethylene glycol, diethylene glycol or glycerin, are particularly suited.
Furthermore, polyether esters of linear dicarboxylic acids of up to 18 C-atoms, and polyether glycols with molecular weights (Mn) between 250 and 2000 are suitable.
Further compounds are sterically hindered and in particular N-dialkylated amines and diamines, in particular polyamines in which the amino groups are separated by means of a short-chain alkyl radical, as well as those with a fatty acid radical.
Further compounds are esters from acids of phosphorus with alkylated phenols, long-chain alcohols and their mixtures.
C:\WINWORD\GAY\NODELETE479122.DOC Further compounds are alkyl oxazolines with at least 6 C atoms in the alkyl radical, which can also contain hetero atoms or hetero group, in particular fatty alkyl oxazolines.
The solvating base component of the multi-component system in accordance with the invention is mainly responsible for the low viscosity of the system, which allows the homogeneous distribution of the system in the lactam melt.
It can be observed that members of the component besides the compellingly required solvation, often unexpectedly take on additional tasks in the multi-component system. For example, they act as mold release agents and shield the system from the entry of moisture if they have a longer alkane chain as the radical R, for example at the N-atom, the CONR or the ester group, or at the ester of phosphorus. Examples, each with the C8 to C18 alkyl radical, are fatty alkyl oxazolines, phthalic acid esters, alkyl pyrrolidone, trisnonylphenyl phosphite, furthermore polyamines with a fatty alkyl radical derived from natural fats, and each with the N-atoms connected via a -CH 2
-CH
2 or -CH 2
-CH
2
-CH
2 bridge.
They can furthermore stabilize the finished product for use over long periods of time. Examples of this are molecules with a HALS structure as light stabilizers, molecules with a sterically hindered phenol as heat stabilizer, and reducing phenolic phosphorous acid esters as a trapping agent for traces of oxygen.
Many of these molecular structures can also have a plasticizing and/or toughness-increasing function. Examples are the N-substituted amides, phthalic acid ester and other ester compounds, such as polyether esters and the esters of Sphosphorus.
Since the molecules of the group a) can take on many additional functions in the polylactam system, besides their function as solvating agent, mixtures of such molecules are of great importance for many applications.
However, solvating molecules which impose high melt-flow (properties) to the system take on a basic task, so that the system can be well and easily distributed in the lactam melt and further the molecules can take on various additional tasks in a supplementary fashion.
The catalysts b) preferably are alkali, alkaline earth or tetraalkyl ammonium lactamates or their mixtures.
C:\WINWORD\GAY\NODELETE\479122.DOC The activators c) are selected from the group of isocyanates, diisocyanates and polyisocyanates, which are blocked with lactam or hydroxy fatty alkyl oxazoline, further carbodiimides and polycarbodiimides.
Mold release agents, stabilizers, dyestuffs, tracers and plasticizers are advantageously employed as use-related additives d).
Possible additives which influence the course of polymerization and the molecular weight distribution, are for example alcohols, polyalcohols and polyether polyols, amines and phenols.
The invention also includes the use of the liquid multi-component system in accordance with the invention for the production of shaped bodies, which can also be composite materials, from polylactams in accordance with the process of anionic lactam polymerization. In this case the multi-component system is used in weight proportions of 0.5 to 15% related to the lactam.
A preferred variant is the use in discontinuous processes.
In continuous process variants, twin-screw extruders are advantageously used.
In connection with the production of composite materials, the pultrusion process is preferred.
Preferred lactams are polycaprolactam, polyenantholactam, polylaurinlactam and their mixtures.
The use of the multi-component system in accordance with the invention is particularly preferred for producing composite materials with a polylactam matrix containing reinforcing 9 9* *9 C C:\WINWORD\GAY\NODELETE\479122.DOC 13.01.97 hkl fiber structures, or for reinforced and non-reinforced tubes, profiled elements, plates, strands which can be pelletized, hollow bodies or cast bodies. In a preferred way the reinforcement fibers are oriented fibers. Thereby the high volume content in which the reinforcement fibers can be used is particularly advantageous. The preferably produced fiber containing granules can be processed into shaped bodies in thermoplastic shaping processes like injection molding.
In a further preferred process variant, pure anhydrous lactam is taken from a storage container and supplied to a mixing device. There the multi-component system is added, preferably in a proportion between 0.5 and 15 weight-%, and is homogeneously distributed in lo0 the melt. The activated lactam melt is now subjected to a shaping process with the application of heat. In special variants, dried filler and reinforcement materials, also in combination with additives that prevent sedimentation, are added to the melt to improvedimensional stability and to reduce shrinkage of the final part.
In each application the course of polymerization is matched to the requirements by means of the fractions of thecatalyst and activator in this system, the fraction of added multi-component system and the control of the temperature of the melt..
It is of advantage, in particular in connection with Lactam-12, to raise the temperature of the melt to 200 to 300°C and in this way to greatly accelerate the polymerization, so that it is terminated in 60 to 300 seconds,without leaving an enlarged amount of unreacted lactam.
When employing the continuous process, the multi-component system is continuously added to an anhydrous lactam melt, is homogeneously intermixed with it and the mixture is continuously conveyed with the aid of suitable conveying elements, and during the process sufficiently polymerized by selecting of the amount of the multi-component system, the melt temperature and the recidence time, so that the melt stream can be directly conducted to the 25 shaping tool, or that it forms a strand that can be pelletized after cooling.
Twin-screw extruders, that permit a multiplicity of modifications, are suitable as conveying elements.
Liquid and/or solid additives, are often preferably added, to the melt which has been polymerized already to a great extend.
30 Suitable additives are, for example, plasticizers, possibly of the ester or polyether types, f** lor sulfonamide plasticizers, which are customary for polyamides, furthermore glass fibers, minerals, flame retardant agents and other polymers which, for example, improve the impact see* resistance, as well as processing aids and stabilizers, such as are customary for polyamides.
These admixed materials and additives can be used in any arbitrary combination, in particular, if they are added after polymerization has mainly ended.
13.01.97 hkl In another preferred variant, casting molds are filled with the activated lactam melt and the cast parts are slowly polymerized at temperatures below the polylactam melting point.
With polycaprolactam, stress-free elements with a low remaining lactam fractions are formed in this way. Such cast elements have an excellent property profile. They are tough, wear resistant and impact resistant.
Well dried fillers and reinforcement materials, such as glass fibers and minerals, are preferably used to increase rigidity and decrease shrinkage.
The activated melt is also used in variants for the roto molding method, wherein hollow bodies of high impact resistance and good sealing properties, in particular against fuels, greases and oils, are the result.
The multi-component system in accordance with the invention is advantageously used for the continuous or discontinuous production of composite materials.
It is of particular advantage that the lactam melt, freshly activated by the multicomponent system, completely impregnates and wets preformed filament structures, such as braids, weaves, knits, embroideries and roving arrangements, after which it is polymerized under the effects of heat and forms a matrix with high tensile strenght, and which can be thermally postformed.
The filament structures must be dry and should not have any surface structures which would hinder polymerization.
The applications include the resin transfer molding process, pultrusion, impregnation of i flat fiber structures for plates and the use for long-fiber-filled granules.
The filament structures are preferably those made of E- glass or carbon fibers.
The shaped bodies produced in this way are also included in the invention.
ooooo DETAILED DESCRIPTION Examples 1 to 11 Examples 1 to 5 describe the production of liquid systems.
It is required to work in a protective gas atmosphere when producing the liquid system.
The component a) is placed into a vessel with an interior temperature measuring device and heated to 30 to 13.01.97 hkl Thereafter the component c) is added while stirring and is homogeneously mixed in.
After a clear solution has developed, the component b) and subsequently the additives if required, are added while the temperature, which must not exceed 70°C, is controlled.
At room temperature, the resultant solutions are liquid and stable when stored.
13.01.97 hkl -11- Table 1: LIQUID MULTI-COMPONENT SYSTEMS NMP: N-methyl-2-pyrrolidone Irganox 1135: Phenolic antioxidant, Irganox 113 5 CIBA-GEIGY AG, Basel (CH) TNPP: Trisnonyiphenil phosphite, Irganox TNPP(R), CIBA-GEIGY AG, Basel (OH) BBSA: Butylbenzene sulfonamide, Della ToII(R), Bayer AG DMPU: N,N'-dimethylpropylene urea TMP: Tripropylene glycolmethyl ether, Dowanol TPM(R), DOW AG, Horgen (CH) DMSO: Dimethylsulfoxide Na-CL Sodium caprolactamate, apprx. 3 to 5 sodium, Pacast AG, Sargans (CH) CD: Substituted diaryl carbodiimide, Stabaxol Rhein Chemie GmbH, Mannheim (ERG) 13.01.97 hkl -12- CD-MDI: Methylene diisocyanate blocked with caprolactam, Grilbond IL6, EMS-CHEMIE AG, Domat/Ems (CH) Bis-Ox:
CL-MDI:
PCD:
Ricinyl-bisoxazoline, Loxamid 8523 Henkel KG, Desseldorf (FRG) Isophoron diisocyanate blocked with caprolactam, Crelan UI(R), Bayer AG Polycarbodiimide, Stabaxol P, Rhein Chemie GmbH, Mannheim (FRG) EXAMPLES 11 to 22 For using the liquid systems to perform the activated anionic lactam polymerization, the following general procedure can be employed.
A lactam melt is placed into a vessel with an interior thermometer and a nitrogen atmosphere and the liquid system is introduced while the temperature is controlled and while stirring.
The period of time until the melt can no longer be stirred is used as the comparison time t for describing the course of the polymerization.
The melt is subsequently polymerized at 175°C for 60 min.
r 13.01.97 hkl -13- Table 2: USE OF THE MULTI-COMPONENT SYSTEMS OF EXAMPLES I TO 11 FOR LACTAM POLYMERIZATION
S
S.
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Claims (19)
1. A liquid multi-component system for performing the anionic lactam polymerisation from at least a basic composition of a) 30 to 80 parts by weight of a liquid solvating component containing at least one liquid solvating compound, wherein the solvating component is able to solvate the catalyst and partly the activator, b) 5 to 40 parts by weight of a catalytic component containing at least one catalyst, c) 5 to 40 parts by weight of an activator component containing at least one activator compound. which add up to 100 parts, and d) additionally of 0 to 50 parts by weight of production and/or use-related 9***ee Sadditives, 15 wherein the solvating compounds of component a) contain aliphatic, cycloaliphatic or aromatic hetero atoms or hetero groups, which are sufficiently alkylated or sterically hindered and which are not capable of undergoing a condensation reaction, and wherein said compounds are •selected from the group consisting of acid amides, lactams, alkylated S 20 lactams, N, N'-dialkylated ureas, which can also be cyclic, carboxylic acid esters, polyether esters with molecular weight (Mn) between 250 and 2000 and ethylene oxide, propylene oxide and butylene oxide segments, or the corresponding copolymers or block-copolymers, sterically hindered phenols, ester of phosphorus, N-alkylated amines or polyamines, N- dialkylated carbamic acid esters, dimethyl sulfoxide and alkyl oxazolines.
2. The multi-component system in accordance with claim 1, wherein the solvating component a) contains at least one solvating compound having several hetero atoms or hetero groups.
3. The multi-component system in accordance with claim 1 or 2, wherein the carboxylic acid esters have ester groups, which are adjacent to each other. X:\iona\Species\I2314.doc
4. The multi-component system in accordance with any one of the preceding claims, wherein the N-alkylated amine and/or polyamines are sterically hindered or N-dialkylated.
5. The multi-component system in accordance with any one of the preceding claims, wherein the lactams are selected from the group of butyrolactam, valerolactam, caprolactam, enantholactam and laurinlactam and their N-alkylated derivatives. 0o 6. The multi-component system in accordance with claim 5, wherein the N- alkylated lactams are selected from the group of N-alkylated C 5 lactam and N alkylated C 6 lactam.
7. A multi-component system in accordance with any one of the preceding 6O 15 claims, wherein the N,N'-alkylated ureas are tetramethyl urea and tetrabutyl urea. a. o o a
8. The multi-component system in accordance with any one of the preceding claims, wherein the cyclic ureas are N,N'-dimethyl ethylene urea and N,N'- dimethyl propylene urea S
9. The multi-component system in accordance with any one of the preceding claims, wherein the carboxylic acid esters are those of phthalic acid, oxalic acid, adipinic acid, malonic acid, succinic acid or maleic acid with alcohols with 1-18 C-atoms, which selectively contain double bonds and hetero atoms, with completely esterified acylated hydroxy acids. The multi-component system in accordance with any one of the preceding claims, wherein the carboxylic acid esters are derived from short-chain alcohol components from the group of alcohols with 1 to 8 C-atoms, ethylene glycol, diethylene glycol and glycerin.
11. The multi-component system in accordance with any one of the preceding claims, wherein the polyetheresters are derived from linear dicarboxylic acids with 7 2 to 18 C-atoms. X:\flon\Spccics 2314.doc -16-
12. The multi-component system in accordance with any one of the preceding claims, wherein the esters of phosphorus are those with alkylated phenols, long- chain alcohols or their mixtures.
13. The multi-component system in accordance with any one of the preceding claims, wherein the alkyl oxazolines have any alkyl substituent with at least 6 C- atoms with or without hetero atoms or hetero groups.
14. The multi-component system in accordance with any one of the preceding claims, wherein the catalyst b) is a lactamate with alkali, alkaline earth or tetraalkyl ammonium cation or their mixture. 0*
15. The multi-component system in accordance with any one of the preceding 15 claims, wherein the activator c) is selected from the group consisting of isocyanates, diisocyanates and polyisocyanates, carbodiimides and polycarbodiimides, blocked with lactam or hydroxy fatty alkyl oxazoline.
16. The multi-component system in accordance with any one of the preceding 20 claims, wherein the additives are selected from the group of mold release agents stabilizers, dyestuffs, tracers and plasticizers. S. 17. Use of the liquid multi-component system in accordance with any one of claims 1 to 16 for producing shaped bodies of polylactam in accordance with the process of activated anionic lactam polymerization.
18. Use in accordance with claim 17, wherein the polylactam is polycaprolactam, polyenantholactam, polylaurinlactam or their mixture.
19. Use in accordance with claim 17 or 18 wherein the process is performed continuously. -17- Use in accordance with claim 17 or 18, wherein the process is performed continuously on a twin-screw extruder or, in connection with composite materials, in accordance with the pultrusion process.
21. Use in accordance with any one of claims 17 to 20, wherein the shaped bodies are composite materials of a reinforcement fiber structure and a matrix of polylactam. .22. Use in accordance with any one of claims 17 to 20, wherein the shaped bodies are tubes, profiles, plates, monofilaments, granules, hollow bodies or cast bodies with or without reinforcement fiber structures.
23. A liquid multi-component system according to claim 1 substantially as hereinbefore described with reference to any of the examples.
24. A use according to claim 17 substantially as hereinbefore described with reference to any of the examples. DATED: 18 April, 2000 PHILLIPS ORMONDE FITZPATRICK Attorneys for: EMS-INVENTA AG
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Application Number | Priority Date | Filing Date | Title |
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DE19603305A DE19603305C2 (en) | 1996-01-25 | 1996-01-25 | Liquid multicomponent system for performing anionic lactam polymerization |
DE19603305 | 1996-01-25 |
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AU1231497A AU1231497A (en) | 1997-07-31 |
AU722606B2 true AU722606B2 (en) | 2000-08-10 |
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EP (1) | EP0786486B1 (en) |
JP (1) | JP3441908B2 (en) |
KR (1) | KR100513025B1 (en) |
CN (1) | CN1104454C (en) |
AR (1) | AR005517A1 (en) |
AU (1) | AU722606B2 (en) |
BR (1) | BR9700770A (en) |
DE (2) | DE19603305C2 (en) |
IN (1) | IN190934B (en) |
PL (1) | PL318123A1 (en) |
TW (1) | TW459002B (en) |
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DE19715679C2 (en) * | 1997-04-15 | 1999-06-02 | Inventa Ag | Process for producing a catalytically active liquid system for triggering the anionic lactam polymerization |
DE19961818C2 (en) | 1999-12-21 | 2002-12-05 | Ems Chemie Ag | Liquid initiator for accelerated anionic lactam polymerization, process for its preparation and use |
DE19961819C2 (en) | 1999-12-21 | 2002-11-14 | Ems Chemie Ag | Liquid initiator for accelerated performance of anionic lactam polymerization, process for its preparation and use |
DE10129049A1 (en) * | 2001-06-15 | 2003-06-26 | Ems Chemie Ag | liquid catalyst |
WO2003053661A1 (en) * | 2001-12-20 | 2003-07-03 | Ems-Chemie Ag | Method for producing composite materials using a thermoplastic matrix |
DE10341811B4 (en) * | 2003-09-10 | 2006-09-28 | Ems-Chemie Ag | Catalyst solution for carrying out the anionic lactam polymerization, process for their preparation and polyamide molding composition |
FR2893622B1 (en) * | 2005-11-24 | 2007-12-21 | Commissariat Energie Atomique | CAPROLACTAM-BASED COMPOSITION, METHOD OF MANUFACTURING SEALING ELEMENT, AND TANK |
CN101007869B (en) * | 2006-01-27 | 2010-09-08 | 中国石油化工股份有限公司 | Anion slurry polymerization method for preparing caprolactam homopolymer and copolymer |
KR100816068B1 (en) | 2007-04-10 | 2008-03-24 | 주식회사 에스앤엠 | Manufacturing methods of auti-fire mc nylon and anti-fire mc nylon thereof |
MY163168A (en) * | 2010-10-07 | 2017-08-15 | Basf Se | Method for producing monomer compositions, and use thereof for producing a molded polyamide part |
US10538624B2 (en) | 2010-10-07 | 2020-01-21 | Basf Se | Process for producing monomer compositions and use of these for producing a polyamide molding |
EP3130622B1 (en) * | 2015-08-11 | 2020-04-08 | LANXESS Deutschland GmbH | Polymerizable composition |
KR20180054708A (en) * | 2015-09-16 | 2018-05-24 | 바스프 에스이 | Anionic polymerization of lactam |
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DE1495848C3 (en) * | 1964-12-10 | 1979-01-11 | Bayer Ag, 5090 Leverkusen | Process for the production of poly-e-caprolactam |
US3575938A (en) * | 1969-01-08 | 1971-04-20 | Monsanto Co | Anionic lactam catalyst system |
DE2035733C3 (en) * | 1970-07-18 | 1982-03-25 | Bayer Ag, 5090 Leverkusen | Process for the anionic polymerization of lactams and catalyst solutions therefor |
DE4002260A1 (en) * | 1990-01-26 | 1991-08-01 | Basf Ag | Stable liq. catalyst for rapid lactam anionic polymerisation - comprises alkali metal lactam, pyrrolidone, poly:alkylene glycol, amine and aromatic hydrocarbon |
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1996
- 1996-01-25 DE DE19603305A patent/DE19603305C2/en not_active Expired - Fee Related
-
1997
- 1997-01-17 TW TW086100456A patent/TW459002B/en not_active IP Right Cessation
- 1997-01-22 AR ARP970100257A patent/AR005517A1/en unknown
- 1997-01-24 DE DE59701456T patent/DE59701456D1/en not_active Expired - Fee Related
- 1997-01-24 KR KR1019970002012A patent/KR100513025B1/en not_active IP Right Cessation
- 1997-01-24 EP EP97101102A patent/EP0786486B1/en not_active Expired - Lifetime
- 1997-01-24 IN IN140CA1997 patent/IN190934B/en unknown
- 1997-01-24 AU AU12314/97A patent/AU722606B2/en not_active Ceased
- 1997-01-24 PL PL97318123A patent/PL318123A1/en unknown
- 1997-01-24 JP JP01105897A patent/JP3441908B2/en not_active Expired - Fee Related
- 1997-01-24 BR BR9700770A patent/BR9700770A/en not_active IP Right Cessation
- 1997-01-27 CN CN97100400A patent/CN1104454C/en not_active Expired - Fee Related
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Also Published As
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BR9700770A (en) | 1998-10-06 |
EP0786486B1 (en) | 2000-04-19 |
CN1161979A (en) | 1997-10-15 |
IN190934B (en) | 2003-09-06 |
JPH09208692A (en) | 1997-08-12 |
DE19603305C2 (en) | 1999-07-22 |
DE59701456D1 (en) | 2000-05-25 |
KR970059201A (en) | 1997-08-12 |
EP0786486A3 (en) | 1998-07-29 |
KR100513025B1 (en) | 2005-12-29 |
PL318123A1 (en) | 1997-08-04 |
TW459002B (en) | 2001-10-11 |
DE19603305A1 (en) | 1997-08-07 |
JP3441908B2 (en) | 2003-09-02 |
EP0786486A2 (en) | 1997-07-30 |
CN1104454C (en) | 2003-04-02 |
AR005517A1 (en) | 1999-06-23 |
AU1231497A (en) | 1997-07-31 |
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