CA2402430A1 - Chain extension process - Google Patents
Chain extension process Download PDFInfo
- Publication number
- CA2402430A1 CA2402430A1 CA002402430A CA2402430A CA2402430A1 CA 2402430 A1 CA2402430 A1 CA 2402430A1 CA 002402430 A CA002402430 A CA 002402430A CA 2402430 A CA2402430 A CA 2402430A CA 2402430 A1 CA2402430 A1 CA 2402430A1
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- CA
- Canada
- Prior art keywords
- melt
- polymer
- polyamide
- acid
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- 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
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G69/04—Preparatory processes
-
- 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
-
- 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
- C08G69/48—Polymers modified by chemical after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyamides (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
The invention relates to a process for preparing a high-molecular polymer by contacting in a melt a difunctional lowermolecular polymer whose functional end groups are -OH or -NH2 groups with carbonylbislactamate, characterized in that the melt also contains an acid or a base as a catalyst. If the difunctional polymer contains a -COOH group, it is preferred for the melt also to contain a bisoxazine or a bisoxazoline.
Description
.-1-CHAIN EXTENSION PROCESS
The invention relates to a process for preparing a high-molecular weight polymer by contacting in a melt a difunctional polymer having a lower molecular weight whose end functional groups are -OH or -NHZ groups with a carbonylbislactamate (CBL) with the following formula:
~CH2~n (~rl~2~n wherein n is an integer from 3 to 15. Preferably the carbonylbislactamate is carbonylbiscaprolactamate (CBC), with n = 5.
A similar process is disclosed in WO 98/47940.
WO 98/47940 describes a process for preparing a high-molecular polyamide by contacting polyamide having a lower molecular weight in the melt with carbonylbiscaprolactamate (CBC).
A drawback of that process is that the reaction proceeds comparatively slowly.
The object of the invention is to provide a process that does not have the aforementioned drawback or has the aforementioned drawback to a lesser extent.
This object is achieved by the melt also containing an acid or a base. The acid or base has the function of a catalyst.
This ensures that the reaction proceeds more rapidly, as is apparent from the fact that the viscosity increases much more rapidly with catalyst than without catalyst. This can be established from for example the increase in the torque of a Brabender in which a blend of a difunctional polymer and CBL is kneaded optionally in the presence of an acid or a base.
Acids that are suitable for use as a catalyst for chain extension in the presence of CBL are LiX, SbZOa, GeOz and As20a, BX3, MgX2, BiX3, SnX4, SbXs, FeX3, GeX4, GaX3, HgX2, ZnX2, AIX3, TiX4, MnX2, ZrX4, R4NX, R4PX, HX, where X = I, Br, CI, F, OR and R = alkyl or aryl. Brpnstedt acids such as HZS04, HN03, HX, H3P04, H3P03, RH2P02, RHZP03, R[(CO)OH]~, with n = 1-6 are also suitable.
Bases that are suitable for use as a catalyst for chain extension in the presence of CBC are Li-versetate, Zn acetylacetonate (acac),M(OH)~, (RO)~M (M= alkali or earth alkali, R = alkyl with C, - CZO or aryl), NR~H4_~OH
(R =
alkyl with C, - CZO or aryl), triamines such as triethylamine, tributylamine, trihexylamine, trioctylamine and cyclic amines such as diazobicyclo[2,2,2]octane (DABCO), dimethylaminopyridine (DMAP), guanidine, morfoline, dibutyl tin dilaurate (DBTDL), dibutyl tin bis(2-ethylhexanoate), dibutyl tin dibutylate, dibutyl tin dimethylate, dibutyl tin dioctanoate.
It is preferred for the catalyst to be a Lewis acid or a Lewis base.
This ensures that the time needed for curing is even shorter.
It is preferred for the Lewis acid or base to be tetraalkoxytitanate, Zr(OR)4, Li versetate, ZnAcAc in which the alkoxy group is for example a butoxy group or an isopropoxy group.
The amount of carbonylbiscaprolactamate used in the process of the invention may vary between wide limits. As a rule, at least about 0.1 % by weight relative to the functional polymer is needed in order to have an appreciable effect. Amounts in excess of 3% by weight do not normally result in any further increase in molecular weight.
One skilled in the art will generally adjust the amount of carbonylbislactamate to suit the number of available functional groups and the viscosity increase that needs to result from the increased molecular weight.
He/she will normally determine the most optimum amount for his/her situation through simple experiment.
A difunctional polymer here and hereinafter means a polymer with two functional groups per molecule consisting of an -OH group or an -NHz group.
Examples of such polymers are polyamides, polyesters, polycarbonates and polyetherpolyols.
The process of the invention can in principle be applied for all types of polyamide. These include at least the aliphatic polyamides, for example polyamide-4, polyamide-6, polyamide-8, polyamide-4,6, polyamide-6,6, 3 CA 02402430 2002-09-06 pCT/NL01/00199 polyamide-6,10, polyamides derived from an aliphatic diamine and an aromatic dicarboxylic acid, for example polyamide-4,T, polyamide-6,T, polyamide-4,1, where T stands for terephthalate and I for isophthalate, copolyamides of linear polyamides and copolyamides of an aliphatic and a partially aromatic polyamide, for example polyamide 6/6,T and 6/6,1.
Suitable polyesters for which the process of the invention may be applied are at least polyesters derived from aliphatic dicarboxylic acids and diols, polyesters of aliphatic and cycloaliphatic diols and aromatic dicarboxylic acids, copolyesters that are partly aliphatic and partly aromatic and polyesters which contain units that are derived from cycloaliphatic dicarboxylic acids.
Examples hereof are polybutylene adipate, polymethylene terephthalate polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, copolyesters of polybutylene adipate and polybutylene terephthalate and the polyesters derived from butane diol and cyclohexanedicarboxylic acid The polyetherpolyols, for which the process of the invention may be applied are polyols, which possess a oxyalkylene structure, composed of a oxyalkylene group, with 1-10 carbon atoms an oxygen atom as repeating unit and which preferably are a diol. Examples of polyetherpolyols are polyoxymethylene, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyheptamethylene glycol, polyhexamethylene glycol and polydecamethylene glycol.
The process of the invention can readily be carried out using the customary techniques and melt blending equipment, for example by blending the lower molecular polyamide and the carbonylbislactamate and optionally other additives in the solid phase, for example in a tumble dryer, whereupon the obtained blend is melted in a customary melt blender, for example a Haake kneader, a Brabender blender or a twin-screw or double-screw extruder. The various components may also be added to the blending equipment separately.
The carbonylbislactamate and catalyst may also be added to a polymer product stream of a functional polymer having a lower molecular weight as it exits from a polymerization reactor in which this polymer was polymerized.
The polymerization process may be operated batch-wise or continuously. In the former case, the residence time in the reactor can be shortened and so productivity can be increased and the postcondensation step can be omitted.
The invention relates to a process for preparing a high-molecular weight polymer by contacting in a melt a difunctional polymer having a lower molecular weight whose end functional groups are -OH or -NHZ groups with a carbonylbislactamate (CBL) with the following formula:
~CH2~n (~rl~2~n wherein n is an integer from 3 to 15. Preferably the carbonylbislactamate is carbonylbiscaprolactamate (CBC), with n = 5.
A similar process is disclosed in WO 98/47940.
WO 98/47940 describes a process for preparing a high-molecular polyamide by contacting polyamide having a lower molecular weight in the melt with carbonylbiscaprolactamate (CBC).
A drawback of that process is that the reaction proceeds comparatively slowly.
The object of the invention is to provide a process that does not have the aforementioned drawback or has the aforementioned drawback to a lesser extent.
This object is achieved by the melt also containing an acid or a base. The acid or base has the function of a catalyst.
This ensures that the reaction proceeds more rapidly, as is apparent from the fact that the viscosity increases much more rapidly with catalyst than without catalyst. This can be established from for example the increase in the torque of a Brabender in which a blend of a difunctional polymer and CBL is kneaded optionally in the presence of an acid or a base.
Acids that are suitable for use as a catalyst for chain extension in the presence of CBL are LiX, SbZOa, GeOz and As20a, BX3, MgX2, BiX3, SnX4, SbXs, FeX3, GeX4, GaX3, HgX2, ZnX2, AIX3, TiX4, MnX2, ZrX4, R4NX, R4PX, HX, where X = I, Br, CI, F, OR and R = alkyl or aryl. Brpnstedt acids such as HZS04, HN03, HX, H3P04, H3P03, RH2P02, RHZP03, R[(CO)OH]~, with n = 1-6 are also suitable.
Bases that are suitable for use as a catalyst for chain extension in the presence of CBC are Li-versetate, Zn acetylacetonate (acac),M(OH)~, (RO)~M (M= alkali or earth alkali, R = alkyl with C, - CZO or aryl), NR~H4_~OH
(R =
alkyl with C, - CZO or aryl), triamines such as triethylamine, tributylamine, trihexylamine, trioctylamine and cyclic amines such as diazobicyclo[2,2,2]octane (DABCO), dimethylaminopyridine (DMAP), guanidine, morfoline, dibutyl tin dilaurate (DBTDL), dibutyl tin bis(2-ethylhexanoate), dibutyl tin dibutylate, dibutyl tin dimethylate, dibutyl tin dioctanoate.
It is preferred for the catalyst to be a Lewis acid or a Lewis base.
This ensures that the time needed for curing is even shorter.
It is preferred for the Lewis acid or base to be tetraalkoxytitanate, Zr(OR)4, Li versetate, ZnAcAc in which the alkoxy group is for example a butoxy group or an isopropoxy group.
The amount of carbonylbiscaprolactamate used in the process of the invention may vary between wide limits. As a rule, at least about 0.1 % by weight relative to the functional polymer is needed in order to have an appreciable effect. Amounts in excess of 3% by weight do not normally result in any further increase in molecular weight.
One skilled in the art will generally adjust the amount of carbonylbislactamate to suit the number of available functional groups and the viscosity increase that needs to result from the increased molecular weight.
He/she will normally determine the most optimum amount for his/her situation through simple experiment.
A difunctional polymer here and hereinafter means a polymer with two functional groups per molecule consisting of an -OH group or an -NHz group.
Examples of such polymers are polyamides, polyesters, polycarbonates and polyetherpolyols.
The process of the invention can in principle be applied for all types of polyamide. These include at least the aliphatic polyamides, for example polyamide-4, polyamide-6, polyamide-8, polyamide-4,6, polyamide-6,6, 3 CA 02402430 2002-09-06 pCT/NL01/00199 polyamide-6,10, polyamides derived from an aliphatic diamine and an aromatic dicarboxylic acid, for example polyamide-4,T, polyamide-6,T, polyamide-4,1, where T stands for terephthalate and I for isophthalate, copolyamides of linear polyamides and copolyamides of an aliphatic and a partially aromatic polyamide, for example polyamide 6/6,T and 6/6,1.
Suitable polyesters for which the process of the invention may be applied are at least polyesters derived from aliphatic dicarboxylic acids and diols, polyesters of aliphatic and cycloaliphatic diols and aromatic dicarboxylic acids, copolyesters that are partly aliphatic and partly aromatic and polyesters which contain units that are derived from cycloaliphatic dicarboxylic acids.
Examples hereof are polybutylene adipate, polymethylene terephthalate polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, copolyesters of polybutylene adipate and polybutylene terephthalate and the polyesters derived from butane diol and cyclohexanedicarboxylic acid The polyetherpolyols, for which the process of the invention may be applied are polyols, which possess a oxyalkylene structure, composed of a oxyalkylene group, with 1-10 carbon atoms an oxygen atom as repeating unit and which preferably are a diol. Examples of polyetherpolyols are polyoxymethylene, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyheptamethylene glycol, polyhexamethylene glycol and polydecamethylene glycol.
The process of the invention can readily be carried out using the customary techniques and melt blending equipment, for example by blending the lower molecular polyamide and the carbonylbislactamate and optionally other additives in the solid phase, for example in a tumble dryer, whereupon the obtained blend is melted in a customary melt blender, for example a Haake kneader, a Brabender blender or a twin-screw or double-screw extruder. The various components may also be added to the blending equipment separately.
The carbonylbislactamate and catalyst may also be added to a polymer product stream of a functional polymer having a lower molecular weight as it exits from a polymerization reactor in which this polymer was polymerized.
The polymerization process may be operated batch-wise or continuously. In the former case, the residence time in the reactor can be shortened and so productivity can be increased and the postcondensation step can be omitted.
In the process of the invention, CBL reacts solely with the -NHZ
groups or the -OH functional groups of the functional polymers. Functional polymers that also possess -COOH functionality react with either the -OH
functional groups or the -NHz functional groups. If -COOH functionality is present in the melt, it is preferred not only for CBL and the catalyst but also a bisoxazine or a bisoxazoline to be present in the process of the invention. This ensures that the reaction proceeds even more rapidly.
It is preferred for the bisoxazoline to be 1,4-phenylenebisoxazoline.
The invention will be elucidated on the bases of the following examples.
Example 1 CBC is added to grinded and dried PET with 2 -OH end groups and a relative viscosity of r~ =1,59 in a molair ratio of 1:2 (CBC:PET). 1 wt%
of catalyst with respect to the amount of CBC was added. All the PET samples were extruded in a laboratory extruder for 15 gram samples at 280° with a residence time of 4 minutes. The resulting viscosities are given in table 1.
CA 02402430 2002-09-06 pC'T/NLO1/00199 Table 1 Acid/Base Relative viscosity Para toluene sulfonic 1.77 acid MgBr2 1.77 NaOC2H5 1.78 DBTDL 1.79 SnCl4 1.81 VO(iOPr)3 1.81 DABCO 1.83 LiOCH3 1.83 Liar 1.83 Lil 1.83 Zn(acac)z 1.84 LiCI 1.87 Zr(acac)4 1.87 Zr(IV)(OC4H9)4 1.88 Li-versetate 1.94 iOPr= isopropoxy Comparative Experiment A
Example 1 was repeated without adding any catalyst. The relative viscosity increased from 1.59 to 1.76 From these experiments it can be concluded that the addition of acids and bases in a process for preparing a high-molecular weight polymer by contacting in a melt a difunctional low-molecular weight polymer with a carbonylbislactamate results in a faster increase in molecular weight and thus chain extension than without an acid or a base.
It may further be concluded that preferably lithium chloride, zirconium(IV)butoxide, zirconium acetylacetonate or lithium versetate are added.
groups or the -OH functional groups of the functional polymers. Functional polymers that also possess -COOH functionality react with either the -OH
functional groups or the -NHz functional groups. If -COOH functionality is present in the melt, it is preferred not only for CBL and the catalyst but also a bisoxazine or a bisoxazoline to be present in the process of the invention. This ensures that the reaction proceeds even more rapidly.
It is preferred for the bisoxazoline to be 1,4-phenylenebisoxazoline.
The invention will be elucidated on the bases of the following examples.
Example 1 CBC is added to grinded and dried PET with 2 -OH end groups and a relative viscosity of r~ =1,59 in a molair ratio of 1:2 (CBC:PET). 1 wt%
of catalyst with respect to the amount of CBC was added. All the PET samples were extruded in a laboratory extruder for 15 gram samples at 280° with a residence time of 4 minutes. The resulting viscosities are given in table 1.
CA 02402430 2002-09-06 pC'T/NLO1/00199 Table 1 Acid/Base Relative viscosity Para toluene sulfonic 1.77 acid MgBr2 1.77 NaOC2H5 1.78 DBTDL 1.79 SnCl4 1.81 VO(iOPr)3 1.81 DABCO 1.83 LiOCH3 1.83 Liar 1.83 Lil 1.83 Zn(acac)z 1.84 LiCI 1.87 Zr(acac)4 1.87 Zr(IV)(OC4H9)4 1.88 Li-versetate 1.94 iOPr= isopropoxy Comparative Experiment A
Example 1 was repeated without adding any catalyst. The relative viscosity increased from 1.59 to 1.76 From these experiments it can be concluded that the addition of acids and bases in a process for preparing a high-molecular weight polymer by contacting in a melt a difunctional low-molecular weight polymer with a carbonylbislactamate results in a faster increase in molecular weight and thus chain extension than without an acid or a base.
It may further be concluded that preferably lithium chloride, zirconium(IV)butoxide, zirconium acetylacetonate or lithium versetate are added.
Claims (4)
1. Process for preparing a high-molecular polymer by contacting in a melt a difunctional lowermolecular polymer whose end functional groups are -OH or-NH2 groups with a carbonylbislactamate with the following formula:
wherein n is an integer from 3 to 15, characterized in that the melt also contains an acid or a base.
wherein n is an integer from 3 to 15, characterized in that the melt also contains an acid or a base.
2. Process according to Claim 1, in which the catalyst is a Lewis acid or a Lewis base.
3. Process according to claim 1 or claim 2, in which the carbonylbislactamate is carbonylbiscaprolactamate.
4. Process according to any one of Claims 1-3, in which the difunctional polymer also contains a -COOH group and in that a bisoxazine or a bisoxazoline is also present in the melt.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL1014604 | 2000-03-10 | ||
NL1014604A NL1014604C2 (en) | 2000-03-10 | 2000-03-10 | Procedure for chain extension. |
PCT/NL2001/000199 WO2001066633A1 (en) | 2000-03-10 | 2001-03-09 | Chain extension process |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2402430A1 true CA2402430A1 (en) | 2001-09-13 |
Family
ID=19770973
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002402430A Abandoned CA2402430A1 (en) | 2000-03-10 | 2001-03-09 | Chain extension process |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP1263864A1 (en) |
JP (1) | JP2003525989A (en) |
CN (1) | CN1416449A (en) |
AU (1) | AU2001242861A1 (en) |
CA (1) | CA2402430A1 (en) |
NL (1) | NL1014604C2 (en) |
WO (1) | WO2001066633A1 (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL1019241C2 (en) * | 2001-10-26 | 2003-05-01 | Dsm Nv | New polymer compositions, as well as the preparation and use thereof. |
CA2474251C (en) | 2002-02-01 | 2009-05-12 | Johnson Polymer, Llc | Oligomeric chain extenders for processing, post-processing and recycling of condensation polymers, synthesis, compositions and applications |
WO2004046156A1 (en) * | 2002-11-20 | 2004-06-03 | Dsm Ip Assets B.V. | Silane coupling agent, process for the preparation of a silane coupling agent, use of said silane coupling agent in a composite or on a substrate, nanoparticles and use thereof in a coating. |
DE10340977B4 (en) | 2003-09-05 | 2006-04-13 | Ticona Gmbh | Polyoxymethylene homo- and copolymers, their preparation and use |
DE10340976B4 (en) | 2003-09-05 | 2006-04-13 | Ticona Gmbh | Polyoxymethylene multiblock copolymers, their preparation and use |
CN100465207C (en) * | 2005-08-31 | 2009-03-04 | 北京化工大学 | Process for preparing high-molecular aliphatic polyester |
DE102007040683A1 (en) | 2007-08-29 | 2009-03-05 | Evonik Degussa Gmbh | Sheathed pipe |
CN101585915B (en) * | 2008-05-23 | 2011-04-20 | 北京化工大学 | Method for preparing biodegradable polyesteramide through chain extension |
DE102008044224A1 (en) | 2008-12-01 | 2010-06-02 | Evonik Degussa Gmbh | Use of a composition for contact with supercritical media |
DE102009001001A1 (en) | 2009-02-19 | 2010-09-02 | Evonik Degussa Gmbh | Use of a conduit for the production of a pipeline laid in the water |
CN102643422A (en) * | 2011-02-21 | 2012-08-22 | 北京化工大学 | Preparation method for biodegradable aliphatic alternating polyester amide |
DE102011007104A1 (en) | 2011-04-11 | 2012-10-11 | Evonik Degussa Gmbh | Polyamide sheathed steel construction tubes for offshore structures |
US8927737B2 (en) | 2011-08-09 | 2015-01-06 | Basf Se | Process for purifying ionic liquids |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3862262A (en) * | 1973-12-10 | 1975-01-21 | Monsanto Co | Lactam-polyol-acyl polyactam terpolymers |
NL8400006A (en) * | 1984-01-03 | 1985-08-01 | Stamicarbon | PROCESS FOR THE CONDENSATION OF IMIDE AND ALKOHOL. |
US4595746A (en) * | 1984-12-17 | 1986-06-17 | Monsanto Company | Promotion of ε-caprolactam polymerization with lactam magnesium halide catalyst and 2-oxo-1-pyrrolidinyl groups |
JP2507379B2 (en) * | 1986-06-23 | 1996-06-12 | 帝人株式会社 | Method for producing high degree of polymerization polyester |
US5200498A (en) * | 1992-01-29 | 1993-04-06 | Monsanto Company | Lactam-lactone copolymer |
BE1009365A3 (en) * | 1995-05-04 | 1997-02-04 | Dsm Nv | High-molecular polyamide. |
AU6856698A (en) * | 1997-04-22 | 1998-11-13 | Dsm N.V. | High-molecular polyamide |
-
2000
- 2000-03-10 NL NL1014604A patent/NL1014604C2/en not_active IP Right Cessation
-
2001
- 2001-03-09 JP JP2001565796A patent/JP2003525989A/en active Pending
- 2001-03-09 WO PCT/NL2001/000199 patent/WO2001066633A1/en not_active Application Discontinuation
- 2001-03-09 EP EP01915913A patent/EP1263864A1/en not_active Withdrawn
- 2001-03-09 CN CN 01806375 patent/CN1416449A/en active Pending
- 2001-03-09 CA CA002402430A patent/CA2402430A1/en not_active Abandoned
- 2001-03-09 AU AU2001242861A patent/AU2001242861A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
WO2001066633A1 (en) | 2001-09-13 |
NL1014604C2 (en) | 2001-09-11 |
JP2003525989A (en) | 2003-09-02 |
CN1416449A (en) | 2003-05-07 |
EP1263864A1 (en) | 2002-12-11 |
AU2001242861A1 (en) | 2001-09-17 |
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