NL1014604C2 - Procedure for chain extension. - Google Patents
Procedure for chain extension. Download PDFInfo
- Publication number
- NL1014604C2 NL1014604C2 NL1014604A NL1014604A NL1014604C2 NL 1014604 C2 NL1014604 C2 NL 1014604C2 NL 1014604 A NL1014604 A NL 1014604A NL 1014604 A NL1014604 A NL 1014604A NL 1014604 C2 NL1014604 C2 NL 1014604C2
- Authority
- NL
- Netherlands
- Prior art keywords
- melt
- international
- examined
- classification
- catalyst
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 21
- 239000003054 catalyst Substances 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 10
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 5
- 239000002879 Lewis base Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000007527 lewis bases Chemical class 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 239000002841 Lewis acid Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 150000007517 lewis acids Chemical group 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000011835 investigation Methods 0.000 claims 3
- -1 H 2 SO 4 Chemical class 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000004952 Polyamide Substances 0.000 description 7
- 229920002647 polyamide Polymers 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 229920001002 functional polymer Polymers 0.000 description 5
- CWRORZJYSUFYHO-UHFFFAOYSA-N (3z)-3-diazobicyclo[2.2.2]octane Chemical compound C1CC2C(=[N+]=[N-])CC1CC2 CWRORZJYSUFYHO-UHFFFAOYSA-N 0.000 description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 229920001007 Nylon 4 Polymers 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920001634 Copolyester Polymers 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- ZDNUPMSZKVCETJ-UHFFFAOYSA-N 2-[4-(4,5-dihydro-1,3-oxazol-2-yl)phenyl]-4,5-dihydro-1,3-oxazole Chemical group O1CCN=C1C1=CC=C(C=2OCCN=2)C=C1 ZDNUPMSZKVCETJ-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- UJEWTUDSLQGTOA-UHFFFAOYSA-N Piretanide Chemical compound C=1C=CC=CC=1OC=1C(S(=O)(=O)N)=CC(C(O)=O)=CC=1N1CCCC1 UJEWTUDSLQGTOA-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229960001085 piretanide Drugs 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
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)
Description
f - 1 - WERKWIJZE VOOR KETENVERLENGING 5f - 1 - METHOD FOR CHAIN EXTENSION 5
De uitvinding heeft betrekking op een werkwijze voor de bereiding van een hoogmoleculair polymeer door in een smelt een difunctioneel 10 laagmoleculair polymeer, waarvan de functionele groepen -OH of -NH2 groepen zijn, in contact te brengen met carbonylbiscaprolactamaat.The invention relates to a process for the preparation of a high-molecular polymer by melt-contacting a difunctional low-molecular polymer, the functional groups of which are -OH or -NH2 groups, with carbonyl biscaprolactamate.
Een dergelijke werkwijze is bekend uit WO 98/47940.Such a method is known from WO 98/47940.
15 WO 98/47940 beschrijft een werkwijze voor de bereiding van een hoogmolecuul polyamide door in de smelt polyamide met een lager molgewicht te mengen met carbonylbiscaprolactamaat (CBC).WO 98/47940 describes a process for preparing a high molecular weight polyamide by melt melting lower molecular weight polyamide with carbonyl bis caprolactamate (CBC).
Nadeel van deze werkwijze is, dat de 20 reaktie relatief traag verloopt.A drawback of this method is that the reaction proceeds relatively slowly.
Doel van de uitvinding is te voorzien in een werkwijze die bovengenoemd nadeel niet, of in mindere mate heeft.The object of the invention is to provide a method which does not have, or to a lesser extent, the above-mentioned drawback.
Dit doel wordt bereikt, doordat in de smelt 25 tevens een zuur of een base als katalysator aanwezig is.This object is achieved in that the melt also contains an acid or a base as a catalyst.
Hierdoor wordt bereikt, dat de reactie sneller verloopt, hetgeen blijkt uit het feit dat dat de viscositeit met katalysator veel sneller toeneemt 30 dan zonder katalysator. Dit kan bijvoorbeeld vastgesteld worden aan de hand van de toename van het koppel van een Brabender waarin een mengsel van een difunctioneel polymeer en CBC al dan niet in aanwezigheid van een katalysator wordt gekneed.This ensures that the reaction proceeds faster, which is evident from the fact that the viscosity increases with catalyst much faster than without catalyst. This can be determined, for example, by the increase in the torque of a Brabender in which a mixture of a difunctional polymer and CBC is kneaded in the presence or not of a catalyst.
1 0 1 46 04 - 2 - · ·1 0 1 46 04 - 2 - · ·
Zuren die geschikt zijn als katalysator voor ketenverlenging in aanwezigheid van CBC zijn LiX, Sb203, Ge02 sn As203, BX3, MgX2/ BiX3, SnX4, SbXs, FeX3/Acids suitable as a catalyst for chain extension in the presence of CBC are LiX, Sb203, Ge02 sn As203, BX3, MgX2 / BiX3, SnX4, SbXs, FeX3 /
GeX4, GaX3, HgX2, ZnX2/ A1X3, TiX4, MnX2, ZrX4, R4NX, R4PX, 5 HX, waarin X = I, Br, Cl, F, OR en R = alkyl of aryl. Br0nstedt zuren als H2S04, HN03, HX, H3P04, H3P03, RH2P02, RH2P03, R [ (CO) OH] n, met n = 1-6 zijn eveneens geschikt.GeX4, GaX3, HgX2, ZnX2 / A1X3, TiX4, MnX2, ZrX4, R4NX, R4PX, 5 HX, where X = I, Br, Cl, F, OR, and R = alkyl or aryl. Brought acids such as H 2 SO 4, HNO 3, HX, H 3 PO 4, H 3 PO 3, RH 2 PO 2, RH 2 PO 3, R [(CO) OH] n, with n = 1-6 are also suitable.
Basen die geschikt zijn als katalysator voor ketenverlenging in aanwezigheid van CBC zijn 10 M(OH)a, (RO)nM (M= Alkali of aardalkali, R = alkyl met Ci - C20 of aryl) , NRnH4.nOH (R = alkyl met Cx - C20 of ary), triamines zoals triethylamine, tributyl amine, trihexylamine, trioctylamine en cyclische amines zoals Diazobicyclo[2,2,2]octaan (DABCO), 15 dimethylaminopyridine (DMAP), Guanidine, Morfoline.Bases suitable as catalyst for chain extension in the presence of CBC are 10 M (OH) a, (RO) nM (M = Alkali or alkaline earth, R = alkyl with C 1 -C 20 or aryl), NRnH4.nOH (R = alkyl with Cx-C20 or ary), triamines such as triethylamine, tributyl amine, trihexylamine, trioctylamine and cyclic amines such as Diazobicyclo [2,2,2] octane (DABCO), dimethylaminopyridine (DMAP), Guanidine, Morpholine.
Bij voorkeur is de katalysator een Lewiszuur of -base. Hierdoor wordt bereikt dat de tijd nodig voor het uitharden nog korter is.Preferably, the catalyst is a Lewis acid or base. This ensures that the time required for curing is even shorter.
Lewiszuren die geschikt zijn als 20 katalysator in de werkwijze volgens de uitvinding zijn Sb203, As203, LiX, BX3, MgX2, BiX3, SnX4, SbX5, FeX3, GeX4, GaX3, HgX2, ZnX2, A1X3, TiX4, MnX2, ZrX4, R4NX, R4PX, HX, waarin X = I, Br, Cl, F, OR en R = alkyl of aryl.Lewis acids suitable as catalyst in the process of the invention are Sb203, As203, LiX, BX3, MgX2, BiX3, SnX4, SbX5, FeX3, GeX4, GaX3, HgX2, ZnX2, A1X3, TiX4, MnX2, ZrX4, R4NX, R4PX, HX, wherein X = I, Br, Cl, F, OR, and R = alkyl or aryl.
Lewisbasen die geschikt zijn als 25 katalysator zijn in de werkwijze volgens de uitvinding zijn tertiair amines waaronder triethylamine, tributylamine, trihexylamine, trioctylamine, cyclische amines zoals diazobicyclo[2,2,2]octaan (DABCO), dimethylaminopyridine (DMAP), Guanidine, en Morfoline. 30 Bij voorkeur is de Lewisbase tetra- alkoxytitanaat, waarin de alkoxygroep bijvoorbeeld een butoxy- of een isopropoxygroep is.Lewis bases which are suitable as catalysts in the process of the invention are tertiary amines including triethylamine, tributylamine, trihexylamine, trioctylamine, cyclic amines such as diazobicyclo [2,2,2] octane (DABCO), dimethylaminopyridine (DMAP), Guanidine, and Morpholine. Preferably, the Lewis base is tetraalkoxy titanate, wherein the alkoxy group is, for example, a butoxy or an isopropoxy group.
1 n 1 ru - 3 -1 n 1 ru - 3 -
De hoeveelheid carbonylbiscaprolactamaat die in de werkwijze volgens de uitvinding wordt toegepast kan tussen ruime grenzen variëren. In het algemeen is tenminste ongeveer 0,1 gew.% t.o.v. het 5 functioneel polymeer nodig om een merkbaar effect te hebben. Hoeveelheden van meer dan 3 gew.% hebben in het algemeen geen verdere verhoging van het molecuulgewicht ten gevolge.The amount of carbonyl biscaprolactamate used in the process of the invention can vary within wide limits. Generally, at least about 0.1% by weight of the functional polymer is required to have a noticeable effect. Amounts greater than 3% by weight generally do not result in any further increase in molecular weight.
In het algemeen zal de vakman de toe te 10 passen hoeveelheid carbonylbiscaprolactamaat afstemmen op het aantal beschikbare functionele groepen en de te realiseren viscositeitsverhoging die uit het verhoogde molecuulgewicht voortvloeit. Hij zal door eenvoudig experimenteren in het algemeen de voor zijn situatie 15 meest optimale hoeveelheid vaststellen.In general, the person skilled in the art will tailor the amount of carbonyl biscaprolactamate to be used to the number of available functional groups and the viscosity increase to be realized which results from the increased molecular weight. He will generally determine the most optimal amount for his situation by simple experimentation.
Onder een functioneel polymeer wordt hier en hierna verstaan een polymeer met twee functionele groepen bestaand uit een -OH, of een -NH2 groep.A functional polymer is here and hereafter understood to mean a polymer with two functional groups consisting of an -OH, or an -NH2 group.
Voorbeelden van dergelijke polymeren zijn 20 polyamiden, polyesters, en polyetherpolyolen.Examples of such polymers are polyamides, polyesters, and polyether polyols.
In principe is de werkwijze van de uitvinding toepasbaar voor alle typen polyamiden. Hieronder vallen tenminste de alifatische polyamiden, bijvoorbeeld polyamide-4, polyamide-6, polyamide-8, 25 polyamide-4,6, polyamide-6,6, polyamide-6,10, polyamiden afgeleid van een alifatisch diamine en een aromatisch dicarbonzuur, bijvoorbeeld polyamide-4,T, polyamide-6,T, polyamide-4,I, waarin T staat voor tereftalaat en I voor isoftalaat, copolyamiden van 30 lineaire polyamiden en copolyamiden van een alifatisch en een deelaromatisch polyamide, bijvoorbeeld polyamide 6/6,T en 6/6,1.In principle, the method of the invention is applicable to all types of polyamides. This includes at least the aliphatic polyamides, for example polyamide-4, polyamide-6, polyamide-8, polyamide-4,6, polyamide-6,6, polyamide-6,10, polyamides derived from an aliphatic diamine and an aromatic dicarboxylic acid, for example polyamide-4, T, polyamide-6, T, polyamide-4, I, wherein T stands for terephthalate and I for isophthalate, copolyamides of 30 linear polyamides and copolyamides of an aliphatic and a partial aromatic polyamide, for example polyamide 6/6, T and 6 / 6.1.
1014604 - 4 -1014604 - 4 -
Geschikte polyesters om de werkwijze volgens de uitvinding aan uit te voren zijn ten minste polyesters afgeleid van alifatische dicarbonzuren en diolen, polyesters van alifatische en cycloalifatische 5 diolen en aromatische dicarbonzuren, copolyesters die gedeeltelijk alifatisch en gedeeltelijk aromatisch zijn en polyesters die eenheden bevatten die zijn afgeleid van cycloalifatische dicarbonzuren. Voorbeelden hiervan zijn polybutyleen adipaat, polyethyleen terephtalaat, 10 polyethyleen naftalaat, polybutyleenterephtalaat, copolyesters van polybultyleenadipaat en polybutyleenterephtalaat en de polyesters afgeleid van butaandiol en cyclohexaandicarbonzuur.Suitable polyesters to demonstrate the process of the invention include at least polyesters derived from aliphatic dicarboxylic acids and diols, polyesters from aliphatic and cycloaliphatic diols and aromatic dicarboxylic acids, copolyesters which are partially aliphatic and partially aromatic, and polyesters containing units that have been derived of cycloaliphatic dicarboxylic acids. Examples of these are polybutylene adipate, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, copolyesters of polybultylene adipate and polybutylene terephthalate and the polyesters derived from butanediol and cyclohexane dicarboxylic acid.
De polyetherpolyolen waarop de werkwijze 15 toepasbaar is, zijn polyolen welke een polyoxyalkyleen structuur bezitten, zijn samengesteld uit een polyoxyalkyleen groep met 20-10 koolstof atomen een zuurstof atoom als repeterende eenheid en welke bij voorkeur een diol zijn. Voorbeelden van 20 polyetherpolyolen zijn polyethyleenglycol, polypropyleenglycol, polytetramethyleenglycol, polyheptamethyleenglycol, polyhexamethyleenglycol en polydecamethyleenglycol.The polyether polyols to which the process is applicable are polyols having a polyoxyalkylene structure, which are composed of a polyoxyalkylene group having 20-10 carbon atoms, an oxygen atom as a repeating unit, and which are preferably a diol. Examples of polyether polyols are polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyheptamethylene glycol, polyhexamethylene glycol and polydecamethylene glycol.
De werkwijze volgens de uitvinding kan op 25 eenvoudige wijze worden uitgevoerd met de gebruikelijke technieken en apparatuur van smeltmengen, bijvoorbeeld door menging van het lager moleculaire polyamide en het carbonylbiscaprolactamaat en desgewenst nog verdere additieven in de vaste toestand, bijvoorbeeld in een 30 tuimeldroger, waarna het verkregen mengsel in een gebruikelijk smeltmengapparaat, bijvoorbeeld een Haakekneder, een Brabendermenger of een enkel- of 1014604 - 5 - dubbelschroefsextruder wordt opgesmolten. De verschillende componenten kunnen ook afzonderlijk aan de mengapparatuur worden toegevoegd.The process according to the invention can be carried out in a simple manner with the usual techniques and equipment of melt blending, for instance by mixing the lower molecular polyamide and the carbonyl bis caprolactamate and, if desired, further additives in the solid state, for example in a tumbler dryer, after which the The resulting mixture is melted in a conventional melt mixer, for example a Haakekneder, a Brabender mixer or a single or 1014604-5 twin screw extruder. The different components can also be added separately to the mixing equipment.
Ook kunnen het carbonylbiscaprolactamaat en 5 de katalysator worden toegevoegd aan een polymeerproduktstroom van een functioneel polymeer met een lager molecuulgewicht bij het verlaten van een polymerisatiereactor waarin dit polymeer werd gepolymeriseerd.Also, the carbonyl biscaprolactamate and the catalyst may be added to a polymer product stream of a lower molecular weight functional polymer upon leaving a polymerization reactor in which this polymer was polymerized.
10 Het polymerisatieproces kan daarbij batchgewijs worden uitgevoerd zowel als continu. In het eerste geval kan daarbij een verkorting van de verblijftijd in de reactor worden gerealiseerd en daarmee een verhoging van de productiviteit en kan de 15 nacondensatiestap worden vermeden.The polymerization process can be carried out batchwise as well as continuously. In the first case, a shortening of the residence time in the reactor can thereby be realized and thus an increase in productivity and the post-condensation step can be avoided.
Daar waar in de werkwijze volgens de vinding carbonylbiscaprolactamaat wordt toegepast, kan CBC geheel of gedeeltelijk worden vervangen door een n-acyllactam.Where carbonyl bis-caprolactamate is used in the process according to the invention, CBC can be wholly or partly replaced by an n-acyl lactam.
20 In de werkwijze volgens de uitvinding reageert CBC uitsluitend met de -NH2 en -OH functionele groepen van de functionele polymeren. Functionele polymeren die eveneens -COOH functionaliteit bezitten reageren met de -OH dan wel -NH2 functionele groepen.In the method of the invention, CBC reacts only with the -NH2 and -OH functional groups of the functional polymers. Functional polymers that also have -COOH functionality react with the -OH or -NH2 functional groups.
25 Indien -COOH functionaliteit in de smet aanwezig is, is bij voorkeur naast CBC en de katalysator in de werkwijze volgens de uitvinding ook een bisoxazine of een bisoxazoline aanwezig. Hierdoor wordt bereikt, dat de reaktie nog sneller verloopt.If -COOH functionality is present in the stain, it is preferable for a bisoxazine or a bisoxazoline to be present in addition to CBC and the catalyst in the process according to the invention. This ensures that the reaction proceeds even faster.
30 Bij voorkeur is het bisoxazoline 1,4-fenyleenbisoxazoline.Preferably, the bisoxazoline is 1,4-phenylene bisoxazoline.
10146041014604
Claims (3)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL1014604A NL1014604C2 (en) | 2000-03-10 | 2000-03-10 | Procedure for chain extension. |
| JP2001565796A JP2003525989A (en) | 2000-03-10 | 2001-03-09 | Chain extension method |
| PCT/NL2001/000199 WO2001066633A1 (en) | 2000-03-10 | 2001-03-09 | Chain extension process |
| AU2001242861A AU2001242861A1 (en) | 2000-03-10 | 2001-03-09 | Chain extension process |
| EP01915913A EP1263864A1 (en) | 2000-03-10 | 2001-03-09 | Chain extension process |
| CA002402430A CA2402430A1 (en) | 2000-03-10 | 2001-03-09 | Chain extension process |
| CN 01806375 CN1416449A (en) | 2000-03-10 | 2001-03-09 | Chain extension process |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL1014604 | 2000-03-10 | ||
| NL1014604A NL1014604C2 (en) | 2000-03-10 | 2000-03-10 | Procedure for chain extension. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NL1014604C2 true NL1014604C2 (en) | 2001-09-11 |
Family
ID=19770973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NL1014604A NL1014604C2 (en) | 2000-03-10 | 2000-03-10 | Procedure for chain extension. |
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. |
| US6984694B2 (en) | 2002-02-01 | 2006-01-10 | Johnson Polymer, Llc | Oligomeric chain extenders for processing, post-processing and recycling of condensation polymers, synthesis, compositions and applications |
| AU2003279627A1 (en) * | 2002-11-20 | 2004-06-15 | Dsm Ip Assests 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 weight aliphatic polyesters |
| 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 |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3862262A (en) * | 1973-12-10 | 1975-01-21 | Monsanto Co | Lactam-polyol-acyl polyactam terpolymers |
| EP0147792A2 (en) * | 1984-01-03 | 1985-07-10 | Stamicarbon B.V. | Process for the condensation of imide and alcohol |
| 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 |
| JPS6399228A (en) * | 1986-06-23 | 1988-04-30 | Teijin Ltd | Production of polyester having high polymerization degree |
| EP0556170A1 (en) * | 1992-01-29 | 1993-08-18 | Monsanto Company | Lactam-lactone copolymers |
| WO1996034909A1 (en) * | 1995-05-04 | 1996-11-07 | Dsm N.V. | High-molecular polyamide |
| WO1998047940A1 (en) * | 1997-04-22 | 1998-10-29 | 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 AU AU2001242861A patent/AU2001242861A1/en not_active Abandoned
- 2001-03-09 CA CA002402430A patent/CA2402430A1/en not_active Abandoned
- 2001-03-09 WO PCT/NL2001/000199 patent/WO2001066633A1/en not_active Ceased
- 2001-03-09 CN CN 01806375 patent/CN1416449A/en active Pending
- 2001-03-09 EP EP01915913A patent/EP1263864A1/en not_active Withdrawn
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3862262A (en) * | 1973-12-10 | 1975-01-21 | Monsanto Co | Lactam-polyol-acyl polyactam terpolymers |
| EP0147792A2 (en) * | 1984-01-03 | 1985-07-10 | Stamicarbon B.V. | Process for the condensation of imide and alcohol |
| 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 |
| JPS6399228A (en) * | 1986-06-23 | 1988-04-30 | Teijin Ltd | Production of polyester having high polymerization degree |
| EP0556170A1 (en) * | 1992-01-29 | 1993-08-18 | Monsanto Company | Lactam-lactone copolymers |
| WO1996034909A1 (en) * | 1995-05-04 | 1996-11-07 | Dsm N.V. | High-molecular polyamide |
| WO1998047940A1 (en) * | 1997-04-22 | 1998-10-29 | Dsm N.V. | High-molecular polyamide |
Non-Patent Citations (1)
| Title |
|---|
| DATABASE WPI Section Ch Week 198823, Derwent World Patents Index; Class A23, AN 1988-158448, XP002157844 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003525989A (en) | 2003-09-02 |
| EP1263864A1 (en) | 2002-12-11 |
| CN1416449A (en) | 2003-05-07 |
| AU2001242861A1 (en) | 2001-09-17 |
| WO2001066633A1 (en) | 2001-09-13 |
| CA2402430A1 (en) | 2001-09-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| NL1014604C2 (en) | Procedure for chain extension. | |
| US20010016630A1 (en) | High-molecular polyamide | |
| JPH07268096A (en) | Star branched polymer and its production | |
| JP2004534884A (en) | Multi-mode polyamide, polyester and polyester amide | |
| JP2002543257A (en) | Polyamide condensation method | |
| KR20070088574A (en) | Method for preparing particles made from thermoplastic polymers and powders obtained thereby | |
| NL1014605C2 (en) | Process for preparing a branched polymer. | |
| EP1476486A1 (en) | Process for preparing a high-molecular polyamide, polyester, copolyester, copolyamide or polyester-amide block copolymer | |
| NL9401346A (en) | Polymers comprising polyether blocks and polyamide blocks. | |
| US4604449A (en) | Process for preparing poly(ester-amides) | |
| EP0149986B1 (en) | Cross-linked nylon block copolymers and process of their preparation | |
| EP0067693A1 (en) | Acid halide and acyllactam functional materials | |
| EP0291948A2 (en) | Polyamideimide elastomer and production thereof | |
| Jakisch et al. | Introduction of a New Coupling Agent for Selective Coupling of Hydroxy and Amino Group‐Containing Polymers | |
| JPH0374254B2 (en) | ||
| JPH03500303A (en) | Amino-functional polyethers containing urea, burette, thiourea, dithioburet, thioamide and/or amide components in their main chains, and urethane/urea prepolymers and polymers produced therefrom | |
| US20030176594A1 (en) | Chain extension process | |
| EP0392633B1 (en) | Process for the condensation of imides and alcohols or amines | |
| JPH0343418A (en) | Polysiloxane-polyamide-based block copolymer | |
| JPS60240727A (en) | Polyamide block copolymer | |
| JP4693784B2 (en) | Method for producing polyester copolymer containing amide bond | |
| EP0404254A1 (en) | N-substituted carbamoyllactam functional compounds and polylactam block copolymers derived therefrom | |
| NL1014603C2 (en) | Thermosetting composition for use in solvent-based coatings and powder coatings, contains a functional resin with hydroxyl or amine groups and a crosslinking agent | |
| JPS60168724A (en) | Crosslinked nylon block copolymer | |
| JP2002504605A (en) | Method for producing a polymer blend from an aminonitrile and a thermoplastic polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PD2B | A search report has been drawn up | ||
| VD1 | Lapsed due to non-payment of the annual fee |
Effective date: 20051001 |