EP0519012A1 - Copolymeres blocs segmentes - Google Patents

Copolymeres blocs segmentes

Info

Publication number
EP0519012A1
EP0519012A1 EP19910907198 EP91907198A EP0519012A1 EP 0519012 A1 EP0519012 A1 EP 0519012A1 EP 19910907198 EP19910907198 EP 19910907198 EP 91907198 A EP91907198 A EP 91907198A EP 0519012 A1 EP0519012 A1 EP 0519012A1
Authority
EP
European Patent Office
Prior art keywords
block copolymer
copolymer according
segments
block
glass transition
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.)
Withdrawn
Application number
EP19910907198
Other languages
German (de)
English (en)
Inventor
Reinoud Jaap Gaymans
Jeanette Louise Molenaar-De Haan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
Original Assignee
Dow Benelux BV
Dow Chemical Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from NL9000510A external-priority patent/NL9000510A/nl
Priority claimed from NL9000512A external-priority patent/NL9000512A/nl
Priority claimed from NL9000509A external-priority patent/NL9000509A/nl
Application filed by Dow Benelux BV, Dow Chemical Co filed Critical Dow Benelux BV
Publication of EP0519012A1 publication Critical patent/EP0519012A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C08G69/44—Polyester-amides
    • 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
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • 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
    • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids

Definitions

  • the invention relates to segmented block copolymers based on non- crystallizable segments and partly crystallizable segments . Depending on the type and properties of the materials constituting the blocks , such blockcopolymers may have different properties .
  • Block copolymers comprising non- crystallizable segments and partly crystallizable segments exhibit the behaviour of semi - crystalline polymers , the difference being that the T g /T m ratio is not invariably 0. 66 (the 2 /3 rule) , but may have a different value.
  • the materials When this ratio is lower than 0 . 6 the materials usually have a thermoplastic elastomer character. At higher values the materials mostly behave as semi- crystalline polymers , such as PET, PBT, nylon 6 and the like. When the value for T g /T m exceeds 0 .7 for the semi - crystalline block copolymers , the materials have an improved balance of properties , since the range between T g and T m , in which range the modulus is from 3 - 20 times lower than the modulus below the T g , is smaller.
  • Thermoplastic elastomers consist in principle of two types of blocks , namely soft or flexible blocks and hard or non- f lexible blocks .
  • the soft blocks are typically formed by amorphous flexible segments with a glass transition temperature of below 0° C .
  • the hard blocks consist of crystallizable segments with a high melting temperature.
  • thermoplastic elastomers behave as elastomers at temperatures below the melting temperature , while above that temperature a thermoplastic behaviour is found. Owing to this , these products are easy to process : easier, often, than pure elastomers , which often combine their elastomeric behaviour with difficult processability. Although thermoplastic elastomers possess a suitable property pattern, a decrease of mechanical properties occurs at temperatures approaching the melting temperature of the hard blocks, so that the temperature range within which the products can be used is fairly limited at the upper end.
  • plastics with a property pattern, which makes it possible to use the plastic for construction purposes or under conditions of extreme temperatures.
  • a number of such semi-crystalline plastics are based on polyesters, such as polybutyleneterephthalate, or on polyamides.
  • melt processability is not yet optimal, which makes it necessary for the plastic to be processed at temperatures far above the glass transition temperature. This is -undesirable in view of polymer degradation and in view of energy consumption. It also means the cycle time is extended.
  • the object of the invention is .to provide new block copolymers, which do not possess the disadvantages described hereabove and which do have a number of advantageous properties hitherto not available.
  • novel block copolymers can, among other things be used as fibre material or as an engineering plastic and exhibit a minor decrease of the modulus above the glass transition temperature, and a good melt processability at temperatures just above the melting temperature.
  • Block copolymers comprising hard, crystallizing segments and soft segments, having thermoplastic and elastomeric properties, can be employed advantageously in the automobile industry.
  • the present invention is based on the surprising insight that by using short, uniform segments for the crystallizable blocks, the materials possess unusual high crystallization rates and the engineering plastics have improved properties.
  • the present invention relates to segmented block copolymers comprising non-crystallizable segments and partly crystallizable segments, in which the partly crystallizable segments have the following formula: - • NH-R2-NH- [C(O) -Ri"C(0) -NH-R -NH]n" -C(O) -R ⁇ -C(O) - [NH-R 2 -NH-C(0) -R x -C(0) ] n - and/or
  • n is an integer which equals 1 , 2 , or 3
  • Ri and R 2 are independently an aliphatic , an alicyclic , or a wholly or partly aromatic group
  • R 3 is a hydrocarbon radical which may or may not be substituted, and in which block copolymers the partly crystallizable segments have a substantially uniform block length.
  • a substantially uniform block length means that virtually all partly crystallizable segments in the polymer have the same value for n.
  • a proportion of at least 70%, preferably at least 85% of all segments have the same length. More preferably, this proportion is at least 90%, and yet more preferably at least 97.5%.
  • Such uniform block length can be obtained by a proper selection of the starting materials for the preparation of the block copolymer. This will be further explained when these materials are discussed.
  • block copolymers of the invention are thermoplastic elastomers and/or engineering plastics.
  • the flexible segments have a glass transition temperature ⁇ 0° C.
  • These block copolymers possess thermoplastic properties and the degree and the rate of crystallization of these copolymers is higher than of block copolymers not according to the invention.
  • a hard block which as such, i.e. as an oligomer with amide groups, exhibits a crystalline structure at temperatures below the melting point.
  • the melting temperature of the segmented block copolymer of this embodiment is preferably > 100°C, more preferably > 150°C, so as to guarantee optimum usability.
  • the melting temperature can be set through the appropriate selection of n, Ri, R , and optionally R 3 .
  • the segmented block copolymer according to the invention exhibits a very good phase separation, i.e. a very good separation of the flexible and the non-flexible phases, while a low glass transition temperature of the soft or flexible phase is retained. Further, a high degree of ordering of the hard phase occurs.
  • one of the most important properties of the products of the invention is that the course of the modulus at temperatures above the glass transition temperature of the soft phase depends on the temperature to a minor extent only. In practice it has been shown possible to employ service temperatures which are fairly close to the melting temperature of the hard, non-flexible phase.
  • the glass transition temperature of the soft blocks is ⁇ 0°C, preferably ⁇ -25°C, and more preferably ⁇ -45°C.
  • the flexible block is formed by the usual flexible segments, which consist of a, preferably difunctional, linear polymer having a molecular weight of 200-4000. This polymer has rubbery properties after incorporation into the block copolymers according to the invention, which is reflected in its glass transition temperature, among other things.
  • polyesters and polyethers preferably based on ethylene oxide , propylene oxide, butyl ene oxide, copolymers , or block copolymers of two or more of those , or hydrogenated or unhydrogenated polybutadiene and polyisobutylene .
  • the flexible segments may be hydroxyl - , carboxyl- , or amine - terminal .
  • the nature of these terminal groups of the flexible block may affect the choice of the hard block, because certain combinations of terminal groups need not necessarily be reactive with all hard blocks .
  • the glass transition temperature of the block copolymer is > 0°C.
  • These materials have typical engineering plastic properties and can also be used as fiber material .
  • segmented block copolymers according to this embodiment of the invention i . e. . with short uniform blocks and short non- crystallizable blocks , have a combination of a T g > 0°C , a T g /T m > 0 . 6 and a high crystallization rate .
  • the non- crystallizable segment pref erably has a molecular weight of 20 to 400 , more preferably of 40 to 250 .
  • Particularly suitable are aliphatic or alicyclic diols , diamine , aminoalcoh ⁇ ls , diacids , amino acids hydroxy acids hydroxyl -terminal chains and the like.
  • the melting temperature of the segmented block copolymer of this embodiment of the invention is preferably > 160°C so as to guarantee optimum usability.
  • the melting temperature can be set by the appropriate selection of n, R i f R 2 and R 3 .
  • the glass transition temperature of the block copolymer is > 130°C. It turned out that such segmented block copolymers according to the invention exhibit very good mechanical properties such as tensile strength, impact resistance , dimensional stability, good tribologic properties and a good solvent - resistance . Further, these products have a high modulus up to the glass transition temperature and a reasonably high modulus between the glass transition temperature and the melting temperature if it is higher. Furthermore, the block copolymers according to this embodiment exhibit a good melt processability at temperatures which are only some tens of degrees above these two transition temperatures.
  • the block- copolymers according to this embodiment of the invention which are built up from blocks with amorphous segments and with semi-crystalline segments have a glass transition temperature of at least 130°C, more preferably at least 150°C.
  • the melting temperature of the segmented block copolymer according to this embodiment is preferably > 200°C so as to guarantee optimum usability.
  • the melting temperature can be set by the appropriate selection of n, R lf R 2 ,and/or R 3 .
  • the T g /T m ratio (in K) is preferably at least 0.6, more in particular at least 0.7, because then the temperature range, i.e. between T g and T m , where the modulus decreases, is minimized.
  • the block copolymers according to this embodiment can be obtained with copolymers built up from segments with an irregular chain pattern and segments with a regular chain pattern. At service temperature these block copolymers have a multiphase structure, comprising one or more amorphous phases and a partly crystalline phase.
  • segments for the amorphous phase i.e. the phase with a low degree of order
  • segments with a molecular weight of at least 70 are used, for example polyamides, polyesters, amorphous esters, hydroxyl-terminal ketones,imides, amides, for instance semi-aromatic ketones, wholly or partly aromatic esters, amides and imides.
  • segments which yield a high glass transition temperature are advantageous to use.
  • n is preferably 1 or 2, because that permits the best possible uniform packing of the chain parts in the crystal.
  • Ri one can choose from an aliphatic, alicyclic or wholly or partly aromatic group, such as a paraphenyl or a naphthyl group, depending on the dicarboxylic acid chosen. A paraphenyl or a 2,5-, or a 2,6-naphthyl group is preferable.
  • R 2 is an aliphatic, alicyclic or wholly or partly aromatic group and preferably a lower, linear alkyl group with 2-8 carbon atoms. More preferably, ethylene, butylene, hexylene or octylene groups are used because they yield the best results.
  • R 3 preferably an aliphatic, aromatic, cycloaliphatic, aralkyl or alkaryl radical which may or may not be substituted is used.
  • 'aromatic group or wholly or partly aromatic group' includes groups in which two or more aromatic rings are connected with each other by a non-aromatic group, including non-hydrocarbon groups, such as ether bonds and the like.
  • the preparation of the starting products for the segments can be carried out in known manner, by reacting the diamine and the dicarboxylic acid or derivative thereof.
  • a diamine preferably 1,2- diaminoethane, l,4-diaminobutane, 1, 6-diaminohexane, 1,8-diaminooctane or paraphenylenedia ine is used.
  • the dicarboxylic acid to be used is preferably terephthalic acid, but it is also possible to use 2,6-naphthalenecarboxylic acid.
  • a diester-diamide is prepared by reacting a diamine with a molar excess of diester of a dicarboxylic acid, such as dimethylterephthalate. In general it will be preferable to use at least a double excess.
  • the ' reaction is preferably carried out in the presence of a catalyst, such as Li(OCH 3 ).
  • a catalyst such as Li(OCH 3 ).
  • the use of a catalyst is not requisite, but generally does promote the reaction positively.
  • a mixture of this starting product for the crystallizable block, and the starting product for the amorphous segment is then condensed to form a prepolymer.
  • This prepolymer can finally be after-condensed to form a segmented block copolymer with the desired properties.
  • the conditions known from the literature can be used.
  • the methods of preparing polyester-based segmented block copolymers can be used.
  • the methods of preparing polyamide-based segmented block copolymers can be used.
  • the prepolymerisation is carried out for 15- 60 min at a temperature ⁇ 225°C, at a pressure > 0.75 bar, followed by maintaining the temperature at a value of ⁇ 200°C for at least 60 min, at a ' pressure ⁇ 0.1 bar.
  • this second phase can be carried out in such a way that first the temperature is raised to a value between 200 and 300°C, at a * pressure between 10 and 50 mbar, for 10-45 min, and then is carried out at a temperature ⁇ 220°C and at a pressure ⁇ 5 mbar, for 45-120 min.
  • the prepolymer thus obtained is after-condensed in solid state at a temperature between 150°C and a temperature of some degrees below the melting point of the polymer, in the presence of a noble gas.
  • the segmented block copolymers according to the invention can be processed into objects in the conventional manner, for example by injection moulding at a temperature above the melting point.
  • the conventional techniques are also used for processing the present copolymers, where appropriate, to form fibres.
  • the conventional additives may be incorporated into the polymer, such as colouring matter, pigments, UV stabilizers, heat stabilizers, as well as fillers, such as soot, silicic acid, clay or glass fibers. It is also possible to mix the products according to the invention with one or more other plastics.
  • a segmented block copolymer was prepared starting from a hydroxyl-terminal polytetramethylene glycol having a molecular weight of 250, and a diester-diamide prepared in the following manner.
  • a mixture of l mol 1, -diaminobutane and 2.5 mol dimethylterephthalate was initially supplied to a reactor and then reacted in the presence of Li(OCH 3 ).
  • Li(OCH 3 ) Li(OCH 3 )
  • the segmented block copolymer was prepared from these two components by polycondensation for 30 min at 160°C and 1 bar. Then the reaction product was heated to 250°C and at that temperature condensed for 10 min by means of a vacuum created by a water jet pump and for 60 min by means of a vacuum created by an oil vacuum pump (0.05 mm Hg) .
  • the block copolymer obtained had an ⁇ in in m-cresol
  • a segmented block copolymer was prepared in the manner described in Example 1 using the same diester-diamide and a mixture of diols. Per mole diester-diamide 0.5 mol hexanediol and 0.5 mol octanediol were used, dissolved in ethanediol. The block copolymer thus obtained had an m-n of 0.42, and one of
  • the block copolymer had a T g of 103°C, a T m of 229°C and a T m -T c of 32°C.
  • a segmented block copolymer was prepared in the manner described in Example 1 using the same diester-diamide and l mol
  • a segmented block copolymer was prepared starting from a hydroxyl-terminal polytetramethylene glycol having a molecular weight of 700, and a diester-diamide prepared in the following 5 manner.
  • the segmented block copolymer was prepared from these two components by polycondensation for 30 min at 160°C and l bar. Then the reaction product was heated to 250°C and at that temperature further condensed for 10 min by means of a 15 vacuum generated by a water jet pump and for 60 min by means of a vacuum generated by an oil vacuum pump (0.05 mm Hg) .
  • the block copolymer (A) obtained had the properties listed in the Table.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Polyamides (AREA)
  • Small-Scale Networks (AREA)
  • Communication Control (AREA)

Abstract

Copolymère bloc segmenté comprenant des segments non cristallisables et des segments partiellement cristallisables, dans lesquels les segments partiellement cristallisables ont la formule -NH-R2-NH-[C(O)-R1-C(O)-NH-R2-NH]n-C(O)-R1-C(O)-[NH-R2-NH-C(O)-R1-C(O)]n- and/or -NH-R3-C(O)- ou un de leurs produits de réaction avec une diamine ou un acide dicarboxylique ou un dérivé d'un acide dicarboxylique, formule dans laquelle n est un nombre entier égal à 1, 2 ou 3, chacun de R1 et R2 sont indépendamment un groupe aliphatique, alicyclique ou entièrement ou partiellement aromatique, et R3 est un radical d'hydrocarbure pouvant être substituée ou non. Dans lesdits copolymères blocs les segments partiellement cristallisables ont une longueur de bloc sensiblement uniforme.
EP19910907198 1990-03-06 1991-03-06 Copolymeres blocs segmentes Withdrawn EP0519012A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
NL9000512 1990-03-06
NL9000510A NL9000510A (nl) 1990-03-06 1990-03-06 Gesegmenteerde blokcopolymeren.
NL9000510 1990-03-06
NL9000512A NL9000512A (nl) 1990-03-06 1990-03-06 Gesegmenteerde blokcopolymeren.
NL9000509 1990-03-06
NL9000509A NL9000509A (nl) 1990-03-06 1990-03-06 Gesegmenteerde blokcopolymeren.

Publications (1)

Publication Number Publication Date
EP0519012A1 true EP0519012A1 (fr) 1992-12-23

Family

ID=27352345

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19910907198 Withdrawn EP0519012A1 (fr) 1990-03-06 1991-03-06 Copolymeres blocs segmentes

Country Status (5)

Country Link
EP (1) EP0519012A1 (fr)
JP (1) JPH05506680A (fr)
AU (1) AU7660291A (fr)
CA (1) CA2077683A1 (fr)
WO (1) WO1991013930A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4308331A1 (de) * 1993-03-16 1994-09-22 Basf Ag Blockcopolyamide
BR9506386A (pt) * 1994-09-30 1997-09-16 Schweizerische Viscose Copoliamida com aperfeiçoado módulo de elasticidade para a fiação em fus o de filmamentos filamentos produzidos com elas e aplicação dos mesmos
ES2307901T3 (es) * 2002-02-21 2008-12-01 Stichting Dutch Polymer Institute Copolimero que contiene uno o mas segmentos amida.
US20050234215A1 (en) * 2002-02-21 2005-10-20 Gaymans Reinoud J Segmented copoymer containing amide segments
WO2007094654A1 (fr) * 2006-02-14 2007-08-23 Stichting Dutch Polymer Institute Procede de preparation de copolymeres segmentes contenant des segments de polyamide
US8450447B2 (en) 2007-03-14 2013-05-28 Dow Global Technologies Llc Copolyesteramides with decreased perfection of the amide sequence
ES2438743T3 (es) * 2009-06-08 2014-01-20 Basf Se Copolímeros de bloque de poliarilenéter segmentados
BR112012015306A2 (pt) 2009-12-22 2016-03-15 Dow Global Technologies Llc poli (bisoxalamida), processo para preparar uma poli (bisoxalamida) e artigo

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3005939A1 (de) * 1980-02-16 1981-09-03 Chemische Werke Hüls AG, 4370 Marl Polyamide fuer form- und ueberzugsmassen
DE3248776A1 (de) * 1982-12-31 1984-07-12 Chemische Werke Hüls AG, 4370 Marl Verwendung von copolyamiden zum heisssiegeln von textilien
EP0275988A3 (fr) * 1987-01-22 1989-11-15 Kuraray Co., Ltd. Copolymères de polyamide
EP0315027A3 (fr) * 1987-11-04 1990-10-31 General Electric Company Copolymère blocs amide-ester et leur procédé de préparation
JPH0641514B2 (ja) * 1988-08-17 1994-06-01 三菱化成株式会社 ブロックコポリアミドの製造法
US4868277A (en) * 1988-08-18 1989-09-19 The Dow Chemical Company Polyamide resins with good toughness properties

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9113930A1 *

Also Published As

Publication number Publication date
CA2077683A1 (fr) 1991-09-07
WO1991013930A1 (fr) 1991-09-19
JPH05506680A (ja) 1993-09-30
AU7660291A (en) 1991-10-10

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